CN109985532A - A kind of preparation method of the ultra-thin composite membrane of chitosan oligosaccharide - Google Patents
A kind of preparation method of the ultra-thin composite membrane of chitosan oligosaccharide Download PDFInfo
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- CN109985532A CN109985532A CN201910368233.XA CN201910368233A CN109985532A CN 109985532 A CN109985532 A CN 109985532A CN 201910368233 A CN201910368233 A CN 201910368233A CN 109985532 A CN109985532 A CN 109985532A
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- 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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Abstract
A kind of preparation method of the ultra-thin composite membrane of chitosan oligosaccharide, belongs to technical field of separation membrane preparation.The present invention uses water-soluble chitosan oligosaccharide for aqueous phase monomers, and pyromellitic trimethylsilyl chloride is oil phase monomer, forms chitosan oligosaccharide active layer by interface polymerization reaction on the poly (ether-sulfone) ultrafiltration membrane surface of different molecular weight cut offs.Hydrophily, biocompatibility and the natural antibacterial ability of chitosan oligosaccharide molecule assign active layer and reduce biomass absorbent and inhibit the characteristic of thalli growth breeding, keep the stability of membrane flux；Poly (ether-sulfone) ultrafiltration membrane can provide powerful mechanical support as porous basement membrane, guarantee physical stability of the composite membrane in long-time use process.The composite membrane can be used for microalgae/ferment product concentration of high biological pollution trend, the fields such as Industrial Wastewater Treatment.
Description
Technical field
The invention belongs to technical field of separation membrane preparation, in particular to the preparation method of a kind of ultra-thin composite membrane of chitosan oligosaccharide.
Background technique
In bioengineering field, microalgae/thallus fermentation liquid is that one kind contains organism, soluble large molecule, electrolysis
The complex mixture of many kinds of substance such as matter.With the fast development of bioengineering and biochemical technology, biological product Downstream processing (divides
From, purifying, concentration) and other process an urgent demands using modernization extracting and developing, purifying and concentration technique, to avoid biography
The technique purpose product rate of recovery of uniting is low, and loss late is high, large labor intensity, and acid, alkali, washing dosage are mostly big etc. scarce with waste liquid discharging amount
It falls into.Thus the processes such as traditional sheet frame, centrifuge, diatomite and evaporation and concentration will gradually be replaced.
In recent years, using ultrafiltration as the membrane technology of representative, have easy to operate, dewatering speed fastly and fermentation liquid cycles of concentration is high
The advantages that, once allowing field scientist to see the dawn for developing inexpensive microalgae/thallus recovery technology.Frustule and secondary generation
It thanks to product bring membrane pollution problem to bring new limitation to ultrafiltration membrane technique and increase many not for the development of the technology
Know number.The business ultrafiltration membrane and microfiltration membranes that Claudia Nurra et al. has investigated different molecular weight cut off (5~400KDa) are to micro-
The influence for the fouling membrane that algae generates is found that while that the pure water flux of microfiltration membranes is maximum, but after changing microalgae liquid into, membrane flux ratio
The ultrafiltration membrane of molecular cut off 5KDa is also low, illustrates organic matter possibly into fenestra and is adsorbed on fenestra inner wall and causes fenestra narrow
Change, so as to cause serious irreversible membrane fouling.Illustrate that the ultrafiltration membrane of small-bore can reduce the blocking of fenestra, is more suitable for frustule
Harvesting.Business ultrafiltration membrane is mainly prepared by organic material at present, and most of organic film material such as polysulfones, polyolefins and is contained
Fluorine class material is hydrophobic material, and antifouling property is poor, and the hydrophily and antibiosis for improving membrane material are to reduce organic matter
The main method of fouling membrane.
Chitosan (Chitosan) is a kind of natural macromolecular material for being widely present in nature, is chitin
It (Chitin) is unique a large amount of existing natural alkaline polysaccharides in living nature through deacetylated treated product.Chitosan
It is dispersed with many hydroxyls and amino on strand, is easy to form a film, is the natural membrane material of a kind of good hydrophilic property, antibacterial, it is great to open
Send out potentiality.Scientists, for supporter, are prepared with polysulfones, Kynoar, PET non-woven fabrics etc. using the method for dip-coating or spraying
Composite hyperfiltration membrane.As substrate, coating chitosan-acetic acid solution prepares compound the polypropylene non-woven fabric that Wang etc. is crossed using ozone treatment
Film.Prepared chitosan complex film has the function of anti-protein and bacterium viscosity, and use has in membrane bioreactor
The advantages that flux height and preventing membrane pollution performance.Although chitosan ultrafiltration membrane prepared by this method has one in terms of preventing membrane pollution
Fixed raising, but its active layer is thicker, flux is lower, easy densification etc. becomes a major obstacle for limiting its application.
Interfacial polymerization may be implemented to prepare ultra-thin active layer, mitigate resistance of the solute by basement membrane.Interfacial polymerization is one
The process of a diffusion control generates one with organic phase monomer reaction research shows that aqueous phase monomers are diffused into organic phase from water phase
The thin densified polymer layer of layer.But the molecular weight of chitosan is big and solution viscosity is high, so that chitosan molecule can not pass through
It diffuses into organic phase reaction and generates reactive layer.Chitosan oligosaccharide is the product that chitosan is further degraded, and is had and chitosan phase
As characteristic, therefore people expect naturally can with chitosan oligosaccharide substitute chitosan prepare ultrafiltration membrane, but in preparation process find meet
It can not such as form a film to various technical problems, still flux is low, film thickness is still undesirable.
Summary of the invention
In view of the shortcomings of the prior art, the object of the present invention is to provide a kind of preparation method of chitosan oligosaccharide composite membrane, the shell
The ultra-thin composite membrane active layer of oligosaccharides is ultra-thin, flux is high, densification performance is high.
Technical scheme is as follows:
A kind of preparation method of the ultra-thin composite membrane of chitosan oligosaccharide, it is characterised in that following steps:
1) basement membrane is fixed on polymer reactor bottom
2) chitosan oligosaccharide aqueous solution is poured into the polymer reactor of step 1)；With
3) water droplet that membrane surface is drawn after pouring out the chitosan oligosaccharide in polymer reactor, it is molten to be subsequently poured into oil phase monomer
Liquid carries out interface polymerization reaction；
4) after polymerization reaction, oil phase monomer is poured out into reactor, the unreacted oil of cleaning membrane surface removal is mutually single
Body；
5) after polymer reactor being dried at 50~70 DEG C, the ultra-thin composite membrane of chitosan oligosaccharide is made；Wherein, locating shell
The molecular weight of oligosaccharides is 3000-10000Da, deacetylation 70-90%.
In some embodiments, the basement membrane is nonwoven fabric base ultrafiltration membrane, it is face-up fixed on double-faced sticking paper
Polymer reactor bottom.
In some embodiments, the nonwoven fabric base ultrafiltration membrane is polysulfones, in polyether sulfone, Kynoar, polypropylene
One kind, molecular cut off 50KDa.
In some embodiments, the oil phase monomer is polynary acyl chlorides, including pyromellitic trimethylsilyl chloride, isophthaloyl
Chlorine, paraphthaloyl chloride etc..
In some embodiments, the oil phase monomer is the alkane for the pyromellitic trimethylsilyl chloride that mass fraction is 0.1~0.5%
Solution；The alkane is n-hexane, hexamethylene, petroleum ether etc..
In some embodiments, the mass fraction of the chitosan oligosaccharide aqueous solution is 1~3%.
In some embodiments, the concrete operations of the step be polymer reactor is moved in hot air drier 50~
It is 5~30 minutes dry at 70 DEG C.
In some embodiments, poured into described in step (2) and (3) chitosan oligosaccharide aqueous solution in interface polymerization reaction device and
The amount of oil phase monomer solution should not have and slightly above membrane surface；Use nonwoven fabric base ultrafiltration membrane for basement membrane, it is face-up
Interface polymerization reaction device bottom is fixed on double-faced sticking paper；
In some embodiments, the concrete operations of step (2) and (3) are to pour this solution into 5 in interface polymerization reaction device
~chitosan oligosaccharide in polymer reactor is poured out after ten minutes after with filter paper draw membrane surface water droplet, then by polymerization reaction
Device moves in draught cupboard, pour into mass fraction be 0.1~0.5% oil phase monomer solution, interface polymerization reaction 1~5 minute；
In some embodiments, after step (4) interface polymerization reaction, oil phase monomer solution is poured out into polymerization reaction
Device cleans film surface with alkane solution such as hexane solution and removes unreacted oil phase monomer such as pyromellitic trimethylsilyl chloride；
The beneficial effects of the present invention are: we have found that can be to activity by the chitosan oligosaccharide of selection particular range molecular weight
The structure of layer is regulated and controled；The ultra-thin composite membrane of prepared chitosan oligosaccharide has good physical and chemical stability (long-term filtering, film
Performance essentially unchangedization), ultra-thin (only tens nanometers of the thickness, in scanning electron of the ultra-thin composite membrane active layer of chitosan oligosaccharide
Do not characterized not come out on microscope), 0.81 is up to than flux.The present invention utilizes the natural characteristic that has of chitosan oligosaccharide, this composite membrane from
Three hydrophily, biocompatibility and antibiotic property aspects enhance preventing membrane pollution performance simultaneously.This composite membrane can biological medicine,
Realize the high-efficient purification filtering and concentration the most economic of fermentation liquid in the fields such as food industry.
Detailed description of the invention
The surface texture scanning electron microscope (SEM) photograph of chitosan oligosaccharide composite membrane made from Fig. 1 embodiment 1.
The surface texture scanning electron microscope (SEM) photograph of chitosan oligosaccharide composite membrane made from Fig. 2 embodiment 2.
The surface texture scanning electron microscope (SEM) photograph of chitosan oligosaccharide composite membrane made from Fig. 3 embodiment 3.
The surface texture schematic diagram of chitosan oligosaccharide composite membrane made from Fig. 4 embodiment 2.
The surface texture atomic force microscopy diagram of chitosan oligosaccharide composite membrane made from Fig. 5-1 embodiment 1.
The surface texture atomic force microscopy diagram of chitosan oligosaccharide composite membrane made from Fig. 5-2 embodiment 2.
The surface texture atomic force microscopy diagram of chitosan oligosaccharide composite membrane made from Fig. 5-3 embodiment 3.
Specific embodiment:
Specific embodiments of the present invention are described in detail below in conjunction with technical solution.It is noted that these embodiments are only used
In illustrating the present invention, rather than limit the scope of the invention.Additionally it is noted that having read in of the invention lecture
After appearance, those skilled in the art equally fall within the application to the various changes of the invention made or modification, such equivalent forms
The appended claims limited range.
Embodiment 1
1) using molecular weight cut off for the nonwoven fabric base ultrafiltration membrane of 50KDa is basement membrane, it is face-up used double-faced sticking paper
It is fixed on interface polymerization reaction device bottom；
2) taking molecular weight is 3000Da, and the chitosan oligosaccharide powder 1g that deacetylation is 90% is dissolved in the pure water of 99g and stirs
Uniformly, the chitosan oligosaccharide aqueous solution that mass fraction is 1% is prepared；It pours this solution into interface polymerization reaction device 1) 10 minutes；
3) water droplet for drawing polyether sulfone membrane surface after pouring out the chitosan oligosaccharide in reactor with filter paper, then by reactor
Move in draught cupboard, pour into mass fraction be 0.1% pyromellitic trimethylsilyl chloride hexane solution, interface polymerization reaction 2 minutes；
4) after interface polymerization reaction, pyromellitic trimethylsilyl chloride is poured out into reactor, cleans film surface with hexane solution
Remove unreacted pyromellitic trimethylsilyl chloride；
5) reactor is moved in hot air drier it is 20 minutes dry at 60 DEG C, finally by the composite membrane prepared from anti-
It answers to take out in device and be stored in pure water.
6) composite membrane is placed in Dead-end ultrafiltration test device, effectively filtering membrane area is 45cm2, operating pressure is
0.1MPa, at room temperature (25 ± 1 DEG C), the pure water flux for testing to obtain diaphragm by feeding liquid of pure water is 261L/m2H, with Jp(0)Table
Show.
7) the chlorella fermentation liquid for selecting autotrophy fermented and cultured is solution to be measured, adjusts the thin of every batch of chlorella solution example
Born of the same parents' concentration is 3,000,000,000/L, organic carbon concentration 2.4mg/L.It is 0.1MPa in operating pressure, is transported under room temperature (25 ± 1 DEG C)
Row 400min tests frustule rejection.Surveyed frustule rejection is 99%.It keeps diaphragm not take out in the device, pours out
Pure water is poured into after chlorella fermentation liquid in device, the pure water flux after testing fouling membrane, with Jp(1)It indicates.In this way, ultra filtration
Membrane flux recovery rate in journey can then be expressed as Jp(1)/Jp(0).The membrane flux recovery rate of composite membrane for measuring the preparation of example 1 is
0.81, and the membrane flux recovery rate that molecular weight cut off is the poly (ether-sulfone) ultrafiltration membrane of 50KDa is only 0.3.
8) diaphragm for filtering chlorella fermentation liquid is taken out out of ultrafiltration apparatus, is installed after being then inverted.With pure water be into
Feed liquid carries out backwash 20min under conditions of operating pressure 0.1MPa, room temperature (25 ± 1 DEG C).Then diaphragm is taken out and is carried out
The adherency situation of frustule on diaphragm is observed in freeze-drying at scanning electron microscope (SEM).It has been observed that chitosan oligosaccharide is multiple under SEM
Close the film surface adherency for the poly (ether-sulfone) ultrafiltration membrane that frustule can be removed from film surface by pure water backwash, and be commercialized by film
Frustule can not be by simply backwashing removal.The experimental results showed that composite membrane prepared by example 1 have it is excellent anti-stick
Attaching organism pollutant performance.
9) using ultrapure water as normal fluid, droplet size is 0.01m L.Ultrapure water droplet freezes in 5s after film surface
Drop is born water in the image of film surface, the measurement of contact angle is then carried out with the software that contact angle measurement carries.Contact angle test
The result shows that the contact angle of composite membrane prepared by example 1 is 67.1 °, and 83.5 ° of commercial polyether sulfone ultrafiltration membrane.Illustrate film table
Face hydrophily is improved to some extent.
Embodiment 2
1) using molecular weight cut off for the nonwoven fabric base ultrafiltration membrane of 50KDa is basement membrane, it is face-up used double-faced sticking paper
It is fixed on interface polymerization reaction device bottom；
2) taking molecular weight is 5000Da, and the chitosan oligosaccharide powder 1g that deacetylation is 70% is dissolved in the pure water of 99g and stirs
Uniformly, the chitosan oligosaccharide aqueous solution that mass fraction is 1% is prepared；It pours this solution into interface polymerization reaction device 1) 10 minutes；
3) water droplet for drawing polyether sulfone membrane surface after pouring out the chitosan oligosaccharide in reactor with filter paper, then by reactor
Move in draught cupboard, pour into mass fraction be 0.1% pyromellitic trimethylsilyl chloride hexane solution, interface polymerization reaction 2 minutes；
4) after interface polymerization reaction, pyromellitic trimethylsilyl chloride is poured out into reactor, cleans film surface with hexane solution
Remove unreacted pyromellitic trimethylsilyl chloride；
5) reactor is moved in hot air drier it is 20 minutes dry at 60 DEG C, finally by the composite membrane prepared from anti-
It answers to take out in device and be stored in pure water.
6) film is placed in Dead-end ultrafiltration test device, effectively filtering membrane area is 45cm2, operating pressure is
0.1MPa, at room temperature (25 ± 1 DEG C), the pure water flux for testing to obtain diaphragm by feeding liquid of pure water is 398L/m2H, with Jp(0)Table
Show.
7) the chlorella fermentation liquid for selecting autotrophy fermented and cultured is solution to be measured, adjusts the thin of every batch of chlorella solution example
Born of the same parents' concentration is 3,000,000,000/L, organic carbon concentration 2.4mg/L.It is 0.1MPa in operating pressure, is transported under room temperature (25 ± 1 DEG C)
Row 400min tests frustule rejection.Surveyed frustule rejection is 99%.It keeps diaphragm not take out in the device, pours out
Pure water is poured into after chlorella fermentation liquid in device, the pure water flux after testing fouling membrane, with Jp(1)It indicates.In this way, ultra filtration
Membrane flux recovery rate in journey can then be expressed as Jp(1)/Jp(0).The membrane flux recovery rate of composite membrane for measuring the preparation of example 2 is
0.75, and the membrane flux recovery rate that molecular weight cut off is the poly (ether-sulfone) ultrafiltration membrane of 50KDa is only 0.3.
8) diaphragm for filtering chlorella fermentation liquid is taken out out of ultrafiltration apparatus, is installed after being then inverted.With pure water be into
Feed liquid carries out backwash 20min under conditions of operating pressure 0.1MPa, room temperature (25 ± 1 DEG C).Then diaphragm is taken out and is carried out
The adherency situation of frustule on diaphragm is observed in freeze-drying at scanning electron microscope (SEM).It has been observed that chitosan oligosaccharide is multiple under SEM
Close the film surface adherency for the poly (ether-sulfone) ultrafiltration membrane that frustule can be removed from film surface by pure water backwash, and be commercialized by film
Frustule can not be by simply backwashing removal.The experimental results showed that chitosan oligosaccharide composite membrane has excellent anti-stick grow nonparasitically upon another plant
Object pollutant performance.
9) using ultrapure water as normal fluid, droplet size is 0.01m L.Ultrapure water droplet freezes in 5s after film surface
Drop is born water in the image of film surface, the measurement of contact angle is then carried out with the software that contact angle measurement carries.Contact angle test
The result shows that the contact angle of composite membrane prepared by embodiment 1 is 67.6 °, and 83.5 ° of commercial polyether sulfone ultrafiltration membrane.Illustrate film
Surface hydrophilicity is improved to some extent.
Embodiment 3
1) using molecular weight cut off for the nonwoven fabric base ultrafiltration membrane of 50KDa is basement membrane, it is face-up used double-faced sticking paper
It is fixed on interface polymerization reaction device bottom；
2) taking molecular weight is 3000Da, and the chitosan oligosaccharide powder 1g that deacetylation is 90% is dissolved in the pure water of 99g and stirs
Uniformly, the chitosan oligosaccharide aqueous solution that mass fraction is 1% is prepared；It pours this solution into interface polymerization reaction device 1) 10 minutes；
3) water droplet for drawing polyether sulfone membrane surface after pouring out the chitosan oligosaccharide in reactor with filter paper, then by reactor
Move in draught cupboard, pour into mass fraction be 0.1% pyromellitic trimethylsilyl chloride hexane solution, interface polymerization reaction 2 minutes；
4) after interface polymerization reaction, pyromellitic trimethylsilyl chloride is poured out into reactor, cleans film surface with hexane solution
Remove unreacted pyromellitic trimethylsilyl chloride；
5) reactor is moved in hot air drier it is 20 minutes dry at 60 DEG C, finally by the composite membrane prepared from anti-
It answers to take out in device and be stored in pure water.
6) film is placed in Dead-end ultrafiltration test device, effectively filtering membrane area is 45cm2, operating pressure is
0.1MPa, at room temperature (25 ± 1 DEG C), the pure water flux for testing to obtain diaphragm by feeding liquid of pure water is 265L/m2H, with Jp(0)Table
Show.
7) the chlorella fermentation liquid for selecting autotrophy fermented and cultured is solution to be measured, adjusts the thin of every batch of chlorella solution example
Born of the same parents' concentration is 3,000,000,000/L, organic carbon concentration 2.4mg/L.It is 0.1MPa in operating pressure, is transported under room temperature (25 ± 1 DEG C)
Row 400min tests frustule rejection.Surveyed frustule rejection is 99%.It keeps diaphragm not take out in the device, pours out
Pure water is poured into after chlorella fermentation liquid in device, the pure water flux after testing fouling membrane, with Jp(1)It indicates.In this way, ultra filtration
Membrane flux recovery rate in journey can then be expressed as Jp(1)/Jp(0).Measure the membrane flux recovery rate of the composite membrane of the preparation of embodiment 3
It is 0.72, and the membrane flux recovery rate that molecular weight cut off is the poly (ether-sulfone) ultrafiltration membrane of 50KDa is only 0.3.
8) diaphragm for filtering chlorella fermentation liquid is taken out out of ultrafiltration apparatus, is installed after being then inverted.With pure water be into
Feed liquid carries out backwash 20min under conditions of operating pressure 0.1MPa, room temperature (25 ± 1 DEG C).Then compound film sheet is taken out
It is lyophilized, the adherency situation of frustule on diaphragm is observed at scanning electron microscope (SEM).It has been observed that shell is few under SEM
The film surface for the poly (ether-sulfone) ultrafiltration membrane that frustule can be removed from film surface by pure water backwash, and be commercialized by sugared composite membrane
The frustule of adherency can not be by simply backwashing removal.The experimental results showed that chitosan oligosaccharide composite membrane have it is excellent anti-stick
Attaching organism pollutant performance.
1) using ultrapure water as normal fluid, droplet size 0.01mL.Ultrapure water droplet freezes in 5s after film surface
Then water droplet carries out the measurement of contact angle in the image of film surface with the software that contact angle measurement carries.Contact angle test knot
Fruit shows that the contact angle of the composite membrane of embodiment preparation is 68.4 °, and 83.5 ° of commercial polyether sulfone ultrafiltration membrane.Illustrate film surface
Hydrophily is improved to some extent.
Claims (9)
1. a kind of preparation method of the ultra-thin composite membrane of chitosan oligosaccharide, comprising the following steps:
1) basement membrane is fixed on polymer reactor bottom；
2) chitosan oligosaccharide aqueous solution is poured into the polymer reactor of step 1)；With
3) water droplet that membrane surface is drawn after pouring out the chitosan oligosaccharide in polymer reactor, is subsequently poured into oil phase monomer solution, into
Row interface polymerization reaction；
4) oil phase monomer after reaction, is poured out into reactor, cleaning membrane surface removes unreacted oil phase monomer；
5) after polymer reactor is dry at 50~70 DEG C, the composite membrane that step (4) prepares is taken out into guarantor from reactor
It deposits in water；
Wherein, the molecular weight of the chitosan oligosaccharide is 3000-10000Da, deacetylation 70-90%.
2. preparation method as described in claim 1, the molecular weight of the chitosan oligosaccharide is 3000 Da, deacetylation 90%.
3. preparation method as described in claim 1, the basement membrane is nonwoven fabric base ultrafiltration membrane.
4. preparation method as claimed in claim 3, the nonwoven fabric base ultrafiltration membrane is polysulfones, polyether sulfone, Kynoar, poly- third
One of alkene, molecular cut off 50KDa.
5. preparation method as described in claim 1, the oil phase monomer is pyromellitic trimethylsilyl chloride, isophthaloyl chloride or terephthaldehyde
Acyl chlorides.
6. preparation method as claimed in claim 5, the oil phase monomer solution is the equal benzene that mass fraction is 0.1%~0.5%
The alkane solution of three formyl chlorides.
7. preparation method as described in claim 1, the mass fraction of the chitosan oligosaccharide aqueous solution is 1%~3%.
8. preparation method as described in claim 1, the concrete operations of the step (5) are that polymer reactor is moved to heated-air drying
It is 5~30 minutes dry at 50~70 DEG C in case.
9. the preparation method of the ultra-thin composite membrane of a kind of chitosan oligosaccharide according to claim 1, it is further characterized in that step (2) and
(3) amount of the chitosan oligosaccharide aqueous solution poured into interface polymerization reaction device and oil phase monomer solution described in should not have and slightly above base
Film surface.
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| CN109985532B (en) | 2021-11-09 |
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