CN107158974A - A kind of high intensity hydrophily NF membrane and preparation method thereof and the application in protein solution desalination processes - Google Patents
A kind of high intensity hydrophily NF membrane and preparation method thereof and the application in protein solution desalination processes Download PDFInfo
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- CN107158974A CN107158974A CN201710360650.0A CN201710360650A CN107158974A CN 107158974 A CN107158974 A CN 107158974A CN 201710360650 A CN201710360650 A CN 201710360650A CN 107158974 A CN107158974 A CN 107158974A
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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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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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
- B01D2325/36—Hydrophilic membranes
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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
- B01D2325/42—Ion-exchange membranes
Abstract
Application the present invention relates to a kind of high intensity hydrophily NF membrane and preparation method thereof and in protein solution desalination processes, belongs to technology field of membrane materials.The NF membrane that the present invention is provided is utilized to be formed between the modifying agent containing polyhydroxy and the SiO of montmorillonite and is bonded, form the network structure of crosslinking, modifying agent also has hydrophobic group because that can constitute preferable compatible structure between basement membrane, realize that the adhesion between montmorillonite and basement membrane is improved simultaneously；Because montmorillonite has preferable ion-exchange performance, when NF membrane is applied into protein solution desalination processes, due to the hydrophily of film, can have preferable cutoff performance and antifouling property to protein, again because montmorillonite has ion-exchange performance, also there is higher transmitance to inorganic salts.
Description
Technical field
The present invention relates to a kind of high intensity hydrophily NF membrane and preparation method thereof and in protein solution desalination processes
Application, belong to technology field of membrane materials.
Background technology
Nanofiltration (Nanofiltration) is a kind of new pressure-driven membrane separating process that developed recently gets up, and is to be situated between
A kind of membrane separation technique between counter-infiltration and ultrafiltration, because its operating pressure is relatively low, has different choice to one, divalent ion
Property, there is higher rejection to small organic molecule, and have the advantages that equipment investment is low, consume energy low [3], so being current state
One of focus of inside and outside UF membrane area research.NF membrane pore diameter range is about in 1~5 ran, the retention molecule of film
Amount about 200~2000.NF membrane is composite membrane mostly, and its surface separation layer is made up of polyelectrolyte, high price salt can be retained and
Through monovalent salt, can molecular cut off more than 100 organic matter and small organic molecule is passed through film, same amino acid can be separated
And protein, the separation of high relative molecular weight and low phase to molecular weight organics is realized, thus it is widely used in food, pharmacy
In chemical industry, biochemistry, environmental protection, the field of metallurgy such as separation, concentration, refined, Industrial Wastewater Treatment, drinking water preparation, material recycle.
Recently as extensive application of the nanofiltration in the industries such as water process, pharmacy, food, to hydrophily NF membrane
Demand greatly improve.However, the hydrophily NF membrane kind with commercial application value is but extremely rarely seen.Therefore, new system
Membrane technology and surface hydrophilic modification method turn into the focus that NF membrane is developed.
Method to the surface progress hydrophilic modifying of NF membrane includes：Grafting modification method, physical modified method（For example it is purple
External irradiation）, inorganic particle doping method.Wherein, inorganic particle doping method is by that will have hydrophilic inorganic particle to add system
In membrane material, the hydrophily for making film using inorganic particle is improved.
But, because material of preparing is generally all polymer, its compatibility between inorganic particle is low, is easily caused film
The intensity of material is not high, easily occurs in the damage during use.
The content of the invention
The purpose of the present invention is：Propose that one kind has hydrophilic NF membrane, this NF membrane has higher intensity, by
In in the high advantage of its hydrophily, it is adaptable to the concentrating and separating process of protein.Technical concept is：Utilize changing containing polyhydroxy
Property agent and the-SiO- of montmorillonite between formed and be bonded, form the network structure of crosslinking, at the same modifying agent also have hydrophobic group because,
Preferable compatible structure can be constituted between basement membrane, realizes that the adhesion between montmorillonite and basement membrane is improved；Due to montmorillonite
,, can be right due to the hydrophily of film when NF membrane is applied into protein solution desalination processes with preferable ion-exchange performance
Protein has preferable cutoff performance and antifouling property, and because montmorillonite has ion-exchange performance, to inorganic salts
Also there is higher transmitance.
Technical scheme is：
The first aspect of the invention：
A kind of preparation method of high intensity hydrophily NF membrane, comprises the following steps：
1st step, the preparation of aqueous phase solution：By weight, 1.2~2.5 parts of montmorillonite is taken, 80~90 parts of deionization is scattered in
In water, 0.2~0.5 part of anion surfactant, 2~4 parts of Piperazine anhydrous and 0.5~0.8 part of formula is added（I）Institute
The compound shown, ultrasonic agitation is uniform, is used as aqueous phase solution；
(I)；
2nd step, the preparation of oil-phase solution：By weight, by pyromellitic trimethylsilyl chloride 5~12 parts be dissolved in 80~85 parts of n-hexane
In, it is well mixed, is used as oil-phase solution；
3rd step, interfacial polymerization：Using milipore filter as basement membrane, basement membrane is soaked in aqueous phase solution, after taking-up, then oil phase is soaked in
In solution, after taking-up, dried in 50~65 DEG C of air blast bellows, then surface washing is carried out with deionized water, obtain high intensity
Hydrophily NF membrane.
In the 1st described step, anion surfactant is any in dodecyl sodium sulfate, lauryl sodium sulfate
A kind of or two kinds of mixing.
In the 3rd described step, ultrafiltration membrane material is selected from polyether sulfone, Kynoar or polysulfones；The retention of milipore filter point
Son amount scope is 8~150,000.
In the 3rd described step, the time that basement membrane is soaked in aqueous phase solution is 3~10min；Basement membrane is soaked in oil-phase solution
Time is 3~10min；Drying time is 30~60min.
The second aspect of the invention：
The NF membrane that above-mentioned preparation method is directly obtained.
The third aspect of the invention：
A kind of desalination process of saliferous protein, is concentrated using above-mentioned NF membrane.
Described protein is BSA；Described salt is NaCl.
Operating parameter during described concentration is：0.5~2.5Mpa of pressure, 10~30 DEG C of temperature.
Montmorillonite is for improving NF membrane to the application in rate and protein retention and the transmitance of raising inorganic salts simultaneously.
Beneficial effect
The NF membrane that the present invention is provided is utilized to be formed between the modifying agent containing polyhydroxy and the-SiO- of montmorillonite and is bonded, and is formed
The network structure of crosslinking, while modifying agent also has hydrophobic group because that can constitute preferable compatible structure between basement membrane, realize
Adhesion between montmorillonite and basement membrane is improved；Because montmorillonite has preferable ion-exchange performance, NF membrane is applied to
During protein solution desalination processes, due to the hydrophily of film, can have preferable cutoff performance and resistance tocrocking to protein
Can, and because montmorillonite has ion-exchange performance, also there is higher transmitance to inorganic salts.
Brief description of the drawings
Fig. 1 is the infared spectrum for the NF membrane that embodiment 3 is prepared.
Embodiment
Embodiment 1
1st step, the preparation of aqueous phase solution：By weight, take in 1.2 parts of montmorillonite, the deionized water for being scattered in 80 parts, then add
Enter 0.2 part of lauryl sodium sulfate, 2 parts of Piperazine anhydrous and 0.5 part of formula（I）Shown compound, ultrasonic agitation is uniform,
It is used as aqueous phase solution；
(I)；
2nd step, the preparation of oil-phase solution：By weight, by pyromellitic trimethylsilyl chloride 5 parts be dissolved in 80 parts of n-hexane, mix
Uniformly, as oil-phase solution；
3rd step, interfacial polymerization：Using poly (ether-sulfone) ultrafiltration membrane as basement membrane (molecular cut off scope is 120,000), basement membrane is soaked in water
3min in phase solution, after taking-up, then is soaked in 3min in oil-phase solution, after taking-up, is dried in 50 DEG C of air blast bellows
30min, then surface washing is carried out with deionized water, obtain high intensity hydrophily NF membrane.
Embodiment 2
1st step, the preparation of aqueous phase solution：By weight, take in .5 parts of montmorillonite 2, the deionized water for being scattered in 90 parts, then add
Enter 0.5 part of lauryl sodium sulfate, 4 parts of Piperazine anhydrous and 0.8 part of formula（I）Shown compound, ultrasonic agitation is uniform,
It is used as aqueous phase solution；
(I)；
2nd step, the preparation of oil-phase solution：By weight, by pyromellitic trimethylsilyl chloride 12 parts be dissolved in 85 parts of n-hexane, mix
Uniformly, as oil-phase solution；
3rd step, interfacial polymerization：Using poly (ether-sulfone) ultrafiltration membrane as basement membrane (molecular cut off scope is 120,000), basement membrane is soaked in water
10min in phase solution, after taking-up, then is soaked in 10min in oil-phase solution, after taking-up, is dried in 65 DEG C of air blast bellows
60min, then surface washing is carried out with deionized water, obtain high intensity hydrophily NF membrane.
Embodiment 3
1st step, the preparation of aqueous phase solution：By weight, take in 1.8 parts of montmorillonite, the deionized water for being scattered in 85 parts, then add
Enter 0.3 part of lauryl sodium sulfate, 3 parts of Piperazine anhydrous and 0.6 part of formula（I）Shown compound, ultrasonic agitation is uniform,
It is used as aqueous phase solution；
(I)；
2nd step, the preparation of oil-phase solution：By weight, by pyromellitic trimethylsilyl chloride 8 parts be dissolved in 82 parts of n-hexane, mix
Uniformly, as oil-phase solution；
3rd step, interfacial polymerization：Using poly (ether-sulfone) ultrafiltration membrane as basement membrane (molecular cut off scope is 120,000), basement membrane is soaked in water
5min in phase solution, after taking-up, then is soaked in 5min in oil-phase solution, after taking-up, is dried in 55 DEG C of air blast bellows
40min, then surface washing is carried out with deionized water, obtain high intensity hydrophily NF membrane.
The surface infared spectrum of obtained NF membrane is as shown in figure 1, wherein, 3436cm-1NH on piperazine ring2Absworption peak,
2929 cm-1With 1430 cm-1It is the vibration performance peak of phenyl ring；1635 cm-1It is acid amides-CONH- characteristic peaks；1222 cm-1It is
R-O-R ' the ether characteristic peaks that modifying agent is.It can be confirmed that being formed between modifying agent and piperazine, pyromellitic trimethylsilyl chloride, montmorillonite
Copolymerization network.
Reference examples 1
Difference with embodiment 3 is：In the preparation of aqueous phase solution, formula is not added（I）Shown compound.
Reference examples 2
Difference with embodiment 3 is：In the preparation of aqueous phase solution, montmorillonite is not added.
Characterize experiment
1st, the tensile strength of NF membrane is determined using tensile testing machine；
2nd, the pure water flux of NF membrane is determined under the conditions of 0.5Mpa；
3rd, the filtration test of saliferous protein solution
Prepare and contain 2wt% bovine serum albumins（BSA）With the 3wt%NaCl aqueous solution, concentrate egg is carried out using above-mentioned NF membrane
In white matter and desalination experiment, filter process, 25 DEG C of feed temperature, filter pressure 1.5Mpa, penetrating fluid is back to material liquid tank progress
Circulation.Filtration time 50min, determines the rejection and NaCl rejection to BSA.
As a result it is as follows：
As can be seen from the table, the composite nanometer filtering film that the present invention is provided has higher intensity and water flux；Wherein, embodiment
3 for reference examples 1, and by adding the modifying agent having compared with polyhydroxy in aqueous phase solution, hydroxyl can be with covering de-
It is crosslinked between-SiO- the keys of stone, realizes the effect that the tensile strength of film is improved；Embodiment 3 can be with relative to reference examples 2
Find out, add montmorillonite, make use of its ion exchangeable, NaCl permeability is improved, and it is de- due to covering
Stone is, with hydrophily, to also improve the rejection to BSA, the separating degree of albumen and salt is improved.
Claims (9)
1. a kind of preparation method of high intensity hydrophily NF membrane, it is characterised in that comprise the following steps：
1st step, the preparation of aqueous phase solution：By weight, 1.2~2.5 parts of montmorillonite is taken, 80~90 parts of deionization is scattered in
In water, 0.2~0.5 part of anion surfactant, 2~4 parts of Piperazine anhydrous and 0.5~0.8 part of formula is added（I）Institute
The compound shown, ultrasonic agitation is uniform, is used as aqueous phase solution；
(I)；
2nd step, the preparation of oil-phase solution：By weight, by pyromellitic trimethylsilyl chloride 5~12 parts be dissolved in 80~85 parts of n-hexane
In, it is well mixed, is used as oil-phase solution；
3rd step, interfacial polymerization：Using milipore filter as basement membrane, basement membrane is soaked in aqueous phase solution, after taking-up, then oil phase is soaked in
In solution, after taking-up, dried in 50~65 DEG C of air blast bellows, then surface washing is carried out with deionized water, obtain high intensity
Hydrophily NF membrane.
2. the preparation method of high intensity hydrophily NF membrane according to claim 1, it is characterised in that the 1st described step
In, anion surfactant is the mixing of any one or two kinds in dodecyl sodium sulfate, lauryl sodium sulfate.
3. the preparation method of high intensity hydrophily NF membrane according to claim 1, it is characterised in that the 3rd described step
In, ultrafiltration membrane material is selected from polyether sulfone, Kynoar or polysulfones；The molecular cut off scope of milipore filter is 8~150,000.
4. the preparation method of high intensity hydrophily NF membrane according to claim 1, it is characterised in that the 3rd described step
In, the time that basement membrane is soaked in aqueous phase solution is 3~10min；The time that basement membrane is soaked in oil-phase solution is 3~10min；Dry
Time is 30~60min.
5. the NF membrane that the preparation method described in any one of Claims 1 to 4 is directly obtained.
6. a kind of desalination process of saliferous protein, it is characterised in that concentrated using the NF membrane described in claim 5.
7. the desalination process of saliferous protein according to claim 6, it is characterised in that described protein is BSA；Institute
The salt stated is NaCl.
8. the desalination process of saliferous protein according to claim 6, it is characterised in that during described concentration
Operating parameter is：0.5~2.5Mpa of pressure, 10~30 DEG C of temperature.
9. montmorillonite is for improving NF membrane to the application in rate and protein retention and the transmitance of raising inorganic salts simultaneously.
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Cited By (2)
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| CN108097062A (en) * | 2017-12-21 | 2018-06-01 | 段艳玲 | It is a kind of for hollow fiber compound nanofiltration membrane of water filter purification and preparation method thereof |
| CN115400612A (en) * | 2022-08-31 | 2022-11-29 | 西北工业大学 | Modified polyamide separation membrane for resisting scaling and oxidation and preparation method thereof |
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