CN109012189A - A method of graphene oxide composite nano filter membrane is prepared using Freeze Drying Technique - Google Patents
A method of graphene oxide composite nano filter membrane is prepared using Freeze Drying Technique Download PDFInfo
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- CN109012189A CN109012189A CN201811075534.5A CN201811075534A CN109012189A CN 109012189 A CN109012189 A CN 109012189A CN 201811075534 A CN201811075534 A CN 201811075534A CN 109012189 A CN109012189 A CN 109012189A
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- 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
- B01D61/027—Nanofiltration
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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
- B01D67/0039—Inorganic membrane manufacture
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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
- B01D69/04—Tubular membranes
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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
- B01D69/06—Flat membranes
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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
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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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
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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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
Abstract
A method of graphene oxide composite nano filter membrane being prepared using Freeze Drying Technique, belongs to nanofiltration membrane separation field.The following steps are included: pre-processing to porous basement membrane, surface impurity is removed；Respectively in deionized water by the dispersion of GO powder, in the way of ultrasonic, centrifugation, GO dispersion liquid is configured；By way of filtering deposition, GO is assembled to porous membrane surface, prepares the GO composite membrane of hygrometric state；By resulting hygrometric state GO film, the water content in film is regulated and controled in such a way that dry gas purges；Under cryogenic by the complete ice crystal of water in GO film, then carries out lyophilization and prepare novel GO nanofiltration (f-GO) film, for the removing of dyestuff, high price salt and organic system small molecular in water, there is good separation property and stability.
Description
Technical field
The present invention relates to a kind of methods that Freeze Drying Technique prepares graphene oxide (GO) composite nanometer filtering film, belong to nanofiltration
UF membrane field.
Background technique
Nanofiltration because its have many advantages, such as it is easy to operate, energy-efficient and without secondary pollution, it is considered to be a kind of liquid phase
High price salt and small organic molecule efficiently separate means in system, and nanofiltration membrane is the key that nanofiltration.Currently, all nanofiltrations
In membrane material, polymer film is most widely used, simple mainly due to its preparation process, high mechanical strength and convenient for being assembled into
Integrated membrane module, is easy to large-scale use.However, polymer nano filter membrane still have chemical stability and thermal stability compared with
The disadvantages such as poor, the easy to pollute and service life is low.
GO not only maintains the superior function of part graphene as the oxidized derivatives of graphene and is easy to make on a large scale
It is standby.In addition, GO can be by simply filtering or spin-coating method is assembled into and possesses the Macro film of two-dimensional nano duct abundant network
Material, thus be considered liquid separation field have boundless application potential [E.N.Wang and R.Karnik,
Nat.Nanotechnol.,2012,7,552.].However, the mass transfer of GO film relies primarily on interlayer spacing, this makes mass transfer path
It greatly prolongs, reduces infiltration rate, to limit the application of GO film.Therefore, how to obtain with Thief zone and selectivity
It is the important research direction of GO film.
At present in research, improving GO membrane flux most effective way is to increase GO piece interlamellar spacing, and researchers are substantially carried out
Of both work: 1) by molecules such as polyamine, polynary acyl chlorides monomers, be chemically crosslinked, led to graphene oxide layer
It crosses and selects various sizes of molecule, play support and regulation piece interlamellar spacing；2) nano particle filling or nano-form technology are utilized,
Realize the building of GO interlayer nanometer mass transfer channel.The above method can improve interlayer transmission channel, adjust GO to a certain extent
Piece interfloor distance improves membrane separating property.But there is itself deficiency in two ways, as small-molecule chemical is crosslinked for mentioning
High permeating flux contribution is smaller；Physical blending introduces the controllable structure that nano particle (template) filling is difficult to realize nanometer transmission channel
Build and particle agglomeration cause fault of construction reduce separation selectivity the problems such as.For this purpose, developing a kind of template skill of structure-controllable
Art is the key that solve the above problems.
Freeze-drying, also known as ice template technology are that the one kind to grow up in the recent period very effective prepares porous material
Method [CN107200583A, CN106084302A, CN107185500A], because its have quickly, easily amplification, environmental-friendly etc.
Feature and by extensive concern.The technology has been used for hydrogel of the preparation comprising macroporous structure (aperture is greater than 20 microns), gas
Gel and porous ceramic film material, these porous materials are widely used in adsorbing separation, enzyme or catalyst immobilization carrier, and raw
The fields such as object organizational project.The present invention is applied to Freeze Drying Technique the preparation of GO film (f-GO), is constructed by ice crystal template
The nanofiltration membrane in efficient mass transfer channel, the separation for the removing of dyestuff, high price salt and organic system small molecular in water.
The present invention is used for the f-GO film of nanofiltration by Freeze Drying Technique preparation, and this method can effectively improve membrane mass transfer speed
Rate, while maintaining compared with high separability energy, the process is simple, reproducible, has very big potential answer in liquid phase separation field
Use prospect.
Summary of the invention
The purpose of the present invention is have the f-GO film of nanometer mass transfer channel using Freeze Drying Technique building.It is dry by freezing
Dry means handle hygrometric state GO film, and the nanofiltration membrane of acquisition is fabricated out nanometer mass transfer channel, so as to improve the mass transfer rate of film.Using
The composite membrane of this method preparation has good separating property for nanofiltration separation field.
Method includes the following steps:
(1) porous basement membrane is pre-processed, removes its surface organic matter, inorganic matter and microorganism；
(2) in deionized water by the dispersion of GO powder, in the way of ultrasound centrifugation, GO dispersion liquid is configured；
(3) by the way of filtering deposition, GO is assembled to porous membrane surface, prepares the GO composite membrane of hygrometric state；
(4) it under cryogenic by the complete ice crystal of water in GO composite membrane, then carries out Decompression Sublimation drying and prepares
Novel graphene oxide (f-GO) film.
Further step (3) further includes following steps: resulting hygrometric state GO composite membrane regulates and controls in such a way that dry gas purges
Water content in film；Preferably so that the content of water is 10~200wt% of dry film in film, further preferably make containing for water in film
Amount is the 100wt% of dry film；
The substrate that f-GO film is used to prepare in the present invention can be the tubular membrane of business or the inorganic porous membrane of plate membrane, film
Material is aluminium oxide, silica, zirconium oxide, and the porous membrane aperture is 0.1~1.0 μm；For assembling in step (2)
GO dispersion liquid mass percent concentration is 0.001~0.5%；The pressure limit that deposition is filtered in step (3) is 0.01~
0.1MPa, deposition time ranges are 0.1~10min；Dry gas purge time is 0~40min in step (4)；It is cold in step (5)
Freezing temperature is -10~-50 DEG C, and ice crystallization time is 0.5~3h, the dry pressure (1~10Pa) of Decompression Sublimation, when lyophilization
Between be 1~10h.
Such film can be used for the removing of dyestuff in water, high price salt and organic phase small molecular.
The principle of technical solution of the present invention is: firstly, preparing hygrometric state GO composite membrane using the method for filtering deposition, preparing
Regulate and control water content in film in journey in such a way that dry gas purges, and freezing processing is carried out by low temperature, when lower than solvent freezing point,
Solvent solidifies, and generates the solvent nucleus of nano-scale, and the method for then carrying out negative pressure distillation removes solvent, to construct spy
The mass transfer channel of different microcellular structure.In addition, passing through water content in adjusting film and freezing conditions during solvent nucleus growth
The controllable building of nanometer transmission channel can be achieved.The method is while increasing substantially the mass transfer rate of oxidation GO composite membrane
Maintain high separating property.
Technical advantage
The present invention has the f-GO film of nanometer mass transfer channel using Freeze Drying Technique building, is improving film permeation flux
Rejection is also maintained simultaneously；This method is similar to mould plate technique, and easy to operate and stable structure has commercial introduction potentiality.
Such film can be used for the removing of dyestuff in water, high price salt and organic phase small molecular, the f-GO nanofiltration membrane prepared using the technology
Separate the aqueous sodium sulfate for separating the methyl blue water solution system of 0.1g/L, the eriochrome black T water solution system of 0.1g/L, 1g/L
The Evans blue methanol solution system of liquid system and 0.1g/L, when operating pressure is 0.1MPa, flux is respectively 30.1L/
m2h bar、29.2L/m2h bar、40.6L/m2H bar and 43.2L/m2h bar；Rejection is followed successively by 97.1%, 96.0%,
61.2% and 78.3%.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the f-GO film section of freeze-drying process in embodiment 1,
Fig. 2 is the scanning electron microscope (SEM) photograph of f-GO film surface in embodiment 1.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, but the present invention is not limited to following embodiments.
Embodiment 1
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is
10cm2, selected GO dispersing agent is deionized water, and graphene oxide dispersion concentration is 0.001g/L.
The preparation method of f-GO film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter,
Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is
The GO dispersion liquid of 0.001g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out
Filtering pressure power is 0.1MPa, and the suction filtration time is 1min；
(4) the hygrometric state oxidation GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice
Crystallization time is 3h；Then carry out the dry 10h of Decompression Sublimation, the dry pressure 1Pa of Decompression Sublimation；Final take out is put into 50 DEG C of bakings
Dry 12h in case；
(5) f-GO film obtained above is used to separate the sodium sulphate water salting liquid of 1g/L, when operating pressure is 0.1MPa
When, rejection and flux to sodium sulphate are respectively 16.8% and 70.5L/m2h bar。
Embodiment 2
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is
10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.5g/L.
The preparation method of f-GO film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter,
Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is
The GO dispersion liquid of 0.5g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out
Filtering pressure power is 0.1MPa, and the suction filtration time is 1min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal
Time is 3h；Then carry out the dry 10h of Decompression Sublimation, the dry pressure 1Pa of Decompression Sublimation；Final take out is put into 50 DEG C of baking ovens
Dry 12h；
(5) f-GO film obtained above is used to separate the sodium sulphate water salting liquid of 1g/L, when operating pressure is 0.1MPa
When, rejection and flux to sodium sulphate are respectively 66.8% and 11.3L/m2h bar。
Embodiment 3
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is
10cm2, selected graphene oxide dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of f-GO film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter,
Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is
The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out
Filtering pressure power is 0.1MPa, and the suction filtration time is 1min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal
Time is 3h；Then carry out the dry 10h of Decompression Sublimation, the dry pressure 1Pa of Decompression Sublimation；Final take out is put into 50 DEG C of baking ovens
Dry 12h；
(5) f-GO film obtained above is used to separate the sodium sulphate water salting liquid of 1g/L, when operating pressure is 0.1MPa
When, rejection and flux to sodium sulphate are respectively 55.2% and 40.6L/m2h bar。
Embodiment 4
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is
10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of f-GO film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter,
Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is
The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out
Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal
Time is 3h；Then carry out the dry 10h of Decompression Sublimation, the dry pressure 1Pa of Decompression Sublimation；Final take out is put into 50 DEG C of baking ovens
Dry 12h；
(5) f-GO film obtained above is used to separate the sodium sulphate water salting liquid of 1g/L, when operating pressure is 0.1MPa
When, rejection and flux to sodium sulphate are respectively 61.2% and 36.6L/m2h bar。
Embodiment 5
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is
10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of f-GO film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter,
Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is
The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out
Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO film prepared in (3) is purged into 10min using drying nitrogen；
(5) by treated in (4), GO composite membrane is directly introduced in freeze drying box, and temperature is -50 DEG C, when ice crystal
Between be 3h；Then carry out the dry 10h of Decompression Sublimation, the dry pressure 1Pa of Decompression Sublimation；Final taking-up, which is put into 50 DEG C of baking ovens, to be done
Dry 12h；
(6) f-GOm obtained above is used to separate the sodium sulphate water salting liquid of 1g/L, when operating pressure is 0.1MPa
When, rejection and flux to sodium sulphate are respectively 62.0% and 34.1L/m2h bar。
Embodiment 6
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is
10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of f-GO film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter,
Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is
The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out
Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO film prepared in (3) is purged into 40min using drying nitrogen；
(5) by treated in (4), GO composite membrane is directly introduced in freeze drying box, and temperature is -50 DEG C, when ice crystal
Between be 3h；Then carry out the dry 10h of Decompression Sublimation, the dry pressure 1Pa of Decompression Sublimation；Final taking-up, which is put into 50 DEG C of baking ovens, to be done
Dry 12h；
(6) f-GOm obtained above is used to separate the sodium sulphate water salting liquid of 1g/L, when operating pressure is 0.1MPa
When, rejection and flux to sodium sulphate are respectively 62.9% and 28.1L/m2h bar。
Embodiment 7
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is
10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of f-GO film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter,
Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is
The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out
Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO film prepared in (3) is purged into 5min using drying nitrogen；
(5) by treated in (4), GO composite membrane is directly introduced in freeze drying box, and temperature is -50 DEG C, when ice crystal
Between be 3h；Then carry out the dry 10h of Decompression Sublimation, the dry pressure 1Pa of Decompression Sublimation；Final taking-up, which is put into 50 DEG C of baking ovens, to be done
Dry 12h；
(6) f-GO film obtained above is used to separate the sodium sulphate water salting liquid of 1g/L, when operating pressure is 0.1MPa
When, rejection and flux to sodium sulphate are respectively 61.5% and 34.1L/m2h bar。
Embodiment 8
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is
10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of f-GO film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter,
Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is
The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out
Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO film prepared in (3) is purged into 10min using drying nitrogen；
(5) by treated in (4), GO composite membrane is directly introduced in freeze drying box, and temperature is -50 DEG C, when ice crystal
Between be 3h；Then carry out the dry 10h of Decompression Sublimation, the dry pressure 1Pa of Decompression Sublimation；Final taking-up, which is put into 50 DEG C of baking ovens, to be done
Dry 12h；
(6) f-GOm obtained above is used to separate the sodium chloride water salting liquid of 1g/L, when operating pressure is 0.1MPa
When, rejection and flux to sodium chloride are respectively 26.8% and 37.1L/m2h bar。
Embodiment 9
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is
10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of f-GO film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter,
Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is
The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out
Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO film prepared in (3) is purged into 10min using drying nitrogen；
(5) by treated in (4), GO composite membrane is directly introduced in freeze drying box, and temperature is -50 DEG C, when ice crystal
Between be 3h；Then carry out the dry 10h of Decompression Sublimation, the dry pressure 1Pa of Decompression Sublimation；Final taking-up, which is put into 50 DEG C of baking ovens, to be done
Dry 12h；
(6) f-GO film obtained above is used to separate the methyl blue aqueous solution of 0.1g/L, when operating pressure is 0.1MPa
When, rejection and flux to methyl blue are respectively 98.1% and 30.1L/m2h bar。
Embodiment 10
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is
10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of f-GO film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter,
Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is
The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out
Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO film prepared in (3) is purged into 10min using drying nitrogen；
(5) by treated in (4), GO composite membrane is directly introduced in freeze drying box, and temperature is -50 DEG C, when ice crystal
Between be 3h；Then carry out the dry 10h of Decompression Sublimation, the dry pressure 1Pa of Decompression Sublimation；Final taking-up, which is put into 50 DEG C of baking ovens, to be done
Dry 12h；
(6) f-GO film obtained above is used to separate the eriochrome black T aqueous solution of 0.1g/L, when operating pressure is 0.1MPa
When, rejection and flux to eriochrome black T are respectively 96.0% and 29.2L/m2h bar。
Embodiment 11
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is
10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of f-GO film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter,
Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is
The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out
Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO film prepared in (3) is purged into 10min using drying nitrogen；
(5) by treated in (4), GO composite membrane is directly introduced in freeze drying box, and temperature is -50 DEG C, when ice crystal
Between be 3h；Then carry out the dry 10h of Decompression Sublimation, the dry pressure 1Pa of Decompression Sublimation；Final taking-up, which is put into 50 DEG C of baking ovens, to be done
Dry 12h；
(6) f-GO film obtained above is used to separate the methyl blue methanol solution of 0.1g/L, when operating pressure is
When 0.1MPa, rejection and flux to methyl blue are respectively 71.6% and 42.2L/m2h bar。
Embodiment 12
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is
10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of f-GO film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter,
Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is
The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out
Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO prepared in (3) is purged into 10min using drying nitrogen；
(5) by treated in (4), GO composite membrane is directly introduced in freeze drying box, and temperature is -50 DEG C, when ice crystal
Between be 3h；Then carry out the dry 10h of Decompression Sublimation, the preferably dry pressure 1Pa of Decompression Sublimation；Final take out is put into 50 DEG C of baking ovens
Middle dry 12h；
F-GO film obtained above is used to separate the Evans blue methanol solution of 0.1g/L, when operating pressure is 0.1MPa
When, rejection and flux to Evans blue are respectively 78.3% and 43.2L/m2h bar。
Claims (9)
1. a kind of method that Freeze Drying Technique prepares graphene oxide nanofiltration (f-GO) composite membrane, which is characterized in that including with
Lower step:
(1) porous basement membrane is pre-processed, removes its surface organic matter, inorganic matter and microorganism；
(2) in deionized water by the dispersion of GO powder, in the way of ultrasound centrifugation, GO dispersion liquid is configured；
(3) by the way of filtering deposition, GO is assembled to porous membrane surface, prepares the GO composite membrane of hygrometric state；
(4) under cryogenic by the complete ice crystal of water in step (4) GO composite membrane, the dry preparation of Decompression Sublimation is then carried out
Novel graphene oxide (f-GO) film out.
2. according to method of claim 1, which is characterized in that preparation oxidation f-GO film substrate can for business tubular membrane or
The inorganic porous membrane of plate membrane, membrane material are aluminium oxide, silica, zirconium oxide, and the porous membrane aperture is 0.1~1.0 μ
m。
3. according to method of claim 1, which is characterized in that the GO dispersion liquid mass percent concentration of assembling be 0.001~
0.5%.
4. according to method of claim 1, which is characterized in that the pressure limit that deposition is filtered in step (3) is 0.01~
0.1MPa, deposition time ranges are 0.1~10min.
5. according to method of claim 1, which is characterized in that step (3) is further comprising the steps of: resulting hygrometric state GO is compound
Film regulates and controls the water content in film in such a way that dry gas purges；Preferably so that in film water content be dry film 10~
200wt%.
6. according to method of claim 1, which is characterized in that the cryogenic temperature in step (4) is -10~-50 DEG C；When ice crystal
Between be 0.5~3h.
7. according to method of claim 1, which is characterized in that then carry out Decompression Sublimation drying, pressure is 1~10Pa, distillation
Drying time is 1~10h.
8. the f-GO nanofiltration membrane being prepared according to the described in any item methods of claim 1-7.
9. according to the application for the f-GO nanofiltration membrane that the described in any item methods of claim 1-7 are prepared, for dyestuff in water,
The removing of high price salt and organic phase small molecular.
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| CN110026092A (en) * | 2019-04-17 | 2019-07-19 | 南京大学 | A kind of nano composite membrane and preparation method for heavy metal retention |
| CN110639371A (en) * | 2019-06-26 | 2020-01-03 | 浙江工业大学 | Preparation method of nano titanium dioxide blended graphene oxide loose nanofiltration membrane and application of nano titanium dioxide blended graphene oxide loose nanofiltration membrane in dye desalination |
| CN112246104A (en) * | 2020-09-30 | 2021-01-22 | 北京碧水源膜科技有限公司 | Reverse osmosis membrane and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110026092A (en) * | 2019-04-17 | 2019-07-19 | 南京大学 | A kind of nano composite membrane and preparation method for heavy metal retention |
| CN110026092B (en) * | 2019-04-17 | 2021-09-28 | 南京大学 | Nano composite membrane for heavy metal interception and preparation method thereof |
| CN110639371A (en) * | 2019-06-26 | 2020-01-03 | 浙江工业大学 | Preparation method of nano titanium dioxide blended graphene oxide loose nanofiltration membrane and application of nano titanium dioxide blended graphene oxide loose nanofiltration membrane in dye desalination |
| CN110639371B (en) * | 2019-06-26 | 2022-05-24 | 浙江工业大学 | Preparation method of nano titanium dioxide blended graphene oxide loose nanofiltration membrane and application of nano titanium dioxide blended graphene oxide loose nanofiltration membrane in dye desalination |
| CN112246104A (en) * | 2020-09-30 | 2021-01-22 | 北京碧水源膜科技有限公司 | Reverse osmosis membrane and preparation method and application thereof |
| CN112246104B (en) * | 2020-09-30 | 2022-06-24 | 北京碧水源膜科技有限公司 | Reverse osmosis membrane and preparation method and application thereof |
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