CN106000121A - Solvent-resistant, corrosion-resistant and high-flux composite nanofiltration membrane and preparation method thereof - Google Patents
Solvent-resistant, corrosion-resistant and high-flux composite nanofiltration membrane and preparation method thereof Download PDFInfo
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- CN106000121A CN106000121A CN201610459976.4A CN201610459976A CN106000121A CN 106000121 A CN106000121 A CN 106000121A CN 201610459976 A CN201610459976 A CN 201610459976A CN 106000121 A CN106000121 A CN 106000121A
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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
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
Abstract
The invention discloses a solvent-resistant, corrosion-resistant and high-flux composite nanofiltration membrane and a preparation method thereof. The method comprises steps as follows: a mixed liquid of a reduced graphene oxide aqueous solution and ammonia water A flows through a porous supporting membrane, reduced graphene oxide is deposited on the porous supporting membrane, and the composite nanofiltration membrane is obtained; the mixed liquid flows through the porous supporting membrane under the action of pressure. According to the method, the preparation process is simple and easy to implement, the cost is relatively low, the porous supporting membrane used in the method is a microfiltration membrane at the relatively low price, and, however, ultrafiltration membranes in the relatively high price are frequently used in the prior art. A graphene composite nanofiltration membrane organic solvent prepared with the method is high in flux and has the organic dye rejection rate close to 100%. A separation layer of the graphene composite nanofiltration membrane prepared with the method comprises solvated graphene and has very good resistance to various organic solvents and corrosive chemical environments.
Description
Technical field
The present invention relates to a kind of corrosion-resistant high-flux composite nanofiltration membrane of solvent resistant and preparation method thereof, belong to membrane technology neck
Territory.
Background technology
Chemical industry and pharmaceutical industry it is frequently necessary to separating-purifying from organic solution medium go out product or reclaim catalyst.Pass
The purification technique of system, such as evaporation and concentration and distillation, the more and equipment of consuming energy needs to take the biggest space.Cause
This, the expense of separating-purifying process generally to account for whole investment and the 40 of operating cost～70%.And developed in recent years
Organic solvent nanofiltration (OSN) membrane separation technique come is the most simple to operate, efficient, and without phase transformation in separation process,
Can at room temperature carry out.Additionally, OSN membrane separation plant can Highgrade integration, space availability ratio is the highest.Therefore,
The introducing of OSN membrane separation technique is expected to be substantially reduced the cost of chemical separation and purification process.
The critical component of OSN membrane separating process is OSN film.OSN film is usually composite membrane, is made up of two parts:
Fine and close stratum disjunctum and porous support layer.Stratum disjunctum is than relatively thin and compact structure, and aperture is less, determines OSN film and divides
From selectivity and solvent flux.And porous support layer is thicker and aperture is relatively big, mainly provide mechanics for stratum disjunctum
Support.Chemical industry typically requires the substantial amounts of organic solution of process, and this just requires that OSN film has enough in organic media
Stability, and the highest selectivity and solvent flux.Current business-like OSN film mainly has polymeric membrane and pottery
Porcelain film.Macromolecule OSN membrane preparation method is simple, and price is relatively cheap, but organic solvent and soda acid etc. are corroded by it
The toleration of environment is poor.General every kind of macromolecule OSN film be only used for filtering separate specific certain or a few
Organic solvent.Pottery OSN film has good organic solvent tolerance and corrosion resistance, but its technology of preparing requires very
Height, price is expensive.The most important thing is, the macromolecule OSN film of application at present and the organic solvent of pottery OSN film lead to
Measure the least, process during a large amount of organic solution the most oversize, can not meet the demand of industrial quarters.It is thus desirable to provide one
Plant solvent resistant, the high-flux nanofiltration membrane of acid-alkali-corrosive-resisting.
Summary of the invention
It is an object of the invention to provide high-flux nanofiltration membrane of a kind of solvent resistant, acid-alkali-corrosive-resisting and preparation method thereof, solve
NF membrane prepared by existing method of having determined is to organic solvent and caustic chemical environments poor resistance, and solvent flux is too low
Problem.
The preparation method of the corrosion-resistant high-flux composite nanofiltration membrane of solvent resistant provided by the present invention, comprises the steps:
The mixed liquor of the aqueous solution of redox graphene Yu ammonia A is flowed through porous support membrane, described oxygen reduction fossil
Ink alkene deposits on described porous support membrane, i.e. obtains described composite nanometer filtering film.
In above-mentioned preparation method, described mixed liquor flows through described porous support membrane under the effect of the pressure.
In above-mentioned preparation method, described mixed liquor flows through described porous support membrane under the effect of sucking filtration, uses sucking filtration
Bottle can realize.
In above-mentioned preparation method, described graphene oxide can be prepared by Hummers.
In above-mentioned preparation method, described redox graphene is prepared according to the method comprised the steps:
Graphene oxide under conditions of hydrazine hydrate exists through reduction reaction and get final product；
Described reduction reaction and is carried out in water in the basic conditions；
Described graphene oxide is 1:0.71～1.43 with the mass ratio of described hydrazine hydrate.
In above-mentioned preparation method, described alkalescence condition is as follows: by adding in the aqueous solution of described graphene oxide
Ammonia B；
Quality-the volumetric concentration of graphene oxide described in the aqueous solution of described graphene oxide can be 0.1～0.25
Mg/mL, concretely 0.25mg/mL；
The mass fraction of described ammonia B can be 1～25%；
The addition of described ammonia B is: described in every 1mL, the aqueous solution of graphene oxide adds described in 3.92～98 μ L
Ammonia B；Concentration according to ammonia B selects addition, such as, if it adds when the concentration of described ammonia B is 1%
Entering amount is 98 μ L, if the concentration of described ammonia B is 25% its addition is 3.92 μ L.
The temperature of described reduction reaction can be 40～90 DEG C, and the time can be 1～3 hour, as carried out at 40 DEG C 3 hours.
In above-mentioned preparation method, the mass fraction of described ammonia A is 0.1%；
Quality-the volumetric concentration of redox graphene described in the aqueous solution of described redox graphene can be
0.1～0.25mg/mL, such as 0.25mg/mL；
Quality-the volumetric concentration of redox graphene described in described mixed liquor can be 1.5～4.5 μ g/mL, specifically may be used
Be 1.5～2.0 μ g/mL, 1.5 μ g/mL or 2.0 μ g/mL.
In above-mentioned preparation method, described porous support membrane can be high molecule microfilter membrane or anodised aluminium perforated membrane；
The aperture of described porous support membrane is 0.22～0.65 μm.
In above-mentioned preparation method, when described mixed liquor flows completely through described porous support membrane, remove described pressure immediately
Power, can obtain the redox graphene composite nanometer filtering film of solvation, and be stored in water or organic solvent so that answering
The redox graphene layer closed in NF membrane remains Solvation State；Described organic solvent can be methanol, ethanol,
Normal propyl alcohol, isopropanol, n-butyl alcohol, ethylene glycol, glycerol, acetone, oxolane, N,N-dimethylformamide or
N-Methyl pyrrolidone etc..
The corrosion-resistant high-flux composite nanofiltration membrane of solvent resistant that the inventive method prepares falls within the protection model of the present invention
Enclose.
In described composite nanometer filtering film, the load capacity of redox graphene is 33.08～110.27mg/m2。
Redox graphene layer (rGO layer) in composite nanometer filtering film of the present invention keeps Solvation State, is conducive to protecting
Hold its loose structure, thus obtain higher solvent flux.
Composite nanometer filtering film of the present invention is formed in porous support membrane surface stacking by rGO (redox graphene) nanometer sheet,
And making rGO layer remain Solvation State, in composite nanometer filtering film, the load capacity of rGO is 33.08mg/m2～110.27
mg/m2。
Compared with dry rGO film, redox graphene film (S-rGO film) knot of solvation prepared by the present invention
Structure is more loose, thus can obtain higher solvent flux.
Compared with prior art, the present invention has a many advantages:
1, the inventive method preparation process is simple and cost is relatively low, and the porous support membrane that the present invention uses is valency
The micro-filtration membrane that lattice are relatively low, and prior art conventional be the ultrafilter membrane that price is higher.
2, the Graphene composite nanometer filtering film organic solvent flux that the inventive method prepares is high, cuts organic dyestuff
Stay rate close to 100%.
The stratum disjunctum of the Graphene composite nanometer filtering film that 3, the inventive method prepares is made up of solvation Graphene,
Various organic solvents and caustic chemical environments had good toleration.
Accompanying drawing explanation
Fig. 1 is electron scanning micrograph, nylon micro-filtration membrane surface scan electricity during wherein Fig. 1 (a) is embodiment 1
Sub-microphotograph, Fig. 1 (b) is that in embodiment 1, the surface of preparation deposits the nylon micro-filtration membrane table having one layer of S-rGO
Surface scan electron micrograph.
Fig. 2 is UV, visible light (UV-Vis) spectrogram that composite membrane separates, and wherein, Fig. 2 (a) is through embodiment 1
UV, visible light (UV-Vis) spectrogram of azovan blue (EB) methanol solution before and after the S-rGO composite membrane separation of preparation,
Fig. 2 (b) is that methylene blue (MB) methanol before and after the HPEI/S-rGO composite membrane of embodiment 4 preparation separates is molten
The UV-Vis spectrogram of liquid.
Fig. 3 is UV, visible light (UV-Vis) spectrogram that composite membrane separates, wherein, and Fig. 3 (a) and Fig. 3 (b)
It is respectively the UV-Vis spectrogram of AF and BY aqueous solution before and after the S-rGO composite membrane of embodiment 1 preparation separates；
The HPEI/S-rGO composite membrane that Fig. 3 (c) and Fig. 3 (d) is respectively through embodiment 4 preparation separates before and after BF and MB
The UV-Vis spectrogram of aqueous solution.
Fig. 4 is after S-rGO composite membrane prepared by embodiment 2 soaks one day in harsh chemical environments, its methanol flow rate
With the change to EB rejection.
Detailed description of the invention
Experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, the most commercially obtain.
In following embodiment, composite nanometer filtering film is to water and the flux of various organic solvent, and the rejection to various dyestuffs
Dead-end filtration (dead-end filtration) device of band stirring is tested.Mixing speed 600 rpms during test,
Composite nanometer filtering film pressure at both sides difference is 1～5bar.
Embodiment 1, prepare Graphene composite nanometer filtering film
1, redox graphene is prepared:
1.1 prepare graphene oxide water solution with Hummers, and preparation method is with reference to L.Huang, Y.R.Li, Q.Q.
Zhou,W.J.Yuan,G.Q.Shi,Adv.Mater.,2015,27,3797-3802.
1.2 quality-the volumetric concentrations recording the graphene oxide water solution that step 1.1 prepares are 7.0g/L.
1.3 add water in the graphene oxide water solution that step 1.1 prepares, and are diluted to the oxidation of concentration 0.25g/L
Graphene aqueous solution.
1.4 graphene oxide water solution taking the preparation of 20mL step 1.3, add 78.4 μ L ammonia (mass fractions 25
Wt%), 7.07 μ L hydrazine hydrates (mass fraction 99wt%), now, graphene oxide and the matter of hydrazine hydrate are added
Amount ratio is 1:0.71, pours 30 milliliters of vials after mix homogeneously into.40 DEG C of baking ovens put into by vial after sealing
Middle heated at constant temperature 3 hours, naturally cools to room temperature stand-by in atmosphere after taking-up.
2, the rGO solution (quality-volumetric concentration of rGO is 0.25mg/mL) of 0.15mL step 1.4 preparation is taken,
Being diluted to 25mL with the ammonia of 0.1wt%, now in mixed liquor, the quality-volumetric concentration of rGO is 1.5 μ g/mL, so
After be poured into the bottle,suction being lined with multi-hole micro leaching film, vacuum filtration makes rGO be deposited in micro-filtration membrane.Multi-hole micro leaching film
For diameter 50mm, the nylon micro-filtration membrane of aperture 0.65 μm.
3, when the water in rGO aqueous solution in step 2 just exhausts, stop sucking filtration immediately, i.e. obtain solvation
Redox graphene composite nanometer filtering film.
4, composite nanometer filtering film prepared by step 3 is saved in water so that redox graphene layer remains solvation
State.
Shown in surface Scanning Electron microphotograph such as Fig. 1 (a) of nylon micro-filtration membrane, surface prepared by the present embodiment sinks
Shown in surface Scanning Electron microphotograph such as Fig. 1 (b) of the long-pending nylon micro-filtration membrane having one layer of S-rGO, can by this figure
To find out, it is uniformly deposited on micro-filtration membrane surface through the inventive method rGO.
In S-rGO composite nanometer filtering film prepared by the present embodiment, the load capacity of rGO is 33.08mg/m2。
The pure water flux of S-rGO composite nanometer filtering film prepared by the present embodiment is up to 89.6L/m2H bar, methanol flux is
76.9L/m2h bar。
Fig. 2 (a) is azovan blue (EB) methanol solution before and after the S-rGO composite membrane prepared through the present embodiment separates
UV, visible light (UV-Vis) spectrogram, it can be seen that EB methanol solution is retained by S-rGO composite nanometer filtering film
Rate is up to 100%.
Fig. 3 (a) and Fig. 3 (b) S-rGO composite membrane that respectively prepared by the present embodiment separates before and after's dyestuff acidity product
Red (AF) aqueous solution and UV, visible light (UV-Vis) spectrogram of dyestuff bright orange (BY) aqueous solution, by two figures
It can be seen that in aqueous, S-rGO composite nanometer filtering film bright orange to dyestuff acid fuchsin (AF) and dyestuff (BY)
Rejection be respectively 92.4% and 99.2%.
Embodiment 2, prepare Graphene composite nanometer filtering film
1, redox graphene is prepared:
Prepare according to the method in embodiment 1.
2,0.2mL rGO solution (quality-volumetric concentration of rGO is 0.25mg/mL) is taken, with the ammonia of 0.1wt%
Being diluted to 25mL, now in mixed liquor, the quality-volumetric concentration of rGO is 2.0 μ g/mL, is then poured into and is lined with
The bottle,suction of multi-hole micro leaching film, vacuum filtration makes redox graphene be deposited in micro-filtration membrane.Multi-hole micro leaching film is straight
Footpath 50mm, the nylon micro-filtration membrane of aperture 0.65 μm.
3, when the water in rGO aqueous solution in step 2 just exhausts, stop sucking filtration immediately, i.e. obtain solvation
Redox graphene composite nanometer filtering film.
4, composite nanometer filtering film prepared by step 3 is saved in methanol so that redox graphene layer remains solvent
Change state.
In S-rGO composite nanometer filtering film prepared by the present embodiment, the load capacity of rGO is 44.10mg/m2。
The pure water flux of S-rGO composite nanometer filtering film prepared by the present embodiment is up to 65.5L/m2H bar, methanol flux is
56.2L/m2h bar。
S-rGO composite nanometer filtering film prepared by the present embodiment is up to 100% to the rejection of EB methanol solution.
S-rGO composite nanometer filtering film prepared by the present embodiment at the sulphuric acid of 0.5mol/L or the potassium hydroxide of 0.5mol/L or
After the nitric acid of 0.5mol/L soaks a sky, its methanol flow rate and to the change of EB rejection as shown in Figure 4,
It can be seen that after S-rGO composite membrane soaks one day in harsh chemical environments, remain to keep its nanofiltration performance, have
Well resistance to chemical corrosion.
Embodiment 3, prepare Graphene composite nanometer filtering film
1, redox graphene is prepared:
Prepare according to the method in embodiment 1.
2,0.15mL rGO solution (quality-volumetric concentration of rGO is 0.25mg/mL) is taken, with the ammonia of 0.1wt%
Water is diluted to 25mL, and now in mixed liquor, the quality-volumetric concentration of rGO is 1.5 μ g/mL, is then poured into pad
Having the bottle,suction of multi-hole micro leaching film, vacuum filtration makes redox graphene be deposited in micro-filtration membrane.Multi-hole micro leaching film is
Diameter 47mm, the anodised aluminium perforated membrane of aperture 0.22 μm.
3, when the water in rGO aqueous solution in step 2 just exhausts, stop sucking filtration immediately, i.e. obtain solvation
Redox graphene composite nanometer filtering film.
4, composite nanometer filtering film prepared by step 3 is saved in methanol so that redox graphene layer remains solvent
Change state.
In S-rGO composite nanometer filtering film prepared by the present embodiment, the load capacity of rGO is 33.08mg/m2。
The methanol flux of S-rGO composite nanometer filtering film prepared by the present embodiment is 70.1L/m2h bar。
S-rGO composite nanometer filtering film prepared by the present embodiment is up to 100% to the rejection of EB methanol solution.
Embodiment 4, prepare Graphene composite nanometer filtering film
The redox graphene composite nanometer filtering film of solvation is prepared according to embodiment 1-3.
By in composite nanometer filter film bubble excess of imports branched polyethylene imine (HPEI) aqueous solution (0.1wt%) of above-mentioned preparation, soak
Steep 30 minutes, then clean film with deionized water.The most positively charged HPEI molecule will be adsorbed onto electronegative
On S-rGO film, and composite membrane is made to become positively charged lotus.This composite membrane is referred to as HPEI/S-rGO composite membrane.
Fig. 2 (b) is HPEI/S-rGO composite membrane separation methylene blue (MB) methanol solution prepared through the present embodiment
UV-Vis spectrogram front and back, it can be seen that HPEI/S-rGO composite membrane is to methylene blue (MB) methanol solution
Rejection is up to 90%.
Fig. 3 (c) and Fig. 3 (d) HPEI/S-rGO composite membrane that respectively prepared by the present embodiment separates before and after's dye base
Property pinkish red (BF) aqueous solution and UV, visible light (UV-Vis) spectrogram of dyestuff methylene blue (MB) aqueous solution,
By two figures it can be seen that in aqueous, HPEI/S-rGO composite membrane (BF) and dyestuff pinkish red to dye base
The rejection of methylene blue (MB) is respectively 97.5% and 98.6%.
Claims (9)
1. a preparation method for the corrosion-resistant high-flux composite nanofiltration membrane of solvent resistant, comprises the steps:
The mixed liquor of the aqueous solution of redox graphene Yu ammonia A is flowed through porous support membrane, described oxygen reduction fossil
Ink alkene deposits on described porous support membrane, i.e. obtains described composite nanometer filtering film.
Preparation method the most according to claim 1, it is characterised in that: described mixed liquor is under the effect of the pressure
Flow through described porous support membrane.
Preparation method the most according to claim 2, it is characterised in that: described mixed liquor is under the effect of sucking filtration
Flow through described porous support membrane.
4. according to the preparation method according to any one of claim 1-3, it is characterised in that: described reduction-oxidation graphite
Alkene is prepared according to the method comprised the steps:
Graphene oxide under conditions of hydrazine hydrate exists through reduction reaction and get final product；
Described reduction reaction and is carried out in water in the basic conditions；
Described graphene oxide is 1:0.71～1.43 with the mass ratio of described hydrazine hydrate.
Preparation method the most according to claim 4, it is characterised in that: described alkalescence condition as follows: by
The aqueous solution of described graphene oxide adds ammonia B；
Quality-the volumetric concentration of graphene oxide described in the aqueous solution of described graphene oxide is 0.1～0.25mg/mL；
The mass fraction of described ammonia B is 1～25%；
The addition of described ammonia B is: described in every 1mL, the aqueous solution of graphene oxide adds described in 3.92～98 μ L
Ammonia B；
The temperature of described reduction reaction is 40～90 DEG C, and the time is 1～3 hour.
6. according to the preparation method according to any one of claim 1-5, it is characterised in that: the matter of described ammonia A
Amount mark is 0.1%；
Quality-the volumetric concentration of redox graphene described in the aqueous solution of described redox graphene is
0.1～0.25mg/mL；
Quality-the volumetric concentration of redox graphene described in described mixed liquor is 1.5～4.5 μ g/mL.
7. according to the preparation method according to any one of claim 1-6, it is characterised in that: described porous support membrane is
High molecule microfilter membrane or anodised aluminium perforated membrane.
8. according to the preparation method according to any one of claim 2-7, it is characterised in that: when described mixed liquor is complete
When flowing through described porous support membrane, remove described pressure immediately, and be stored in water or organic solvent.
9. the corrosion-resistant high-flux composite nanofiltration membrane of solvent resistant that prepared by method according to any one of claim 1-8.
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| CN106621831A (en) * | 2016-12-06 | 2017-05-10 | 中国科学院生态环境研究中心 | Method for performing fast in-situ conversion on microfiltration or ultrafiltration membrane into nanofiltration membrane |
| CN106964263A (en) * | 2017-04-27 | 2017-07-21 | 山东金城石墨烯科技有限公司 | A kind of preparation method and application of the graphene NF membrane of solvent resistant resistant |
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| CN109081430A (en) * | 2018-09-17 | 2018-12-25 | 中车环境科技有限公司 | It can accelerate the preparation method of the reproducibility graphene oxide Modified Membrane of water treatment procedure |
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