CN108816061A - A kind of fold graphene nanofiltration membrane - Google Patents
A kind of fold graphene nanofiltration membrane Download PDFInfo
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- CN108816061A CN108816061A CN201810753804.7A CN201810753804A CN108816061A CN 108816061 A CN108816061 A CN 108816061A CN 201810753804 A CN201810753804 A CN 201810753804A CN 108816061 A CN108816061 A CN 108816061A
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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
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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Abstract
The invention discloses a kind of fold graphene nanofiltration membranes, nanofiltration membrane is located on porous support membrane, nanofiltration film thickness controllability is good, 4nm-100nm can be crossed over, there are the control of wide scope, and surface folding to flux and rejection, greatly improves the infiltrating area of graphene nanofiltration membrane, and then improve that nanometer filtering film water flux prepared by the flux present invention is high, antifouling property is good, there is rejection and higher salt rejection rate to organic dyestuff close to 100%.Preparation method is simple by the present invention, controllability is strong, lower production costs and pollution-free, therefore has a good application prospect in nanofiltration field.
Description
Technical field
The invention belongs to technical field of membrane, and in particular to a kind of fold graphene nanofiltration membrane.
Background technique
Nanofiltration membrane is a kind of pressure-actuated seperation film of molecular cut off between 200-1000Da.Nanofiltration has
Low energy consumption, Low investment, low-maintenance cost, the feature of easy to operate, high reliablity and high throughput, it can replace instead in many occasions
Infiltration, therefore nanofiltration membrane and nanofiltration are in food chemistry industry, pharmaceuticals industry, sewage treatment, the fields such as desalination industry
It is widely used.
Existing nanofiltration membrane is mostly compound structure film, i.e., one layer is formed on porous support layer has selection centrifugation
Polymeric skin.And cortex is obtained with the method for interfacial polymerization.It is needed during this nanofiltration membrane preparation method
Two kinds of very high monomers of reactivity react in organic phase and water phase, therefore its production process can generate certain environment dirt
It contaminates and obtained nanofiltration membrane often has the shortcomings that anti-pollution anti-chlorine performance is poor.
Using the very big width-thickness ratio of graphene and graphene oxide, good dispersibility can be by simple in water
Vacuum filtration method obtains graphene film on porous support layer.The finder Geim seminar of graphene reports this for the first time
After separation field has very tempting application prospect, application of the graphene film in seperation film field causes graphene film
Global extensive concern.
The graphene nanofiltration membrane that Adv.Funct.Mater.2013,23,3693-3700 is reported can have organic dyestuff
>99% or more rejection and also have to Na2SO2 solution 60% rejection, this has benefited from accurate layer between graphene layer
Between nano pore and surface of graphene oxide negative electrical charge abundant.But since the restriction for being limited to permeability and selectivity is closed
System, the water flux of the graphene nanofiltration membrane of existing report are all lower.Nanofiltration membrane be a kind of molecular cut off 200-1000Da it
Between pressure-actuated seperation film.Nanofiltration has low energy consumption, Low investment, low-maintenance cost, easy to operate, high reliablity and height
The characteristics of flux, it can replace in many occasions it is reverse osmosis, therefore nanofiltration membrane and nanofiltration food chemistry industry,
Pharmaceuticals industry, sewage treatment, the fields such as desalination industry are widely used.
Existing nanofiltration membrane is mostly compound structure film, i.e., one layer is formed on porous support layer has selection centrifugation
Polymeric skin.And cortex is obtained with the method for interfacial polymerization.It is needed during this nanofiltration membrane preparation method
Two kinds of very high monomers of reactivity react in organic phase and water phase, therefore its production process can generate certain environment dirt
It contaminates and obtained nanofiltration membrane often has the shortcomings that anti-pollution anti-chlorine performance is poor.
Using the very big width-thickness ratio of graphene and graphene oxide, good dispersibility can be by simple in water
Vacuum filtration method obtains graphene film on porous support layer.The finder Geim seminar of graphene reports this for the first time
After separation field has very tempting application prospect, application of the graphene film in seperation film field causes graphene film
Global extensive concern.
Summary of the invention
The purpose of the present invention is be especially lauched in high salt and high operating pressure for graphene nanometer filtering film water flux is lower
The problems such as flux is lower provides a kind of high throughput, is especially still able to maintain higher flux under high operating pressure and high salt concentration
Fold graphene nanofiltration membrane.
The purpose of the present invention is what is be achieved through the following technical solutions：A kind of fold graphene nanofiltration membrane, the nanofiltration membrane
On porous support membrane, obtained by following steps：
(1) it is filtered on AAO basilar memebrane and obtains the graphene oxide membrane that thickness is not more than 100nm；
(2) surface is fitted with to the AAO basilar memebrane of graphene film with face-up where graphene film, is placed on the water surface；
AAO basilar memebrane is pressed, so that AAO basilar memebrane sinks, graphene film floats on the water surface.
(3) graphene film for floating on the water surface is picked up from the bottom up with porous support membrane, so that graphene film is laid in
Open support film surface, naturally dry.
Further, in the step 2, pressing position is the edge of AAO basilar memebrane.
Further, in the step 1 graphene with a thickness of 4nm.
Further, the porosity on the surface of the AAO basilar memebrane is not less than 40%.
Further, it is fine to be selected from MCE film, glass fiber filter, glass fiber filter (GF), quartz for the porous support membrane
Tie up filter membrane (QZ), polycarbonate leaching film (PC), nylon fiber filter membrane (NL), teflon membrane filter (PTFE), polypropylene (PP),
Kynoar (PVDF), cellulose mixture filter membrane (MCE), acetic acid/acetic acid filter membrane (CA), nitric acid filter membrane (CN), regenerated fiber
Plain filter membrane (RC), polyether sulfone (PES), ceramic filtration membrane are one such.
Further, the porous support membrane is MCE film.
Compared with prior art, the present invention having many advantages：
1. this method preparation process is green, easy to operate and cost is relatively low, whole process carries out in water phase, is not related to
Any organic solvent and hypertoxic Hazardous Chemical Substances；
2. graphene nanofiltration film thickness controllability prepared by is good, can cross over 4nm-100nm, have to flux and rejection
The control of wide scope；
3. graphene nanofiltration film surface prepared by greatly improves graphene nanofiltration there are the face fold of film level
The infiltrating area of film, and then improve flux；
4. graphene oxide used in graphene film made from placed 3 months or more at room temperature, have knot well
Structure and chemical stability.
Detailed description of the invention
Fig. 1 is the flow diagram of AAO substrate film stripping graphene film.
Fig. 2 is the experimentation figure of embodiment 1AAO substrate film stripping graphene film.
Fig. 3 is the experimentation figure of comparative example 1MCE substrate film stripping graphene film.
Fig. 4 is the atomic force microscopy diagram of graphene film made from embodiment 1.
Fig. 5 is the atomic force microscopy diagram of graphene film made from embodiment 2.
Fig. 6 is the atomic force microscopy diagram of graphene film made from embodiment 3.
Fig. 7 is the scanning figure for the graphene film that embodiment 1 is prepared.
Specific embodiment
The present invention is specifically described below by embodiment, the present embodiment is served only for doing further the present invention
It is bright, it should not be understood as limiting the scope of the invention, those skilled in the art makes one according to the content of foregoing invention
A little nonessential changes and adjustment belong to protection scope of the present invention.
Embodiment 1：
As shown in Figure 1, being filtered and being surpassed in AAO basilar memebrane by suction filtration method by the concentration of control graphene solution
Thin graphene oxide membrane；Surface is fitted with to the AAO basilar memebrane (porosity 40%) of graphene oxide membrane, with graphene film
Place it is face-up, be placed on the water surface, such as Fig. 1 a and 2a；AAO basilar memebrane is pressed, such as Fig. 2 b, AAO basilar memebrane starts to sink, such as
Fig. 2 c, finally, AAO basilar memebrane is sunken to bottom of a cup, graphene film (in virtual coil) floats on the water surface, such as Fig. 1 b and 2d.
The graphene film for floating on the water surface is picked up from the bottom up with MCE film, so that graphene film is laid in MCE film table
Face, after natural drying, as shown in fig. 7, surface has a large amount of folds；It is tested with a thickness of 4nm by atomic force microscope, is such as schemed
Shown in 4.
Through above step, the pure water flux of film is up to 32L/m2H bar, to the Na of 0.01mol/L2SO4Solution rejection can
Up to 84% or more, to direct yellow dye rejection up to 92% or more.
After film is placed 3 months in air environment, pure water flux and rejection are basically unchanged.
Embodiment 2：
By controlling the concentration of graphene solution, filter to obtain ultra-thin oxygen reduction in AAO basilar memebrane by suction filtration method
Graphite alkene film；Surface is fitted with to the AAO basilar memebrane (porosity 60%) of graphene oxide membrane, where graphene film
Up, it being placed on the water surface, presses AAO substrate film edge, AAO basilar memebrane starts to sink, finally, AAO basilar memebrane is sunken to bottom of a cup,
Graphene film floats on the water surface, and graphene film is successfully removed.
The graphene film for floating on the water surface is picked up from the bottom up with regenerated cellulose filter membrane (RC), so that graphene film is flat
Be laid on substrate surface, after natural drying, obtain the graphene film of surface folding, by atomic force microscope test its with a thickness of
14nm, as shown in Figure 5.
Through above step, the pure water flux of film is up to 28L/m2H bar, to the Na of 0.01mol/L2SO4Solution rejection can
Up to 92% or more, to direct yellow dye rejection up to 95% or more.
After film is placed 3 months in air environment, pure water flux and rejection are basically unchanged.
Embodiment 3：
By controlling the concentration of graphene solution, filter to obtain ultra-thin oxygen reduction in AAO basilar memebrane by suction filtration method
Graphite alkene film；Surface is fitted with to the AAO basilar memebrane (porosity 60%) of graphene oxide membrane, where graphene film
Up, it being placed on the water surface, presses AAO substrate film edge, AAO basilar memebrane starts to sink, finally, AAO basilar memebrane is sunken to bottom of a cup,
Graphene film floats on the water surface, and graphene film is successfully removed.
The graphene film for floating on the water surface is picked up from the bottom up with acetic acid/acetic acid filter membrane (CA), so that graphene film is flat
Be laid on substrate surface, after natural drying, obtain the graphene film of surface folding, by atomic force microscope test its with a thickness of
100nm, as Fig. 6 shows.
Through above step, the pure water flux of film is up to 21L/m2H bar, to the Na of 0.01mol/L2SO4Solution rejection can
Up to 95% or more, to direct yellow dye rejection up to 99% or more.
After film is placed 3 months in air environment, pure water flux and rejection are basically unchanged.
Comparative example 1
According to the suction filtration method of such as embodiment 2, filter to obtain the redox graphene with a thickness of 14nm in MCE basilar memebrane
Then surface is fitted with the MCE basilar memebrane (porosity 60%) of redox graphene film, where graphene film by film
Up, it being placed on the water surface, shown in Fig. 3 a, presses MCE substrate film edge, MCE basilar memebrane does not sink, shown in Fig. 3 b, graphene
Film stripping failure.
It should be noted that suction method is the method for most uniformly preparing graphene film generally acknowledged at present, in certain suction filtration
Under liquid measure, concentration can be regulated and controled to control the thickness of graphene film, thickness is minimum to can be one layer of graphene, with stone
The increase of black alkene concentration, under pressure, newly-increased graphene is gradually filled into the gap of first layer graphene, so that first
Layer graphene is gradually filled up completely, and then develops into the second layer, constantly repeatedly above step, can be prepared thickness and be arrived across 2 layers
The graphene nano film of up to ten thousand layers of graphene.Therefore, those skilled in the art can be adjusted by simple experiment parameter and can be obtained
Obtain the graphene film with a thickness of 4nm.
Claims (6)
1. a kind of fold graphene nanofiltration membrane, which is characterized in that the nanofiltration membrane is located on porous support membrane, passes through following steps
It obtains：
(1) it is filtered on AAO basilar memebrane and obtains the graphene oxide membrane that thickness is not more than 100nm.
(2) surface is fitted with to the AAO basilar memebrane of graphene film with face-up where graphene film, is placed on the water surface；Pressing
AAO basilar memebrane, so that AAO basilar memebrane sinks, graphene film floats on the water surface.
(3) graphene film for floating on the water surface is picked up from the bottom up with porous support membrane so that graphene film be laid in it is porous
Support film surface, naturally dry.
2. nanofiltration membrane according to claim 1, which is characterized in that in the step 2, pressing position is AAO basilar memebrane
Edge.
3. nanofiltration membrane according to claim 1, which is characterized in that graphene with a thickness of 4nm in the step 1.
4. nanofiltration membrane according to claim 1, which is characterized in that the porosity on the surface of the AAO basilar memebrane is not less than
40%.
5. nanofiltration membrane according to claim 1, which is characterized in that the porous support membrane is selected from MCE film, glass fibre is filtered
Film, glass fiber filter (GF), quartz fibre filter membrane (QZ), polycarbonate leaching film (PC), nylon fiber filter membrane (NL), polytetrafluoro
Ethylene filter membrane (PTFE), polypropylene (PP), Kynoar (PVDF), cellulose mixture filter membrane (MCE), acetic acid/acetic acid filter membrane
(CA), nitric acid filter membrane (CN), regenerated cellulose filter membrane (RC), polyether sulfone (PES), ceramic filtration membrane etc. are one such.
6. nanofiltration membrane according to claim 5, which is characterized in that the porous support membrane is MCE film.
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| CN201810753804.7A CN108816061B (en) | 2018-07-10 | 2018-07-10 | Folded graphene nanofiltration membrane |
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| CN201810753804.7A CN108816061B (en) | 2018-07-10 | 2018-07-10 | Folded graphene nanofiltration membrane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111821867A (en) * | 2020-07-10 | 2020-10-27 | 浙江大学 | Self-supporting reduced graphene oxide nanofiltration membrane and preparation method and application thereof |
Citations (3)
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| CN102671549A (en) * | 2012-04-10 | 2012-09-19 | 浙江大学 | Preparation method of graphene-based composite separation membrane device |
| US20170065939A1 (en) * | 2015-09-08 | 2017-03-09 | Gwangju Institute Of Science And Technology | Membrane based on graphene and method of manufacturing same |
| US20180071684A1 (en) * | 2016-09-12 | 2018-03-15 | Georgia Tech Research Corporation | Black Liquor Concentration by a Membrane Comprising Graphene Oxide on Porous Polymer |
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2018
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| CN102671549A (en) * | 2012-04-10 | 2012-09-19 | 浙江大学 | Preparation method of graphene-based composite separation membrane device |
| US20170065939A1 (en) * | 2015-09-08 | 2017-03-09 | Gwangju Institute Of Science And Technology | Membrane based on graphene and method of manufacturing same |
| US20180071684A1 (en) * | 2016-09-12 | 2018-03-15 | Georgia Tech Research Corporation | Black Liquor Concentration by a Membrane Comprising Graphene Oxide on Porous Polymer |
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| CN111821867A (en) * | 2020-07-10 | 2020-10-27 | 浙江大学 | Self-supporting reduced graphene oxide nanofiltration membrane and preparation method and application thereof |
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