CN105771685A - Novel metal-organic framework material separation membrane based on carbon nanotube substrate and preparation method thereof - Google Patents
Novel metal-organic framework material separation membrane based on carbon nanotube substrate and preparation method thereof Download PDFInfo
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- CN105771685A CN105771685A CN201610170616.2A CN201610170616A CN105771685A CN 105771685 A CN105771685 A CN 105771685A CN 201610170616 A CN201610170616 A CN 201610170616A CN 105771685 A CN105771685 A CN 105771685A
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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
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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
- 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
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
Abstract
The invention relates to a novel separation membrane with high performance and a preparation method thereof. The membrane is prepared from high-flux directionally-arranged carbon nanotubes serving as a substrate, and a ZIF (Zeolitic Imidazolate Framework) type metal-organic framework material with high selectivity serving as a separation layer. The preparation method comprises the following steps: (1) preparing a directionally-arranged carbon nanotube substrate on a microfiltration membrane through a vacuum filtration method; (2) growing a ZIF type metal-organic framework material surface layer on the carbon nanotube substrate through an interface method. In conjunction with high transmission properties of inner channels and tube gaps of carbon nanotube material tubes and the three-dimensional micro-pore structure of the ZIF type metal-organic framework material, the prepared novel metal-organic framework material separation membrane based on the carbon nanotube substrate has high permeability and high selectivity in a membrane separation process. The novel separation membrane shows superior separating performance in a nano-filtration process, and a basis is laid for the design and preparation of a large-flow efficient separation membrane.
Description
Technical field
The present invention relates to prepare a kind of novel high-performance separation film, refer specifically in the CNT substrate aligned raw
Long ZIF type metal-organic-framework material top layer；This Novel separation film is applied to nanofiltration separation process can realize high flux and height
Selectivity.
Background technology
Have now found that the hydrophobicity of CNT and atomically smooth inner surface, suction when fluid passes through can be greatly reduced
The quick transmission of attached power and frictional force, beneficially hydrone.CNT also have good mechanical performance, chemical stability,
High length-diameter ratio and high specific surface area, these characteristics make CNT have the biggest advantage in separation film application aspect.At present,
CNT for preparative separation film mainly include CNT in film main body in random alignment with align two kinds.Tradition
In polymer/carbon nano-tube blend film prepared by blending method, CNT is lack of alignment, although preparation method is the simplest in this
Single, but CNT endoporus superelevation can not be given full play to and transport the advantage of speed.And the carbon nanometer being orientated based on height in-line arrangement
The standby carbon nano-tube film of control can make full use of the high-transmission of CNT and realize separating the high osmosis of film, but caliber at present
For several nanometers or CNT relatively costly less than 1 nm, and it is difficult to prepare the highly homogeneous CNT of Diameter distribution.
The duct type complexity of metal-organic framework materials is various, can obtain duct and hole, the pore structure of nano-scale
Controlled and homogeneous, it possesses that porosity is high, specific surface area is big, density is little and the chemical stability feature such as preferably.Metal-organic bone
Frame material Pore Characteristics of a great variety and different materials is different, and this project with ZIF type metal-organic framework materials is mainly
Research object.ZIF type metal-organic framework materials possesses three-dimensional micropore duct, good heat endurance and chemical stability.
The nanometer porous Structure and stability of ZIF type metal-organic framework materials makes it can become high performance membrane material, particularly its
The little molecule selectivity that hole dimension can make molecular dimension suitable passes through, thus realizes separating the high selectivity of film.It has been reported that can
On different perforated substrates, growth obtains the ZIF film of densification continuously, and prepared ZIF film can be as gas separation membrane or infiltration vapour
Change film and show the selectivity of excellence.
In conjunction with high osmosis and the high selectivity of ZIF film of carbon nano-tube film, if being combined one layer of tool over the carbon nanotube film
There are nanoscale aperture and the homogeneous ZIF separating layer of pore-size distribution, i.e. can obtain possessing high performance Novel separation film.The present invention carries
A kind of novel metal based on CNT substrate-organic framework material separation film and preparation method thereof, this preparation method are supplied
Using orientational alignment carbon nano-tube for substrate CNT substrate surface grow one layer of ZIF type metal-organic framework materials as
Separating layer.The nanoscale aperture of ZIF type metal-organic framework materials allows small molecule solvent (water, methyl alcohol, ethanol etc.) by also
Efficiently retain the solute that molecular dimension is bigger, it is ensured that selectivity；The CNT substrate of orientation is conducive to as fluid passage
Improve the solvent molecule mass transfer rate through film, be remarkably improved permeability.Therefore novel metal based on CNT substrate-
Organic framework material separation film for separation of liquid mixtures can simultaneously optimum choice and permeability, thus solve the Gao Xuan of film
Selecting property and this double-barreled question of high osmosis.
Summary of the invention
The present invention provides a kind of based on CNT and the Novel separation film of ZIF type metal-organic framework materials and system
Preparation Method；Such Novel separation film need to first prepare CNT substrate, then grows ZIF type metal-organic framework in substrate
Material separating layer.The present invention proposes membrane preparation method and comprises the steps: that (1) filtration method prepares the CNT base of in-line arrangement orientation
The end.Hydrophily carboxyl-functional carbon nano tube is scattered in solvent by a certain percentage, obtains through ultrasonic disperse finely dispersed
Carbon nano tube dispersion liquid；Selecting hydrophobic micropore filter membrane, utilize between hydrophilic CNT and hydrophobic filter membrane is close and distant
Water active force, obtains the CNT substrate of part in-line arrangement orientation through vacuum filtration.(2) interface method growth ZIF type metal-organic
Framework material separating layer.Appropriate divalent metal salt is dissolved in water and is configured to aqueous metal ligand solution, by appropriate 2-methylimidazole
It is dissolved in ethanol and n-hexane mixed liquor is configured to oil phase organic ligand solution.Under room temperature, by prepared CNT substrate first
Immerse in aqueous metal ligand solution and stand certain time, make the divalent metal in the abundant adsorption aqueous solution of carboxyl carbon nanotube
Salt；Take out CNT substrate and immerse oil phase organic ligand solution again, make divalent metal salt join with the 2-methylimidazole in oil phase
Position reaction, generates one layer of ZIF type metal-organic framework materials at substrate surface.Prepared primary membrane is at a certain temperature
It is heat-treated, finally repeatedly cleans with deionized water and ethanol, remove unreacted monomer and solvent.Repeat above-mentioned interface raw
Long (including successively immersing the aqueous solution, oil solution and heat treatment step) several times after, obtain CNT substrate after vacuum drying
The Novel separation film of upper growth ZIF type metal-organic framework separating layer.
As preferably: in described step 1), CNT is SWCN, double-walled carbon nano-tube or multi-wall carbon nano-tube
Pipe.
In described step 1), solvent is water, methyl alcohol, ethanol or ethylene glycol etc., carbon nano tube dispersion liquid concentration is 0.05 ~
0.15 g/L, the ultrasonic disperse time is 2-4 h.
In described step 1), miillpore filter aperture is 0.1 ~ 0.2 μm, material be polytetrafluoroethylene (PTFE), polyvinylidene fluoride or
Polypropylene.
Described step 2) in divalent metal salt be zinc nitrate, zinc chloride, zinc acetate, cobalt nitrate, cobalt chloride or cobalt acetate
One, divalent salts concentration of aqueous solution is 0.05-0.10 mol/L.
Described step 2) in 2-methylimidazole oil solution concentration be 0.2-1.0 mol/L, in mixed solvent ethanol and just oneself
Alkane volume ratio is 1:4 ~ 1:8.
Described step 2) in immerse the aqueous solution time be 12 ~ 24 h, immerse oil solution time be 2 ~ 6 h.
Described step 2) in heat treatment temperature be 60 ~ 80 ° of C, heat treatment time is 2 ~ 6 h.
Described step 2) median surface growth number of repetition be 2-4 time.
Described step 2) in baking temperature be room temperature to 80 ° C, drying time is 12 ~ 24 h.
Beneficial effect: grow the novel separation prepared by ZIF separating layer in the CNT substrate of in-line arrangement orientation
Film, i.e. may utilize the nanoscale aperture of ZIF type metal-organic framework materials, homogeneous loose structure, again can be in conjunction with CNT
Excellent mass-transfer performance so that this kind of Novel separation film is provided simultaneously with high selectivity and high osmosis.
Accompanying drawing explanation
Fig. 1 is the surface scan Electronic Speculum figure of polytetrafluoroethylene (PTFE) miillpore filter.
Fig. 2 is the surface scan Electronic Speculum figure of ZIF type metal-organic framework separation film.
Fig. 3 is the XRD spectra of ZIF type metal-organic framework separation film.
Fig. 4 is the surface scan Electronic Speculum figure of CNT substrate.
Fig. 5 is the surface scan of the Novel separation film growing ZIF type metal-organic framework separating layer in CNT substrate
Electronic Speculum figure.
Fig. 6 is the XRD spectra of the Novel separation film growing ZIF type metal-organic framework separating layer in CNT substrate.
Detailed description of the invention
The present invention provides a kind of novel metal based on CNT substrate-organic framework material separation film and and preparation
Method, concrete comparative example and embodiment are as follows.Separation film prepared by comparative example and embodiment is evaluated and tested it by dead-end filtration device
Separating property；UF membrane test condition is 25 ° of C, 0.5 MPa, and feed liquid side mixing speed is 600 rpm, and the effective area of film is 4
cm2.Pressurization runs about 1h and carries out film after precompressed makes film properties stable, collecting per-meate side product, Analyze & separate in the set time
Performance.The feed liquid used is the Congo red aqueous solution of 20 ppm, by UV spectrophotometer measuring solution concentration.
The evaluation of membrane separating property includes permeation flux (J) and the rejection (R) of film, is calculated by following formula respectively；In formula M and
V respectively penetrates penetrating fluid quality and the volume of film, and A is membrane area, and t is the operating time, CfWith CpIt is respectively solute component to exist
Concentration in feed liquid and penetrating fluid.
Comparative example.
Weigh the Co (NO of 3 mmol3)2·6H2O is dissolved in the mixed liquor of 25 ml water and is made into cobalt saline solution, 20 mmol 2-
Methylimidazole is dissolved in the mixed liquor of 5 ml ethanol and 20 ml n-hexanes and is made into 2-methylimidazole oil solution.By aperture be 0.2 μm,
The hydrophobic polytetrafluoroethylene (PTFE) miillpore filter of a diameter of 5.0 cm is with immersing cobalt saline solution, left at room temperature after a small amount of ethanol wet
Take out after 12 h, then immerse 2-methylimidazole oil solution and stand 2 h；Filter membrane surface is become purple from white, it was demonstrated that cobalt salt and 2-
Methylimidazole complexation reaction ZIF-67 nano particle.Under 60 ° of C, 2 h it are heat-treated after taking out filter membrane from oil solution.Prepared
Primary membrane is heat-treated at a certain temperature, then with deionized water and ethanol cleaning filter membranes repeatedly, unreacted to remove
Monomer and solvent.After repeating above-mentioned interface growth (including successively immersing the aqueous solution, oil solution and heat treatment step) twice, 80 ° of C
Obtain pure ZIF-67 after lower vacuum drying 12 h and separate film.
Fig. 1 is the surface scan Electronic Speculum figure of polytetrafluoroethylene (PTFE) miillpore filter, and Fig. 2 is ZIF type metal-organic prepared by this example
The surface scan Electronic Speculum figure of skeleton separation film, in figure, the porous surface of visible polytetrafluoroethylene (PTFE) miillpore filter is by ZIF-67 nanometer
Particle covers.Fig. 3 is the XRD spectra of ZIF type metal-organic framework separation film prepared by this example, the characteristic peak presented in figure
It coincide with ZIF-67 type metal-organic framework materials and polytetrafluoroethylmaterial material feature structure.Table 1 is ZIF type metal-organic bone
The pure water flux of frame separation film and the performance of nanofiltration separation aqueous dye solutions.
Embodiment
Being dispersed in water by multi-walled carbon nano-tubes carboxy-functionalized for hydrophily, CNT addition is 0.1 g/L, room
The lower ultrasonic disperse 2h of temperature obtains finely dispersed carbon nano tube dispersion liquid.By aperture be 0.2 μm, a diameter of 5.0 cm hydrophobic
Polytetrafluoroethylene (PTFE) miillpore filter is with after a small amount of ethanol wet, and the carbon nano tube dispersion liquid measuring 5 ml obtains part through vacuum filtration
The CNT substrate of in-line arrangement orientation.Prepared CNT substrate is submerged initially in cobalt saline solution, after left at room temperature 12 h
Take out, then immerse 2-methylimidazole oil solution and stand 2 h；Filter membrane surface is become purple from white, it was demonstrated that cobalt salt and 2-methyl miaow
Azoles complexation reaction ZIF-67 nano particle.Under 60 ° of C, 2 h it are heat-treated after taking out filter membrane from oil solution.Prepared primary membrane
Be heat-treated at a certain temperature, then with deionized water and ethanol cleaning filter membranes repeatedly, with remove unreacted monomer and
Solvent.After repeating above-mentioned interface growth (including successively immersing the aqueous solution, oil solution and heat treatment step) twice, vacuum under 80 ° of C
Obtain growing in CNT substrate the Novel separation film of ZIF type metal-organic framework separating layer after being dried 12 h.
Fig. 4 is the surface scan Electronic Speculum figure of CNT substrate prepared by this example, by vacuum filtration method poly-seen from figure
CNT substrate it is prepared on the surface of tetrafluoroethene miillpore filter.Fig. 5 be in CNT substrate grow ZIF type metal-
The Novel separation film of organic backbone separating layer, the surface of CNT substrate seen from comparison diagram 4 and Fig. 5 is by ZIF-67 nanoparticle
Son covers.Fig. 6 is the Novel separation film growing ZIF type metal-organic framework separating layer in CNT substrate prepared by this example
XRD spectra, the characteristic peak presented in figure and ZIF-67 type metal-organic framework materials, carbon nano-tube material and polytetrafluoroethyl-ne
Alkene material feature structure is coincide.Table 1 be the pure water flux of ZIF type metal-organic framework separation film and nanofiltration separation dyestuff water-soluble
The performance of liquid.The different performances separating films in contrast table 1, the rejection finding ZIF type metal-organic framework separation film the highest but
Flux is minimum；And Novel separation film is because grown ZIF type metal-organic framework separating layer in CNT substrate, it retains
Rate is apparently higher than CNT substrate but slightly below ZIF type metal-organic framework separation film, and its flux is then ZIF type metal-have
More than 2 times of machine skeleton separation film.Comprehensive permeability of the membrane and selectivity, the Novel separation film that the present invention provides shows excellence
Separating property, can further apply separation other mixture system.
Table 1 is different separates film pure water flux and separating property (operation temperature: 25 ° of C, operation pressure: 0.5 MPa)
Claims (8)
1. novel metal based on CNT substrate-organic framework material separation film and a preparation thereof, preparation method includes
Following steps: be scattered in by a certain percentage in solvent by carboxyl-functional carbon nano tube, obtain finely dispersed through ultrasonic disperse
Carbon nano tube dispersion liquid；Select hydrophobic micropore filter membrane, obtain the CNT substrate of part in-line arrangement orientation through vacuum filtration；Room
Under temperature, prepared CNT substrate is submerged initially in divalent metal saline solution standing certain time, takes out CNT
Standing certain time in 2-methylimidazole oil solution is immersed again after substrate；Divalent metal salt and the 2-first in oil solution in the aqueous solution
After base imidazoles complexation reaction, generate one layer of ZIF type metal-organic framework materials at CNT substrate surface；At the beginning of Suo Zhibei
Filming is heat-treated at a certain temperature, then after repeatedly cleaning with deionized water and ethanol, repeats above-mentioned interface growth and (depend on
Secondary including immerses the aqueous solution, oil solution and heat treatment step) several times, after vacuum drying, obtain this kind of Novel separation film.
Preparation method the most according to claim 1, it is characterised in that described carboxyl-functional carbon nano tube is that single wall carbon is received
One in mitron, double-walled carbon nano-tube or multi-walled carbon nano-tubes, the solvent of carbon nano tube dispersion liquid be water, methyl alcohol, ethanol or
Ethylene glycol etc..
Preparation method the most according to claim 1, it is characterised in that described miillpore filter aperture is 0.1 ~ 0.2 μm, material
Matter is polytetrafluoroethylene (PTFE), polyvinylidene fluoride or polypropylene.
Preparation method the most according to claim 1, it is characterised in that described divalent metal salt is zinc nitrate, zinc chloride, vinegar
Acid zinc, cobalt nitrate, cobalt chloride or the one of cobalt acetate, divalent salts concentration of aqueous solution is 0.02-0.20 mol/L.
Preparation method the most according to claim 1, it is characterised in that described 2-methylimidazole oil solution concentration is 0.1-
1.5 mol/L, in mixed solvent, ethanol and n-hexane volume ratio are 1:3 ~ 1:10.
Preparation method the most according to claim 1, it is characterised in that the time of the described immersion aqueous solution is 6 ~ 36 h, leaching
The time entering oil solution is 1 ~ 12 h.
Preparation method the most according to claim 1, it is characterised in that described heat treatment temperature is 40 ~ 80 ° of C, during heat treatment
Between be 1 ~ 12 h.
Preparation method the most according to claim 1, it is characterised in that described interface growth number of repetition is 1-6 time, is dried
Temperature is room temperature to 110 ° C, and drying time is 12 ~ 48 h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107126848A (en) * | 2017-04-21 | 2017-09-05 | 华南理工大学 | A kind of ultra-thin g C3N4/ MOF hybridized films and preparation method thereof |
| CN110141973A (en) * | 2018-02-13 | 2019-08-20 | 中国石油化工股份有限公司 | A kind of inorganic-organic coordination compound seperation film and its preparation method and application |
| CN110585863A (en) * | 2019-10-15 | 2019-12-20 | 中国石油大学(华东) | Gas separation membrane based on multi-walled carbon nanotube interpenetrating ZIF-8-polyether block amide |
| CN115109261A (en) * | 2022-05-20 | 2022-09-27 | 华南理工大学 | Preparation method of two-dimensional MOFs film and application of two-dimensional MOFs film in field of photoelectric detectors |
| CN115116764A (en) * | 2022-07-12 | 2022-09-27 | 安徽大学 | Zinc ion mixed super capacitor positive electrode material CZIF-67-CNTs, preparation method and application |
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| CN115109261B (en) * | 2022-05-20 | 2023-05-23 | 华南理工大学 | Preparation method of two-dimensional MOFs film and application of two-dimensional MOFs film in field of photoelectric detectors |
| CN115116764A (en) * | 2022-07-12 | 2022-09-27 | 安徽大学 | Zinc ion mixed super capacitor positive electrode material CZIF-67-CNTs, preparation method and application |
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