CN107469648A - A kind of preparation method of polytetrafluoroethylhollow hollow fiber composite membrane - Google Patents
A kind of preparation method of polytetrafluoroethylhollow hollow fiber composite membrane Download PDFInfo
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- CN107469648A CN107469648A CN201610396865.3A CN201610396865A CN107469648A CN 107469648 A CN107469648 A CN 107469648A CN 201610396865 A CN201610396865 A CN 201610396865A CN 107469648 A CN107469648 A CN 107469648A
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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
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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
- B01D67/0002—Organic 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
- B01D69/08—Hollow fibre 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
Abstract
The present invention relates to the method that one kind prepares metal organic framework (MOFs) film in polytetrafluoroethylhollow hollow fiber carrier surface.Continuous crackless MOFs films are prepared on polytetrafluoroethylhollow hollow fiber membrane surface by the method for " seeded heat treatment diauxic growth ".It is characterized in that crystal seed and Haloport F is set effectively to combine by heat-treating methods after seeded, so as to the continuous MOFs films of inductive formation.The inventive method has certain universality, and operating method is simple, easily controllable.
Description
Technical field
It is compound that in polytetrafluoroethylhollow hollow fiber carrier surface metal organic framework (MOFs) is prepared the present invention relates to one kind
The method of film.
Background technology
Metal-organic framework materials (MOFs) are a kind of hybrid inorganic-organic porous materials, the pore structure with three-dimensional, one
As using transition metal ions as tie point, organic ligand position support Special composition 3D extension.MOFs materials have porous, compare table
Area is big, the property such as excellent rear modified, is being catalyzed, and has extensive potential application in energy storage and gas adsorbing separation
Value.Wherein imidazoles metal organic framework compound (ZIFs) is a branch of MOFs materials, has higher chemistry steady
Qualitative and heat endurance, it is a kind of metal-organic framework materials (C.J.D.AnhPhan, Fernando of great development prospect
J.Uribe-Romo,Carolyn B.Knobler,Michael O’keeffe,And Omar M.Yaghi*,Accounts of
chemical research,2010,43,58-67.)。
In recent years, the preparation of MOFs films receives the very big concern of researcher both domestic and external, especially in all kinds of supporters
It is upper to prepare continuous flawless MOFs composite membranes.The support carrier materials mentioned in document report have aluminum oxide, titanium dioxide, carbon
Nanotube, zinc oxide, polyether sulfone, Fypro etc. (J.Yao and H.Wang, Chemical Society reviews,
2014,43,4470-4493.).The inorganic carrier physical and chemical stability such as aluminum oxide is preferable, but production cost is high, and polyether sulfone etc. is organic
Carrier production cost is relatively low, and aperture is easily adjusted, and is more beneficial for practical application, but has that chemical stability is bad simultaneously, machinery
The shortcomings of intensity is poor.In addition to carrier membrane material, the form of film is also the problem of needing to consider when carrier selects, due in
Hollow fiber perforated membrane has self-supporting, when being fabricated to membrane module with higher loading density, the manufacture of per membrane area
Cost is relatively low, and pressure-resistant stability is higher, and MOFs is prepared on doughnut carrier has bigger actual application value.But compare
The chip carriers such as Flat Membrane are played, MOFs adhesive abilities on hollow-fibre membrane are poor, prepared on doughnut membrane carrier continuous
The difficulty of fine and close MOFs films is bigger.Therefore it is to prepare MOFs to consider the suitable perforated membrane of selection as the MOFs carriers grown
One basic problem of film.
Generally, absolute methanol, DMF, N, N- diethylformamides, chlorine are needed in MOFs building-up processes
It is imitative to wait organic solvent, so must take into consideration stability of the membrane material in these organic solvents.Polytetrafluoroethylene (PTFE) (PTFE) material
With prominent chemical stability, excellent high and low temperature resistance and good corrosion resistance, it is practically insoluble in all known
Organic solvent, if during using poly tetrafluoroethylene as MOFs film-forming carriers, can not by limited using organic solvent.
There is document report to point out that the key for preparing continuous zero defect composite membrane is to improve the adhesion between carrier and MOFs,
Uniformly firm crystal seed layer is obtained, this is also the emphasis and difficult point of MOFs films research.Researcher develops a variety of methods and improves load
The caking property of body and MOFs, for example, flawless ZIF-8 can be prepared using coating material modification alumina carrier surface
(K.Huang,Z.Dong,Q.Li and W.Jin,Chemical communications,2013,49,10326-10328.)；
The MOFs associativity preparations good with dimethyl silicone polymer (PDMS) can also be used and mix crystal seed layer, so as in variety carrier
Prepare MOFs films (W.Li, G.Zhang, C.Zhang, Q.Meng, Z.Fan and C.Gao, Chemical
communications,2014,50,3214-3216)；For example hot inocalation method of special seeded method can be also obtained in carrier
MOFs films (K.Tao, L.Cao, Y.Lin, C.Kong and L.Chen, Journal of Materials that surface is well combined
Chemistry A,2013,1,13046.)。
Polytetrafluoroethylhollow hollow fiber membrane surface energy is relatively low, and hydrophobicity is extremely strong, therefore is difficult to pass through above conventional method
Obtain the crystal seed layer that adhesion is good, homogeneity is good.MOFs films, which are prepared, on polytetrafluoroethylhollow hollow fiber surface yet there are no text so far
Offer report.
The content of the invention
The present invention provides one kind and prepares metal organic framework (MOFs) film in polytetrafluoroethylhollow hollow fiber carrier surface
Method：Polytetrafluoroethyl-ne alkenes concentration dispersion liquid is added in seeded solution, is gathered by what heat treatment made to contain in dispersion liquid
Tetrafluoroethene pellet melting, as MOFs crystal seeds and the binding agent of carrier, the two is well combined, and makes crystal seed in polytetrafluoroethyl-ne
The surface further growth of alkene film is composite membrane.The method overcomes polytetrafluoroethylmaterial material poor compatibility, crystal and easily homogeneously grown
The deficiencies of.Concrete technical scheme comprises the following steps：
A) by the metal organic framework seed particles of the same race with the metal organic framework film of required growth, polytetrafluoroethyl-ne alkenes
Dispersion liquid, solvent, which are sufficiently mixed, prepares seeded solution, in polytetrafluoroethylhollow hollow fiber membrane surface seeded；It is described pre-
The surface for applying crystal seed is inner surface, outer surface or the surfaces externally and internally of polytetrafluoroethylhollow hollow fiber membrane；
B) it is put into stove and is heat-treated after the polytetrafluoroethylhollow hollow fiber membrane after seeded is dried；
C) institute's transition-containing metal ion and organic ligand solution in growth metal organic framework film needed for preparing respectively, fully
MOFs diauxic growth solution is used as after mixing, the film after heat treatment, which is placed in this solution, makes seeded surface and diauxic growth
Solution contacts, and carries out diauxic growth, the further crystallization of crystal；
D) by the Membrane cleaning after the diauxic growth in c), the unreacted composition of surface residual is removed, and is put into baking oven and does
It is dry, obtain required composite membrane；
E) in order that the more preferable film forming of metal organic framework particle, can be repeated 1 times the above by step c) and d), obtain required multiple
Close film.
The preparation method of described polytetrafluoroethylhollow hollow fiber composite membrane, it is characterised in that：Described polytetrafluoroethylene (PTFE)
Hollow-fibre membrane average pore size is 0.01 μm -0.3 μm, preferably 0.05 μm -0.15 μm.
The preparation method of described polytetrafluoroethylhollow hollow fiber composite membrane, it is characterised in that：The metal organic framework
Including but not limited to IRMOF series, Cu-BTC is serial, class zeolite imidazole skeleton series compound (ZIFs), appointing in MIL series
Anticipate one or more mixtures, any one or more mixture in preferably ZIFs series and MIL series.
The preparation method of described polytetrafluoroethylhollow hollow fiber composite membrane, it is characterised in that：Described polytetrafluoroethylene (PTFE)
Class dispersion liquid, including polytetrafluoroethylene (PTFE) (PTFE) dispersion liquid, the Meltability polytetrafluorethyletubular that mass concentration is 10wt%-60wt%
(PFA) one or more mixtures in dispersion liquid, polytetrafluoroethyl-ne propylene (FEP) dispersion liquid.The dispersant contained in dispersion liquid
It is 0.05wt%-5wt% perfluorooctanoic acids including mass concentration, one kind in ω-hydrogen perfluoro-heptanoic acid and ω-hydrogen perfluoro-pelargonic acid potassium
Or a variety of mixtures.
The preparation method of described polytetrafluoroethylhollow hollow fiber composite membrane, it is characterised in that：The seeded solution
Solvent used is deionized water, absolute methanol, absolute ethyl alcohol, N,N-dimethylformamide, N, N- diethylformamides, chlorine
One or more mixtures in imitative, ethylene glycol, 1-METHYLPYRROLIDONE, acetone, ether, dimethyl sulfoxide (DMSO)；It is preferred that deionization
Water, absolute methanol, absolute ethyl alcohol, N,N-dimethylformamide and one or more mixtures therein；Wherein, seeded is molten
Metal organic framework seed particles account for 0.05wt%-5wt% in liquid, and polytetrafluoroethyl-ne vinyl resin is accounted for as 0.5wt%-20wt%.
10nm-20 μm of the particle diameter of metal organic framework seed particles.
The preparation method of described polytetrafluoroethylhollow hollow fiber composite membrane, it is characterised in that：Poly- four after seeded
PVF hollow-fibre membrane drying temperature is 30 DEG C -90 DEG C, drying time 1h-5h, and drying mode is is dried in vacuo, vacuum
For 0-0.1MPa；Heat treatment temperature is 200 DEG C -380 DEG C, preferably 280 DEG C -310 DEG C；Heat treatment time is 30s-300s, preferably
60s-180s。
The preparation method of described polytetrafluoroethylhollow hollow fiber composite membrane, it is characterised in that：The diauxic growth solution
Solvent used is deionized water, absolute methanol, absolute ethyl alcohol, N,N-dimethylformamide, N, N- diethylformamides, chlorine
One or more mixtures in imitative, ethylene glycol, 1-METHYLPYRROLIDONE, acetone, ether, dimethyl sulfoxide (DMSO)；It is preferred that deionization
Water, absolute methanol, N,N-dimethylformamide or one or more mixtures therein；In the diauxic growth solution, transition
Metal ion solution accounts for 0.05wt%-5wt%, and organic ligand solution accounts for 0.05wt%-5wt%.
The preparation method of described polytetrafluoroethylhollow hollow fiber composite membrane, it is characterised in that：Film after seeded is put
The time that diauxic growth is carried out in this solution is 2-24h, preferably 4-12h, and the temperature of diauxic growth is 30 DEG C -150 DEG C.
The preparation method of described polytetrafluoroethylhollow hollow fiber composite membrane, it is characterised in that：The polytetrafluoro of diauxic growth
Ethene hollow-fibre membrane drying temperature is 30 DEG C -90 DEG C, drying time 1h-5h, and drying mode is vacuum drying, and vacuum is
0-0.1MPa。
The preparation method of described polytetrafluoroethylhollow hollow fiber composite membrane, it is characterised in that：Diauxic growth synthesizes metal
The number of organic framework film is 1-5 times, preferably 2-4 times；Diauxic growth synthesis metal organic framework film thickness is 0.01 μm of -20 μ
M, preferably 1-10 μm.
The method that the inventive method prepares polytetrafluoroethylene (PTFE) organic hollow fiber composite membrane is succinctly easy, has necessarily general
Adaptive, it is adaptable to prepare a variety of polytetrafluoroethylhollow hollow fiber composite membranes.The present invention overcomes polytetrafluoroethylmaterial material
The deficiencies of poor compatibility, crystal easily homogeneously grow, solve MOFs materials be difficult on polytetrafluoroethylhollow hollow fiber carrier into
The technological difficulties of film, the adhesion of MOFs and carrier is improved by the method for " seeded-heat treatment-diauxic growth ", can
Continuous crackless MOFs functional layers are grown in polytetrafluoroethylhollow hollow fiber membrane surface orientation.In addition, MOFs is controlled
Growth on polytetrafluoroethylhollow hollow fiber membrane surface suppresses its growth inside carrier film simultaneously, can improve UF membrane effect
Rate, membrane area is reduced, so as to reduce cost.Composite membrane using MOFs as separating. functional layer has expanded the hollow fibre of polytetrafluoroethylene (PTFE)
The application field of film and MOFs materials is tieed up, the extreme isolating environment such as high/low temperature can be widely suitable for.
Brief description of the drawings
Fig. 1 ZIF-8 crystal seed electromicroscopic photographs；
The electromicroscopic photograph of Fig. 2 polytetrafluoroethylhollow hollow fiber original film inner surfaces；
Fig. 3 polytetrafluoroethylhollow hollow fiber composite membrane inner surface electromicroscopic photographs.
Embodiment
Embodiment 1
By the ZIF-8 seed particles (Electronic Speculum characterizes photo and sees accompanying drawing 1) that 0.2g particle diameters are 150nm, 7gPFA concentration dispersion liquids
(solid content 30wt%), 80g deionized waters, which are sufficiently mixed, is prepared into seeded solution, in poly- four that average pore size is 0.08 μm
PVF hollow-fibre membrane inner surface seeded (Electronic Speculum characterizes photo and sees accompanying drawing 2)；(vacuum is for vacuum drying at 50 DEG C
0.1MPa) after 3h, film is placed in 300 DEG C of stove and is heat-treated 120s.
0.9g anhydrous zinc chlorides and 2.5g 2-methylimidazoles are dissolved in 30g and 50g deionized water respectively, and two parts molten
After liquid is mixed evenly, the film after heat treatment is placed in this solution, makes the inner surface of film and diauxic growth abundant into film liquid
Contact, 6h is kept at 40 DEG C, the inner surface of film is then cleaned with methanol, and (vacuum 0.1MPa) is dried in vacuo at 40 DEG C
2h.This building-up process is repeated 2 times (Electronic Speculum characterizes photo and sees accompanying drawing 3), and gained metallic framework film average thickness is 0.8 μm.
Embodiment 2
It is 100nmZIF-8 seed particles by 0.15g particle diameters, 5gFEP concentrates dispersion liquid (solid content 50wt%), and 70mL is gone
Ionized water, 10g absolute ethyl alcohols, which are sufficiently mixed, is prepared into seeded solution, in the polytetrafluoroethylene (PTFE) that average pore size is 0.12 μm
Empty fiber membrane inner surface seeded；After being dried in vacuo (vacuum 0.1MPa) 5h at 40 DEG C, film is placed in 280 DEG C of stove
It is heat-treated 180s.
1.325g zinc nitrates and 3.745g benzimidazoles are dissolved in 20g and 60g N,N-dimethylformamide (DMF) respectively
In, after two parts of solution are mixed evenly, the film after heat treatment is placed in this solution, make the inner surface of film and diauxic growth into
Film liquid is fully contacted, and 10h is kept at 80 DEG C, and the inner surface of film is then cleaned with methanol, and in 60 DEG C of vacuum drying, (vacuum is
0.1MPa)5h.This building-up process is repeated 4 times.Gained metallic framework film average thickness is 2.5 μm.
Embodiment 3
By the ZIF-9-67 seed particles that 0.25g particle diameters are 300nm, 8.0g PTFE concentration dispersion liquid (solid contents
60wt%), 70g deionized waters, 10mL DMFs (DMF), which are sufficiently mixed, is prepared into seeded solution, flat
The polytetrafluoroethylhollow hollow fiber membrane outer surface seeded that equal aperture is 0.2 μm；(vacuum is for vacuum drying at 50 DEG C
0.1MPa) after 3h, film is placed in 340 DEG C of stove and is heat-treated 100s.
1.28g cabaltous nitrate hexahydrates, 0.46g benzimidazoles, 0.32g2- methylimidazoles is molten, 20g N are dissolved separately in,
In dinethylformamide (DMF), after three parts of solution are mixed evenly, the film after heat treatment is placed in this solution, makes film
Outer surface fully contacted into film liquid with diauxic growth, 8h is kept at 130 DEG C, then with DMF (DMF)
The outer surface of film is cleaned, (vacuum 0.1MPa) 4h is dried in vacuo at 80 DEG C.This building-up process is repeated 3 times.Gained metal bone
Frame film average thickness is 5.4 μm.
Claims (10)
- A kind of 1. preparation method of polytetrafluoroethylhollow hollow fiber composite membrane, using polytetrafluoroethylhollow hollow fiber perforated membrane as load Body, by the method for " seeded-heat treatment-diauxic growth ", continuous metal organic framework film is generated in its spatial induction； It is characterised in that it includes following steps：A) the metal organic framework seed particles of the same race with the metal organic framework film of required growth, polytetrafluoroethyl-ne alkenes are disperseed Liquid, solvent, which are sufficiently mixed, prepares seeded solution, in polytetrafluoroethylhollow hollow fiber membrane surface seeded；The precoating is brilliant The surface of kind is inner surface, outer surface or the surfaces externally and internally of polytetrafluoroethylhollow hollow fiber membrane；B) it is put into stove and is heat-treated after the polytetrafluoroethylhollow hollow fiber membrane after seeded is dried；C) institute's transition-containing metal ion and organic ligand solution in growth metal organic framework film needed for preparing respectively, are sufficiently mixed MOFs diauxic growth solution is used as afterwards, and the film after heat treatment, which is placed in this solution, makes seeded surface and diauxic growth solution Contact, carry out diauxic growth, the further crystallization of crystal；D) by the Membrane cleaning after the diauxic growth in c), the unreacted composition of surface residual is removed, and is put into baking oven and dries, is obtained To required composite membrane；E) in order that the more preferable film forming of metal organic framework particle, can be repeated 1 times the above by step c) and d), obtain required compound Film.
- 2. the preparation method of polytetrafluoroethylhollow hollow fiber composite membrane according to claim 1, it is characterised in that：Described Polytetrafluoroethylhollow hollow fiber membrane average pore size is 0.01 μm -0.3 μm, preferably 0.05 μm -0.15 μm.
- 3. the preparation method of polytetrafluoroethylhollow hollow fiber composite membrane according to claim 1, it is characterised in that：The gold Category organic backbone includes but is not limited to IRMOF series, Cu-BTC series, class zeolite imidazole skeleton series compound (ZIFs), MIL Any one or more mixture in series, preferably ZIFs series and any one or more mixture in MIL-n series.
- 4. the preparation method of polytetrafluoroethylhollow hollow fiber composite membrane according to claim 1, it is characterised in that：Described Polytetrafluoroethyl-ne alkenes dispersion liquid, including mass concentration are 10wt%-60wt% polytetrafluoroethylene (PTFE) (PTFE) dispersion liquid, meltability One or more mixtures in polytetrafluoroethylene (PTFE) (PFA) dispersion liquid, polytetrafluoroethyl-ne propylene (FEP) dispersion liquid；The dispersant contained in dispersion liquid is 0.05wt%-5wt% perfluorooctanoic acids including mass concentration, ω-hydrogen perfluoro-heptanoic acid With one or more mixtures in ω-hydrogen perfluoro-pelargonic acid potassium.
- 5. the preparation method of polytetrafluoroethylhollow hollow fiber composite membrane according to claim 1, it is characterised in that：It is described pre- The solvent applied used in seed-solution is deionized water, absolute methanol, absolute ethyl alcohol, N,N-dimethylformamide, N, N- diethyl One or more mixtures in formamide, chloroform, ethylene glycol, 1-METHYLPYRROLIDONE, acetone, ether, dimethyl sulfoxide (DMSO)；It is excellent Select deionized water, absolute methanol, absolute ethyl alcohol, N,N-dimethylformamide and one or more mixtures therein；Wherein, in advance Apply metal organic framework seed particles in seed-solution and account for 0.05wt%-5wt%, polytetrafluoroethyl-ne vinyl resin is accounted for as 0.5wt%- 20wt%；10nm-20 μm of the particle diameter of metal organic framework seed particles.
- 6. the preparation method of polytetrafluoroethylhollow hollow fiber composite membrane according to claim 1, it is characterised in that：Precoating is brilliant Polytetrafluoroethylhollow hollow fiber membrane drying temperature after kind is 30 DEG C -90 DEG C, and drying time 1h-5h, drying mode is vacuum Dry, vacuum 0-0.1MPa；Heat treatment temperature is 200 DEG C -380 DEG C, preferably 280 DEG C -310 DEG C；Heat treatment time is 30s-300s, preferably 60s-180s.
- 7. the preparation method of polytetrafluoroethylhollow hollow fiber composite membrane according to claim 1, it is characterised in that：Described two Solvent used in secondary growth solution is deionized water, absolute methanol, absolute ethyl alcohol, N,N-dimethylformamide, N, N- diethyl One or more mixtures in formamide, chloroform, ethylene glycol, 1-METHYLPYRROLIDONE, acetone, ether, dimethyl sulfoxide (DMSO)；It is excellent Select deionized water, absolute methanol, N,N-dimethylformamide or one or more mixtures therein；The diauxic growth solution In, transition metal ion solution accounts for 0.05wt%-5wt%, and organic ligand solution accounts for 0.05wt%-5wt%.
- 8. the preparation method of polytetrafluoroethylhollow hollow fiber composite membrane according to claim 1, it is characterised in that：Precoating is brilliant It is 2-24h, preferably 4-12h that film after kind, which is placed in this solution and carries out time of diauxic growth, the temperature of diauxic growth is 30 DEG C- 150℃。
- 9. the preparation method of polytetrafluoroethylhollow hollow fiber composite membrane according to claim 1, it is characterised in that：Two is secondary Long polytetrafluoroethylhollow hollow fiber membrane drying temperature is 30 DEG C -90 DEG C, and drying time 1h-5h, drying mode is done for vacuum It is dry, vacuum 0-0.1MPa.
- 10. the preparation method of polytetrafluoroethylhollow hollow fiber composite membrane according to claim 1, it is characterised in that：It is secondary The number of growth synthesis metal organic framework film is 1-5 times, preferably 2-4 times；Diauxic growth synthesizes metal organic framework film thickness For 0.01 μm -20 μm, preferably 1-10 μm.
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| CN109304102A (en) * | 2018-10-25 | 2019-02-05 | 南京工业大学 | A kind of preparation method of novel metal organic backbone ZIF-300 film |
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