CN107081068A - Infiltrating and vaporizing membrane and preparation method thereof - Google Patents
Infiltrating and vaporizing membrane and preparation method thereof Download PDFInfo
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- 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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
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Abstract
The invention provides a kind of infiltrating and vaporizing membrane and preparation method thereof.The preparation method comprises the following steps：S1 will be 0.3nm~0.5nm porous material including aperture, the raw material of polymer, crosslinking agent, catalysts and solvents is mixed, and form casting solution；S2, basement membrane is combined with polymer, is formed the cross-linked layer for being dispersed with porous material, is obtained infiltrating and vaporizing membrane.Because the porous material of aperture within the above range has the affinity and porous with butanone, so as to be effectively improved separating property of the infiltrating and vaporizing membrane to butanone/aqueous mixtures using above-mentioned porous material, above-mentioned preparation method is simply easy to implement, with potential application prospect.
Description
Technical field
The present invention relates to chemical separation technology field, in particular to a kind of infiltrating and vaporizing membrane and preparation method thereof.
Background technology
Butanone can be aoxidized and reduced and be anti-due to having carbonyl and the active hydrogen adjacent with carbonyl in its molecule
Should, therefore a kind of important industrial chemicals and intermediate can be used as in Chemical Manufacture.In addition, butanone is to various fibers, synthesis
Resin, grease etc. have extremely strong solvability, frequently as the solvent of high-molecular compound, applied to paint, coating, oil refining,
The fields such as dyestuff, medicine, lubricating oil dewaxing, adhesive, printing-ink.Therefore, butanone is used as a kind of raw material, solvent and cleaning agent
Had a wide range of applications in actual production process.In the production and application process of butanone, the mixing of butanone/water can be produced
Solution, with butanone increase in demand and it is production-scale it is continuous expand, butanone is further dehydrated, purifies and increasingly attracts attention,
Also the requirement of energy-conserving and environment-protective is more conformed to.Therefore, the separation of butanone/aqueous mixtures has great importance in chemical field.
Current butanone/aqueous mixtures are separated mainly using the mode such as azeotropic distillation and extraction, be there is separating energy consumption height, are operated
Bad environments, the shortcomings of environmental pollution is serious, processing cost is high, technological process is complicated, it is difficult to realize commercial Application.It is new in recent years
Emerging infiltration evaporation membrane separation technique, relative to traditional butanone/aqueous mixtures separation method, with low energy consumption, high efficiency, nothing
The features such as secondary pollution, it is considered as most potential new technology.Infiltration evaporation membrane separation technique relies primarily on dissolving-diffusion machine
Reason, membrane material plays central role to the selective difference of butanone and water to separation process.Therefore, for preferentially saturating with butanone
Cross the selection of the membrane material of ability and prepare very crucial.At present, for the preferential transmission of butanone infiltrating and vaporizing membrane research phase
To less, available membrane material scope is narrower.
The content of the invention
It is a primary object of the present invention to provide a kind of infiltrating and vaporizing membrane and preparation method thereof, to solve in the prior art should
Separating effect is poor caused by infiltrating and vaporizing membrane for separating butanone/aqueous mixtures is small to the selective difference of butanone and water
The problem of.
To achieve these goals, according to an aspect of the invention, there is provided a kind of preparation method of infiltrating and vaporizing membrane,
Comprise the following steps：S1, by including porous material, polymer, crosslinking agent, catalysts and solvents of the aperture for 0.3nm~0.5nm
Raw material mixing, formed casting solution；S2, basement membrane is combined with the polymer in casting solution, is dispersed with membrane surface formation many
The cross-linked layer of Porous materials, obtains infiltrating and vaporizing membrane.
Further, porous material is zeolite imidazole skeleton material, preferably ZIF-67 particles.
Further, the particle diameter of ZIF-67 particles is 1~100nm, more preferably 10~50nm.
Further, in step sl, the load capacity of ZIF-67 particles be polymer 1~70wt%, preferably 10~
40wt%.
Further, in step sl, raw material is mixed using ultrasonic blending technology.
Further, polymer is selected from the dimethyl silicone polymer with different functional groups, poly- trimethyl silicane propine and gathered
Any of ether amide block copolymer is a variety of, functional group be selected from hydroxyl, vinyl, alkoxy, epoxy radicals, pi-allyl,
Aminopropyl and aryloxy group, preferred polymers are hydroxyl dimethyl silicone polymer or vinyldimethicone.
Further, the material for forming basement membrane is selected from any of polysulfones, polyacrylonitrile and Kynoar or a variety of,
It is preferred that basement membrane is Flat Membrane, hollow-fibre membrane, rolled film or tubular membrane, preferably crosslinking agent is selected from tetraethyl orthosilicate, positive silicic acid third
Any of ester and butyl silicate are a variety of.
Further, step S2 includes procedure below：S21, basement membrane is impregnated into casting solution, and the time preferably impregnated is
1~30min；S22, makes basement membrane carry out heat cross-linking with polymer, the preferably time of heat cross-linking is 1~24h, preferably heat cross-linking temperature
Spend for 40~180 DEG C, more preferably 50~90 DEG C.
Further, in step s 2, repeat step S21 and step S22 is one or many.
Further, before step S1, the step of preparation method also includes preparing ZIF-67 particles, including following mistake
Journey：Cabaltous nitrate hexahydrate, 2-methylimidazole and solvent are mixed to get mixed solution, preferably cabaltous nitrate hexahydrate in mixed solution
Mass concentration be 1~50%, the mass concentration of 2-methylimidazole is 5~80%；Mixed solution is stirred, solid-liquid is obtained
Mixture, the time preferably stirred is 1~24h；ZIF-67 particles are isolated from solidliquid mixture, it is preferred to use centrifugal process from
ZIF-67 particles are isolated in solidliquid mixture.
Further, before step S2, the step of preparation method also includes pre-processing basement membrane, including following mistake
Journey：Remove the residual organic matter of membrane surface, it is preferred to use ethanol or water are soaked to remove the residual of membrane surface to basement membrane
Organic matter is stayed, the time preferably soaked is 0.5~24h；Basement membrane is put into suction filtration in deionized water, the time of preferably suction filtration is
0.5~24h.
According to another aspect of the present invention there is provided a kind of infiltrating and vaporizing membrane, including basement membrane and it is arranged at basement membrane at least
The cross-linked layer of one side surface, infiltrating and vaporizing membrane also includes the porous material being scattered in cross-linked layer, and the aperture of porous material is
0.3nm~0.5nm.
Further, porous material is zeolite imidazole skeleton material, preferably ZIF-67 particles.
Further, the particle diameter of ZIF-67 particles is 1~100nm, more preferably 10~50nm.
Further, the load capacity of ZIF-67 particles is the 1~70wt%, preferably 10~40wt% of cross-linked layer.
Further, the material for forming basement membrane is selected from any of polysulfones, polyacrylonitrile and Kynoar or a variety of,
It is preferred that basement membrane is Flat Membrane, hollow-fibre membrane, rolled film or tubular membrane.
Apply the technical scheme of the present invention there is provided a kind of preparation method of infiltrating and vaporizing membrane, first will in the preparation method
Raw material including the porous material that aperture is 0.3nm~0.5nm, polymer, crosslinking agent, catalysts and solvents is mixed, and forms casting
Film liquid, then by making the polymer in casting solution be crosslinked in membrane surface, forms the cross-linked layer for being dispersed with above-mentioned porous material,
Infiltrating and vaporizing membrane is obtained, because the porous material of aperture within the above range has the affinity and porous with butanone, from
And it is effectively improved separating property of the infiltrating and vaporizing membrane to butanone/aqueous mixtures, above-mentioned preparation side using above-mentioned porous material
Method is simply easy to implement, with potential application prospect.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.
Below with reference to figure, the present invention is further detailed explanation.
Brief description of the drawings
The Figure of description for constituting the part of the present invention is used for providing a further understanding of the present invention, and of the invention shows
Meaning property embodiment and its illustrate be used for explain the present invention, do not constitute inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 shows a kind of preparation method schematic flow sheet for infiltrating and vaporizing membrane that embodiment of the present invention is provided；
Fig. 2 be embodiment 1 provide infiltrating and vaporizing membrane preparation method in ZIF-67 particles XRD；And
Fig. 3 is ZIF-67 particulate scan electron microscopes in the preparation method of the offer infiltrating and vaporizing membrane of embodiment 1.
Embodiment
It should be noted that in the case where not conflicting, the embodiment in the present invention and the feature in embodiment can phases
Mutually combination.Describe the present invention in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
In order that those skilled in the art more fully understand the present invention program, below in conjunction with the embodiment of the present invention
Accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only
The embodiment of a part of the invention, rather than whole embodiments.Based on the embodiment in the present invention, ordinary skill people
The every other embodiment that member is obtained under the premise of creative work is not made, should all belong to the model that the present invention is protected
Enclose.
It should be noted that term " first " in description and claims of this specification and above-mentioned accompanying drawing, "
Two " etc. be for distinguishing similar object, without for describing specific order or precedence.It should be appreciated that so using
Data can exchange in the appropriate case, so as to embodiments of the invention described herein.In addition, term " comprising " and " tool
Have " and their any deformation, it is intended that covering is non-exclusive to be included, for example, containing series of steps or unit
Process, method, system, product or equipment are not necessarily limited to those steps clearly listed or unit, but may include without clear
It is listing to Chu or for the intrinsic other steps of these processes, method, product or equipment or unit.
From background technology, in the prior art applied to separation butanone/aqueous mixtures infiltrating and vaporizing membrane to butanone and
Separating effect is poor caused by the selective difference of water is small.The present inventor studied regarding to the issue above there is provided
A kind of preparation method of infiltrating and vaporizing membrane, as shown in figure 1, comprising the following steps：S1, it is 0.3nm~0.5nm that will include aperture
Porous material, polymer, crosslinking agent, catalysts and solvents raw material mixing, formed casting solution；S2, by basement membrane and casting solution
In polymer be combined, be dispersed with the cross-linked layer of above-mentioned porous material in membrane surface formation, obtain infiltrating and vaporizing membrane.
In above-mentioned preparation method due to will be first 0.3nm~0.5nm porous material including aperture, polymer, crosslinking agent,
The raw material mixing of catalysts and solvents, forms casting solution, then by making polymer in the surface-crosslinked of basement membrane, formation is dispersed with
The cross-linked layer of above-mentioned porous material, obtains infiltrating and vaporizing membrane, so as to utilize porous material and butanone with above-mentioned pore diameter range
Affinity and porous be effectively improved separating property of the infiltrating and vaporizing membrane to butanone/aqueous mixtures, above-mentioned preparation side
Method is simply easy to implement, with potential application prospect.
The exemplary embodiment party of the preparation method of the infiltrating and vaporizing membrane provided according to the present invention is provided
Formula.However, these illustrative embodiments can be implemented by many different forms, and it should not be construed to be limited solely to
Embodiments set forth herein.It should be appreciated that thesing embodiments are provided so that disclosure herein is thorough
And it is complete, and the design of these illustrative embodiments is fully conveyed to those of ordinary skill in the art.
First, step S1 is performed：To be 0.3nm~0.5nm porous material, polymer, crosslinking agent, catalysis including aperture
The raw material mixing of agent and solvent, forms casting solution.Above-mentioned porous material can be ZIF-8, and ZIF-71 or other porous materials are such as
MIL-53, in order to realize the preferably separation to butanone/aqueous mixtures using above-mentioned porous material, it is preferable that above-mentioned porous material
Expect for zeolite imidazole skeleton material (ZIFs), it is further preferable that above-mentioned porous material is ZIF-67 particles.
In order to improve separating effect of the above-mentioned ZIF-67 particles to butanone/aqueous mixtures, it is preferable that the grain of ZIF-67 particles
Footpath is 1~100nm, more preferably 10~50nm；And, it is preferable that the load capacity of ZIF-67 particles for polymer 1~
70wt%, more preferably 10~40wt%.In order that blending is better achieved in raw material, it is preferable that will using ultrasonic blending technology
Raw material is mixed.Those skilled in the art can carry out Rational choice according to prior art to the process conditions of ultrasound blending.
In a preferred embodiment, before step S1, preparation method also includes the step for preparing ZIF-67 particles
Including procedure below suddenly,：Cabaltous nitrate hexahydrate, 2-methylimidazole and solvent are mixed to get mixed solution；Mixed solution is entered
Row stirring, obtains solidliquid mixture；ZIF-67 particles are isolated from solidliquid mixture, it is preferred to use centrifugal process is mixed from solid-liquid
ZIF-67 particles are isolated in thing.In order to improve the reaction efficiency of cabaltous nitrate hexahydrate and 2-methylimidazole, preferably mixed solution
The mass concentration of middle cabaltous nitrate hexahydrate is 1~50%, and the mass concentration of 2-methylimidazole is 5~80%, preferably states stirring
Time is 1~24h.
After execution of step S1, step S2 is performed：Basement membrane is combined with the polymer in casting solution, in membrane surface
The cross-linked layer for being dispersed with above-mentioned porous material is formed, infiltrating and vaporizing membrane is obtained.Porous material is dispersed with above-mentioned cross-linked layer, but it is many
Porous materials are not belonging to the component in cross-linked layer, are the porous of 0.3nm~0.5nm due to being dispersed with aperture in above-mentioned infiltrating and vaporizing membrane
Material, so that infiltrating and vaporizing membrane can be effectively improved to fourth using the affinity and porous of above-mentioned porous material and butanone
The separating property of ketone/aqueous mixtures.
In order to obtain infiltrating and vaporizing membrane, above-mentioned steps S2 can specifically include procedure below：S21, casting is impregnated into by basement membrane
In film liquid；S22, makes polymer carry out heat cross-linking.In order to improve the combined efficiency between above-mentioned polymer and above-mentioned basement membrane, dipping
Time be preferably 1~30min, the time of heat cross-linking is preferably 1~24h, and the temperature of heat cross-linking is preferably 40~180 DEG C, more
Preferably 50~90 DEG C；And, it is preferable that in above-mentioned steps S2, repeat step S21 and step S22 is one or many.
Selection is optimized by the species to above-mentioned basement membrane and above-mentioned polymer, it is possible to increase the infiltration vapour being prepared from
Change the performance of film, it is preferable that the polymer used in step S1 is selected from the dimethyl silicone polymer with different functional groups, poly- three
Any of methyl silicon propine and polyether amide block copolymer are a variety of, functional group be selected from hydroxyl, vinyl, alkoxy,
Epoxy radicals, pi-allyl, aminopropyl and aryloxy group etc., it is further preferable that polymer is hydroxyl dimethyl silicone polymer or vinyl
Dimethyl silicone polymer；And, it is preferable that the material of the formation basement membrane used in step S2 is selected from polysulfones, polyacrylonitrile and gathered
Any of vinylidene is a variety of, and basement membrane can be Flat Membrane, hollow-fibre membrane, rolled film or tubular membrane.In order to carry
Cross-linking efficiency between high above-mentioned polymer and above-mentioned basement membrane, crosslinking agent can be selected from tetraethyl orthosilicate, positive silicic acid propyl ester, silicic acid
Any of butyl ester is a variety of.
In a preferred embodiment, before step S2, preparation method also includes what basement membrane was pre-processed
Step, including procedure below：Remove the residual organic matter of membrane surface；Basement membrane is put into suction filtration in deionized water.By to base
Film is pre-processed, it is possible to increase the cross-linking efficiency of basement membrane in step s 2 with polymer, in order to further improve basement membrane with
The cross-linking efficiency of polymer, it is preferred to use ethanol or water are soaked to remove the residual organic matter of membrane surface to basement membrane, leaching
The time of bubble is preferably 0.5~24h, and the time of suction filtration is preferably 0.5~24h.
According to further aspect of the application there is provided a kind of infiltrating and vaporizing membrane, including basement membrane and it is arranged at basement membrane extremely
The cross-linked layer of a few side surface, infiltrating and vaporizing membrane also includes the porous material being scattered in cross-linked layer, and the aperture of porous material
For 0.3nm~0.5nm.Due to being dispersed with the porous material that aperture is 0.3nm~0.5nm in above-mentioned infiltrating and vaporizing membrane, so that sharp
Infiltrating and vaporizing membrane pair is effectively improved with porous material and the affinity of butanone and porous with above-mentioned pore diameter range
The separating property of butanone/aqueous mixtures.
In order to realize the preferably separation to butanone/aqueous mixtures using above-mentioned porous material, it is preferable that above-mentioned porous material
Expect for zeolite imidazole skeleton material (ZIFs), it is further preferable that above-mentioned porous material is ZIF-67 particles.It is above-mentioned in order to improve
Separating effect of the ZIF-67 particles to butanone/aqueous mixtures, it is preferable that the particle diameter of ZIF-67 particles is 1~100nm, more preferably
For 10~50nm；And, it is preferable that the load capacity of ZIF-67 particles be cross-linked layer 1~70wt%, more preferably 10~
40wt%.
In order to improve the performance of infiltrating and vaporizing membrane, it is preferable that the material for forming basement membrane is selected from polysulfones, polyacrylonitrile and gathers inclined
Any of PVF is a variety of, and basement membrane is Flat Membrane, hollow-fibre membrane, rolled film or tubular membrane；Now, handed over basement membrane
The polymer that connection forms cross-linked layer can be selected from the dimethyl silicone polymer with different functional groups, poly- trimethyl silicane propine and gather
Any of ether amide block copolymer is a variety of, functional group be selected from hydroxyl, vinyl, alkoxy, epoxy radicals, pi-allyl,
Aminopropyl, aryloxy group, it is preferable that above-mentioned polymer is hydroxyl dimethyl silicone polymer or vinyldimethicone.
Infiltrating and vaporizing membrane that the application is provided and preparation method thereof is further illustrated below in conjunction with embodiment.
Embodiment 1
The present embodiment prepares the MIL-53 particles that the porous material that infiltrating and vaporizing membrane uses is 110nm for particle diameter, and basement membrane is
Polysulfone material, flat plate ultrafiltration membrane, membrane area is 28cm2, polymer is hydroxyl-terminated injecting two methyl siloxane (OH-PDMS), solvent
For normal heptane, preparation method comprises the following steps：
1st, polysulfones basement membrane is placed in 36h in 30wt% ethanol/waters, removes the organic matter of membrane surface, be then immersed in
Suction filtration 36h is stand-by in ionized water；
2nd, by normal heptane, above-mentioned polymer, tetraethyl orthosilicate, dibutyl tin laurate polydimethylsiloxanes in mass ratio
Alkane:Tetraethyl orthosilicate:Dibutyl tin laurate=1:0.1:0.005 is configured to solution, then that MIL-53 is evengranular
It is distributed in solution and forms casting solution, wherein, the load capacity of MIL-53 particles is the 0.5wt% of polymer；
3rd, the polysulfones Flat Membrane pre-processed in step 1 is impregnated into the casting solution in step 2 at room temperature, impregnated
0.8min makes ZIF-67/PDMS be compound to polysulfones membrane surface；
4th, the MIL-53/PDMS hybridized films prepared in step 3 are placed in 200 DEG C of vacuum drying oven and are crosslinked 36h, obtained
To infiltrating and vaporizing membrane.
Embodiment 2
The present embodiment prepares basement membrane that infiltrating and vaporizing membrane uses for polysulfone material, and flat plate ultrafiltration membrane, membrane area is 28cm2,
Polymer is hydroxyl-terminated injecting two methyl siloxane (OH-PDMS), and solvent is normal heptane, and preparation method comprises the following steps：
1st, using water as solvent, 0.45g cabaltous nitrate hexahydrate and 5.5g 2-methylimidazole are dissolved respectively at room temperature
In 3ml and 20ml deionized waters, stirring 0.8h obtains solidliquid mixture after being well mixed, and solidliquid mixture centrifugal treating is obtained
To solid powder, respectively washing three times of water and ethanol, then dry and grind respectively, obtain the ZIF-67 particles that particle diameter is 110nm；
2nd, polysulfones basement membrane is placed in 36h in 30wt% ethanol/waters, removes the organic matter of membrane surface, be then immersed in
Suction filtration 36h is stand-by in ionized water；
3rd, by normal heptane, above-mentioned polymer, tetraethyl orthosilicate, dibutyl tin laurate polydimethylsiloxanes in mass ratio
Alkane:Tetraethyl orthosilicate:Dibutyl tin laurate=1:0.1:0.005 be configured to solution, then will be prepared in step 1
Evengranular are distributed in solution of ZIF-67 forms casting solution, wherein, the load capacity of ZIF-67 particles is polymer
0.5wt%；
4th, the polysulfones Flat Membrane pre-processed in step 2 is impregnated into the casting solution in step 3 at room temperature, impregnated
0.8min makes ZIF-67/PDMS be compound to polysulfones membrane surface；
5th, the ZIF-67/PDMS hybridized films prepared in step 4 are placed in 200 DEG C of vacuum drying oven and are crosslinked 36h, obtained
To infiltrating and vaporizing membrane.
Embodiment 3
The present embodiment prepares basement membrane that infiltrating and vaporizing membrane uses for polyacrylonitrile material, flat plate ultrafiltration membrane, and membrane area is
28cm2, polymer is poly- trimethyl silicane propine (PTMSP), and solvent is normal heptane, and preparation method comprises the following steps：
1st, using water as solvent, 0.45g cabaltous nitrate hexahydrate and 5.5g 2-methylimidazole are dissolved respectively at room temperature
In 3ml and 20ml deionized waters, stirring 6h obtains solidliquid mixture after being well mixed, and solidliquid mixture centrifugal treating is obtained
Solid powder, respectively washing three times of water and ethanol, then dry and grind respectively, obtain the ZIF-67 particles that particle diameter is 100nm；
2nd, polyacrylonitrile basement membrane is placed in 2h in 30wt% ethanol/waters, removes the organic matter of membrane surface, be then immersed in
Suction filtration 4h is stand-by in deionized water；
3rd, by normal heptane, above-mentioned polymer, tetraethyl orthosilicate, dibutyl tin laurate polydimethylsiloxanes in mass ratio
Alkane:Tetraethyl orthosilicate:Dibutyl tin laurate=1:0.1:0.005 is configured to solution, the ZIF- for then preparing step 1
67 evengranular are distributed in this solution form casting solution, wherein, the load capacity of ZIF-67 particles is the 20wt% of polymer；
4th, at room temperature by the polyacrylonitrile flat film immersion pre-processed in step 2 into the casting solution in step 3, leaching
Stain 3min makes ZIF-67/PTMSP be compound to polyacrylonitrile basement membrane surface；
5th, the vacuum drying oven that the ZIF-67/PTMSP hybridized films prepared in step 4 are placed on into 80 DEG C is crosslinked 12h, obtains
Infiltrating and vaporizing membrane.
Embodiment 4
The present embodiment prepares basement membrane that infiltrating and vaporizing membrane uses for polyvinylidene fluoride material, flat plate ultrafiltration membrane, and membrane area is
28cm2, high molecular polymer is polyetheramides (PEBA), and solvent is DMF, and preparation method includes following step
Suddenly：
1st, using water as solvent, 0.45g cabaltous nitrate hexahydrate and 5.5g 2-methylimidazole are dissolved respectively at room temperature
Well mixed to obtain mixed solution in 3ml and 20ml deionized waters, stirring mixed solution 6h obtains solidliquid mixture, will be solid
Liquid mixture centrifugal treating obtains solid powder, and respectively washing three times of water and ethanol, then dry and grind, obtaining particle diameter is respectively
100nm ZIF-67 particles；
2nd, Kynoar basement membrane is placed in 2h in 30wt% ethanol/waters, removes the organic matter of membrane surface, then soak
Suction filtration 4h is stand-by in deionized water；
3rd, N,N-dimethylformamide, above-mentioned polymer, tetraethyl orthosilicate, dibutyl tin laurate are gathered in mass ratio
Dimethyl siloxane:Tetraethyl orthosilicate:Dibutyl tin laurate=1:0.1:0.005 is configured to solution, then by step 1
Evengranular are distributed in this solution of ZIF-67 prepared forms casting solution, wherein, the load capacity of ZIF-67 particles is poly-
The 20wt% of compound；
4th, at room temperature by the polyvinylidene fluoride flat film immersion pre-processed in step 2 into the casting solution in step 3,
Dipping 5min makes ZIF-67/PEBA be compound to Kynoar basement membrane surface；
5th, the vacuum drying oven that the ZIF-67/PEBA hybridized films prepared in step 4 are placed on into 80 DEG C is crosslinked 12h, obtains
Infiltrating and vaporizing membrane.
Embodiment 5
The difference of the preparation method and embodiment 4 of the infiltrating and vaporizing membrane that the present embodiment is provided is：
In step 1, the ZIF-67 particles that particle diameter is 1nm are obtained by grinding.
Embodiment 6
The difference of the preparation method and embodiment 4 of the infiltrating and vaporizing membrane that the present embodiment is provided is：
In step 1, the ZIF-67 particles that particle diameter is 10nm are obtained by grinding.
Embodiment 7
The difference of the preparation method and embodiment 4 of the infiltrating and vaporizing membrane that the present embodiment is provided is：
In step 1, the ZIF-67 particles that particle diameter is 50nm are obtained by grinding.
Embodiment 8
The difference of the preparation method and embodiment 3 of the infiltrating and vaporizing membrane that the present embodiment is provided is：
In step 1, the mass concentration of cabaltous nitrate hexahydrate is 1%, the mass concentration of 2-methylimidazole in mixed solution
For 5%, stirring mixed solution 1h obtains solidliquid mixture.
Embodiment 9
The difference of the preparation method and embodiment 3 of the infiltrating and vaporizing membrane that the present embodiment is provided is：
In step 1, the mass concentration of cabaltous nitrate hexahydrate is 50%, the mass concentration of 2-methylimidazole in mixed solution
For 60%, stirring mixed solution 24h is to obtain solidliquid mixture.
Embodiment 10
The difference of the preparation method and embodiment 3 of the infiltrating and vaporizing membrane that the present embodiment is provided is：
In step 1, the mass concentration of cabaltous nitrate hexahydrate is 15%, the mass concentration of 2-methylimidazole in mixed solution
For 80%, stirring mixed solution 24h is to obtain solidliquid mixture.
Embodiment 11
The difference of the preparation method and embodiment 3 of the infiltrating and vaporizing membrane that the present embodiment is provided is：
In step 2, polyacrylonitrile basement membrane is placed in 0.5h in 30wt% ethanol/waters, removes the organic matter of membrane surface,
Then suction filtration 0.5h in deionized water is soaked stand-by.
Embodiment 12
The difference of the preparation method and embodiment 3 of the infiltrating and vaporizing membrane that the present embodiment is provided is：
In step 2, polyacrylonitrile basement membrane is placed in 24h in 30wt% ethanol/waters, removes the organic matter of membrane surface,
Then suction filtration 24h in deionized water is soaked stand-by.
Embodiment 13
The difference of the preparation method and embodiment 3 of the infiltrating and vaporizing membrane that the present embodiment is provided is：
In step 3, the load capacity of ZIF-67 particles is the 10wt% of polymer.
Embodiment 14
The difference of the preparation method and embodiment 3 of the infiltrating and vaporizing membrane that the present embodiment is provided is：
In step 3, the load capacity of ZIF-67 particles is the 70wt% of polymer.
Embodiment 15
The difference of the preparation method and embodiment 3 of the infiltrating and vaporizing membrane that the present embodiment is provided is：
In step 4, by the polyvinylidene fluoride flat film immersion pre-processed into casting solution 1min, make ZIF-67/
PEBA is compound to Kynoar basement membrane surface；
In steps of 5, ZIF-67/PEBA hybridized films are placed in 40 DEG C of vacuum drying oven and are crosslinked 1h, obtain permeating vapour
Change film.
Embodiment 16
The difference of the preparation method and embodiment 3 of the infiltrating and vaporizing membrane that the present embodiment is provided is：
In step 4, by the polyvinylidene fluoride flat film immersion pre-processed into casting solution 30min, make ZIF-67/
PEBA is compound to Kynoar basement membrane surface；
In steps of 5, ZIF-67/PEBA hybridized films are placed in 180 DEG C of vacuum drying oven and are crosslinked 24h, permeated
Vaporize film.
XRD and scanning electron microscope analysis are carried out to the ZIF-67 particles obtained in above-described embodiment 2, as a result such as the institutes of Fig. 2 and 3
Show, the porous granule prepared in above-described embodiment 1 to 16 /PDMS hybridized films are subjected to infiltration evaporation in infiltration evaporation membrane cisterna
It can test, test condition is：Material liquid is butanone/aqueous mixtures that butanone content is 1wt%, and feed temperature is 60 DEG C, under film
Trip lateral pressure is 240Pa, and the infiltration evaporation film properties measured are as shown in the table：
The infiltrating and vaporizing membrane prepared in the embodiment of the present application 1 to 12 is can be seen that from above-mentioned test result to be respectively provided with
Higher permeation flux and separation factor, it is achieved thereby that being efficiently separated to butanone/aqueous mixtures.
As can be seen from the above description, the above embodiments of the present invention realize following technique effect：
1st, aperture is dispersed in polymer and prepares hybridized film by the application for 0.3nm~0.5nm porous material, and
Infiltration evaporation applied to butanone/aqueous mixtures is separated, and preparation method is simple and easy to do, and because above-mentioned porous material is to butanone
Preferential adsorption ability and the porous of itself, effectively increase the separating effect of film；
2nd, dispersiveness of the ZIF-67 particles in casting solution can be improved by ultrasound blending, it is ensured that high filler loading capacity ZIF-
The separating property of 67 hybridized films.
3rd, by controlling synthesis condition to prepare ZIF-67 nano particles, shape in polymer solution is then evenly spread to
Into casting solution, ZIF-67/ polymer is compounded in membrane surface using infusion process, by be chemically crosslinked formed it is more fine and close can
Allow the infiltrating and vaporizing membrane that butanone is preferentially passed through.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (16)
1. a kind of preparation method of infiltrating and vaporizing membrane, it is characterised in that comprise the following steps：
S1, the raw material including aperture for 0.3nm~0.5nm porous material, polymer, crosslinking agent, catalysts and solvents is mixed
Close, form casting solution；
S2, the basement membrane is combined with the polymer in the casting solution, is dispersed with membrane surface formation described
The cross-linked layer of porous material, obtains the infiltrating and vaporizing membrane.
2. preparation method according to claim 1, it is characterised in that the porous material is zeolite imidazole skeleton material,
Preferably ZIF-67 particles.
3. preparation method according to claim 2, it is characterised in that the particle diameter of the ZIF-67 particles is 1~100nm,
More preferably 10~50nm.
4. preparation method according to claim 2, it is characterised in that in the step S1, the ZIF-67 particles
Load capacity is the 1~70wt%, preferably 10~40wt% of the polymer.
5. preparation method according to claim 1, it is characterised in that in the step S1, using ultrasonic blending technology
The raw material is mixed.
6. preparation method according to claim 1, it is characterised in that the polymer is selected from poly- with different functional groups
Any of dimethyl siloxane, poly- trimethyl silicane propine and polyether amide block copolymer are a variety of, functional group's choosing
From hydroxyl, vinyl, alkoxy, epoxy radicals, pi-allyl, aminopropyl and aryloxy group, preferably described polymer is the poly- diformazan of hydroxyl
Radical siloxane or vinyldimethicone.
7. preparation method according to claim 6, it is characterised in that the material for forming the basement membrane is selected from polysulfones, poly- third
Any of alkene nitrile and Kynoar are a variety of, and preferably described basement membrane is Flat Membrane, hollow-fibre membrane, rolled film or tubular type
Film, preferably described crosslinking agent is selected from any of tetraethyl orthosilicate, positive silicic acid propyl ester and butyl silicate or a variety of.
8. preparation method according to any one of claim 1 to 7, it is characterised in that the step S2 includes following mistake
Journey：
S21, the basement membrane is impregnated into the casting solution, and the time of preferably described dipping is 1~30min；
S22, makes the basement membrane carry out heat cross-linking with the polymer, the time of preferably described heat cross-linking is 1~24h, preferably institute
The temperature for stating heat cross-linking is 40~180 DEG C, more preferably 50~90 DEG C.
9. preparation method according to claim 8, it is characterised in that in the step S2, repeat the step
S21 and the step S22 are one or many.
10. the preparation method according to any one of claim 2 to 7, it is characterised in that before the step S1, institute
State the step of preparation method also includes preparing the ZIF-67 particles, including procedure below：
Cabaltous nitrate hexahydrate, 2-methylimidazole and solvent are mixed to get mixed solution, six described in preferably described mixed solution
The mass concentration of nitric hydrate cobalt is 1~50%, and the mass concentration of the 2-methylimidazole is 5~80%；
The mixed solution is stirred, solidliquid mixture is obtained, the time of preferably described stirring is 1~24h；
The ZIF-67 particles are isolated from the solidliquid mixture, it is preferred to use centrifugal process is divided from the solidliquid mixture
Separate out the ZIF-67 particles.
11. preparation method according to any one of claim 1 to 7, it is characterised in that before the step S2, institute
State the step of preparation method also includes pre-processing the basement membrane, including procedure below：
Remove the residual organic matter of the membrane surface, it is preferred to use ethanol or water are soaked described to remove to the basement membrane
The residual organic matter of membrane surface, the time of preferably described immersion is 0.5~24h；
The basement membrane is put into suction filtration in deionized water, the time of preferably described suction filtration is 0.5~24h.
12. a kind of infiltrating and vaporizing membrane, it is characterised in that including basement membrane and be arranged at the crosslinking of a basement membrane at least side surface
Layer, the infiltrating and vaporizing membrane also includes the porous material being scattered in the cross-linked layer, and the aperture of the porous material is
0.3nm~0.5nm.
13. infiltrating and vaporizing membrane according to claim 12, it is characterised in that the porous material is zeolite imidazole skeleton material
Material, preferably ZIF-67 particles.
14. infiltrating and vaporizing membrane according to claim 13, it is characterised in that the particle diameter of the ZIF-67 particles is 1~
100nm, more preferably 10~50nm.
15. infiltrating and vaporizing membrane according to claim 13, it is characterised in that the load capacity of the ZIF-67 particles is described
1~70wt% of cross-linked layer, preferably 10~40wt%.
16. infiltrating and vaporizing membrane according to claim 12, it is characterised in that formed the basement membrane material be selected from polysulfones,
Any of polyacrylonitrile and Kynoar are a variety of, preferably described basement membrane be Flat Membrane, hollow-fibre membrane, rolled film or
Tubular membrane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109173749A (en) * | 2018-09-04 | 2019-01-11 | 宁波市电力设计院有限公司 | A kind of hydrophilic porous film, preparation method and application |
| CN109433021A (en) * | 2018-11-28 | 2019-03-08 | 常州大学 | Have both the osmosis vaporizing compound membrane and preparation method thereof of solvent resistance and excellent small molecular alcohol separating property |
| CN109499373A (en) * | 2018-12-04 | 2019-03-22 | 杭州惟创科技有限公司 | A kind of hollow fiber pervaporation membrane and preparation method |
| CN110180414A (en) * | 2019-06-06 | 2019-08-30 | 上海电气集团股份有限公司 | A kind of infiltration evaporation membrane material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103182251A (en) * | 2013-03-20 | 2013-07-03 | 北京工业大学 | Method for preparing organic/inorganic alcohol-permselective pervaporation composite membrane |
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- 2017-05-02 CN CN201710302686.3A patent/CN107081068B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103182251A (en) * | 2013-03-20 | 2013-07-03 | 北京工业大学 | Method for preparing organic/inorganic alcohol-permselective pervaporation composite membrane |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109173749A (en) * | 2018-09-04 | 2019-01-11 | 宁波市电力设计院有限公司 | A kind of hydrophilic porous film, preparation method and application |
| CN109433021A (en) * | 2018-11-28 | 2019-03-08 | 常州大学 | Have both the osmosis vaporizing compound membrane and preparation method thereof of solvent resistance and excellent small molecular alcohol separating property |
| CN109433021B (en) * | 2018-11-28 | 2021-06-18 | 常州大学 | Pervaporation composite membrane with solvent resistance and excellent small molecular alcohol separation performance and preparation method thereof |
| CN109499373A (en) * | 2018-12-04 | 2019-03-22 | 杭州惟创科技有限公司 | A kind of hollow fiber pervaporation membrane and preparation method |
| CN110180414A (en) * | 2019-06-06 | 2019-08-30 | 上海电气集团股份有限公司 | A kind of infiltration evaporation membrane material and preparation method thereof |
| CN110180414B (en) * | 2019-06-06 | 2021-12-31 | 上海电气集团股份有限公司 | Pervaporation membrane material and preparation method thereof |
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