CN109173749A - A kind of hydrophilic porous film, preparation method and application - Google Patents
A kind of hydrophilic porous film, preparation method and application Download PDFInfo
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- CN109173749A CN109173749A CN201811025487.3A CN201811025487A CN109173749A CN 109173749 A CN109173749 A CN 109173749A CN 201811025487 A CN201811025487 A CN 201811025487A CN 109173749 A CN109173749 A CN 109173749A
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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
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/268—Drying gases or vapours by diffusion
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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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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Abstract
The invention proposes a kind of hydrophilic porous films and preparation method thereof.The hydrophilic porous film material is MOF, molecular sieve or using organosilicon as parent, and MOF is doped to the MOF- organosilicon formed in organosilicon；And the hydrophilic porous film is support carrier with porous material.The hydrophilic porous film shows have good hydrophilic wet-out property compared with high-hydrophilic and water penetration flux, can be used as based Dehumidification Membranes applied to fields such as gas separation, purifying and air dewettings.
Description
Technical field
The invention belongs to thin-film material and air dewetting technical field more particularly to a kind of hydrophilic porous film, its
Preparation method and application
Background technique
Air dewetting technology has a wide range of applications in electric power, industrial production, health care, daily life.Such as: electricity
Substation, power transformation box in Force system, the power source of operated pneumatic valve, instrument and meter for automation in industrial production, chemical industry, medical product
Protection gas of baling line etc. all should be that dry air to prevent water steam from condensing at a lower temperature causes production accident.
In addition, the places such as library, museum in daily life are also required to the humid control of air in a certain range.
Traditional dehumidifying technology includes molecular sieve adsorption, soluble-salt absorption process, freeze-drying etc..Molecular sieve absorption
The production gas dew point of method is low (- 40 DEG C), but needs to regenerate, cumbersome.Soluble-salt absorption process needs timing addition salt, and salt
The discharge of solution pollutes the environment.The device is complicated for freeze-drying, and energy consumption is high, and it is high to produce gas dew point.
Membrane method dehumidifying is one of the dehumidifying technology risen in recent years, with energy saving, pollution-free, equipment is simple, product gas dew point
The features such as low, therefore there is apparent advantage compared with traditional dehumidifying technology.In this method, nothing can be divided into according to membrane material film
Machine film, organic film.Organic film has good hydrophily and gas sieve performance, but its flux is often very low, and makes
Also higher with the pressure needed in the process, this is for the more demanding of equipment.In contrast, inoranic membrane has flux height, resistance to height
The advantages that temperature, organic solvent-resistant, acid and alkali-resistance, good antimicrobial erosion and rigidity and mechanical strength, has in UF membrane field
There is good application.Therefore, preferred inoranic membrane dehumidifies when membrane method dehumidifying.
Summary of the invention
Status in view of the above technology, the present invention provide a kind of hydrophilic porous film, which has good hydrophilic remove
Wet performance can be used as based Dehumidification Membranes application.
Technical solution provided by the invention are as follows: a kind of hydrophilic porous film, it is characterized in that: the hydrophilic porous film
Material is MOF or molecular sieve, or using organosilicon as parent, and MOF is doped to the MOF- formed in organosilicon to be had
Machine silicon；Also, the hydrophilic porous film is support carrier with porous material.
And the hydrophilic porous film is support carrier with porous material.
Metal-organic framework materials (Metal-OrganicFrameworks, abbreviation MOF), refer to transition metal ions with
Organic ligand passes through the crystalline porous material with periodic network structure that is self-assembly of, with high porosity, low-density,
Bigger serface, duct rule, aperture is adjustable and topological structure diversity and the advantages that Scalability.The MOF material
It is unlimited, including CAU-1, NH2One of-MIL-53, ZIF-8 are several.
Molecular sieve is a kind of artificial synthesized hydrated aluminosilicate (zeolite) with screening molecular action or natural boiling
One of stone, including type T molecular sieve, 4A type molecular sieve and 3A type molecular sieve are several.
The support carrier is porous material, and specific material is unlimited, including porous α-Al2O3Ceramic material and porous oxygen
Compound material etc..The structure type of the support carrier is unlimited, including tubular structure, laminated structure etc..
The present invention also provides a kind of methods for preparing above-mentioned hydrophilic porous film.Specifically: by hydrophilic porous material
Material, which is evenly spread to, obtains solution in solvent；The solution is coated on the support carrier, it is more to obtain hydrophily after dry
Hole film；Alternatively, introducing solution on the support carrier by Best-Effort request, hydrophilic porous film is obtained after dry.
The preparation method of the hydrophilic porous material is unlimited, including solvent structure etc..
Preferably, the partial size of the hydrophilic porous material is 20nm~1000nm.
Preferably, the mass fraction of hydrophilic porous material is 1~20% in the solution.
Compared with prior art, the present invention uses MOF or molecular sieve, is that support carrier forms hydrophily with porous material
Porous membrane has the following beneficial effects:
(1) hydrophilic porous film have high porosity, low-density, bigger serface, duct rule, aperture is adjustable,
Topological structure diversity and Scalability, and the advantage strong with support carrier binding force.
(2) hydrophilic porous film shows to have good hydrophilic except moist compared with high-hydrophilic and water penetration flux
Can, it can be used as based Dehumidification Membranes applied to fields such as gas separation, purifying and air dewettings.
(3) hydrophilic porous film preparation method is simple, mild condition, it is simple and easy to do, be easy to be enlarged.
Detailed description of the invention
Fig. 1 is the SEM picture of metal organic framework ZIF-8 in the embodiment of the present invention 1；
Fig. 2 a is the SEM picture of ZIF-8- organosilicon composite film surface in the embodiment of the present invention 1；
Fig. 2 b is the SEM picture of ZIF-8- organosilicon composite membrane cross-section in the embodiment of the present invention 1；
Fig. 3 is the XRD diagram of ZIF-8- organosilicon composite membrane in the embodiment of the present invention 1；
Fig. 4 is the wet-out property schematic diagram of ZIF-8- organosilicon composite membrane in the embodiment of the present invention 1；
Fig. 5 is the SEM picture of T molecular sieve in the embodiment of the present invention 2；
Fig. 6 a is the SEM picture on T molecular sieve film surface in the embodiment of the present invention 2；
Fig. 6 b is the SEM picture in T molecular sieve film section in the embodiment of the present invention 2；
Fig. 7 is the XRD diagram of T molecular sieve film in the embodiment of the present invention 2；
Fig. 8 is the air dewetting performance schematic diagram of T molecular sieve film at normal temperature in the embodiment of the present invention 2.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and embodiments, it should be pointed out that embodiment described below
It is intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1:
In the present embodiment, hydrophilic porous film is metal organic framework ZIF-8 film, and the hydrophilic porous film
With porous α-Al2O3Hollow ceramic fibre pipe is support carrier, and the length is 25cm, diameter 12mm, average pore size is 1.5 μm.
In the present embodiment, the preparation method of the hydrophilic porous film is specific as follows:
(1) preparation of ZIF-8- organosilane precursor solution
0.18gZIF-8 is taken to be scattered in 50g organic silicon solution, and it is small with magnetic stirring apparatus to be vigorously mixed at room temperature for 7
When, it is ultrasonically treated 2 hours later, obtains finely dispersed ZIF-8- organosilane precursor solution.
Wherein, the preparation of ZIF-8 uses reported synthetic method.In the present embodiment, the preparation method of ZIF-8 is specific
It is: the methylimidazole of 258mg zinc nitrate and 263mg is dissolved in respectively in the methanol of 20mL, obtains two kinds of solution；Then,
Both solution are mixed, are stirred for obtaining milky white solution in 5 minutes；The milky white solution is stood aging 24 hours, uses first
Alcohol cleaning obtained product 4~5 times, product is finally placed on 80 degree of oven dryings for 24 hours, obtains ZIF-8.ZIF- obtained
8 SEM schemes as shown in Figure 1, the average particle diameter size of molecular sieve is about 50nm.
(2) on tubular porous support ZIF-8- organosilicon composite membrane preparation
The support carrier both ends are sealed, is put in 140 DEG C of baking ovens and preheats 20 minutes, then take out vertical immediately immerse
Into ZIF-8- organosilane precursor solution made from above-mentioned steps (1), takes out, be then put in 80 DEG C of baking ovens after being kept for 30 seconds
It is 2 hours dry, it obtains with porous α-Al2O3Hollow ceramic fibre pipe is the ZIF-8- organosilicon composite membrane for supporting carrier.
Fig. 2 a and 2b are respectively the SEM picture in ZIF-8- organosilicon composite film surface obtained above and section, from the SEM
It is continuous, complete film layer that picture, which can be seen that the ZIF-8- organosilicon composite membrane, and the thickness of film layer is about 100nm.
Fig. 3 is the XRD diagram of the ZIF-8- organosilicon composite membrane, it can be seen from the figure that the ZIF-8- organosilicon composite membrane
With ZIF-8 characteristic peak.
The ZIF-8- organosilicon composite membrane is placed in a 1m at normal temperature2Confined space, Fig. 4 is to be put into the ZIF-8-
The relative humidity versus time curve of the confined space after organosilicon composite membrane, the relative humidity (Relative
Humidity) the ratio of the absolute humidity in representation space and the saturated humidity ratio of synthermal gentle pressure.The change curve
Show to be put into after the ZIF-8- organosilicon composite membrane that relative humidity falls below 20% or so in 60 minutes time and spaces, explanation
ZIF-8- organosilicon composite membrane obtained has excellent wet-out property, can be used as based Dehumidification Membranes application.
Embodiment 2:
In the present embodiment, hydrophilic porous film is T molecular sieve film, and the hydrophilic porous film is with porous α-
Al2O3Hollow ceramic fibre pipe is support carrier, and the length is 25cm, diameter 12mm, average pore size is 1.5 μm.
In the present embodiment, the preparation method of the hydrophilic porous film is specific as follows:
(1) preparation of T molecular sieve precursor solution
It takes the T molecular sieve of 0.5g to be scattered in 50g aqueous solution, and is vigorously mixed at room temperature for 7 hours with magnetic stirring apparatus,
It is ultrasonically treated 2 hours later, obtains finely dispersed T molecular sieve precursor solution.
Wherein, the preparation of type T molecular sieve uses reported synthetic method.In this implementation, template is in synthesis material
Tetramethylammonium hydroxide (TMAOH), silicon source are silica solution, and silicon source is sodium metaaluminate (NaAlO2), alkali source is NaOH and KOH.Respectively
The molar ratio proportion of raw material is 18.2SiO2:1Al2O3:4.2Na2O:1.5K2O:1.82TMAOH:212.7H2O.Specifically synthesized
Journey is as follows:
Firstly, being dissolved NaOH and KOH with deionized water, and it is vigorously stirred with mechanical agitator；Then will
NaAlO2Powder is added gradually in above-mentioned lye, and is stirred to clarify；Silica solution is slowly added drop-wise in solution again, in room
Temperature obtains milk shape Synthesis liquid after lower stirring 12 hours；Synthesis liquid is transferred in the kettle containing polytetrafluoroethyllining lining, in 393K
Lower reaction 48 hours；Finally, collecting the product in reaction kettle, paint is washed to neutrality, is forged in the Muffle furnace of 823K high temperature after dry
It burns 6 hours, obtains type T molecular sieve.
Fig. 5 is the SEM picture of type T molecular sieve obtained, and the average particle diameter size of molecular sieve is about 400nm.
(2) on tubular porous support T molecular sieve film preparation
The support carrier both ends are sealed, is put in 140 DEG C of baking ovens and preheats 20 minutes, then take out vertical immediately immerse
It into T molecular sieve precursor solution made from above-mentioned steps (1), is taken out after being kept for 20 seconds, is then put in 80 DEG C of baking ovens dry 2
Hour, it obtains with porous α-Al2O3Hollow ceramic fibre pipe is the T molecular sieve film for supporting carrier.
Fig. 6 a and 6b are that the SEM in T molecular sieve film surface and section schemes on porous carrier obtained above respectively.From the figure
As can be seen that the T molecular sieve film obtained is continuous, complete film layer, film surface pattern is similar with embodiment 1, film layer
The defects of and pin hole it is seldom.
Fig. 7 is the XRD diagram of the T molecular sieve film, it can be seen from the figure that the T molecular sieve film has T molecular sieve feature
Peak.
Fig. 8 is the T molecular sieve film in normal-temp.-dehumidifying performance schematic diagram, should be the result shows that when 60min in space
Relative humidity falls below 30%, illustrates that the T molecular sieve based Dehumidification Membranes being prepared have excellent wet-out property.
The T molecular sieve film is placed in a 1m at normal temperature2Confined space, Fig. 4 is after being put into the T molecular sieve film
The relative humidity versus time curve of the confined space, the change curve show to be put into after the T molecular sieve film at 60 points
Relative humidity falls below 30% or so in the time and space of clock, illustrates that T molecular sieve film obtained has excellent wet-out property,
It can be used as based Dehumidification Membranes application.
Technical solution of the present invention and beneficial effect is described in detail in embodiment described above, it should be understood that
Above is only a specific embodiment of the present invention, it is not intended to restrict the invention, it is all to be done in spirit of the invention
Any modification and improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of hydrophilic porous film, it is characterized in that: the hydrophilic porous film material is MOF or molecular sieve, or
Person is that MOF is doped to the MOF- organosilicon formed in organosilicon using organosilicon as parent；Also, it is described hydrophilic porous
Film is support carrier with porous material.
2. hydrophilic porous film as described in claim 1, it is characterized in that: the MOF material includes CAU-1, NH2-MIL-
53, one of ZIF-8 or several；
The molecular sieve includes one of type T molecular sieve, 4A type molecular sieve and 3A type molecular sieve or several.
3. hydrophilic porous film as described in claim 1, it is characterized in that: the support carrier includes porous α-Al2O3Pottery
Ceramic material and porous oxide material.
4. hydrophilic porous film as described in claim 1, it is characterized in that: the support carrier is tubular structure or piece
Shape structure.
5. the preparation method of the hydrophilic porous film as described in any claim in Claims 1-4, it is characterized in that: will
Hydrophilic porous material, which is evenly spread to, obtains solution in solvent；The solution is coated on the support carrier, after dry
Obtain hydrophilic porous film；Alternatively, introducing solution on the support carrier by Best-Effort request, hydrophily is obtained after dry
Porous membrane.
6. the preparation method of hydrophilic porous film as claimed in claim 5, it is characterized in that: by described in solvent structure
Hydrophilic porous material.
7. the preparation method of hydrophilic porous film as claimed in claim 5, it is characterized in that: the hydrophilic porous material
Partial size is 20nm~1000nm.
8. the preparation method of hydrophilic porous film as claimed in claim 5, it is characterized in that: hydrophily is more in the solution
The mass fraction of Porous materials is 1~20%.
9. application of the hydrophilic porous film as based Dehumidification Membranes as described in any claim in Claims 1-4.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111298665A (en) * | 2020-02-25 | 2020-06-19 | 常州大学 | UIO-66-NH2Doped organic silicon high-salt wastewater treatment membrane and preparation method thereof |
| CN112495197A (en) * | 2020-11-30 | 2021-03-16 | 杭州科百特科技有限公司 | Polyvinylidene fluoride filtering membrane and preparation method and application thereof |
| CN112680177A (en) * | 2020-12-22 | 2021-04-20 | 晟大科技(南通)有限公司 | Low-density high-temperature-resistant pouring sealant and preparation method thereof |
| CN114053888A (en) * | 2021-11-19 | 2022-02-18 | 泰州九润环保科技有限公司 | Hydrophilic conductive distillation membrane and preparation method and use method thereof |
| CN114259888A (en) * | 2021-12-21 | 2022-04-01 | 中国科学院过程工程研究所 | Molecular sieve-metal organic framework composite membrane and preparation method and application thereof |
| JP7492241B2 (en) | 2019-03-14 | 2024-05-29 | 国立大学法人広島大学 | Gas dehumidification device and gas dehumidification method |
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Application publication date: 20190111 |