CN106823863B - Metal organic framework hybridized film, preparation method and application - Google Patents
Metal organic framework hybridized film, preparation method and application Download PDFInfo
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- CN106823863B CN106823863B CN201510883685.3A CN201510883685A CN106823863B CN 106823863 B CN106823863 B CN 106823863B CN 201510883685 A CN201510883685 A CN 201510883685A CN 106823863 B CN106823863 B CN 106823863B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
Metal organic framework hybridized film, preparation method and application.Metal organic framework hybridized film of the invention uses metal organic framework particle UiO-66 and/or UiO-66-NH2Instead of traditional inorganic filler, it is made into casting solution jointly with high molecular polymer, then form a film in carrier surface using dip-coating method, drying.Metal organic framework hybridized film prepared by the present invention is separating CO from flue gas and natural gas2There is good application prospect in field, and the manufacturing process of hybridized film is simple, low in cost, environmental-friendly, has actual industrial applications meaning.
Description
Technical field
The invention belongs to membrane technology separation fields, and in particular to a kind of preparation method of metal organic framework hybridized film and its
CO is being separated from flue gas and natural gas2The application in field.
Background technique
The CO discharged from fossil energy industry2It is considered as one of the principal element of Global Greenhouse Effect, it is effectively real
Existing CO2Separation and removal Sustainable Socioeconomic Development will be had very important effect.CO at present2Separation method master
There are solvent absorption, pressure swing adsorption method, low temperature processing and membrane separation process.Four kinds of methods are each advantageous, but from development prospect
From the point of view of, have land occupation few, the membrane separation process of the advantages such as with low investment, at low cost has more prospects for commercial application.
Film is the core component of membrane separating process, by its material composition can be divided into following three classes: i.e. organic film, inoranic membrane and
Hybrid organic-inorganic film.Organic film because its membrane material is at low cost, the advantages that easy to form due to be widely used, however organic film exists
There is unsurmountable defects in terms of thermal stability, mechanical stability and chemical stability.Inoranic membrane thermal stability is good, can grow
Phase operates at high temperature, but it prepares poor repeatability, at high cost.Hybrid organic-inorganic film introduces inanimate matter in organic network
Point improves organic network structure using the high mechanical strength of inorganic particle to enhance the solvent resistant and high temperature resistance of film, and has
The flexibility of machine network also overcomes the hard crisp rapid wear disadvantage of inoranic membrane.In addition, the highly selective duct of the inorganic particle of doping
Further improve the separating property of hybridized film.The hybridized film for thus having had both organic film and inoranic membrane advantage, which has become, works as cephacoria
The research hotspot in field.
Typical inorganic filler is zeolite molecular sieve, carbon molecular sieve, silicon and silica nano particle, metal oxide
Deng.In recent years, a kind of novel porous material, that is, metal-organic framework materials (metal-organic frameworks, below
Abbreviation MOFs) just become UF membrane because of its large specific surface area, cellular structure, size and many excellent properties such as surface nature is adjustable
" new lover " in field.MOFs is to be formed to have periodical infinite net by metal ion or ion cluster and oxygen-containing or nitrogen organic ligand
The crystalline material of network structure.Compared with traditional inorganic filler, organic group rich in MOFs skeleton, with organic film
Material has better compatibility, so as to preferably avoid hybridized film phase boundary planar defect.UiO-66(UiO,University of
Oslo) class MOFs material (UiO-66 and UiO-66-NH2) it is to be matched by zirconium ion and terephthalic acid (TPA) or 2- amino terephthalic acid (TPA)
The three-dimensional framework material that position obtains, with high-specific surface area, good thermal stability and chemical stability.
Summary of the invention:
For solution, organic membrane stability is poor in the prior art, inorganic film preparation poor repeatability, defect at high cost, the present invention
A kind of hybridized film for replacing traditional inorganic filler to prepare with metal organic framework particle (MOFs) is provided, can be used for flue gas
With CO is separated in natural gas2。
Technical purpose of the invention is achieved through the following technical solutions:
In a first aspect, the present invention provides the preparation methods of metal organic framework hybridized film, comprising the following steps:
1. metal organic framework particle is added in high molecular polymer wiring solution-forming, ultrasonic disperse forms casting solution；
2. 1. casting solution that step is prepared is formed a film using dip-coating method in carrier surface, drying；
Wherein, the metal organic framework particle is UiO-66 and/or UiO-66-NH2。
Second aspect, the present invention provide the metal organic framework hybridized film prepared by the above method.
The third aspect, the present invention provide metal organic framework hybridized film described above in separation CO2In application.
It is separated using the metal organic framework hybridized film that preparation method of the invention synthesizes from flue gas and natural gas
CO2There is good application prospect in field, and the manufacturing process of hybridized film is simple, low in cost, environmental-friendly, has actual industry
Change application value.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of metal organic framework UiO-66 crystal synthesized by embodiment 1；
Fig. 2 is the scanning electron microscope diagram of metal organic framework UiO-66 crystal synthesized by embodiment 1；
Fig. 3 is the X-ray diffractogram of metal organic framework hybridized film prepared by embodiment 2；
Fig. 4 is the scanning electron microscope diagram of metal organic framework hybridized film prepared by embodiment 2.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Present invention firstly provides a kind of preparation methods of metal organic framework hybridized film, comprising the following steps:
1. metal organic framework particle is added in high molecular polymer wiring solution-forming, ultrasonic disperse forms casting solution；
2. 1. casting solution that step is prepared is formed a film using dip-coating method in carrier surface, drying；
Wherein, the metal organic framework particle is UiO-66 and/or UiO-66-NH2。
Further, in the preparation process in accordance with the present invention, step 1. described in casting solution metal organic framework particle with
Mass fraction is calculated as 0.5~10%, preferably 0.5~2.5%, and the partial size of the metal organic framework particle is 50~200nm.
In method made above, metal organic framework the particle UiO-66 and/or UiO-66-NH2Preparation method
It is known to the skilled person, conventional method preparation can be used, as a further preference, solvent-thermal method preparation can be used.
The preparation of one of embodiment more preferably, UiO-66 can refer to document: [the Chem.Eur.J.17 (2011) such as Schaate
6643-6651]。
Further, in the preparation process in accordance with the present invention, step 1. described in casting solution high molecular polymer with quality
Score is calculated as 2~10%；The high molecular polymer is polysulfones (PSF) and/or polyimides (P84), preferably polyimides.
Further, in the preparation process in accordance with the present invention, step 1. described in will be used in high molecular polymer wiring solution-forming
Solvent is N,N-dimethylformamide (DMF) or chloroform.
Further, in the preparation process in accordance with the present invention, step 2. described in carrier be inorganic porous carrier, pore size
For 70nm~1 μm；As a further preference, the carrier is selected from α-Al2O3Carrier, γ-Al2O3Carrier, TiO2Carrier or not
Become rusty one of steel carrier, and the pattern of carrier can select chip carrier or tubular carrier as needed.
Further, in the preparation process in accordance with the present invention, step 2. described in the temperature that uses of dip-coating method for 25~
50 DEG C, pull rate is 20~60mm/min, and the residence time is 10~30s, and lifting number is 1~3 time.
Further, in the preparation process in accordance with the present invention, step 2. described in the condition of drying be dry at 25~120 DEG C
6~64h.This process keeps film solidification forming complete, and will wherein remaining solvent and additive remove completely.The wherein drying
It is preferred that using constant pressure and dry or vacuum drying.
Further, in made as described above method, the present invention provides a kind of most preferred technical solution, the gold
Belong to organic backbone hybridized film to prepare using following methods:
1. polyimides is dissolved in n,N-Dimethylformamide, metal organic framework particle UiO-66, ultrasound point is added
It dissipates, forms casting solution, UiO-66 is 0.5~2.5% based on mass fraction in the casting solution, and polyimides is based on mass fraction
It is 2~10%, the partial size of the UiO-66 is 120~180nm；
2. 1. casting solution that step is prepared is using dip-coating method in porous α-Al2O3Carrier surface film forming, drying, institute
State α-Al2O3The aperture of carrier is 70~300nm.
Second aspect, the present invention provides the metal organic framework hybridized films prepared by made as described above method.
The third aspect, the present invention provide the metal organic framework hybridized film in separation CO2In application, be particularly suitable for
CO is separated from flue gas and natural gas2。
Following specific embodiments are to further illustrate the contents of the present invention, are not construed as any type of to the present invention
Limitation.
Embodiment 1
In this embodiment, it is prepared for UiO-66 crystal.
UiO-66 is prepared for by Schaate etc. [Chem.Eur.J.17 (2011) 6643-6651] formula reported in the literature
Crystal:
Synthesis liquid is prepared as follows: 0.080g zirconium chloride being dissolved in 20mL DMF, 0.057g is added after dissolution
Terephthalic acid (TPA), ultrasonic 1min then continuously add 0.610g acetic acid, and ultrasonic 30s is mixed.Synthesis liquid is placed in reaction kettle,
120 DEG C of baking oven reactions are for 24 hours.Product is centrifugated and is cleaned with DMF.
It synthesizes obtained metal-organic framework materials and UiO-66 crystal is turned out to be by X-ray diffraction, as shown in Figure 1.From
It can be seen that the partial size of UiO-66 crystal is about 150nm in electron scanning micrograph Fig. 2.
Embodiment 2
In this embodiment, the method is prepared for UiO-66-P84 hybridized film through the invention.
In the present embodiment, used carrier is α-Al2O3, surface layer aperture is 70nm, and sheet, diameter is 18 millimeters, with a thickness of
1 millimeter.Carrier uses deionized water, acetone washing using preceding respectively.
Preparing the specific experiment of metal organic framework hybridized film, steps are as follows: UiO-66 crystal prepared by Example 1
0.128g is dispersed in 7.000g DMF, and the P84/DMF solution 2.097g that P84 mass fraction is 20% is then added, adds
8.001g DMF, the mass fraction of UiO-66 is 0.74wt.% in prepared casting solution, and the concentration of P84 is 2.43wt.%.
Later, using Best-Effort request machine (WPTL0.01, Shenyang Kejing Auto-instrument Co., Ltd.) by carrier
Dip-coating in the casting solution 30s and with the speed of 60mm/min pull-out.The film is solidified for 24 hours at 25 DEG C, is solidified at 100 DEG C
Then 18h keeps other 18h in 100 DEG C under vacuum, obtains UiO-66-P84 hybridized film.
Metal organic framework hybridized film UiO-66-P84 obtained above confirms to contain in hybridized film by X-ray diffraction
UiO-66, as shown in Figure 3.It can be seen that the film being prepared is uniformly and fine and close from electron scanning micrograph Fig. 4.
Admixture of gas separation test: the UiO-66-P84 hybridized film that synthesis obtains is fitted into membrane module and carries out gas point
From performance test, test condition are as follows: room temperature test, unstripped gas CO2/CH4Gaseous mixture or CO2/N2(volume ratio 1:1 is mixed for gaseous mixture
Close, total flow 100mL/min), purge gass He, flow 50mL/min.
Measure gas separating property are as follows: CO2Permeation flux be 7.92 × 10-9mol/(m2SPa), CO2/CH4Separation
Coefficient is 70.4, CO2/N2Separation is 36.0.
Comparative example 1
In this comparative example, pure P84 organic film is prepared for by dip-coating method.
Taking 2.440g mass fraction is 20% P84/DMF solution, is scattered in the DMF of 16.012g, is stirred evenly
P84 mass fraction is 2.64% in the solution obtained afterwards.Then by α-Al2O3Piece dip-coating 30s in the solution, and with 60mm/
The speed of min pulls out.Later, which is solidified for 24 hours at 25 DEG C, solidifies 18h at 100 DEG C, then under vacuum in 100 DEG C
Keep other 18h.
Admixture of gas separates test condition with embodiment 2, acquired results are as follows: CO2Permeation flux be 3.22 × 10- 8mol/(m2SPa), CO2/CH4Separation is 4.23, CO2/N2Separation is 5.70.As the result is shown for CO2/CH4
Or CO2/N2The separation of mixture, the purer P84 film properties of UiO-66-P84 hybridized film are more excellent.
Claims (6)
1. the preparation method of metal organic framework hybridized film, comprising the following steps:
1. polyimides is dissolved in n,N-Dimethylformamide, metal organic framework particle UiO-66, ultrasonic disperse, shape is added
At casting solution, UiO-66 is 0.5~2.5% based on mass fraction in the casting solution, polyimides is 2 based on mass fraction~
The partial size of 10%, the UiO-66 are 120~180nm；
2. 1. casting solution that step is prepared is using dip-coating method in porous α-Al2O3Carrier surface film forming, drying, the α-
Al2O3The aperture of carrier is 70~300nm.
2. preparation method according to claim 1, which is characterized in that step 2. described in dip-coating method use temperature
It is 25~50 DEG C, pull rate is 20~60mm/min, and the residence time is 10~30s, and lifting number is 1~3 time.
3. preparation method according to claim 1, which is characterized in that step 2. described in drying condition be 25~120
Dry 6~64h at DEG C.
4. the metal organic framework hybridized film of the preparation of method described in claims 1 to 3 any one.
5. metal organic framework hybridized film as claimed in claim 4 is in separation CO2In application.
6. application according to claim 5, which is characterized in that the metal organic framework hybridized film be used for from flue gas and
CO is separated in natural gas2。
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