CN106823863A - Metal organic framework hybridized film, its preparation method and application - Google Patents
Metal organic framework hybridized film, its preparation method and application Download PDFInfo
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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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Abstract
Metal organic framework hybridized film, its 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, casting solution is made into jointly with high molecular polymer, then using dip-coating method in carrier surface film forming, 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, with low cost, environment-friendly, with actual industrial applications meaning.
Description
Technical field
The invention belongs to membrane technology separation field, and in particular to a kind of preparation side of metal organic framework hybridized film
Method and its separating CO from flue gas and natural gas2The application in field.
Background technology
The CO discharged from fossil energy industry2It is considered as one of principal element of Global Greenhouse Effect, effectively
Realize CO2Separation and removal will have very important effect to Sustainable Socioeconomic Development.At present
CO2Separation method mainly have solvent absorption, pressure swing adsorption method, low temperature processing and membrane separation process.Four kinds
Method is each advantageous, but from the point of view of development prospect, the film of reduced investment, cost low advantage few with taking up an area
Partition method has more prospects for commercial application.
Film is the core component of membrane separating process, and following three class can be divided into by its material composition：I.e. organic film,
Inoranic membrane and hybrid organic-inorganic film.Organic film because its membrane material low cost, be easy to shaping the advantages of apply
Extensively, however organic film existed in terms of heat endurance, mechanical stability and chemical stability it is unconquerable
Defect.Inoranic membrane heat endurance is good, can operate at high temperature for a long time, but it prepares poor repeatability, cost
It is high.Hybrid organic-inorganic film introduces inorganic particle in organic network, using the high mechanical properties of inorganic particle
Improve organic network structure to strengthen the solvent resistant and resistance to elevated temperatures of film, and the flexibility of organic network is also gram
The hard crisp rapid wear shortcoming of inoranic membrane is taken.Additionally, the high selectivity duct of the inorganic particle of doping further carries
The separating property of hybridized film high.Thus having had organic film and the hybridized film of inoranic membrane advantage concurrently has turned into current
The study hotspot in film field.
Typical inorganic filler is zeolite molecular sieve, carbon molecular sieve, silicon and silica nano particle, metal
Oxide etc..In recent years, a kind of new porous material is metal-organic framework materials (metal-organic
Frameworks, hereinafter referred to as MOFs) because its specific surface area is big, pore passage structure, size and surface nature are adjustable
Etc. many excellent properties just " new lover " as UF membrane field.MOFs be by metal ion or ion cluster with
Oxygen-containing or nitrogen organic ligand forms the crystalline material with periodicity infinite network structure.It is inorganic with traditional
Filler is compared, and containing abundant organic group in MOFs skeletons, has more preferable compatibility with organic film material,
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 somebody with somebody by zirconium ion and terephthalic acid (TPA) or 2- amino terephthalic acid (TPA)s
The three-dimensional framework material that position obtains, it has high-specific surface area, good heat endurance and chemical stability.
The content of the invention：
For solution, organic membrane stability is poor in the prior art, inorganic film preparation poor repeatability, the defect of high cost,
The present invention provides prepared by a kind of inorganic filler traditional with metal organic framework particle (MOFs) replacement
Hybridized film, can be used in flue gas and natural gas separate CO2。
Technical purpose of the invention is achieved through the following technical solutions：
In a first aspect, the invention provides the preparation method of metal organic framework hybridized film, comprising the following steps：
1. by high molecular polymer wiring solution-forming, metal organic framework particle, ultrasonic disperse is added to form casting
Film liquid；
2. the casting solution for 1. step being prepared is using dip-coating method in carrier surface film forming, drying；
Wherein, the metal organic framework particle is UiO-66 and/or UiO-66-NH2。
Second aspect, the present invention provides the metal organic framework hybridized film prepared by the above method.
The third aspect, the present invention provides the above metal organic framework hybridized film and is separating CO2In application.
The metal organic framework hybridized film synthesized using preparation method of the invention is from flue gas and natural gas
Middle separation CO2There is good application prospect in field, and the manufacturing process of hybridized film is simple, with low cost, environment
Close friend, with actual industrial applications meaning.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of the metal organic framework UiO-66 crystal synthesized by embodiment 1；
Fig. 2 is the scanning electron microscope diagram of the metal organic framework UiO-66 crystal synthesized by embodiment 1；
Fig. 3 is the X-ray diffractogram of the metal organic framework hybridized film prepared by embodiment 2；
Fig. 4 is the scanning electron microscope diagram of the metal organic framework hybridized film prepared by embodiment 2.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein
Specific embodiment be merely to illustrate and explain the present invention, be not intended to limit the invention.
Present invention firstly provides a kind of preparation method of metal organic framework hybridized film, comprise the following steps：
1. by high molecular polymer wiring solution-forming, metal organic framework particle, ultrasonic disperse is added to form casting
Film liquid；
2. the casting solution for 1. step being prepared is using dip-coating method in carrier surface film forming, 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 metal organic framework in casting solution
Particle is calculated as 0.5~10%, preferably 0.5~2.5%, the grain of the metal organic framework particle with mass fraction
Footpath is 50~200nm.
In method made above, metal organic framework the particle UiO-66 and/or UiO-66-NH2's
Preparation method is known to the skilled person, and can be prepared using conventional method, as it is further preferably,
Can be prepared using solvent-thermal method.Used as one of preferred implementation method, the preparation of UiO-66 refers to text
Offer：Schaate etc. [Chem.Eur.J.17 (2011) 6643-6651].
Further, in the preparation process in accordance with the present invention, step 1. described in high molecular polymer in casting solution
2~10% are calculated as with mass fraction；The high molecular polymer be polysulfones (PSF) and/or polyimides (P84),
Preferably polyimides.
Further, in the preparation process in accordance with the present invention, step 1. described in high molecular polymer is made into it is molten
Liquid solvent for use 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 is 70nm~1 μm；As further preferably, the carrier is selected from α-Al2O3Carrier,
γ-Al2O3Carrier, TiO2One kind in carrier or stainless steel carrier, the pattern of carrier can be selected as needed
Chip carrier or tubular carrier.
Further, in the preparation process in accordance with the present invention, step 2. described in dip-coating method use temperature
It it is 25~50 DEG C, pull rate is 20~60mm/min, the residence time is 10~30s, and lifting number of times is 1~3
It is secondary.
Further, in the preparation process in accordance with the present invention, step 2. described in dry condition be 25~120 DEG C
6~64h of lower drying.This process makes film solidification forming completely, and the solvent that will wherein remain and additive removal
Totally.Wherein described drying preferably uses constant pressure and dry or vacuum drying.
Further, in made as described above method, the invention provides a kind of most preferred technical scheme,
The metal organic framework hybridized film is prepared using following methods：
1. polyimides is dissolved in DMF, adds metal organic framework particle UiO-66,
Ultrasonic disperse, forms casting solution, and UiO-66 is calculated as 0.5~2.5% with mass fraction in the casting solution, gathers
Acid imide is calculated as 2~10% with mass fraction, and the particle diameter of the UiO-66 is 120~180nm；
2. the casting solution for 1. step being prepared is using dip-coating method in porous α-Al2O3Carrier surface film forming,
Drying, the α-Al2O3The aperture of carrier is 70~300nm.
Second aspect, the invention provides the metal organic framework hybridized film prepared by made as described above method.
The third aspect, the present invention provides the metal organic framework hybridized film and is separating CO2In application, especially
It from flue gas and natural gas suitable for separating CO2。
Following specific embodiments are not construed as any to the present invention to further illustrate present disclosure
The limitation of form.
Embodiment 1
In this embodiment, it is prepared for UiO-66 crystal.
It is prepared for by the formula of Schaate etc. [Chem.Eur.J.17 (2011) 6643-6651] document report
UiO-66 crystal：
Synthesis liquid is prepared as follows：0.080g zirconium chlorides are dissolved in 20mL DMF, are added after dissolving
0.057g terephthalic acid (TPA)s, ultrasonic 1min then continuously adds 0.610g acetic acid, and ultrasonic 30s is mixed.To close
It is placed in reactor into liquid, 120 DEG C of baking ovens react 24h.Cleaned by product centrifugation and with DMF.
The metal-organic framework materials that synthesis is obtained turn out to be UiO-66 crystal by X-ray diffraction, such as Fig. 1 institutes
Show.It can be seen that the particle diameter of UiO-66 crystal is about 150nm from electron scanning micrograph Fig. 2.
Embodiment 2
In this embodiment, UiO-66-P84 hybridized films are prepared for by the method for the invention.
In the present embodiment, used carrier is α-Al2O3, top layer aperture is 70nm, sheet, a diameter of 18 milli
Rice, thickness is 1 millimeter.Carrier is washed with deionized water, acetone respectively using preceding.
The specific experiment step for preparing metal organic framework hybridized film is as follows：UiO-66 prepared by Example 1 is brilliant
Body 0.128g is dispersed in 7.000g DMF, then adds the P84/DMF solution that P84 mass fractions are 20%
2.097g, adds 8.001g DMF, and the mass fraction of UiO-66 is 0.74wt.% in prepared casting solution,
The concentration of P84 is 2.43wt.%.Afterwards, Best-Effort request machine (WPTL0.01, Shenyang Kejing is used
Auto-instrument Co., Ltd.) carrier dip-coating 30s and is drawn with the speed of 60mm/min in the casting solution
Go out.The film is solidified into 24h at 25 DEG C, 18h is solidified at 100 DEG C, then under vacuo in 100 DEG C of holdings
Other 18h, obtains UiO-66-P84 hybridized films.
Metal organic framework hybridized film UiO-66-P84 obtained above is confirmed in hybridized film by X-ray diffraction
Containing UiO-66, as shown in Figure 3.It can be seen that the film for preparing from electron scanning micrograph Fig. 4
It is uniform and fine and close.
Admixture of gas separates test：The UiO-66-P84 hybridized films that obtain will be synthesized be fitted into membrane module is carried out
Gas separating property is tested, and test condition is：Room temperature is tested, and unstripped gas is CO2/CH4Gaseous mixture or CO2/N2
Gaseous mixture (volume ratio 1:1 mixing, total flow is 100mL/min), purge gass are He, and flow is 50mL/min.
Measuring gas separating property is：CO2Permeation flux be 7.92 × 10-9mol/(m2SPa), CO2/CH4
Separation is 70.4, CO2/N2Separation is 36.0.
Comparative example 1
Herein in comparative example, pure P84 organic films are prepared for by dip-coating method.
The P84/DMF solution that 2.440g mass fractions are 20% is taken, is scattered in the DMF of 16.012g,
P84 mass fractions are 2.64% in the solution obtained after stirring.Then by α-Al2O3Piece dip-coating is in the solution
Middle 30s, and pulled out with the speed of 60mm/min.Afterwards, the film is solidified into 24h at 25 DEG C, at 100 DEG C
Lower solidification 18h, then keeps other 18h in 100 DEG C under vacuo.
Admixture of gas separates test condition with embodiment 2, and acquired results are：CO2Permeation flux be
3.22×10-8mol/(m2SPa), CO2/CH4Separation is 4.23, CO2/N2Separation is 5.70.As a result
Display is for CO2/CH4Or CO2/N2The separation of mixture, the purer P84 film properties of UiO-66-P84 hybridized films
It is more excellent.
Claims (14)
1. the preparation method of metal organic framework hybridized film, comprises the following steps：
1. by high molecular polymer wiring solution-forming, metal organic framework particle, ultrasonic disperse is added to form casting
Film liquid；
2. the casting solution for 1. step being prepared is using dip-coating method in carrier surface film forming, drying；
Wherein, the metal organic framework particle is UiO-66 and/or UiO-66-NH2。
2. preparation method according to claim 1, it is characterised in that step 1. described in casting solution
Middle metal organic framework particle is calculated as 0.5~10% with mass fraction.
3. preparation method according to claim 1, it is characterised in that step 1. described in metal have
The particle diameter of machine skeleton particle is 50~200nm.
4. preparation method according to claim 1, it is characterised in that step 1. described in casting solution
Middle high molecular polymer is calculated as 2~10% with mass fraction.
5. preparation method according to claim 1, it is characterised in that the high molecular polymer is
Polysulfones and/or polyimides.
6. preparation method according to claim 1, it is characterised in that step 1. described in by high score
Sub- polymer wiring solution-forming solvent for use is N,N-dimethylformamide or chloroform.
7. preparation method according to claim 1, it is characterised in that step 2. described in carrier be
Inorganic porous carrier, pore size is 70nm~1 μm.
8. preparation method according to claim 7, it is characterised in that the carrier is selected from α-Al2O3
Carrier, γ-Al2O3Carrier, TiO2One kind in carrier or stainless steel carrier.
9. preparation method according to claim 1, it is characterised in that step 2. described in impregnate and carry
The temperature that daraf(reciprocal of farad) is used is 25~50 DEG C, and pull rate is 20~60mm/min, and the residence time is 10~30s,
Lifting number of times is 1~3 time.
10. preparation method according to claim 1, it is characterised in that step 2. described in dry
Condition is dry 6~64h at 25~120 DEG C.
11. preparation methods according to claim 1, it is characterised in that the metal organic framework is miscellaneous
Change film to be prepared using following methods：
1. polyimides is dissolved in DMF, adds metal organic framework particle UiO-66,
Ultrasonic disperse, forms casting solution, and UiO-66 is calculated as 0.5~2.5% with mass fraction in the casting solution, gathers
Acid imide is calculated as 2~10% with mass fraction, and the particle diameter of the UiO-66 is 120~180nm；
2. the casting solution for 1. step being prepared is using dip-coating method in porous α-Al2O3Carrier surface film forming,
Drying, the α-Al2O3The aperture of carrier is 70~300nm.
Metal organic framework hybridized film prepared by the method described in 12. claim 1~11 any one.
Metal organic framework hybridized film described in 13. claims 12 is separating CO2In application.
14. applications according to claim 13, it is characterised in that the metal organic framework hydridization
Film is used to separate CO from flue gas and natural gas2。
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| CN107837690A (en) * | 2017-12-14 | 2018-03-27 | 济南大学 | Flat mixed-matrix forward osmosis membrane and preparation method based on metal organic framework ZIF 8 |
| CN107983172A (en) * | 2017-12-13 | 2018-05-04 | 济南大学 | Flat mixed-matrix forward osmosis membrane and preparation method based on metal organic framework MIL-100 (Fe) |
| CN107983159A (en) * | 2017-12-29 | 2018-05-04 | 济南大学 | Acetyl cellulose blend doughnut forward osmosis membrane based on metal organic framework MIL-100 (Fe) |
| CN107998902A (en) * | 2017-12-13 | 2018-05-08 | 济南大学 | Flat mixed-matrix forward osmosis membrane and preparation method based on metal organic framework MIL-53 |
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