CN103877871A - Composite separating membrane and preparation method and application thereof - Google Patents
Composite separating membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN103877871A CN103877871A CN201410126482.5A CN201410126482A CN103877871A CN 103877871 A CN103877871 A CN 103877871A CN 201410126482 A CN201410126482 A CN 201410126482A CN 103877871 A CN103877871 A CN 103877871A
- Authority
- CN
- China
- Prior art keywords
- composite
- membrane
- counterdie
- separating film
- composite separating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention provides a composite separating membrane and a preparation method and application thereof. The composite separating membrane comprises a bottom membrane, and is characterized in that the bottom membrane is attached to a transition layer; the transition layer consists of metal organic frame materials. The invention also discloses a method for preparing the composite membrane. The method comprises the following steps: sequentially and ultrasonically dispersing the metal organic frame materials to form suspension; and coating the suspension made of the metal organic frame materials and a solution of separating layer materials on the bottom membrane to sequentially form the transition layer and a separating layer. The separating membrane is simple in preparation method and is easy to control and can be used for the preparation process of various composite membranes in the separating membrane industry. Compared with a conventional high polymer material transition layer, the composite separating membrane has high physical and chemical stability and mechanical performance and has wide application prospects.
Description
Technical field
The present invention relates to membrane technology, relate in particular to a kind of composite separating film, its preparation method and application.
Background technology
It is the problem that chemical field often need to be faced that raw material or product are carried out to purification isolation, membrane separation technique because having the advantage such as efficiency is high, easy amplification be used widely gradually, bringing into play more and more important effect in fields such as resource, the energy, environment, health and conventional art transformations.Membrane material and membrane preparation technology are two principal elements that determine membrane separating property, and the film of unsymmetric structure could meet industrial needs, therefore film will be made under many circumstances to the composite membrane with ultra-thin cortex.
On the other hand, make composite membrane required counterdie and be often prepared from by phase inversion, the film surface obtaining often exists that roughness is higher, the unequal problem of pore-size distribution, and some even exists some larger defective hole.The film of high selectivity and high osmosis will be difficult to obtain having concurrently if make composite membrane with this counterdie.For this present situation, frequent by counterdie being modified to improve surperficial pore structure in industry, conventional method be dimethyl silicone polymer (PDMS) that differential permeability can be excellent or the contour permeable material of poly-trimethyl silicane propine (PTMSP) as transition zone, then apply separating layer material thereon and prepare sandwich diaphragm.After the modification of PDMS, the situation on film surface be improved significantly, be easy to form densification as thin as a wafer on its surface and separating layer uniformly, thus all good composite membranes of the permeability of obtaining and separation property.But in practical application, the physics and chemistry stability deficiency of macromolecular material transition zone can cause film properties to decline seriously, has a strong impact on the service life of film.
The inorganic-organic hybridization nano porous material that nearly 10 years classes are called as metal organic frame (metal organic framework, MOF) has been subject to extensive concern, becomes the study hotspot of field of new.It refers to by the nitrogen of aromatic acid or alkali, the multiple tooth organic ligand of oxygen and inorganic metal center is combined by coordinate bond the dimensional network structure crystal forming, from various open reports, this material is how synthetic by hydro-thermal or solvent thermal process, the existing commercialized supply (HKUST-1, MIL-53, ZIF-8 etc. can be provided as Sigma-Aldrich company) of metal organic frame material of Partial Species, [structure-activity relationship of metal-organic framework materials and design are conveniently easy to get, Zhong Chongli etc., Science Press].If IRMOF is under the condition of heating, Zn (NO
3) 4H
2o and terephthalic acid (TPA) be synthetic [the Eddaoudi M obtaining in diethyl ammonium formate, Kim J, Rosi N, Vodak D, Wachter J, O ' Keeffe M, Yaghi O M.Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage.Science, 2002,295:469-472]; Williams etc. have synthesized HKUST-1, claim again Cu-BTC, it is in the mixed solution of glycol/water, to heat with 1,3,5-Benzenetricarboxylic acid and copper nitrate [the Chui S S Y obtaining, Lo S M F, Charmant J P H, Orpen A G, Williams I D.A chemically functionalizable nanoporous material[Cu
3(TMA)
2(H
2o)
3]
n.Science, 1999,283:1148-1150]; Versailles, France university has synthesized MIL material [the Ferey G of various structures by water under high pressure thermal response; Mellot-Draznieks C; Serre C; Millange F; Dutour J, Surble S, Margiolaki I.A chromium terephthalate-based solid with unusually large pore volumes and surface area.Science; 2005,309:2040-2042]; CPL series MOF material is synthetic by the Kitagawa seminar of Kyoto Univ Japan, and it is to synthesize [Angew chem Int Ed, 1999,38:140-143] by hexa-coordinate metallic element and neutral nitrogen-containing hetero lopps part coordination; Yaghi seminar has developed again the MOF material of ZIF series, and it utilizes the Zn of divalence or Co to react and form with imidazole ligands, comprises multiple different structure [Nature, 2008, the 453:207-211 such as ZIF-5, ZIF-9, ZIF-8, ZIF-11; Science, 2008,319:939-943]; PCN series material is succeeded in developing [J Am Chem Soc, 2006,128:11734-11735 by the agro-industrial university of Texas, USA; J Am Chem Soc, 2007,129:1858-1859; J Am Chem Soc, 2008,130:1012-1016; ] Uio series material is the material of a class based on metal zirconium, with Uio-66 typical case the most, it is to be connected and to form ［ Chem Mater, 2011,23:1700-1718 ］ with 12 terephthalic acids organic ligands by the regular octahedron containing zirconium.
Summary of the invention
The object of the invention is to, for the problem in above-mentioned existing composite membrane preparation, a kind of composite separating film and preparation method thereof is proposed, counterdie surface in this composite separating film forms transition zone after metal organic frame (MOF) material is modified, more easily make composite membrane at film surface coating separating layer solution, the composite membrane that described method is made has the separating layer of thinner more homogeneous, shows higher permeability.
For achieving the above object, the technical solution used in the present invention is: a kind of composite separating film, comprise counterdie, and described counterdie adheres to transition zone, and described transition zone is made up of metal organic frame material (MOF).
Metal organic frame material of the present invention (MOF) be selected from but be not limited to IRMOF, HKUST-1, MIL series material, CPL series material, ZIF series material, PCN series material, UiO series material, mixed ligand MOF material and or hybrid metal MOF material in one or more.
IRMOF series material of the present invention comprises: IRMOF-1, IRMOF-2, IRMOF-3, IRMOF-4, IRMOF-6, IRMOF-7, IRMOF-8, IRMOF-9, IRMOF-10, IRMOF-11, IRMOF-12, IRMOF-13, IRMOF-14, IRMOF-15, IRMOF-16 etc.
MIL series material of the present invention comprises: MIL-47, MIL-53, MIL-68, MIL-100, MIL-101, MIL-177 etc.
CPL series material of the present invention comprises: CPL-1, CPL-2, CPL-5 etc.
ZIF series material of the present invention comprises ZIF-5, ZIF-9, ZIF-8, ZIF-11, ZIF-68, ZIF-69, ZIF-70, ZIF-80, ZIF-81, ZIF-82, ZIF-90 etc.
PCN series material of the present invention comprises: PCN-6, PCN-11, PCN-10, PCN-14 etc.
UiO series material of the present invention comprises: Uio-66 etc.
Further, the particle diameter of the particle of described metal organic frame material material distributes between 1～5000nm, is preferably 1～500nm, more preferably 10～100nm.
Further, described counterdie is flat plate ultrafiltration membrane, dull and stereotyped microfiltration membranes, hollow fiber ultrafiltration membrane or hollow fiber microfiltration membrane.
Further, the material of described counterdie is one or more in polysulfones (PSf), polyether sulfone (PES), polyacrylonitrile (PAN), PEI (PEI), Kynoar (PVDF), polyimides (PI) and Merlon (PC), ceramic membrane or glass-film.
Further, the aperture on described counterdie surface is 10-2000nm, is preferably 10-100nm, more preferably 10-30nm.
Described transition zone is also with separating layer, and the optional scope of material of separating layer is wider, comprises cellulose and derivative thereof, polysulfones, various polyamide and polyimides and silicon-containing polymer material, polyethers copolyamide etc.
The preparation method who the invention also discloses a kind of composite separating film, comprises the following steps: on counterdie, after plating organic framework materials suspension, be at room temperature dried 20～240min; After heating 5～240min again at 40～120 ℃, take out; The counterdie that adheres to MOF transition zone is immersed in to 5s～30min in separating layer solution, at room temperature dry 2～120min; At 40～120 ℃, heat 5～240min and obtain composite membrane.
The solution that it is 0.5wt.%～10wt.% that separating layer solution of the present invention refers to the concentration obtaining after separating layer material dissolves is in compatible organic solvent, as organic solvents such as n-hexane, normal heptane, dimethyl formamide, oxolane, ethanol, water, n-butanols.
Further, the compound method of described metal organic frame material suspension is: metal organic frame material is divided and added in solvent for 1～10 time, and ultrasonic 10～120min, is mixed with the suspension that concentration is 0.1wt.%～5wt.%, be preferably more preferably 3～6 times 2～8 times; Described solvent is one or more the mixing in water, methyl alcohol, ethanol, acetone, n-hexane, isooctane, normal heptane, gasoline, benzinum.
Pre-treating method before described counterdie coating transition zone solution is, with the surface of washed with de-ionized water counterdie, to remove dust and the greasy dirt on counterdie surface, and dry.
Another object of the present invention is to provide above-mentioned composite separating film or its preparation method to separate and the application in infiltration evaporation field at nanofiltration, counter-infiltration, gas.
The invention discloses a kind of composite separating film and preparation method thereof, have the following advantages compared with prior art:
(1) in conventional method PDMS or PTMSP etc. as problems such as the resistance to solvent ability of existing of transition zone, and composite separating film of the present invention forms transition zone by counterdie surface is modified with porous MOF material, can effectively make up the defect of porous counterdie, overcome hole and oozed phenomenon, improve the resistance of composite membrane to solvent, and overcome.
(2) MOF material gas permeability is strong, and physics or chemical stability are higher compared with PDMS, is therefore desirable buffer layer material.
(3) preparation method of composite separating film of the present invention simple, be easy to control, can be used for the composite membrane preparation of various separation processes, as Nano filtering composite membrane, reverse osmosis composite membrane, just permeate composite membrane, gas separation membrane, the integrated gasification combined film of infiltration, be with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the structural representation of composite separating film of the present invention;
In figure, the transition zone that 1 counterdie, 2, MOF particle form, 3 separating layers.
The specific embodiment
Below in conjunction with embodiment, the present invention is further described:
The infiltration of composite separating film prepared by the embodiment of the present invention and separating property adopt pure CO
2and N
2infiltration rate J and CO
2/ N
2gas selectivity α
cO2/N2characterize.
CO
2and N
2infiltration rate J calculate and obtain by following formula:
In formula:
Under V-test condition, permeate the flux of gas, cm
3
T-testing time, s
A-effective film area, cm
2
Δ p-permeable membrane pressure reduction, cmHg
T
0, p
0temperature and pressure under-test condition, K, cmHg
CO
2with N
2gas selectivity α
cO2/N2be the infiltration rate J of two kinds of gases
cO2and J
n2ratio:
The raw material information relating in following embodiment:
Zeolite imidazate frame structure material ZIF-7 nano particle is pressed document (Tao Li, Yichang Pan, Klaus-Viktor Peinmann, Zhiping Lai, Carbon dioxide selective mixed matrix composite membrane containing ZIF-7nano-fillers, Journal of Membrane Science, 425-426 (2013): 235-242) method synthetic.Synthetic method is as follows: 0.453gZn (NO
3)
26H
2o and 1.154g benzimidazole add the DMF of 150mL after mixing, under room temperature, stir 23h.By centrifugal the product obtaining and by washed with methanol 3 times, ZIF-7 particle diameter is between 30～35nm.
Polyacrylonitrile counterdie: pure water flux is 100L/ (m
2h), molecular cut off is 150,000.
Polyethers copolyamide (PEBA): Arkema company, product type is
1657.
Dimethyl silicone polymer (PDMS): GE company, RTV-615.
Reference examples 1
The disclosed a kind of composite separating film of this reference examples adopts following steps to be prepared from:
(1) PEBA is dissolved in to the PEBA solution that is configured to 2wt.% in ethanol/water (mass ratio=7:3 of second alcohol and water) mixed solvent, places 2h deaeration;
(2) clean polyacrylonitrile counterdie surface, and dry;
(3) film immersion of step (2) is kept, after 1min, film being taken out from solution in the solution of step (1), 20min at room temperature dries in the shade;
(4) film of step (3) gained is put into convection oven further dry under the condition of heating, baking temperature is 80 ℃, takes out after heating 30min in baking oven.
With said method test compound film to pure CO
2and N
2permeance property and separating property, test result is: J
n2=6.9GPU, J
cO2=126GPU, α=18.2.This composite membrane surface defectiveness, poor selectivity.
Reference examples 2
The disclosed a kind of composite separating film of this reference examples adopts following steps to be prepared from:
(1) PEBA is dissolved in to the solution that is configured to 4wt.% in ethanol/water (ethanol: water=7:3, mass ratio) mixed solvent, places 2h deaeration;
(2) clean polyacrylonitrile counterdie surface, and dry;
(3) film immersion of step (2) is kept, after 1min, film being taken out from solution in the solution of step (1), 20min at room temperature dries in the shade;
(4) film of step (3) gained is put into convection oven further dry under the condition of heating, baking temperature is 80 ℃, takes out after heating 30min in baking oven.
Test compound film is to pure CO
2and N
2permeance property and separating property, test result is: J
n2=0.6GPU, J
cO2=37.3GPU, α=62.2.This composite membrane has high selectivity, hypotonicity.
Reference examples 3
The disclosed a kind of composite separating film of this reference examples adopts following steps to be prepared from:
(1) clean polyacrylonitrile counterdie surface, and dry;
(2) by PDMS(RTV615, GE company produces, and A, B constituent mass ratio are 10) be dissolved in normal heptane, be mixed with transition zone solution, solution concentration is 5wt.%; PEBA is dissolved in ethanol/water (ethanol: water=7:3) mixed solvent by a certain percentage, is mixed with separating layer solution, solution concentration is 2wt.%; Above-mentioned two kinds of solution are equal standing and defoaming 2h before using;
(3) counterdie of step (1) be impregnated in the transition zone solution of step (2), take out, 60min at room temperature dries in the shade;
(4) film immersion of step (3) is kept, after 10min, film being taken out from solution in the PEBA of 2wt.% solution, 20min at room temperature dries in the shade;
(5) film of step (4) gained is put into convection oven further dry under the condition of heating, baking temperature is 80 ℃, takes out after heating 30min in baking oven.
Test compound film is to pure CO
2and N
2permeance property and separating property, test result is: J
n2=2.1GPU, J
cO2=110GPU, α=52.4.The film soak at room temperature of testing is retested after 48h in n-hexane, and test result is: J
n2=5.2GPU, J
cO2=118GPU, α=22.7.
Embodiment 1
The present embodiment discloses a kind of composite separating film and preparation method thereof, as shown in Figure 1, comprises the transition zone 2 that counterdie 1, MOF particle form, separating layer 3.The present embodiment composite membrane adopts following steps to be prepared from:
(1) clean polyacrylonitrile counterdie surface, and dry;
(2) ZIF-7 is divided and add in pure water for 5 times, ultrasonic 60min, is mixed with the suspension that concentration is 1wt.% simultaneously, for subsequent use.
(3) suspension of the ZIF-7 of coating step (2) on the counterdie of step (1), at room temperature dries in the shade after 60min, after 80 ℃ of further dry 2h, takes out;
(4) film immersion of step (3) is kept, after 1min, film being taken out from solution in the PEBA of 2wt.% solution, 20min at room temperature dries in the shade;
(5) film of step (4) gained is put into convection oven further dry under the condition of heating, baking temperature is 80 ℃, takes out after heating 30min in baking oven, obtains the composite membrane take ZIF-7 as transition zone.
Test compound film is to pure CO
2and N
2permeance property and separating property, test result is: J
n2=1.9GPU, J
cO2=112GPU, α=58.9.The composite membrane that the present embodiment prepares has higher selective and permeability simultaneously.
The present embodiment discloses a kind of composite separating film and preparation method thereof, and the present embodiment composite separating film adopts following steps to be prepared from:
(1) clean polyacrylonitrile counterdie surface, and dry;
(2) ZIF-7 is divided and add in pure water for 5 times, ultrasonic 60min, is mixed with the suspension that concentration is 1.5wt.% simultaneously, for subsequent use.
(3) suspension of the ZIF-7 of coating step (2) on the counterdie of step (1), at room temperature dries in the shade after 60min, after 80 ℃ of further dry 2h, takes out;
(4) film immersion of step (3) is kept, after 1min, film being taken out from solution in the PEBA of 2wt.% solution, 20min at room temperature dries in the shade;
(5) film of step (4) gained is put into convection oven further dry under the condition of heating, baking temperature is 80 ℃, takes out after heating 30min in baking oven, obtains the composite membrane take ZIF-7 as transition zone.
Test compound film is to pure CO
2and N
2permeance property and separating property, test result is: J
n2=1.9GPU, J
cO2=111GPU, α=58.4.The film soak at room temperature of testing is retested after 48h in n-hexane, and test result is: J
n2=2.0GPU, J
cO2=113GPU, α=56.5.
Interpretation of result:
In reference examples 1, when PEBA concentration lower (2wt%), due to hole, to blend solution concentration too low, can not on counterdie, form flawless separating layer, and therefore the composite membrane infiltration rate of preparation is higher, and separation is low.While further increasing PEBA concentration (4wt%) in reference examples 2, although can form comparatively complete separating layer, show as high separation, the separating layer forming is blocked up, and composite membrane infiltration rate is low.These two embodiment show that directly coating is difficult to obtain having the composite membrane of high selectivity and high osmosis simultaneously.
In reference examples 3, adopt PDMS conventional in gas separation membrane field as transition zone, ooze in the hole having reduced in PEBA solution coating procedure.After extending dip time, PEBA solution forms and does not almost have defective separating layer on PDMS cortex, but silastic-layer is damaged in the time being immersed in varsol, and then has affected the performance of composite membrane, shows as separation and greatly reduces.
In embodiment 1, adopt nanometer MOF particle modification counterdie, the granule of Nano grade gos deep into fenestra or is adsorbed in film surface, prevent that PEBA solution from penetrating into fenestra, therefore finally formed the thin and PEBA separating layer of homogeneous, the composite membrane obtaining shows high osmosis energy and separating property simultaneously.
In embodiment 2, improved the concentration of MOF particle, but because MOF itself is porous material, gas permeability is very high, therefore the penetration property of composite membrane entirety is not affected.N-hexane is to MOF particle without any destructiveness simultaneously, and the penetration property that therefore soaks caudacoria does not change substantially.
Above result and analyze known, composite separating film of the present invention, transition zone adopts nanometer MOF material, compared with not adding transition zone, composite membrane can have higher permeability and selective simultaneously; Compared with common transition layer material PDMS, MOF material during as transition zone composite membrane have the ability of stronger chemically-resistant solvent.
Finally it should be noted that: above each embodiment, only in order to technical scheme of the present invention to be described, is not intended to limit; Although the present invention is had been described in detail with reference to aforementioned each embodiment, those of ordinary skill in the art is to be understood that: its technical scheme that still can record aforementioned each embodiment is modified, or some or all of technical characterictic is wherein equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. a composite separating film, comprises counterdie, it is characterized in that, described counterdie adheres to transition zone, and described transition zone is made up of metal organic frame material.
2. composite separating film according to claim 1, it is characterized in that, described metal organic frame material be selected from HKUST-1, IRMOF series material, MIL series material, CPL series material, ZIF series material, PCN series material, UiO series material, mixed ligand MOF material and or hybrid metal MOF material in one or more.
3. according to composite separating film described in claim 1 or 2, it is characterized in that, the particle diameter of the particle of described metal organic frame material distributes between 1～5000nm.
4. composite separating film according to claim 1, is characterized in that, described counterdie is flat plate ultrafiltration membrane, dull and stereotyped microfiltration membranes, hollow fiber ultrafiltration membrane or hollow fiber microfiltration membrane.
5. according to composite separating film described in claim 1 or 2, it is characterized in that, the material of described counterdie is one or more in polysulfones, polyether sulfone, polyacrylonitrile, PEI, Kynoar, polyimides and Merlon, ceramic membrane or glass-film.
6. according to composite separating film described in claim 1 or 4, it is characterized in that, the aperture on described counterdie surface is 10～2000nm.
7. composite separating film according to claim 1, is characterized in that, described transition zone is also with separating layer.
8. a preparation method for composite separating film described in claim 1-7 any one, is characterized in that, comprises the following steps:
(1) on described counterdie, after plating organic framework materials suspension, be at room temperature dried 20～240min; After heating 5～240min again at 40～120 ℃, take out;
(2) the counterdie that adheres to MOF transition zone is immersed in to 5s～30min in separating layer solution, at room temperature dry 2～120min; At 40～120 ℃, heat 5～240min.
9. preparation method according to claim 8, it is characterized in that, the compound method of described metal organic frame material suspension is: metal organic frame material is divided and added in solvent for 1～10 time, and ultrasonic 10～120min, is mixed with the suspension that concentration is 0.1wt.%～5wt.%; Described solvent is one or more the mixing in water, methyl alcohol, ethanol, acetone, n-hexane, isooctane, normal heptane, gasoline, benzinum.
10. described in claim 1-7 any one, described in composite separating film or claim 8 or 9, method separates and the application in infiltration evaporation field in nanofiltration, counter-infiltration, gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410126482.5A CN103877871B (en) | 2014-03-31 | 2014-03-31 | A kind of composite separating film, its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410126482.5A CN103877871B (en) | 2014-03-31 | 2014-03-31 | A kind of composite separating film, its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103877871A true CN103877871A (en) | 2014-06-25 |
| CN103877871B CN103877871B (en) | 2016-01-06 |
Family
ID=50947193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410126482.5A Active CN103877871B (en) | 2014-03-31 | 2014-03-31 | A kind of composite separating film, its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103877871B (en) |
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104209021A (en) * | 2014-09-03 | 2014-12-17 | 北京林业大学 | Preparation method of aromatic polyamide film modified by ZIF-8 type metal-organic framework material |
| CN105032208A (en) * | 2015-06-24 | 2015-11-11 | 江南大学 | Novel blended gas separation membrane based on metal supramolecular polymer |
| CN105233713A (en) * | 2014-07-03 | 2016-01-13 | 中国科学院过程工程研究所 | Preparation method for penetrative and evaporative ethanol-permeable composite membrane |
| CN105372320A (en) * | 2015-10-29 | 2016-03-02 | 南京大学 | Method for preparing nano porous channel based on imidazate framework ZIF-90 which is of zeolite structure and synthesized at tip end of capillary tube and application thereof |
| CN105797595A (en) * | 2016-05-13 | 2016-07-27 | 高学理 | Preparation method and application of high-water-stability metal organic framework compound material |
| CN105879704A (en) * | 2016-03-26 | 2016-08-24 | 上海大学 | Preparation method and application of mixed matrix membrane containing zeolite imidazolate framework material |
| CN106178999A (en) * | 2016-07-08 | 2016-12-07 | 山东大学 | A kind of preparation method of LBL self-assembly metallic organic framework composite membrane |
| CN107020020A (en) * | 2017-05-22 | 2017-08-08 | 天津工业大学 | A kind of preparation method of new MOFs PVDF composite membranes |
| CN107051414A (en) * | 2015-12-28 | 2017-08-18 | 尤雷卡特股份公司 | Method for limiting porous granule emission gases |
| CN107158977A (en) * | 2017-05-24 | 2017-09-15 | 天津大学 | High-molecule metal organic framework materials hydridization faciliated diffusion composite membrane and its preparation and application |
| JP2017202449A (en) * | 2016-05-11 | 2017-11-16 | 国立大学法人岐阜大学 | Method for separating solvent mixed liquor, and metal organic structure separation membrane used therefor |
| CN107519772A (en) * | 2017-08-17 | 2017-12-29 | 河南科技大学 | A kind of Thief zone ultrafiltration composite ceramic coat film and preparation method thereof |
| CN107722289A (en) * | 2017-11-02 | 2018-02-23 | 中国科学技术大学 | A kind of seperation film and preparation method thereof of organic ligand for MOF and preparation method thereof, a kind of MOF containing organic ligand |
| CN107847877A (en) * | 2015-07-28 | 2018-03-27 | 北川工业株式会社 | The manufacture method of reverse osmosis membrane |
| CN108283889A (en) * | 2017-01-10 | 2018-07-17 | 中国科学院宁波材料技术与工程研究所 | A kind of composite membrane, preparation method and the application in gas separation, purifying |
| CN108310985A (en) * | 2018-03-15 | 2018-07-24 | 天津工业大学 | A kind of MOF-199 PVDF matrix blend films and preparation method with high resistance tocrocking |
| CN108939958A (en) * | 2017-05-27 | 2018-12-07 | 南京工业大学 | The method for improving support type MOF film gas separating property using polymer coating |
| CN109235044A (en) * | 2018-08-29 | 2019-01-18 | 华南理工大学 | A kind of polyvinylidene fluoride nanometer tunica fibrosa and its preparation method and application loading ZIF-8 |
| CN109248571A (en) * | 2018-10-19 | 2019-01-22 | 天津大学 | Method by the preparation of chemical bridging for the mixed substrate membrane containing nano-grade molecular sieve of carbon dioxide separation |
| CN109529634A (en) * | 2018-10-30 | 2019-03-29 | 南京理工大学 | The preparation method of metal organic framework ZIF-67-PVDF hollow-fibre membrane |
| CN109910392A (en) * | 2019-02-11 | 2019-06-21 | 东华大学 | Conducive to the jute fiber reinforced polypropylene composite material for separating and recycling and its preparation |
| CN110540938A (en) * | 2019-07-10 | 2019-12-06 | 浙江理工大学 | Ordered oriented co-immobilized enzyme membrane reactor and preparation method and application thereof |
| CN110801736A (en) * | 2019-11-07 | 2020-02-18 | 哈尔滨学院 | Preparation method of organic solvent-resistant and difficult-to-peel nanofiltration membrane |
| CN110917822A (en) * | 2019-12-06 | 2020-03-27 | 天津工业大学 | High-flux high-selectivity thin-layer composite membrane for hydrogen separation and preparation method thereof |
| CN111111464A (en) * | 2020-01-06 | 2020-05-08 | 南京荷风智能科技有限公司 | Structural design and preparation method of ultrahigh carbon dioxide gas selective separation composite membrane |
| CN111450717A (en) * | 2020-04-24 | 2020-07-28 | 北京工业大学 | High-performance polymer organic solvent nanofiltration membrane and preparation method thereof |
| CN111530300A (en) * | 2020-05-18 | 2020-08-14 | 北京工商大学 | Dual-functional composite membrane, preparation method and application thereof, and method for removing plasticizer in white spirit |
| CN111579656A (en) * | 2020-04-14 | 2020-08-25 | 北京工商大学 | Pretreatment device and method for extracting flavor components in wine or beverage products |
| CN111701459A (en) * | 2020-07-01 | 2020-09-25 | 浙江工业大学 | Nitrogen-heterocycle-containing polyaryletherketone/sulfone ultra/micro-filtration membrane and structure regulation method thereof |
| CN111888948A (en) * | 2020-06-29 | 2020-11-06 | 青海盐湖工业股份有限公司 | Separation membrane capable of extracting cesium ions in brine and preparation method thereof |
| CN114515517A (en) * | 2022-02-22 | 2022-05-20 | 华中科技大学 | Polymer composite membrane for in-situ growth of MOF (Metal organic framework) middle layer in low-temperature water phase, preparation and application |
| CN115087495A (en) * | 2020-02-06 | 2022-09-20 | 日东电工株式会社 | Separation membrane and metal-organic structure |
| CN115193271A (en) * | 2021-04-14 | 2022-10-18 | 西陇科学股份有限公司 | Pervaporation composite membrane with ultrathin separation active layer and preparation method thereof |
| CN116531968A (en) * | 2023-03-26 | 2023-08-04 | 山东科技大学 | Spraying-assisted construction double-interlayer forward osmosis composite membrane and preparation method thereof |
| CN117258552A (en) * | 2023-11-21 | 2023-12-22 | 中国农业大学 | Nanofiltration membrane with permeability and selectivity and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890305A (en) * | 2010-04-01 | 2010-11-24 | 大连理工大学 | Method for preparing metallic organic frame films |
| CN102580565A (en) * | 2012-01-19 | 2012-07-18 | 大连理工大学 | Preparation method for high-performance metal organic framework film |
| CN102617646A (en) * | 2012-02-29 | 2012-08-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method of nanoscale metal organic framework materials |
| CN102773025A (en) * | 2011-05-12 | 2012-11-14 | 珠海市吉林大学无机合成与制备化学重点实验室 | Method for preparing metal organic framework (MOF) membrane |
| CN103182251A (en) * | 2013-03-20 | 2013-07-03 | 北京工业大学 | Method for preparing organic/inorganic alcohol-permselective pervaporation composite membrane |
| WO2013122334A1 (en) * | 2012-02-15 | 2013-08-22 | 한국과학기술연구원 | Membrane for water treatment comprising metal-organic framework and method for manufacturing same |
| CN103464001A (en) * | 2013-08-05 | 2013-12-25 | 大连理工大学 | Preparation method of metal organic framework membrane for CO2 separation |
| CN103566772A (en) * | 2013-10-16 | 2014-02-12 | 浙江大学 | Preparation method and application of metal organic framework thin film on surface of macroporous high polymer hollow fiber pipe |
-
2014
- 2014-03-31 CN CN201410126482.5A patent/CN103877871B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890305A (en) * | 2010-04-01 | 2010-11-24 | 大连理工大学 | Method for preparing metallic organic frame films |
| CN102773025A (en) * | 2011-05-12 | 2012-11-14 | 珠海市吉林大学无机合成与制备化学重点实验室 | Method for preparing metal organic framework (MOF) membrane |
| CN102580565A (en) * | 2012-01-19 | 2012-07-18 | 大连理工大学 | Preparation method for high-performance metal organic framework film |
| WO2013122334A1 (en) * | 2012-02-15 | 2013-08-22 | 한국과학기술연구원 | Membrane for water treatment comprising metal-organic framework and method for manufacturing same |
| CN102617646A (en) * | 2012-02-29 | 2012-08-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method of nanoscale metal organic framework materials |
| CN103182251A (en) * | 2013-03-20 | 2013-07-03 | 北京工业大学 | Method for preparing organic/inorganic alcohol-permselective pervaporation composite membrane |
| CN103464001A (en) * | 2013-08-05 | 2013-12-25 | 大连理工大学 | Preparation method of metal organic framework membrane for CO2 separation |
| CN103566772A (en) * | 2013-10-16 | 2014-02-12 | 浙江大学 | Preparation method and application of metal organic framework thin film on surface of macroporous high polymer hollow fiber pipe |
Cited By (53)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105233713A (en) * | 2014-07-03 | 2016-01-13 | 中国科学院过程工程研究所 | Preparation method for penetrative and evaporative ethanol-permeable composite membrane |
| CN105233713B (en) * | 2014-07-03 | 2019-07-12 | 中国科学院过程工程研究所 | A kind of preparation method of the saturating alcohol composite membrane of infiltration evaporation |
| CN104209021A (en) * | 2014-09-03 | 2014-12-17 | 北京林业大学 | Preparation method of aromatic polyamide film modified by ZIF-8 type metal-organic framework material |
| CN105032208A (en) * | 2015-06-24 | 2015-11-11 | 江南大学 | Novel blended gas separation membrane based on metal supramolecular polymer |
| CN105032208B (en) * | 2015-06-24 | 2017-08-01 | 江南大学 | A kind of blending gas separation membrane based on metal supermolecular polymer |
| CN107847877A (en) * | 2015-07-28 | 2018-03-27 | 北川工业株式会社 | The manufacture method of reverse osmosis membrane |
| CN107847877B (en) * | 2015-07-28 | 2020-11-24 | 北川工业株式会社 | Method for producing reverse osmosis membrane |
| CN105372320A (en) * | 2015-10-29 | 2016-03-02 | 南京大学 | Method for preparing nano porous channel based on imidazate framework ZIF-90 which is of zeolite structure and synthesized at tip end of capillary tube and application thereof |
| CN105372320B (en) * | 2015-10-29 | 2019-05-31 | 南京大学 | Prepare the method and its application of nano pore |
| CN107051414B (en) * | 2015-12-28 | 2021-08-27 | 尤雷卡特股份公司 | Method for limiting gas emission from porous particles |
| CN107051414A (en) * | 2015-12-28 | 2017-08-18 | 尤雷卡特股份公司 | Method for limiting porous granule emission gases |
| CN105879704A (en) * | 2016-03-26 | 2016-08-24 | 上海大学 | Preparation method and application of mixed matrix membrane containing zeolite imidazolate framework material |
| JP2017202449A (en) * | 2016-05-11 | 2017-11-16 | 国立大学法人岐阜大学 | Method for separating solvent mixed liquor, and metal organic structure separation membrane used therefor |
| CN105797595A (en) * | 2016-05-13 | 2016-07-27 | 高学理 | Preparation method and application of high-water-stability metal organic framework compound material |
| CN106178999B (en) * | 2016-07-08 | 2018-09-07 | 山东大学 | A kind of preparation method of LBL self-assembly metal organic framework composite membrane |
| CN106178999A (en) * | 2016-07-08 | 2016-12-07 | 山东大学 | A kind of preparation method of LBL self-assembly metallic organic framework composite membrane |
| CN108283889A (en) * | 2017-01-10 | 2018-07-17 | 中国科学院宁波材料技术与工程研究所 | A kind of composite membrane, preparation method and the application in gas separation, purifying |
| CN108283889B (en) * | 2017-01-10 | 2021-08-17 | 中国科学院宁波材料技术与工程研究所 | Composite membrane, preparation method thereof and application thereof in gas separation and purification |
| CN107020020A (en) * | 2017-05-22 | 2017-08-08 | 天津工业大学 | A kind of preparation method of new MOFs PVDF composite membranes |
| CN107158977B (en) * | 2017-05-24 | 2019-11-08 | 天津大学 | Macromolecule-metal-organic framework material hydridization faciliated diffusion composite membrane and its preparation and application |
| CN107158977A (en) * | 2017-05-24 | 2017-09-15 | 天津大学 | High-molecule metal organic framework materials hydridization faciliated diffusion composite membrane and its preparation and application |
| CN108939958A (en) * | 2017-05-27 | 2018-12-07 | 南京工业大学 | The method for improving support type MOF film gas separating property using polymer coating |
| CN108939958B (en) * | 2017-05-27 | 2021-08-20 | 南京工业大学 | Method for improving gas separation performance of supported MOF (metal organic framework) membrane by utilizing polymer coating |
| CN107519772B (en) * | 2017-08-17 | 2019-08-13 | 河南科技大学 | A kind of Thief zone ultrafiltration composite ceramic coat film and preparation method thereof |
| CN107519772A (en) * | 2017-08-17 | 2017-12-29 | 河南科技大学 | A kind of Thief zone ultrafiltration composite ceramic coat film and preparation method thereof |
| CN107722289A (en) * | 2017-11-02 | 2018-02-23 | 中国科学技术大学 | A kind of seperation film and preparation method thereof of organic ligand for MOF and preparation method thereof, a kind of MOF containing organic ligand |
| CN107722289B (en) * | 2017-11-02 | 2020-08-28 | 中国科学技术大学 | Organic ligand for MOF (metal organic framework), preparation method of organic ligand, separation membrane containing organic ligand MOF and preparation method of separation membrane |
| CN108310985A (en) * | 2018-03-15 | 2018-07-24 | 天津工业大学 | A kind of MOF-199 PVDF matrix blend films and preparation method with high resistance tocrocking |
| CN109235044A (en) * | 2018-08-29 | 2019-01-18 | 华南理工大学 | A kind of polyvinylidene fluoride nanometer tunica fibrosa and its preparation method and application loading ZIF-8 |
| CN109235044B (en) * | 2018-08-29 | 2020-04-28 | 华南理工大学 | ZIF-8 loaded polyvinylidene fluoride nanofiber membrane and preparation method and application thereof |
| CN109248571A (en) * | 2018-10-19 | 2019-01-22 | 天津大学 | Method by the preparation of chemical bridging for the mixed substrate membrane containing nano-grade molecular sieve of carbon dioxide separation |
| CN109529634A (en) * | 2018-10-30 | 2019-03-29 | 南京理工大学 | The preparation method of metal organic framework ZIF-67-PVDF hollow-fibre membrane |
| CN109910392A (en) * | 2019-02-11 | 2019-06-21 | 东华大学 | Conducive to the jute fiber reinforced polypropylene composite material for separating and recycling and its preparation |
| CN109910392B (en) * | 2019-02-11 | 2021-01-19 | 东华大学 | Fibrilia reinforced polypropylene composite material beneficial to separation and recovery and preparation thereof |
| CN110540938A (en) * | 2019-07-10 | 2019-12-06 | 浙江理工大学 | Ordered oriented co-immobilized enzyme membrane reactor and preparation method and application thereof |
| CN110801736A (en) * | 2019-11-07 | 2020-02-18 | 哈尔滨学院 | Preparation method of organic solvent-resistant and difficult-to-peel nanofiltration membrane |
| CN110801736B (en) * | 2019-11-07 | 2020-09-29 | 哈尔滨学院 | Preparation method of organic solvent-resistant and difficult-to-peel nanofiltration membrane |
| CN110917822A (en) * | 2019-12-06 | 2020-03-27 | 天津工业大学 | High-flux high-selectivity thin-layer composite membrane for hydrogen separation and preparation method thereof |
| CN111111464B (en) * | 2020-01-06 | 2021-12-17 | 南京荷风智能科技有限公司 | Structural design and preparation method of ultrahigh carbon dioxide gas selective separation composite membrane |
| CN111111464A (en) * | 2020-01-06 | 2020-05-08 | 南京荷风智能科技有限公司 | Structural design and preparation method of ultrahigh carbon dioxide gas selective separation composite membrane |
| CN115087495A (en) * | 2020-02-06 | 2022-09-20 | 日东电工株式会社 | Separation membrane and metal-organic structure |
| CN111579656A (en) * | 2020-04-14 | 2020-08-25 | 北京工商大学 | Pretreatment device and method for extracting flavor components in wine or beverage products |
| CN111450717B (en) * | 2020-04-24 | 2022-03-22 | 北京工业大学 | High-performance polymer organic solvent nanofiltration membrane and preparation method thereof |
| CN111450717A (en) * | 2020-04-24 | 2020-07-28 | 北京工业大学 | High-performance polymer organic solvent nanofiltration membrane and preparation method thereof |
| CN111530300A (en) * | 2020-05-18 | 2020-08-14 | 北京工商大学 | Dual-functional composite membrane, preparation method and application thereof, and method for removing plasticizer in white spirit |
| CN111888948A (en) * | 2020-06-29 | 2020-11-06 | 青海盐湖工业股份有限公司 | Separation membrane capable of extracting cesium ions in brine and preparation method thereof |
| CN111888948B (en) * | 2020-06-29 | 2022-06-21 | 青海盐湖工业股份有限公司 | Separation membrane capable of extracting cesium ions in brine and preparation method thereof |
| CN111701459A (en) * | 2020-07-01 | 2020-09-25 | 浙江工业大学 | Nitrogen-heterocycle-containing polyaryletherketone/sulfone ultra/micro-filtration membrane and structure regulation method thereof |
| CN115193271A (en) * | 2021-04-14 | 2022-10-18 | 西陇科学股份有限公司 | Pervaporation composite membrane with ultrathin separation active layer and preparation method thereof |
| CN114515517A (en) * | 2022-02-22 | 2022-05-20 | 华中科技大学 | Polymer composite membrane for in-situ growth of MOF (Metal organic framework) middle layer in low-temperature water phase, preparation and application |
| CN116531968A (en) * | 2023-03-26 | 2023-08-04 | 山东科技大学 | Spraying-assisted construction double-interlayer forward osmosis composite membrane and preparation method thereof |
| CN116531968B (en) * | 2023-03-26 | 2024-03-22 | 山东科技大学 | Spraying-assisted construction double-interlayer forward osmosis composite membrane and preparation method thereof |
| CN117258552A (en) * | 2023-11-21 | 2023-12-22 | 中国农业大学 | Nanofiltration membrane with permeability and selectivity and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103877871B (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103877871A (en) | Composite separating membrane and preparation method and application thereof | |
| Liu et al. | Microstructural engineering and architectural design of metal–organic framework membranes | |
| CN106621864B (en) | MOFs- cross-linked polyethylene glycol diacrylate mixed substrate membrane containing nano-grade molecular sieve and preparation and application | |
| Goh et al. | Metal–organic frameworks (MOFs)‐based mixed matrix membranes (MMMs) for gas separation: a review on advanced materials in harsh environmental applications | |
| Marti et al. | Simple fabrication method for mixed matrix membranes with in situ MOF growth for gas separation | |
| Wang et al. | Ceramic tubular MOF hybrid membrane fabricated through in situ layer‐by‐layer self‐assembly for nanofiltration | |
| Ge et al. | Porous polyethersulfone-supported zeolitic imidazolate framework membranes for hydrogen separation | |
| Pinnau et al. | Ultrathin multicomponent poly (ether sulfone) membranes for gas separation made by dry/wet phase inversion | |
| Iarikov et al. | Review of CO2/CH4 separation membranes | |
| Winarta et al. | Metal–organic framework‐based mixed‐matrix membranes for gas separation: an overview | |
| US7815712B2 (en) | Method of making high performance mixed matrix membranes using suspensions containing polymers and polymer stabilized molecular sieves | |
| Fang et al. | Metal and covalent organic frameworks for membrane applications | |
| US20080141858A1 (en) | Gas Separations Using High Performance Mixed Matrix Membranes | |
| CN102451621A (en) | Polyether-b-polyamide multilayer composite film and preparation method thereof | |
| CN106390768A (en) | Zeolite imidazate framework/polyamide composite membrane and preparation method thereof | |
| WO2009061560A1 (en) | High performance mixed matrix membranes incorporating at least two kinds of molecular sieves | |
| CN103657458A (en) | PEBA (Polyether block amide) composite film as well as preparation method and application thereof | |
| Ataeivarjovi et al. | Study on CO2 desorption behavior of a PDMS–SiO2 hybrid membrane applied in a novel CO2 capture process | |
| CN103100313A (en) | Polyether-b-polyamide (PEBA)/polyethyleneglycol (PEG) or polyoxyethylene (PEO) blend membrane, and preparation and application thereof | |
| Li et al. | Effects of minor SO2 on the transport properties of fixed carrier membranes for CO2 capture | |
| CN102580567B (en) | Composite carbon diaphragm with mesoporous and microporous gradient structure and preparation method for diaphragm | |
| CN109499394A (en) | A kind of carbon monoxide seperation film and its preparation method and application | |
| JP7182120B2 (en) | Separation membrane and laminate | |
| CN110975646B (en) | Preparation method of hollow fiber composite membrane for separating carbon dioxide in mixed gas | |
| CN105032216B (en) | A kind of attapulgite polyethers b polyamide mixed substrate membrane containing nano-grade molecular sieve and preparation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A composite separation membrane, its preparation method and application Effective date of registration: 20230927 Granted publication date: 20160106 Pledgee: China CITIC Bank Co.,Ltd. Dalian Branch Pledgor: DALIAN EUROFILM INDUSTRIAL Ltd. Registration number: Y2023980059270 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |