CN105561807B - Prepare method and the application of Woelm Alumina/zirconia composite carrier support Co IM mIM films - Google Patents
Prepare method and the application of Woelm Alumina/zirconia composite carrier support Co IM mIM films Download PDFInfo
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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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
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Abstract
The invention discloses a kind of method for preparing Woelm Alumina/zirconia composite carrier support Co IM mIM films and application；Preparation method is first to prepare one layer of zirconium oxide film layer in macroporous aluminium oxide matrix surface, Co IM mIM films are generated in zirconium oxide film layer surface by secondary growth method again, the Woelm Alumina of preparation/zirconia composite carrier support Co IM mIM membrane structures are fine and close, continuous, free of surface defects；The separating-purifying of low-quality combustion gas is used it for, not only good separating effect, and resistance to elevated temperatures is good, stablizes at high temperature, does not ftracture, and preferable separating property is kept at high temperature.
Description
Technical field
The present invention relates to a kind of fine and close continuous poriferous metal of the preparation on alumina-zirconia composite porous carriers is organic
The method of frame structure compound (MOFs) film, and Woelm Alumina/zirconia composite carrier support Co-IM-mIM films low
Application in quality combustion gas purification, belongs to novel film materials technical field.
Background technology
Because the device of membrane separation technique is simple, energy consumption is relatively low, and the good characteristic such as separative efficiency height, membrane separation technique is
As one of important industrial means.The application that low-quality combustion gas is purified for low-quality combustion gas there is into weight using membrane separation technique
The practical significance wanted, with higher temperature when many low-quality combustion gas prepare, so it is excellent to develop a kind of separating property
Different and resistant to elevated temperatures molecular screen membrane has important practical significance.
In the more than ten years in past, metal-organic framework compound (MOFs) is because it is in terms of gas separation and storage
Potentiality and be synthesized by the concern of researchers, hundreds of kinds of metal-organic framework compound,
And this numeral is still increasing.Because metal-organic framework compound has diversified pore structure and pore size,
And special some specific absorption affinity so that it turns into the excellent selection for preparing molecular screen membrane.
Due to MOFs architectural characteristic, MOFs materials are prepared into molecular screen membrane and cause the extensive emerging of researcher
Interest, the MOFs films of numerous species have been developed, but because the adhesion property of MOFs materials is very low and easy at high temperature
The characteristic of cracking, it is still a kind of challenge to prepare a kind of homogeneous, flawless MOFs films.Carrier is close intact for synthesizing
Sunken film has important influence, and it is most important for successfully synthesizing film to find a kind of suitable carrier.Up to the present, scientific research work
The substrates such as authors' generally use aluminum oxide, copper mesh are successfully prepared a small amount of MOFs material membranes, but seldom input as carrier
Seldom in industrial production, with high costs and non-refractory turns into an important factor for hindering its commercial Application.
If a kind of densification can be developed, continuously, zero defect and resistant to elevated temperatures film, different works is adapted to for MOFs films
Industry gas isolating environment has important meaning.
The content of the invention
The defects of existing for existing MOFs material membranes, it is an object of the invention to be to provide a kind of compact structure,
Continuously, the method for Woelm Alumina free of surface defects/zirconia composite carrier support Co-IM-mIM films.
Another the purpose of the present invention is to be to provide the Woelm Alumina/zirconia composite carrier support Co-IM-
The application of mIM films, the separating-purifying of low-quality combustion gas is used it for, not only with preferable separating effect, and heat-resisting quantity
Can be good, stablize at high temperature, do not ftracture, and keep preferable separating property at high temperature.
In order to realize above-mentioned technical purpose, the invention provides one kind to prepare Woelm Alumina/zirconia composite carrier branch
The method for supportting Co-IM-mIM films, this method comprise the following steps：
(1) zirconia particles in zirconia particles suspension are supported on to certain of macropore alumina supporter by czochralski method
One surface, after drying, it is placed under 600~800 DEG C of high temperature and is calcined, zirconium oxide film is formed on the surface of macroporous aluminium oxide matrix
Layer, produces Woelm Alumina/zirconia composite carrier；
(2) by divalent cobalt, imidazoles and methylimidazole ultrasonic disperse in organic solvent, in 10~40 DEG C of stirring reactions
6~12 hours, it is separated by filtration, obtains metal organic framework crystal seed；
(3) it is metal organic framework crystal seed is scattered in organic solvent, metal organic framework crystal seed is born by czochralski method
It is loaded in the zirconium oxide film layer surface of Woelm Alumina/zirconia composite carrier；
(4) Woelm Alumina after kind of crystal seed/zirconia composite carrier is fixed in a kettle, adds cobalt containing divalence
The mixed solution of salt, imidazoles and methylimidazole, reactor is sealed, is reacted at 100~140 DEG C, in Woelm Alumina/oxidation
The zirconium oxide film layer surface of zirconium complex carrier forms Co-IM-mIM films, washs, and dries, produces.
One layer of hole of Surface Creation in technical scheme first in macroporous aluminium oxide is relatively small zirconium oxide
Layer, zirconia layer is combined preferably with alumina layer, and surface is rich in micropore, on this basis, on zirconia layer kind particle compared with
The more uniform crystal seed of small and particle diameter distribution, the Co-IM-mIM films that are subsequently generated can be made fine and close, smooth, it is free of surface defects, solve
The technical barrier of continuous uniform densification Co-IM-mIM films can not be prepared in the prior art.
Preferable scheme, zirconia particles granularity are 100~500nm.From the zirconia particles of appropriate particle diameter, make oxidation
Zirconium can be embedded in the hole system of macroporous aluminium oxide, enhance adhesion between the two.
Preferable scheme, the addition mol ratio of divalent cobalt, imidazoles and methylimidazole in (2) is 1:0.5~5:0.5
~5.By selecting appropriate synthesis ratio, constitutionally stable complex is advantageously formed, and can suitably adjust crystal size
To be adapted to kind of a crystalline substance.
Preferable scheme, the reaction condition prepared in (2) in seed crystal process are small for 10~40 DEG C of stirring reactions 6~12
When, by selecting appropriate reaction temperature and time, advantageously form that particle is smaller and evengranular crystal seed is to be adapted to kind
It is brilliant.It is 0.5~5 μm that metal organic framework seed particles granularity, which can be controlled,.
Preferable scheme, the roasting time in (1) are 1~5h.
Preferable scheme, the reaction time in (4) are 6~48 hours.
Preferable scheme, divalent cobalt, imidazoles and two in the solution containing divalent cobalt, imidazoles and methylimidazole in (4)
Methylimidazole mol ratio is 1:0.5~5:0.5~5.
Preferable scheme, the metal organic framework crystal seed in (3) disperse to make metal organic framework crystal seed in organic solvent
Mass percent concentration reach 1%~5%.
Preferable scheme, the czochralski method in (3), lifting number are 2~5 times, keep Woelm Alumina/oxygen during lifting every time
Changing zirconium complex carrier, residence time is 5~30 seconds in the solution, multiple to Woelm Alumina/zirconium oxide every time after the completion of lifting
Close carrier to be dried, then lifted next time.
Preferable scheme, the alumina substrate surface apertures of Woelm Alumina/zirconia composite carrier are 1~5 micron, oxygen
It is 0.1~0.5 micron to change zirconium coating surface apertures.
Present invention also offers the application of Woelm Alumina/zirconia composite carrier support Co-IM-mIM films, can apply
Purified in low-quality combustion gas.
Woelm Alumina/zirconia composite carrier that the present invention uses is sheet or hollow fiber.
Technical scheme Woelm Alumina/zirconia composite carrier supports Co-IM-mIM films to low-quality combustion gas
Good separating effect, can be selectively by H2And CH4Purification.
Preferable scheme, under 15~100 DEG C of temperature environments, from including H2、N2、CO2And CH4Low-quality combustion gas in it is real
Existing N2And CO2With H2And CH4Separation.The high-temperature resistant result of Woelm Alumina/zirconia composite carrier support Co-IM-mIM films
It is good, not only stablize at high temperature, do not ftracture, and keep preferable separating property at high temperature.
Compared with the prior art, the advantageous effects that technical scheme is brought：
1st, technical scheme, which solves prior art, can not prepare continuous, uniform, fine and close Co-IM-mIM films
Problem；First passage introduces the zirconium oxide film layer of micropore on macroporous aluminium oxide surface, then plants brilliant, film, can obtain continuous flat
The Co-IM-mIM films whole, consistency is high；
2nd, the film-forming process that technical scheme proposes is simply efficient, has a good application prospect；
3rd, Woelm Alumina made from technical scheme/zirconia composite carrier support Co-IM-mIM films can
Effectively by H2And CH4From H2、N2、CO2And CH4Separating-purifying in the low-quality combustion gas of composition, the film can be in different separation rings
Preferable separating property is kept at a temperature of border, there is good thermal stability, it is easy to overcome Co-IM-mIM films in the prior art
Pintsch process, and under high temperature the defects of inferior separating effect, widened the application field of Co-IM-mIM films.
Brief description of the drawings
【Fig. 1】(a) be the CO-IM-mIM crystal prepared under normal temperature condition XRD；(b) it is in 120 DEG C of CO- prepared
The XRD of IM-mIM crystal.
【Fig. 2】The SEM figures of the zirconium oxide film prepared for embodiment 1.
【Fig. 3】The SEM figures of the CO-IM-mIM crystal seeds prepared for embodiment 1.
【Fig. 4】Preparing Woelm Alumina/zirconia composite carrier for embodiment 1 supports the SEM of Co-IM-mIM films to scheme.
【Fig. 5】Preparing Woelm Alumina/zirconia composite carrier for embodiment 2 supports the SEM of Co-IM-mIM films to scheme.
【Fig. 6】The SEM figures of CO-IM-mIM films are supported for porous alumina carrier prepared by comparative example 1.
【Fig. 7】The SEM figures of the CO-IM-mIM crystal seeds prepared for comparative example 2.
【Fig. 8】The Woelm Alumina prepared for comparative example 2/zirconia composite carrier supports the SEM of CO-IM-mIM films
Figure.
Embodiment 1
Particle diameter distribution 20-500n Zirconia particles are added into stabilizer and are made into the acetone suspension that mass content is 4wt%
Liquid, zirconium oxide is introduced into porous alumina support using czochralski method, the lifting time is 30s, is put into after being dried at 100 DEG C
600 DEG C of Muffle kiln roasting 4h, obtains Woelm Alumina/zirconia composite carrier；
2.32g metal salt cobalt nitrates, 2.6g methylimidazoles, 2g imidazoles are dissolved in 350 ml methanols, at 25 DEG C
Stirring reaction 12 hours, is separated by filtration, and obtains metal organic framework CO-IM-mIM crystal seeds；
Use czochralski method kind brilliant in 4wt%CO-IM-mIM methanol solutions Woelm Alumina/zirconia composite carrier,
It is 4 times to lift number, and holding carrier is 30 seconds in the time of crystal seed liquid when lifting every time, by carrier at 60 DEG C after having lifted every time
Lower drying 6 was as a child lifted next time again；
By 0.58g metal salt cobalt nitrates, o.65g methylimidazole, 0.5g imidazoles are dissolved in 80 ml methanols, ultrasound 10
Minute dissolving.Carrier after kind of learning from else's experience is brilliant is disposed vertically in a kettle, and 80 milliliters of mother liquors prepared are added into reactor
In, reactor is put into 120 DEG C of vacuum drying chamber after sealing and reacts 24h.Then prepared what is taken out from reactor
Co-IM-mIM films be put into 100 ml methanols and soak 4 hours, finally dry 6 hours, produce at 80 DEG C.
Gas at normal temperature is tested：The Co-IM-mIM films prepared are put into gas permeation device and carry out gas separation test,
First purged before test with He gas, then with testing gas ventilation 10 minutes, the pressure differential at holding film both ends is during test
60KPa, test result H2Infiltration capacity be 16.96 × 10-6mol·m-2·s-1·Pa-1, H2/CO2, H2/N2And H2/CH4's
Separation factor is respectively 6.84,5.37,3.8.
Gas separation test under different temperatures：The Co-IM-mIM films prepared are put into homemade gas separator,
Then whole gas separator is put into Muffle furnace, gas path pipe is placed in Water Tank with Temp.-controlled, and keeps Muffle furnace and perseverance
Warm bath temperature degree always, changes the temperature of Muffle furnace and Water Tank with Temp.-controlled, tests gas separating property under different temperatures, test result
For：
At 25 DEG C：H2Infiltration capacity be 16.96 × 10-6mol·m-2·s-1·Pa-1, H2/CO2, H2/N2With d H2/CH4's
Separation factor is respectively 6.84,5.37,3.8.
At 40 DEG C：H2Infiltration capacity be 16.71 × 10-6mol·m-2·s-1·Pa-1, H2/CO2, H2/N2With d H2/CH4's
Separation factor is respectively 6.43,5.37,3.84.
At 55 DEG C：H2Infiltration capacity be 16.34 × 10-6mol·m-2·s-1·Pa-1, H2/CO2, H2/N2With d H2/CH4's
Separation factor is respectively 5.96,5.45,3.89.
At 70 DEG C：H2Infiltration capacity be 16.19 × 10-6mol·m-2·s-1·Pa-1, H2/CO2, H2/N2With d H2/CH4's
Separation factor is respectively 5.58,5.43,3.92.
At 90 DEG C：H2Infiltration capacity be 15.98 × 10-6mol·m-2·s-1·Pa-1, H2/CO2, H2/N2With d H2/CH4's
Separation factor is respectively 5.23,5.49,3.98.
Embodiment 2
Particle diameter distribution 20-500n Zirconia particles are added into stabilizer and are made into the acetone suspension that mass content is 4wt%
Liquid, zirconium oxide is introduced into porous alumina support using czochralski method, the lifting time is 30s, is put into after being dried at 100 DEG C
600 DEG C of Muffle kiln roasting 4h, obtains Woelm Alumina/zirconia composite carrier；
2.32g metal salt cobalt nitrates, 2.6g methylimidazoles, 2g imidazoles are dissolved in 350 ml methanols, at 25 DEG C
Stirring reaction 12 hours, is separated by filtration, and obtains metal organic framework CO-IM-mIM crystal seeds；
Use czochralski method kind brilliant in 2wt%CO-IM-mIM methanol solutions Woelm Alumina/zirconia composite carrier,
It is 4 times to lift number, and holding carrier is 30 seconds in the time of crystal seed liquid when lifting every time, by carrier at 60 DEG C after having lifted every time
Lower drying 6 was as a child lifted next time again；
By 0.58g metal salt cobalt nitrates, o.65g methylimidazole, 0.5g imidazoles are dissolved in 80 ml methanols, ultrasound 10
Minute dissolving.Carrier after kind of learning from else's experience is brilliant is disposed vertically in a kettle, and 80 milliliters of mother liquors prepared are added into reactor
In, reactor is put into 120 DEG C of vacuum drying chamber after sealing and reacts 12h.Then prepared what is taken out from reactor
Co-IM-mIM films be put into 100 ml methanols and soak 4 hours, finally dry 6 hours, produce at 80 DEG C.
Gas at normal temperature is tested：The Co-IM-mIM films prepared are put into gas permeation device and carry out gas separation test,
First purged before test with He gas, then with testing gas ventilation 10 minutes, the pressure differential at holding film both ends is during test
60KPa, test result H2Infiltration capacity be 17.37 × 10-6mol·m-2·s-1·Pa-1, H2/CO2, H2/N2And H2/CH4's
Separation factor is respectively 6.95,5.25,3.69.
Comparative example 1
By 2.32g metal salt cobalt nitrates, 2.6g methylimidazoles, 2g imidazoles ultrasonic dissolution is in 350 ml methanols, 25
Stirring reaction 12 hours, are separated by filtration at DEG C, obtain metal organic framework CO-IM-mIM crystal seeds；
Use czochralski method kind brilliant in 4wt%CO-IM-mIM methanol solutions porous alumina carrier, lifting number is 4
Secondary, holding carrier is 30 seconds in the time of crystal seed liquid when lifting every time, dries carrier 6 hours at 60 DEG C after having lifted every time
Time is lifted next time again；
By 0.58g metal salt cobalt nitrates, o.65g methylimidazole, 0.5g imidazoles are dissolved in 80 ml methanols, ultrasound 10
Minute dissolving.Carrier after kind of learning from else's experience is brilliant is disposed vertically in a kettle, and 80 milliliters of mother liquors prepared are added into reactor
In, reactor is put into 120 DEG C of vacuum drying chamber after sealing and reacts 24h.Then prepared what is taken out from reactor
Co-IM-mIM films be put into 100 ml methanols and soak 4 hours, finally dry 6 hours, produce at 80 DEG C.
By the SEM figures of film as can be seen that can not directly be synthesized by this macropore alumina supporter continuous, flawless
Co-IM-mIM films.
Comparative example 2
Particle diameter distribution 20-500n Zirconia particles are added into stabilizer and are made into the acetone suspension that mass content is 4wt%
Liquid, zirconium oxide is introduced into porous alumina support using czochralski method, the lifting time is 30s, is put into after being dried at 100 DEG C
600 DEG C of Muffle kiln roasting 4h, obtains Woelm Alumina/zirconia composite carrier；
By 2.32g metal salt cobalt nitrates, 2.6g methylimidazoles, 2g imidazoles ultrasonic dissolution will match somebody with somebody in 350 ml methanols
Good organic solvent is put into reactor, and then reactor is placed at 120 DEG C and reacts 24h, drying is separated after filtering, obtains gold
Belong to organic backbone crystal seed；
Use czochralski method kind brilliant in 4wt%CO-IM-mIM methanol solutions porous alumina carrier, lifting number is 4
Secondary, holding carrier is 30 seconds in the time of crystal seed liquid when lifting every time, dries carrier 6 hours at 60 DEG C after having lifted every time
Time is lifted next time again；
By 0.58g metal salt cobalt nitrates, o.65g methylimidazole, 0.5g imidazoles are dissolved in 80 ml methanols, ultrasound 10
Minute dissolving.Carrier after kind of learning from else's experience is brilliant is disposed vertically in a kettle, and 80 milliliters of mother liquors prepared are added into reactor
In, reactor is put into 120 DEG C of vacuum drying chamber after sealing and reacts 24h.Then prepared what is taken out from reactor
Co-IM-mIM films be put into 100 ml methanols and soak 4 hours, finally dry 6 hours, produce at 80 DEG C.
By the SEM of film figure as can be seen that the Co-IM-mIM films surface irregularity that is synthesized by the method and discontinuously,
Bulky grain crystal accumulation is together.
Claims (10)
1. prepare the method for Woelm Alumina/zirconia composite carrier support Co-IM-mIM films, it is characterised in that：Including following
Step：
(1) zirconia particles in zirconia particles suspension are supported on to a certain table of macropore alumina supporter by czochralski method
Face, after drying, it is placed under 600~800 DEG C of high temperature and is calcined, zirconium oxide film layer is formed on the surface of macroporous aluminium oxide matrix,
Produce Woelm Alumina/zirconia composite carrier；
(2) by divalent cobalt, imidazoles and methylimidazole ultrasonic disperse in organic solvent, 10~40 DEG C of stirring reactions 6~
12 hours, it is separated by filtration, obtains metal organic framework crystal seed；
(3) it is metal organic framework crystal seed is scattered in organic solvent, metal organic framework crystal seed is supported on by czochralski method
The zirconium oxide film layer surface of Woelm Alumina/zirconia composite carrier；
(4) Woelm Alumina after kind of crystal seed/zirconia composite carrier is fixed in a kettle, added containing divalent cobalt, miaow
The mixed solution of azoles and methylimidazole, reactor is sealed, is reacted at 100~140 DEG C, it is multiple in Woelm Alumina/zirconium oxide
The zirconium oxide film layer surface for closing carrier forms Co-IM-mIM films, washs, and dries, produces.
2. the method according to claim 1 for preparing Woelm Alumina/zirconia composite carrier support Co-IM-mIM films,
It is characterized in that：Described zirconia particles granularity is 100~500nm.
3. the method according to claim 1 for preparing Woelm Alumina/zirconia composite carrier support Co-IM-mIM films,
It is characterized in that：(2) the addition mol ratio of divalent cobalt, imidazoles and methylimidazole in is 1:0.5~5:0.5~5；(4)
In in the solution containing divalent cobalt, imidazoles and methylimidazole divalent cobalt, imidazoles and methylimidazole mol ratio be 1:0.5~
5:0.5~5.
4. the method according to claim 1 for preparing Woelm Alumina/zirconia composite carrier support Co-IM-mIM films,
It is characterized in that：(1) roasting time in is 1~5h；(4) reaction time in is 6~48 hours.
5. the method according to claim 1 for preparing Woelm Alumina/zirconia composite carrier support Co-IM-mIM films,
It is characterized in that：Described metal organic framework seed particles granularity is 0.5~5 μm.
6. the method according to claim 1 for preparing Woelm Alumina/zirconia composite carrier support Co-IM-mIM films,
It is characterized in that：(3) the scattered quality hundred for making metal organic framework crystal seed in organic solvent of metal organic framework crystal seed in
Specific concentration is divided to reach 1%~5%.
7. the method according to claim 1 for preparing Woelm Alumina/zirconia composite carrier support Co-IM-mIM films,
It is characterized in that：(3) czochralski method in, lifting number are 2~5 times, keep Woelm Alumina/zirconium oxide compound during lifting every time
Residence time is 5~30 seconds to carrier in the solution, and every time after the completion of lifting, Woelm Alumina/zirconia composite carrier is entered
Row drying, then lifted next time.
8. prepare Woelm Alumina/zirconia composite carrier support Co-IM-mIM according to any one of claim 1~7
The method of film, it is characterised in that：The alumina substrate surface apertures of described Woelm Alumina/zirconia composite carrier are 1~5
Micron, zirconia coating surface apertures are 0.1~0.5 micron.
9. Woelm Alumina prepared by any one of claim 1~7 methods described/zirconia composite carrier support Co-IM-mIM
The application of film, it is characterised in that：Purified applied to low-quality combustion gas.
10. the application of Woelm Alumina according to claim 9/zirconia composite carrier support Co-IM-mIM films, it is special
Sign is：Under 15~100 DEG C of temperature environments, from including H2、N2、CO2And CH4Low-quality combustion gas in realize N2And CO2With H2
And CH4Separation.
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| CN106064087B (en) * | 2016-06-08 | 2018-08-17 | 南京工业大学 | Method for preparing VOCs catalytic combustion catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011224553A (en) * | 2010-03-29 | 2011-11-10 | Fujifilm Corp | Gas separation membrane, method for producing the same, method for separating gas mixture using them, gas separation membrane module, and gas separation device |
| CN102580565A (en) * | 2012-01-19 | 2012-07-18 | 大连理工大学 | Preparation method for high-performance metal organic framework film |
| CN102794115A (en) * | 2012-08-01 | 2012-11-28 | 大连理工大学 | Preparation method of metal organic framework ZIF-8 (zero insert force-9) film |
-
2015
- 2015-12-15 CN CN201510932741.8A patent/CN105561807B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011224553A (en) * | 2010-03-29 | 2011-11-10 | Fujifilm Corp | Gas separation membrane, method for producing the same, method for separating gas mixture using them, gas separation membrane module, and gas separation device |
| CN102580565A (en) * | 2012-01-19 | 2012-07-18 | 大连理工大学 | Preparation method for high-performance metal organic framework film |
| CN102794115A (en) * | 2012-08-01 | 2012-11-28 | 大连理工大学 | Preparation method of metal organic framework ZIF-8 (zero insert force-9) film |
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