CN104058426B - The method that temperature-switching method prepares the molecular screen membranes of SAPO 34 - Google Patents
The method that temperature-switching method prepares the molecular screen membranes of SAPO 34 Download PDFInfo
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Abstract
The invention discloses a kind of method that temperature-switching method prepares the molecular screen membranes of SAPO 34, step includes：1) molecular sieve seeds of SAPO 34 are synthesized；2) molecular sieve seeds of SAPO 34 are uniformly coated onto on porous carrier；3) synthesis mother liquid of the molecular screen membranes of SAPO 34 is prepared；4) by step 2) porous carrier of the molecular sieve seeds of SAPO 34 of being coated with for preparing is dipped into aging in synthesis mother liquid；5) hydrothermal crystallizing 0.1~5 hour at 200~260 DEG C, then reduces temperature and continues hydrothermal crystallizing 0.1~96 hour；6) it is calcined, removed template method obtains the molecular screen membranes of SAPO 34.The present invention prepares the controllable molecular screen membranes of SAPO 34 of thickness using temperature-switching method, and the thickness of molecular screen membrane is successfully down into 1 micron, so as to significantly reduce the resistance to mass tranfer of the molecular screen membranes of SAPO 34, the permeability of film is improved.
Description
Technical field
The present invention relates to the preparation method of chemical field, more particularly to SAPO-34 molecular screen membranes.
Background technology
Organic zeolite membrane is to prepare one layer of continuous, fine and close, uniform molecular sieve on porous support and obtain.Due to nothing
Machine molecular screen membrane has the advantages that homogeneous aperture, high temperature resistant, anti-chemical solvent and ion-exchangeable therefore anti-in Membrane catalysis
Should, gas separation, Liquid Penetrant vaporization separation and the field such as environmental protection have huge application potential.For example, in CO2Removing neck
Domain, because membrane separation device has the advantages that low energy consumption, continuity operation, low equipment investment, small volume, easy care, therefore it is non-
Often it is adapted to high CO2The harsh isolating environment of content.
At present, the method for organic zeolite membrane is prepared on porous support mainly Vacuum-assisted method method, secondary synthesis
Method etc..
Vacuum-assisted method method is that porous carrier is directly placed into synthesis mother liquid, under hydrothermal conditions, molecular sieve is existed
Carrier surface grows film forming.This method is simple to operate, but the quality of film is affected by many factors, needs repeatedly crystallization to synthesize, this
So that molecular screen membrane is thicker.
Two-step fabrication is, by porous carrier seeded, then to be placed in synthesis mother liquid situ hydrothermal crystallizing film forming.The party
Method is the improvement to Vacuum-assisted method method.The Chinese invention patent application of Application No. 200580008446.8 discloses one kind
High-selectivity supported SAPO membranes, by making at least one surface of porous membrane supporter be contacted with aged synthesis gel,
Prepare high-selectivity supported SAPO membranes.The Chinese invention patent application of Application No. 200810050714.8 discloses one
The preparation method of the SAPO-34 molecular screen membranes of selectively separating methane gas is planted, the method for inducing secondary synthesis using crystal seed is synthesized
Go out the SAPO-34 molecular screen membranes of separating methane gas.
Temperature-switching method is a kind of new molecular screen membrane synthetic method, and this method is that carrier is immersed in mother liquor, higher
At a temperature of hydro-thermal process certain time, form certain thickness gel layer in carrier surface；Then hydrothermal temperature is reduced, is slowed down point
The grown in thickness of sub- sieve membrane, forms thin molecular screen membrane.For example, Wang etc. synthesizes NaY type molecular screen membranes using temperature-switching method, have
The infiltration evaporation performance [Microporous Mesoporous Mater.182 (2013) 250-258] of good organic solvent.
But not yet useful temperature-switching method synthesizes the document report of SAPO-34 molecular screen membranes at present.
SAPO-34 molecular screen membranes thickness prepared by common incubation water heating method (220 DEG C crystallization 5 hours) is more than 5 microns
(as shown in Figure 1).20 DEG C of temperature, system pressure 4000kPa, gas feed rate is 12000mL/min, and a mole composition is 50/
The CO measured under the conditions of 50%2/CH4Gas separation selectivity is 55 or so, CO2Permeability be about 8 × 10-7mol/(m2·
s·Pa)。
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of method that temperature-switching method prepares SAPO-34 molecular screen membranes, it can
So that the thickness and resistance to mass tranfer of SAPO-34 molecular screen membranes is greatly reduced, the permeability of film is improved.
In order to solve the above technical problems, the method that the temperature-switching method of the present invention prepares SAPO-34 molecular screen membranes, step includes：
1) SAPO-34 molecular sieve seeds are synthesized；
2) SAPO-34 molecular sieve seeds are uniformly coated onto on porous carrier；
3) synthesis mother liquid of SAPO-34 molecular screen membranes is prepared；
4) by step 2) porous carrier of SAPO-34 molecular sieve seeds of being coated with for preparing is dipped into aging in synthesis mother liquid；
5) hydrothermal crystallizing 0.1~5 hour at 200~260 DEG C, then reduces temperature continuation hydrothermal crystallizing 0.1~96 small
When；
6) it is calcined, removed template method obtains SAPO-34 molecular screen membranes.
Above-mentioned steps 1) in, the synthesis step of SAPO-34 molecular sieve seeds is：Silicon source is added to tetraethyl ammonium hydroxide
In solution, after being fully hydrolyzed, plus silicon source and phosphoric acid, stirring, crystal seed reaction solution is obtained, then can be heated at 120~230 DEG C
Crystallization 2~72 hours, obtains SAPO-34 molecular sieve seeds.The preferable mol ratio of the crystal seed reaction solution is：1Al2O3:1~
2P2O5:0.3~0.6SiO2:1~3 (TEA)2O:55~150H2O。
Above-mentioned steps 2) in, the shape of porous carrier can be single channel tubulose, multichannel tubulose, tabular or hollow fibre
Tubulose etc. is tieed up, material can be ceramics, stainless steel, aluminum oxide, titanium dioxide, zirconium dioxide, silica, carborundum or nitridation
Silicon etc., aperture is between 2~2000 nanometers.The method that SAPO-34 molecular sieve seeds are coated on porous carrier can be used
Brushing, dip-coating, spraying or spin coating；Using dip-coating method when, the ethanol solution concentrations of SAPO-34 molecular sieve seeds is 0.01
~1wt%.
Above-mentioned steps 3) in, the preparation steps of synthesis mother liquid are：Silicon source is added in phosphoric acid solution, after being fully hydrolyzed,
Silicon source, tetraethyl ammonium hydroxide and di-n-propylamine stirring are added, the synthesis mother liquid of SAPO-34 molecular screen membranes is obtained.Synthesis mother liquid
Preferable mol ratio be：1Al2O3:1~2P2O5:0.1~0.6SiO2:1~8TEAOH:0~3DPA:30~1000H2O。
Above-mentioned steps 1) and 3) in the silicon source used can use aluminium isopropoxide, aluminium hydroxide, pure aluminum, aluminium salt, oxidation
Aluminium or hydrated alumina；Silicon source can use Ludox, esters of silicon acis, silicon aerosol or sodium metasilicate.
Above-mentioned steps 4) in, the time of aging can be 0.01~5 hour in porous carrier immersion synthesis mother liquid.
Above-mentioned steps 5) in, the temperature for continuing hydrothermal crystallizing is 150~200 DEG C.
The present invention prepares the controllable SAPO-34 molecular screen membranes of thickness using temperature-switching method, by the thickness of molecular screen membrane successfully
1 micron is down to, so as to significantly reduce the resistance to mass tranfer of SAPO-34 molecular screen membranes, the permeability of film is improved.
Brief description of the drawings
Fig. 1 is surface and the SEM (SEM) of section of SAPO-34 molecular screen membranes prepared by common hydro-thermal method
Photo.Wherein, (a) figure is the SEM photograph on film surface, and (b) figure is the SEM photograph of film section.
Fig. 2 is surface and the SEM (scanning electron microscopies of section of SAPO-34 molecular screen membranes prepared by the embodiment of the present invention 1
Mirror) photo.Wherein, (a) figure is the SEM photograph on film surface, and (b) figure is the SEM photograph of film section.
Fig. 3 is surface and the SEM photograph of section of SAPO-34 molecular screen membranes prepared by the embodiment of the present invention 2.Wherein, (a)
Figure is the SEM photograph on film surface, and (b) figure is the SEM photograph of film section.
Fig. 4 is surface and the SEM photograph of section of SAPO-34 molecular screen membranes prepared by the embodiment of the present invention 3.Wherein, (a)
Figure is the SEM photograph on film surface, and (b) figure is the SEM photograph of film section.
Fig. 5 is surface and the SEM photograph of section of SAPO-34 molecular screen membranes prepared by the embodiment of the present invention 4.Wherein, (a)
Figure is the SEM photograph on film surface, and (b) figure is the SEM photograph of film section.
Fig. 6 is surface and the SEM photograph of section of SAPO-34 molecular screen membranes prepared by the embodiment of the present invention 5.Wherein, (a)
Figure is the SEM photograph on film surface, and (b) figure is the SEM photograph of film section.
Fig. 7 is surface and the SEM photograph of section of SAPO-34 molecular screen membranes prepared by the embodiment of the present invention 6.Wherein, (a)
Figure is the SEM photograph on film surface, and (b) figure is the SEM photograph of film section.
Fig. 8 is surface and the SEM photograph of section of SAPO-34 molecular screen membranes prepared by the embodiment of the present invention 7.Wherein, (a)
Figure is the SEM photograph on film surface, and (b) figure is the SEM photograph of film section.
Embodiment
Have for technology contents, feature and effect to the present invention and more specifically understand, in conjunction with accompanying drawing, to present invention detailed description
It is as follows：
Embodiment 1
The present embodiment temperature-switching method prepares comprising the following steps that for SAPO-34 molecular screen membranes：
Step 1,2.46g deionized waters are added in 31.13g tetraethyl ammonium hydroxides solution (TEAOH, 35wt%), then
Weigh 7.56g aluminium isopropoxides to be added in previous solu, be stirred at room temperature 2-3 hours；Then 1.665g Ludox is added dropwise
(40wt%), is stirred 1 hour；8.53g phosphoric acid solutions (H is finally slowly added dropwise3PO4, 85wt%), it is stirred overnight.Using microwave plus
Heat, the crystallization 7h at 180 DEG C.After product takes out, centrifuge, wash, drying obtains SAPO-34 molecular sieve seeds.
Step 2, the porous ceramic pipe that selection aperture is 100nm is cleaned after drying, outside as carrier, the end seal glaze of carrier two
Surface is sealed with Teflon tap, and SAPO-34 molecular sieve seeds are brushed into the inner surface to earthenware.
Step 3,7.56g aluminium isopropoxides are added in 4.27g phosphoric acid solutions (85wt%) and 43.8g deionized waters, filled
Divide after hydrolysis, sequentially add 0.83g Ludox (40wt%), 7.78g tetraethyl ammonium hydroxides (35wt%) and 3g di-n-propylamines
(DPA), it is stirred overnight, obtains the synthesis mother liquid of molecular screen membrane, its mol ratio is：1Al2O3:1P2O5:0.3SiO2:1TEAOH:
1.6DPA:150H2O。
Step 4, the porous carrier for being coated with SAPO-34 molecular sieve seeds prepared by step 2 is placed in 100ml reactor
In, synthesis mother liquid is poured into, temperature at 220 DEG C after hydrothermal crystallizing 1h, is adjusted to 180 DEG C, continues hydrothermal crystallizing by aged at room temperature 3h
5h, is washed, and is dried, is obtained SAPO-34 molecular screen membranes.
Step 5, SAPO-34 molecular sieves membrane tube step 4 obtained vacuum baking 4h at 400 DEG C, removed template method (rises
Gentle rate of temperature fall is 1K/min), obtain SAPO-34 molecular screen membranes.The surface of gained SAPO-34 molecular screen membranes and section are such as
Shown in Fig. 2, it can be seen that carrier surface is completely covered by cubic crystal, it is crosslinked between crystal good (scheming referring to a)；Film
Thickness is more uniform, about 1 micron (scheming referring to b).
CO is carried out to gained SAPO-34 molecular screen membranes2/CH4Gas separation is tested, and test condition is：20 DEG C of temperature, air
Pressure 102.4kPa, gas feed rate is 12000mL/min, and a mole composition is 50/50%.Determined and permeated with soap film flowmeter
The gas flow of side；The gas for analyzing per-meate side with gas chromatograph (Shimadzu -2014C) is constituted.
The calculation formula of gas permeability：P=V/ (S*P).Wherein, V is infiltration gas (CO2Or CH4) flow, unit
mol/s；S is membrane area, unit m2；P is the pressure differential of membrane tube feed side and per-meate side, unit Pa.
Separation selectivity calculation formula：F=pCO2/pCH4, i.e. CO2With CH4The ratio between permeability.
Gas separation test result is as shown in table 1, under 4.0MPa, the CO of the SAPO-34 molecular sieve membrane tubes2Permeability
For 14.3 × 10-7mol/(m2SPa), CO2/CH4Separation selectivity be 20.
The CO of the SAPO-34 molecular sieve membrane tubes of the embodiment 1 of table 12/CH4Gas separation test result
Embodiment 2
It is with the difference of embodiment 1：In step 4, the time for continuing hydrothermal crystallizing at 180 DEG C is 9h.Remaining
Step is same as Example 1.
Surface and the section of gained SAPO-34 molecular screen membranes are as shown in figure 3, it can be seen that carrier surface is by cube
Crystal is completely covered, and is crosslinked between crystal good (scheming referring to a)；The thickness of film is more uniform, about 1.5 microns (scheming referring to b).
The CO of the SAPO-34 molecular sieve membrane tubes2/CH4Gas separation test result is as shown in table 2, under 4.0MPa, its CO2
Permeability be 18.6 × 10-7mol/(m2SPa), CO2/CH4Separation selectivity be 16.
The CO of the SAPO-34 molecular sieve membrane tubes of the embodiment 2 of table 22/CH4Gas separation test result
Embodiment 3
It is with the difference of embodiment 1：In step 4, the time for continuing hydrothermal crystallizing at 180 DEG C is 16.5h.Its
Remaining step is same as Example 1.
Surface and the section of gained SAPO-34 molecular screen membranes are as shown in figure 4, it can be seen that carrier surface is by cube
Crystal is completely covered, and is crosslinked between crystal good (scheming referring to a)；The thickness of film is more uniform, about 3.5 microns (scheming referring to b).
The CO of the SAPO-34 molecular sieve membrane tubes2/CH4Gas separation test result is as shown in table 3, under 4.0MPa, its CO2
Permeability be 19.5 × 10-7mol/(m2SPa), CO2/CH4Separation selectivity be 24.
The CO of the SAPO-34 molecular screen membranes of the embodiment 3 of table 32/CH4Gas separation test result
Embodiment 4
It is with the difference of embodiment 1：In step 4, the time of hydrothermal crystallizing is 2h at 220 DEG C.Remaining step
It is same as Example 1.
Surface and the section of gained SAPO-34 molecular screen membranes are as shown in figure 5, it can be seen that carrier surface is by cube
Crystal is completely covered, and is crosslinked between crystal good (scheming referring to a)；The thickness of film is more uniform, about 4 microns (scheming referring to b).
To the CO of the SAPO-34 molecular sieve membrane tubes2/CH4Gas separation test result is as shown in table 4, under 4.0MPa, its
CO2Permeability be 14.7 × 10-7mol/(m2SPa), CO2/CH4Separation selectivity be 42.
The CO of the SAPO-34 molecular sieve membrane tubes of the embodiment 4 of table 42/CH4Gas separation test result
Embodiment 5
It is with the difference of embodiment 1：In step 4, the time of hydrothermal crystallizing is 2h at 220 DEG C, at 180 DEG C
The time for continuing hydrothermal crystallizing is 16.5h.Remaining step is same as Example 1.
Surface and the section of gained SAPO-34 molecular screen membranes are as shown in fig. 6, it can be seen that carrier surface is by cube
Crystal is completely covered, and is crosslinked between crystal good (scheming referring to a)；The thickness of film is more uniform, about 5 microns (scheming referring to b).
The CO of the SAPO-34 molecular sieve membrane tubes2/CH4Gas separation test result is as shown in table 5.Under 4.0MPa, its CO2
Permeability be 8.55 × 10-7mol/(m2SPa), CO2/CH4Separation selectivity be 76.
The CO of the SAPO-34 molecular screen membranes of the embodiment 5 of table 52/CH4Gas separation test result
Embodiment 6
It is with the difference of embodiment 1：In step 4, the first hydrothermal crystallizing 1h at 240 DEG C, then temperature is adjusted to 180
DEG C, continue hydrothermal crystallizing 5h.Remaining step is same as Example 1.
Surface and the section of gained SAPO-34 molecular screen membranes are as shown in fig. 7, it can be seen that carrier surface is by cube
Crystal is completely covered, and is crosslinked between crystal good (scheming referring to a)；The thickness of film is more uniform, about 1.5 microns (scheming referring to b).
The CO of the SAPO-34 molecular sieve membrane tubes2/CH4Gas separation test result is as shown in table 6.Under 4.0MPa, its CO2
Permeability be 14.1 × 10-7mol/(m2SPa), CO2/CH4Separation selectivity be 26.
The CO of the SAPO-34 molecular screen membranes of the embodiment 6 of table 62/CH4Gas separation test result
Embodiment 7
It is with the difference of embodiment 1：In step 4, the first hydrothermal crystallizing 2h at 240 DEG C, then temperature is adjusted to 180
DEG C, continue hydrothermal crystallizing 5h.Remaining step is same as Example 1.
Surface and the section of gained SAPO-34 molecular screen membranes are as shown in figure 8, it can be seen that carrier surface is by cube
Crystal is completely covered, and is crosslinked between crystal good (scheming referring to a)；The thickness of film is more uniform, about 4 microns (scheming referring to b).
The CO of the SAPO-34 molecular sieve membrane tubes2/CH4Gas separation test result is as shown in table 7.Under 4.0MPa, its CO2
Permeability be 11.8 × 10-7mol/(m2SPa), CO2/CH4Separation selectivity be 54.
The CO of the SAPO-34 molecular screen membranes of the embodiment 7 of table 72/CH4Gas separation test result
Claims (10)
1. the method that temperature-switching method prepares SAPO-34 molecular screen membranes, step includes：
1) SAPO-34 molecular sieve seeds are synthesized；
2) SAPO-34 molecular sieve seeds are uniformly coated onto on porous carrier；
3) synthesis mother liquid containing template of SAPO-34 molecular screen membranes is prepared；
4) by step 2) porous carrier of SAPO-34 molecular sieve seeds of being coated with for preparing is dipped into aging in synthesis mother liquid；
5) hydrothermal crystallizing 0.1~5 hour at 200~260 DEG C, then reduces temperature to 150~180 DEG C, continues hydrothermal crystallizing
0.1~96 hour；
6) it is calcined, removed template method obtains SAPO-34 molecular screen membranes.
2. according to the method described in claim 1, it is characterised in that step 1), the synthesis step bag of SAPO-34 molecular sieve seeds
Include：Silicon source is added in tetraethyl ammonium hydroxide solution, after being fully hydrolyzed, plus silicon source and phosphoric acid, stirring, obtain crystal seed reaction
Liquid, then heating crystallization, obtains SAPO-34 molecular sieve seeds.
3. method according to claim 2, it is characterised in that step 1), heating crystallization 2~72 is small at 120~230 DEG C
When.
4. method according to claim 2, it is characterised in that step 1), include Al in the crystal seed reaction solution2O3、
P2O5、SiO2, tetraethyl ammonium hydroxide, their mol ratio is：1Al2O3:1~2P2O5:0.3~0.6SiO2:2~6 tetrems
Base ammonium hydroxide:55~150H2O。
5. according to the method described in claim 1, it is characterised in that step 2), the shape of porous carrier include single channel tubulose,
Multichannel tubulose, tabular, doughnut tubulose, material include ceramics, stainless steel, aluminum oxide, titanium dioxide, zirconium dioxide,
Silica, carborundum, silicon nitride, aperture are 2~2000 nanometers.
6. according to the method described in claim 1, it is characterised in that step 2), the painting method bag of SAPO-34 molecular sieve seeds
Include brushing, dip-coating, spraying, spin coating.
7. according to the method described in claim 1, it is characterised in that step 3), the preparation steps of synthesis mother liquid include：By silicon source
It is added in phosphoric acid solution, after being fully hydrolyzed, adds silicon source, tetraethyl ammonium hydroxide and di-n-propylamine stirring, obtain SAPO-34
The synthesis mother liquid of molecular screen membrane.
8. the method according to claim 2 or 7, it is characterised in that source of aluminium includes aluminium isopropoxide, aluminium hydroxide, list
Matter aluminium, aluminium salt, aluminum oxide；The silicon source includes Ludox, esters of silicon acis, silicon aerosol, sodium metasilicate.
9. the method according to claim 1 or 7, it is characterised in that include Al in synthesis mother liquid2O3、P2O5、SiO2、
TEAOH, DPA, their mol ratio is：1Al2O3:1~2P2O5:0.1~0.6SiO2:1~8TEAOH:0~3DPA:30~
1000H2O。
10. according to the method described in claim 1, it is characterised in that step 4), porous carrier aging 0.01 in synthesis mother liquid
~5 hours.
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| CN107746065A (en) * | 2017-12-06 | 2018-03-02 | 武汉工程大学 | A kind of method for preparing the molecular screen membrane of high-performance SAPO 34 |
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| CN105983344B (en) * | 2015-02-03 | 2021-03-23 | 中国科学院上海高等研究院 | Method for separating gas-liquid/liquid mixture by pervaporation and vapor permeation of ion exchange SAPO-34 molecular sieve membrane |
| CN105983345B (en) * | 2015-02-03 | 2021-03-19 | 中国科学院上海高等研究院 | Method for separating gas-liquid/liquid mixture by pervaporation and vapor permeation of SAPO-34 molecular sieve membrane prepared by xerogel method |
| CN107840352B (en) * | 2016-09-19 | 2020-08-07 | 中国石油化工股份有限公司 | Preparation method of SAPO molecular sieve membrane |
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| CN103420391A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Small grain SAPO-34 molecular sieve preparation method |
| CN103506015A (en) * | 2012-06-11 | 2014-01-15 | 中国科学院上海高等研究院 | Method for preparing ion exchange SAPO-34 molecular sieve membrane |
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| CN103420391A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Small grain SAPO-34 molecular sieve preparation method |
| CN103506015A (en) * | 2012-06-11 | 2014-01-15 | 中国科学院上海高等研究院 | Method for preparing ion exchange SAPO-34 molecular sieve membrane |
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