CN103894076B - The method that ion exchange prepares high-performance molecular screen membrane is carried out in the molten state - Google Patents
The method that ion exchange prepares high-performance molecular screen membrane is carried out in the molten state Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Abstract
The invention discloses a kind of method for carrying out ion exchange in the molten state and preparing high-performance molecular screen membrane, including：Fusing point is supported on less than the metal salt of calcination temperature and is gone on the molecular screen membrane of template agent removing, after dry, less than calcination temperature and higher than at a temperature of metal salt fusing point, molten state ion exchange carried out, the molecular screen membrane of ion exchange is made；Wherein, calcination temperature is calcination temperature when removing the template in molecular screen membrane.The method can significantly improve the CO of molecular screen membrane2/CH4Selectivity.
Description
Technical field
The present invention relates to a kind of preparation method of molecular screen membrane, and ion friendship is carried out in the molten state more particularly to a kind of
Change the method for preparing high-performance molecular screen membrane.
Background technology
The whole world is about 3 tcms to the Year's consumption of natural gas, accounts for the 23.7% of energy aggregate demand.Natural gas exists
Occupy critical role in global energy strategy.The content of methane accounts for 75%-90% in natural gas, in addition, usually contains big
Hydrocarbon and some impurity such as the ethane of amount, propane, butane.These impurity include water, carbon dioxide, nitrogen, hydrogen sulfide
Deng having seriously affected the storage and transport of natural gas.Therefore, annual 5000000000 dollars of the cost in the whole world is used for natural gas purification, mainly
It is the CO removed in natural gas2.According to statistics, natural gas of the U.S. more than 20% is due to excessive CO2Content and need depth
Reason.CO of the Shell Oil Company in the gas field of Russian Sakhalin, Indonesia and South China Sea2Content is even
Up to more than 40%.
At present, CO2Removing process mainly has organic amine absorption and UF membrane.Wherein, although organic amine absorbing and removing technique
Comparative maturity, but there are the shortcomings of equipment investment is high, bulky, system maintenance is complicated, absorbent regeneration high energy consumption；And film point
From having the advantages that energy consumption is low, continuity operates, equipment investment is low, small, easy care, very big concern is received
[Ind.Eng. Chem.Res.41(2002)1393].Although traditional polymeric membrane has obtained widely in separation field
Using, but the defects of due to high molecular material nature, in high pressure CO2Under can produce plasticizing phenomenon, so as to cause selectivity
Decline to a great extent.And molecular screen membrane has excellent heat, chemistry and mechanical stability, high pressure CO is very suitable for2Harsh separation
Environment.
Numerous studies, which are reported, to be shown, T [J.Mater.Chem.14 (2004) 924], the DDR of aperture
[Micropor.Mesopor. Mater.68 (2004) 71] and SAPO-34 [J.Membr.Sci.363 (2010) 29 and its draw
Text] molecular screen membrane is most suitable for CO2-CH4Separation, because CO2Diffusion in small pore molecular sieve crystal duct is far faster than CH4, can
To obtain high separation selectivity, so as to reduce the methane loss during natural gas processing.SAPO-34 is that have
The aperture silicon phosphorus aluminium profiles molecular sieve of CHA structure, its aperture are 0.38 nanometer, are very suitable for CO2-CH4Separation.CO2And CH4Point
Subdynamics diameter is respectively 0.33 and 0.38 nanometer, diffusion coefficient very different (the molecule screening) in SAPO-34 ducts, together
When, the CO of polarity2Absorption of the molecule in SAPO-34 ducts is stronger, and absorption also selects CO2。
The separating property of molecular screen membrane is affected by various factors：Such as framework si-al ratio, crystal seed size, template kind
Class, the thickness of film, cation type, CO2The influence of the conditions such as concentration, support, roasting condition, defect mending method
[J.Membr. Sci.335 (2009) 32 and its quotation].Wherein, ion exchange is that one kind simply effectively improves molecular sieve
Film CO2/CH4The method of selectivity.
Hydrogen ion in molecular sieve crystal is exchanged for alkaline metal ion can strengthen the alkalescence of molecular sieve, and it is right to improve its
Sour gas (such as CO2) adsorptive selectivity.Meanwhile the introducing of metal ion can also change the duct size of molecular sieve, so that
Change the diffusion selectivity of gas.Walton etc. is respectively adopted different types of cation and carries out ion to X-type and Y type molecular sieve
Exchange, the results showed that, the molecular sieve CO that different ions exchange2Adsorption capacity increase rate Cs+＜ Rb+＜ K+＜ Na+＜ Li+
[Micropor. Mesopor.Mater.91(2006)78].Yang etc. carries out high alumina beta-molecular sieve in alkali metal and alkaline earth gold is bent
Ion exchange, the molecular sieve CO that different ions exchange2Adsorption capacity increase rate Mg2+＜ Cs+＜ Ca2+＜ Ba2+＜ Li+＜ Na+
＜ K+[Micropor. Mesopor.Mater.135(2010)90].The NaY types that the report alkali metal ion such as Kusakabe exchanges
Molecular screen membrane is than the permeability [J.Membr.Sci.148 (1998) 13] with higher that alkaline-earth metal ions exchange.
Hasegawa etc. is had found through K+、Rb+And Cs+The NaY molecular sieve film of exchange, its CO2/N2Separation selectivity brings up to 34 from 19~
40[Sep.Purif.Technol.22-23 (2001)319].Sun Jihong etc. makes sodium form low silicon-aluminum X first with lithium ion aqueous solution
Type molecular sieve has certain lithium ion exchanged degree, then obtains lithium type low silicon aluminum of the exchange degree more than 96% with solid phase exchange process
X-type molecular sieve (China Patent No.： 200710121786.2).Hong etc. uses Li+、Na+、K+、NH4 +And Cu2+In non-aqueous solution
Ion exchange H-SAPO-34 molecular screen membranes, make CO2/CH4Separation selectivity improves 60%, but CO2Permeability has decline
[Micropor.Mesopor.Mater. 106(2007)140]。
However, it is gold salt in the wrong to be dissolved in solvent salting liquid is made that traditional ion-exchange, which prepares molecular screen membrane, so
Molecular sieve powder or film are placed in solution afterwards and carry out ion exchange.This ion-exchange process speed is slow, point being prepared
The CO of sub- sieve membrane2/CH4Selectivity need to be improved.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of ion exchange that carries out in the molten state to prepare high-performance point
The method of sub- sieve membrane.In this way, the gas separating property of molecular screen membrane, such as CO can be improved2/CH4Selectivity.
Handed in order to solve the above technical problems, the ion exchange of carry out in the molten state of the present invention prepares high performance ion
The method for changing molecular screen membrane, including step：
Fusing point is bent salt and be supported on less than the gold of calcination temperature and is gone on the molecular screen membrane of template agent removing, after dry, low
In calcination temperature and higher than at a temperature of metal salt fusing point, molten state ion exchange is carried out, the molecular screen membrane of ion exchange is made；
Wherein, calcination temperature is calcination temperature when removing the template in molecular screen membrane.
The molecular screen membrane for removing template agent removing includes：SAPO-34、ZSM-5、Silicalite-1、TS-1、AlPO-
18、 SAPO-18、AlPO4- 5, SAPO-5, DDR, MCM-22, Beta and A molecular screen membrane, is preferably SAPO-34 molecular screen membranes.
In the metal salt, its cation includes：Alkali metal, alkaline-earth metal and transition metal ions；The moon in metal salt
Ion includes：Anaerobic acid ion and oxygen-containing acid ion；Wherein, anaerobic acid ion includes：F-、Cl-、Br-、I-And S-；Contain
Oxygen acid group includes：NO3 -、ClO3 -、ClO4 -、SO4 2-、CO3 2-And CH3COO-。
The metal salt includes：Sodium nitrate, potassium nitrate, lithium nitrate, rubidium nitrate, magnesium nitrate, sodium chlorate, sodium perchlorate, chlorine
Sour calcium, potassium chlorate, Potassium Benzoate, magnesium benzoate, sodium acetate, potassium acetate, lithium acetate, lithium formate, sodium formate, potassium formate and formic acid
Calcium.Typical metal salt fusing point can be as shown in table 1.
The fusing point of 1 typical metal salt of table
It is described that fusing point is supported on to the method bag gone on the molecular screen membrane of template agent removing less than the metal salt of calcination temperature
Include：By dip coating, spin-coating method, spraying process or spread coating, metal salt is supported on to front, the reverse side and positive and negative two of molecular screen membrane
Face.Wherein, dip coating, its operating procedure are：Molecular screen membrane is placed in the metal salt solution that concentration is 0.01~50wt%,
Soaked 1 second~2 days at -40~100 DEG C.The concentration of the metal salt solution is preferably 0.1~5wt%, and soaking time is preferably
1 second~180 minutes；Solvent in metal salt solution can arbitrarily dissolve the organic and inorganic solvent or more that the gold bends salt
The mixture of kind solvent, including：Acetone, water, alcohols etc..
The temperature range of the drying is：Room temperature~200 DEG C.
The condition of the molten state ion exchange is：The temperature of ion exchange is 100~500 DEG C, the time of ion exchange
For 1~8 it is small when；Processing atmosphere in ion exchange includes：Vacuum, inert gas, air, pure oxygen or diluted oxygen；From
Heating rate during son exchanges is 0.1~5 °C/min.
The molecular screen membrane of ion exchange produced by the present invention, is that a kind of gas separation that can be used in sour gas system is de-
The molecular screen membrane removed；Wherein, which includes：CO2-CH4System, CO2-H2System and CO2-N2System.I.e. should be from
The molecular screen membrane that son exchanges can be used for including following gas separation or removing：CO2-CH4Separation, CO2-H2Separation and CO2-N2Point
From.
Wherein, the method for preparing high performance SAPO-34 molecular screen membranes for carrying out ion exchange in the molten state, bag
Include following steps：
1) synthesis of SAPO-34 molecular sieve seeds
By silicon source, (silicon source includes：Aluminium isopropoxide, Al (OH)3, pure aluminum, including aluminum nitrate, aluminium chloride, aluminum sulfate and phosphorus
The aluminium salt of sour aluminium etc.) it is added in tetraethyl ammonium hydroxide (TEAOH) solution, after being fully hydrolyzed, sequentially add Ludox and phosphorus
Acid, when stirring 12~96 is small, obtains crystal seed reaction solution, and then, microwave heats at 170~210 DEG C, when crystallization 4~7 is small, from
The heart, is washed, dry, obtains SAPO-34 molecular sieve seeds；
Wherein, the component molar proportioning in crystal seed reaction solution is：1Al2O3: 1~2P2O5: 0.3~0.6SiO2: 1~3
(TEA)2O: 55~150H2O (total Water in crystal seed reaction solution)；
2) crystal seed coats
Selecting porous ceramic pipe, two end seal glaze of carrier, after cleaning drying, outer surface sealing (can such as be used and used as carrier
Teflon tap wraps up) after, SAPO-34 molecular sieve seeds are applied to the inner surface of porous ceramic pipe, SAPO-34 molecules must be coated with
Sieve the ceramic tube of crystal seed；
3) synthesis of SAPO-34 molecular screen membranes
Aluminium isopropoxide is added in phosphoric acid solution, after being fully hydrolyzed, sequentially add Ludox, tetraethyl ammonium hydroxide and
Di-n-propylamine (DPA), when stirring 12~96 is small, obtains the synthesis mother liquid of molecular screen membrane；Wherein, the component molar in synthesis mother liquid
Match and be：1Al2O3: 1~1.5P2O5: 0.3~0.6SiO2: 1~2TEAOH: 1.5~2.0DPA: 70~150H2O；
Then, the ceramic tube for being coated with SAPO-34 molecular sieve seeds prepared by step 2) is placed in reaction kettle, is added and is divided
The synthesis mother liquid of sub- sieve membrane, at 210~230 DEG C, when hydrothermal crystallizing 3~24 is small, is washed, dry, obtains SAPO-34 molecular sieves
Membrane tube；
4) template agent removing is removed in roasting
The SAPO-34 molecular sieves membrane tube that step 3) is obtained roasted at 370~700 DEG C 2~8 it is small when, obtain remove mould
The SAPO-34 molecular screen membranes of plate agent (organic amine tetraethyl ammonium hydroxide)；
5) by gold salt in the wrong be supported on that step 4) obtains go on the SAPO-34 molecular screen membranes of template agent removing after, it is dry, low
In step 4) calcination temperature and higher than at a temperature of metal salt fusing point, carry out molten state ion-exchange treatment 1~8 it is small when, obtain
To high performance SAPO-34 molecular screen membranes.In this step, ion-exchange temperature used is lower than calcination temperature and is melted than golden salt in the wrong
Point is high, so as to melt metal salt, its metal cation is carried out ion exchange with the cation in molecular screen membrane.
In the step 1), the size of SAPO-34 molecular sieve seeds is 50~1000 nanometers.
In the step 2), the aperture of porous ceramic pipe is 5 nanometers~2000 nanometers, its material includes：Al2O3、TiO2、
ZrO2、SiC；Coating method includes：Spread coating and dip coating.
In the step 4), calcination atmosphere includes：Inert gas (such as nitrogen or argon gas), vacuum, air, oxygen and
The dilution oxygen of arbitrary proportion；In roasting, heating and rate of temperature fall are no more than 2K/ minutes.
In the step 5), selected metal salt is as described above.
In step 5), the method that metal salt is supported on the SAPO-34 molecular screen membranes of template agent removing includes：Pass through dip-coating
Metal salt, is supported on front, reverse side (one contacted with carrier of SAPO-34 molecular screen membranes by method, spin-coating method or spread coating
Face) and tow sides.Wherein, the operating procedure of dip coating is：By SAPO-34 molecular screen membranes be placed in concentration for 0.01~
In the metal salt solution of 50wt%, soaked 1 second~2 days under -40~100 °C.The concentration that the gold bends salting liquid is preferably 0.1~
5wt%, soaking time are preferably 1 second~180 minutes.Solvent in gold salting liquid in the wrong can arbitrarily dissolve the metal salt
Organic and inorganic solvent or multi-solvents mixture, such as include：Acetone and water.
In step 5), dry temperature range is：Room temperature~200 DEG C；The temperature of ion exchange is (i.e. less than the roasting of step 4)
Burn temperature and higher than the temperature of metal salt fusing point) it is preferably 100~500 DEG C, the processing atmosphere in ion exchange includes：Vacuum,
Inert gas (including：Nitrogen, argon gas and helium etc.), air, pure oxygen or diluted oxygen；Heating rate in ion exchange
For 0.1~5 DEG C/min.
The present invention uses new ion-exchange process, and fusing point is loaded to less than the metallic salt of calcination temperature and has been taken off
On the molecular screen membrane surface of template agent removing, then, (raise temperature in the temperature higher than metal salt fusing point and be higher than gold used
Belong to salt fusing point, to melt metal salt) under carry out ion exchange.The metal salt of load be in molten condition under, can with molecular screen membrane
Cation carry out ion exchange, so as to significantly improve the CO of molecular screen membrane2/CH4Selectivity.
Brief description of the drawings
The present invention is described in further detail with embodiment below in conjunction with the accompanying drawings：
Fig. 1 is SEM (scanning electron microscope) figure of the SAPO-34 molecular sieve seeds in embodiment 1；
Fig. 2 is the XRD diagram of the SAPO-34 molecular sieve seeds in embodiment 1；
Fig. 3 is the SEM figures of the SAPO-34 molecular screen membranes (without ion exchange) in embodiment 1, wherein, (a) is molecular sieve
The SEM figures of film surface, (b) are that the SEM of molecular screen membrane section schemes；
Fig. 4 is the SEM figures of the SAPO-34 molecular screen membranes after nitric acid lithium ion exchanged in embodiment 1；
Fig. 5 is the SEM figures of the SAPO-34 molecular screen membranes through potassium acetate ion exchange in embodiment 2, wherein, (a) is film
Pipe top view, (b) are membrane tube sectional view；
Fig. 6 is the distribution map of aluminium, silicon, phosphorus and potassium element in embodiment 2 on SAPO-34 films (by KAc exchanges) surface,
Wherein, (a) is aluminium element distribution map, and (b) is element silicon distribution map, and (c) is P elements distribution map, and (d) is potassium element distribution map.
Embodiment
Embodiment 1 is soaked with 1wt% lithium nitrates acetone soln, and 300 DEG C of air intermediate ions exchanges 8 prepare Li-SAPO- when small
34 molecular screen membranes
Step 1：2.46g deionized waters are added in 31.13g tetraethyl ammonium hydroxides solution (TEAOH, 35wt%), then
7.56g aluminium isopropoxides are weighed to be added in previous solu, be stirred at room temperature 2-3 it is small when；Then 1.665g Ludox is added dropwise
(40wt%), when stirring 1 is small；8.53g phosphoric acid solutions (H is finally slowly added dropwise3PO4, 85wt%), it is stirred overnight.Using microwave plus
Heat, when crystallization 7 is small at 180 DEG C.After product takes out, centrifugation, deionized water washing, drying, obtains SAPO-34 molecular sieves crystalline substance
Kind.The SEM figures of SAPO-34 molecular sieve seeds, as shown in Figure 1, crystal seed is the flat crystal of 300 × 300 × 100nm.SAPO-34
The XRD spectrum of molecular sieve seed, as shown in Fig. 2, be pure SAPO-34 crystalline phases, no stray crystal.
Step 2：It is clean to dry as carrier, two end seal glaze of carrier to choose the porous alumina ceramic pipe that aperture is 50nm
Afterwards, outer surface is sealed with Teflon tap, and SAPO-34 molecular sieve seeds are brushed the inner surface to ceramic tube.
Step 3：By 4.27g phosphoric acid solutions (H3PO4, 85wt%) mixed with 43.8g deionized waters, stir 5min, Ran Houjia
Enter 7.56g aluminium isopropoxides, be stirred at room temperature 3 it is small when；0.83g Ludox (40wt%) is added, stirs 30min at room temperature；So
7.78g tetraethyl ammonium hydroxides solution (TEAOH, 35wt%) is added dropwise afterwards, when stirring 1 is small at room temperature；It is eventually adding 3.0g bis- just
Propylamine, after stirring 30min at room temperature, is stirred overnight at 50 DEG C, obtains the synthesis mother liquid of SAPO-34 molecular screen membranes.By step 2
The ceramic tube for being coated with SAPO-34 crystal seeds prepared is placed in reaction kettle, the synthesis mother liquid of molecular screen membrane is added, at 220 DEG C
When hydrothermal crystallizing 5 is small, after taking-up, is rinsed well with deionized water, be put into baking oven and dry, obtain SAPO-34 molecular screen membranes
Pipe.
Wherein, the surface of the SAPO-34 molecular screen membranes without ion exchange and section SEM figures, as shown in Figure 3.Surface SEM
In figure, display carrier surface is completely covered by SAPO-34 crystal, is crosslinked between crystal perfect；In section SEM figures, display
The thickness of SAPO-34 molecular screen membranes is about 5 microns.
Step 4：When by the membrane tube that step 3 obtains, vacuum baking 4 is small at 400 DEG C, removed template method (heating and cooling speed
Rate is 1K/min), then carry out CO2/CH4Gas separation test.
Step 5：The membrane tube that step 4 is obtained is cooled to room temperature, and is placed in 3min in 1wt% lithium nitrate acetone solns, room temperature
Under dry.
Step 6：By the membrane tube that step 5 obtains in 300 DEG C of air atmospheres, (heating and rate of temperature fall when ion exchange 8 is small
It is 1 °C/min), then carry out CO2/CH4Gas separation test.
Wherein, the SEM figures of the SAPO-34 molecular screen membranes after nitric acid lithium ion exchanged, as shown in Figure 4, it is seen that ion is handed over
Change and the pattern of film is had not significant impact.
CO2/CH4Gas separates test condition：20 DEG C, atmospheric pressure 102.4kPa of temperature, gas feed rate are
4000mL/min, a mole composition is 50/50% (i.e. CO2∶CH4Molar ratio be 1: 1).With soap film flowmeter measure per-meate side
Gas flow；Formed with the gas of gas chromatograph (Shimadzu -2014C) analysis per-meate side.
The calculation formula of gas permeability：P=V/ (S*P).Wherein, V is infiltration gas (CO2Or CH4) flow, unit
Mol/s, S are 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.
The gas separation test result of molecular sieve membrane tube is as shown in table 2 before and after ion exchange.Two pieces points after ion exchange
Sub- sieve membrane CO2/CH4The separation selectivity of gaseous mixture is 93,48, and 40%, 33% has been respectively increased compared with before exchanging.
The CO of 2 embodiment 1 of table2/CH4Gas separation test result
Note：The pressure differential of membrane tube feed side and per-meate side is 3.99MPa
The 1wt% potassium acetate aqueous solution soakings of embodiment 2,300 °C of air intermediate ions exchanges 8 prepare K-SAPO-34 when small
Molecular screen membrane
It is with the difference of embodiment 1, in step 5, effective 1wt% potassium acetates of molecular screen membrane that step 4 is obtained
Aqueous solution soaking 3min, dries at room temperature.Remaining step is same as Example 1.Crystal seed used is the piece of 300 × 300 × 100nm
Shape crystal.Fig. 5 is molecular screen membrane SEM figures after ion exchange, as shown in Figure 5, it is seen that ion exchange does not have the pattern of film
Significantly affect.
CO2/CH4Gas separation test method is same as Example 1, and test result is as shown in table 3.Molecule after ion exchange
Sieve membrane CO2/CH4The separation selectivity of gaseous mixture is 60, and 33% has been respectively increased compared with before exchanging.
The CO of 3 embodiment 2 of table2/CH4Gas separation test result
Note：The pressure differential of membrane tube feed side and per-meate side is 3.99MPa
In addition, in the present embodiment, aluminium, silicon, phosphorus and potassium element the SAPO-34 film surfaces through KAc ion exchanges distribution,
As shown in Figure 6.Wherein, silicon, phosphorus and aluminium element distribute very evenly, this is normal, because these three elements are all
The constitution element of SAPO-34 molecular sieve crystal skeletons.It is also ratio although the uniformity of potassium element distribution is not so good as these three elements
More uniform, without the potassium element rich region of bulk, this explanation potassium ion is to be ion exchanged, rather than simply in table
Face deposits.
Embodiment 3 is soaked with 1wt% sodium nitrate aqueous solutions, and 310 DEG C of air intermediate ions exchanges 8 prepare Na-SAPO-34 when small
Molecular screen membrane
It is with the difference of embodiment 1, in step 5, the effective 1wt% sodium nitrate of molecular screen membrane that step 4 is obtained
Aqueous solution soaking 3min, dries at room temperature.Calcination temperature in step 4 is 310 °C.Remaining step is same as Example 1.It is used
Crystal seed is the flat crystal of 300 × 300 × 100nm.
CO2/CH4Gas separation test method is same as Example 1, and test result is as shown in table 4.Molecule after ion exchange
Sieve membrane CO2/CH4The separation selectivity of gaseous mixture is 63, and 29% has been respectively increased compared with before exchanging.
The CO of 4 embodiment 3 of table2/CH4Gas separation test result
Note：The pressure differential of membrane tube feed side and per-meate side is 3.99MPa.
Claims (8)
1. a kind of carry out the method that ion exchange prepares Ion exchange-Size exclusion film in the molten state, it is characterised in that including
Step：
Metal salt of the fusing point less than calcination temperature is supported on the SAPO-34 molecular screen membranes for removing template agent removing, after dry,
Less than calcination temperature and higher than at a temperature of metal salt fusing point, molten state ion exchange is carried out, the molecular sieve of ion exchange is made
Film；The metal salt is alkali metal salt；
Wherein, calcination temperature is calcination temperature when removing the template in molecular screen membrane.
2. the method as described in claim 1, it is characterised in that：Anion in the metal salt includes：Anaerobic acid ion
With oxygen-containing acid ion；
Wherein, anaerobic acid ion includes：F-、Cl-、Br-、I-And S-；Oxygen-containing acid group includes：NO3 -、ClO3 -、ClO4 -、SO4 2-、
CO3 2-And CH3COO-。
3. the method as described in claim 1, it is characterised in that：It is described to be supported on metal salt of the fusing point less than calcination temperature
The method gone on the SAPO-34 molecular screen membranes of template agent removing includes：By dip coating, spin-coating method, spraying process or spread coating, by gold
Belong to front, reverse side and tow sides that salt is supported on molecular screen membrane.
4. method as claimed in claim 3, it is characterised in that：The dip coating, its operating procedure are：Molecular screen membrane is placed in
Concentration is in the metal salt solution of 0.01~50wt%, is soaked 1 second~2 days at -40~100 DEG C.
5. method as claimed in claim 4, it is characterised in that：The concentration of the metal salt solution is 0.1~5wt%；Immersion
Time is 1 second~180 minutes；Solvent in metal salt solution includes：Acetone, water, alcohols.
6. the method as described in claim 1, it is characterised in that：The temperature range of the drying is：Room temperature~200 DEG C.
7. the method as described in claim 1, it is characterised in that：The condition of the molten state ion exchange is：
The temperature of ion exchange is 100~500 DEG C, when the time of ion exchange is 1~8 small；
Processing atmosphere in ion exchange includes：Vacuum, inert gas, air, pure oxygen or diluted oxygen；
Heating rate in ion exchange is 0.1~5 DEG C/min.
8. the method as described in claim 1, it is characterised in that：The molecular screen membrane of the ion exchange is that one kind can be used for acidity
The molecular screen membrane of gas separation removal in gas system；Wherein, which includes：CO2-CH4System, CO2-H2
System and CO2-N2System.
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| CN108816269B (en) * | 2018-06-11 | 2021-06-08 | 中国科学院广州能源研究所 | Core-shell metal hybrid silicate-1/SAPO-5 composite molecular sieve ceramic membrane and preparation method thereof |
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| US7119245B1 (en) * | 2001-10-25 | 2006-10-10 | Sandia Corporation | Synthesis of an un-supported, high-flow ZSM-22 zeolite membrane |
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| CN1308019A (en) * | 1999-12-30 | 2001-08-15 | 中国科学院大连化学物理研究所 | Porous metal-silicon aluminium phosphate molecular sieve and its synthesis process |
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| CN101279207A (en) * | 2008-05-20 | 2008-10-08 | 吉林大学 | Preparation of SAPO-34 molecular sieve film for selectively separating methane gas |
| CN101767034B (en) * | 2008-12-31 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method of catalysis material containing ZSM-5/Y type composite molecular sieve |
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| US7119245B1 (en) * | 2001-10-25 | 2006-10-10 | Sandia Corporation | Synthesis of an un-supported, high-flow ZSM-22 zeolite membrane |
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