CN103894076A - Method for preparing high-performance molecular sieve membrane through ion exchange at melting state - Google Patents
Method for preparing high-performance molecular sieve membrane through ion exchange at melting state Download PDFInfo
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Abstract
The invention discloses a method for preparing a high-performance molecular sieve membrane through ion exchange at a melting state. The method comprises the steps of loading metal salt with the melting point being lower than a roasting temperature onto a molecular sieve membrane with a template agent being removed, drying the molecular sieve membrane, and carrying out melting-state ion exchange under the situation that the temperature is lower than the roasting temperature and higher than the melting point of metal salt to obtain the ion exchange molecular sieve membrane, wherein the roasting temperature is generated when the template agent in the molecular sieve membrane is removed. By the method, the CO2/CH4 selectivity of the molecular sieve membrane can be remarkably improved.
Description
Technical field
The present invention relates to a kind of preparation method of molecular screen membrane, particularly relate to a kind of method that high-performance molecular screen membrane is prepared in ion-exchange of carrying out under molten condition.
Background technology
The whole world is about 3 tcms to the Year's consumption of natural gas, accounts for 23.7% of energy aggregate demand.Natural gas occupies critical role in global energy strategy.In natural gas, the content of methane accounts for 75%-90%, in addition, conventionally contains hydrocarbon and some impurity such as a large amount of ethane, propane, butane.These impurity comprise water, carbon dioxide, nitrogen, hydrogen sulfide etc., have had a strong impact on storage and the transportation of natural gas.Therefore, the whole world is annual spends 5,000,000,000 dollars for natural gas purification, is mainly the CO removing in natural gas
2.According to statistics, the U.S. exceedes 20% natural gas due to too high CO
2content and need advanced treating.The CO of the Shell Oil Company in the gas field of Russian Sakhalin, Indonesia and South China Sea
2content is even up to more than 40%.
At present, CO
2removing process mainly contains organic amine absorption and film separates.Wherein, although there is the shortcomings such as equipment investment is high, bulky, system maintenance is complicated, absorbent regeneration energy consumption height in organic amine absorbing and removing technique comparative maturity; And film separates advantages such as having energy consumption is low, continuity operation, equipment investment is low, volume is little, easy care, receive very big concern [Ind.Eng.Chem.Res.41 (2002) 1393].Although traditional polymeric membrane is widely used at separation field, due to the defect of macromolecular material nature, at high pressure CO
2lower can generation plastifies phenomenon, thereby causes optionally declining to a great extent.And molecular screen membrane has excellent heat, chemistry and mechanical stability, be applicable to very much high pressure CO
2harsh isolating environment.
Large quantity research report shows, the T[J.Mater.Chem.14 (2004) 924 of aperture], DDR[Micropor.Mesopor.Mater.68 (2004) 71] and SAPO-34[J.Membr.Sci.363 (2010) 29 and quoted passage thereof] the most applicable CO of molecular screen membrane
2-CH
4separate, because CO
2diffusion in small pore molecular sieve crystal duct is far faster than CH
4, can obtain high separation selectivity, thereby can reduce the methane loss in natural gas processing process.SAPO-34 is the aperture silicon phosphorus aluminium type molecular sieve with CHA structure, and its aperture is 0.38 nanometer, is applicable to very much CO
2-CH
4separate.CO
2and CH
4molecular dynamics diameter be respectively 0.33 and 0.38 nanometer, greatly (molecule screening) of diffusion coefficient difference in SAPO-34 duct, meanwhile, the CO of polarity
2the absorption of molecule in SAPO-34 duct is stronger, and CO is also selected in absorption
2.
The separating property of molecular screen membrane is subject to the impact of many factors: as framework si-al ratio, crystal seed size, Template Types, the thickness of film, cation type, CO
2the impact [J.Membr.Sci.335 (2009) 32 and quoted passage thereof] of the conditions such as concentration, support, roasting condition, defect mending method.Wherein, ion-exchange is that one simply and effectively improves molecular screen membrane CO
2/ CH
4optionally method.
Hydrogen ion in molecular sieve crystal is exchanged for to alkaline metal ion and can strengthens the alkalescence of molecular sieve, improve its to sour gas (as CO
2) adsorptive selectivity.Meanwhile, the introducing of metal ion also can change the duct size of molecular sieve, thereby the diffusion of change gas is selective.Walton philosophy adopts different types of cation to carry out ion-exchange to X-type and Y zeolite, and result shows, the molecular sieve CO of different ions exchange
2adsorption capacity increase rate Cs
+< Rb
+< K
+< Na
+< Li
+[Micropor.Mesopor.Mater.91 (2006) 78].High alumina beta-molecular sieve is carried out to alkali metal to Yang etc. and alkaline earth gold is bent ion-exchange, the molecular sieve CO of different ions exchange
2adsorption capacity increase rate Mg
2+< Cs
+< Ca
2+< Ba
2+< Li
+< Na
+< K
+[Micropor.Mesopor.Mater.135 (2010) 90].What the NaY type molecular screen membrane of the report alkali metal ion exchanges such as Kusakabe exchanged than alkaline-earth metal ions has higher permeability [J.Membr.Sci.148 (1998) 13].Hasegawa etc. find through K
+, Rb
+and Cs
+the NaY molecular screen membrane of exchange, its CO
2/ N
2separation selectivity is brought up to 34～40[Sep.Purif.Technol.22-23 (2001) 319 from 19].Sun Jihong etc. first utilize lithium ion aqueous solution to make sodium type low silicon-aluminum X type molecular sieve have certain lithium ion exchanged degree, then obtain by solid phase exchange process the lithium type low silicon aluminum X-shape molecular sieve (China Patent No.: 200710121786.2) that exchange degree is greater than 96%.The Li such as Hong
+, Na
+, K
+, NH
4 +and Cu
2+at non-aqueous solution intermediate ion exchange H-SAPO-34 molecular screen membrane, make CO
2/ CH
4separation selectivity improves 60%, but CO
2permeability has decline [Micropor.Mesopor.Mater.106 (2007) 140].
But it is gold to be bent to salt be dissolved in and make salting liquid in solvent that traditional ion-exchange is prepared molecular screen membrane, then molecular sieve powder or film is placed in to solution and carries out ion-exchange.This ion-exchange process speed is slow, the CO of the molecular screen membrane preparing
2/ CH
4selectively need to improve.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method that high-performance molecular screen membrane is prepared in ion-exchange of carrying out under molten condition.By the method, can improve the gas separating property of molecular screen membrane, as CO
2/ CH
4selectively.
For solving the problems of the technologies described above, of the present inventionly under molten condition, carry out the method that high performance Ion exchange-Size exclusion film is prepared in ion-exchange, comprise step:
Fusing point is bent to salt lower than the gold of sintering temperature and load on the molecular screen membrane of removing template, after being dried, at lower than sintering temperature and the temperature higher than slaine fusing point, carry out molten state ion-exchange, make the molecular screen membrane of ion-exchange;
Wherein, sintering temperature when sintering temperature is the template of removing in molecular screen membrane.
The described molecular screen membrane of having removed template comprises: SAPO-34, ZSM-5, Silicalite-1, TS-1, AlPO-18, SAPO-18, AlPO
4-5, SAPO-5, DDR, MCM-22, Beta and A molecular screen membrane, be preferably SAPO-34 molecular screen membrane.
In described slaine, its cation comprises: alkali metal, alkaline-earth metal and transition metal ions; Anion in slaine comprises: oxygen-free acid radical ion and oxyacid radical ion; Wherein, oxygen-free acid radical ion comprises: F
-, Cl
-, Br
-, I
-and S
-; Oxyacid root comprises: NO
3 -, ClO
3 -, ClO
4 -, SO
4 2-, CO
3 2-and CH
3cOO
-.
Described slaine comprises: sodium nitrate, potassium nitrate, lithium nitrate, rubidium nitrate, magnesium nitrate, sodium chlorate, sodium perchlorate, calcium chlorate, potassium chlorate, Potassium Benzoate, magnesium benzoate, sodium acetate, potassium acetate, lithium acetate, lithium formate, sodium formate, potassium formate and calcium formate.Typical slaine fusing point can be as shown in table 1.
The fusing point of the typical slaine of table 1
The described method that fusing point is loaded on the molecular screen membrane of removing template lower than the slaine of sintering temperature comprises: by dip coating, spin-coating method, spraying process or spread coating, slaine is loaded on to front, reverse side and the tow sides of molecular screen membrane.Wherein, dip coating, its operating procedure is: molecular screen membrane is placed in to the metal salt solution that concentration is 0.01～50wt%, soaks 1 second～2 days at-40～100 ℃.The concentration of this metal salt solution is preferably 0.1～5wt%, and soak time is preferably 1 second～and 180 minutes; Solvent in metal salt solution can be can dissolve arbitrarily this gold to bend the organic and inorganic solvent of salt or the mixture of multi-solvents, comprising: acetone, water, alcohols etc.
Described dry temperature range is: room temperature～200 ℃.
The condition of described molten state ion-exchange is: the temperature of ion-exchange is 100～500 ℃, and the time of ion-exchange is 1～8 hour; Processing atmosphere in ion-exchange comprises: the oxygen of vacuum, inert gas, air, pure oxygen or dilution; Heating rate in ion-exchange is 0.1～5 ° of C/min.
The molecular screen membrane of the ion-exchange that the present invention makes is a kind of molecular screen membrane of the gas separation removal that can be used for sour gas system; Wherein, this sour gas system comprises: CO
2-CH
4system, CO
2-H
2system and CO
2-N
2system.The molecular screen membrane of i.e. this ion-exchange can be used for comprising that following gas separates or removes: CO
2-CH
4separation, CO
2-H
2separate and CO
2-N
2separate.
Wherein, for carry out the method that high performance SAPO-34 molecular screen membrane is prepared in ion-exchange under molten condition, comprise the steps:
1) SAPO-34 molecular sieve crystal seed is synthetic
By aluminium source, (aluminium source comprises: aluminium isopropoxide, Al (OH)
3, pure aluminum, comprises the aluminium salt of aluminum nitrate, aluminium chloride, aluminum sulfate and aluminum phosphate etc.) join in tetraethyl ammonium hydroxide (TEAOH) solution, fully, after hydrolysis, add successively Ludox and phosphoric acid, stir 12～96 hours, obtain crystal seed reactant liquor, then, heating using microwave at 170～210 ℃, crystallization 4～7 hours, centrifugal, washing, dry, obtain SAPO-34 molecular sieve crystal seed;
Wherein, the component mole proportioning in crystal seed reactant liquor is: 1Al
2o
3: 1～2P
2o
5: 0.3～0.6SiO2: 1～3 (TEA)
2o: 55～150H
2o (total Water in crystal seed reactant liquor);
2) crystal seed applies
Select porous ceramic pipe as carrier, carrier two ends envelopes glaze, after cleaning and drying, after outer surface sealing (wrapping up with Teflon tap as adopted), SAPO-34 molecular sieve crystal seed is applied to the inner surface of porous ceramic pipe, must have applied the earthenware of SAPO-34 molecular sieve crystal seed;
3) SAPO-34 molecular screen membrane is synthetic
Aluminium isopropoxide is joined in phosphoric acid solution, fully, after hydrolysis, add successively Ludox, tetraethyl ammonium hydroxide and di-n-propylamine (DPA), stir 12～96 hours, obtain the synthesis mother liquid of molecular screen membrane; Wherein, mole proportioning of the component in synthesis mother liquid is: 1Al
2o
3: 1～1.5P
2o
5: 0.3～0.6SiO
2: 1～2TEAOH: 1.5～2.0DPA: 70～150H
2o;
Then, by step 2) coating prepared the earthenware of SAPO-34 molecular sieve crystal seed be placed in reactor, add the synthesis mother liquid of molecular screen membrane, at 210～230 ℃, hydrothermal crystallizing 3～24 hours, washing, dry, obtain SAPO-34 molecular screen membrane pipe;
4) template is removed in roasting
By step 3) roasting 2～8 hours at 370～700 ℃ of the SAPO-34 molecular screen membrane pipe that obtains, obtain removing the SAPO-34 molecular screen membrane of template (organic amine tetraethyl ammonium hydroxide);
5) gold is bent to salt and loads on step 4) on the SAPO-34 molecular screen membrane of the removal template that obtains after, dry, lower than step 4) sintering temperature and temperature higher than slaine fusing point under, carry out molten state ion-exchange treatment 1～8 hour, obtain high performance SAPO-34 molecular screen membrane.In this step, ion-exchange temperature used is lower and higher than gold salt fusing point in the wrong than sintering temperature, thereby energy deposite metal salt makes the cation in its metal cation and molecular screen membrane carry out ion-exchange.
Described step 1) in, SAPO-34 molecular sieve crystal seed is of a size of 50～1000 nanometers.
Described step 2) in, the aperture of porous ceramic pipe is 5 nanometer～2000 nanometers, its material comprises: Al
2o
3, TiO
2, ZrO
2, SiC; Coating process comprises: spread coating and dip coating.
Described step 4) in, calcination atmosphere comprises: the dilution oxygen of inert gas (as nitrogen or argon gas), vacuum, air, oxygen and arbitrary proportion; In roasting, intensification and rate of temperature fall are no more than 2K/ minute.
Described step 5) in, selected slaine is described above.
Step 5) in, the method that slaine loads on the SAPO-34 molecular screen membrane of removing template comprises: by dip coating, spin-coating method or spread coating, slaine is loaded on to front, reverse side (one side contacting with carrier) and the tow sides of SAPO-34 molecular screen membrane.Wherein, the operating procedure of dip coating is: SAPO-34 molecular screen membrane is placed in to the metal salt solution that concentration is 0.01～50wt%, soaks 1 second～2 days under-40～100 ° of C.This gold is bent the concentration of salting liquid and is preferably 0.1～5wt%, and soak time is preferably 1 second～and 180 minutes.The solvent that gold is bent in salting liquid can be to dissolve arbitrarily the organic and inorganic solvent of this slaine or the mixture of multi-solvents, as comprises: acetone and water.
Step 5) in, dry temperature range is: room temperature～200 ℃; The sintering temperature of the temperature (lower than step 4) of ion-exchange and higher than the temperature of slaine fusing point) be preferably 100～500 ℃, the processing atmosphere in ion-exchange comprises: the oxygen of vacuum, inert gas (comprising: nitrogen, argon gas and helium etc.), air, pure oxygen or dilution; Heating rate in ion-exchange is 0.1～5 ℃/min.
The present invention adopts novel ion-exchange process, fusing point is loaded to lower than the metallic salt of sintering temperature on the molecular screen membrane surface of removed template method, then, at the temperature higher than slaine fusing point (temperature that raises and higher than slaine fusing point used, with deposite metal salt), carry out ion-exchange.The slaine of load is under molten condition, can with molecular screen membrane in cation carry out ion-exchange, thereby significantly improve the CO of molecular screen membrane
2/ CH
4selectively.
Accompanying drawing explanation
Below in conjunction with accompanying drawing and the specific embodiment, the present invention is further detailed explanation:
Fig. 1 is SEM (ESEM) figure of the SAPO-34 molecular sieve crystal seed in embodiment 1;
Fig. 2 is the XRD figure of the SAPO-34 molecular sieve crystal seed in embodiment 1;
Fig. 3 is the SEM figure of the SAPO-34 molecular screen membrane (without ion-exchange) in embodiment 1, wherein, (a) is the SEM figure on molecular screen membrane surface, is (b) the SEM figure of molecular screen membrane section;
Fig. 4 is the SEM figure of the SAPO-34 molecular screen membrane after lithium nitrate ion-exchange in embodiment 1;
Fig. 5 is the figure of the SEM through the SAPO-34 of potassium acetate ion-exchange molecular screen membrane in embodiment 2, wherein, (a) is film pipe top view, is (b) film pipe cutaway view;
Fig. 6 is aluminium, silicon, phosphorus and potassium element in embodiment 2 distribution map on SAPO-34 film (through KAc exchange) surface, wherein, (a) be aluminium element distribution map, (b) be element silicon distribution map, (c) being P elements distribution map, is (d) potassium element distribution map.
The specific embodiment
Embodiment 1 use 1wt% lithium nitrate acetone soln soaks, 8 hours preparation Li-SAPO-34 molecular screen membranes of 300 ℃ of air intermediate ion exchanges
Step 1: add 2.46g deionized water in 31.13g tetraethyl ammonium hydroxide solution (TEAOH, 35wt%), then take 7.56g aluminium isopropoxide and join in aforementioned solution, stirring at room temperature 2-3 hour; Then drip 1.665g Ludox (40wt%), stir 1 hour; The last 8.53g phosphoric acid solution (H that slowly drips
3pO
4, 85wt%), stirring is spent the night.Adopt heating using microwave, crystallization 7 hours at 180 ℃.After product takes out, centrifugal, deionized water washing, dries, and obtains SAPO-34 molecular sieve crystal seed.The SEM figure of SAPO-34 molecular sieve crystal seed, as shown in Figure 1, the flat crystal that crystal seed is 300 × 300 × 100nm.The XRD collection of illustrative plates of SAPO-34 molecular sieve crystal seed as shown in Figure 2, is pure SAPO-34 crystalline phase, without stray crystal.
Step 2: choose aperture and be the porous alumina ceramic pipe of 50nm as carrier, carrier two ends envelope glaze, after cleaning and drying, outer surface seals with Teflon tap, SAPO-34 molecular sieve crystal seed is brushed to the inner surface of earthenware.
Step 3: by 4.27g phosphoric acid solution (H
3pO
4, 85wt%) mix with 43.8g deionized water, stir 5min, then add 7.56g aluminium isopropoxide, at room temperature stir 3 hours; Add 0.83g Ludox (40wt%), under room temperature, stir 30min; Then drip 7.78g tetraethyl ammonium hydroxide solution (TEAOH, 35wt%), under room temperature, stir 1 hour; Finally add 3.0g di-n-propylamine, under room temperature, stir after 30min, at 50 ℃, stir and spend the night, obtain the synthesis mother liquid of SAPO-34 molecular screen membrane.Coating prepared by step 2 earthenware of SAPO-34 crystal seed be placed in reactor, add the synthesis mother liquid of molecular screen membrane, hydrothermal crystallizing 5 hours at 220 ℃, after taking-up, rinse well by deionized water, put into baking oven and dry, obtain SAPO-34 molecular screen membrane pipe.
Wherein, without surface and the section SEM figure of the SAPO-34 molecular screen membrane of ion-exchange, as shown in Figure 3.In the SEM figure of surface, show that carrier surface is covered completely by SAPO-34 crystal, crosslinked perfect between crystal; In section SEM figure, show that the thickness of SAPO-34 molecular screen membrane is about 5 microns.
Step 4: the film pipe that step 3 is obtained vacuum baking 4 hours at 400 ℃, removed template method (heat up and rate of temperature fall is 1K/min), then carries out CO
2/ CH
4gas discrete testing.
Step 5: the film pipe that step 4 is obtained is cooled to room temperature, is placed in 1wt% lithium nitrate acetone soln 3min, under room temperature, dries.
Step 6: the film pipe that step 5 is obtained is in 300 ℃ of air atmospheres, and ion-exchange 8 hours (intensification and rate of temperature fall are 1 ° of C/min), then carries out CO
2/ CH
4gas discrete testing.
Wherein, the SEM figure of the SAPO-34 molecular screen membrane after lithium nitrate ion-exchange, as shown in Figure 4, visible ion-exchange does not have a significant effect to the pattern of film.
CO
2/ CH
4gas discrete testing condition: 20 ℃ of temperature, atmospheric pressure 102.4kPa, gas feed rate is 4000mL/min, mole consisting of 50/50% (is CO
2: CH
4mol ratio be 1: 1).Measure the gas flow of per-meate side with soap film flowmeter; Analyze the gas composition of per-meate side with gas chromatograph (Shimadzu-2014C).
The computing formula of gas permeability: p=V/ (S*P).Wherein, V is infiltration gas (CO
2or CH
4) flow, the mol/s of unit, S is membrane area, the m of unit
2; P is the pressure differential of film pipe feed side and per-meate side, the Pa of unit.
Separation selectivity computing formula: f=p
cO2/ p
cH4, i.e. CO
2with CH
4the ratio of permeability.
Before and after ion-exchange, the gas discrete testing result of molecular screen membrane pipe is as shown in table 2.Two molecular screen membrane CO after ion-exchange
2/ CH
4the separation selectivity of gaseous mixture is 93,48, has improved respectively 40%, 33% compared with before exchange.
The CO of table 2 embodiment 1
2/ CH
4gas discrete testing result
Note: the pressure differential of film pipe feed side and per-meate side is 3.99MPa
Embodiment 2 use 1wt% potassium acetate aqueous solution soaking, 8 hours preparation K-SAPO-34 molecular screen membranes of 300 ° of C air intermediate ion exchanges
Be with the difference of embodiment 1, in step 5, the effective 1wt% potassium acetate of the molecular screen membrane aqueous solution soaking 3min that step 4 is obtained, dries under room temperature.All the other steps are identical with embodiment 1.Crystal seed used is the flat crystal of 300 × 300 × 100nm.Fig. 5 is the molecular screen membrane SEM figure after ion-exchange, and as shown in Figure 5, visible ion-exchange does not have a significant effect to the pattern of film.
CO
2/ CH
4gas discrete testing method is identical with embodiment 1, and test result is as shown in table 3.Molecular screen membrane CO after ion-exchange
2/ CH
4the separation selectivity of gaseous mixture is 60, has improved respectively 33% compared with before exchange.
The CO of table 3 embodiment 2
2/ CH
4gas discrete testing result
Note: the pressure differential of film pipe feed side and per-meate side is 3.99MPa
In addition, in the present embodiment, aluminium, silicon, phosphorus and potassium element are in the distribution on the SAPO-34 film surface through KAc ion-exchange, as shown in Figure 6.Wherein, the distributing very evenly of silicon, phosphorus and aluminium element, this is normal, because these three kinds of Constitution Elements that element is all SAPO-34 molecular sieve crystal skeleton.Although the uniformity that potassium element distributes is not as these three kinds of elements, is also more uniform, there is no the potassium element rich region of bulk, this explanation potassium ion is by ion-exchange, rather than simply at surface deposition.
Embodiment 3 use 1wt% sodium nitrate aqueous solutions soak, 8 hours preparation Na-SAPO-34 molecular screen membranes of 310 ℃ of air intermediate ion exchanges
Be with the difference of embodiment 1, in step 5, the effective 1wt% sodium nitrate aqueous solution of molecular screen membrane that step 4 is obtained soaks 3min, under room temperature, dries.Sintering temperature in step 4 is 310 ° of C.All the other steps are identical with embodiment 1.Crystal seed used is the flat crystal of 300 × 300 × 100nm.
CO
2/ CH
4gas discrete testing method is identical with embodiment 1, and test result is as shown in table 4.Molecular screen membrane CO after ion-exchange
2/ CH
4the separation selectivity of gaseous mixture is 63, has improved respectively 29% compared with before exchange.
The CO of table 4 embodiment 3
2/ CH
4gas discrete testing result
Note: the pressure differential of film pipe feed side and per-meate side is 3.99Mpa.
Claims (11)
1. under molten condition, carry out the method that Ion exchange-Size exclusion film is prepared in ion-exchange, it is characterized in that, comprise step:
Fusing point is loaded on lower than the slaine of sintering temperature on the molecular screen membrane of removing template, after being dried, at lower than sintering temperature and the temperature higher than slaine fusing point, carry out molten state ion-exchange, make the molecular screen membrane of ion-exchange;
Wherein, sintering temperature when sintering temperature is the template of removing in molecular screen membrane.
2. the method for claim 1, is characterized in that: the described molecular screen membrane of having removed template comprises: SAPO-34, ZSM-5, Silicalite-1, TS-1, AlPO-18, SAPO-18, AlPO
4-5, SAPO-5, DDR, MCM-22, Beta and A molecular screen membrane.
3. method as claimed in claim 2, is characterized in that: the described molecular screen membrane of having removed template is SAPO-34 molecular screen membrane.
4. the method for claim 1, is characterized in that: in described slaine, its cation comprises: metal and transition metal ions on alkali metal, alkali; Anion in slaine comprises: oxygen-free acid radical ion and oxyacid radical ion;
Wherein, oxygen-free acid radical ion comprises: F
-, Cl
-, Br
-, I
-and S
-; Oxyacid root comprises: NO
3 -, ClO
3 -, ClO
4 -, SO
4 2-, CO
3 2-and CH
3cOO
-.
5. method as claimed in claim 4, is characterized in that: described gold is bent salt and comprised: sodium nitrate, potassium nitrate, lithium nitrate, rubidium nitrate, magnesium nitrate, sodium chlorate, sodium perchlorate, calcium chlorate, potassium chlorate, Potassium Benzoate, magnesium benzoate, sodium acetate, potassium acetate, lithium acetate, lithium formate, sodium formate, potassium formate and calcium formate.
6. the method for claim 1, it is characterized in that: the described method that fusing point is loaded on the molecular screen membrane of removing template lower than the slaine of sintering temperature comprises: by dip coating, spin-coating method, spraying process or spread coating, slaine is loaded on to front, reverse side and the tow sides of molecular screen membrane.
7. method as claimed in claim 6, is characterized in that: described dip coating, its operating procedure is: molecular screen membrane is placed in to the metal salt solution that concentration is 0.01～50wt%, soaks 1 second～2 days at-40～100 ℃.
8. method as claimed in claim 7, is characterized in that: the concentration of described metal salt solution is 0.1～5wt%; Soak time is 1 second～180 minutes; Solvent in metal salt solution comprises: acetone, water, alcohols.
9. the method for claim 1, is characterized in that: described dry temperature range is: room temperature～200 ℃.
10. the method for claim 1, is characterized in that: the condition of described molten state ion-exchange is:
The temperature of ion-exchange is 100～500 ℃, and the time of ion-exchange is 1～8 hour;
Processing atmosphere in ion-exchange comprises: the oxygen of vacuum, inert gas, air, pure oxygen or dilution;
Heating rate in ion-exchange is 0.1～5 ° of C/min.
11. the method for claim 1, is characterized in that: the molecular screen membrane of described ion-exchange is a kind of molecular screen membrane of the gas separation removal that can be used for sour gas system; Wherein, this sour gas system comprises: CO
2-CH
4system, CO
2-H
2system and CO
2-N
2system.
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| CN107433140A (en) * | 2017-09-24 | 2017-12-05 | 韩小学 | A kind of preparation method of high flux molecular screen membrane |
| CN108816269A (en) * | 2018-06-11 | 2018-11-16 | 中国科学院广州能源研究所 | A kind of hud typed metal hybrid silicate-1/SAPO-5 composite molecular screen ceramic membrane and preparation method thereof |
| WO2019030322A1 (en) | 2017-08-10 | 2019-02-14 | Total Research & Technology Feluy | Meapo-18 membranes with lamellar crystal morphology and their preparation |
| CN115707510A (en) * | 2021-08-18 | 2023-02-21 | 中国科学院大连化学物理研究所 | Preparation method and application of modified MOR molecular sieve |
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| CN108816269A (en) * | 2018-06-11 | 2018-11-16 | 中国科学院广州能源研究所 | A kind of hud typed metal hybrid silicate-1/SAPO-5 composite molecular screen ceramic membrane and preparation method thereof |
| 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 |
| CN115707510A (en) * | 2021-08-18 | 2023-02-21 | 中国科学院大连化学物理研究所 | Preparation method and application of modified MOR molecular sieve |
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