CN103506015A - Method for preparing ion exchange SAPO-34 molecular sieve membrane - Google Patents
Method for preparing ion exchange SAPO-34 molecular sieve membrane Download PDFInfo
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- CN103506015A CN103506015A CN201210191146.XA CN201210191146A CN103506015A CN 103506015 A CN103506015 A CN 103506015A CN 201210191146 A CN201210191146 A CN 201210191146A CN 103506015 A CN103506015 A CN 103506015A
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- sapo
- molecular sieve
- screen membrane
- molecular screen
- sieve membrane
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Abstract
The invention discloses a method for preparing ion exchange SAPO-34 molecular sieve membrane, comprising the following steps of: (1) synthesizing SAPO-34 molecular sieve seeds; (2) loading the SAPO-34 molecular sieve seeds on a porous carrier; (3) synthesizing a SAPO-34 molecular sieve membrane; (4) loading a metal salt with a melting point lower than a roasting temperature in a step (5) on the SAPO-34 molecular sieve membrane; and (5) high temperature roasting to remove a template, and simultaneously carrying out ion exchange to obtain the ion exchange SAPO-34 molecular sieve membrane. By loading metal salts with a low melting point on the surface of the molecular sieve membrane, the method combines two steps: template removal and ion exchange, into one step, thereby simplifying a preparation process of the SAPO-34 molecular sieve membrane, reduces synthesis cost, and simultaneously raising gas separating performance of the SAPO-34 molecular sieve membrane.
Description
Technical field
The present invention relates to technical field of chemical separation, particularly relate to a kind of method of preparing ion-exchange SAPO-34 molecular screen membrane.
Background technology
Natural gas is and oil, coal important energy source and chemical raw material arranged side by side.The whole world, to nearly 3 tcm/years of the Year's consumption of natural gas, accounts for 23.7% of energy aggregate demand.
Natural gas contains some impurity conventionally, as water, carbon dioxide, nitrogen, hydrogen sulfide etc.In order to reach pipeline, carry requirement, all natural gases all will be through processing in various degree.Natural gas purification is maximum at present industrial gasses processing procedure, and approximately 5,000,000,000 dollars/year of world markets, are mainly from natural gas, to remove CO
2.According to statistics, the U.S. surpasses 20% natural gas due to too high CO
2content and need advanced treating.The Shell Oil Company are in the gas field of Russian Sakhalin, the CO in the gas field of Indonesia and South China Sea
2content is even up to more than 40%.
Organic amine absorbing and removing CO
2be very ripe technique, obtained commercial Application widely.But amine absorbs the following problem that exists, as high in equipment investment, bulky, system maintenance is complicated, absorbent regeneration energy consumption is high.
Film separation has the advantages such as energy consumption is low, continuity operation, equipment investment is low, volume is little, easy care, has received very big concern [Ind.Eng.Chem.Res.41 (2002) 1393].Polymeric membrane has the advantages such as low, the easy processing processing of cost, but due to the defect of macromolecular material nature, polymeric membrane can not be processed high CO
2the natural gas of content, because high pressure CO
2can plastify polymeric membrane, cause selectively declining to a great extent.For polymeric membrane, inoranic membrane has excellent chemistry, heat and mechanical stability, is very suitable for harsh isolating environment.Molecular screen membrane, as representational a kind of in inoranic membrane, has uniform molecular scale duct and unique absorption property, and it can utilize the difference of gas molecule diffusion coefficient and the difference of absorption property to realize separated.The molecular sieve by selection with suitable aperture, the diffusion coefficient of gas with various molecule in molecular sieve pore passage can have the difference of several orders of magnitude, therefore can obtain high diffusion selective (molecule screening).Meanwhile, the selective absorption of gas molecule in molecular sieve crystal duct also can obtain considerable selective [Ind.Eng.Chem.Res.48 (2009) 4638].
About molecular screen membrane, remove the CO in natural gas
2existing a large amount of report, but 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
4separation, 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 that the aperture silicon phosphorus aluminium type molecular sieve ，Qi aperture with CHA structure is 0.38 nanometer, is applicable to very much CO
2-CH
4separated.CO
2and CH
4molecular dynamics diameter be respectively 0.33 and 0.38 nanometer, diffusion coefficient difference greatly (molecule screening) 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 SAPO-34 molecular screen membrane is subject to 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.Zhang Yanfeng etc. have developed novel synthetic, roasting and defect mending method, have improved greatly separating property and the preparation repeatability of film.Under 4.6MPa pressure reduction, CO
2permeability reached 8.2 * 10
-7mol/ (m
2sPa), CO
2/ CH
4selectively surpassed 55(U.S. Patent Application No.: US 20120006194A1).
John L Fa Er Konas etc., by least one surface of porous membrane supporter is contacted with aging synthesized gel rubber, are prepared high-selectivity supported SAPO membranes (Chinese Patent Application No.: 200580008446.8).The synthetic methods of employing crystal seed induction secondary such as Zhu Guangshan synthesize the SAPO-34 molecular screen membrane (Chinese Patent Application No.: 200810050714.8) of separating methane gas.Lee's generation light etc. synthesizes for CO
2/ CH
4separated high flux and the SAPO-34 film of high selectivity (Chinese Patent Application No.: 200780017302.8), under 222kPa feed pressure and 138kPa pressure reduction, for 50/50CO
2/ CH
4mixture (295K) has the CO that is greater than 100
2/ CH
4selectively.(the U.S. Patent Application No.: research US 20120006194A1) shows such as Falconer, roasting SAPO-34 molecular screen membrane under vacuum and inert atmosphere, can more thoroughly remove template, and the existence of oxygen can cause the generation of coking, thereby reduce the CO of molecular screen membrane
2permeability.The SAPO-34 molecular screen membrane of preparing under 4.6MPa, at N
2and the vacuum condition template agent removing that goes down, its CO
2permeability ratio is airborne has improved nearly one times, and has selectively declined 8～9%.
Ion-exchange is to improve molecular screen membrane CO
2/ CH
4a kind of simple and effective method optionally.Hydrogen ion in molecular sieve crystal is exchanged for to the alkalescence that alkaline metal ion can strengthen molecular sieve, improve its to sour gas (as CO
2) adsorptive selectivity.The introducing of metal ion also can change the duct size of molecular sieve, thereby the diffusion of change gas is selective.The NaY type molecular screen membrane of the report alkali metal ion such as Kusakabe exchange has a higher permeability [J.Membr.Sci. 148 (1998) 13] than alkaline-earth metal ions exchange.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 by solid phase exchange process, obtain the lithium type low silicon aluminum X-shape molecular sieve (Chinese Patent Application No.: 200710121786.2) that exchange degree is greater than 96%.The Li such as Hong
+, Na
+, K
+, NH
4 +and Cu
2+the H-SAPO-34 molecular screen membrane that exchanges roasting at non-aqueous solution intermediate ion, makes CO
2/ CH
4separation selectivity improves 60%, but CO
2permeability has decline [Microporous Mesoporous Mater.106 (2007) 140 – 146].
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of preparing ion-exchange SAPO-34 molecular screen membrane, and it can improve the gas separating property of SAPO-34 molecular screen membrane.
For solving the problems of the technologies described above, the present invention prepares the method for ion-exchange SAPO-34 molecular screen membrane, comprises the steps:
1) synthetic SAPO-34 molecular sieve crystal seed;
2) SAPO-34 molecular sieve crystal seed is loaded on porous carrier;
3) synthetic SAPO-34 molecular screen membrane;
4) on SAPO-34 molecular screen membrane load fusing point lower than the slaine of the sintering temperature of step 5);
5) dry, at 370～700 ℃, roasting is 2～24 hours, obtains the SAPO-34 molecular screen membrane of ion-exchange.
Described step 1), can adopt following method of operating: aluminium isopropoxide is joined in tetraethyl ammonium hydroxide solution, fully, after hydrolysis, add successively Ludox and phosphoric acid, stirring is spent the night, and obtains crystal seed mother liquor, and mole proportioning of crystal seed mother liquor is: 1Al
2o
3: 1～2P
2o
5: 0.3～0.6SiO
2: 1～3 (TEA)
2o: 55～150H
2o; Then, at 170～210 ℃, crystallization 4～7 hours, centrifugal, washing, dry, obtain SAPO-34 molecular sieve crystal seed.
Described step 3), can adopt following method of operating: aluminium isopropoxide is joined in phosphoric acid solution, fully after hydrolysis, add successively Ludox, tetraethyl ammonium hydroxide and di-n-propylamine, stirring is spent the night, and obtains the synthesis mother liquid of molecular screen membrane, and mole proportioning of 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) load prepared the porous carrier of SAPO-34 molecular sieve crystal seed be placed in reactor, add molecular screen membrane synthesis mother liquid, at 210～230 ℃, hydrothermal crystallizing 5 hours, washing, dry, obtain SAPO-34 molecular screen membrane.
In described step 4), the cation of selected slaine can be main group metal (as alkali metal, alkaline-earth metal) or transition metal, and anion can be that anaerobic acid group is (as F
-, Cl
-, Br
-, I
-, S
-) or oxyacid root (as NO
3 -, ClO
3 -, ClO
4 -, CO
3 2-).Typical slaine has sodium nitrate, lithium nitrate, rubidium nitrate, magnesium nitrate, potassium nitrate, sodium chlorate, sodium perchlorate etc., and its fusing point is as shown in table 1.
The fusing point of the typical slaine of table 1
The solvent of slaine can be to dissolve arbitrarily the organic and inorganic solvent of this slaine or the mixture of multi-solvents, such as water, alcohol, ketone etc.
Slaine can load on the front of molecular screen membrane, also can load on the reverse side (one side contacting with carrier) of molecular screen membrane, also can tow sides load.The method of loading metal-salt can adopt (but being not limited to) dip coating, and concrete operations are: SAPO-34 molecular screen membrane prepared by step 3) is placed in the metal salt solution that concentration is 0.01～50wt%, soaks 1 second～2 day at 40～100 ℃.Preferably, the concentration of metal salt solution is 0.1～5wt%, and soak time is 1～180 minute.
In described step 5), during oven dry, temperature used can be room temperature～200 ℃.Sintering temperature be controlled at 370～420 ℃ better, roasting time be controlled at 4～8 hours better.Calcination atmosphere can be vacuum, inert gas, purity oxygen, air or with the oxygen of inert gas (as nitrogen, argon gas) dilution.
The present invention is by the metallic salt lower than sintering temperature at molecular screen membrane area load fusing point, make template removal and two steps of ion-exchange of SAPO-34 molecular screen membrane be combined into a step (during high-temperature roasting removed template method, the metallic salt of load is molten state, can with molecular screen membrane in cation carry out in situ ion-exchange), thereby greatly simplified the preparation process of SAPO-34 molecular screen membrane, reduced its synthetic cost, separating property and the repeatability of SAPO-34 molecular screen membrane have also been improved simultaneously, make SAPO-34 molecular screen membrane can also there is very high CO when thering is higher gas permeability
2/ CH
4selectively.
The specific embodiment
Embodiment 1 is without ion-exchange, and under vacuum condition, SAPO-34 molecular screen membrane is prepared in roasting
Step 1: add 2.46g deionized water in 31.13g tetraethyl ammonium hydroxide solution (TEAOH, 35%), then take 7.56g aluminium isopropoxide and join in aforementioned solution, stirring at room 2-3 hour; Then drip 1.665g Ludox (40%), stir 1 hour; The last 8.53g phosphoric acid solution (H that slowly drips
3pO
4, 85%), stirring is spent the night.Adopt heating using microwave, at 180 ℃, crystallization is 7 hours.After product takes out, centrifugal, washing, dries, and obtains SAPO-34 molecular sieve crystal seed.
Step 2: choose aperture and be the porous ceramic pipe of 100nm 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, 85%) mix with 43.8g deionized water, stir 5min, then add 7.56g aluminium isopropoxide, at room temperature stir 3 hours; Add 0.83g Ludox (40%), under room temperature, stir 30min; Then drip 7.78g tetraethyl ammonium hydroxide solution (TEAOH, 35%), 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.By the coating of step 2 preparation the earthenware of SAPO-34 crystal seed be placed in reactor, add the synthesis mother liquid of molecular screen membrane, at 220 ℃, hydrothermal crystallizing is 5 hours, takes out afterflush clean, puts into baking oven and dries.
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.
CO
2/ CH
4gas discrete testing condition: 20 ℃ of temperature, atmospheric pressure 102.4kPa, gas feed rate is 4000mL/min, mole consists of 50/50%.With soap film flowmeter, measure the gas flow of per-meate side; With gas chromatograph (Shimadzu-2014C), analyze the gas composition of per-meate side.
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.
The gas discrete testing result of different molecular sieve membrane pipe is as shown in table 2.
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 1% sodium nitrate solutions soak, and vacuum baking is prepared Na-SAPO-34 molecular screen membrane
Be with the difference of example 1, after completing steps 3, before carry out step 4, effective 1% sodium nitrate solution of molecular screen membrane that step 3 is prepared soaks 10min, then puts into baking oven and dries.All the other steps are identical with embodiment 1.
CO
2/ CH
4gas discrete testing method is identical with embodiment 1, and test result is as shown in table 3.CO
2/ CH
4the separation selectivity of gaseous mixture is 81, compares with the SAPO-34 molecular screen membrane without ion-exchange in embodiment 1, has improved 40%.
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
Embodiment 3 use 1% potassium nitrate solutions soak, and vacuum baking is prepared K-SAPO-34 molecular screen membrane
Be with the difference of example 1, after completing steps 3, before carry out step 4, effective 1% potassium nitrate solution of the molecular screen membrane of step 3 preparation soaked to 3min, then put into baking oven and dry.All the other steps are identical with embodiment 1.
CO
2/ CH
4gas discrete testing method is identical with embodiment 1, and test result is as shown in table 4.CO
2/ CH
4the separation selectivity of gaseous mixture is 73, compares with the SAPO-34 molecular screen membrane without ion-exchange in embodiment 1, has improved 26%.
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
The acetone soln of embodiment 4 use 1% lithium nitrates soaks, and vacuum baking is prepared Li-SAPO-34 molecular screen membrane
Be with the difference of example 1, after completing steps 3, before carry out step 4, the acetone soln of effective 1% lithium nitrate of molecular screen membrane of step 3 preparation soaked to 3min, then put into baking oven and dry.All the other steps are identical with embodiment 1.
CO
2/ CH
4gas discrete testing method is identical with embodiment 1, and test result is as shown in table 5.CO
2/ CH
4the separation selectivity of gaseous mixture is 70, compares with the SAPO-34 molecular screen membrane without ion-exchange in embodiment 1, has improved 21%.
The CO of table 5 embodiment 4
2/ CH
4gas discrete testing result
Note: the pressure differential of film pipe feed side and per-meate side is 3.99MPa
Embodiment 5 use 1% sodium nitrate solutions soak, and under different atmosphere, Na-SAPO-34 molecular screen membrane is prepared in roasting
Be with the difference of example 1: after completing steps 3, before carry out step 4, effective 1% sodium nitrate solution of the molecular screen membrane of step 3 preparation is soaked to 3min, then put into baking oven and dry; In step 4, in removed template method process, sintering atmosphere adopts respectively air, nitrogen, oxygen.All the other steps are identical with embodiment 1.
CO
2/ CH
4gas discrete testing method is identical with embodiment 1, and test result is as shown in table 6.The SAPO-34 molecular screen membrane that roasting makes respectively under air, nitrogen and oxygen atmosphere, its CO
2/ CH
4the separation selectivity of gaseous mixture is respectively 76,73 and 79, compares with the SAPO-34 molecular screen membrane without ion-exchange in embodiment 1, has improved respectively 31%, 26% and 36%.
The CO of table 6 embodiment 5
2/ CH
4gas discrete testing result
Note: the pressure differential of film pipe feed side and per-meate side is 3.99MPa
Embodiment 6 use 2% sodium nitrate solutions soak, and vacuum baking is prepared Na-SAPO-34 molecular screen membrane
Be with the difference of embodiment 1, after step 3 completes, before carry out step 4, effective 2% sodium nitrate solution of the molecular screen membrane of step 3 preparation soaked to 3min, then put into baking oven and dry.All the other steps are identical with embodiment 1.
CO
2/ CH
4gas discrete testing method is identical with embodiment 1, and test result is as shown in table 7.CO
2/ CH
4the separation selectivity of gaseous mixture is 72, compares with the SAPO-34 molecular screen membrane without ion-exchange in embodiment 1, has improved 24%.
The CO of table 7 embodiment 6
2/ CH
4gas discrete testing result
Note: the pressure differential of film pipe feed side and per-meate side is 3.99MPa.
Claims (9)
1. the method for preparing ion-exchange SAPO-34 molecular screen membrane, comprises step:
1) synthetic SAPO-34 molecular sieve crystal seed;
2) SAPO-34 molecular sieve crystal seed is loaded on porous carrier;
3) synthetic SAPO-34 molecular screen membrane; It is characterized in that, also comprise step:
4) on SAPO-34 molecular screen membrane load fusing point lower than the slaine of the sintering temperature of step 5);
5) dry, at 370～700 ℃, roasting is 2～24 hours, obtains the SAPO-34 molecular screen membrane of ion-exchange.
2. method according to claim 1, is characterized in that, step 4), and the cation of described slaine is main group metal or transition metal, anion is anaerobic acid group or oxyacid root.
3. method according to claim 1 and 2, it is characterized in that, step 4), the method of loading metal-salt is dip coating, operating procedure is: SAPO-34 molecular screen membrane prepared by step 3) is placed in the metal salt solution that concentration is 0.01～50wt%, soaks 1 second～2 day at-40～100 ℃.
4. method according to claim 3, is characterized in that, step 4), and the concentration of described metal salt solution is 0.1～5wt%.
5. method according to claim 3, is characterized in that, step 4), and soak time is 1～180 minute.
6. method according to claim 1, is characterized in that, step 5), and bake out temperature is room temperature～200 ℃.
7. method according to claim 1, is characterized in that, step 5), and sintering temperature is 370～420 ℃.
8. method according to claim 1, is characterized in that, step 5), and roasting time is 4～8 hours.
9. method according to claim 1, is characterized in that, step 5), and calcination atmosphere is the oxygen of vacuum, inert gas, purity oxygen, air or dilution.
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Cited By (4)
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| CN104058426A (en) * | 2014-06-30 | 2014-09-24 | 中国科学院上海高等研究院 | Method for preparing SAPO-34 zeolite membrane in temperature changing mode |
| CN104355316A (en) * | 2014-09-03 | 2015-02-18 | 中国科学院上海高等研究院 | Preparation method for SAPO-34 molecular sieve membrane |
| WO2016124592A1 (en) * | 2015-02-03 | 2016-08-11 | Shanghai Advanced Research Institute, Chinese Academy Of Sciences | Pervaporation and vapor-permeation separation method of gas-liquid mixtures and liquid mixtures by ion exchanged sapo-34 molecular sieve membrane |
| CN105983345A (en) * | 2015-02-03 | 2016-10-05 | 中国科学院上海高等研究院 | Method for separating gas-liquid/liquid mixtures through pervaporation and vapor permeation by SAPO-34 molecular sieve membrane prepared by xerogel method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058426A (en) * | 2014-06-30 | 2014-09-24 | 中国科学院上海高等研究院 | Method for preparing SAPO-34 zeolite membrane in temperature changing mode |
| CN104058426B (en) * | 2014-06-30 | 2017-09-29 | 中国科学院上海高等研究院 | The method that temperature-switching method prepares the molecular screen membranes of SAPO 34 |
| CN104355316A (en) * | 2014-09-03 | 2015-02-18 | 中国科学院上海高等研究院 | Preparation method for SAPO-34 molecular sieve membrane |
| CN104355316B (en) * | 2014-09-03 | 2016-08-24 | 中国科学院上海高等研究院 | The preparation method of SAPO-34 molecular screen membrane |
| WO2016124592A1 (en) * | 2015-02-03 | 2016-08-11 | Shanghai Advanced Research Institute, Chinese Academy Of Sciences | Pervaporation and vapor-permeation separation method of gas-liquid mixtures and liquid mixtures by ion exchanged sapo-34 molecular sieve membrane |
| CN105983344A (en) * | 2015-02-03 | 2016-10-05 | 中国科学院上海高等研究院 | Method for separating gas-liquid/liquid mixtures through pervaporation and vapor permeation by ion-exchange SAPO-34 molecular sieve membrane |
| CN105983345A (en) * | 2015-02-03 | 2016-10-05 | 中国科学院上海高等研究院 | Method for separating gas-liquid/liquid mixtures through pervaporation and vapor permeation by SAPO-34 molecular sieve membrane prepared by xerogel method |
| 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 |
| 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 |
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