CN101279207A - Preparation of SAPO-34 molecular sieve film for selectively separating methane gas - Google Patents
Preparation of SAPO-34 molecular sieve film for selectively separating methane gas Download PDFInfo
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- CN101279207A CN101279207A CNA2008100507148A CN200810050714A CN101279207A CN 101279207 A CN101279207 A CN 101279207A CN A2008100507148 A CNA2008100507148 A CN A2008100507148A CN 200810050714 A CN200810050714 A CN 200810050714A CN 101279207 A CN101279207 A CN 101279207A
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Abstract
The invention relates to a novel method of SAPO-34 molecular sieve membrane for selectively separating methane gas by crystal guidance and secondary synthesis. The method includes three steps, namely synthesizing crystal seed, preparing basement membrane of crystal seed and synthesizing SAPO-34 molecular sieve membrane, in particular to the following steps: phosphoric acid, TEAOH and silica sol are added into adequately hydrolyzed aluminium isopropoxide to prepare a crystal seed solution of the molecular sieve and the molecular sieve composite mother solution; the crystal seed solution of the molecular sieve is prepared to be suspension after crystallization and rinsing for dripping onto a treated carrier; a basement membrane of crystal seed acquired is placed in a reaction kettle and is added with the molecular sieve composite mother solution for crystallization at a temperature ranging from 150 DEG C to 180 DEG C for 3 through 20 days, which is taken out for cleaning and drying and then is followed with actively removing a template agent at a temperature ranging from 400 DEG C to 600 DEG C. Synthesizing the molecular sieve membrane with the method of the invention is suitable for various porous supports with smooth surface, which is of high repetitiveness, good orientation, excellent separating property and ultrahigh gas permeability and is suitable for industrial application.
Description
Technical field
The invention belongs to the preparation field of molecular screen membrane, be specifically related to the preparation method that a kind of crystal seed is induced the SAPO-34 molecular screen membrane of secondary synthesis of selective separating methane gas.
Background technology
Film is two thing phase spaces are separated and to make it interrelated, takes place to get involved mutually in the middle of quality and energy transmission course one.The traditional separation method that the film separation process is known with people, as evaporation, fractionation is compared, and its outstanding advantage is the efficient height, and energy consumption is low, and the operating condition gentleness is simple and easy, also has some other characteristics in addition, thereby is widely used, and development is rapidly.Diffusion barrier has been widely used in food and drink with corresponding membrane separation technique, medical and health, and biotechnology, chemical industry metallurgical, more and more important effect is being brought into play in fields such as environmental project.
Zeolite molecular sieve film is a class novel inorganic film that grows up nearest more than ten years.It is high temperature resistant, corrosion-resistant except having the microporous inorganic film, and swelling outside the general characters such as easy cleaning and regeneration, does not also have the aperture less than 1nm and distribution homogeneous, and the cation in the zeolite crystal can be exchanged, and silica alumina ratio such as can regulate at characteristic.Its membrane aperture homogeneous can provide very high selectivity, the straight hole road can make the gas rapid diffusion, higher environmental stability can be used for the pyroreaction system, thereby the zeolite intracrystalline pore can be modified and strengthen absorption and permselective property, good whole has than the better absorption of sieve particle it, infiltration and separating property.The carrier-less film that is formed by zeolite or carrier film is arranged, as having the new material of reaction with the separation of double function, progress is very fast since the nineties in 20th century, becomes the focus of new catalytic material and new process study aspect.
Aluminium silicophosphate molecular sieve series (SAPOs) is important in the novel phosphate molecule sieve family.They are by SiO
2, AlO
2 -And PO
3 2+The microporous crystal that unit, three kinds of four sides constitutes.Because phosphorus is the one of the chief elements that its skeleton is formed, they show the physicochemical characteristics that many Si-Al zeolites do not have.SAPO-34 is its important a member, structurally be similar to chabasie, but have more excellent performance at aspects such as absorption and catalysis, being applied in especially has very high selectivity to ethene, propylene among the MTO process, and obtain industrial application, become the important goal of international counterparts exploitation.
Separating carbon dioxide is a significant process in the natural gas processing from methane, because carbon dioxide reduces energy value, has acid under the water existence condition and corrosivity and be unfavorable for transportation and storage.Handle CO at present
2Method comprise that ammonia absorption separates with polymer film, but the ammonia adsorption plant is complicated and expensive, and higher CO
2Dividing potential drop can reduce its separating power by plasticizing polymerization thing film.By contrast, the microporous inorganic film is with its outstanding machinery, chemistry and heat endurance, higher resistance to corrosion and at high CO
2Divide the stability of depressing, have separation of C O from natural gas
2Potentiality.Compare with the widely used large pore molecular sieve of tradition, small pore molecular sieve (such as T (aperture 0.41nm), the aperture of DDR (0.36 * 0.44nm) and SAPO-34 (0.38nm)) and methane are approximate, but greater than carbon dioxide.Simultaneously, it is to CO
2Adsorption capacity be better than it to CH
4Adsorption capacity.Therefore these films are based on to CO
2/ CH
4The comprehensive function of the difference of competitive Adsorption ability and diffusivity and have higher selectivity.
At present reported in literature is used for separation of C O
2/ CH
4The carrier of SAPO-34 film mainly comprise porous ceramics piece, porous ceramic pipe, porous stainless steel disc and porous stainless steel, method mainly comprises the synthetic and diauxic growth of original position hydro-thermal.People such as Sturt are reported in seed surface and modify the synthetic SAPO-34 film of method two secondary growth that is adsorbed on behind the electric charge on the carrier (Chinese patent application number 97193836.9), but for carrier with big aperture, the method can not be synthesized the film of continuous densification, and does not have gas separation effect; People such as Noble are reported on the porous supporter the synthetic SAPO-34 film of original position hydro-thermal (Chinese patent application number 200580008446.8), people such as Min Enze are reported in the synthetic SAPO-34 film (Chinese patent application 96106353.X) of dull and stereotyped porous ceramic surface original position, but because in-situ synthetic method only is applicable to that the less carrier of porosity is (as potsherd, earthenware) can't be applied to the great carrier of porosity (as stainless steel wire mesh, 100～300 orders), and a large amount of molecular sieves are formed in the hole, the enlarged in thickness that causes film, simultaneously, the orientation of the uncontrollable synthetic film of in-situ method, molecular sieve is piled up in carrier surface and inside at random, the path that causes gas to pass through increases, thereby greatly reduce the permeability of film, can't realize commercial Application.For the preparation of super large porosity carrier surface aluminium phosphate molecular sieve film, also there is not the patent report at present.
Summary of the invention
The object of the present invention is to provide a kind of novel method that is coated with the synthetic aluminum phosphate SAPO-34 molecular screen membrane of crystal seed secondary of dripping that adopts.
The method is applicable to the porous carrier of various surfacings, and particularly the large aperture carrier that can't use for conventional method (aperture is greater than 10 microns) still has good synthetic effect.Adopt this method synthesizing molecular sieve film repeatability high, favorable orientation when having the good separation performance, has the gas permeability of superelevation, is suitable for commercial Application.
Step of the present invention is as follows:
A: synthetic crystal seed
The proportioning of crystal seed reactant liquor is: 1mol Al
2O
3: 0.7～1.5mol H
3PO
4: 0.3mol SiO
2: 1～1.5mol TEAOH: 50～100mol H
2O after the abundant hydrolysis of aluminium isopropoxide, adds phosphoric acid, tetraethyl ammonium hydroxide and Ludox, is 5～6 with hydrochloric acid conditioning solution pH value, and in 150～180 ℃ of hydrothermal crystallizings 1～3 day, product was washed and dried, and obtains the crystal seed powder, and its grain size is 0.3～8 micron;
B: preparation crystal seed basement membrane
Crystal seed powder in the steps A is made into the suspension of 1～20g/L, behind the carrier cleaning, drying, drips crystal seed suspension on its surface, the heating solvent evaporated obtains the crystal seed basement membrane on carrier;
C: synthetic SAPO-34 molecular screen membrane
The proportioning of molecular screen membrane synthesis mother liquid is: 1mol Al
2O
3: 0.7～1.5mol H
3PO
4: 0.3molSiO
2: 1～1.5mol TEAOH: 100～300mol H
2O after the abundant hydrolysis of aluminium isopropoxide, adds phosphoric acid, tetraethyl ammonium hydroxide and Ludox; Crystal seed basement membrane with step B places reactor then, add molecular sieve synthesis mother liquid,, take out afterwash and dry in 150～180 ℃ of hydrothermal crystallizings 3～20 days, template agent TEAOH is removed in activation under 400～600 ℃ of temperature again, then prepares the SAPO-34 molecular screen membrane on carrier.
The carrier of the molecular screen membrane that employing the inventive method is synthetic also is applicable to the porous and the non-porous matrix of other surfacings, as monocrystalline silicon piece, and sheet glass, silica, aluminium oxide, titanium dioxide, sheet metal or stainless steel wire mesh (100～500 order) can be used for fields such as sensor or optoelectronic device.
The cleaning of carrier is that carrier is placed ultrasonic cleaner, uses washed with de-ionized water 3～5 times, each 5～10 minutes, uses 30～50% H again
2O
2After soaking 10～20h, put into 75～85 ℃ of baking ovens and dry.
The present invention when preparing crystal seed layer, adopt to carrier surface drip be coated with the crystal seed aqueous solution after the method for evaporate to dryness, make carrier surface can adhere to the height-oriented crystal seed layer of one deck with very big porosity, and the control hydrothermal synthesizing condition is grown up crystal seed, so just obtained the ultra-thin and height-oriented film of one deck, such film is because above characteristics, have and exceed the character of the gas permeability of 1～2 order of magnitude of other reported in literature SAPO-34 film at present, good reproducibility has good prospect aspect commercial Application simultaneously.
Adopt the synthetic molecular screen membrane of the inventive method to show do not have stray crystal to generate through SEM and XRD detection, the film surface generates the fine and close continuous orientation film of one deck.
Adopt the synthetic molecular screen membrane of the inventive method to carry out the gas discrete testing, prove that synthetic film has higher selectivity and, good reproducibility simultaneously, suitable commercial Application considerably beyond the permeability of other film.Be illustrated below by specific embodiment.
Description of drawings
The XRD diffraction pattern of synthetic SAPO-34 crystal seed among Fig. 1: the embodiment 1; The 9.4 degree peaks that occur among the figure are (100) crystal face characteristic peak of SAPO-34, and synthetic product is the product that hope obtains really as seen from the figure, and peak intensity is very high, proves that degree of crystallization is better;
The XRD diffraction pattern of synthetic SAPO-34 molecular screen membrane among Fig. 2: the embodiment 1; The 9.4 degree peaks that occur among the figure are (100) crystal face characteristic peak of SAPO-34, and only higher relatively at the peak intensity of this direction, and therefore synthetic as can be known film has orientation, and the reason that peak intensity is totally not high is that the film that synthesizes is thinner, and diffraction is not strong;
The SEM photo of synthetic SAPO-34 crystal seed among Fig. 3: the embodiment 1; The crystal size homogeneous, particle diameter less (3～4 microns);
Drip the SEM photo be coated with the carrier back side behind the crystal seed among Fig. 4: the embodiment 1; As seen crystal seed is arranged by certain orientation (100) direction;
The SEM photo in the SAPO-34 molecular screen membrane front of synthesizing on the wire netting surface among Fig. 5: the embodiment 1; As seen He Cheng film has orientation, and it is oriented to (100) direction;
Among Fig. 6: the embodiment 4 at the SEM photo that melts synthetic SAPO-34 molecular screen membrane front, sand sheet surface; Synthetic film has the pattern (the SAPO-34 crystal structure belongs to rhombohedral system, and pattern is similar to cube) of SAPO-34, and is fine and close;
The SEM photo in the SAPO-34 molecular screen membrane front of synthesizing on porous alumina ceramic sheet surface among Fig. 7: the embodiment 5; Synthetic film has the pattern (being similar to cube) of SAPO-34, and is fine and close;
Fig. 8: the SEM photo in synthetic SAPO-34 molecular screen membrane front in the comparative example 3; The fine and close still poor orientation of film;
Fig. 9: the SEM photo in synthetic SAPO-34 molecular screen membrane front in the comparative example 4; Film is fine and close and have orientation, is oriented to (100) direction;
The specific embodiment
Embodiment 1
Steps A: SAPO-34 molecular sieve crystal seed synthetic
2 gram aluminium isopropoxides are added in the 5 gram deionized waters, fully stir hydrolysis.Drip 1 gram phosphoric acid solution (H
3PO
4, mass fraction 85%), the 8.47 gram tetraethyl ammonium hydroxide aqueous solution (TEAOH, mass fraction 20%), 0.32 gram Ludox (SiO
2The aqueous solution, mass fraction 30%), adding 0.3 gram concentrated hydrochloric acid solution (HCl, mass fraction 37%), reaction mother liquor pH value is 6,180 ℃ of hydrothermal crystallizings 3 days at this moment, and product takes out the back and cleans oven dry with deionized water, gets the crystal seed powder, and its grain size is 3～5 microns.
Step B: preparation crystal seed basement membrane
In the crystal seed powder that steps A obtains, add deionized water, be made into the suspension of 3g/L, with 300 order stainless steel wire meshes (Bashan Precision Filter Material Co., Ltd., Xinxiang City) ultrasonic cleaner (KQ-100DE type numerical control supersonic washer, Kunshan Ultrasonic Instruments Co., Ltd.) uses washed with de-ionized water 3 times, each 5 minutes, use 30% H again
2O
2After soaking 12h, putting into 85 ℃ of baking ovens dries, suspension is evenly dropped in the stainless (steel) wire surface, consumption is 1 milliliter/square centimeter, dry moisture to wire netting surface attachment one deck white crystal seed layer with the 1000W resistance furnace, be the crystal seed basement membrane, the thickness that microscopically is observed crystal seed layer is about 30 microns.
Step C: synthetic SAPO-34 molecular screen membrane
1 gram aluminium isopropoxide is added in the 10 gram deionized waters, fully stir hydrolysis.Drip 0.734 gram phosphoric acid solution (H
3PO
4, mass fraction 85%), the 3.5 gram tetraethyl ammonium hydroxide aqueous solution (TEAOH, mass fraction 20%), 0.3 gram Ludox (SiO
2, mass fraction 30%), be stirred to evenly, obtain the molecular sieve mother liquor; The crystal seed basement membrane that step B is obtained places the molecular sieve mother liquor again, one was same as under 180 ℃ of temperature conditions hydrothermal crystallizing 15 days, product takes out afterwash and dries, and then remove the template agent in 600 ℃ of activation, then prepare the SAPO-34 molecular screen membrane, characterize then and the gas separation test at carrier surface.
Be with the difference of embodiment 1, behind the end of synthesis, repeat embodiment 1 step C, synthesize the SAPO-34 molecular screen membrane once again, to repair the intergranular defective on film surface.As can be seen from Table 1, the separating property of film further improves.
Embodiment 3
Be with the difference of embodiment 1, carry out parallel test with three samples by this proportioning, to test its repeatability, all the other are with embodiment 1.The results are shown in Table 2, and the method repeatability better as can be known.
Embodiment 4
Be with the difference of embodiment 1, suspension concentration is 5g/L among the step B, it is smooth with 2000 order sand paperings to melt sand sheet (Changchun China space glass apparatus Co., Ltd), cleans 3 times with ultrasonic cleaner (KQ-100DE type numerical control supersonic washer, Kunshan Ultrasonic Instruments Co., Ltd.), each 5 minutes, put into 85 ℃ of baking ovens and dry, suspension is evenly dropped in melt sand sheet surface, consumption is 1 milliliter/square centimeter, with 1000W electric furnace oven dry moisture, make the crystal seed basement membrane; The synthetic method of film is with embodiment 1 step C, and its result is similar to Example 1, sees accompanying drawing 6.
Be that with the difference of embodiment 4 use carrier to be porous alumina ceramic sheet (Dalian Chemical Physics Research Institute's commodity), all the other methods are with embodiment 4.Its result is similar to Example 1, sees accompanying drawing 7.
Embodiment 6
Be with the difference of embodiment 4, suspension concentration is 2g/L, use carrier to be slide (Changchun China space glass apparatus Co., Ltd), with ultrasonic cleaner (KQ-100DE type numerical control supersonic washer, Kunshan Ultrasonic Instruments Co., Ltd.) cleans 3 times, each 5 minutes, to put into 85 ℃ of baking ovens and dry, all the other methods are with embodiment 4.Because carrier is fine and close, so do not survey its separating property.
Embodiment 7
Be with the difference of embodiment 4, suspension concentration is 2g/L, the use carrier is fine and close stainless steel substrates (Changchun Xiang chemical industry in morning Co., Ltd), with ultrasonic cleaner (KQ-100DE type numerical control supersonic washer, Kunshan Ultrasonic Instruments Co., Ltd.) cleans 3 times, each 5 minutes, to put into 85 ℃ of baking ovens and dry, all the other methods are with embodiment 4.Because carrier is fine and close, so do not survey its separating property.
The film of embodiment 1,3 is carried out XRD and SEM characterizes, prove that synthetic SAPO-34 film has consistent orientation, and synthetic film is very thin, therefore have the permeability that is higher than the SAPO-34 film that additive method synthesizes.
For this inventive method is compared, select some comparative examples to test.
Comparative example 1
Be that with the difference of embodiment 1 concentrated hydrochloric acid that adds in the steps A (HCl, mass fraction 37%) quality is 0.5 gram, this moment, reaction mother liquor pH value was 5, and all the other are with embodiment 1.The crystal seed that this example generates very big (greater than 10 microns, and embodiment 1 synthetic crystal seed particle diameter only is 3～4 microns), the gas discrete testing is come to nothing, and the size of visible crystal seed is very big to the influence of the separating property of the gas of the synthetic film of the method.
Comparative example 2
Be that with the difference of embodiment 1 concentration of crystal seed suspension is 15g/L among the step B, all the other are with embodiment 1.Because thicker (＞50 microns of the crystal seed layer of preparation, and embodiment 1 synthetic film thickness only is 30 microns), film that can't synthesis of densified, the gas separating experiment does not have effect, and the thickness that as seen prepares crystal seed layer is bigger to the influence of the separating property of the gas of the synthetic film of the method.
Comparative example 3
Be that with the difference of embodiment 1 quality that adds distilled water among the step C is 5 grams, all the other are with embodiment 1.By table 1 as seen, the selectivity of film descends, and the proportioning of embodiment 1 is better.
Comparative example 4
Be that with the difference of embodiment 1 the hydrothermal crystallizing time is 3 days among the step C, all the other are with embodiment 1.By table 1 as seen, the selectivity of film descends, and the time of embodiment 1 is comparatively suitable.
Comparative example 5
Be that with the difference of embodiment 1 carrier among the step B is the porous ceramics piece that polishes smooth afterwash, all the other are with embodiment 1.By table 1 as seen, the gas permeability of film descends, and proves that metal mesh carrier has more advantage aspect commercial Application.
Carry out the gas discrete testing for embodiment and the synthetic film of comparative example, 0.02Mpa falls in pressure, and 25 ℃ of temperature are by the ratio V of the gas flow rate before the film
CO2/ V
CH4=1, characterize by the CO behind the film with gas-chromatography (Tianjin, island GC-14C)
2With CH
4Flow velocity V
CO2With V
CH4, calculate and select the factor and permeability, wherein CO
2/ CH
4Selection factor a=(V
CO2/ V
CH4)
Behind the film/ (V
CO2/ V
CH4)
Before the film, CO
2Permeability p=V
CO2/ S*P, V
CO2Be CO
2Flow velocity, the mol/s of unit, membrane area when S is separation, the m of unit
2, P falls for the film pressure at both sides, the Pa of unit, with the results are shown in Table 1:
Table 1:SAPO-34 film is to CO
2/ CH
4Separating property
By table 1 as seen, comparing embodiment 1, comparative example 1,2, the character of crystal seed and the concentration of suspension have tangible influence to SAPO-34 film synthetic; Comparing embodiment 1, comparative example 3,4, the SAPO-34 molecular screen membrane can make under big synthesis condition changes, and is suitable for industry and amplifies; Comparing embodiment 1, comparative example 5, the permeability of SAPO-34 film that with the stainless (steel) wire is carrier has favorable industrial application prospect apparently higher than traditional porous ceramics piece; Comparing embodiment 1,2, repeatedly growth can improve the selectivity of synthetic film to gas, improves separative efficiency.
Several films synthetic among the embodiment 3 are carried out the gas discrete testing, and the results are shown in Table 2:
The repeatability of table 2:SAPO-34 molecular screen membrane
By table 2 as seen, same batch of synthetic film has good repeatability, is suitable for large-scale industrial production.
Claims (4)
1, the preparation method of the SAPO-34 molecular screen membrane of selectively separating methane gas, its step is as follows:
A: synthetic crystal seed,
The proportioning of crystal seed reactant liquor is: 1mol Al
2O
3: 0.7～1.5mol H
3PO
4: 0.3mol SiO
2: 1～1.5mol TEAOH: 50～100mol H
2O after the abundant hydrolysis of aluminium isopropoxide, adds phosphoric acid, tetraethyl ammonium hydroxide and Ludox, and regulator solution pH value is 5～6, and in 150～180 ℃ of hydrothermal crystallizings 1～3 day, the product washing was dried, and obtains the crystal seed powder;
B: preparation crystal seed basement membrane,
Crystal seed powder in the steps A is made into the suspension of 1～20g/L, behind the carrier cleaning, drying, drips crystal seed suspension on its surface, the heating solvent evaporated obtains the crystal seed basement membrane on carrier;
C: synthetic SAPO-34 molecular screen membrane,
The proportioning of molecular screen membrane synthesis mother liquid is: 1mol Al
2O
3: 0.7～1.5mol H
3PO
4: 0.3molSiO
2: 1～1.5mol TEAOH: 100～300mol H
2O after the abundant hydrolysis of aluminium isopropoxide, adds phosphoric acid, tetraethyl ammonium hydroxide and Ludox; Crystal seed basement membrane with step B places reactor then, add molecular sieve synthesis mother liquid,, take out afterwash and dry in 150～180 ℃ of hydrothermal crystallizings 3～20 days, the template agent is removed in activation under 400～600 ℃ of temperature again, then prepares the SAPO-34 molecular screen membrane on carrier.
2, the preparation method of the SAPO-34 molecular screen membrane of selectively separating methane gas as claimed in claim 1 is characterized in that: the pH value of regulating the crystal seed reactant liquor with hydrochloric acid.
3, the preparation method of the SAPO-34 molecular screen membrane of selectively separating methane gas as claimed in claim 1 is characterized in that: carrier is monocrystalline silicon piece, sheet glass, silica, aluminium oxide, titanium dioxide, sheet metal or 100～500 order stainless steel wire meshes.
4, as the preparation method of the SAPO-34 molecular screen membrane of any one described selectively separating methane gas of claim 1～3, it is characterized in that: the cleaning of carrier is that carrier is placed ultrasonic cleaner, with washed with de-ionized water 3～5 times, each 5～10 minutes, use 30～50% H again
2O
2After soaking 10～20h, put into 75～85 ℃ of baking ovens and dry.
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