CN110508158B - Method for preparing ultrathin SAPO-34 molecular sieve membrane - Google Patents
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Abstract
The invention relates to a method for preparing an ultrathin SAPO-34 molecular sieve membrane, which comprises the steps of preparing SAPO-34 nanometer crystal seeds; coating SAPO-34 nano seed crystals on a porous carrier tube; preparing ultra-concentrated SAPO-34 molecular sieve membrane synthesis mother liquor; placing the porous carrier tube in a molecular sieve membrane synthesis mother solution, placing the porous carrier tube in a drying oven for heating, performing hydrothermal crystallization to obtain an SAPO-34 molecular sieve membrane, and then washing and drying the SAPO-34 molecular sieve membrane; and (3) roasting at high temperature to remove the template agent to obtain the activated SAPO-34 molecular sieve membrane. Compared with the prior art, the method effectively reduces the thickness of the SAPO-34 molecular sieve membrane to 800 nanometers, thereby greatly reducing mass transfer resistance and improving permeability, and the method is also suitable for synthesizing other SAPO (silicon phosphorus aluminum type) or AlPO (phosphorus aluminum type) molecular sieve membranes.
Description
Technical Field
The invention relates to the field of membrane separation, in particular to a method for preparing an ultrathin SAPO-34 molecular sieve membrane.
Background
Natural gas is an important energy source and chemical raw material in parallel with petroleum and coal. The natural gas usually contains 75% to 90% of methane as a main component, and hydrocarbons such as ethane, propane, butane, and other impurities including water, carbon dioxide, nitrogen, hydrogen sulfide, and the like. The presence of these impurities seriously affects the storage and transportation of natural gas and is strictly controlled. Thus, the world costs $ 50 billion per yearFor purifying natural gas, mainly removing CO in natural gas2. Statistically, more than 20% of natural gas fields in the United states are due to excessive CO2Content and requires advanced treatment. CO from Shell oil company in Natural gas fields in Russian Kaolin island, Indonesia and south China sea2The content is even up to more than 40 percent. The traditional amine absorption can remove CO in natural gas2However, the method has the problems of high desorption energy consumption, large equipment investment, complex maintenance and the like, and is difficult to be industrially applied.
A large number of research reports show that the membrane separation has the advantages of low energy consumption, continuous operation, low equipment investment, small volume, easy maintenance and the like, and CO is produced2The removal field has huge application potential [ Ind. Eng. chem. Res.41(2002) 1393)]. The molecular sieve membrane has excellent thermal, chemical and mechanical stability, and is especially suitable for high pressure high CO2The purification of natural gas content, and the traditional polymer membrane cannot be applied to such a harsh separation environment due to the plasticizing phenomenon. The molecular sieve membrane has the advantages of unique molecular sieving, selective adsorption and the like, and can be used for removing CO from natural gas2Have received increasing attention in the field.
In different molecular sieve membranes, small pore T [ j. mater. chem.14(2004)924]、DDR[Micropor.Mesopor.Mater.68(2004)71]And SAPO-34[ J.Membr.Sci.363(2010)29 and references thereto]Molecular sieve membranes are best suited for CO2/CH4Separation due to CO2The diffusion in the crystal pore canal of the small pore molecular sieve is far faster than that of CH4Extremely high separation selectivity can be obtained, and thus methane loss in the natural gas treatment process can be reduced. SAPO-34 is a small pore silicoaluminophosphate type molecular sieve with the CHA structure, the pore diameter of which is 0.38 nanometers, and is very suitable for CO2-CH4And (5) separating. CO 22And CH4The molecular dynamics diameters of (1) are respectively 0.33 and 0.38 nm, the difference of diffusion coefficients in SAPO-34 pore channels is extremely large (molecular sieving), and simultaneously, polar CO2The adsorption of molecules in SAPO-34 pore channels is strong, and CO is also selected for adsorption2. The separation performance of the SAPO-34 molecular sieve membrane is influenced by the framework silica-alumina ratio, the size of the seed crystal, the type of the template agent, the thickness of the membrane, the type of the cation, and CO2Influence of conditions such as concentration, carrier properties, firing conditions, defect repair method [ J.Membr.Sci.335(2009)32 and citation thereof]。
Although the separation performance of SAPO-34 molecular sieve membranes has been greatly improved in the past year, [ J.Membr.Sci.,2018,565,311- & 321, J.Membr.Sci.2018,552,13-21, Microporous.Mesoporous.Mater.,2017,241,392- & 399, Microporous.Mesoporous.Mater.2016,225,261-271 ], the high cost and the low permeability severely restrict the commercial application of the SAPO-34 molecular sieve membranes. The cost of the molecular sieve membrane is composed of the main raw material cost and the preparation cost. The synthesis of SAPO-34 molecular sieve membranes requires porous ceramic tubes as carriers, which is relatively costly. In addition, the synthesis of the SAPO-34 molecular sieve membrane needs tetraethyl ammonium hydroxide as an organic template agent, and the price is higher. The synthesis of the SAPO-34 molecular sieve membrane usually needs hydrothermal synthesis for 4-5 hours at 220 ℃, a high-pressure crystallization kettle and higher energy consumption are needed, and certain potential safety hazards exist. In addition to raw material costs and manufacturing costs, the permeability of the manufactured membrane tubes also has a direct impact on the cost of the membrane tubes. In general, the permeability of a membrane tube is inversely proportional to the thickness of the membrane, with thinner membranes having less mass transfer resistance and thus higher permeability. And the permeability of a membrane tube is inversely proportional to the unit price of the membrane (usually calculated as the area of the membrane). The thickness of the SAPO-34 molecular sieve membrane prepared by the conventional synthesis method is about 2-5 microns. If the thickness of the membrane can be reduced to less than 1 micron, the permeability of the membrane can be greatly improved, and the unit cost of the membrane can be reduced.
To reduce the thickness of the molecular sieve membrane, the simplest method is to increase the concentration of the mother liquor (e.g., reduce H)2O/Al2O3Molar ratio). The increase of the concentration of the mother liquor promotes the nucleation, which is beneficial to obtaining smaller molecular sieve crystals and thinner molecular sieve membranes. Mother liquor formula concentration H of traditional SAPO-34 molecular sieve membrane2O/Al2O3The molar ratio is 50-200, and the thickness of the SAPO-34 molecular sieve membrane prepared by hydrothermal synthesis is usually 2-4 microns, so that the mass transfer resistance is large and the permeability is low. Increase of mother liquor concentration (H)2O/Al2O3A molar ratio of about 50) is a large increase in the viscosity of the mother liquor, which is severeThe double image affects the uniformity of the mother liquor and is not favorable for the film formation of the molecular sieve film. Such as further increasing the concentration of the mother liquor (H)2O/Al2O3The molar ratio is reduced to about 10), the mother liquor is basically slurry or even dry, and can not be uniformly contacted with the porous ceramic carrier tube, so that a high-quality molecular sieve membrane can not be obtained.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing an ultrathin SAPO-34 molecular sieve membrane.
The purpose of the invention can be realized by the following technical scheme:
a method for preparing ultra-thin SAPO-34 molecular sieve membrane is to prepare low-viscosity ultra-concentrated synthetic mother liquor (H) by adopting special mixing steps2O/Al2O3Molar ratio of<20,TEAOH/Al2O3The molar ratio is between 1 and 10). The ultra-high mother liquor concentration effectively promotes nucleation, resulting in smaller SAPO-34 crystals and a substantial reduction in membrane thickness. The special mixing step greatly reduces the viscosity of the mother liquor, ensures the uniformity and the fluidity of the mother liquor and is beneficial to forming a high-quality SAPO-34 molecular sieve membrane. The method effectively reduces the thickness of the SAPO-34 molecular sieve membrane to 800 nanometers, thereby greatly reducing the mass transfer resistance and improving the permeability, and specifically comprises the following steps:
1) synthesis of SAPO-34 molecular sieve seed crystal
Mixing and dissolving an aluminum source, tetraethylammonium hydroxide (TEAOH, a template agent), water, a silicon source and a phosphorus source to obtain a seed crystal reaction solution. Wherein, the molar ratio of the seed crystal synthesis mother liquor is as follows: 1.0Al2O3:1～2.0P2O5:0.1～0.8SiO2:2～8.0TEAOH:10～100H2O, microwave synthesis is carried out for 7 hours at 443K, centrifugation, washing and drying are carried out, and SAPO-34 nanometer seed crystals with the particle diameter not more than 300 nanometers are obtained;
in this step, the specific preparation method of the seed crystal reaction solution may be as follows:
adding an aluminum source into a tetraethylammonium hydroxide (TEAOH) solution, hydrolyzing, sequentially adding a silicon source and a phosphorus source, and stirring to obtain a seed crystal reaction solution; further, the operation may be: and mixing tetraethyl ammonium hydroxide solution and deionized water, adding an aluminum source into the solution, stirring at room temperature for 2-3 hours, dropwise adding a silicon source, stirring for 0.5-2 hours, slowly dropwise adding a phosphorus source solution, and stirring for 12-24 hours to obtain a seed crystal reaction solution.
2) Seed coating
Coating SAPO-34 molecular sieve seed crystals on the inner surface of the porous carrier to obtain the porous carrier coated with the SAPO-34 molecular sieve seed crystals; the coating method of the molecular sieve seed crystal comprises brush coating, dip coating, spray coating and spin coating; when dip coating is adopted, the concentration of the SAPO-34 nanometer seed crystal dip coating liquid is 1 wt%.
3) Synthesis of SAPO-34 molecular sieve membrane
A. Uniformly mixing an aluminum source, a phosphorus source, a silicon source, tetraethylammonium hydroxide, di-n-propylamine (DPA) and water to form a molecular sieve membrane synthesis mother liquor;
wherein, the mol ratio of the aluminum source, the phosphorus source, the silicon source, tetraethyl ammonium hydroxide, di-n-propylamine (DPA) to the total water amount in the molecular sieve membrane synthesis mother liquor is as follows: 1Al2O3:0.5～3.5P2O5:0.05～0.6SiO2:0.5～8TEAOH:0.1～6DPA:3～30H2O；
In the step A, the operation steps of forming the molecular sieve membrane synthesis mother liquor are as follows:
mixing tetraethyl ammonium hydroxide with water, then adding an aluminum source, and stirring for 1-5 hours to obtain a clear and transparent solution; putting the solution in an oven at 80 ℃ for heating to remove excessive water; and then adding a silicon source, stirring for 0.5-2 hours, adding a phosphorus source, stirring for 0.5-2 hours, then adding di-n-propylamine, and stirring for 2 hours to obtain a uniform molecular sieve membrane synthesis mother liquor. The synthesis mother liquor is nearly clear and transparent, has low viscosity and high uniformity and fluidity. It is noted that heating to remove water after mixing all the raw materials does not lead to a large increase in the viscosity of the mother liquor. The traditional SAPO-34 molecular sieve membrane mother liquor is prepared by mixing phosphoric acid and an aluminum source, and then sequentially adding a silicon source and a template agent. Such a feeding sequence also leads to an increase in the viscosity of the mother liquor, which is detrimental to the synthesis of the molecular sieve membrane.
B. Placing the porous carrier coated with the SAPO-34 molecular sieve seed crystal prepared in the step 2) into a molecular sieve membrane synthesis mother solution, soaking and aging for 2-8 hours at room temperature-80 ℃, and crystallizing for 2-10 hours in an oven at 180-240 ℃ to synthesize an SAPO-34 molecular sieve membrane tube;
4) roasting to remove template agent
Roasting the SAPO-34 molecular sieve membrane tube obtained in the step 3) at 370-500 ℃ for 2-8 hours to obtain the SAPO-34 molecular sieve membrane without the template agent.
In the steps 1) and 3), the aluminum source comprises: aluminum isopropoxide, Al (OH)3Simple substance aluminum and aluminum salt. Wherein the aluminum salt comprises: aluminum nitrate, aluminum chloride, aluminum sulfate, and aluminum phosphate.
In the steps 1) and 3), the phosphorus source comprises: phosphoric acid; the silicon source includes: ethyl orthosilicate, methyl orthosilicate, silica sol, white carbon black, sodium silicate and water glass.
In the step 1), the size of the SAPO-34 molecular sieve seed crystal is 50-1000 nanometers.
In the step 2), the porous carrier comprises a porous ceramic tube, wherein the pore diameter of the porous ceramic tube is 5-2000 nm, and the porous ceramic tube is made of the following materials: al (Al)2O3、TiO2、ZrO2SiC and silicon nitride.
In the seed crystal coating of the step 2), the specific steps are as follows: glazing two ends of the porous carrier, cleaning, drying, sealing the outer surface, and then coating SAPO-34 molecular sieve crystal seeds on the inner surface of the porous carrier; the coating method comprises the following steps: brush coating and dip coating.
In the step 4), the roasting atmosphere comprises: inert gas, vacuum, air, oxygen, and diluted oxygen in any proportion; during roasting, the heating rate and the cooling rate are not more than 2K/min.
Mother liquor formula concentration H of traditional SAPO-34 molecular sieve membrane2O/Al2O3The molar ratio is 50-200, and the thickness of the SAPO-34 molecular sieve membrane prepared by hydrothermal synthesis is usually 2-4 microns, so that the mass transfer resistance is large and the permeability is low.
Compared with the prior art, the invention prepares the low-viscosity ultra-concentrated synthetic mother liquor (H) by adopting a special mixing step2O/Al2O3Molar ratio of<20,TEAOH/Al2O3The molar ratio is between 1 and 10). The ultra-high mother liquor concentration effectively promotes nucleation, resulting in smaller SAPO-34 crystals and a substantial reduction in membrane thickness. The special mixing step greatly reduces the viscosity of the mother liquor, ensures the uniformity and the fluidity of the mother liquor and is beneficial to forming a high-quality SAPO-34 molecular sieve membrane. The method effectively reduces the thickness of the SAPO-34 molecular sieve membrane to 600 nanometers, thereby greatly reducing the mass transfer resistance and improving the permeability. By high pressure CO2/CH4Gas mixture separation tests show that the SAPO-34 molecular sieve membrane has excellent CO2/CH4The gas separation performance and the permeability are greatly improved. The method is also suitable for synthesizing other types of SAPO (silicoaluminophosphate) or AlPO (aluminophosphate) molecular sieve membranes.
Drawings
FIG. 1 is a scanning electron micrograph of the surface and the cross section of a SAPO-34 molecular sieve membrane prepared in example 1;
FIG. 2 is a scanning electron micrograph of the surface and the cross section of the SAPO-34 molecular sieve membrane prepared in example 2;
FIG. 3 is a scanning electron micrograph of the surface and the cross section of the SAPO-34 molecular sieve membrane prepared in example 3;
FIG. 4 is a scanning electron micrograph of the surface and the cross section of the SAPO-34 molecular sieve membrane prepared in example 4;
FIG. 5 is a scanning electron micrograph of the surface and the cross section of the SAPO-34 molecular sieve membrane prepared in example 5;
FIG. 6 is a scanning electron micrograph of the surface and cross section of the SAPO-34 molecular sieve membrane prepared in example 6.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
A method for preparing ultra-thin SAPO-34 molecular sieve membrane is to prepare low-viscosity ultra-concentrated synthetic mother liquor (H) by adopting special mixing steps2O/Al2O3Molar ratio of<20,TEAOH/Al2O3The molar ratio is between 1 and 10). The ultra-high mother liquor concentration effectively promotes nucleation, resulting in smaller SAPO-34 crystals and a substantial reduction in membrane thickness. The special mixing step greatly reduces the viscosity of the mother liquor, ensures the uniformity and the fluidity of the mother liquor and is beneficial to forming a high-quality SAPO-34 molecular sieve membrane. Aluminum hydroxide is used as an aluminum source, cubic SAPO-34 crystals are obtained under a high-concentration formula, and the cubic SAPO-34 crystals are favorable for cross-linking among the crystals, film formation and defect generation. Aluminum isopropoxide is used as an aluminum source, so that flaky crystals are easily formed, and the crystal crosslinking and film forming are not facilitated. The method effectively reduces the thickness of the SAPO-34 molecular sieve membrane to 800 nanometers, thereby greatly reducing the mass transfer resistance and improving the permeability, and specifically comprises the following steps:
1) synthesis of SAPO-34 molecular sieve seed crystal
Mixing and dissolving an aluminum source, tetraethylammonium hydroxide (TEAOH, a template agent), water, a silicon source and a phosphorus source to obtain a seed crystal reaction solution, specifically, adding the aluminum source into the TEAOH solution, hydrolyzing, sequentially adding the silicon source and the phosphorus source, and stirring to obtain the seed crystal reaction solution; further, the operation may be: mixing tetraethyl ammonium hydroxide solution with deionized water, adding an aluminum source into the solution, stirring at room temperature for 2-3 hours, then dropwise adding a silicon source, stirring for 0.5-2 hours, then slowly dropwise adding a phosphorus source solution, and stirring for 12-24 hours to obtain seed crystal reaction liquid, wherein the molar ratio of each component in the seed crystal reaction liquid is as follows: 1.0Al2O3:2.0P2O5:0.6SiO2:4.0TEAOH:75H2O, performing microwave synthesis on the obtained seed crystal reaction liquid for 7 hours at 443K, centrifuging, washing and drying to obtain SAPO-34 molecular sieve seed crystals with the size of 50-1000 nanometers;
2) seed coating
Coating SAPO-34 molecular sieve seed crystals on the inner surface of the porous carrier to obtain the porous carrier coated with the SAPO-34 molecular sieve seed crystals; the coating method of the molecular sieve seed crystal comprises brush coating, dip coating, spray coating and spin coating; when dip coating is adopted, the concentration of SAPO-34 nanometer seed crystal dip coating liquid is 1 wt%, the porous carrier comprises a porous ceramic tube, wherein the aperture of the porous ceramic tube is 5-2000 nanometers, and the porous ceramic tube is made of the following materials: al (Al)2O3、TiO2、ZrO2SiC and silicon nitride.
3) Synthesis of SAPO-34 molecular sieve membrane
A. Mixing tetraethyl ammonium hydroxide with water, then adding an aluminum source, and stirring for 1-5 hours to obtain a clear and transparent solution; putting the solution in an oven at 80 ℃ for heating to remove excessive water; and then adding a silicon source, stirring for 0.5-2 hours, adding a phosphorus source, stirring for 0.5-2 hours, then adding di-n-propylamine, and stirring for 2 hours to obtain a uniform molecular sieve membrane synthesis mother liquor. The synthesis mother liquor is nearly clear and transparent, has low viscosity and high uniformity and fluidity. It is noted that heating to remove water after mixing all the raw materials does not lead to a large increase in the viscosity of the mother liquor. The traditional SAPO-34 molecular sieve membrane mother liquor is prepared by mixing phosphoric acid and an aluminum source, and then sequentially adding a silicon source and a template agent. Such a feeding sequence also leads to an increase in the viscosity of the mother liquor, which is not favorable for the synthesis of the molecular sieve membrane, and the molar ratio of the aluminum source, the phosphorus source, the silicon source, the tetraethylammonium hydroxide, the di-n-propylamine (DPA) to the total water in the mother liquor for the synthesis of the molecular sieve membrane is: 1Al2O3:0.5～3.5P2O5:0.05～0.6SiO2:0.5～8TEAOH:0.1～6DPA:3～30H2O；
B. Placing the porous carrier coated with the SAPO-34 molecular sieve seed crystal prepared in the step 2) into a molecular sieve membrane synthesis mother solution, soaking and aging for 2-8 hours at room temperature-80 ℃, and crystallizing for 2-10 hours in an oven at 180-240 ℃ to synthesize an SAPO-34 molecular sieve membrane tube;
4) roasting to remove template agent
Roasting the SAPO-34 molecular sieve membrane tube obtained in the step 3) for 2-8 hours at 370-500 ℃, wherein the roasting atmosphere comprises: inert gas, vacuum, air, oxygen, and diluted oxygen in any proportion; during roasting, the heating rate and the cooling rate are not more than 2K/min, and the SAPO-34 molecular sieve membrane without the template agent is obtained.
In steps 1), 3), the aluminum source comprises: aluminum isopropoxide, Al (OH)3Simple substance aluminum and aluminum salt. Wherein the aluminum salt comprises: aluminum nitrate, aluminum chloride, aluminum sulfate and aluminum phosphate, the phosphorus source comprising: phosphoric acid; the silicon source includes: ethyl orthosilicate, methyl orthosilicate, silica sol, white carbon black, sodium silicate and water glass.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
Example 1
Synthesis of conventional SAPO-34 molecular sieve membranes (control test)
In this example, a conventional SAPO-34 zeolite membrane synthesis formula and method are adopted to synthesize the SAPO-34 zeolite membrane (mother liquor formula 1 Al)2O3:1P2O5:0.3SiO2:1TEAOH:150H2O:1.6DPA, crystallization at 220 degrees celsius for 5 hours). The method comprises the following specific steps:
step 1, synthesis of SAPO-34 nanometer crystal seed
Mixing and dissolving an aluminum source (aluminum isopropoxide), tetraethylammonium hydroxide (TEAOH, template), water, a silicon source (Ludox AS-40) and a phosphorus source (phosphoric acid) to obtain a seed crystal reaction solution. Wherein, the molar ratio of the seed crystal synthesis mother liquor is as follows: 1.0Al2O3:2.0P2O5:0.6SiO2:4.0TEAOH:75H2O, performing microwave synthesis for 7 hours at 443K, centrifuging, washing and drying to obtain SAPO-34 molecular sieve crystal seeds;
in this step, the specific preparation method of the seed crystal reaction solution may be as follows:
adding aluminum isopropoxide into tetraethyl ammonium hydroxide TEAOH solution, hydrolyzing, sequentially adding a silicon source (silica sol Ludox AS-40) and a phosphorus source (phosphoric acid), and stirring to obtain seed crystal reaction liquid; further, the operation may be: and mixing tetraethyl ammonium hydroxide solution and deionized water, adding an aluminum source into the solution, stirring at room temperature for 2-3 hours, dropwise adding a silicon source, stirring for 0.5-2 hours, slowly dropwise adding a phosphorus source solution, and stirring for 12-24 hours to obtain a seed crystal reaction solution.
And 2, selecting a porous ceramic tube with the aperture of 100nm as a carrier, glazing two ends of the carrier, cleaning, drying, sealing the outer surface by using a tetrafluoro belt, and brushing the SAPO-34 molecular sieve seed crystal on the inner surface of the ceramic tube.
Step 3, mixing aluminum isopropoxide, water and phosphoric acid, and stirring for 2 hours; adding silica sol (Ludox AS-40), and stirring for 1 hour; tetraethylammonium hydroxide (organic templating agent, TEAOH) and dipropylamine were then added and stirred for 2 hours to obtain a synthesis mother liquor. The molar ratio of the mother liquor is as follows: 1Al2O3:1P2O5:0.3SiO2:1TEAOH:150H2O：1.6DPA。
And 4, placing the porous carrier coated with the SAPO-34 molecular sieve seed crystal prepared in the step 2 into a crystallization kettle, pouring synthetic mother liquor, standing for 3 hours at room temperature, heating and crystallizing for 5 hours in a 220 ℃ oven, cooling the reaction kettle, taking out the synthesized molecular sieve membrane tube, and thoroughly cleaning and drying the molecular sieve membrane tube.
And 5, roasting the SAPO-34 molecular sieve membrane tube obtained in the step 4 at 400 ℃ for 4 hours in vacuum, and removing the template agent (the heating rate and the cooling rate are both 1K/min) to obtain the SAPO-34 molecular sieve membrane.
Subjecting the obtained SAPO-34 molecular sieve membrane to CO2/CH4Gas separation test, the test conditions were: the temperature was 25 ℃, the atmospheric pressure was 102.4kPa, the feed gas flow was 4000mL/min, and the molar composition was 50/50%. Measuring the gas flow at the permeation side by using a soap film flowmeter; the gas composition on the permeate side was analyzed by gas chromatography (Shimadzu-2014C).
Calculation formula of gas permeability: p is V/(sxp). Wherein V is a permeate gas (CO)2Or CH4) The flow rate of (2) is in mol/S, S is the membrane area, m2(ii) a P is the pressure difference between the feed side and the permeate side of the membrane tube, in Pa.
Separation selectivity calculation formula: f ═ pCO2/pCH4I.e. CO2And CH4The permeability of (c).
The surface and the section of the obtained SAPO-34 molecular sieve membrane are shown in figure 1, and as can be seen from the figure, the surface of the carrier is completely covered by square SAPO-34 crystals, and the cross-linking among the crystals is good (see the left figure); the thickness of the film was relatively uniform, about 5 microns (see right panel). Prepared SAPO-34 molecular sieve membrane pair CO2-CH4The separation has better performance, and CO is separated under the pressure difference of 0.14Mpa2The permeability reaches 13.2 x 10-7mol/(m2s.Pa), and CO2-CH4The separation selectivity was 164. At 4MPa, CO2The permeability reaches 4.1 x 10-7mol/(m2s.Pa), and CO2-CH4The separation selectivity was 39.
The results of the gas separation tests of the SAPO-34 molecular sieve membrane tubes are shown in table 1.
Table 1 CO of example 12/CH4Gas separation test results
(feed gas: 50 CO)2:50CH4mol％,298K)
Example 2
This example prepares SAPO-34 molecular sieve membrane (H of mother liquor) in an ultra-concentrated synthesis mother liquor2O/Al2O3Reduced from 150 to 20 for the conventional formulation), mother liquor formulation 1Al2O3:1P2O5:0.3SiO2:1TEAOH:20H2O1.6 DPA, and crystallizing at 220 ℃ for 5 hours.
The difference from the example 1 is that the feeding sequence of the SAPO-34 molecular sieve membrane synthesis mother liquor in the step 3 is as follows: mixing tetraethyl ammonium hydroxide with water, then adding aluminum hydroxide, and stirring for 1-5 hours to obtain a clear and transparent solution; putting the solution in an oven at 80 ℃ for heating to remove excessive water; then adding a silicon source, stirring for 0.5-2 hours, adding a phosphorus source, stirring for 0.5-2 hours, adding dipropylamine, and stirring for 2 hours to obtain uniform componentsAnd (4) synthesizing a mother solution by using the subsieve sieve membrane. The synthesis mother liquor is nearly clear and transparent, has low viscosity and high uniformity and fluidity. The final molar ratio of the mother liquor is as follows: 1Al2O3:1P2O5:0.3SiO2:1TEAOH:20H2O:1.6 DPA. The rest of the procedure was the same as in example 1.
CO2/CH4The gas separation test method was the same as in example 1, and the test results are shown in table 2. FIG. 2 is a surface and cross-sectional SEM image of a prepared SAPO-34 molecular sieve membrane. In FIG. 2, it is shown that the support surface is completely covered with square SAPO-34 crystals and the cross-linking between the crystals is perfect. The thickness of the SAPO-34 molecular sieve membrane is about 2 microns, which is 50% thinner than the membrane tube prepared in example 1. This indicates an increase in the mother liquor concentration (in this example H is added2O/Al2O3From 150 to 20) is effective in promoting nucleation, resulting in smaller crystals and thinner film thickness. CO of the corresponding, SAPO-34 molecular sieve membrane2-CH4The separation performance is also greatly improved. Especially CO2Permeability, at 0.14MPa, from 13.2X 10-7mol/(m2s.Pa) to
22.3×10-7mol/(m2s.Pa), the selectivity decreased slightly to 124. Permeability at 4MPa from 4.1X 10-7mol/(m2s.Pa) to 7.8X 10-7mol/(m2s.Pa) due to the mass transfer resistance being reduced by the thinning of the film thickness, while CO2-CH4The selectivity decreases only slightly.
Table 2 CO of example 22/CH4Gas separation test results
(feed gas: 50 CO)2:50CH4mol％,298K)
Example 3
This example prepares SAPO-34 molecular sieve membrane (H of mother liquor) in an ultra-concentrated synthesis mother liquor2O/Al2O3Compared with 150 reduction from the conventional formulaTo 10), mother liquor formulation 1Al2O3:1P2O5:0.3SiO2:1TEAOH:10H2O1.6 DPA, and crystallizing at 220 ℃ for 5 hours.
The difference from the example 1 is that the feeding sequence of the SAPO-34 molecular sieve membrane synthesis mother liquor in the step 3 is as follows: mixing tetraethyl ammonium hydroxide with water, then adding aluminum hydroxide, and stirring for 1-5 hours to obtain a clear and transparent solution; putting the solution in an oven at 80 ℃ for heating to remove excessive water; and then adding a silicon source, stirring for 0.5-2 hours, adding a phosphorus source, stirring for 0.5-2 hours, adding dipropylamine, and stirring for 2 hours to obtain a uniform molecular sieve membrane synthesis mother liquor. The synthesis mother liquor is nearly clear and transparent, has low viscosity and high uniformity and fluidity. The final molar ratio of the mother liquor is as follows: 1Al2O3:1P2O5:0.3SiO2:1TEAOH:10H2O:1.6 DPA. The rest of the procedure was the same as in example 1.
CO2/CH4The gas separation test method was the same as in example 1, and the test results are shown in table 3. FIG. 3 is a surface and cross-sectional SEM image of a prepared SAPO-34 molecular sieve membrane. In FIG. 3, it is shown that the support surface is completely covered with square SAPO-34 crystals and the cross-linking between the crystals is perfect. The thickness of the SAPO-34 molecular sieve membrane is about 1.8 microns, and is greatly reduced compared with the thickness of the membrane tube prepared in the example 1. This indicates an increase in the mother liquor concentration (in this example H is added2O/Al2O3From 150 to 10) is effective in promoting nucleation, resulting in smaller crystals and thinner film thickness. CO of the corresponding, SAPO-34 molecular sieve membrane2-CH4The separation performance is also greatly improved. Especially CO2Permeability, at 0.14MPa, from 13.2X 10-7mol/(m2s.Pa) to 24.6X 10-7mol/(m2s.Pa), the selectivity dropped to 75. The selectivity is lower at 4 MPa. The increase in permeability is attributed to the decrease in mass transfer resistance due to the thinning of the film thickness. CO 22-CH4The selectivity is greatly reduced, probably because of the increase of the mother liquor concentration and the reduction of the uniformity of the mother liquor viscosity, which is related to the film forming qualityThere is a large adverse effect.
Table 3 CO of example 32/CH4Gas separation test results
(feed gas: 50 CO)2:50CH4mol％,298K)
Example 4
This example prepares SAPO-34 molecular sieve membrane (H of mother liquor) in an ultra-concentrated synthesis mother liquor2O/Al2O3Ratio 10, TEAOH/Al2O34) mother liquor formula 1Al2O3:1P2O5:0.3SiO2:4TEAOH:10H2O1.6 DPA, and crystallizing at 220 ℃ for 5 hours.
The difference from the example 1 is that the feeding sequence of the SAPO-34 molecular sieve membrane synthesis mother liquor in the step 3 is as follows: mixing tetraethyl ammonium hydroxide with water, then adding aluminum hydroxide, and stirring for 1-5 hours to obtain a clear and transparent solution; putting the solution in an oven at 80 ℃ for heating to remove excessive water; and then adding a silicon source, stirring for 0.5-2 hours, adding a phosphorus source, stirring for 0.5-2 hours, adding dipropylamine, and stirring for 2 hours to obtain a uniform molecular sieve membrane synthesis mother liquor. The synthesis mother liquor is nearly clear and transparent, has low viscosity and high uniformity and fluidity. The final molar ratio of the mother liquor is as follows: 1Al2O3:1P2O5:0.3SiO2:4TEAOH:10H2O:1.6 DPA. The rest of the procedure was the same as in example 1.
CO2/CH4The gas separation test method was the same as in example 1, and the test results are shown in table 4. FIG. 4 is a surface and cross-sectional SEM image of a prepared SAPO-34 molecular sieve membrane. In FIG. 4, it is shown that the support surface is completely covered with SAPO-34 crystals and the cross-linking between the crystals is perfect. The thickness of the SAPO-34 molecular sieve membrane is about 1.2 microns. The film thickness was further reduced from 5 μm in example 1 and 2 μm in examples 2 and 3 to 1.2 μm as compared with examples 1,2 and 3. Corresponding, SAPO-34 minCO of sub-sieve membrane2-CH4The separation performance is also greatly improved. Especially CO2Permeability, at 0.14MPa, from 13.2X 10-7mol/(m2s.Pa) to 38.5X 10-7mol/(m2s.Pa). This shows that the thinning of the film thickness greatly reduces the mass transfer resistance and increases the CO2Permeability of (2), and CO2-CH4The selectivity is essentially unchanged. At 4MPa, CO2Permeability of 12.3X 10-7mol/(m2S.pa) but with a lower selectivity of only 8.
Table 4 CO of example 42/CH4Gas separation test results
(feed gas: 50 CO)2:50CH4mol％,298K)
Example 5
This example prepares SAPO-34 molecular sieve membrane (H of mother liquor) in an ultra-concentrated synthesis mother liquor2O/Al2O3Ratio 10, TEAOH/Al2O34) mother liquor formula 1Al2O3:1P2O5:0.3SiO2:4TEAOH:10H2O1.6 DPA, and crystallizing at 220 ℃ for 5 hours. This example is a control of example 4, the only difference being that the aluminum source is aluminum isopropoxide.
The difference from the example 1 is that the feeding sequence of the SAPO-34 molecular sieve membrane synthesis mother liquor in the step 3 is as follows: mixing tetraethyl ammonium hydroxide with water, then adding aluminum isopropoxide, and stirring for 1-5 hours to obtain a clear and transparent solution; putting the solution in an oven at 80 ℃ for heating to remove excessive water; and then adding a silicon source, stirring for 0.5-2 hours, adding a phosphorus source, stirring for 0.5-2 hours, adding dipropylamine, and stirring for 2 hours to obtain a uniform molecular sieve membrane synthesis mother liquor. The synthesis mother liquor is nearly clear and transparent, has low viscosity and high uniformity and fluidity. The final molar ratio of the mother liquor is as follows: 1Al2O3:1P2O5:0.3SiO2:4TEAOH:10H2O:1.6 DPA. The rest of the procedure was the same as in example 1.
CO2/CH4The gas separation test method was the same as in example 1, and the test results are shown in table 5. FIG. 5 is a surface and cross-sectional SEM image of a prepared SAPO-34 molecular sieve membrane. In FIG. 5, it is shown that the support surface is completely covered with flaky SAPO-34 crystals, which is different from the cubic SAPO-34 crystals prepared under the same conditions using aluminum hydroxide as an aluminum source. The thickness of the SAPO-34 molecular sieve membrane is about 1 micron. The film thickness was greatly reduced from 5 μm in example 1 and 2 μm in examples 2 and 3, as compared with examples 1,2 and 3. However, the flaky crystals are not favorable for cross-linking between the crystals to form a membrane, and correspondingly, the SAPO-34 molecular sieve membrane is used for CO2-CH4The separation selectivity is essentially absent, approaching 1. This indicates that in the high concentration mother liquor, aluminum isopropoxide was used as an aluminum source to obtain flaky SAPO-34 crystals, which are not favorable for forming a crosslinked membrane, and the SAPO-34 molecular sieve membrane is thin but almost non-selective. In the embodiment 4, aluminum hydroxide is used as an aluminum source, so that cubic SAPO-34 crystals are obtained, the cross-linking film forming is facilitated, and the selectivity of the film tube is high.
TABLE 5 CO of example 52/CH4Gas separation test results
(feed gas: 50 CO)2:50CH4mol％,298K)
Example 6
This example prepares SAPO-34 molecular sieve membrane (H of mother liquor) in an ultra-concentrated synthesis mother liquor2O/Al2O3Ratio 10, TEAOH/Al2O34) mother liquor formula 1Al2O3:1P2O5:0.3SiO2:4TEAOH:10H2O1.6 DPA, and crystallizing at 220 ℃ for 5 hours. This example is a control of example 4, the only difference being that the pre-seeded carrier tube was placed in the mother liquor and allowed to stand at room temperature for 1 hour (example 4 is3 hours)
The difference from the example 1 is that the feeding sequence of the SAPO-34 molecular sieve membrane synthesis mother liquor in the step 3 is as follows: mixing tetraethyl ammonium hydroxide with water, then adding an aluminum source, and stirring for 1-5 hours to obtain a clear and transparent solution; putting the solution in an oven at 80 ℃ for heating to remove excessive water; and then adding a silicon source, stirring for 0.5-2 hours, adding a phosphorus source, stirring for 0.5-2 hours, adding dipropylamine, and stirring for 2 hours to obtain a uniform molecular sieve membrane synthesis mother liquor. The synthesis mother liquor is nearly clear and transparent, has low viscosity and high uniformity and fluidity. The final molar ratio of the mother liquor is as follows: 1Al2O3:1P2O5:0.3SiO2:4TEAOH:10H2O:1.6 DPA. The rest of the procedure was the same as in example 1.
CO2/CH4The gas separation test method was the same as in example 1, and the test results are shown in table 6. FIG. 6 is a surface and cross-sectional SEM image of a prepared SAPO-34 molecular sieve membrane. In FIG. 6, it is shown that the support surface is completely covered with SAPO-34 crystals, and the cross-linking between the crystals is perfect. The thickness of the SAPO-34 molecular sieve membrane is about 0.8 microns. CO of the corresponding, SAPO-34 molecular sieve membrane2-CH4The separation performance is also greatly improved. Especially CO2Permeability, at 0.14MPa, from 13.2X 10-7mol/(m2s.Pa) to 49.5X 10-7mol/(m2s.Pa) with substantially unchanged selectivity. Under 4MPa, the permeability reaches 16 multiplied by 10-7mol/(m2s.Pa) and the selectivity is 8. This shows that the thinning of the film thickness greatly reduces the mass transfer resistance and increases the CO2Permeability of (d). The aging time of this example was reduced from 3 hours to 1 hour. The reduction of the aging time is beneficial to avoiding excessive dissolved crystal seeds under the condition of high-concentration mother liquor, thereby being beneficial to forming a high-quality molecular sieve membrane.
Table 6 CO of example 62/CH4Gas separation test results
(feed gas: 50 CO)2:50CH4mol％,298K)
In the description herein, references to the description of "one embodiment," "an example," "a specific example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. A method for preparing an ultrathin SAPO-34 molecular sieve membrane is characterized by comprising the following steps:
preparing SAPO-34 nanometer crystal seeds;
coating SAPO-34 nano seed crystals on a porous carrier tube;
preparing ultra-concentrated SAPO-34 molecular sieve membrane synthesis mother liquor;
when preparing the mother liquid for synthesizing the ultra-concentrated SAPO-34 molecular sieve membrane, Al in the mother liquid2O3、P2O5、SiO2、TEAOH、H2O, DPA is controlled to be 1.0: 0.5-2.0: 0.05-0.6: 1.0-8.0: 3-20: 0.1-6;
when the mother solution for synthesizing the SAPO-34 molecular sieve membrane is prepared, tetraethyl ammonium hydroxide is mixed with water, an aluminum source is added, and the mixture is stirred for 1-5 hours to obtain a clear and transparent solution; putting the solution in an oven at 80 ℃ for heating to remove excessive water; then adding a silicon source, stirring for 0.5-2 hours, adding a phosphorus source, stirring for 0.5-2 hours, then adding di-n-propylamine, and stirring for 2 hours to obtain a uniform molecular sieve membrane synthesis mother liquor;
placing the porous carrier tube in a molecular sieve membrane synthesis mother solution, aging at room temperature for 0.5-3 hours, then placing the porous carrier tube in an oven for high-temperature hydrothermal synthesis to obtain an SAPO-34 molecular sieve membrane, and then washing and drying;
and (3) roasting at high temperature to remove the template agent to obtain the activated SAPO-34 molecular sieve membrane.
2. The method for preparing the ultra-thin SAPO-34 zeolite membrane of claim 1, wherein Al in mother liquor is added during the preparation of SAPO-34 nanocrystal2O3、P2O5、SiO2、TEAOH、H2Controlling the molar ratio of O to be 1.0: 2.0: 0.6: 4.0: 75, and carrying out microwave synthesis at 443K for 7 hours to obtain SAPO-34 nano seed crystals with the particle diameter not more than 300 nanometers.
3. The method for preparing the ultra-thin SAPO-34 molecular sieve membrane according to claim 1, wherein the porous support tube has a shape of a single-channel tube, a multi-channel tube, a flat plate or a hollow fiber tube, and is made of a material selected from ceramics, stainless steel, alumina, titania, zirconia, silica, silicon carbide or silicon nitride, and the pore diameter is 2-2000 nm.
4. The method for preparing the ultra-thin SAPO-34 zeolite membrane of claim 1, wherein the coating method of the SAPO-34 nanocrystal seeds comprises brushing, dipping, spraying or spin coating.
5. The method for preparing the ultrathin SAPO-34 molecular sieve membrane as claimed in claim 4, wherein when the seed crystal is coated by a dip coating method, the concentration of the SAPO-34 nano seed crystal dip coating solution is 0.01-2 wt%.
6. The method of claim 1, wherein the aluminum source comprises aluminum isopropoxide, aluminum hydroxide, elemental aluminum, aluminum salt, alumina, or hydrated alumina; the silicon source comprises silica sol, silicate ester or silica aerosol.
7. The method for preparing the ultra-thin SAPO-34 molecular sieve membrane of claim 6, wherein the aluminum source is aluminum hydroxide.
8. The method for preparing the ultra-thin SAPO-34 molecular sieve membrane according to claim 1, wherein the temperature of the hydrothermal crystallization is 473 to 573K for 2 to 10 hours.
9. The method for preparing the ultrathin SAPO-34 molecular sieve membrane according to claim 1, wherein the roasting temperature is controlled to be 370-500 ℃ during high-temperature roasting, and the roasting time is controlled to be 2-8 h.
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