CN111099636A - Preparation method of modified SAPO molecular sieve membrane - Google Patents
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Abstract
The invention relates to a preparation method of a silicoaluminophosphate SAPO molecular sieve membrane, which mainly solves the problem that the existing SAPO molecular sieve membrane preparation technology is insufficient. The method comprises the steps of carrying out alkali treatment on a silicon source in a coating liquid in advance, coating a crystal seed layer and the coating liquid on a carrier in sequence, and then refluxing and drying a molecular sieve membrane prepared by gas phase in-situ crystallization in a solution containing an amination reagent to obtain the amine modified SAPO-34 molecular sieve membrane. The technical scheme is simple to operate, and the obtained SAPO molecular sieve membrane has the advantages of good repeatability, good compactness and uniformity, high quality, low preparation cost, contribution to cyclic utilization of the template agent and capability of being used in industrial production of the molecular sieve membrane.
Description
Technical Field
The invention relates to a preparation method of an SAPO molecular sieve membrane.
Background
The membrane separation technology is a new separation, purification and purification technology, and is widely applied to the fields of food, beverage, metallurgy, paper making, textile, pharmacy, automobile, biology, chemical industry and the like. The inorganic membrane can be classified into an inorganic membrane and an organic membrane according to the membrane material, and the inorganic membrane has excellent chemical stability, thermal stability and mechanical strength compared to the organic membrane. The molecular sieve membrane is a representative inorganic membrane, and has a pore channel with a certain shape, a controllable structure, adjustable and uniform pore diameter distribution, and the pore diameter size is close to the molecular size. The molecular sieve membrane has specific pore structure, so that the molecular sieve membrane has selective permeability and shape-selective catalysis, and can be modified by ion exchange. The molecular sieve membrane has attractive application prospects in the fields of membrane separation, membrane catalysis, membrane reactors and the like due to the separation and catalysis at the molecular level, and has become a research hotspot of inorganic membrane materials in recent years.
The molecular sieve membranes can be divided into three major types, namely filling membranes (embedded membranes), self-supporting membranes and supporting membranes, and the supporting molecular sieve membranes have all the characteristics of molecular sieves, so that the supporting molecular sieve membranes become the molecular sieve membranes with the most development potential. The preparation method of the supporting molecular sieve membrane mainly comprises four types, namely a hydrothermal in-situ generation method, a secondary growth method, a microwave synthesis method and a gas phase crystallization method. The secondary growth method is the most common membrane making method, namely, a layer of pre-synthesized nano-scale molecular sieve crystal is attached to a support body to be used as a seed crystal, and then the seed crystal is immersed into a synthetic liquid for continuous crystallization, so that the growth of the inner plane of the molecular sieve seed crystal is promoted, cracks are reduced, and a continuous molecular sieve membrane is formed. The molecular sieve membrane prepared by the gas phase crystallization method is mainly characterized in that a synthetic liquid is coated on a support body or a support body with pre-attached seed crystals by a spin-coating method or a dipping method, and then the molecular sieve membrane is obtained by crystallization by a gas phase transfer method, so that the membrane layer is thicker due to hydrothermal crystallization and resource waste caused by large-scale use of a template agent is avoided.
In the preparation method of the molecular sieve membrane, the silicon source is directly used, the crystal grains are not uniform, the particles are large, and the formed molecular sieve membrane has many defects and is not beneficial to separation of mixed gas; the in-situ generation method and the secondary growth method are that a molecular sieve is nucleated and grows through a hydrothermal system, so that the shape of particles and the density of crystal nuclei on a carrier cannot be controlled, and a film on the carrier is uneven; in-situ generation method does not use seed crystal, so that the molecular sieve membrane has low compactness; the research on the molecular sieve membrane is mainly focused on the silicon-aluminum oxide material, the research on the silicon-phosphorus-aluminum molecular sieve membrane is less, and the research has a great difference from the industrial application requirements in the aspects of membrane preparation technology, preparation cost, separation effect and the like, and needs to be further researched and solved.
In order to overcome the above defects, a preparation method of a high-quality, simple and environment-friendly synthetic silicon-phosphorus-aluminum molecular sieve membrane is particularly needed.
Disclosure of Invention
The invention aims to solve the technical problem that the prior SAPO molecular sieve membrane preparation technology is not sufficient. The invention provides a novel preparation method of an SAPO molecular sieve membrane, and the material has good compactness and repeatability.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a preparation method of an SAPO molecular sieve membrane comprises the following steps: and (3) preparing the SAPO molecular sieve membrane, and performing amine modification on the SAPO molecular sieve membrane.
In the technical scheme, the preparation of the SAPO molecular sieve membrane comprises the following steps:
a) treating the carrier with acid and alkali respectively;
b) coating the seed crystal on the treated carrier;
c) mixing a phosphorus source, an aluminum source, an alkali-treated silicon source and water to obtain silicon-phosphorus-aluminum oxide sol, wherein the phosphorus source generates P theoretically2O5Theoretical production of Al from measured and aluminium sources2O3Theoretical production of SiO from metered and silicon sources2The weight ratio of the mixture is as follows: h2O/Al2O3＝1～200；SiO2/Al2O3＝0.03～0.90；P2O5/Al2O30.05 to 2.80; coating the silicon-phosphorus-aluminum oxide solution on the carrier subjected to the step b), and performing gas phase crystallization;
or mixing a phosphorus source, an aluminum source, an alkali-treated silicon source, a template agent R1 and water to obtain the silicon-phosphorus-aluminum oxide sol, wherein the phosphorus source generates P theoretically2O5Theoretical production of Al from measured and aluminium sources2O3Theoretical production of SiO from metered and silicon sources2The weight ratio of the mixture is as follows: h2O/Al2O3＝1～200；SiO2/Al2O3＝0.03～0.90；P2O5/Al2O3＝0.05～2.80；R1/Al2O30.1-15, crystallizing in liquid phase; the alkali treatment is realized by placing a silicon source in an alkaline solution for heating reflux, preferably in triethylamine for reflux.
In the above technical scheme, the gas phase crystallization is specifically carried out by placing the mixture on the upper part of a reaction kettle, adding the mixture of a template agent and water into the bottom of the reaction kettle, wherein the ratio of the template agent/water is 0.003-1, preferably 0.001-2, and reacting at 220 ℃ for 0.1-5 days; the template agent is at least one selected from tetraethyl ammonium hydroxide, tetraethyl ammonium bromide, triethylamine and ethylenediamine.
In the technical scheme, the liquid phase crystallization is specifically that the liquid phase crystallization is placed in a solution containing an SAPO molecular sieve mother solution and reacts for 0.1 to 5 days at the temperature of 150-; in the step c), the crystallization temperature is 160-210 ℃, and the crystallization time is 0.2-4 days.
In the above steps, the phosphorus source, the aluminum source, the alkali-treated silicon source and water are mixed uniformly at-20 ℃ to 100 ℃, preferably, the aluminum source is mixed in the water, the phosphorus source is added while stirring, the mixture is stirred vigorously for 3 to 4 hours to be hydrolyzed completely to obtain a white milk-like uniform solution, then the alkali-treated silicon source is added, and the mixture is stirred to obtain the silicon-phosphorus-aluminum oxide sol. So as to improve the compactness of the molecular sieve membrane. In the above technical scheme, the alkali for treating the carrier is at least one selected from sodium hydroxide, potassium hydroxide, ammonia water, tetraethyl ammonium hydroxide, tetraethyl ammonium bromide, triethylamine or ethylenediamine; the acid is at least one selected from hydrochloric acid, nitric acid or sulfuric acid.
In the technical scheme, the treatment in the step a) is specifically that after 0.1-2% of acid and 0.1-2% of alkali are soaked for 0.5-48 hours, the solution is washed to be neutral, dried and roasted for later use; the concentration of the acid-base soaking is 0.2-1.5%, and the treatment time is 1-24 hours.
In the above technical solution, the seed crystal is coated by at least one of coating and pulling, preferably, pulling is performed several times.
In the above technical solution, the silicon source is selected from at least one of silica sol, tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate or silica sol; the aluminum source is at least one selected from aluminum isopropoxide, pseudo-boehmite, alumina, aluminum nitrate, aluminum chloride or aluminum sulfate; the phosphorus source is at least one selected from phosphoric acid, ammonium phosphate, diammonium phosphate, ammonium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium hydrogen phosphate, sodium phosphate, disodium hydrogen phosphate and sodium hydrogen phosphate.
In the technical scheme, the weight ratio of the silicon-phosphorus-aluminum mixture is selected from the following components: h2O/Al2O3＝3.00～13.00；SiO2/Al2O3＝0.07～0.80；P2O5/Al2O3＝0.06～2.30。
In the above technical scheme, the template agent is at least one selected from tetraethyl ammonium hydroxide, triethylamine or ethylenediamine.
In the technical scheme, the amine modification specifically comprises the steps of cooling a reaction kettle after the reaction is finished, washing, drying to obtain the SAPO type molecular sieve membrane, refluxing the SAPO type molecular sieve membrane in a solution containing the aminating reagent, preferably refluxing the SAPO type molecular sieve membrane in a toluene solution containing the aminating reagent, and drying to obtain the amine modified SAPO molecular sieve membrane; the amination reagent is at least one of organic reagents containing N atoms, such as ethylenediamine, N-hexylamine or octylamine.
In the technical scheme, the crystallization temperature is 160-210 ℃, and the crystallization time is 0.2-4 days.
The carrier is alumina.
The invention carries out amine modification on the SAPO molecular sieve membrane, and the obtained molecular sieve membrane has better performance. In the process of preparing the SAPO molecular sieve membrane, the silicon source is decomposed into uniform silicon dioxide small particles by alkali treatment, so that the generated silicon-phosphorus-aluminum molecular sieve membrane has good compactness and few defects. The secondary growth method and the gas phase crystallization method are organically combined, the obtained silicon-phosphorus-aluminum molecular sieve membrane has good continuity, the thickness of the silicon-phosphorus-aluminum molecular sieve membrane is easy to control, and the silicon-phosphorus-aluminum molecular sieve membrane is compact and has good repeatability. The silicon-phosphorus-aluminum molecular sieve membrane is obtained through gas phase crystallization, and the thickness of the silicon-phosphorus-aluminum molecular sieve membrane can be further regulated and controlled by regulating the crystallization times. The preparation method has the advantages of simple preparation process, easy control, high crystallinity and high quality of the silicon-phosphorus-aluminum molecular sieve membrane, and obtains better technical effect.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) photograph of the SAPO molecular sieve membrane obtained in [ example 1 ].
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
12.3g of aluminum isopropoxide was mixed in ionized water, 11.97g of phosphoric acid was added while stirring, and strong stirring was carried out for 3-4 hours to completely hydrolyze and obtain a white milky homogeneous solution. Then, 6g of silica sol refluxed in triethylamine solution was added thereto, and the mixture was stirred at room temperature for 3 hours. Sealing two ends of an alumina ceramic tube which is subjected to acid-base treatment and is precoated with 0.3g of Sapo-34 seed crystal, vertically putting the alumina ceramic tube into the mixed solution, pulling the alumina ceramic tube for several times, drying the alumina ceramic tube at room temperature, putting the alumina ceramic tube on the upper part of a stainless steel reaction kettle with a polytetrafluoroethylene lining body, adding a mixed solution of 3g of template agent tetraethylammonium hydroxide and 10g of water into the bottom of the reaction kettle, sealing the reaction kettle, and standing the reaction kettle under the self pressure for crystallization at 200 ℃ for 48 hours. And after crystallization, taking out the carrier, then refluxing the SAPO-34 molecular sieve membrane obtained after washing, drying and roasting at 550 ℃ in a toluene solution containing ethylenediamine for 12 hours, and drying to obtain the amine modified SAPO-34 molecular sieve membrane. XRD results show that the obtained product is an SAPO molecular sieve membrane. SEM is shown in figure 1.
The weight ratio of each component is as follows: SiO 22/Al2O3＝0.4；P2O5/Al2O3＝1.1；H2O/Al2O3＝7
[ example 2 ]
12.3g of aluminum isopropoxide is weighed and mixed in ionized water, 11.97g of phosphoric acid is added while stirring, and strong stirring is carried out for 3-4h to ensure that the aluminum isopropoxide is completely hydrolyzed and a white milk-shaped uniform solution is obtained. Then, 6g of silica sol subjected to reflux treatment in a triethylamine solution was added, and after stirring at room temperature for 0.5h, 60g of a template agent R1 was added, and the mixture was stirred for 2 h. Sealing two ends of an alumina ceramic tube which is subjected to acid-base treatment and is precoated with 0.3g of Sapo-34 seed crystal, vertically putting the tube into the mixed solution, pulling the tube for a plurality of times, airing the tube at room temperature, and then putting the tube into a stainless steel reaction kettle with a polytetrafluoroethylene lining body for standing and crystallizing for 24 hours at 200 ℃. And (3) taking out the ceramic tube after crystallization is finished, drying, roasting at 550 ℃ to obtain the SAPO-34 molecular sieve membrane, refluxing in a toluene solution containing ethylenediamine for 12 hours, and drying to obtain the amine modified SAPO-34 molecular sieve membrane. XRD results show that the obtained product is an SAPO-34 molecular sieve membrane.
The weight ratio of each component is as follows: SiO 22/Al2O3＝0.4；P2O5/Al2O3＝1.1；H2O/Al2O3＝7；R1/Al2O3＝10
[ examples 3 to 12 ]
SAPO molecular sieve membranes were prepared according to the procedures and conditions of example 1, except that the raw material (table 1) ratios, the types of templates, the crystallization temperature, and other parameters were changed, as shown in table 1. Characterization of the synthesized product indicated that the result had a crystal structure similar to that of [ example 1 ].
TABLE 1
[ example 13 ] amine-free modified SAPO-34 molecular sieve membrane
12.3g of aluminum isopropoxide is weighed and mixed in ionized water, 11.97g of phosphoric acid is added while stirring, and strong stirring is carried out for 3-4h to ensure that the aluminum isopropoxide is completely hydrolyzed and a white milk-shaped uniform solution is obtained. Then, 6g of silica sol subjected to reflux treatment in a triethylamine solution was added, and after stirring at room temperature for 0.5h, 60g of a template agent R1 was added, and the mixture was stirred for 2 h. Sealing two ends of an alumina ceramic tube which is subjected to acid-base treatment and is precoated with 0.3g of Sapo-34 seed crystal, vertically putting the tube into the mixed solution, pulling the tube for a plurality of times, airing the tube at room temperature, and then putting the tube into a stainless steel reaction kettle with a polytetrafluoroethylene lining body for standing and crystallizing for 24 hours at 200 ℃. And (4) taking out the ceramic tube after crystallization is finished, and then drying and roasting at 550 ℃ to obtain the SAPO-34 molecular sieve membrane.
The weight ratio of each component is as follows: SiO 22/Al2O3＝0.4；P2O5/Al2O3＝1.1；H2O/Al2O3＝7；R1/Al2O3＝10
The molecular sieve membrane (a) prepared in example 1, the molecular sieve membrane (B) prepared in example 2, and the molecular sieve membrane (C) prepared in example 13 were subjected to CO2And CH4The mixed gas was separated, and the results are shown below.
Claims (10)
1. A preparation method of an SAPO molecular sieve membrane comprises the following steps: and (3) preparing the SAPO molecular sieve membrane, and performing amine modification on the SAPO molecular sieve membrane.
2. The method for preparing the SAPO molecular sieve membrane of claim 1, wherein the step of preparing the SAPO molecular sieve membrane comprises the steps of:
a) treating the carrier with acid and alkali respectively;
b) coating the seed crystal on the treated carrier;
c) mixing a phosphorus source, an aluminum source, an alkali-treated silicon source and water to obtain silicon-phosphorus-aluminum oxide sol, wherein the phosphorus source generates P theoretically2O5Theoretical production of Al from measured and aluminium sources2O3Theoretical production of SiO from metered and silicon sources2The weight ratio of the mixture is as follows: h2O/Al2O3＝1～200；SiO2/Al2O3＝0.03～0.90；P2O5/Al2O30.05 to 2.80; coating the silicon-phosphorus-aluminum oxide solution on the carrier subjected to the step b), and performing gas phase crystallization; or mixing a phosphorus source, an aluminum source, an alkali-treated silicon source, a template agent R1 and water to obtain the silicon-phosphorus-aluminum oxide sol, wherein the phosphorus source generates P theoretically2O5Theoretical production of Al from measured and aluminium sources2O3Theoretical production of SiO from metered and silicon sources2The weight ratio of the mixture is as follows: h2O/Al2O3＝1～200；SiO2/Al2O3＝0.03～0.90；P2O5/Al2O3＝0.05～2.80；R1/Al2O30.1-15, crystallizing in liquid phase; the alkali treatment is realized by putting a silicon source in an alkaline solution for heating and refluxing.
3. The method for preparing SAPO molecular sieve membrane according to claim 2, wherein the alkali for treating the carrier in step a) is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, tetraethylammonium hydroxide, tetraethylammonium bromide, triethylamine, and ethylenediamine; the acid is selected from at least one of hydrochloric acid, nitric acid and sulfuric acid.
4. The preparation method of the SAPO molecular sieve membrane of claim 2, wherein the treatment in step a) is specifically carried out by soaking 0.1-2% of acid and 0.1-2% of alkali for 0.5-48 hours, then washing to neutrality, drying, and roasting for later use; preferably, the concentration of the acid-base soaking is 0.2-1.5%, and the treatment time is 1-24 hours.
5. The method for preparing SAPO molecular sieve membrane of claim 2, wherein the seed crystal is coated in step b) by at least one of coating or lifting.
6. The method for preparing SAPO molecular sieve membrane of claim 2, wherein in step c) the silicon source is selected from the group consisting of silica sol, at least one of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate, and silica sol; the aluminum source is selected from at least one of aluminum isopropoxide, pseudo-boehmite, alumina, aluminum nitrate, aluminum chloride and aluminum sulfate; the phosphorus source is at least one selected from phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium hydrogen phosphate, sodium phosphate, disodium hydrogen phosphate and sodium hydrogen phosphate; the template agent is at least one selected from tetraethyl ammonium hydroxide, tetraethyl ammonium bromide, triethylamine and ethylenediamine.
7. The method for preparing the amine modified SAPO molecular sieve membrane of claim 1, wherein the amine modification is specifically that the SAPO type molecular sieve membrane is refluxed in a solution containing an amination reagent and dried to obtain the amine modified SAPO molecular sieve membrane; preferably, the amination reagent is selected from at least one of ethylenediamine, N-hexylamine and octylamine N-atom containing organic reagents.
8. The method for preparing the SAPO molecular sieve membrane according to claim 2, wherein the gas phase crystallization is specifically performed by placing the SAPO molecular sieve membrane on the upper part of a reaction kettle, adding a mixture of a template agent and water into the bottom of the reaction kettle, wherein the template agent/water is 0.003-1, preferably 0.001-2, and reacting at 220 ℃ for 0.1-5 days; the template agent is at least one selected from tetraethyl ammonium hydroxide, tetraethyl ammonium bromide, triethylamine and ethylenediamine.
9. The method for preparing the SAPO molecular sieve membrane as claimed in claim 2, wherein the liquid phase crystallization is carried out by placing the SAPO molecular sieve mother liquor in a solution containing the SAPO molecular sieve mother liquor, and reacting at 150-220 ℃ for 0.1-5 days; in the step c), the crystallization temperature is 160-210 ℃, and the crystallization time is 0.2-4 days.
10. A molecular sieve membrane obtainable by the process of any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113198334A (en) * | 2021-05-07 | 2021-08-03 | 宿州中粮生物化学有限公司 | NaA molecular sieve membrane and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060079725A1 (en) * | 2004-08-03 | 2006-04-13 | Shiguang Li | Membranes for highly selective separations |
| CN107840352A (en) * | 2016-09-19 | 2018-03-27 | 中国石油化工股份有限公司 | The preparation method of SAPO molecular sieve film |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060079725A1 (en) * | 2004-08-03 | 2006-04-13 | Shiguang Li | Membranes for highly selective separations |
| CN107840352A (en) * | 2016-09-19 | 2018-03-27 | 中国石油化工股份有限公司 | The preparation method of SAPO molecular sieve film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113198334A (en) * | 2021-05-07 | 2021-08-03 | 宿州中粮生物化学有限公司 | NaA molecular sieve membrane and preparation method and application thereof |
| CN113198334B (en) * | 2021-05-07 | 2021-11-30 | 宿州中粮生物化学有限公司 | NaA molecular sieve membrane and preparation method and application thereof |
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