CN109928407B - Synthesis method of SAPO-34 molecular sieve - Google Patents
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Abstract
The invention discloses a synthesis method of an SAPO-34 molecular sieve, belonging to the field of molecular sieve synthesis. Mixing phosphoric acid, water, an aluminum source and a silicon source to obtain gel; drying the gel until the water is completely evaporated; then the mixture is put into a reactor for crystallization reaction; and finally, washing and drying the obtained solid product to obtain the SAPO-34 molecular sieve. The synthesis method of the invention can synthesize the SAPO-34 molecular sieve with high crystallinity under the condition of low organic template dosage, and the synthesis pressure is normal pressure, and the production cost is low and safe.
Description
Technical Field
The invention relates to a synthesis method of a molecular sieve, belonging to the field of synthesis of molecular sieve catalytic materials.
Background
Zeolitic molecular sieves are important adsorption and catalytic materials in the chemical industry. The unique properties and importance of natural zeolites have been discovered and appreciated by humans in the nineteenth century. Attempts were subsequently made to synthesize artificial zeolites using high temperature hydrothermal synthesis techniques (temperatures above 200 ℃ and high pressures above 100 atm) in an attempt to mimic the geological formation conditions of natural zeolites. In 1850 s, low-temperature hydrothermal synthesis technology (reaction temperature 25-150 deg.C, reaction pressure one to several tens of atmospheres) was developed to synthesize A, X, L, Y, mordenite and other zeolites with low Si/Al ratio. Greatly reduces the synthesis difficulty and the production cost. With the development of the petroleum industry, the synthesis technology of zeolite has also made great progress, and not only hundreds of types of new structure zeolite have been developed, but also different synthesis methods such as solvothermal synthesis, microwave synthesis, gas phase synthesis, very dense synthesis, and space synthesis have been developed.
Hydrothermal synthesis is the most common zeolite synthesis method, and generally, a silicon source, an aluminum source, an alkali, a template agent and water are made into gel, and then zeolite crystals are synthesized in a high-temperature closed environment under the autogenous pressure condition of one to tens of atmospheric pressures.
Patent CN101096274A discloses a preparation method of aluminum-rich Beta zeolite, which comprises the steps of firstly preparing silicon-aluminum cogel from a silicon source and an aluminum source in the presence of a hydrolytic agent, and crushing the silicon-aluminum cogel after aging and roasting to obtain a silicon-aluminum source; then adding the solution consisting of tetraethylammonium cation, ammonium ion, fluorine ion and water, placing the solution in a closed reactor, and carrying out hydrothermal crystallization to obtain a zeolite product.
Patent US 6827924 discloses a method for synthesizing nano EU-1 zeolite, which comprises mixing template agent tetraethyl ammonium hydroxide, additives such as methanol and toluene with silica-alumina source, placing in a closed reactor, and finally synthesizing nano EU-1 zeolite by hydrothermal crystallization.
Patent CN101254929A discloses a preparation method of NaY molecular sieve with high silica-alumina ratio, which does not use organic template agent, the synthesis method is hydrothermal crystallization, the crystallization reaction is carried out by two steps, after the first step crystallization reaction is finished, silicon-aluminum gel is added into the reaction system, finally NaY molecular sieve is obtained by hydrothermal crystallization.
The microwave synthesis method is similar to the hydrothermal synthesis method, except that the heating mode adopts a microwave heating mode. For example, CN104556129A discloses a microwave synthesis method of a superfine T-type molecular sieve zeolite membrane, which comprises polishing a carrier tube, ultrasonically cleaning and drying, and soaking and drying in a T-type molecular sieve solution; then putting the mixture into crystallized mother liquor, and adopting microwave heating to synthesize the T-shaped molecular sieve zeolite membrane.
Patent CN105967203A discloses a preparation method of a fly ash MFI zeolite molecular sieve, which comprises activating fly ash, mixing with cetyl trimethyl ammonium bromide, ethyl orthosilicate and deionized water, and placing into a reaction kettle for microwave heating crystallization to synthesize the MFI zeolite molecular sieve.
The gas-phase synthesis method is a new type molecular sieve preparation method, and is characterized by that firstly, the synthetic raw material is made into dry glue, then the dry glue is placed in the upper portion of reactor, and the mixed solution of water or template agent is placed in the lower portion of reactor, and the dry glue is not contacted with liquid, then under the condition of high-temp. self-produced pressure the crystallization reaction can be made. For example, patent CN1583561A discloses a method for preparing ferrierite from crystal in vapor phase, which is to prepare a mixture of alkali metal, trivalent element oxide, quadrivalent element oxide and water into gel, dehydrate to obtain dry gel, and crystallize in tetrahydrofuran/water vapor phase to synthesize ferrierite.
Patent CN101962195A is a method for preparing titanium silicalite TS-1 with multilevel pore channels, and the TS-1 zeolite is synthesized by adopting a gas phase method. The patent uses sugar-containing reaction materials to prepare dry glue, the sugar is carbonized in the process of preparing the dry glue, and finally TS-1 zeolite is synthesized under the condition that the dry glue is not contacted with a solution.
The ultra-concentrated system synthesis method is very similar to the hydrothermal crystallization method, but the two methods are different essentially. The extremely-concentrated system synthesis method has the advantages that the water consumption is extremely low, the synthesis raw materials are similar to solid in the crystallization process, and the material transmission cannot be carried out like in a solution system. For example, patent CN101402049A discloses a method for preparing a methanol-to-propylene catalyst, which comprises mixing a silicon source, an aluminum source, an organic template, alkali, and water; evaporating and concentrating at high temperature to form wet colloidal state; finally, the ZSM-5 zeolite is crystallized in a crystallization kettle.
CN102060309A patent, a mordenite and its preparation method, preparing initial gel mixture, then carrying out crystallization reaction of the first stage at 60 deg.C-120 deg.C to form zeolite microcrystal; finally, the temperature is raised to 120-200 ℃ for the second stage of crystallization reaction to synthesize the mordenite. The molar ratio of water/silicon dioxide in the crystallization system is 1-7, the water content is extremely low, and the method also belongs to the synthesis of an extremely concentrated system.
The ionic liquid synthesis is a special zeolite molecular sieve synthesis technology. The ionic liquid is an organic salt composed of organic cations and organic or inorganic anions, and is in a liquid state at high temperature. The synthesis of the molecular sieve in the ionic liquid can be carried out under normal pressure, so that the reaction pressure can be reduced, and the safety risk is reduced. But expensive ionic liquid is needed to participate in the reaction, and the large-scale industrial popularization and application difficulty is high.
At present, most zeolite molecular sieves are synthesized with certain difficulty, synthesis conditions are generally harsh, high-temperature and high-pressure synthesis is mostly adopted, and potential safety hazards are high. Although the ionic liquid synthesis method can synthesize zeolite under normal pressure, the use of the ionic liquid greatly increases the synthesis cost. Therefore, the reaction temperature and the synthesis pressure are reduced, and the cheap synthesis raw materials are used, so that the method is one of the main research directions for reducing the production cost and improving the production safety.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a synthetic method of an SAPO-34 molecular sieve. The synthesis method provided by the invention belongs to normal pressure synthesis, the production cost is low, and the properties of the prepared SAPO-34 zeolite molecular sieve can meet the requirements of the catalytic industry.
The invention provides a synthetic method of an SAPO-34 molecular sieve, which comprises the following steps:
(1) firstly, mixing phosphoric acid, water, an aluminum source and a silicon source, and uniformly mixing to obtain gel;
(2) drying the gel obtained in the step (1) at the temperature of 80-160 ℃ until the water is completely evaporated;
(3) filling the material obtained in the step (2) into a reactor, and introducing steam containing a template agent into the reactor for crystallization reaction when the temperature of the reactor is higher than 100 ℃;
(4) and (4) washing and drying the solid product obtained in the step (3) to obtain the SAPO-34 molecular sieve.
In the method, the aluminum source in the step (1) is one or more of aluminum isopropoxide, aluminum sulfate, aluminum chloride and aluminum nitrate; the silicon source is ethyl orthosilicate and/or white carbon black.
In the method, the molar ratio of the phosphoric acid, the silicon source, the aluminum source and the water in the step (1) is 0.6-1.2P: 0.05-0.3 SiO2:Al:20～100H2O, preferably 0.7 to 1.1P:0.08 to 0.25SiO2: Al:25～90H2O。
In the method, the reactor in the step (3) is provided with a gas inlet pipeline and a gas outlet pipeline, wherein the gas inlet pipeline is communicated with water vapor containing a template agent, and the gas outlet pipeline is communicated with the outside atmosphere and is used for keeping the pressure in the reactor at normal pressure.
In the method, the mass ratio of the template to the steam in the steam containing the template in the step (3) is 2-20: 100, preferably 3-18: 100, and the template is diethylamine.
In the method, the crystallization reaction temperature in the step (3) is 170-230 ℃, and the reaction time is 20-100 h; the preferable reaction temperature is 180-220 ℃, and the reaction time is 25-90 h.
In the method of the present invention, the washing in step (4) is washing with distilled water; the drying condition is that the treatment is carried out for 5-15 h under the condition of 100-150 ℃, and preferably for 6-12 h under the condition of 110-140 ℃.
The SAPO-34 molecular sieve synthesized by the invention is a porous crystal material, belongs to silicoaluminophosphate series molecular sieves and has a structure similar to chabazite; the surface area is 400-700 m2A pore volume of 0.2 to 0.5 cm/g3/g。
The SAPO-34 molecular sieve provided by the invention can be used as an adsorbent for separating gas and liquid mixtures, can also be used as a carrier or a catalyst component of a catalyst, and is particularly suitable for being used as a catalytic material for preparing olefin from methanol.
Compared with the existing synthesis method of the SAPO-34 molecular sieve, the method has the following advantages:
(1) the existing synthesis technology of zeolite molecular sieve is basically carried out under high pressure condition, high pressure explosion danger exists in the production process, and the production equipment also needs to meet the requirement of high temperature and pressure resistance, so the production cost is high. The synthesis technology of the zeolite molecular sieve provided by the invention is carried out under normal pressure, so that the danger of high-pressure explosion is avoided, and the production equipment uses non-high-temperature pressure-resistant materials, so that the production cost is greatly saved.
(2) In the method, the SAPO-34 molecular sieve with small crystal grains can be obtained by adding the water vapor containing the template agent, so that the catalytic performance of the SAPO-34 molecular sieve is improved, the consumption of the template agent can be reduced, and the synthesis cost is reduced.
Drawings
FIG. 1 is an XRD spectrum of a sample obtained in example 1.
FIG. 2 is an XRD spectrum of a sample obtained in comparative example 1.
Detailed Description
The synthesis method of SAPO-34 molecular sieve of the present invention is described in detail by the following specific examples, but is not limited to the examples.
Example 1
4.5mL of phosphoric acid is dissolved in 50mL of distilled water, 7.5g of aluminum isopropoxide is added, 5mL of ethyl orthosilicate is added after the solution is completely dissolved, and the mixture is stirred for 30 min. Then dried at 100 ℃ until the water is completely evaporated. Then placing the obtained mixture into a reactor (the air inlet pipeline of the reactor is communicated with a water vapor source containing 5wt% of diethylamine, and the air outlet pipeline is communicated with the external atmosphere), when the temperature of the reactor is raised to 200 ℃, starting to introduce 100 ℃ water vapor, and crystallizing for 60 hours under the condition. And finally, washing the solid product to be neutral, drying at 120 ℃ for 12h to obtain a sample with the number of CL1, wherein an XRD (X-ray diffraction) spectrum of the obtained sample is shown in figure 1 and is a SAPO-34 molecular sieve with high crystallinity.
Example 2
Dissolving 1.5mL of phosphoric acid in 30mL of distilled water, adding 8.5g of aluminum isopropoxide, adding 15mL of ethyl orthosilicate after complete dissolution, and stirring for 30 min. Then dried at 100 ℃ until the water is completely evaporated. Then placing the obtained mixture into a reactor (the air inlet pipeline of the reactor is communicated with a water vapor source containing 20wt% of diethylamine, and the air outlet pipeline is communicated with the external atmosphere), when the temperature of the reactor is raised to 220 ℃, starting to introduce 100 ℃ water vapor, and crystallizing for 65 hours under the condition. And finally, washing the solid product to be neutral, and drying at 120 ℃ for 12h to obtain a sample with the number of CL2, wherein the sample is a SAPO-34 molecular sieve with high crystallinity.
Example 3
Dissolving 10mL of phosphoric acid in 100mL of distilled water, adding 5g of aluminum isopropoxide, adding 3.5mL of ethyl orthosilicate after complete dissolution, and stirring for 30 min. Then dried at 100 ℃ until the water is completely evaporated. Then placing the obtained mixture in a reactor (the air inlet pipeline of the reactor is communicated with a water vapor source containing 2wt% of diethylamine, and the air outlet pipeline is communicated with the external atmosphere), when the temperature of the reactor is raised to 180 ℃, starting to introduce 100 ℃ water vapor, and crystallizing for 25 hours under the condition. And finally, washing the solid product to be neutral, and drying at 120 ℃ for 12h to obtain a sample with the number of CL3, wherein the sample is a SAPO-34 molecular sieve with high crystallinity.
Example 4
Dissolving 7mL of phosphoric acid in 35mL of distilled water, adding 8.5g of aluminum isopropoxide, adding 5mL of ethyl orthosilicate after complete dissolution, and stirring for 30 min. Then dried at 100 ℃ until the water is completely evaporated. Then placing the obtained mixture into a reactor (the air inlet pipeline of the reactor is communicated with a water vapor source containing 20wt% of diethylamine, and the air outlet pipeline is communicated with the external atmosphere), when the temperature of the reactor is raised to 185 ℃, starting to introduce 100 ℃ water vapor, and crystallizing for 90 hours under the condition. And finally, washing the solid product to be neutral, and drying at 120 ℃ for 12h to obtain a sample with the number of CL4, wherein the sample is a SAPO-34 molecular sieve with high crystallinity.
Example 5
6.5mL of phosphoric acid was dissolved in 55mL of distilled water, 7.5g of aluminum isopropoxide was added, 3.5mL of ethyl orthosilicate was added after the solution was completely dissolved, and the mixture was stirred for 30 min. Then dried at 100 ℃ until the water is completely evaporated. Then placing the obtained mixture into a reactor (the gas inlet pipeline of the reactor is communicated with a water vapor source containing 5.5wt% of diethylamine, and the gas outlet pipeline is communicated with the external atmosphere), when the temperature of the reactor is raised to 200 ℃, starting to introduce 100 ℃ water vapor, and crystallizing for 70 hours under the condition. And finally, washing the solid product to be neutral, and drying at 120 ℃ for 12h to obtain a sample with the number of CL5, wherein the sample is a SAPO-34 molecular sieve with high crystallinity.
Comparative example 1
SAPO-34 molecular sieve is synthesized according to a conventional hydrothermal synthesis method, and the material ratio is similar to that of example 1.
Dissolving 4.5mL of phosphoric acid in 50mL of distilled water, adding 7.5g of aluminum isopropoxide, adding 5mL of ethyl orthosilicate after complete dissolution, adding 2.5mL of diethylamine, and stirring for 30 min. Placing into a closed reactor, and crystallizing at 200 deg.C for 60 h. Finally, the solid product is washed to be neutral and dried for 12h at 120 ℃, the obtained sample is named as CL6, and the XRD spectrum of the obtained sample is shown in figure 2 and is SAPO-34 molecular sieve, but the crystallinity is lower. The synthetic pressure of the system is about 0.9MPa, which is far higher than the pressure of the invention, and the danger of high-pressure explosion exists.
Comparative example 2
And synthesizing the SAPO-34 molecular sieve according to a conventional hydrothermal synthesis method.
Dissolving 4.5mL of phosphoric acid in 50mL of distilled water, adding 7.5g of aluminum isopropoxide, adding 5mL of ethyl orthosilicate after complete dissolution, adding 30mL of diethylamine, and stirring for 30 min. Placing into a closed reactor, and crystallizing at 200 deg.C for 60 h. Finally, the solid product is washed to be neutral and dried for 12h at 120 ℃, the obtained sample is named as CL7, the obtained sample is SAPO-34 molecular sieve, the crystallinity of the SAPO-34 molecular sieve is equivalent to that of the invention, but the dosage of the template agent is too high. And the synthetic pressure of the system is about 0.9MPa, which is far higher than the pressure of the invention, and the danger of high-pressure explosion exists.
Table 1 shows properties of samples obtained in examples and comparative examples
Note: the relative crystallinity given in table 1 is referenced to the crystallinity of CL 1.
Claims (13)
1. A synthetic method of an SAPO-34 molecular sieve comprises the following steps:
(1) firstly, mixing phosphoric acid, water, an aluminum source and a silicon source, and uniformly mixing to obtain gel;
(2) drying the gel obtained in the step (1) until the water is completely evaporated;
(3) filling the material obtained in the step (2) into a reactor, and introducing steam containing a template agent into the reactor for crystallization reaction when the temperature of the reactor is higher than 100 ℃, wherein the reactor is provided with an air inlet pipeline and an air outlet pipeline, the air inlet pipeline is communicated with the steam containing the template agent, the air outlet pipeline is communicated with the external atmosphere, and the template agent is diethylamine;
(4) and (4) washing and drying the solid product obtained in the step (3) to obtain the SAPO-34 molecular sieve.
2. The method for synthesizing the SAPO-34 molecular sieve of claim 1, wherein: the aluminum source in the step (1) is one or more of aluminum isopropoxide, aluminum sulfate, aluminum chloride and aluminum nitrate.
3. The method for synthesizing the SAPO-34 molecular sieve of claim 1, wherein: in the step (1), the silicon source is tetraethoxysilane and/or white carbon black.
4. The method for synthesizing the SAPO-34 molecular sieve of claim 1, wherein: the drying in the step (1) is carried out at the temperature of 80-160 ℃.
5. The method for synthesizing the SAPO-34 molecular sieve of claim 1, wherein: in the step (1), the molar ratio of the phosphoric acid to the silicon source to the aluminum source to the water is 0.6-1.2P: 0.05-0.3 SiO2:Al:20～100H2O。
6. The method for synthesizing the SAPO-34 molecular sieve of claim 1, wherein: in the step (1), the molar ratio of the phosphoric acid to the silicon source to the aluminum source to the water is 0.7-1.1P: 0.08-0.25 SiO2: Al:25～90H2O。
7. The method for synthesizing the SAPO-34 molecular sieve of claim 1, wherein: the mass ratio of the template agent to the steam in the steam containing the template agent in the step (3) is 2-20: 100.
8. The method for synthesizing the SAPO-34 molecular sieve of claim 1, wherein: the mass ratio of the template agent to the steam in the steam containing the template agent in the step (3) is 3-18: 100.
9. The method for synthesizing the SAPO-34 molecular sieve of claim 1, wherein: in the step (3), the crystallization reaction temperature is 170-230 ℃, and the reaction time is 20-100 h.
10. The method for synthesizing the SAPO-34 molecular sieve of claim 1, wherein: in the step (3), the crystallization reaction temperature is 180-220 ℃, and the reaction time is 25-90 h.
11. The method for synthesizing the SAPO-34 molecular sieve of claim 1, wherein: the washing in the step (4) is washing by using distilled water; the drying condition is that the treatment is carried out for 5-15 hours at the temperature of 100-150 ℃.
12. The method for synthesizing the SAPO-34 molecular sieve of claim 1, wherein: the washing in the step (4) is washing by using distilled water; the drying condition is that the treatment is carried out for 6-12 h at the temperature of 110-140 ℃.
13. The method for synthesizing the SAPO-34 molecular sieve of claim 1, wherein: the synthesized SAPO-34 molecular sieve is a porous crystal material, belongs to silicoaluminophosphate series molecular sieves and has a chabazite structure; the surface area is 400-700 m2A pore volume of 0.2 to 0.5 cm/g3/g。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102372288A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing SAPO-34 molecular sieve |
| CN102464340A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for synthesizing silicoaluminophosphate (SAPO)-34 molecular sieve |
| CN103420388A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Metal ion-containing silicon-phosphorus-aluminum molecular sieve preparation method |
| CN103539145A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Preparation method of SAPO (Si, Al, P, O)-34 molecular sieve |
| CN105460946A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Method for synthesizing SAPO-34 molecular sieves |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372288A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing SAPO-34 molecular sieve |
| CN102464340A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for synthesizing silicoaluminophosphate (SAPO)-34 molecular sieve |
| CN103420388A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Metal ion-containing silicon-phosphorus-aluminum molecular sieve preparation method |
| CN103539145A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Preparation method of SAPO (Si, Al, P, O)-34 molecular sieve |
| CN105460946A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Method for synthesizing SAPO-34 molecular sieves |
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Effective date of registration: 20230909 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |