阅读说明：本技术 一种介孔sapo-34分子筛及其合成方法 (Mesoporous SAPO-34 molecular sieve and synthetic method thereof ) 是由 范峰 凌凤香 张会成 王少军 杨春雁 金鑫 于 2019-10-30 设计创作，主要内容包括：本发明公开了一种介孔SAPO-34分子筛及其合成方法,所述SAPO-34分子筛具有丰富的介孔结构,有利于物质传递。所述SAPO-34分子筛合成方法首先对炭材料进行超声处理和碱处理；接着与磷酸、异丙醇铝、正硅酸乙酯、吗啉和水混合,晶化合成SAPO-34分子筛。本发明提供的SAPO-34分子筛合成方法,可以解决介孔结构分子筛合成困难的问题。(The invention discloses a mesoporous SAPO-34 molecular sieve and a synthesis method thereof, wherein the SAPO-34 molecular sieve has a rich mesoporous structure and is beneficial to substance transfer. The SAPO-34 molecular sieve synthesis method comprises the steps of firstly carrying out ultrasonic treatment and alkali treatment on a carbon material; then mixing with phosphoric acid, aluminum isopropoxide, ethyl orthosilicate, morpholine and water, and crystallizing to synthesize the SAPO-34 molecular sieve. The SAPO-34 molecular sieve synthesis method provided by the invention can solve the problem of difficulty in mesoporous structure molecular sieve synthesis.)

1. A synthetic method of a mesoporous SAPO-34 molecular sieve comprises the following steps:

(1) mixing a carbon material with an organic solvent, carrying out ultrasonic treatment, and then carrying out separation and drying treatment;

(2) mixing the solid-phase material obtained in the step (1), inorganic base and water for treatment, and then washing and drying;

(3) mixing the material obtained in the step (2) with sodium hydroxide, an alcohol solvent, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and water, and then carrying out solid-liquid separation;

(4) mixing phosphoric acid, aluminum isopropoxide, ethyl orthosilicate, water and the carbon material obtained by solid-liquid separation in the step (3) to prepare gel, drying, adding morpholine and water to perform crystallization reaction, and finally washing, drying and performing heat treatment to obtain the SAPO-34 molecular sieve.

2. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: the diameter of the carbon material in the step (1) is 5-10 nm.

3. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: in the step (1), the ultrasonic frequency adopted by ultrasonic treatment is 15KHz-10MHz, the power is 20-100W/L according to the volume of the solution, and the ultrasonic time is 10-70 min, preferably 20-60 min.

4. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: the organic solvent in the step (1) is an alcohol solvent, and is specifically one or more of ethanol, propanol and butanol.

5. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: the mass ratio of the carbon material to the organic solvent in the step (1) is 10-20: 100.

6. the method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: in the step (1), the drying is carried out for 5-15 h at the temperature of 100-140 ℃.

7. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: in the step (2), the inorganic base is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.

8. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: in the step (2), the mass ratio of the inorganic base to the carbon material to the water is 2-6: 9-21: 100, preferably 3-5: 10-20: 100.

9. the method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: the treatment condition in the step (2) is treatment for 1-6 h at 50-90 ℃, preferably treatment for 2-5 h at 60-80 ℃.

10. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: the washing in the step (2) is washing by deionized water until the washing is neutral; the drying in the step (2) is drying for 5-15 hours at the temperature of 100-140 ℃.

11. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: the alcohol solvent in the step (3) can be one or more of ethanol, propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, propylene glycol and butanediol, and is preferably propanol and/or isopropanol.

12. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: the mass ratio of the carbon material, the sodium hydroxide, the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, the alcohol solvent and the water in the step (3) is 4-11: 0.4-1.1: 9-21: 78-110: 100, preferably 5 to 10: 0.5-1: 10-20: 80-100: 100.

13. the method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: the treatment temperature in the step (3) is 55-95 ℃, and preferably 60-90 ℃; the treatment time is 1-6 h, preferably 2-5 h.

14. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: the initial material molar ratio in the step (4) is as follows: 0.65-2.6P: 0.18 to 1.1SiO₂：A1₂O₃：30～210H₂O, preferably 0.7-2.5P: 0.2 to 1SiO₂：A1₂O₃：40～200H₂O。

15. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: in the step (4), the mass ratio of the carbon material to the silicon source is 0.2-1.2: 1, preferably 0.3 to 1.1: 1.

16. the method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: the molar ratio of the materials in the crystallization reaction in the step (4) is as follows: 0.65-2.6P: 0.18 to 1.1SiO₂：A1₂O₃：2.4～11H₂O: 0.9-2.1 morpholine, preferably 0.7-2.5P: 0.2 to 1SiO₂：A1₂O₃：2.5～10H₂O: 1-2 morpholine; wherein the mass ratio of the carbon material to the aluminum isopropoxide is 0.2-1.2: 1, preferably 0.3 to 1.1: 1.

17. the method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: and (4) drying the gel for 5-15 hours at the temperature of 100-140 ℃.

18. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: the crystallization reaction temperature in the step (4) is 170-230 ℃, the reaction time is 20-100 h, preferably 180-220 ℃, and the reaction time is 25-90 h.

19. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: the heat treatment in the step (4) is carried out for 1-7 hours, preferably 2-6 hours at 350-650 ℃, preferably 400-600 ℃.

20. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 1, wherein the method comprises the following steps: the carbon material in the step (1) is prepared by adopting the following method: mixing the mesoporous silicon, the saccharides and water, and drying, high-temperature treatment, alkali treatment, washing and drying to obtain the carbon material.

21. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 20, wherein the method comprises the following steps: the mesoporous silicon is an SBA-15 molecular sieve, and the aperture is 5-10 nm; the saccharide is sucrose and/or glucose; wherein the mass ratio of the saccharides to the mesoporous silicon to the water is 18-55: 4-11: 100, preferably 20 to 50: 5-10: 100.

22. the method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 20, wherein the method comprises the following steps: the drying is carried out for 5-15 h at the temperature of 100-140 ℃.

23. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 20, wherein the method comprises the following steps: the high-temperature treatment is roasting for 1-11 h, preferably 2-10 h, at 500-900 ℃ in an inert atmosphere; the inert atmosphere is nitrogen, argon or helium, preferably nitrogen.

24. The method for synthesizing the mesoporous SAPO-34 molecular sieve of claim 20, wherein the method comprises the following steps: the alkali treatment is carried out by using sodium hydroxide, and the mass ratio of the sodium hydroxide to the carbon material to the water is (9-21): 9-21: 100, preferably 10 to 20: 10-20: 100, respectively; the alkali treatment temperature is 150-200 ℃, and preferably 160-180 ℃; the treatment time is 5-16 h, preferably 6-15 h.

25. A mesoporous SAPO-34 molecular sieve, characterized by: the mesoporous SAPO-34 molecular sieve is synthesized by the method of any one of claims 1 to 24.

26. The mesoporous SAPO-34 molecular sieve of claim 25, wherein: the total specific surface area of the SAPO-34 molecular sieve is 350-550 m²The mesoporous specific surface area is 50-150 m²The pore diameter of the mesoporous material is 5-10 nm.

Technical Field

The invention belongs to the technical field of preparation of porous inorganic materials, and particularly relates to a SAPO-34 molecular sieve and a synthesis method thereof.

Background

SAPO molecular sieves are a class of crystalline silicoaluminophosphates, first developed by united states carbide corporation. Among them, the silicoaluminophosphate molecular sieve SAPO-34 with the CHA topological structure shows excellent catalytic performance in the reaction of preparing olefin from methanol due to the special pore channel structure and the proper acid property.

CN103818928A discloses a method for rapidly synthesizing a high-crystallinity SAPO-34 molecular sieve, which comprises fully stirring pseudo-boehmite in deionized water, and then slowly adding phosphoric acid to fully peptize the pseudo-boehmite; then adding a silicon source and stirring uniformly, and then adding an organic amine mixed template agent and stirring; stirring and then putting the obtained solution into a reaction kettle; crystallizing the reaction kettle; and after crystallization is finished, washing, drying and baking to obtain the product molecular sieve.

CN105600801A discloses a method for synthesizing a microporous SAPO-34 molecular sieve, which is characterized in that in the synthesis process, besides a microporous template agent, an organic phosphine surfactant is added as a mesoporous template agent, so that the obtained SAPO-34 molecular sieve has a microporous structure and mesopores.

CN105585022A discloses a method for synthesizing a flaky nano SAPO-34 molecular sieve, which is to add a specific organic additive into a gel mixed by an aluminum source, a phosphorus source, a silicon source, a template agent and water, stir the mixture evenly, add the nano SAPO-34 molecular sieve as a seed crystal, and prepare the SAPO-34 molecular sieve by temperature-changing crystallization.

CN101121530A discloses a method for synthesizing SAPO-34 molecular sieve with a framework rich in Si (4Al) structure, which can control the form and the quantity of Si coordination environment of the framework of the molecular sieve by mainly modulating the adding proportion of silicon in the initial gel for synthesis, so as to synthesize the SAPO-34 molecular sieve with Si (4Al) as the main coordination environment. The molecular sieve is used for preparing the olefin catalyst from methanol after being roasted, and can effectively improve the selectivity of ethylene and propylene.

However, the SAPO-34 molecular sieve prepared by the conventional method is a microporous material, and the pore diameter is less than 2 nm. The transfer rate of reactants and products is slow in the catalytic reaction, and the catalytic performance of the catalyst is seriously reduced. Therefore, the SAPO-34 molecular sieve with the mesoporous structure is urgently needed to be developed to solve the mass transfer problem and improve the catalytic performance of the molecular sieve.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a mesoporous SAPO-34 molecular sieve and a synthesis method thereof. The SAPO-34 molecular sieve provided by the invention contains abundant mesoporous structures, and solves the problem that mesopores are difficult to form in the conventional synthesized mesoporous SAPO-34 molecular sieve.

The first aspect of the method provides a mesoporous SAPO-34 molecular sieve, wherein the molecular sieve crystal is an SAPO-34 molecular sieve, and the total specific surface area is 350-550 m²The mesoporous specific surface area is 50-150 m²The most probable pore diameter range of the mesopores is 5-10 nm.

The second aspect of the invention provides a synthesis method of a mesoporous SAPO-34 molecular sieve, which comprises the following steps:

(1) under the ultrasonic condition, mixing the carbon material with an organic solvent, and then carrying out separation and drying treatment;

(2) mixing the solid-phase material obtained in the step (1), inorganic base and water for treatment, and then washing and drying;

(3) mixing the material obtained in the step (2) with sodium hydroxide, an alcohol solvent, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and water, and then carrying out solid-liquid separation;

(4) mixing phosphoric acid, aluminum isopropoxide, ethyl orthosilicate, water and the carbon material obtained by solid-liquid separation in the step (3) to prepare gel, drying, adding morpholine and water to perform crystallization reaction, and finally washing, drying and performing heat treatment to obtain the SAPO-34 molecular sieve.

In the method for synthesizing the mesoporous SAPO-34 molecular sieve, the diameter of the carbon material in the step (1) is 5-10 nm. The carbon material can be purchased from commercial products or prepared by the existing method. The preparation method comprises the steps of mixing the SBA-15 molecular sieve, the saccharides and water, drying, treating at high temperature, treating with alkali, washing and drying to obtain the carbon material.

In the method, the most probable pore diameter of the mesoporous silicon is 5-10 nm, wherein the mesoporous silicon is SBA-15 molecular sieve; the saccharide is sucrose and/or glucose; wherein the mass ratio of the saccharides to the mesoporous silicon to the water is 18-55: 4-11: 100, preferably 20 to 50: 5-10: 100.

in the method, the drying is carried out for 5-15 hours at the temperature of 100-140 ℃. The high-temperature treatment is roasting for 1-11 hours, preferably 2-10 hours, at 500-900 ℃ in an inert atmosphere. The inert atmosphere may be nitrogen, argon or helium, preferably nitrogen.

In the method, the alkali treatment is carried out by using sodium hydroxide, and the mass ratio of the sodium hydroxide to the carbon material to the water is (9-21): 9-21: 100, preferably 10 to 20: 10-20: 100. the alkali treatment temperature is 150-200 ℃, and preferably 160-180 ℃; the treatment time is 5-16 h, preferably 6-15 h. The washing is to wash and filter by deionized water until the washing is neutral.

In the synthesis method of the mesoporous SAPO-34 molecular sieve, the ultrasonic frequency adopted in the ultrasonic treatment in the step (1) is 15KHz-10MHz, the power is 20-100W/L according to the volume of the solution, and the ultrasonic time is 10-70 min, preferably 20-60 min.

In the method for synthesizing the mesoporous SAPO-34 molecular sieve, the organic solvent in the step (1) is an alcohol solvent, and specifically may be one or more of ethanol, propanol and butanol.

In the synthesis method of the mesoporous SAPO-34 molecular sieve, the mass ratio of the carbon material to the organic solvent in the step (1) is 10-20: 100.

in the method for synthesizing the mesoporous SAPO-34 molecular sieve, the drying in the step (1) is performed for 5-15 hours at the temperature of 100-140 ℃.

In the synthesis method of the mesoporous SAPO-34 molecular sieve, the inorganic base in the step (2) is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide, and the mass ratio of the inorganic base to the carbon material to water is (2-6): 9-21: 100, preferably 3-5: 10-20: 100.

in the method for synthesizing the mesoporous SAPO-34 molecular sieve, the treatment condition in the step (2) is treatment for 1-6 hours at 50-90 ℃, preferably treatment for 2-5 hours at 60-80 ℃.

In the method for synthesizing the mesoporous SAPO-34 molecular sieve, the washing in the step (2) is washing with deionized water until the washing is neutral. The drying in the step (2) is drying for 5-15 hours at the temperature of 100-140 ℃.

In the above method for synthesizing the mesoporous SAPO-34 molecular sieve, the alcohol solvent in step (3) may be one or more of ethanol, propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, and butanediol, and is preferably propanol and/or isopropanol.

In the synthesis method of the mesoporous SAPO-34 molecular sieve, the mass ratio of the carbon material, the sodium hydroxide, the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, the alcohol solvent and the water in the step (3) is 4-11: 0.4-1.1: 9-21: 78-110: 100, preferably 5 to 10: 0.5-1: 10-20: 80-100: 100.

in the method for synthesizing the mesoporous SAPO-34 molecular sieve, the treatment temperature in the step (3) is 55-95 ℃, and preferably 60-90 ℃; the treatment time is 1-6 h, preferably 2-5 h.

In the synthesis method of the mesoporous SAPO-34 molecular sieve, the molar ratio of the initial materials in the step (4) is as follows: 0.65-2.6P: 0.18 to 1.1SiO₂：A1₂O₃：30～210H₂O, preferably 0.7-2.5P: 0.2 to 1SiO₂：A1₂O₃：40～200H₂O。

In the method for synthesizing the mesoporous SAPO-34 molecular sieve, the mass ratio of the carbon material to the silicon source in the step (4) is 0.2-1.2: 1, preferably 0.3 to 1.1: 1.

in the method for synthesizing the mesoporous SAPO-34 molecular sieve, the molar ratio of the materials in the crystallization reaction in the step (4) is as follows: 0.65-2.6P: 0.18 to 1.1SiO₂：A1₂O₃：2.4～11H₂O: 0.9-2.1 morpholine, preferably 0.7-2.5P: 0.2 to 1SiO₂：A1₂O₃：2.5～10H₂O: 1-2 morpholine. Wherein the mass ratio of the carbon material to the aluminum isopropoxide is 0.2-1.2: 1, preferably 0.3 to 1.1: 1.

in the method for synthesizing the mesoporous SAPO-34 molecular sieve, the gel in the step (4) is dried for 5-15 hours at the temperature of 100-140 ℃.

In the method for synthesizing the mesoporous SAPO-34 molecular sieve, the crystallization reaction temperature in the step (4) is 170-230 ℃, the reaction time is 20-100 hours, preferably 180-220 ℃, and the reaction time is 25-90 hours.

In the method for synthesizing the mesoporous SAPO-34 molecular sieve, the washing in the step (4) is washing and filtering by deionized water until the washing is neutral; the drying is carried out for 5-15 h at the temperature of 100-140 ℃; the heat treatment is carried out for 1-7 h, preferably 2-6 h at 350-650 ℃, preferably 400-600 ℃.

The mesoporous SAPO-34 molecular sieve provided by the invention has abundant mesopores, is favorable for mass transfer, can be used as a catalyst carrier or an acid catalyst component, and can be used for a methanol-to-olefin reaction or other catalytic reactions.

Compared with the prior art, the mesoporous SAPO-34 molecular sieve and the synthesis method thereof provided by the invention have the following advantages:

(1) the SAPO-34 molecular sieve has abundant mesoporous structures, is beneficial to the transfer of macromolecular substances, has no mass transfer bottleneck in the aspect of macromolecular catalysis, and has high catalytic activity.

(2) The SAPO-34 molecular sieve can adjust various control parameters according to requirements to control the proportion of mesopores in the material, and meets the requirements of different catalytic environments.

(3) According to the SAPO-34 molecular sieve synthesis method, the carbon material can effectively enter the SAPO-34 molecular sieve crystal through the treatment operation of the carbon material, so that the SAPO-34 molecular sieve with the mesoporous structure can be obtained after the carbon material is subsequently removed. The method solves the technical problems that in the existing preparation method, the carbon material and the raw materials such as a silicon source, an aluminum source and the like in the raw materials for preparing the SAPO molecular sieve are difficult to form effective physical and chemical effects with the raw materials due to huge property difference, the carbon material is difficult to enter crystal nuclei in the high-temperature synthesis process of the molecular sieve, most of the carbon material is excluded from the molecular sieve crystals, and cannot enter the crystals, so that the mesoporous structure cannot be provided for the molecular sieve. The method of the invention can lead the carbon material to smoothly enter the molecular sieve crystal in the process of synthesizing the SAPO-34 molecular sieve by modifying the carbon material, thereby synthesizing the SAPO-34 molecular sieve with the mesoporous structure.

(4) The invention relates to a method for synthesizing an SAPO-34 molecular sieve, which is used for synthesizing the molecular sieve in a low-water environment and belongs to solid-phase synthesis. The transfer speed of various materials in the synthesis process is very low, so that the repulsion action of the silicon-aluminum material on the carbon material is weak, the carbon material can effectively enter the molecular sieve crystal, and the mesoporous pore canal can be formed.

Drawings

FIG. 1 is a graph of the pore size distribution of a sample of SAPO-34 molecular sieve obtained in example 2.

Detailed Description

The synthesis method of the SAPO-34 molecular sieve of the invention is described in detail by the following specific examples and comparative examples, but is not limited to the following examples and comparative examples.

In the inventive examples and comparative examples, the pore structure parameter of the material was N₂Performing adsorption-desorption characterization, and calculating the total specific surface area according to a BET formula; the mesoporous area is calculated according to a t-Plot method, and the aperture is calculated by adopting a BJH method; the crystal structure of the material was characterized using X-ray diffraction (XRD).

Example 1

Preparing a carbon material:

uniformly mixing 800g of SBA-15 molecular sieve, 3500g of cane sugar and 10000g of deionized water, filtering, and drying at 120 ℃ for 12 hours. Then the mixture is treated for 5 hours at 800 ℃ under the condition of nitrogen. Then, the mixture is uniformly mixed with 1500g of sodium hydroxide and 10000g of deionized water, and the mixture is treated for 10 hours at 170 ℃. Then filtering and washing to be neutral, and drying for 12h at 120 ℃ to obtain the carbon material.

Example 2

155g of the carbon material obtained in example 1 and 1200g of ethanol are mixed and treated in ultrasound for 30min, the frequency of the ultrasound is 1MHz, the power is 50W/L according to the volume of the solution, and then the mixture is filtered and dried for 12h at 120 ℃. And uniformly mixing the obtained carbon material with 35g of sodium hydroxide and 1000g of deionized water, treating at 63 ℃ for 4.3h, filtering and washing to be neutral, and drying at 120 ℃ for 12h to obtain the carbon material. And then 80g of carbon material is uniformly mixed with 7.5g of sodium hydroxide, 135g of propanol, 800g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and 800g of deionized water, treated at 60 ℃ for 5 hours, filtered and collected. Then 9.55g of carbon material, 8.62g of phosphoric acid, 21.31g of aluminum isopropoxide, 15.25g of ethyl orthosilicate and 52g of deionized water are mixed uniformly and dried at 120 ℃ for 12 h. Then the mixture is put into a reactor, 15.7g of deionized water and 7.28g of morpholine are added, crystallization is carried out for 35h at 190 ℃, finally the solid product is washed, dried for 12h at 120 ℃ and treated for 3.5h at 410 ℃, and the obtained sample is CL1 and is a pure SAPO-34 molecular sieve.

Example 3

A starting carbon material was prepared according to the method of example 1. Then 100g of carbon material and 1000g of propanol are mixed and put into ultrasonic to be processed for 20min, the frequency of the ultrasonic is 15KHz, the power is 100W/L according to the volume of the solution, and then the mixture is filtered and dried for 12h at 120 ℃. And uniformly mixing the carbon material with 30g of sodium hydroxide and 1000g of deionized water, treating at 60 ℃ for 5 hours, filtering and washing to be neutral, and drying at 120 ℃ for 12 hours to obtain the carbon material. Then 100g of carbon material is taken to be uniformly mixed with 10g of sodium hydroxide, 200g of isopropanol, 1000g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and 1000g of deionized water, treated at 60 ℃ for 5 hours, filtered and collected. Then 6.81g of carbon material, 7.62g of phosphoric acid, 22.70g of aluminum isopropoxide, 2.31g of ethyl orthosilicate and 40g of deionized water are mixed uniformly and dried at 120 ℃ for 12 h. Then placing the mixture into a reactor, adding 5g of deionized water and 9.68g of morpholine, crystallizing at 180 ℃ for 25h, finally washing the solid product, drying at 120 ℃ for 12h, and treating at 400 ℃ for 6h to obtain a sample with the number of CL2, which is a pure SAPO-34 molecular sieve.

Example 4

A starting carbon material was prepared according to the method of example 1. Then 150g of carbon material and 1100g of butanol are mixed and put into ultrasound for treatment for 35min, the frequency of the ultrasound is 1MHz, the power is 50W/L according to the volume of the solution, and then the mixture is filtered and dried for 12h at 120 ℃. And uniformly mixing the carbon material with 55g of sodium hydroxide and 1000g of deionized water, treating at 75 ℃ for 5.5h, filtering and washing to be neutral, and drying at 120 ℃ for 12h to obtain the carbon material. Then 75g of carbon material is taken to be uniformly mixed with 7.75g of sodium hydroxide, 111g of isopropanol, 785g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and 1000g of deionized water, treated at 75 ℃ for 4 hours, filtered and collected. 13.87g of carbon material, 7.15g of phosphoric acid, 23.57g of aluminum isopropoxide, 11.15g of ethyl orthosilicate and 105g of deionized water are uniformly mixed, and then dried at 120 ℃ for 12 hours. Then loading into a reactor, adding 18.6 g deionized water and 7.01g morpholine, crystallizing at 200 ℃ for 40h, finally washing the solid product, drying at 120 ℃ for 12h, and treating at 510 ℃ for 3h to obtain a sample with the number of CL3, which is a pure SAPO-34 molecular sieve.

Example 5

A starting carbon material was prepared according to the method of example 1. And then 138g of carbon material and 1080g of ethanol are mixed and put into ultrasonic waves for treatment for 35min, the frequency of the ultrasonic waves is 1MHz, the power is 50W/L according to the volume of the solution, and then the mixture is filtered and dried for 12h at the temperature of 120 ℃. And then uniformly mixing the carbon material with 41g of sodium hydroxide and 980g of deionized water, treating for 4.5h at 75 ℃, filtering and washing to be neutral, and drying for 12h at 120 ℃ to obtain the carbon material. Then 85g of carbon material is taken and evenly mixed with 8.65g of sodium hydroxide, 121g of propanol, 785g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and 1020g of deionized water, treated for 5h at 67 ℃, filtered and collected. Then 15.77g of carbon material, 5.62g of phosphoric acid, 20.17g of aluminum isopropoxide, 9.50g of ethyl orthosilicate and 77g of deionized water are mixed uniformly and then dried at 120 ℃ for 12 hours. Then the mixture is put into a reactor, 7.54 g deionized water and 6.25g morpholine are added, crystallization is carried out for 56h at 210 ℃, finally the solid product is washed, dried for 12h at 120 ℃ and treated for 3h at 540 ℃, and the obtained sample is CL4 and is a pure SAPO-34 molecular sieve.

Example 6

A starting carbon material was prepared according to the method of example 1. Then 100g of carbon material and 500g of ethanol are mixed and put into ultrasonic waves for treatment for 60min, the frequency of the ultrasonic waves is 10MHz, the power is 20W/L according to the volume of the solution, and then the mixture is filtered and dried for 12h at 120 ℃. And then uniformly mixing the carbon material with 50g of sodium hydroxide and 500g of deionized water, treating for 2 hours at 80 ℃, filtering and washing to be neutral, and drying for 12 hours at 120 ℃ to obtain the carbon material. Then 5g of carbon material is taken to be uniformly mixed with 0.5g of sodium hydroxide, 10g of isopropanol, 80g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and 100g of deionized water, treated at 90 ℃ for 2h, filtered and collected. Then, 24.96g of carbon material, 13.61g of phosphoric acid, 22.70g of aluminum isopropoxide, 11.57g of ethyl orthosilicate and 200g of deionized water are uniformly mixed, and then dried at 120 ℃ for 12 hours. Then the mixture is put into a reactor, 20g of deionized water and 19.36g of morpholine are added, crystallization is carried out for 90 hours at 220 ℃, finally the solid product is washed, dried for 12 hours at 120 ℃ and treated for 2 hours at 600 ℃, and the obtained sample is CL5 and is a pure SAPO-34 molecular sieve.

Comparative example 1

Referring to the data of example 2, a starting carbon material was prepared according to the method of example 1. 155g of the carbon material obtained in example 1 and 1200g of ethanol are mixed and treated in ultrasound for 30min, the frequency of the ultrasound is 1MHz, the power is 50W/L according to the volume of the solution, and then the mixture is filtered and dried for 12h at 120 ℃. And uniformly mixing the obtained carbon material with 35g of sodium hydroxide and 1000g of deionized water, treating at 63 ℃ for 4.3h, filtering and washing to be neutral, and drying at 120 ℃ for 12h to obtain the carbon material. Then 9.55g of carbon material, 8.62g of phosphoric acid, 21.31g of aluminum isopropoxide, 15.25g of ethyl orthosilicate and 52g of deionized water are mixed uniformly and dried at 120 ℃ for 12 h. Then the mixture is put into a reactor, 15.7g of deionized water and 7.28g of morpholine are added, crystallization is carried out for 35h at 190 ℃, finally the solid product is washed, dried for 12h at 120 ℃ and treated for 3.5h at 410 ℃, and the obtained sample is named as CL7 and is SAPO-34 molecular sieve. However, the material contains almost no mesopores and is a common microporous molecular sieve.

Comparative example 2

Referring to the data of example 2, a starting carbon material was prepared according to the method of example 1. 155g of the carbon material obtained in example 1 and 1200g of ethanol are mixed and treated in ultrasound for 30min, the frequency of the ultrasound is 1MHz, the power is 50W/L according to the volume of the solution, and then the mixture is filtered and dried for 12h at 120 ℃. And then 80g of carbon material is uniformly mixed with 7.5g of sodium hydroxide, 135g of propanol, 800g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and 800g of deionized water, treated at 60 ℃ for 5 hours, filtered and collected. Then 9.55g of carbon material, 8.62g of phosphoric acid, 21.31g of aluminum isopropoxide, 15.25g of ethyl orthosilicate and 52g of deionized water are mixed uniformly and dried at 120 ℃ for 12 h. Then the mixture is put into a reactor, 15.7g of deionized water and 7.28g of morpholine are added, crystallization is carried out for 35h at 190 ℃, finally the solid product is washed, dried for 12h at 120 ℃ and treated for 3.5h at 410 ℃, and the obtained sample is named as CL6 and is SAPO-34 molecular sieve. Comparative example 1 has a lower content of mesopores than example 2, which indicates that the treatment effect of the method used in the comparative example is slightly insufficient, and a high-quality SAPO-34 molecular sieve containing mesopores cannot be prepared.

TABLE 1 physicochemical Properties of samples obtained in examples and comparative examples