Preparation method of multistage porous material

A multi-stage pore and solution technology, applied in chemical instruments and methods, inorganic chemistry, molecular sieve catalysts, etc., can solve problems such as large loss of specific surface area and pore volume, loss of catalytic activity, and increased cost of synthetic composite molecular sieves

Active Publication Date: 2019-03-05
PETROCHINA CO LTD
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AI Technical Summary

Problems solved by technology

The disadvantage of this method is that the preparation time is longer
[0013] The preparation methods of micro-mesoporous composite materials mentioned in the above documents or patents are either complicated in process or take a long time in the synthesis process
CN102000604A introduces a microwave treatment process in the process of synthesizing Y / MCM-41 composite molecular sieve, increases auxiliary equipment, and greatly increases the cost of synthesizing composite molecular sieve
In addition, the mesoporous part in the micro-mesoporous composite material mentioned in the above documents or patents is irregular pores
In the above patents, heteropolyacids are generally loaded or mixed with macroporous amorphous structure materials such as alumina and silica-alumina, but these materials have relatively low specific surface area compared with regular and ordered mesoporous materials, which reduces the specific surface area of ​​heteropolyacids. Catalytic activity
Due to the small pore size of microporous molecular sieves and relatively large heteropolyacid molecules, the loss of specific surface area and pore volume after loading is large, and it is difficult to exert catalytic activity.
The mesoporous molecular sieves developed in recent years have greatly improved the specific surface area, pore volume and pore size of molecular sieves. However, mesoporous molecular sieves such as SBA-15 and MCM-41 have poor thermal stability. Collapse, prone to permanent loss of catalytic activity

Method used

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  • Preparation method of multistage porous material
  • Preparation method of multistage porous material
  • Preparation method of multistage porous material

Examples

Experimental program
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Effect test

Embodiment 1

[0055] Embodiment 1: the synthesis of Y / SBA-6 / ZSM-12 / ASA hierarchical porous material

[0056] (1) Preparation of guiding agent: Take 24.7g of sodium hydroxide (Beijing Chemical Plant, analytically pure) and add it to 45.9g of water, stir until the sodium hydroxide is completely dissolved, then add 6.5g of sodium metaaluminate (researched by Shandong Aluminum Industry Co., Ltd. Institute, Industrial Products, Al 2 o 3 content 49.1wt%), stirred until the sodium metaaluminate was completely dissolved to obtain sodium metaaluminate solution A. 70g solution A and 100g water glass (Beijing Red Star Soda Soda Factory, SiO 2 Content 27.81wt%, Na 2 O content 8.74wt%) was poured into 65.5g of deionized water successively, stirred evenly, and aged at 30° C. for 22 hours to obtain the directing agent.

[0057] (2) Preparation of SBA-6 and ZSM-12 composite molecular sieve slurry: according to SBA-6 molecular sieve: ZSM-12 molecular sieve: aqueous solution ratio is 1:1:5, disperse the ...

Embodiment 2

[0061] Unless otherwise specified, the sources of each raw material are the same as in Example 1.

[0062] (1) Preparation of guiding agent: Take 24.7g of sodium hydroxide and add it to 45.9g of water, stir until the sodium hydroxide is completely dissolved, then add 6.5g of sodium metaaluminate, and stir until the sodium metaaluminate is completely dissolved to obtain metaaluminate Sodium solution A. Pour 70g of solution A and 100g of water glass into 65.5g of deionized water in sequence, stir evenly, and then statically age at 30°C for 22 hours to obtain the directing agent.

[0063] (2) Preparation of SBA-6 and ZSM-12 molecular sieve slurry: according to the ratio of SBA-6 molecular sieve: ZSM-12 molecular sieve: aqueous solution is 1:0.5:3, 2g of SBA-6 molecular sieve and 1g of ZSM-12 molecular sieve are dispersed in 6g of 6wt% scandium nitrate and 5wt% boric acid aqueous solution, heated to 70-80°C, stirred at constant temperature for 2 hours, to obtain SBA-6 and ZSM-12 ...

Embodiment 3

[0067] Unless otherwise specified, the sources of each raw material are the same as in Example 1.

[0068] (1) Preparation of guiding agent: Take 24.7g of sodium hydroxide and add it to 45.9g of water, stir until the sodium hydroxide is completely dissolved, then add 6.5g of sodium metaaluminate, and stir until the sodium metaaluminate is completely dissolved to obtain metaaluminate Sodium solution A. Pour 70g of solution A and 100g of water glass into 65.5g of deionized water in sequence, stir evenly, and then statically age at 30°C for 22 hours to obtain the directing agent.

[0069] (2) Preparation of SBA-6 and ZSM-12 composite molecular sieve slurry: according to SBA-6 molecular sieve: ZSM-12 molecular sieve: aqueous solution ratio is 1:0.75:4, the SBA-6 molecular sieve of 2g and the ZSM-12 molecular sieve of 1.5g Disperse in 8g of an aqueous solution of 7wt% scandium nitrate and 5wt% boric acid, heat to 70-80°C, and stir at a constant temperature for 2 hours to obtain SB...

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Abstract

The invention provides a preparation method of a multistage porous material. The preparation method comprises following steps: step one, preparing a guiding agent; step two, preparing SBA-6 and ZSM-12composite molecular sieve slurry; step three, preparing Y/SBA-6 and ZSM-12 composite molecular sieve slurry; and step four, preparing a Y/SBA-6/ZSM-12/ASA multistage porous material. The prepared multistage porous material has the characteristics that the crystal grains of the NaY molecular sieve of the composite molecular sieve of the multistage porous material are small (100 to 400 nm), the silicon/aluminum ratio of the framework is high; the thermal stability is improved, compared with a corresponding NaY molecular sieve, the heat destroying temperature is increased by at least 5 DEG C, and a micro-meso pore structure, which is formed by micro pores with a diameter less than 1 nm and mesopores with a diameter of 3 to 10 nm, is formed.

Description

technical field [0001] The invention provides a method for preparing a hierarchically porous material, in particular to a method for preparing a Y / SBA-6 / ZSM-12 / ASA hierarchically porous material. Background technique [0002] Molecular sieve complex refers to a composite material that combines molecular sieves and other substances through the interaction between molecules, atoms or ions. Regular materials with mesoporous structures such as MCM-41 mesoporous molecular sieves are suitable for the transformation of organic macromolecules due to their large pore structure, but their poor thermal stability, hydrothermal stability and weak acidity limit their Applications of this type of material in the field of catalysis. The research on microporous-mesoporous composite materials based on high stability and strong acidic microporous molecular sieves has important industrial application value. [0003] With the continuous development of catalytic applications of molecular sieves...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B39/00B01J29/80
CPCB01J29/005B01J29/0308B01J29/084B01J29/70B01J29/80C01B39/00C01P2002/60C01P2006/14C01P2006/17C01P2006/32
Inventor 李海岩孙发民谢方明姜维张全国丛丽茹赵檀关旭董春明王亮于春梅秦丽红马守涛吴显军张文成郭金涛王刚焦庆雨孙宏磊李军吕倩王甫村
Owner PETROCHINA CO LTD
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