Y-type molecular sieve with ultra-high mesoporous content and preparation method of Y-type molecular sieve

A technology of molecular sieve and mass ratio, applied in the direction of octahedral crystalline aluminosilicate zeolite, crystalline aluminosilicate zeolite, etc., can solve the problems of skeleton collapse, limited application of Y-type molecular sieve, lack of effective connection, etc., and achieve rich secondary Pore ​​structure, effect of improving thermal and hydrothermal stability

Active Publication Date: 2015-07-08
CHINA UNIV OF PETROLEUM (BEIJING)
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the article published by Krijn P.de Jong et al. in 2001 (Angew.Chem.Int.Ed.2001, 40, No.6) made an in-depth study of the Y-type prepared by hydrothermal dealumination by 3D-TEM technology. The mesoporous properties of molecular sieves found that the mesoporous structure mostly exists in the form of cavities inside the molecular sieve crystal, and the mesopores are only connected by micropores, lacking effective communication.
[0007] The alkali treatment method newly developed in recent years is also an effective means to create mesopores, but it has always been used in the desiliconization of high-silicon molecular sieves (such as ZSM-5, with an atomic silicon-aluminum ratio of not less than 15) to create mesoporous pores. There are not many applications of Y-type molecular sieves with aluminum ratio
[0008] Acid treatment dealumination to create mesoporous pores is mostly used in molecular sieves with low silicon-aluminum ratio. However, for Y-type molecular sieves, the synthetic NaY molecular sieve has a low silicon-aluminum ratio and high aluminum content in the framework. The acid treatment should consider the degree of dealumination, which is slightly different. Caution will cause the skeleton to completely collapse

Method used

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  • Y-type molecular sieve with ultra-high mesoporous content and preparation method of Y-type molecular sieve

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Embodiment 1

[0043] This embodiment provides a Y-type molecular sieve with ultra-high mesoporous content, which is prepared by the following steps:

[0044] Weigh 20.0g of the NaY zeolite sample that was dried overnight and place it in a quartz reaction tube, inject nitrogen gas, and do a good job of leak detection. After the preparation is completed, set the nitrogen purge rate to 50mL / min (glass rotameter); set The temperature rise program of the reaction furnace: from the initial temperature of 30°C to 500°C after 100 minutes, keep it for 120 minutes; stop heating at this time, and when the temperature naturally drops to 270°C, start to pass SiCl 4 saturated N 2 (N 2 After loading with SiCl 4 Liquid container, in bubble form will be SiCl 4 saturated N 2 Gas carried out), at the same time, after 40 minutes at a heating rate of 4 ℃ / min to 430 ℃, stop feeding SiCl 4 saturated N 2 , alone N 2 Continue to purge for 120 minutes, then stop heating and cool down naturally;

[0045] Ta...

Embodiment 2

[0052] This embodiment provides a Y-type molecular sieve with ultra-high mesoporous content, which is prepared by the following steps:

[0053] Weigh 20.0 g of NH dried overnight 4 The Y zeolite sample is placed in a quartz reaction tube, helium gas is introduced, and the helium gas purge rate is set at 50mL / min (glass rotameter); the heating program of the reaction furnace is set: from the initial temperature of 30°C to 500°C after 100min Keep it for 120 minutes after ℃; stop heating at this time, when the temperature naturally drops to 270 ℃, start to pass SiCl 4 Saturated He, while heating up to 510°C at a heating rate of 4°C / min for 1h, stop feeding SiCl 4 Saturated He, continue purging with He alone for 120min, then stop heating and cool down naturally;

[0054] Take out the sample and wash and dry to obtain DY molecular sieve with high silicon-aluminum ratio;

[0055] Take 10g of DY molecular sieve sample with high silicon-aluminum ratio, add it to 100g of hydrochlori...

Embodiment 3

[0063] This embodiment provides a Y-type molecular sieve with ultra-high mesoporous content, which is prepared by the following steps:

[0064] Weigh 20.0g of the NaY zeolite sample that was dried overnight and place it in a quartz reaction tube, inject nitrogen gas, and do a good job of leak detection. After the preparation is completed, set the nitrogen purge rate to 50mL / min (glass rotameter); Furnace heating program: From the initial temperature of 30°C to 500°C after 100 minutes, keep it for 120 minutes; stop heating at this time, and when the temperature naturally drops to 270°C, start to pass SiCl 4 saturated N 2 At the same time, the temperature was raised to 510°C at a heating rate of 3°C / min for 80 minutes, and the SiCl 4 saturated N 2 After, separate N 2 Continue purging for 120 minutes, then stop heating and cool down naturally. The samples were taken out and washed and dried to obtain a DY molecular sieve with a high silicon-aluminum ratio.

[0065] Take 10g ...

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Abstract

The invention provides a Y-type molecular sieve with an ultra-high mesoporous content and a preparation method of the Y-type molecular sieve. The method comprises the following steps: pre-treating Y-type zeolites for 1-5 hours at 300-600 DEG C; cooling to 200-600 DEG C; in an anhydrous drying environment, introducing dry gas saturated by a dealuminating silicon-reinforcing agent into the pre-treated Y-type zeolites and carrying out reaction for 0.5-7 hours to obtain a coarse product; or in the anhydrous dry environment, raising the temperature at a constant speed to 250-700 DEG C, introducing dry gas saturated by the dealuminating silicon-reinforcing agent into the pre-treated Y-type zeolites simultaneously and carrying out reaction for 0.5-7 hours to obtain a coarse product, wherein the introducing speed of the dry gas saturated by the dealuminating silicon-reinforcing agent is 50mL/minute; carrying out acid treatment on the coarse product; and carrying out alkaline treatment on the coarse product after acid treatment to obtain the Y-type molecular sieve. The invention further provides the Y-type molecular sieve with the ultra-high mesoporous content by virtue of the method. The sieve is the Y-type molecular sieve which is high in silica-alumina ratio, wide in range and high in mesoporous content; and the preparation method is simple to operate and low in raw material cost.

Description

technical field [0001] The invention relates to a molecular sieve and a preparation method thereof, in particular to a Y-type molecular sieve with ultra-high mesoporous content and a preparation method thereof, belonging to the technical field of molecular sieve preparation. Background technique [0002] Because Y-type molecular sieve has suitable acidity, high specific surface area and good thermal stability, it is widely used in catalytic cracking reaction. However, as a microporous molecular sieve, Y-type molecular sieves have disadvantages such as poor accessibility to acid sites and slow intracrystalline diffusion. [0003] In order to solve such problems, in the past 20 years, a large number of studies have aimed to form mesopores and macropores in microporous molecular sieves to form a hierarchical pore state and reduce diffusion limitations. Experimental methods include soft and hard templates. Pores, hydrothermal, acid treatment, alkali treatment and other post-tre...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B39/24
Inventor 申宝剑袁德林高雄厚王宝杰赵红娟李浩王闻年康春燕郭巧霞任申勇曾鹏晖包立业郭成玉李江成孙建学郑庆庆申波俊
Owner CHINA UNIV OF PETROLEUM (BEIJING)
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