Modified Y molecular sieve and preparation method thereof

Abstract

The invention relates to a modified Y molecular sieve, the modified Y molecular sieve is a small-grain mesoporous modified Y molecular sieve, the molar ratio of silicon oxide to aluminum oxide is 8-60, the content of sodium oxide is less than 0.1 wt%, the unit cell parameter is 2.433-2.452 nm, the relative crystallinity is 60-100%, the crystal particle size is less than 500 nm, the micropore volume is 0.20-0.32 mL / g, and the mesoporous index M is 1.7-5.0. The invention also relates to a preparation method of the modified Y molecular sieve. The modified Y molecular sieve provided by the method can be directly used as an acidic component of a cracking catalyst, and has excellent conversion capacity, higher middle distillate selectivity and low light hydrocarbon component yield when being used for heavy oil hydrocracking.

Description

technical field

[0001] The present invention relates to the field of Y molecular sieves, in particular to a modified Y molecular sieve with enhanced mesoporous properties and a preparation method thereof, more particularly, to a modified Y molecular sieve suitable for use in hydrocracking catalysts, which can effectively improve the performance of the catalyst. Background technique

[0002] Y molecular sieve belongs to faujasite zeolite with a three-dimensional twelve-membered ring microporous structure. The ratio of silicon to aluminum (SiO) of the Y molecular sieve just synthesized 2 / Al 2 O 3 molar ratio) is lower, and has a large space for modification. Therefore, modified Y molecular sieves such as USY, SSY, DAY, etc. have the characteristics of high cracking activity and good cracking selectivity, and are the main acidic components of the most commonly used hydrocracking catalysts. However, with the increasingly prominent trend of crude oil heavier, the content of...

Examples

Embodiment 1

[0060] 10.0g of raw material Y-1 molecular sieve was added to the vacuum reaction kettle, and the pressure in the kettle was reduced to 0.1 atm and maintained at 50°C; 100g of aqueous solutions of 0.05mol / L methylamine and 0.10mol / L ammonia were prepared, Under the condition that the vacuum degree is kept at 0.1 atmosphere, the aqueous solution is added into the reaction kettle. After the addition is completed, the stirring is continued for 10 minutes, and then air is introduced to restore the normal pressure state. Then, it was stirred at 60° C. for 10 minutes, filtered, dried, and calcined to obtain a modified Y molecular sieve without metal ions, numbered MY-1.

[0061] The specific properties of Y-1 and MY-1 are shown in Table 1 and Figure 1A and Figure 1B shown. Depend on Figure 1A and Figure 1B The comparison shows that the position of each diffraction peak in the XRD spectrum after modification is almost unchanged, the degree of reduction of the diffraction peak i...

Embodiment 2

[0063] 20.0g of raw material Y-2 molecular sieve was added to the vacuum reaction kettle, and the pressure in the kettle was reduced to 0.09 atmosphere at 400°C and maintained; 100g of aqueous solutions of 0.8mol / L ethylamine and 0.50mol / L ammonia were prepared, Under the condition that the vacuum degree is kept at 0.1 atmosphere, the aqueous solution is added into the reaction kettle. After the addition is completed, the stirring is continued for 10 minutes, and then air is introduced to restore the normal pressure state. Stir at 80° C. for 5 hours, filter, dry, and calcine to obtain a modified Y molecular sieve without metal ions, numbered MY-2.

[0064] The specific properties of Y-2 and MY-2 are shown in Table 1 and Figure 2A and Figure 2B shown. Depend on Figure 2A and Figure 2B The comparison shows that the position of each diffraction peak in the XRD spectrum after modification is almost unchanged, the degree of reduction of the diffraction peak is low, and the ...

Embodiment 3

[0066] Add 8.0 g of raw material Y-3 molecular sieve into the vacuum reaction kettle, and at 200 ° C, reduce the pressure in the kettle to 0.09 atmospheric pressure and keep it; prepare 100 g of an aqueous solution of 0.5 mol / L ethylenediamine and 0.15 mol / L ammonia, Under the condition of keeping the vacuum degree at 0.09 atmospheres, the aqueous solution was added into the reaction kettle. After the addition was completed, stirring was continued for 5 minutes, and then air was introduced to restore the normal pressure state. Stirring at 40° C. for 50 minutes, filtering, drying, and calcining to obtain a modified Y molecular sieve without metal ions, numbered MY-3.

[0067] The specific properties of Y-3 and MY-3 are shown in Table 1 and Figure 3A and Figure 3B shown. Depend on Figure 3A and Figure 3B The comparison shows that the position of each diffraction peak in the XRD spectrum after modification is almost unchanged, the degree of reduction of the diffraction peak...

technical field

[0001] The present invention relates to the field of Y molecular sieves, in particular to a modified Y molecular sieve with enhanced mesoporous properties and a preparation method thereof, more particularly, to a modified Y molecular sieve suitable for use in hydrocracking catalysts, which can effectively improve the performance of the catalyst. Background technique

[0002] Y molecular sieve belongs to faujasite zeolite with a three-dimensional twelve-membered ring microporous structure. The ratio of silicon to aluminum (SiO) of the Y molecular sieve just synthesized 2 / Al 2 O 3 molar ratio) is lower, and has a large space for modification. Therefore, modified Y molecular sieves such as USY, SSY, DAY, etc. have the characteristics of high cracking activity and good cracking selectivity, and are the main acidic components of the most commonly used hydrocracking catalysts. However, with the increasingly prominent trend of crude oil heavier, the content of...

Examples

Embodiment 1

[0060] 10.0g of raw material Y-1 molecular sieve was added to the vacuum reaction kettle, and the pressure in the kettle was reduced to 0.1 atm and maintained at 50°C; 100g of aqueous solutions of 0.05mol / L methylamine and 0.10mol / L ammonia were prepared, Under the condition that the vacuum degree is kept at 0.1 atmosphere, the aqueous solution is added into the reaction kettle. After the addition is completed, the stirring is continued for 10 minutes, and then air is introduced to restore the normal pressure state. Then, it was stirred at 60° C. for 10 minutes, filtered, dried, and calcined to obtain a modified Y molecular sieve without metal ions, numbered MY-1.

[0061] The specific properties of Y-1 and MY-1 are shown in Table 1 and Figure 1A and Figure 1B shown. Depend on Figure 1A and Figure 1B The comparison shows that the position of each diffraction peak in the XRD spectrum after modification is almost unchanged, the degree of reduction of the diffraction peak i...

Embodiment 2

[0063] 20.0g of raw material Y-2 molecular sieve was added to the vacuum reaction kettle, and the pressure in the kettle was reduced to 0.09 atmosphere at 400°C and maintained; 100g of aqueous solutions of 0.8mol / L ethylamine and 0.50mol / L ammonia were prepared, Under the condition that the vacuum degree is kept at 0.1 atmosphere, the aqueous solution is added into the reaction kettle. After the addition is completed, the stirring is continued for 10 minutes, and then air is introduced to restore the normal pressure state. Stir at 80° C. for 5 hours, filter, dry, and calcine to obtain a modified Y molecular sieve without metal ions, numbered MY-2.

[0064] The specific properties of Y-2 and MY-2 are shown in Table 1 and Figure 2A and Figure 2B shown. Depend on Figure 2A and Figure 2B The comparison shows that the position of each diffraction peak in the XRD spectrum after modification is almost unchanged, the degree of reduction of the diffraction peak is low, and the ...

Embodiment 3

[0066] Add 8.0 g of raw material Y-3 molecular sieve into the vacuum reaction kettle, and at 200 ° C, reduce the pressure in the kettle to 0.09 atmospheric pressure and keep it; prepare 100 g of an aqueous solution of 0.5 mol / L ethylenediamine and 0.15 mol / L ammonia, Under the condition of keeping the vacuum degree at 0.09 atmospheres, the aqueous solution was added into the reaction kettle. After the addition was completed, stirring was continued for 5 minutes, and then air was introduced to restore the normal pressure state. Stirring at 40° C. for 50 minutes, filtering, drying, and calcining to obtain a modified Y molecular sieve without metal ions, numbered MY-3.

[0067] The specific properties of Y-3 and MY-3 are shown in Table 1 and Figure 3A and Figure 3B shown. Depend on Figure 3A and Figure 3B The comparison shows that the position of each diffraction peak in the XRD spectrum after modification is almost unchanged, the degree of reduction of the diffraction peak...

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