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A modified Y-type molecular sieve and its preparation method

A molecular sieve and modification technology, applied in the direction of crystalline aluminosilicate zeolite, fajhedral crystalline aluminosilicate zeolite, etc., can solve the problem that the secondary pore volume and crystallinity of the depth of dealumination are difficult to balance, affect the performance, and modify the Y Molecular sieve crystallinity damage and other problems

Active Publication Date: 2018-10-12
CHINA PETROLEUM & CHEM CORP +1
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AI Technical Summary

Problems solved by technology

[0003] Chinese patent CN96120016.2 discloses a Y-type molecular sieve with high silicon crystallinity and its preparation method. 4 NaY is used as the reaction raw material. First, ammonium hexafluorosilicate is used to dealuminate silicon, then perform hydrothermal treatment, and finally treat with aluminum salt solution. The obtained Y molecular sieve maintains a high degree of crystallinity while deeply dealuminated. However, The pore volume of the obtained modified Y molecular sieve should be low, which is not conducive to the contact and reaction of macromolecular reactants;
[0004] U.S. Patent No. 4,036,739 discloses a hydrocracking method, which discloses a method for modifying Y-type molecular sieves. At a temperature of 315 to 899 ° C, and at least 0.5 psi water vapor is contacted for a period of time to obtain modified Y The unit cell constant of the molecular sieve is 2.440~2.464nm; the treated Y molecular sieve is subjected to ammonium exchange to obtain an intermediate with a sodium content of less than 1%; then, a modified Y molecular sieve with a unit cell constant less than 2.440nm is obtained. The process is relatively harsh, so that the crystallinity of the obtained modified Y molecular sieve is severely damaged, and the crystallinity is low, which affects its performance
[0005] The existing Y-type molecular sieve modification technology has the problems of dealumination depth, silicon-aluminum ratio, secondary pore volume and crystallinity. When the dealumination depth increases, the silicon-aluminum ratio increases, and the secondary pore structure increases, the crystallinity tend to be more destructive; vice versa

Method used

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  • A modified Y-type molecular sieve and its preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] (1) Take 200g of NaY molecular sieve raw powder prepared in the laboratory, mix it with ammonium nitrate with a concentration of 1.5mol / L according to the liquid-solid ratio of 4:1, exchange at 80°C for 2 hours, repeat this process twice, and the exchanged Y molecular sieve Na content in Na 2 O is calculated as 2.3%;

[0022] (2) Hydrothermally treat the Y molecular sieve obtained in step (1) at 550°C and 0.1Mpa for 2 hours;

[0023] (3) Mix the Y molecular sieve obtained in step (2) with sodium nitrate with a concentration of 2.0mol / L according to the liquid-solid ratio of 5:1, exchange at 70°C for 1 hour, repeat this process twice, and the Na in the exchanged Y molecular sieve content in Na 2 O is calculated as 3.0%;

[0024] (4) The molecular sieve obtained in step (3) is mixed with 0.8 mol / L ammonium fluorosilicate solution according to the liquid-solid ratio of 5:1 and beaten, and treated at 90°C for 2 hours;

[0025] (5) The Y molecular sieve treated with ammo...

Embodiment 2

[0027] (1) Take 200g of NaY molecular sieve raw powder prepared in the laboratory, mix it with ammonium chloride with a concentration of 2.0mol / L according to the liquid-solid ratio of 5:1, exchange at 85°C for 2 hours, repeat this process twice, and the exchanged Y Na content in molecular sieve is Na 2 O is calculated as 1.7%;

[0028] (2) The Y molecular sieve obtained in step (1) was hydrothermally treated at 530°C and 0.1Mpa for 1.5 hours;

[0029] (3) Mix the Y molecular sieve obtained in step (2) with sodium nitrate with a concentration of 1.5mol / L according to the liquid-solid ratio of 5:1, exchange at 80°C for 1 hour, repeat this process twice, and the Na in the exchanged Y molecular sieve The content is 2.6% as Na2O;

[0030] (4) The molecular sieve obtained in step (3) is mixed with ammonium fluorosilicate solution with a concentration of 0.5 mol / L according to the liquid-solid ratio of 5:1 and beaten, and treated at 95°C for 2 hours;

[0031] (5) The Y molecular ...

Embodiment 3

[0033] (1) Take 200g of NaY molecular sieve raw powder prepared in the laboratory, mix it with ammonium nitrate with a concentration of 1.2mol / L according to the liquid-solid ratio of 3:1, exchange at 80°C for 2 hours, repeat this process twice, and the exchanged Y molecular sieve Na content in Na 2 O is calculated as 2.5%;

[0034] (2) The Y molecular sieve obtained in step (1) was hydrothermally treated at 550°C and 0.1Mpa for 2 hours;

[0035] (3) Mix the Y molecular sieve obtained in step (2) with a sodium chloride solution with a concentration of 1.7mol / L according to the liquid-solid ratio of 5:1, exchange at 65°C for 1 hour, repeat this process 3 times, and the Y molecular sieve after exchange Na content in Na 2O is calculated as 2.8%;

[0036] (4) The molecular sieve obtained in step (3) is mixed with ammonium fluorosilicate solution with a concentration of 0.7mol / L according to the liquid-solid ratio of 10:1 and beaten, and treated at 85°C for 2 hours;

[0037] (5...

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Abstract

The invention discloses a modified Y-type molecular sieve and a preparation method thereof. The preparation method comprises: (1) carrying out ammonium salt ion exchange in an ammonium salt solution by using NaY zeolite as raw powder to achieve a Na2O weight content of less than 3.0%; (2) carrying out hydrothermal treatment on the Y molecular sieve obtained in the step (1); (3) carrying out sodium ion exchange on the Y molecular sieve obtained in the step (2) in a sodium salt solution; and (4) carrying out ammonium hexafluorosilicate dealuminzation silicon supplementing treatment on the Y molecular sieve obtained in the step (3), filtering, drying, and calcining to obtain the final modified Y-type molecular sieve. According to the present invention, with the method, the high-silicon and high-crystallinity modified Y molecular sieve being rich in mesoporous structure can be obtained.

Description

technical field [0001] The invention relates to a modified Y-type molecular sieve and a preparation method thereof, in particular to a modified Y-type molecular sieve rich in mesoporous structure with high silicon and high crystallinity and a preparation method thereof. Background technique [0002] Hydrocracking technology has many advantages such as strong feedstock adaptability, flexible production scheme, high selectivity of target products and good product quality, and plays an important role in the process of crude oil lightening and clean fuel production. For the hydrocracking process, its core is a hydrocracking catalyst, which is a typical dual-function catalyst, and its active center is composed of a hydrogenation center and a cracking center. The hydrogenation active center of the hydrocracking catalyst usually exists in the form of active metal sulfides of Group VI and Group VIII in the periodic table of elements, and the cracking active center of the hydrocracki...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C01B39/24
CPCC01B39/24C01P2006/12C01P2006/14C01P2006/17
Inventor 柳伟杜艳泽秦波张晓萍董立廷阮彩安
Owner CHINA PETROLEUM & CHEM CORP
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