Catalytic cracking catalyst

A catalytic cracking and catalyst technology, applied in the field of heavy oil catalytic cracking catalyst and its preparation, can solve the problems of poor thermal and hydrothermal stability, reduce zeolite selectivity, destroy zeolite structure, etc., and achieve high heavy oil conversion capacity and high heavy oil conversion activity , the effect of good coke selectivity

Active Publication Date: 2018-08-28
CHINA PETROLEUM & CHEM CORP +1
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Problems solved by technology

Rare earth-containing high-silicon Y-type zeolite can be prepared by performing multiple rare-earth ion exchanges and multiple high-temperature roasting on NaY zeolite. Zeolite has the following disadvantages: the structure of zeolite can be destroyed due to too harsh hydrothermal treatment conditions, and Y-type zeolite with a high silicon-aluminum ratio cannot be obtained; although the production of aluminum outside the framework is beneficial to improving the stability of zeolite and forming new acid centers, However, too much aluminum outside the framework reduces the selectivity of zeolite; in addition, many dealuminated holes in zeolite cannot be filled by silicon migrated from the framework in time, which often causes lattice defect

Method used

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Embodiment approach

[0038] In the catalytic cracking catalyst preparation method provided by the present invention, the preparation method of the modified Y-type molecular sieve, an embodiment comprises the following steps:

[0039] (1) carry out ion exchange reaction with NaY molecular sieve (also claiming NaY zeolite) and rare earth solution, filter, wash, obtain the Y-type molecular sieve of the conventional unit cell size containing rare earth that sodium oxide content reduces; Said ion exchange is usually stirred, Exchange at a temperature of 15-95°C, preferably 65-95°C, for 30-120 minutes;

[0040] (2) The Y-type molecular sieve with the rare earth-containing conventional unit cell size whose sodium oxide content is reduced is roasted for 4.5 to 7 hours at a temperature of 350 to 480° C. in an atmosphere containing 30 to 90% by volume of water vapor, and dried to obtain water A Y-type molecular sieve with a reduced unit cell constant content of less than 1% by weight; the unit cell constant...

Embodiment 1

[0049] Get 2000 grams of NaY molecular sieves (calculated on a dry basis) and add them to 20 liters of decationized aqueous solution and stir to make them evenly mixed. Add 600ml of RE(NO 3 ) 3 Solution (rare earth solution concentration is RE 2 o 3 Calculated as 319g / L), stirred, heated to 90-95°C and kept for 1 hour, then filtered, washed, and the filter cake was dried at 120°C to obtain a unit cell constant of 2.471nm and a sodium oxide content of 7.0% by weight. 2 o 3 A Y-type molecular sieve with a total rare earth content of 8.8% by weight is then calcined for 6 hours at a temperature of 390°C in an atmosphere containing 50% by volume of water vapor and 50% by volume of air to obtain a Y-type molecular sieve with a unit cell constant of 2.455nm. After that, carry out Drying process, so that its water content is less than 1% by weight, and then according to SiCl 4 : Y-type molecular sieve (dry basis) = 0.5: 1 weight ratio, feed SiCl vaporized by heating 4 Gas, at a t...

Embodiment 2

[0053] Get 2000 grams of NaY molecular sieves (on a dry basis) and add them to 25 liters of decationized aqueous solution and stir to make them evenly mixed. Add 800 ml of RECl 3 solution (in RE 2 o 3 The calculated solution concentration is: 319g / L), stirred, heated up to 90-95°C for 1 hour, then filtered, washed, and the filter cake was dried at 120°C to obtain a unit cell constant of 2.471nm and a sodium oxide content of 5.5% by weight , with RE 2 o 3 A Y-type molecular sieve with a total rare earth content of 11.3% by weight is then calcined at a temperature of 450°C and 80% water vapor for 5.5 hours to obtain a Y-type molecular sieve with a unit cell constant of 2.461nm, and then dried to reduce its water content at 1 wt%, then follow SiCl 4 : Y-type zeolite = 0.6:1 weight ratio, feed SiCl vaporized by heating 4 The gas was reacted for 1.5 hours at a temperature of 480° C., and then washed with 20 liters of deionized water, and then filtered to obtain a modified Y-ty...

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Abstract

The invention relates to a catalytic cracking catalyst, which contains a modified Y-type molecular sieve, an alumina binder and clay, wherein the modified Y-type molecular sieve contains 5-12 wt% of oxidized rare earth and 0.1-0.7 wt% of sodium oxide, and has the total pore volume of 0.33-0.39 mL/g, the pore volume of the secondary pores with the pore size of 2-100 nm in the modified Y-type molecular sieve accounts for 10-25% of the total pore volume, the unit cell constant is 2.440-2.455 nm, the non-framework aluminum content in the modified Y-type molecular sieve is not more than 20% of thetotal aluminum content, the lattice collapse temperature is not below 1050 DEG C, and a ratio of the amount of B acid to the amount of L acid is not less than 2.50. According to the present invention,the catalytic cracking catalyst has advantages of high heavy oil conversion activity, low coke selectivity, high diesel yield, high liquefied gas yield, high light-oil yield and high total liquid recovery.

Description

technical field [0001] The invention relates to a heavy oil catalytic cracking catalyst and a preparation method thereof. Background technique [0002] At present, the industrial production of high-silicon Y-type zeolite mainly adopts the hydrothermal method. Rare earth-containing high-silicon Y-type zeolite can be prepared by performing multiple rare-earth ion exchanges and multiple high-temperature roasting on NaY zeolite. Zeolite has the following disadvantages: the structure of zeolite can be destroyed due to too harsh hydrothermal treatment conditions, and Y-type zeolite with a high silicon-aluminum ratio cannot be obtained; although the production of aluminum outside the framework is beneficial to improving the stability of zeolite and forming new acid centers, However, too much aluminum outside the framework reduces the selectivity of zeolite; in addition, many dealuminated holes in zeolite cannot be filled by silicon migrated from the framework in time, which often ...

Claims

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Application Information

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IPC IPC(8): B01J29/08
CPCB01J29/088B01J2229/18
Inventor 周灵萍张蔚琳许明德田辉平朱玉霞
Owner CHINA PETROLEUM & CHEM CORP
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