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A catalytic cracking catalyst

A catalytic cracking and catalyst technology, applied in catalytic cracking, physical/chemical process catalysts, molecular sieve catalysts, etc., can solve the problems of destroying the zeolite structure, reducing the selectivity of zeolite, and not being able to obtain the silicon-aluminum ratio, etc., and achieve less non-framework aluminum content , high heavy oil conversion activity, and low coke selectivity

Active Publication Date: 2020-03-24
CHINA PETROLEUM & CHEM CORP +1
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Problems solved by technology

At present, the industrial production of high-silicon Y-type zeolite mainly adopts the hydrothermal method: NaY zeolite is subjected to multiple rare earth ion exchange and high-temperature hydrothermal roasting for multiple times, and high-silicon Y-type zeolite containing rare earths can be prepared, which is also the preparation of high-silicon Y-type zeolite. Silica Y-type zeolite is the most conventional method, but the disadvantage of preparing rare earth high-silicon Y-type zeolite by hydrothermal method is that the structure of zeolite will be destroyed due to too harsh hydrothermal treatment conditions, and Y-type zeolite with high silicon-aluminum ratio cannot be obtained ; Although the generation of extra-framework aluminum is beneficial to the stability of the zeolite and the formation of new acid centers, too much extra-framework aluminum reduces the selectivity of the zeolite; in addition, many dealuminated holes in the zeolite cannot be removed by the framework in time. Migrated silicon often causes lattice defects of zeolite, and the crystallization retention of zeolite is low; therefore, the thermal and hydrothermal stability of rare earth-containing high-silicon Y-type zeolite prepared by hydrothermal method is poor, which is manifested in Its lattice collapse temperature is low, and its crystallinity retention rate and specific surface area retention rate are low after hydrothermal aging
However, the prior art does not propose how to further improve the heavy oil cracking activity of gas-phase ultrastable molecular sieves.
[0005] The existing magnesium-containing high-silicon Y zeolite cracking catalyst has low heavy oil cracking activity and low diesel selectivity

Method used

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Embodiment approach

[0038] In the preparation method of catalytic cracking catalyst provided by the present invention, in the preparation method of the magnesium-containing modified Y-type molecular sieve, in step (4), the ultra-stable modified Y-type molecular sieve obtained in step (3) is modified with magnesium compound deal with. One embodiment includes adding the ultra-stable modified Y-type molecular sieve filter cake sample or dried sample obtained in step (3) into a solution containing a magnesium compound such as a magnesium salt, stirring at 5-50°C for 10-120 Minutes, then, add ammonia water, adjust the pH of the solution to 7.5-10, stir evenly, filter, and rinse with neutral water, after that, dry the filter cake and place it in a muffle furnace for 1 hour at 500-650°C For example, within 1-5 hours or 2-3 hours, a magnesium-modified high-silicon ultra-stable Y-type molecular sieve is obtained. Wherein, in the amount of the magnesium-containing compound solution and the molecular sieve...

Embodiment 1

[0050] 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

[0054] 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 Gas, at a temperature of 480 ° C, reacted for 1.5 hours, after that, washed with 20 liters of decationized water, and then filtered, the molecular sieve filt...

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Abstract

The invention relates to a catalytic cracking catalyst, which contains a magnesium-containing modified Y-type molecular sieve, an alumina binder and clay, wherein the magnesium-modified high-silicon ultra-stable Y-type molecular sieve contains 4-10 wt% of oxidized rare earth, 0.1-4 wt% of magnesium oxide and 0.3-0.8 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 10-30% 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 the total aluminum content, and the lattice collapse temperature is not below 1045 DEG C. According to the present invention, the modified Y-type molecular sieve has advantages of high heavy oil conversion activity, low coke selectivity, high diesel yield, high light-oil yield and high total liquid recovery.

Description

technical field [0001] The invention relates to a magnesium-containing highly stable modified Y-type molecular sieve and a preparation method thereof. Background technique [0002] The catalytic cracking catalyst containing magnesium-containing high-silicon Y-type zeolite is used for the conversion of heavy oil to increase the production of diesel oil. At present, the industrial production of high-silicon Y-type zeolite mainly adopts the hydrothermal method: NaY zeolite is subjected to multiple rare earth ion exchange and high-temperature hydrothermal roasting for multiple times, and high-silicon Y-type zeolite containing rare earths can be prepared, which is also the preparation of high-silicon Y-type zeolite. Silica Y-type zeolite is the most conventional method, but the disadvantage of preparing rare earth high-silicon Y-type zeolite by hydrothermal method is that the structure of zeolite will be destroyed due to too harsh hydrothermal treatment conditions, and Y-type zeo...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/08C10G11/05
CPCB01J29/088C10G11/05C10G2300/1037C10G2300/70C10G2400/04
Inventor 周灵萍张蔚琳许明德陈振宇田辉平朱玉霞
Owner CHINA PETROLEUM & CHEM CORP
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