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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 reducing zeolite selectivity, destroying zeolite structure, high Y-type zeolite, etc., and achieve high heavy oil conversion activity, high The effect of heavy oil conversion ability and high hydrothermal stability

Active Publication Date: 2020-01-07
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

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 defects of zeolite, and the crystallization retention of zeolite is relatively low. Low
However, the Y molecular sieve prepared by this method has poor thermal and hydrothermal stability, and under certain conditions, it can only increase the content of isobutane, but cannot effectively increase the content of isomeric hydrocarbons in gasoline.
[0007] The performance of the ultra-stable molecular sieves prepared by the hydrothermal method or the gas phase method in the prior art cannot well meet the current needs of processing heavy oil and inferior oil and improving the quality of gasoline

Method used

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Embodiment approach

[0048] In the preparation method of the catalytic cracking catalyst provided by the present invention, an embodiment of the preparation method of the modified Y-type molecular sieve includes the following steps:

[0049] (1) Carry out ion exchange reaction of NaY molecular sieve (also called NaY zeolite) with the mixed solution of soluble calcium salt and rare earth salt, filter and wash to obtain Y-type molecular sieve of conventional unit cell size containing calcium and rare earth with reduced sodium oxide content ; The ion exchange is usually exchanged for 30 to 120 minutes under the conditions of stirring and a temperature of 15 to 95°C, preferably 65 to 95°C;

[0050] (2) the Y-type molecular sieve of the conventional unit cell size containing calcium and rare earth with reduced sodium oxide content is calcined 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, A Y-type molecular sieve with a r...

Embodiment 1

[0059] Take 2000 grams of NaY molecular sieve (on a dry basis) and add it to 20 liters of decationized aqueous solution, stir to make it evenly mixed, and add 345 ml of Ca(NO) 3 ) 2 solution (the concentration of the solution in terms of CaO is 248g / L), then add 300ml of RE (NO 3 ) 3 solution (rare earth solution concentration in RE 2 O 3 Calculated as 319g / L), stirred, heated 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 2.471 nm, a sodium oxide content of 6.6% by weight, and calcium as CaO. Content 4.9% by weight, RE 2 O 3 The Y-type molecular sieve with a rare earth content of 4.4% 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. Drying treatment so that its water content is less than 1 wt%, followed by SiCl 4 : Y-type molecu...

Embodiment 2

[0063] Take 2000 grams of NaY molecular sieves (on a dry basis) and add them to 25 liters of decationized aqueous solution, stir to mix them evenly, and add 368 ml of CaCl 2 Solution (concentration of solution in terms of CaO: 248g / L), 400ml of RECl 3 solution (with RE 2 O 3 The calculated solution concentration is: 319g / L), stirred, heated to 90~95 ℃ and kept for 1 hour, then filtered, washed, and the filter cake was dried at 120 ℃ to obtain a unit cell constant of 2.471 nm and a sodium oxide content of 5.2% by weight , Calculated as CaO, the calcium content is 8.7% by weight, with RE 2 O 3 Y-type molecular sieve with a rare earth content of 5.7% by weight was 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 make it low in water content. at 1 wt%, then according to SiCl 4 : Y-type zeolite = 0.6:1 weight ratio, pass through heated and vaporized SiCl 4 The...

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Abstract

The catalytic cracking catalyst comprises a modified Y-type molecular sieve, an alumina binder and clay; according to the modified Y-type molecular sieve, the CaO content of the modified Y-type molecular sieve is 0.3-4% by weight, the RE2O3 content is 2 to 7 wt%, the content of sodium oxide is 0.1 wt%-0.5 wt%, the total pore volume is 0.33 mL / g to 0.39 mL / g, the pore volume of secondary pores withthe pore diameter of 2nm-100nm of the modified Y-type molecular sieve accounts for 10%-25% of the total pore volume, the lattice constant is 2.440 to 2.455nm, the content of non-framework aluminum inthe modified Y-type molecular sieve is not higher than 20% of the total aluminum content, the lattice collapse temperature is not lower than 1050 DEG C, and the ratio of the amount of acid B to the amount of acid L is not lower than 2.30. The catalytic cracking catalyst has the advantages of higher heavy oil conversion activity, lower coke selectivity, higher gasoline yield, higher isomeric C4 yield and higher isomeric hydrocarbon content in gasoline.

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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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/08B01J37/30B01J37/10B01J35/10C10G11/05
CPCB01J29/088B01J37/30B01J37/10C10G11/05B01J2229/183B01J2229/16B01J2229/32B01J35/617B01J35/633B01J35/647
Inventor 袁帅周灵萍田辉平张蔚琳沙昊陈振宇
Owner CHINA PETROLEUM & CHEM CORP
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