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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 high Y-type zeolite, destroy zeolite structure, zeolite lattice defects, etc., and achieve high thermal and hydrothermal stability. , the effect of high conversion capacity of heavy oil and high yield of light oil

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, and it is even more difficult to increase the content of dimethyl isomerization. Hydrocarbon / Monomethyl isomeric hydrocarbon ratio
[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

[0042]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:

[0043] (1) carry out ion exchange reaction with NaY molecular sieve (also claiming NaY zeolite) and soluble calcium salt solution, filter, wash, obtain the Y-type molecular sieve of the regular unit cell size containing calcium that sodium oxide content reduces; Said ion exchange is usually in Stir and exchange for 30-120 minutes at a temperature of 15-95°C, preferably 65-95°C;

[0044] (2) Calcium-containing conventional unit cell size Y-type molecular sieve with reduced sodium oxide content 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 of the Y-type mo...

Embodiment 1

[0055] Get 2000 grams of NaY molecular sieves (on a dry basis) and add to 20 liters of decationized aqueous solution and stir to make it evenly mixed, and add 689ml of Ca(NO 3 ) 2 solution (concentration in terms of CaO is 248g / 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 2.471nm and a sodium oxide content of 6.6 % by weight, a Y-type molecular sieve with a calcium content of 9.8% by weight based on CaO, and 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 with a unit cell constant of 2.454nm Molecular sieves, followed by drying to a water content of less than 1% by weight, followed by SiCl 4 : Y-type molecular sieve (dry basis) = 0.5: 1 weight ratio, feed SiCl vaporized by heating 4 Gas, at a temperature of 400°C, reacted for 2 hours, after that, washed with 20 liters of decation...

Embodiment 2

[0059] 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 734ml of CaCl 2 solution (concentration in terms of CaO: 248g / 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 2.471nm and a sodium oxide content of It is a Y-type molecular sieve with a calcium content of 5.2% by weight and a calcium content of 8.7% by weight based on CaO, and then roasts it at a temperature of 450° C. under 80% water vapor for 5.5 hours to obtain a Y-type molecular sieve with a unit cell constant of 2.460 nm. After that, it is dried treated so that its water content is less than 1% by weight, and then according to 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 th...

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Abstract

The invention discloses a 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 themodified Y-type molecular sieve is 0.7 wt%-6.3 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 with the 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 in the modified Y-type molecular sieve is not higher than 20% of the total aluminum content, the lattice collapse temperature is not lower than 1040 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 high heavy oil conversion activity, low coke selectivity, high gasoline yield, high liquefied gas yield, high liquid yield and high light oil yield, and gasoline has high isohydrocarbon content and high dimethyl isohydrocarbon content.

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): B01J29/08B01J37/30B01J35/10B01J37/10C10G11/05
CPCB01J29/084B01J37/0018B01J37/30B01J37/10C10G11/05B01J2229/16B01J2029/081B01J35/633
Inventor 袁帅周灵萍田辉平沙昊陈振宇张蔚琳
Owner CHINA PETROLEUM & CHEM CORP