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Catalytic cracking catalyst and preparation and application thereof

A catalytic cracking and catalyst technology, applied in catalytic cracking, physical/chemical process catalysts, molecular sieve catalysts, etc., can solve problems such as inability to obtain silicon-aluminum ratio, inability to effectively increase gasoline isomeric hydrocarbon content, high Y-type zeolite, etc.

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, unsatisfactory reactivity and selectivity, and can only increase the content of isobutane under certain conditions, 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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  • Catalytic cracking catalyst and preparation and application thereof
  • Catalytic cracking catalyst and preparation and application thereof
  • Catalytic cracking catalyst and preparation and application thereof

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Experimental program
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Effect test

Embodiment approach

[0045] 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:

[0046] (1) carry out ion exchange reaction with NaY molecular sieve (also claiming NaY zeolite) and soluble magnesium salt solution, filter, wash, obtain the Y type molecular sieve of the conventional unit cell size containing magnesium 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;

[0047] (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 ...

Embodiment 1

[0059] 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, add 492ml of Mg(NO 3 ) 2 solution (concentration in terms of MgO 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 magnesium content of 5.7% by weight based on MgO, 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 molecular sieve with a unit cell constant of 2.455nm 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 li...

Embodiment 2

[0063] Get 2000 grams of NaY molecular sieves (on a dry basis) and add to 25 liters of decationized aqueous solution and stir to make it evenly mixed, add 524ml of MgCl 2 solution (concentration in terms of MgO: 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 A Y-type molecular sieve with 5.2% by weight and a magnesium content of 6.2% by weight based on MgO 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 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 then filtered to obtain a modified Y-type molecular...

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Abstract

The invention discloses a catalytic cracking catalyst as well as preparation and application thereof. The catalyst contains a modified Y-type molecular sieve, an aluminum oxide binder and clay; according to the modified Y-type molecular sieve, the content of magnesium oxide in the modified Y-type molecular sieve is 0.5-4.5 wt%; the content of sodium oxide is 0.1 wt%-0.5 wt%; the total pore volumeis 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-skeleton 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 in the total acid amount of the modified Y-type molecular sieve, which is measured by pyridine adsorption infrared method at 200 DEG C, is not lower than 2.30; when the molecular sieve is used for ultraviolet and visible light analysis, the ultraviolet and visible absorption spectrum is not absorbed at the wavelengthof 285-295 nm. The catalytic cracking catalyst is used for catalytic cracking of heavy oil, and has the advantages of low coke selectivity, high gasoline yield, high liquefied gas yield and high isohydrocarbon content in gasoline.

Description

technical field [0001] The invention relates to a catalyst for catalytic cracking of heavy oil, its preparation method and application. 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...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/08C10G11/05
CPCB01J29/084C10G11/05B01J2229/18B01J35/633B01J35/651B01J35/647
Inventor 袁帅田辉平陈振宇周灵萍张蔚琳沙昊
Owner CHINA PETROLEUM & CHEM CORP
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