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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 problems such as low lattice collapse temperature, zeolite lattice defects, and inability to obtain silicon-aluminum ratio

Active Publication Date: 2020-03-24
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. The disadvantages of zeolite are: because too harsh hydrothermal treatment conditions will destroy the structure of zeolite, Y-type zeolite with high silicon-alumina ratio cannot be obtained; although the production of aluminum outside the framework is very important for improving the stability of zeolite and forming new acid centers Beneficial, but 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, often resulting in lattice defects of zeolite, and the crystallization of zeolite remains Therefore, the thermal and hydrothermal stability of the rare earth-containing high-silicon Y-type zeolite prepared by the hydrothermal method is relatively poor, which is manifested in the low lattice collapse temperature, the crystallinity retention rate and the ratio of crystallinity after hydrothermal aging. low surface area retention
The cracking activity of the catalyst made of the zeolite as the active component is not high, and the conversion rate of heavy oil is low
[0013] Existing cracking catalysts of ultra-stable Y-type molecular sieves containing phosphorus and rare earths have low cracking activity for heavy oil and poor coke selectivity

Method used

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preparation example Construction

[0063] The preparation method of catalytic cracking catalyst provided by the present invention, one embodiment, the preparation method of the modified Y-type molecular sieve containing phosphorus and rare earth comprises the following steps:

[0064](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;

[0065] (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...

Embodiment 1

[0076] 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 cooling, Add molecular sieves to 6 liters of aqueous solution containing 35 grams of phosphoric acid, raise the temperature to 90°C, and perform phosphorus modification treatment for 30 minutes. After that, filter and wa...

Embodiment 2

[0081] 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 was then calcined 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 2.461 nm. After cooling, the molecular sieve was added to a solution containing 268 grams of In 6 liters of ammonium phosphate aqueous solution, the temperature was raised to 60°C, and the phosphorus modification treatment was carried out for 50 minutes. After that, the molecular sieve was filtered and was...

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Abstract

A catalytic cracking catalyst containing a modified Y-type molecular sieve containing phosphorus and rare earth, alumina and clay containing additives. The modified Y-type molecular sieve containing phosphorus and rare earth contains 4 to 11 wt% rare earth, 0.05 to 10 wt% % phosphorus, 0.1~0.7% by weight sodium oxide, pore volume is 0.33~0.39mL / g, the volume of 2~100nm pores accounts for 15~30% of the total pore volume, the unit cell constant is 2.440~2.455nm, non-framework aluminum accounts for the total Less than 20% of aluminum, the lattice collapse temperature is greater than 1050°C, and the ratio of B acid content to L acid content is not less than 2.50. The catalytic cracking catalyst has high heavy oil cracking activity, good coke selectivity, high gasoline yield, and high liquefied gas yield and total liquid collection.

Description

technical field [0001] The invention relates to a catalytic cracking catalyst and a preparation method thereof. Background technique [0002] With the increasing weight of catalytic cracking raw oil and the increasingly stringent environmental protection regulations, catalytic cracking catalysts are required to improve the conversion capacity of heavy oil and at the same time produce more gasoline. The key to obtaining high-yield gasoline is that the active component of the catalyst, that is, the rare earth high-silicon Y-type zeolite, can keep the crystal structure intact, have high thermal and hydrothermal stability, and have strong acidity and low acid density. [0003] 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. The disadvantages of zeolite...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/08B01J35/10C10G11/05
CPCC10G11/05B01J29/088B01J2229/14B01J2229/18B01J35/617B01J35/651B01J35/633B01J35/647
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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