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Catalytic cracking catalyst, preparation method and applications thereof

A catalytic cracking and catalyst technology, used in catalyst activation/preparation, physical/chemical process catalysts, molecular sieve catalysts, etc., can solve the problem that ultra-stable molecular sieves cannot meet the requirements of processing hydrogenation LCO catalytic cracking catalysts, and zeolite crystal retention is low. , poor selectivity, etc., to achieve good catalytic cracking catalytic performance, high LCO conversion efficiency, and less non-framework aluminum content.

Active Publication Date: 2020-02-25
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0009] At present, the industrial production of high-silicon Y-type zeolite mainly adopts the hydrothermal method, and the NaY zeolite is subjected to multiple rare earth ion exchange and high-temperature roasting, and high-silicon Y-type zeolite containing rare earths can be prepared, which is also the preparation of high-silicon Y-type zeolite. The most conventional method for Y-type zeolite, 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 production of external aluminum is beneficial to improve the stability of zeolite and form new acid centers, too much aluminum outside the framework reduces the selectivity of zeolite. In addition, many dealuminated holes in zeolite cannot be migrated out of the framework in time. The filling of the silicon often causes the lattice defects of the zeolite, and the crystallization retention of the zeolite is low. The lattice collapse temperature is low, the crystallinity retention rate and specific surface area retention rate are low after hydrothermal aging, and the selectivity is poor
However, pore structure analysis showed that gas-phase ultrastable molecular sieves have no secondary pores
[0013] The properties of ultra-stable molecular sieves prepared by hydrothermal method or gas phase method in the prior art cannot well meet the needs of processing hydrogenation LCO catalytic cracking catalysts

Method used

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  • Catalytic cracking catalyst, preparation method and applications thereof
  • Catalytic cracking catalyst, preparation method and applications thereof
  • Catalytic cracking catalyst, preparation method and applications thereof

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preparation example Construction

[0067] The preparation method of the catalyst described in the present disclosure can refer to existing methods, for example, according to the methods disclosed in patents CN1098130A and CN1362472A. Typically comprising the steps of forming a slurry comprising modified Y molecular sieve, binder, clay and water, spray drying, optionally washing and drying. Spray drying, washing, and drying are prior art, and there is no special requirement in this disclosure.

[0068] The second aspect of the present disclosure provides a method for preparing the catalytic cracking catalyst described in the first aspect of the present disclosure. The method includes: preparing a modified Y-type molecular sieve, forming a modified Y-type molecular sieve comprising the modified Y-type molecular sieve, alumina binder, clay and water slurry, and spray drying to obtain the catalytic cracking catalyst;

[0069] Wherein, the preparation of modified Y-type molecular sieve comprises the following steps...

Embodiment 1

[0106] Take 2000g NaY molecular sieve (calculated on a dry basis) and add it to 20L decationized aqueous solution and stir to make it 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 up to 90-95°C and kept for 1h, 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; then bake it 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, and then dry it Treated so that its water content is less than 1% by weight; 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 temperature of 400°C, react for 2 hours, aft...

Embodiment 2

[0109] Take 2000g NaY molecular sieve (on a dry basis) and add it to 25L decationized aqueous solution and stir to make it evenly mixed, add 800mL of RECl 3 solution (in RE 2 o 3 The calculated solution concentration is: 319g / L), stirred, heated up to 90-95°C and maintained for 1h, then filtered and 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. under 80 volume percent water vapor for 5.5 hours to obtain a Y-type molecular sieve with a unit cell constant of 2.461 nm. Afterwards, it is dried to make its water content Below 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, react for 1.5h, after that, wash with 20L decationized water, then filter, and then add the filter cake t...

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Abstract

The invention relates to a catalytic cracking catalyst, a preparation method and applications thereof, wherein the catalyst comprises 10-50 wt% of a modified Y-type molecular sieve, 10-40 wt% of an alumina binder (calculated as alumina), and 10-80 wt% of clay (calculated as dry base), wherein the modified Y-type molecular sieve comprises (calculated as the weight of the dry base of the modified Y-type molecular sieve) 5-12 wt% of rare earth elements (calculated as oxide), 0.1-0.7 wt% of sodium oxide, 0.1-2.5 wt% of gallium oxide, and 0.1-2.5 wt% of zirconium oxide, the total pore volume of themodified Y-type molecular sieve is 0.33-0.39 mL / g, the pore volume of the secondary pores with a pore size of 2-100 nm accounts for 10-25% of the total pore volume, the cell constant is 2.440-2.455 nm, the lattice collapse temperature is not lower than 1050 DEG C, the non-skeleton aluminum accounts for not more than 20% of the total aluminum content, and a ratio of the amount of the acid B to theamount of the acid L in the amount of the strong acid is not less than 3.0. According to the invention, with the application of the catalyst in processing hydrogenation of LCO, the LCO conversion efficiency is high, the coke selectivity is low, the yield of gasoline rich in aromatic hydrocarbon and the yield of propylene are high, and the concentration of propylene in liquefied gas is high.

Description

technical field [0001] The present disclosure relates to a catalytic cracking catalyst and its preparation method and application. Background technique [0002] Light aromatics such as benzene, toluene and xylene (BTX) are important basic organic chemical raw materials, widely used in the production of polyester, chemical fiber, etc., and demand has been strong in recent years. Light aromatics such as benzene, toluene and xylene (BTX) mainly come from catalytic reforming and steam cracking processes using naphtha as raw material. Due to the shortage of naphtha raw materials, there is a large market gap for light aromatics. [0003] Catalytic cracking light cycle oil (LCO) is an important by-product of catalytic cracking, which is rich in aromatic hydrocarbons, especially polycyclic aromatic hydrocarbons, and belongs to the low-quality diesel fraction. With the development and change of market demand and environmental protection requirements, LCO is greatly restricted as a ...

Claims

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Application Information

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IPC IPC(8): B01J29/08B01J37/10B01J37/28B01J37/30C10G49/08
CPCB01J29/088B01J37/0018B01J37/10B01J37/28B01J37/30B01J2229/18C10G49/08
Inventor 周灵萍姜秋桥沙昊袁帅许明德张蔚琳陈振宇田辉平
Owner CHINA PETROLEUM & CHEM CORP
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