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Modified Y-type molecular sieve and a preparation method thereof

A molecular sieve and modification technology, applied in molecular sieve catalysts, chemical instruments and methods, and hydrocarbon oil treatment, can solve the problems of destroying zeolite structure, low conversion rate of heavy oil, and reducing zeolite selectivity, etc., and achieve high conversion efficiency, heat and The effect of high hydrothermal stability and low coke selectivity

Active Publication Date: 2020-02-28
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] However, the preparation of rare earth high-silicon Y-type zeolite by hydrothermal method has its disadvantages: too harsh hydrothermal treatment conditions will destroy the structure of zeolite, making it impossible to obtain Y-type zeolite with higher silicon-aluminum ratio; Zeolite stability and formation of new acid sites are beneficial, but excess extra-framework aluminum reduces zeolite selectivity
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] However, the existing ultra-stable Y-type molecular sieves containing phosphorus and rare earths have low heavy oil cracking activity and poor coke selectivity.

Method used

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  • Modified Y-type molecular sieve and a preparation method thereof
  • Modified Y-type molecular sieve and a preparation method thereof
  • Modified Y-type molecular sieve and a preparation method thereof

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preparation example Construction

[0052] One embodiment of the present invention further provides a method for preparing the above-mentioned modified Y-type molecular sieve, comprising the following steps:

[0053] (1) carry out ion exchange reaction with NaY molecular sieve and rare earth salt solution, to obtain the Y-type molecular sieve that the unit cell size containing rare earth that sodium oxide content reduces does not change;

[0054] (2) Roasting the Y-type molecular sieve whose unit cell size containing the rare earth after ion exchange does not change, to obtain the Y-type molecular sieve whose unit cell constant is reduced;

[0055] (3) carry out phosphorus modification treatment to the Y-type molecular sieve with reduced unit cell constant after roasting, to introduce phosphorus in the molecular sieve;

[0056] (4) reacting the molecular sieve after phosphorus modification treatment with silicon tetrachloride to carry out dealumination and silicon supplementation to obtain a gas-phase ultrastabl...

Embodiment 1

[0106] 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 (concentration of rare earth salt solution in RE 2 o 3 Calculated as 319g / L, RE is a mixed rare earth of La and Ce, and La is calculated by the mass of rare earth oxide 2 o 3 : Ce 2 o 3=3:2), 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, a sodium oxide content of 7.0wt%, and RE 2 o 3 A Y-type molecular sieve with a total rare earth content of 8.8wt%.

[0107] Afterwards, the molecular sieve was calcined for 6 hours at a temperature of 390° C. in an atmosphere containing 50 volume percent water vapor and 50 volume percent air to obtain a Y-type molecular sieve with a unit cell constant of 2.455 nm.

[0108] After cooling, add Y-type molecular sieve with a unit cell consta...

Embodiment 2

[0114] 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, RE is a mixed rare earth of La and Ce, and La is calculated by the mass of rare earth oxide 2 o 3 : Ce 2 o 3 =3:2), stirred, heated to 90-95°C for 1 hour, 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 5.5wt%, expressed as RE 2 o 3 A Y-type molecular sieve with a total rare earth content of 11.3 wt%.

[0115] Afterwards, the molecular sieve was 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.

[0116] After cooling, add a Y-type molecular sieve with a unit cell constant of 2.461nm into 6 liters of aqueous solution in which 268 grams of amm...

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Abstract

One embodiment of the invention provides a modified Y-type molecular sieve and a preparation method thereof, wherein the modified Y-type molecular sieve comprises 4-11 wt% of rare earth (calculated asrare earth oxide), not more than 0.7 wt% of sodium (calculated as sodium oxide), 0.5-5 wt% of zinc (calculated as zinc oxide), and 0.05-10 wt% of phosphorus (calculated as phosphorus pentoxide), theskeleton silicon-alumina ratio is 7-14 based on SiO2 / Al2O3 molar ratio, the mass of the non-skeleton aluminum accounts for not more than 20% of the total aluminum mass, and the pore volume of secondary pores with a pore size of 2-100 nm accounts for 15-30% of the total pore volume. According to the invention, the modified Y-type molecular sieve contains phosphorus, rare earth and zinc modificationcomponents, has advantages of high crystallinity, high thermal stability, high hydrothermal stability and rich secondary pores, is used for catalytic cracking of hydrogenated LCO (light cycle oil), and has advantages of low coke selectivity and high conversion efficiency of reactants.

Description

technical field [0001] The invention relates to a Y-type molecular sieve, in particular to a modified Y-type molecular sieve which can be used for processing hydrogenated LCO catalytic cracking and a preparation method thereof. Background technique [0002] Y-type molecular sieves (also known as Y-type zeolites) have been the main active component of catalytic cracking (FCC) catalysts since they were first used in the 1960s. 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. Type zeolite is the most conventional method. [0003] However, the preparation of rare earth high-silicon Y-type zeolite by hydrothermal method has its disadvantages: too harsh hydrothermal treatment conditions will ...

Claims

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Application Information

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IPC IPC(8): B01J29/08B01J35/10C01B39/24C10G11/05
CPCB01J29/088C01B39/24C10G11/05C10G2300/70B01J35/60B01J35/647B01J35/651
Inventor 沙昊周灵萍袁帅姜秋桥许明德张蔚琳陈振宇田辉平
Owner CHINA PETROLEUM & CHEM CORP
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