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A phosphorus-containing and rare earth modified Y-type molecular sieve rich in secondary pores and its preparation method

A technology of molecular sieve and secondary pores, which is applied in the field of modified Y-type molecular sieve and its preparation, can solve the problems of low zeolite cracking activity and low conversion rate of heavy oil, and achieve high stability, high heavy oil cracking activity, and high hydrothermal The effect of stability

Active Publication Date: 2020-06-16
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The zeolite has low cracking activity and low conversion rate of heavy oil

Method used

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  • A phosphorus-containing and rare earth modified Y-type molecular sieve rich in secondary pores and its preparation method
  • A phosphorus-containing and rare earth modified Y-type molecular sieve rich in secondary pores and its preparation method
  • A phosphorus-containing and rare earth modified Y-type molecular sieve rich in secondary pores and its preparation method

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Experimental program
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Embodiment approach

[0047] In the preparation method of the modified Y-type molecular sieve provided by the present invention, in step (4), the gas-phase ultrastable modified Y-type molecular sieve obtained in step (3) is contacted with an acid solution for reaction (the present invention is called channel cleaning modification, Referred to as channel cleaning, or acid treatment modification). One embodiment, the reaction of the gas-phase ultra-stable modified Y-type molecular sieve obtained in step (3) in contact with the acid solution is to react the gas-phase ultra-stable modified molecular sieve, that is, the gas-phase ultra-stable modified Y-type molecular sieve is mixed with acid solution, and reacts for a period of time, then the molecular sieve after reaction is separated from acid solution, such as through filtration and separation, and then through optional washing (washing is to remove residual Na in the zeolite + , Cl - and Al 3+ and other soluble by-products, such as washing condit...

Embodiment 1

[0065] 2000Kg (dry basis weight) skeleton SiO 2 / Al 2 o 3 Be 4.6 NaY type zeolite (sodium oxide content 13.5% by weight, Sinopec Catalyst Qilu Branch Company produces) joins and is equipped with 20m 3 In the water exchange tank, stir well at 25°C and then add 600L RECl 3 Solution (RECl 3 The rare earth concentration in the solution is expressed as RE 2 o 3 Calculated as 319g / L), after stirring for 60 minutes, filter, wash, and the filter cake is continuously sent to a flash drying oven for drying; obtain a Y-type molecular sieve with a rare earth-containing conventional unit cell size with reduced sodium oxide content, and its sodium oxide content It is 7.0% by weight, and the unit cell constant is 2.471nm. Then, it is sent into a roasting furnace for modification: control the material atmosphere temperature at 390° C., and roast for 6 hours under 50% water vapor (containing 50 volume % water vapor in the atmosphere); then, The molecular sieve material is introduced into...

Embodiment 2

[0069] 2000Kg (dry basis weight) skeleton SiO 2 / Al 2 o 3 Be 4.6 NaY type zeolite (sodium oxide content 13.5% by weight, Sinopec Catalyst Qilu Branch Company produces) joins and is equipped with 20m 3 In the primary exchange tank of decationized water, at 90°C, stir evenly and then add 800L RECl 3 Solution (RECl 3 The rare earth concentration in the solution is expressed as RE 2 o 3 Calculated as 319g / L), stirred for 60 minutes; filtered, washed, and the filter cake was sent to a flash drying oven for drying to obtain a Y-type molecular sieve with a rare earth-containing conventional unit cell size with a reduced sodium oxide content, and its sodium oxide content was 5.5 % by weight, the unit cell constant is 2.471nm; then, it is sent into a roasting furnace, and roasted for 5.5 hours at a temperature (atmosphere temperature) of 450°C and an 80% water vapor atmosphere; then, the molecular sieve material enters the roasting furnace for roasting and drying treatment, and th...

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Abstract

A phosphorus- and rare earth-containing modified Y-type molecular sieve rich in secondary pores and a preparation method thereof. The modified Y-type molecular sieve has a rare earth oxide content of 4 to 11 wt%, a phosphorus content of 0.05 to 10 wt%, and a sodium oxide content. The content does not exceed 0.5% by weight, the total pore volume is 0.4~0.48mL / g, the pore volume of the secondary pores accounts for 20~38% of the total pore volume, the unit cell constant is 2.440nm~2.455nm, and the non-framework aluminum content accounts for the total The aluminum content is not higher than 10%, the lattice collapse temperature is not lower than 1060°C, and the ratio of B acid amount to L acid amount is not lower than 3.50. The preparation method of the molecular sieve includes the steps of exchanging rare earths, hydrothermal roasting, gas phase ultra-stable modification, acid treatment and introducing phosphorus. The modified Y-type molecular sieve has higher heavy oil conversion activity and lower coke selectivity. It has higher gasoline yield, liquefied gas yield, light oil yield and total liquid yield.

Description

technical field [0001] The present invention relates to a highly stable modified Y-type molecular sieve and its preparation method, and further relates to a high-stability Y-type molecular sieve used for catalytic cracking of hydrocarbon oil in the absence of hydrogen and its preparation method. Background technique [0002] Y-type molecular sieves have been the main active component of catalytic cracking (FCC) catalysts since they were first used in the 1960s. However, with the intensification of heavy crude oil, the content of polycyclic compounds in FCC raw materials increased significantly, but their diffusion capacity in zeolite channels decreased significantly. The pore size of Y-type molecular sieve as the main active component is only 0.74nm, and it is directly used to process heavy fractions such as residual oil. The accessibility of the active center of the catalyst will become the main obstacle to the cracking of polycyclic compounds contained therein. [0003] ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/08B01J35/10C10G11/05
CPCC10G11/05B01J29/088C10G2300/70B01J35/651B01J35/633B01J35/647
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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