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Secondary-pore-rich modified Y type molecular sieve containing phosphorus and rare earth, and preparation method thereof

A molecular sieve and secondary pore technology, 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, non-skeleton aluminum The effect of less content

Active Publication Date: 2018-08-28
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

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

Method used

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  • Secondary-pore-rich modified Y type molecular sieve containing phosphorus and rare earth, and preparation method thereof
  • Secondary-pore-rich modified Y type molecular sieve containing phosphorus and rare earth, and preparation method thereof
  • Secondary-pore-rich modified Y type molecular sieve containing phosphorus and rare earth, and preparation method thereof

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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

The invention provides a secondary-pore-rich modified Y type molecular sieve containing phosphorus and rare earth, and a preparation method thereof. In the modified Y type molecular sieve, the contentof rare earth oxide is 4 to 11 wt%; the content of phosphorus is 0.05 to 10 wt%; the content of sodium oxide is no more than 0.5 wt%; a total pore volume is 0.4 to 0.48 mL / g; the pore volume of secondary pores accounts for 20 to 38% of the total pore volume; a lattice constant is 2.440 nm to 2.455 nm; the content of non-framework aluminum is no more than 10% of total aluminum content; lattice collapse temperature is no less than 1060 DEG C; and a ratio of the amount of acid B to the amount of acid L is no less than 3.50. A preparation method for the molecular sieve comprises the following steps: exchanging of rare earth; hydrothermal roasting; gas-phase ultrastable modification; acid treatment; and introduction of phosphorus. The modified Y type molecular sieve has higher heavy oil conversion activity, low coke selectivity, and 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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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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