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A kind of highly stable modified Y-type molecular sieve that produces more dimethyl isomeric hydrocarbons and its preparation method

A molecular sieve and modification technology, applied in molecular sieve catalysts, chemical instruments and methods, catalyst activation/preparation, etc., can solve the problems of inability to effectively increase the content of gasoline isomeric hydrocarbons, the inability to increase the content of dimethyl isomeric hydrocarbons, sieve heat and Solve problems such as poor hydrothermal stability, achieve high stability, high crystallinity, and low coke selectivity

Active Publication Date: 2021-01-08
CHINA PETROLEUM & CHEM CORP +1
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Problems solved by technology

[0002] 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 addition of silicon often causes lattice defects of zeolite, and the crystallization retention of zeolite is low
However, the Y-type molecular sieves containing Mg and Ca prepared by existing methods have poor thermal and hydrothermal stability, and usually can only increase the content of isobutane, but cannot effectively increase the content of isomeric hydrocarbons in gasoline, and cannot increase the content of dimethyl isobutane. hydrocarbon content

Method used

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  • A kind of highly stable modified Y-type molecular sieve that produces more dimethyl isomeric hydrocarbons and its preparation method
  • A kind of highly stable modified Y-type molecular sieve that produces more dimethyl isomeric hydrocarbons and its preparation method
  • A kind of highly stable modified Y-type molecular sieve that produces more dimethyl isomeric hydrocarbons and its preparation method

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Embodiment approach

[0036] The preparation method of the modified Y-type molecular sieve provided by the invention, a kind of embodiment comprises the following steps:

[0037] (1) carry out ion exchange reaction with NaY molecular sieve (also claiming NaY zeolite) and soluble calcium salt solution, filter, wash, obtain the Y-type molecular sieve of the regular unit cell size containing calcium that sodium oxide content reduces; Said ion exchange is usually in Stir and exchange for 30-120 minutes at a temperature of 15-95°C, preferably 65-95°C;

[0038] (2) Calcium-containing conventional unit cell size Y-type molecular sieve with reduced sodium oxide content 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 1% by weight; the unit cell constant of the Y-type molecular sieve with a reduced unit cell constant is 2.45...

Embodiment 1

[0047]Get 2000 grams of NaY molecular sieves (on a dry basis) and add to 20 liters of decationized aqueous solution and stir to make it evenly mixed, and add 689ml of Ca(NO 3 ) 2 solution (concentration in terms of CaO is 248g / L), stirred, heated 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 6.6 % by weight, a Y-type molecular sieve with a calcium content of 9.8% by weight based on CaO, and 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 with a unit cell constant of 2.454nm Molecular sieves, followed by drying to a water content of less than 1% by weight, followed by 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, reacted for 2 hours, after that, washed with 20 liters of decationi...

Embodiment 2

[0050] 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 734ml of CaCl 2 solution (concentration in terms of CaO: 248g / L), stirred, heated 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 It is a Y-type molecular sieve with a calcium content of 5.2% by weight and a calcium content of 8.7% by weight based on CaO, and then roasts it 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 2.460 nm. After that, it is dried treated so that its water content is less than 1% by weight, and then according to SiCl 4 : Y-type zeolite = 0.6:1 weight ratio, feed SiCl vaporized by heating 4 The gas was reacted for 1.5 hours at a temperature of 480° C., and then washed with 20 liters of deionized water, and th...

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Abstract

A highly stable modified Y-type molecular sieve that is prolific in producing dimethyl isomerized hydrocarbons and a preparation method thereof. The CaO content of the modified Y-type molecular sieve is 0.7 to 6.3% by weight, and Na 2 The O content is 0.1~0.5% by weight, the total pore volume is 0.33~0.39mL / g, the pore volume of the secondary pores of 2~100nm accounts for 10~25% of the total pore volume, and the unit cell constant is 2.440~2.455nm. The proportion of skeleton aluminum content to the total aluminum content is not higher than 20%, the lattice collapse temperature is not lower than 1040°C, and the ratio of B acid amount to L acid amount measured at 200°C using the pyridine adsorption infrared method is not lower than 2.30. The preparation method includes the steps of ion exchange, modification treatment under certain temperature and water vapor conditions, and reaction with silicon tetrachloride. The modified Y-type molecular sieve has lower coke selectivity, higher gasoline yield, liquefied gas yield, higher isomeric hydrocarbon content in gasoline, dimethyl isomeric hydrocarbon content / monomethyl The content of isomeric hydrocarbons is relatively high.

Description

technical field [0001] The invention relates to a high-stability Y-type molecular sieve used for heavy oil catalytic cracking to produce more dimethyl isomeric hydrocarbons and a preparation method thereof. Background technique [0002] 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 zeo...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/08B01J35/10B01J37/30B01J37/10C10G11/05
CPCB01J29/084B01J37/30B01J37/10C10G11/05B01J2229/16B01J2029/081B01J35/633
Inventor 袁帅周灵萍田辉平陈振宇张蔚琳沙昊
Owner CHINA PETROLEUM & CHEM CORP
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