Super-stable Y-type molecular sieve containing phosphorus and rare earth, and preparation method thereof

A molecular sieve and rare earth technology, applied in molecular sieve catalysts, chemical instruments and methods, processing hydrocarbon oil, etc., can solve the problems of low crystallinity retention rate and specific surface area retention rate, low catalyst cracking activity, and low heavy oil cracking activity, etc. Achieve the effect of low coke selectivity, high stability and low content

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

AI Technical Summary

Problems solved by technology

Rare earth-containing high-silicon Y-type zeolite can be prepared by performing multiple rare-earth ion exchanges and multiple high-temperature roasting on NaY zeolite. The disadvantages of zeolite are: because too harsh hydrothermal treatment conditions will destroy the structure of zeolite, Y-type zeolite with high silicon-alumina ratio cannot be obtained; although the production of aluminum outside the framework is very important for improving the stability of zeolite and forming new acid centers Beneficial, but too much aluminum outside the framework reduces the selectivity of zeolite; in addition, many dealuminated holes in zeolite cannot be filled by silicon migrated from the framework in time, often result

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  • Super-stable Y-type molecular sieve containing phosphorus and rare earth, and preparation method thereof
  • Super-stable Y-type molecular sieve containing phosphorus and rare earth, and preparation method thereof
  • Super-stable Y-type molecular sieve containing phosphorus and rare earth, and preparation method thereof

Examples

Experimental program
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Example Embodiment

[0041] In one embodiment, the phosphorus modification treatment condition is: adding the Y-type molecular sieve powder sample with a reduced unit cell constant to an exchange solution containing phosphorus compounds, and performing an exchange reaction of 10-100 at 15-100°C Minutes, filter and wash; wherein the weight ratio of water to molecular sieve in the exchange liquid is 2 to 5, preferably 3 to 4, and phosphorus (with P 2 O 5 The weight ratio of calculated) to molecular sieve is 0.0005 to 0.10, preferably 0.001 to 0.05.

[0042] In step (3), the calcined molecular sieve is also dried, so that the water content in the Y-type molecular sieve with a reduced unit cell constant is preferably not more than 1% by weight. The drying may adopt existing methods, such as air drying, drying, and flash drying.

[0043] In the method for preparing the modified Y molecular sieve provided by the present invention, in step (4), SiCl 4 : The weight ratio of Y-type zeolite (on a dry basis) is p...

Example Embodiment

[0055] Example 1

[0056] Take 2000 grams of NaY molecular sieve (calculated on a dry basis) and add it to 20 liters of decationized aqueous solution and stir to make it evenly mixed, and add 600 ml of RE (NO 3 ) 3 Solution (the concentration of rare earth solution is in RE 2 O 3 It is 319g / L), stirred, heated to 90~95℃ for 1 hour, then filtered and washed, and the filter cake was dried at 120℃ to obtain a unit cell constant of 2.471nm, sodium oxide content of 7.0% by weight, and RE 2 O 3 A Y-type molecular sieve with a rare earth content of 8.8% by weight is then calcined at a temperature of 390°C in an atmosphere containing 50% by volume of water vapor and 50% by volume of air for 6 hours to obtain a Y-type molecular sieve with a unit cell constant of 2.455 nm. After cooling, The molecular sieve was added to 6 liters of aqueous solution containing 35 grams of phosphoric acid, and the temperature was raised to 90°C for 30 minutes of phosphorus modification treatment. After that, t...

Example Embodiment

[0058] Example 2

[0059] Take 2000 grams of NaY molecular sieve (calculated on a dry basis) and add it to 25 liters of de-cationized aqueous solution and stir to mix evenly, then add 800 ml of RECl 3 Solution (in RE 2 O 3 The calculated solution concentration is: 319g / L), stirred, heated to 90~95℃ for 1 hour, then filtered, washed, and the filter cake was dried at 120℃ to obtain a unit cell constant of 2.471nm and a sodium oxide content of 5.5% by weight , To RE 2 O 3 The Y-type molecular sieve with a rare earth content of 11.3% by weight was calcined at 450°C and 80% water vapor for 5.5 hours to obtain a Y-type molecular sieve with a unit cell constant of 2.461 nm. After cooling, the molecular sieve was added to the dissolved 268 grams In 6 liters of ammonium phosphate aqueous solution, the temperature was raised to 60°C for 50 minutes of phosphorus modification treatment. After that, the molecular sieve was filtered and washed, and the filter cake was dried to make the water co...

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Abstract

The invention relates to a super-stable Y-type molecular sieve containing phosphorus and rare earth, wherein the Y-type molecular sieve contains 4-11 wt% of rare earth, 0.05-10 wt% of phosphorus and 0.1-0.7 wt% of sodium oxide, and has the pore volume of 0.33-0.39 mL/g, the pore volume of the pores with the pore size of 2-100 nm accounts for 15-30% of the total pore volume, the unit cell constantis 2.440-2.455 nm, the non-framework aluminum accounts for less than 20% of the total aluminum, the lattice collapse temperature is more than 1050 DEG C, and a ratio of the amount of B acid to the amount of L acid is not less than 2.50. The preparation method comprises: preparing a rare earth-containing Y-type molecular sieve having a conventional unit cell size, calcining for 4.5-7 h at a temperature of 350-480 DEG C under 30-90% by volume of steam atmosphere, carrying out phosphorus modification treatment, and carrying out a contact reaction with silicon tetrachloride gas. According to the present invention, the Y-type molecular sieve has advantages of good hydrothermal stability, high heavy oil conversion activity, low coke selectivity, high heavy oil conversion diesel yield, high liquefied gas yield and high total liquid recovery.

Description

technical field [0001] The invention relates to an ultra-stable Y-type molecular sieve containing phosphorus and rare earth and a preparation method thereof. Background technique [0002] At present, the industrial production of high-silicon Y-type zeolite mainly adopts the hydrothermal method. Rare earth-containing high-silicon Y-type zeolite can be prepared by performing multiple rare-earth ion exchanges and multiple high-temperature roasting on NaY zeolite. The disadvantages of zeolite are: because too harsh hydrothermal treatment conditions will destroy the structure of zeolite, Y-type zeolite with high silicon-alumina ratio cannot be obtained; although the production of aluminum outside the framework is very important for improving the stability of zeolite and forming new acid centers Beneficial, but too much aluminum outside the framework reduces the selectivity of zeolite; in addition, many dealuminated holes in zeolite cannot be filled by silicon migrated from the f...

Claims

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Application Information

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IPC IPC(8): B01J29/08B01J35/10C10G11/05
CPCB01J29/088B01J35/1023B01J35/1038B01J2229/14B01J2229/18C10G11/05C10G2300/1055C10G2400/02
Inventor 周灵萍张蔚琳许明德张杰潇田辉平朱玉霞
Owner CHINA PETROLEUM & CHEM CORP
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