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A kind of phosphorus-containing beta molecular sieve and preparation method thereof

A molecular sieve and aluminum content technology, applied in the direction of molecular sieve catalysts, molecular sieves and alkali exchange compounds, chemical instruments and methods, etc., can solve problems affecting product distribution, etc., and achieve the effect of reducing coke yield, increasing yield, and improving conversion rate

Active Publication Date: 2019-11-15
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to the shape-selective effect of molecular sieves, when the kinetic size of the reactant molecules exceeds the pore size of the microporous molecular sieve, the reactant molecules cannot diffuse into the interior of the molecular sieve; Selective reactions, affecting product distribution

Method used

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  • A kind of phosphorus-containing beta molecular sieve and preparation method thereof
  • A kind of phosphorus-containing beta molecular sieve and preparation method thereof

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preparation example Construction

[0030] The present invention also provides a preparation method of the phosphorus-containing Beta molecular sieve provided by the present invention, the preparation method comprising: a, carrying out alkali treatment on the sodium-type Beta molecular sieve in an alkaline solution, and after filtering and washing, the alkali-treated Molecular sieve; b, the alkali-treated molecular sieve obtained in step a is dealuminated in a complex acid dealumination agent solution composed of fluosilicic acid, organic acid and inorganic acid, and after filtering and washing, the dealuminated molecular sieve is obtained; c . After the dealuminated molecular sieve obtained in step b is subjected to phosphorus modification treatment and roasting treatment, the phosphorus-containing Beta molecular sieve is obtained.

[0031] According to the present invention, the sodium-type Beta molecular sieve is well known to those skilled in the art. For details, please refer to U.S. Patent No. 3,308,069 and...

Embodiment 1

[0053] With 100gBeta molecular sieve (catalyst Qilu branch production, SiO 2 / Al 2 O 3 =25, the sodium oxide content is 4.5% by weight, the same below; dry basis mass) is added with water and beaten to obtain a molecular sieve slurry with a solid content of 10% by weight, and 11.1g of high alkali sodium metaaluminate solution (Na 2 O is 290g / L, Al 2 O 3 40g / L, the solution density is 1.353g / mL), heated to 50°C and stirred at constant temperature for 0.5h, filtered and washed until neutral; the filter cake was beaten with water to obtain a molecular sieve slurry with a solid content of 20% by weight, and 5.3g Oxalic acid, then slowly add 51g hydrochloric acid (mass fraction 10%) and 17g fluosilicic acid (concentration 20%) dropwise at the same time, raise the temperature to 50°C and stir at a constant temperature for 1h, filter, wash and dry to obtain a filter cake; add water to beat the filter cake to obtain a solid content of 40 wt% molecular sieve slurry, 6.8gH 3 PO 4 ...

Embodiment 2

[0072]Add water to 100g Beta molecular sieve (mass on dry basis) to prepare a molecular sieve slurry with a solid content of 10% by weight, add 17g NaOH (purity 96%), heat up to 50°C and stir at a constant temperature for 0.5h, filter and wash until neutral; add water to beat the filter cake to obtain a solid Molecular sieve slurry with a content of 20% by weight, 16g of oxalic acid was added during stirring, and then 108g of hydrochloric acid (mass fraction 10%) and 26g of fluosilicic acid (concentration of 20%) were slowly added dropwise at the same time, the temperature was raised to 50°C and stirred at a constant temperature for 1 hour, filtered, washed and dried Obtain a filter cake; Add water to the filter cake and make a slurry to obtain a molecular sieve slurry with a solid content of 40% by weight, and mix 11.8gH 3 PO 4 (concentration 85%) was dissolved in 90g of water, mixed with filter cake, impregnated and dried; the obtained sample was roasted at 550° C. for 2 hou...

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Abstract

The invention discloses a phosphorus-containing Beta molecular sieve and a preparation method thereof, wherein the Al distribution parameter D of the molecular sieve is more than or equal to 0.4 and is less than or equal to 0.8, the specific surface area of the micropores of the molecular sieve is 420-520 m<2> / g, the volume of the mesopores of the molecular sieve accounts for 30-70% of the total pore volume, the amount of the strong acid of the molecular sieve accounts for 20-60% of the total acid amount, a ratio of the acid B to the acid L is 20-100, and the phosphorus content (calculated asP2O5) of the molecular sieve is 0.3-10 wt% by using the dry base weight of the molecular sieve as the reference. According to the present invention, the catalyst prepared by using the phosphorus-containing Beta molecular sieve as the active component can improve the middle distillate oil conversion rate, increase the yield of gasoline and lower-carbon olefins, and reduce the coke yield in the catalytic cracking.

Description

technical field [0001] The invention relates to a phosphorus-containing Beta molecular sieve and a preparation method thereof. Background technique [0002] In 1967, Wadlinger et al. of Mobile Company used sodium aluminate, silica gel, tetraethylammonium hydroxide (TEAOH) and water for mixed crystallization to synthesize Beta molecular sieve (Beta molecular sieve). Beta molecular sieve has the characteristics of high silicon-aluminum ratio, and Si-Al has a wider modulation range. Marens et al. used decane as a probe reaction to reveal the 12-membered ring skeleton structure of Beta molecular sieves; in 1988, Newsam and Higgins et al. used structural models and simulated powder diffraction to determine the stacking fault structure of Beta molecular sieves for the first time. Beta molecular sieve has a twelve-membered ring intersecting channel structure, the twelve-membered ring pore diameter of the one-dimensional channel parallel to the (001) crystal plane is 0.57-0.75nm, a...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/70C01B39/10
CPCB01J29/7007B01J2229/18C01B39/10C01P2006/12
Inventor 庄立刘建强欧阳颖罗一斌舒兴田
Owner CHINA PETROLEUM & CHEM CORP