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

A molecular sieve and ammonium exchange technology, which is applied in molecular sieve catalysts, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems of poor hydrothermal stability, difficult production, high discharge of three wastes, etc., and achieve weak cracking ability and keep gasoline Effect of octane number and improvement of gasoline yield

Active Publication Date: 2019-02-01
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
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Problems solved by technology

[0013] In the prior art, the direct synthesis of high silicon-aluminum ratio ZSM-5 molecular sieves requires the use of expensive templates, which is costly, difficult to produce, and high waste discharge, and the synthesized ZSM-5 molecular sieves usually have finer crystal grains (100~ 300nm), poor hydrothermal stability, difficult to popularize and apply in catalytic cracking catalyst

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

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preparation example Construction

[0038] The present invention also provides a preparation method of the phosphorus-containing MFI structure molecular sieve, the method comprising: a. performing ammonium exchange on the sodium type MFI structure molecular sieve to obtain ammonium exchange molecular sieve; The total dry basis weight is the basis, and the sodium content of the ammonium-exchanged molecular sieve is less than 0.2% by weight; b, the ammonium-exchanged molecular sieve obtained in step a is placed in a complex acid dealuminizing agent solution composed of fluosilicic acid, organic acid and inorganic acid After dealumination, filtration and washing, the dealumination molecular sieve is obtained; c, after the dealumination molecular sieve obtained in step b is subjected to phosphorus modification treatment and roasting treatment, the phosphorus-containing MFI structure molecular sieve is obtained.

[0039] According to the method of the present invention, the sodium-type MFI molecular sieve is well know...

Embodiment 1

[0061] With ZSM-5 molecular sieve (catalyst Qilu branch production, no amine synthesis, n(SiO 2 ) / n(Al 2 o 3 )=27) with NH 4 Cl solution exchange wash to Na 2 O content is lower than 0.2% by weight, filters to obtain filter cake; Get above-mentioned molecular sieve 100g (dry basis) and add water and be mixed with the molecular sieve slurry of solid content 10% by weight, add oxalic acid 20g in stirring, then 200g hydrochloric acid (mass fraction 10%) and 167g of fluosilicic acid (mass fraction 3%) was added in parallel, and the addition time was 30 minutes; the temperature was raised to 65°C and stirred for 1 hour, filtered and washed until the filtrate was neutral; the filter cake was beaten with water to obtain a molecular sieve slurry with a solid content of 40% by weight, and added 2.4gH 3 PO 4 (Concentration: 85% by weight), homogeneously mixed and dipped, dried, and roasted at 550° C. for 2 hours. Molecular sieve A was obtained, and the physical and chemical proper...

Embodiment 2

[0077] With ZSM-5 molecular sieve (catalyst Qilu branch production, no amine synthesis, n(SiO 2 ) / n(Al 2 o 3 )=27) with NH 4 Cl solution exchange wash to Na 2 O content is lower than 0.2% by weight, filters to obtain filter cake; Get above-mentioned molecular sieve 100g (dry basis) and add water and be mixed with the molecular sieve slurry of solid content 10% by weight, add citric acid 40g in stirring, then add 100g sulfuric acid (mass fraction 10%) and 500g of fluosilicic acid (3% by mass) were added in parallel, and the addition time was 30min; the temperature was raised to 45°C and stirred for 1h, filtered and washed until the filtrate was neutral; the filter cake was beaten with water to obtain a molecular sieve slurry with a solid content of 40% by weight, Add 2.0gH 3 PO 4 (Concentration: 85% by weight), homogeneously mixed and dipped, dried, and roasted at 550° C. for 2 hours. Molecular sieve B was obtained, and the physical and chemical properties, micro-reaction...

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Abstract

The invention discloses a phosphorus containing MFI structure molecular sieve and a preparation method of the molecular sieve. According to the phosphorus containing MFI structure molecular sieve, n(SiO2) / n(Al2O3) is larger than 100; with P2O5 for calculation and the dry basis weight of the molecular sieve being a reference, the phosphorus content of the molecular sieve is 0.1-5wt%; the Al distribution parameter D of the molecular sieve meets the equation of 0.5<=D<=0.8; the proportion of the medium pore volume to the total pore volume of the molecular sieve is 15-30vt%; the proportion of the strong acid amount to the total acid amount of the molecular sieve is 60-80%, and the ratio of the amount of acid B to the amount of acid L is 20-100. The phosphorus containing MFI structure molecular sieve serves as an active component for preparing catalysts or auxiliaries, and in a petroleum hydrocarbon catalytic cracking reaction, the gasoline octane value can be effectively increased while the gasoline yield is kept, or the gasoline yield is increased while the gasoline octane value is kept.

Description

technical field [0001] The invention relates to a phosphorus-containing MFI structure molecular sieve and a preparation method thereof. Background technique [0002] In recent years, the number of domestic motor vehicles has continued to rise, supporting the strong demand for domestic gasoline terminal consumption. It is expected that during the "Twelfth Five-Year Plan" period, the production, sales and ownership of motor vehicles will continue to grow, and the demand for gasoline will maintain an upward trend. During the "Twelfth Five-Year Plan" period, the average annual growth rate of automobile sales is 11%, driving the demand for gasoline to maintain an average annual growth rate of 5%. It is estimated that the apparent consumption of gasoline will reach 98Mt by 2015. With a new round of dedicated propylene capacity coming on stream, global propylene supply will significantly outpace expected demand growth over the next five years. It is predicted that global propylen...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/40C10G11/05
Inventor 欧阳颖罗一斌庄立舒兴田
Owner CHINA PETROLEUM & CHEM CORP
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