Phosphorus and loading metal containing MFI structure molecular sieve and preparation method thereof

A technology of loading metals and molecular sieves, which is applied in the direction of molecular sieve catalysts, chemical instruments and methods, and the petroleum industry. Effect of Aromatics Content

Active Publication Date: 2016-11-23
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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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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  • Phosphorus and loading metal containing MFI structure molecular sieve and preparation method thereof

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preparation example Construction

[0041] The present invention also provides a method for preparing the phosphorus-containing and metal-loaded MFI molecular sieve, the method comprising: a. performing ammonium exchange on a sodium-type MFI molecular sieve to obtain an ammonium exchange molecular sieve; Based on the total dry basis weight of the ammonium-exchanged molecular sieve, the sodium content of the ammonium-exchanged molecular sieve is less than 0.2% by weight; Dealuminated molecular sieves are obtained in the dealuminated agent solution, filtered and washed; c, the dealuminated molecular sieves obtained in step b are subjected to phosphorus modification treatment, metal loading treatment and roasting treatment to obtain The phosphorus-containing and metal-loaded MFI molecular sieves.

[0042] According to the method of the present invention, the sodium-type MFI molecular sieve is well known to those skilled in the art, and can be obtained by amine-free crystallization, or obtained by roasting a molecul...

Embodiment 1

[0065] 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) and 6.6gZn(NO 3 ) 2 ·6H 2 O, homogeneously mixed dipping, drying, 550 ℃ roasting treatment for 2 hours. Molecular sieve A was obtained, and th...

Embodiment 2

[0081] 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) and 3.6 grams of Ga 2 (SO 4 ) 3 ·16H 2 O, homogeneously mixed dipping, drying, 550 ℃ roasting treatment for 2 hours. Molecular sieve B was obtained, and the phys...

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Abstract

The invention discloses a phosphorus and loading metal containing MFI structure molecular sieve. According to the phosphorus and loading metal 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%; with loading metal oxides for calculation and the dry basis weight of the molecular sieve being a reference, the loading metal content of the molecular sieve is 0.5-5wt%; 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 and loading metal 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 and metal-loaded molecular sieve with MFI structure 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 predicte...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/40B01J29/46C10G11/05
Inventor 欧阳颖罗一斌庄立舒兴田
Owner CHINA PETROLEUM & CHEM CORP
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