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

A technology of supporting metals and molecular sieves, applied in molecular sieve catalysts, chemical instruments and methods, molecular sieves and alkali exchange compounds, etc., can solve the problems of poor hydrothermal stability, difficult production, and high three-waste discharge, and achieve low total acid content and reduced Cracking activity, effect of increasing aromatics content

Active Publication Date: 2020-01-10
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
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  • 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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  • A kind of MFI structure molecular sieve containing phosphorus and loaded metal and preparation method thereof

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[0037] The present disclosure also provides a preparation method of the phosphorus-containing and metal-loaded MFI structural molecular sieves provided in the present disclosure, the preparation method comprising: a, performing ammonium exchange treatment on the sodium-type MFI structural molecular sieves to obtain ammonium exchange molecular sieves; wherein, Calculated in sodium oxide and based on the total dry basis weight of ammonium-exchanged molecules, the sodium content of the ammonium-exchanged molecular sieve is less than 0.2% by weight; Carry out dealumination treatment in the composite acid dealumination agent solution composed of acid, and after filtering and washing, obtain dealumination molecular sieve; c, after carrying out phosphorus modification treatment and load metal loading treatment on the dealumination molecular sieve obtained in step b to obtain a modified molecular sieve; d, subjecting the modified molecular sieve obtained in step c to hydrothermal roast...

Embodiment 1

[0063] 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 30min; the temperature was raised to 65°C and stirred at a constant temperature for 1h, filtered and washed until the filtrate was neutral, and the filter cake was beaten with water to obtain a molecular sieve slurry with a solid content of 40% by weight; 2.4 g H 3 PO 4 (Concentration 85% by weight) and 6.6gZn(NO 3 ) 2 ·6H 2 O was dissolved in deionized water, and ammonia water was added to adjust the pH=6, then added to the mo...

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%) Add 500 g of fluosilicic acid (3% by mass) in parallel for 30 minutes; raise the temperature to 45° C. and stir at a constant temperature for 1 hour, filter and wash until the filtrate is neutral; add water to the filter cake and beat to obtain a molecular sieve slurry with a solid content of 40% by weight; 2.0gH 3 PO 4 (concentration 85% by weight) and 3.6 grams of Ga 2 (SO 4 ) 3 16H 2 O was dissolved in deionized water, and ammonia water was added to adjust the pH to 4, then added to the molecular sieve slurry, mixed ev...

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Abstract

The invention discloses a phosphorus-containing and supported-metal-containing MFI structure molecular sieve and a preparation method thereof, wherein the n(SiO2) / n(Al2O3) of the molecular sieve is greater than 100, the phosphorus content of the molecular sieve is 0.1-5 wt%, the supported metal content of the molecular sieve is 0.5-5 wt%, the Al distribution parameter D (Al) of the molecular sieveis more than or equal to 0.5 and is less than or equal to 0.8, the supported metal distribution parameter D (M) of the molecular sieve is more than or equal to 2 and is less than or equal to 10, thevolume of the mesopores of the molecular sieve accounts for 15-30% of the total pore volume, the amount of the strong acid of the molecular sieve accounts for 60-80% of the total acid amount, and a ratio of the acid B to the acid L is 20-100. According to the present invention, with the catalyst or the auxiliary agent prepared by using the phosphorus-containing and supported-metal-containing MFI structure molecular sieve as the active component, the yield and the octane number of gasoline can be improved in the catalytic cracking reaction of petroleum hydrocarbons while the olefin content in gasoline can be effectively reduced.

Description

technical field [0001] The present disclosure relates to a phosphorus-containing and metal-supported MFI molecular sieve and a preparation method thereof. Background technique [0002] With the continuous upgrading of gasoline standards in my country, the control of olefin content in gasoline is becoming increasingly strict. The current National IV standard limits the olefin content of gasoline to a volume fraction of not higher than 28%, and the National V gasoline standard further reduces the olefin content to a volume fraction of not higher than 24%. In developed countries such as Europe and the United States, gasoline standards are more stringent on the olefin content. For example, the California 3 standard limits the gasoline olefin content to no more than 6% by volume, and the Euro 5 standard does not exceed 18%. [0003] FCC gasoline accounts for more than 60% of the gasoline pool in my country, and the high olefin content in FCC gasoline has become one of the bottle...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G11/05B01J29/84C01B39/02
CPCB01J29/84C01B39/026C10G11/05C10G2300/1033C10G2300/305C10G2400/02
Inventor 欧阳颖罗一斌庄立刘建强舒兴田
Owner CHINA PETROLEUM & CHEM CORP
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