A kind of MFI structure molecular sieve containing phosphorus and loaded metal 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, molecular sieves and alkali exchange compounds, etc., can solve the problems of poor hydrothermal stability, difficult production, high discharge of three wastes, etc., and achieve low total acid content and reduction Cracking activity, effect of increasing aromatics content

Active Publication Date: 2019-12-27
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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  • A kind of MFI structure molecular sieve containing phosphorus and loaded metal and preparation method thereof

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preparation example Construction

[0040] The present disclosure also provides a method for preparing the phosphorus-containing and metal-loaded MFI molecular sieve provided in the present disclosure, the preparation method comprising: a. After filtering and washing the MFI molecular sieve slurry obtained by crystallization, to obtain a water-washed molecular sieve; Wherein, based on sodium oxide and the total dry weight of the washed molecular sieve, the sodium content of the washed molecular sieve is less than 3% by weight; b, the water-washed molecular sieve obtained in step a is desiliconized in an alkaline solution, and carried out After filtering and washing, desiliconized molecular sieves are obtained; c, the desiliconized molecular sieves obtained in step b are subjected to ammonium exchange treatment to obtain ammonium exchanged molecular sieves; wherein, in terms of sodium oxide and based on the total dry basis weight of ammonium exchanged molecular sieves, the obtained The sodium content of the ammoni...

Embodiment 1

[0068] Crystallized ZSM-5 molecular sieve (produced by Catalyst Qilu Branch, synthesized without amine method, n(SiO 2 ) / n(Al 2 o 3 )=27) filter out mother liquor, wash with water to Na 2 O content is lower than 3.0% by weight, filter to obtain filter cake; Take above-mentioned molecular sieve 100g (dry basis) and add in 1000g 2.0% NaOH solution, heat up to 65 ℃, after reacting for 30min, after rapidly cooling to room temperature, filter, wash to filtrate neutral. Then, add 800g water to the filter cake to make a slurry, add 40g NH 4 Cl, heated to 75°C, exchanged for 1h, to Na 2 O content is lower than 0.2% by weight, filters, washes, and obtains molecular sieve filter cake; Get above-mentioned molecular sieve 50g (dry basis) and add water and be mixed with the molecular sieve slurry of solid content 10% by weight, add oxalic acid 11g in stirring, then 110g hydrochloric acid (mass fraction 10%) and 92g of fluosilicic acid (mass fraction 3%) were added in parallel, and the...

Embodiment 2

[0096] Crystallized ZSM-5 molecular sieve (produced by Catalyst Qilu Branch, synthesized without amine method, n(SiO 2 ) / n(Al 2 o 3 )=27) filter out mother liquor, wash with water to Na 2 O content is lower than 3.0% by weight, filter to obtain filter cake; Get above-mentioned molecular sieve 100g (dry basis) and add in 1500g 2.4% NaOH solution, heat up to 60 ℃, after reacting for 45min, after rapidly cooling to room temperature, filter, wash to filtrate neutral. Then, add 800g water to the filter cake to make a slurry, add 40g NH 4 Cl, heated to 75°C, exchanged for 1h, to Na 2 O content is lower than 0.2% by weight, filters, washes, obtains molecular sieve filter cake; Get above-mentioned molecular sieve 50g (dry basis) and add water and be mixed with the molecular sieve slurry of solid content 10% by weight, add citric acid 22g in stirring, then 55g sulfuric acid (mass Fraction 10%) and 280g fluosilicic acid (mass fraction 3%) were added in parallel, and the addition ti...

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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 0.6 and is less than or equal to 0.85, the volume of the mesopores of the molecular sieve accounts for 40-80% of the total pore volume, the volume of the mesopores with the pore size of 2-20 nm accounts for more than 90% of the total mesopore 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 acidB to the acid L is 15-80. 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): C01B39/02C01B39/38B01J29/40
CPCB01J29/405C01B39/026C01B39/38C01P2006/12C01P2006/14C01P2006/16C01P2006/17
Inventor 罗一斌欧阳颖刘建强庄立舒兴田
Owner CHINA PETROLEUM & CHEM CORP
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