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 in production costs, popularization and application, etc., and achieve the suppression of non-selective side reactions on the surface, strengthening Strong effect of aromatization performance, isomerization ability and aromatization ability

Active Publication Date: 2020-02-28
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

As mentioned above, the synthesis of molecular sieves with high silicon-aluminum ratio is difficult to be popularized and applied in catalytic cracking catalysts due to production costs, environmental pollution, and poor hydrothermal stability caused by fine grains.

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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

[0047] 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

[0075] Crystallized ZSM-5 molecular sieve (produced by Catalyst Qilu Branch Company, 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,...

Embodiment 2

[0101] Crystallized ZSM-5 molecular sieve (produced by Catalyst Qilu Branch Company, 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 add...

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Abstract

The invention discloses a phosphorus-containing and supported-metal-containing MFI molecular sieve and a preparation method thereof, wherein the n(SiO2) / n(Al2O3) of the molecular sieve is greater than100, the phosphorus content of the molecular sieve is 0.1-5 wt%, the supported metal content of the molecular sieve is 0.1-5 wt%, the Al distribution parameter D (Al) of the molecular sieve is 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 acid B 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 asthe active component, the yield of gasoline in the catalytic cracking reaction of petroleum hydrocarbons can be maintained while the octane number of gasoline can be effectively increased, or the octane value of gasoline can be maintained while the yield of gasoline is improved.

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] In recent years, the number of domestic motor vehicles has continued to grow, supporting the strong demand for domestic gasoline terminal consumption. It is expected that during the "Twelfth Five-Year Plan" period, the average annual growth rate of automobile sales will be 11%, driving the demand for gasoline to maintain a steady growth rate of 5% per year. 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. With global propylene capacity forecast to increase by 30Mt over the next five years, while demand growth is expected to be only 22Mt, this gap between supply and demand could lead to lower propylene prices. [0003] Driven by market demand and economic benefits, oil refiner...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/40C01B39/38C10G11/05
CPCB01J29/405B01J2229/186B01J2229/40C01B39/026C01B39/38C01P2006/12C01P2006/14C01P2006/16C01P2006/17C10G11/05C10G2300/104C10G2300/1044C10G2300/305
Inventor 欧阳颖庄立罗一斌刘建强舒兴田
Owner CHINA PETROLEUM & CHEM CORP
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