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

A molecular sieve and nanotechnology, which is applied in the field of phosphorus-containing MFI structure molecular sieves and its preparation, can solve the problems of poor hydrothermal stability in production costs, popularization and application, etc., to suppress surface non-selective side reactions, reduce cracking activity, and reduce coking loss. live effect

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

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 phosphorus-containing MFI structure molecular sieve and preparation method thereof

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preparation example Construction

[0044] The present disclosure also provides a method for preparing the phosphorus-containing MFI structure molecular sieve provided by the present disclosure. The preparation method includes: a. After filtering and washing the MFI structure molecular sieve slurry obtained by crystallization, a water-washed molecular sieve is obtained; Sodium and based on the total dry weight of the water-washed molecular sieve, the sodium content of the water-washed molecular sieve is less than 3% by weight; b. The water-washed molecular sieve obtained in step a is subjected to desilication treatment in an alkaline solution, and after filtering and washing , To obtain a desilication molecular sieve; c. The desilication molecular sieve obtained in step b is subjected to ammonium exchange treatment to obtain an ammonium exchange molecular sieve; wherein, the ammonium exchange molecular sieve is calculated based on sodium oxide and based on the total dry basis weight of the ammonium exchange molecul...

Embodiment 1

[0072] Crystallized ZSM-5 molecular sieve (produced by the catalyst Qilu branch, synthesized by amine-free method, n(SiO 2 ) / n(Al 2 O 3 )=27) Filter out the mother liquor, wash with water until Na 2 If the O content is less than 3.0% by weight, filter to obtain a filter cake; add 100g of the above molecular sieve (dry basis) to 1000g of 2.0% NaOH solution, raise the temperature to 65°C, react for 30 minutes, quickly cool to room temperature, filter, and wash to the filtrate neutral. Then, add 800g of water to the filter cake to make a slurry, and add 40g of NH 4 Cl, heated to 75°C, exchanged for 1h, to Na 2 The O content is less than 0.2% by weight, filtered and washed to obtain a molecular sieve filter cake; take 50g of the above molecular sieve (dry basis) and add water to prepare a molecular sieve slurry with a solid content of 10% by weight, add 11g of oxalic acid during stirring, and then add 110g of hydrochloric acid (mass fraction) 10%) and 92g fluorosilicic acid (mass fr...

Embodiment 2

[0096] Crystallized ZSM-5 molecular sieve (produced by Qilu Branch of the catalyst, synthesized by amine-free method, n(SiO 2 ) / n(Al 2 O 3 )=27) Filter out the mother liquor, wash with water until Na 2 O content is less than 3.0% by weight, filtered to obtain a filter cake; add 100g of the above molecular sieve (dry basis) to 1500g 2.4% NaOH solution, warm up to 60°C, react for 45 minutes, quickly cool to room temperature, filter and wash to the filtrate neutral. Then, add 800g of water to the filter cake to make a slurry, and add 40g of NH 4 Cl, heated to 75°C, exchanged for 1h, to Na 2 The O content is less than 0.2% by weight, filtered and washed to obtain a molecular sieve filter cake; take 50g of the above molecular sieve (dry basis) and add water to prepare a molecular sieve slurry with a solid content of 10% by weight, add 22g of citric acid during stirring, and then add 55g of sulfuric acid (mass Fraction 10%) and 280g fluorosilicic acid (mass fraction 3%) were added in ...

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Abstract

The present disclosure provides a phosphorus-containing MFI-structure molecular sieve and a preparation method thereof, wherein the n(SiO2) / n(Al2O3) of the molecular sieve is more than 100, the phosphorus content (calculated as P2O5) of the molecular sieve is 0.1-5 wt% by using the dry base weight of the molecular sieve as the reference, the Al distribution parameter D 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 MFI-structure molecular sieve as the active component, theyield 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 MFI structure 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. During the "Twelfth Five-Year Plan" period, car sales are expected to increase by 11% annually, driving gasoline demand to maintain an average annual growth of 5%. With the commissioning of a new round of dedicated propylene production capacity, global propylene supply will significantly exceed the expected demand growth in the next five years. It is predicted that the global propylene production capacity will increase by 30Mt in the next five years, while demand growth is expected to be only 22Mt. This gap between supply and demand may lead to lower propylene prices. [0003] Driven by market demand and economic benefits, refineries adopt a production plan th...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C01B39/06C01B39/10B01J29/70C10G11/05
CPCB01J29/70C01B39/06C01B39/10C01P2006/14C01P2006/17C10G11/05C10G2300/305C10G2400/02
Inventor 庄立欧阳颖罗一斌刘建强舒兴田
Owner CHINA PETROLEUM & CHEM CORP
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