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A kind of MFI structure molecular sieve rich in mesoporous phosphorus and rare earth and preparation method thereof

A technology of molecular sieves and rare earths, applied in molecular sieve catalysts, chemical instruments and methods, hydrocarbon cracking and hydrocarbon production, etc., can solve the problems that the improvement effect of ethylene yield and selectivity is not obvious enough, and achieve good shape selectivity and enhanced synergistic effect , the effect of enriching the mesoporous structure

Active Publication Date: 2021-03-12
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] In the prior art, the effect of modulating the properties of molecular sieves is mostly focused on the improvement of the yield and selectivity of propylene and butene, and the effect of improving the yield and selectivity of ethylene is not obvious enough

Method used

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preparation example Construction

[0040] The present invention also provides a preparation method of the provided mesoporous phosphorus-containing and rare earth-containing MFI molecular sieve, the method comprising:

[0041] a. Filtrating and washing the MFI structure molecular sieve slurry obtained by crystallization to obtain a water-washed molecular sieve; wherein, the sodium content of the water-washed molecular sieve is less than 5% by weight, calculated as sodium oxide and based on the total dry weight of the water-washed molecular sieve;

[0042] b. Desiliconizing the water-washed molecular sieve obtained in step a in an alkaline solution, and filtering and washing to obtain an alkali-washed molecular sieve;

[0043] c. Perform ammonium exchange treatment on the alkali-washed molecular sieve obtained in step b to obtain ammonium-exchanged molecular sieve; wherein, the sodium content of the ammonium-exchanged molecular sieve is less than 0.2 in terms of sodium oxide and based on the total dry weight of t...

Embodiment 1

[0066] 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 The O content (on a dry basis) is lower than 5.0% by weight, and the filter cake is obtained by filtration; 100 g (dry basis) of the above-mentioned molecular sieve is added to 1000 g of 2.0% by weight of NaOH solution, the temperature is raised to 65° C., and after 30 minutes of reaction, it is rapidly cooled to room temperature Afterwards, filter and wash until the filtrate is 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 2The O content (on a dry basis) is lower than 0.2% by weight, filtered and washed to obtain a molecular sieve filter cake; 50 g (dry basis) of the above molecular sieve filter cake is taken, and the filter cake is beaten with water to obtain a molecular sieve slurry with a solid content of 40...

Embodiment 2

[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 The O content (on a dry basis) is lower than 5.0% by weight, and the filter cake is obtained by filtration; 100 g (dry basis) of the above-mentioned molecular sieve is added to 1000 g of 2.0% by weight of NaOH solution, the temperature is raised to 65° C., and after 30 minutes of reaction, it is rapidly cooled to room temperature Afterwards, filter and wash until the filtrate is 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 The O content (on a dry basis) is lower than 0.2% by weight, filtered and washed to obtain a molecular sieve filter cake; 50 g (dry basis) of the above molecular sieve filter cake is taken, and the filter cake is beaten with water to obtain a molecular sieve slurry with a solid content of 4...

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Abstract

The present invention relates to a kind of MFI structure molecular sieve rich in mesoporous phosphorus and rare earth and preparation method thereof, the n(SiO 2 ) / n(Al 2 o 3 ) is greater than 15 and less than 70; with P 2 o 5 Calculated and based on the dry weight of the molecular sieve, the phosphorus content of the molecular sieve is 1-15% by weight; based on the oxide of the loaded metal and based on the dry weight of the molecular sieve, the content of the loaded metal M1 in the molecular sieve is 1-10% by weight, and the content of the loaded metal M2 is 0.1-5% by weight, wherein the loaded metal M1 is selected from one or both of lanthanum and cerium, and the loaded metal M2 is selected from iron, cobalt, nickel, copper, manganese, One of zinc, tin, bismuth and gallium; the proportion of the mesopore volume of the molecular sieve to the total pore volume is 40-70% by volume. The molecular sieve with MFI structure provided by the invention has better ethylene selectivity in the petroleum hydrocarbon catalytic cracking reaction, and can produce more propylene and BTX at the same time.

Description

technical field [0001] The invention relates to a phosphorus- and rare-earth-rich molecular sieve with an MFI structure and a preparation method thereof. Background technique [0002] Since the 21st century, crude oil price fluctuations and rapid technological progress have promoted the development of the global petrochemical industry in the direction of diversification of raw materials and low cost, especially the rapid expansion of petrochemical production capacity in areas rich in light hydrocarbon resources in the Middle East, shale gas in North America and China. The development of the coal chemical industry has brought a huge impact on the traditional petrochemical industry that uses naphtha as raw material, and the large-scale marketization of ethane to ethylene technology has also challenged the production of low-carbon olefins from naphtha steam cracking. In comparison, the cash cost of ethylene production via the traditional naphtha route is high and the cost compe...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/46C10G11/05C07C4/06C07C11/04C07C11/06C07C15/08C07C15/04C07C15/06
CPCB01J29/46C07C4/06C10G11/05C10G2300/70C10G2400/20C10G2400/30C07C11/04C07C11/06C07C15/08C07C15/04C07C15/06Y02P20/52
Inventor 欧阳颖罗一斌刘建强庄立李明罡舒兴田
Owner CHINA PETROLEUM & CHEM CORP
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