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Catalytic cracking catalyst and preparation method thereof

A catalytic cracking and catalyst technology, applied in catalytic cracking, physical/chemical process catalysts, molecular sieve catalysts, etc., can solve the problem of low yield of low-carbon olefins and achieve good selectivity of low-carbon olefins and excellent hydrothermal stability Effect

Active Publication Date: 2014-05-14
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the catalyst prepared by using the beta zeolite obtained by this method still has the problem that the yield of low-carbon olefins (ethylene, propylene and butene) is not high when it is used for the production of low-carbon olefins from naphtha cracking

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  • Catalytic cracking catalyst and preparation method thereof
  • Catalytic cracking catalyst and preparation method thereof
  • Catalytic cracking catalyst and preparation method thereof

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preparation example Construction

[0022] The preparation method of the phosphorus-modified β molecular sieve of the present invention comprises that the raw powder of the β molecular sieve (sodium type β molecular sieve containing an organic template) is passed through at least two different The overlapping temperature range treatment is obtained by removing the template agent and then performing phosphorus modification. More specifically, it includes the following steps:

[0023] (1) The sodium-type β molecular sieve is exchanged with ammonium to make the Na on the molecular sieve 2 The O content is less than 0.2% by weight;

[0024] (2) After drying the molecular sieve obtained in step (1), treat it at a temperature range of 200-400°C for at least 0.5 hours, and then heat it up to a temperature range of 500-800°C within at most 2 hours and treat it for at least 0.5 hours to remove the template agent;

[0025] (3) Introducing phosphorus-containing compounds to modify molecular sieves;

[0026] (4) Baking ...

preparation Embodiment 1

[0037] Naβ molecular sieve (produced by Qilu Catalyst Factory, SiO 2 / Al 2 o 3 =25 molar ratio, sodium oxide content 4.5% by weight, the same below) with NH 4 Cl solution exchange wash to Na 2 The O content is lower than 0.2% by weight, and the filter cake is obtained by filtration; dried, and the obtained sample is calcined at 350°C for 2 hours, then heated (heating rate 5°C / min) to 550°C, and calcined for 4 hours to remove the template agent; add 14.6 kgH 3 PO 4 (concentration 85% by weight) was dissolved in 90 kg of water, mixed with 100 kg of the above-mentioned roasted molecular sieve, impregnated and dried; the obtained sample was roasted at 500°C for 2 hours, that is, the molecular sieve provided by the present invention, denoted as B1. The physical data of the samples and 27 Al MAS NMR peak area ratios are listed in Table 1.

preparation Embodiment 2

[0039] Naβ molecular sieve (produced by Qilu Catalyst Factory, SiO 2 / Al 2 o 3 =25) with NH 4 Cl solution exchange wash to Na 2 The O content is lower than 0.2% by weight, and the filter cake is obtained by filtration; dried, and the obtained sample is roasted at 350°C for 2 hours, then heated to 550°C for 4 hours in 30 minutes to remove the templating agent; add 9.6 kg (NH 3 ) 2 HPO 4 (concentration 85% by weight) dissolved in 90 kg of water, mixed with 100 kg of the above-mentioned roasted molecular sieve, impregnated and dried; the obtained sample was roasted at 550°C and 100% water vapor for 2 hours, that is, the molecular sieve provided by the present invention, denoted as B2 . The physical data of the samples and 27 Al MAS NMR peak area ratios are listed in Table 1.

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Abstract

The invention discloses a catalytic cracking catalyst and a preparation method thereof, the catalytic cracking catalyst includes (a)15%-65% of a natural mineral, (b) 10%-30% of an oxide and (c) 25%-75% of a mixture of a MFI structure molecular sieve and a phosphorus-modified beta molecular sieve; the phosphorus-modified beta molecular sieve comprises 3-10 wt% by P2O5 of phosphorus, and in the 27Al MAS NMR (Magic Angle Spinning Nuclear Magnetic Resonance) of the molecular sieve, the ratio of resonance signal peak area at the chemical shift of 40+-3ppm to resonance signal peak area at the chemical shift of 54+-3ppm is greater than or equal to 1. The preparation method of the catalyst comprises the steps of mixing and pulping of the phosphorus-modified beta molecular sieve, the natural mineral and a non-polar oxide adhesive, and spray drying, and the preparation method of the phosphorus-modified beta molecular sieve is as follows: programmed heating of beta molecular sieve raw powder to bake to remove a template agent, and then phosphorus modification. The catalytic cracking catalyst is applied to preparation of propylene by catalytic cracking of naphtha, and the low-carbon olefin production rate is higher.

Description

technical field [0001] The invention relates to a fluidized bed catalyst for catalytic cracking to produce olefins, in particular to a beta molecular sieve-containing catalyst for producing ethylene, propylene and butene through a fluidized catalytic cracking process using naphtha as a raw material. Background technique [0002] Ethylene, propylene and butene are very important chemical raw materials. At present, naphtha steam cracking is mainly used in the world to produce these low-carbon olefins. This method has many shortcomings such as high reaction temperature and high energy consumption. In order to overcome these problems, a lot of research on catalytic cracking technology has been carried out at home and abroad. It is expected that through the introduction of catalysis, on the one hand, the reaction temperature can be appropriately reduced, coking and energy consumption can be reduced, and on the other hand, the yield of low-carbon olefins can also be increased, mak...

Claims

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Application Information

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IPC IPC(8): B01J29/80C10G11/05C07C11/02C07C4/06
CPCY02P20/52
Inventor 许本静欧阳颖龙军朱玉霞孙敏王丽霞田辉平罗一斌刘俊
Owner CHINA PETROLEUM & CHEM CORP
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