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Modified ZSM-5 molecular sieve, and preparation method and application thereof

A technology of ZSM-5 and molecular sieve, which is applied in molecular sieve catalysts, chemical instruments and methods, and hydrocarbon oil treatment, etc. It can solve the problems of low yield of low-carbon olefins and insufficient cracking ability of heavy and inferior crude oil, and achieve improved pore structure, The effect of improving stability

Active Publication Date: 2021-10-26
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0013] The purpose of the present invention is to provide a modified ZSM-5 molecular sieve and its preparation method and application in order to overcome the insufficient cracking ability of molecular sieves to heavy and inferior crude oil and the low yield of low-carbon olefins in the prior art. When ZSM-5 molecular sieve is used in catalytic cracking reaction, it has stronger cracking ability, higher yield of low-carbon olefins, and higher selectivity of propylene

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  • Modified ZSM-5 molecular sieve, and preparation method and application thereof

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Embodiment approach

[0051] According to a preferred embodiment of the present invention, in the modified ZSM-5 molecular sieve, the mesopore volume with a pore diameter of 5nm to 20nm accounts for more than 85% of the total mesopore volume, more preferably more than 90%, for example, 90-96% of the total mesopore volume. %. In this preferred situation, the pore structure of the modified ZSM-5 molecular sieve is conducive to improving the catalytic performance of the modified ZSM-5 molecular sieve in the catalytic cracking reaction.

[0052] According to the present invention, preferably, the mesopore volume of the modified ZSM-5 molecular sieve accounts for 30-50% of the total pore volume of the modified ZSM-5 molecular sieve. In this preferred situation, it is beneficial to the production and diffusion of the reaction product, thereby avoiding the coking and deactivation of the modified ZSM-5 molecular sieve.

[0053] According to a preferred embodiment of the present invention, the SiO of the m...

specific Embodiment approach

[0079] The present invention has a wide selection range for the first solvent described in step (1), as long as the environment for exchanging ZSM-5 molecular sieve with alkali and alkaline earth metal elements can be provided. Preferably, the first solvent is water. The present invention has no particular limitation on the water, which can be water of various hardness, and commonly used tap water, distilled water, purified water and deionized water can all be used. In a specific embodiment of the present invention, the first solvent is neutral water, which is also called distilled water.

[0080] The present invention has a wide range of options for the amount of the first solvent, and can be properly selected according to the amount of the ZSM-5 molecular sieve and the compound of the alkali and alkaline earth metal, as long as the contact environment described in step (1) can be provided. Can. Preferably, relative to 100 parts by weight of the ZSM-5 molecular sieve, the a...

Embodiment 1

[0134] Prepare modified ZSM-5 molecular sieve according to the method of the present invention, concrete steps are as follows:

[0135] (1) Take ZSM-5 molecular sieve (SiO 2 / Al 2 o 3 The molar ratio is 27) 100g (dry basis weight), add 600g neutral water (also known as distilled water in the present invention), 20g of NaOH solution (molar concentration is 0.833mol / L) and 20g of MgO, heat up to 70°C, contact After reacting for 2 h, it was cooled to room temperature, and then filtered, washed and dried successively to obtain a solid product.

[0136] (2) get the solid product 80g (dry basis weight) that step (1) obtains, make a slurry with 640g water, then add the H of 20% by weight that the weight content of 40g 2 SO 4 1. 60g of oxalic acid, heated up to 70°C, after acid treatment for 2 hours, followed by filtration, washing and drying;

[0137] (3) Take step (2) to obtain 50g (dry basis weight) of product, add 200g neutral water, 5.23g zirconium oxychloride, 4.33g cerous ...

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Abstract

The invention relates to the field of molecular sieve preparation, and discloses a modified ZSM-5 molecular sieve. The molecular sieve comprises a ZSM-5 molecular sieve and alkaline earth metal elements; on the basis of the dry basis weight of the modified ZSM-5 molecular sieve, in terms of oxide, the content of the alkaline earth metal element is 10-30 wt%; the molar ratio of SiO2 to Al2O3 of the modified ZSM-5 molecular sieve is 15 to 50; the mesoporous volume of the modified ZSM-5 molecular sieve accounts for 25-60% of the total pore volume of the modified ZSM-5 molecular sieve; and the ratio of the amount of the acid B to the amount of the acid L of the modified ZSM-5 molecular sieve is 8-45. When the modified ZSM-5 molecular sieve is applied to a catalytic cracking reaction, the cracking capability is stronger, the yield of low-carbon olefin is higher, and the propylene selectivity is higher.

Description

technical field [0001] The invention relates to the field of molecular sieve preparation, in particular to a modified ZSM-5 molecular sieve and its preparation method and application. Background technique [0002] my country's propylene production capacity has grown rapidly in recent years. my country's crude oil is heavy, and light hydrocarbons and naphtha resources are scarce. Therefore, the development of catalytic cracking technology that produces more propylene is suitable for my country's national conditions. [0003] Some domestic research institutes attach great importance to the research of low-carbon olefin production technology. In the late 1980s, the Academy of Petrochemical Sciences (referred to as "Science Academy") developed a catalytic cracking technology (DCC) that uses heavy oil as a raw material to produce light olefins. The process uses a modified five-membered ring mesoporous zeolite catalyst , use the riser plus fluidized bed or riser reactor to increa...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B39/38B01J29/40C07C4/10C07C11/06C10G11/05
CPCC01B39/38B01J29/405C07C4/10C10G11/05C01P2006/17C01P2006/16B01J2229/183C10G2300/1081C10G2400/02C10G2400/06C07C11/06Y02P20/52
Inventor 张杰潇于善青凤孟龙李家兴杨民田辉平
Owner CHINA PETROLEUM & CHEM CORP
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