ZSM-5 composite molecular sieve with a core-shell structure and preparation method and application thereof

A ZSM-5, composite molecular sieve technology, applied in molecular sieve catalysts, chemical instruments and methods, condensation between hydrocarbons and non-hydrocarbons to produce hydrocarbons, etc. and other problems, to achieve the effect of preventing side reactions, improving selectivity, and increasing diffusion rate

Active Publication Date: 2014-05-21
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Silicalite-1 / ZSM-5 composite molecular sieve is a kind of isomorphic composite molecular sieve with core-shell structure and MFI topology. ZSM-5 molecular sieve is completely wrapped by Silicalite-1 molecular sieve, and Silicalite-1 The type selection effect of ZSM-5 composite molecular sieve is better than that of ZSM-5 molecular sieve, but the conversion rate is reduced due to the lack of acidity on the surface
[0005] In CN101723401A, a ZSM-5 molecular sieve composite molecular sieve with a core-shell structure with different silicon-aluminum ratios was synthesized, and a ZSM-5 zeolite molecular sieve with a relatively low silicon-aluminum ratio was used as a seed crystal and added to a high-silicon-aluminum ratio shell phase rubber Among them, the ZSM-5 molecular sieve composite molecular sieve with core-shell structure was synthesized by hydrothermal method, but the microporous structure mainly exists in this structure, which affects the diffusion process and limits the diffusion of macromolecules, so it cannot be applied to the macromolecular reaction process.

Method used

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  • ZSM-5 composite molecular sieve with a core-shell structure and preparation method and application thereof
  • ZSM-5 composite molecular sieve with a core-shell structure and preparation method and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0025] Add sodium hydroxide and aluminum sulfate to deionized water, weigh tetrapropylammonium bromide and add it to the solution, and after it is completely dissolved, add ZSM-5 molecular sieve (the molar ratio of silicon oxide to aluminum oxide is 25) into the solution After stirring evenly, add CTAB, continue stirring for half an hour, add silica sol, stir evenly, put it into a stainless steel crystallization kettle, crystallize at a constant temperature of 160°C for 60 hours, then wash, dry, and roast to obtain ZSM-5 composite molecular sieve. The properties of molecular sieves are shown in Table 1.

[0026] The molar ratio of the system composed of sodium hydroxide, template agent, water, aluminum source, surfactant and silicon source: 10.0Na 2 O:45SiO 2 :Al 2 o 3 :10.2(TPA) 2 O:CTAB:4722H 2 O, the mass ratio of the added ZSM-5 molecular sieve to the above system is 1:23.

Embodiment 2

[0028] Add sodium hydroxide and aluminum sulfate to deionized water, weigh tetrapropylammonium bromide and add it to the solution, and after it is completely dissolved, add ZSM-5 molecular sieve (the molar ratio of silicon oxide to aluminum oxide is 38) into the solution After stirring evenly, add CTAB, continue stirring for half an hour, add silica sol, stir evenly, put it into a stainless steel crystallization kettle, crystallize at a constant temperature of 170°C for 60 hours, then wash, dry, and roast to obtain ZSM-5 composite molecular sieve. The properties of molecular sieves are shown in Table 1.

[0029] The molar ratio of the system composed of sodium hydroxide, template agent, water, aluminum source, surfactant and silicon source: 9.4Na 2 O:45SiO 2 :Al 2 o 3 :10.2(TPA) 2 O:1.5CTAB:4166H 2 O, the mass ratio of the added ZSM-5 molecular sieve to the above system is 1:27.

Embodiment 3

[0031] Add sodium hydroxide and sodium aluminate to deionized water, weigh tetrapropylammonium bromide and add it to the sodium hydroxide solution, and dissolve ZSM-5 molecular sieve (the molar ratio of silicon oxide to aluminum oxide is 73) Add it into the solution, stir evenly, add CTAB, continue stirring for half an hour, add silica sol, stir evenly, put it into a stainless steel crystallization kettle, crystallize at a constant temperature of 170°C for 48 hours, then wash, dry, and roast to obtain ZSM- 5 Composite molecular sieves. The properties of molecular sieves are shown in Table 1.

[0032] The molar ratio of the system composed of sodium hydroxide, template agent, water, aluminum source, surfactant and silicon source: 9.4Na 2 O:30SiO 2 :Al 2 o 3 :10.2(TPA) 2 O:0.5CTAB:4166H 2 O, the mass ratio of the added ZSM-5 molecular sieve to the above system is 1:23.

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Abstract

The invention discloses a ZSM-5 composite molecular sieve with a core-shell structure, a preparation method and an application thereof. The molecular sieve is characterized in that: the core phase is a ZSM-5 molecular sieve, the shell phase is a ZSM-5 molecular sieve with a mesoporous structure, the total molar ratio of silica to alumina is 30-80, the total specific surface area is 460-550 m2/g, the total pore volume is 0.25-0.38 ml/g, the size of the mesopore in the shell phase is 2-2.5 nm, the specific surface area of the mesopore in the shell phase is 480-650 m2/g, and the pore volume of the mesopore in the shell phase is 0.2-0.31 ml/g. The preparation method comprises the following steps: firstly performing crystallization of a mixture containing sodium hydroxide, a template, water, a silicon source, an aluminium source, a surfactant and the ZSM-5 molecular sieve, then performing washing, drying, roasting of the crystallized product to obtain the ZSM-5 composite molecular sieve. The composite molecular sieve is applicable to aromatic hydrocarbon conversion reaction, and has the advantages of high conversion rate and selectivity, and long catalyst life.

Description

technical field [0001] The invention belongs to the field of molecular sieve synthesis, and in particular relates to a ZSM-5 composite molecular sieve with a core-shell structure and a preparation method and application thereof. Background technique [0002] At present, composite molecular sieves have attracted more and more researchers' attention, and various composite molecular sieves have been synthesized continuously. In 2006, Younes Bouizi (Chem Mater 2006, 18, 4959~4966) reported a composite molecular sieve Silicalite-1 / MFI with a core-shell structure. In the method, ZSM-5 molecular sieve is wrapped with Silicalite-1 molecular sieve to form a core-shell composite molecular sieve with ZSM-5 as the core and Silicalite-1 as the shell, and the coverage rate is 70% through one synthesis process. The specific synthesis process is as follows: first, nano-scale Silicalite-1 seeds are deposited on the surface of ZSM-5 molecular sieves through tetrapropylammonium hydroxide, tet...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B39/40B01J29/40B01J35/10B01J32/00C07C15/08C07C2/86
CPCY02P20/52
Inventor 张喜文秦波张志智刘全杰
Owner CHINA PETROLEUM & CHEM CORP
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