Core-shell type SAPO-34-coated ZSM-5 molecular sieve catalyst and preparation method thereof

A technology of SAPO-34 and ZSM-5, which is applied in the field of core-shell SAPO-34@ZSM-5 molecular sieve catalyst and its preparation, can solve problems such as two-phase separation, time consumption limitation, and reduction of zeolite crystallinity, and meet the conditions Relatively mild, increase the service life, the effect of easy raw materials

Pending Publication Date: 2022-07-15
TAIYUAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The post-treatment method (acid or alkali treatment) is used to extract aluminum or silicon atoms in the zeolite framework to cause lattice defects, so that intracrystalline mesopores are generated in the zeolite crystal, but this method is easy to cause crystal damage and reduce the zeolite. Crystallinity, the released amorphous silicon and aluminum species are easy to block the micropore channels
The use of mesoporous templates and small-molecule organic amines (structure-directing agents) tends to cause incompatibility between templates during the growth of zeolite, which can easily lead to two-phase separation or miscellaneous crystals
In addition, a large amount of waste gas is generated in the process of removing the template agent, which is likely to cause environmental pollution
No matter which method is used, the acid center of the catalyst skeleton will be weakened, so that the catalytic active sites of the catalyst will be greatly reduced during the reaction, which will further affect the reaction performance of the catalyst.
Moreover, complex synthetic procedures, expensive mesoporous templates, and a large amount of time consumption severely limit industrial applications.

Method used

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  • Core-shell type SAPO-34-coated ZSM-5 molecular sieve catalyst and preparation method thereof
  • Core-shell type SAPO-34-coated ZSM-5 molecular sieve catalyst and preparation method thereof
  • Core-shell type SAPO-34-coated ZSM-5 molecular sieve catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Example 1: Preparation of SAPO-34@ZSM-5

[0027] (1) Weigh 6.12g of aluminum isopropoxide and dissolve it in a solution of 30.3mL of distilled water and 35.3mL of tetrapropylammonium hydroxide, stir until completely dissolved, then add 3.6mL of ethyl orthosilicate and 4.0mL of phosphoric acid in sequence. After mixing evenly, it was transferred into a stainless steel reaction kettle with a volume of 100 mL, and hydrothermally crystallized at 180 °C for 3 days. The crystallized sample was washed to neutrality and dried at 80°C overnight to obtain solid powder;

[0028] (2) 160g distilled water, 1.6g cetyltrimethylammonium bromide, 40mL isopropanol, 1mL ammonia water, 1.6ml ethyl orthosilicate and 2g SAPO-34 molecular sieve obtained in step (1) Put it into it, stir at 30 °C for 3 h, the final product was washed with distilled water, and dried at 80 °C overnight to obtain core-shell SAPO-34@MCM-41;

[0029](3) Weigh 10.98g of ethyl orthosilicate, 10.37g of tetrapropylamm...

Embodiment 2

[0032] For the preparation of SAPO-34@ZSM-5, in step (1), 7.01 g of ammonium dihydrogen phosphate was used, and the rest were the same as in Example 1.

Embodiment 3

[0034] For the preparation of SAPO-34@ZSM-5, in step (1), 4.23 g of ammonium monohydrogen phosphate was used, and the rest were the same as in Example 1.

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Abstract

The invention provides a core-shell type SAPO-34-coated ZSM-5 zeolite catalyst and a preparation method thereof, an SAPO-34 microsphere (about 2 microns) formed by stacking nano polycrystalline aggregates is used as a core, a layer of MCM-41 material is deposited on the outer surface of the SAPO-34 microsphere, and then a shell layer MCM-41 in-situ zeolitization is induced by adding a ZSM-5 seed crystal precursor solution to form ZSM-5 zeolite particles (about 150 nm) by using a traditional hydrothermal synthesis method. According to the core-shell type SAPO-34-coated ZSM-5 zeolite catalyst prepared by the preparation method disclosed by the invention, the surface of the SAPO-34 is modified by utilizing the deposited MCM-41, so that the problem that the SAPO-34 crystal is damaged in an alkaline environment system for synthesizing the SAPO-34-coated ZSM-5 is effectively solved. The preparation method provided by the invention has the advantages of easily available raw materials, simple process, relatively mild conditions and the like, can realize industrial application, and has wide application prospects in solving the problem of energy shortage.

Description

technical field [0001] The invention belongs to the field of inorganic materials, in particular to a core-shell type SAPO-34@ZSM-5 molecular sieve catalyst and a preparation method thereof. Background technique [0002] Zeolite molecular sieve is a kind of crystalline material with framework structure, which has been widely used in catalysis, adsorption separation, biotechnology due to its unique microporous structure, adjustable acidity, good thermal / hydrothermal stability and chemical stability. and other fields. Among them, SAPO-34 molecular sieve is one of the important members of the SAPO series. SAPO-34 has a CHA topology, which is composed of SiO 4 , AlO 4 and PO 4 A three-dimensional cross-channel structure formed by interconnecting tetrahedra through oxygen bridges. It has high selectivity to ethylene and propylene in MTO-catalyzed reaction. However, the traditional SAPO-34 zeolite severely limits the mass transfer and diffusion of product molecules in the mic...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/00C07C1/20C07C11/04C07C11/06
CPCB01J29/005C07C1/20B01J29/85B01J29/40C07C11/04C07C11/06
Inventor 汪全华范彬彬李瑞丰刘砚超张丽晨马晓森白亚东郑家军
Owner TAIYUAN UNIV OF TECH
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