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Core-shell type aromatic conversion catalyst, preparation method and application thereof

A catalyst and core-shell type technology, which is applied in the field of core-shell aromatics conversion catalysts and its preparation, can solve the problems of strong acidity on the outer surface of molecular sieve catalysts, fast deactivation speed, and low selectivity of aromatics shape-selective catalysts, so as to reduce product Effects of carbon deactivation rate, acid density reduction, and catalyst selectivity improvement

Inactive Publication Date: 2010-06-09
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] One of the technical problems to be solved by the present invention is that there are problems in the prior art that the outer surface of the molecular sieve catalyst is strongly acidic, the deactivation speed is fast, and the shape selectivity of aromatics is low. A new core-shell aromatics conversion catalyst is provided.

Method used

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  • Core-shell type aromatic conversion catalyst, preparation method and application thereof
  • Core-shell type aromatic conversion catalyst, preparation method and application thereof
  • Core-shell type aromatic conversion catalyst, preparation method and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0019] Mix 10 grams of 25% by weight TPAOH aqueous solution, 28 grams of tetraethyl orthosilicate, and 140 grams of water, add 1 ml of 35% (weight) HF acid aqueous solution, stir for 4 hours, and then add 20 grams of SiO 2 / Al 2 o 3 20 ZSM-5 nuclear phase molecular sieves were put into a 1-liter stainless steel crystallization kettle with stirring, sealed, heated to 180°C, and crystallized at a constant temperature for 1 day, with a stirring speed of 100 rpm. At the end of crystallization, quench the solid product, filter the solid product, wash until the pH of the washing solution is 7, dry at 110°C overnight, and then bake in a muffle furnace at 550°C for 4 hours to obtain the core-shell molecular sieve CS1. The shell SiO 2 / Al 2 o 3 After analysis, it was found to be 300, and the core-shell ratio was 2.5. Its X-ray diffraction characterization pattern is shown in the attached figure 1 .

[0020] The core-shell molecular sieve CS1 is added to a 10% by weight ammonium ...

Embodiment 2

[0023] 1.3 grams of ethylamine, 13.5 grams of water glass (containing SiO 2 25.8 wt%, Na 2 O 7.3% by weight) mixed with 70 grams of water, added 2 milliliters of triethanolamine, stirred for 1 hour, then added 7 grams of SiO 2 / Al 2 o 3 20 ZSM-5 nuclear phase molecular sieves were put into a 100 ml stainless steel crystallization kettle, sealed, heated to 180°C, and crystallized at constant temperature for 1 day. At the end of the crystallization, quench the solid product, filter, wash, and dry overnight at 110°C to obtain the core-shell molecular sieve CS2, and the shell SiO 2 / Al2 o 3 The molar ratio was analyzed to be 50 and the core / shell weight ratio was 2:1.

[0024] After ion-exchanging the core-shell molecular sieve CS2 according to the method described in Example 1, the core-shell molecular sieve CS2 and Al 2 o 3 Binders were mixed, stirred and kneaded, extruded into rods, dried in the air and calcined in a muffle furnace at 550°C for 4 hours to obtain the cor...

Embodiment 3

[0026] Mix 2.6 grams of TPABr, 0.4 grams of sodium hydroxide, 28 grams of ethyl orthosilicate, and 140 grams of water, add 0.5 grams of NaBr, stir for 8 hours, and then add 8 grams of SiO 2 / Al 2 o 3 It is a 40-nuclear phase molecular sieve ZSM-5, put it into a 1-liter stainless steel crystallization kettle with stirring, seal it, raise the temperature to 150°C, and crystallize at a constant temperature for 2 days at a stirring speed of 200 rpm. At the end of the crystallization, quench the solid product, filter, wash, and dry overnight at 110°C to obtain a core-shell molecular sieve CS3 with a core / shell ratio of 2.5:1, and the shell SiO 2 / Al 2 o 3 The molar ratio was 500.

[0027] After ion-exchanging the core-shell molecular sieve CS3 according to the method described in Example 1, the core-shell molecular sieve CS3 and TiO 2 Binders were mixed, stirred and kneaded, extruded into rods, dried in the air and calcined in a muffle furnace at 550°C for 4 hours to obtain th...

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Abstract

The invention relates to a core-shell type aromatic conversion catalyst, a preparation method and application thereof, mainly solving the problems of strong acidity of an outside surface, rapid inactivation speed and low selectivity of aromatic shape selective catalysis in previous molecular sieve based catalysts. The invention adopts the following technical scheme: the preparation method that ZSM-5 crystal grain is taken as a core and a high silicon MF1 molecular sieve shell layer is formed on the outside surface of the core crystal by secondary growth is used for synthesizing the core-shell type zeolite molecular sieve with tightly-bonded core and shell and communicated pore canals, then the catalyst is prepared by shaping and baking 10-100% of core-shell type zeolite molecular sieves and the balance binder in terms of weight percent to better solve the above problems. The invention can be used in industrial production of aromatic conversion reactions of toluene disproportionation, toluene methylation, xylene isomerisation, trimethylbenzene cracking, cumin cracking and styralyl alcohol alkylating.

Description

technical field [0001] The invention relates to a core-shell aromatic hydrocarbon conversion catalyst, a preparation method and application thereof. Background technique [0002] Zeolite molecular sieves have been widely used in the catalytic process of petroleum refining and processing since the 1960s because of their regular pores, adjustable acidity and alkalinity, and shape-selective sieving. Cracking of hydrogen compounds, conversion of aromatics, isomerization, alkylation, shape-selective reforming, dehydration, MTG and other catalytic reactions. Among them, zeolite molecular sieves such as mordenite, ZSM-5 zeolite, and Beta zeolite are usually used to prepare catalysts in the industrial process of aromatics conversion. However, with the development of petroleum refining and petrochemical industry, people put forward higher and higher requirements for the catalytic activity and selectivity of molecular sieves. Since there are acid sites on both the inner and outer su...

Claims

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Application Information

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IPC IPC(8): B01J29/80B01J29/40B01J35/02C07C15/02C07C6/02C07C4/00C07C2/00
Inventor 孔德金刘志成
Owner CHINA PETROLEUM & CHEM CORP
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