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Core-shell type hydrogenation catalyst and preparation method thereof

A hydrogenation catalyst, core-shell technology, applied in catalysts, hydrogenation to hydrocarbons, molecular sieve catalysts, etc., can solve problems such as lack of compatibility, achieve excellent catalytic performance, shorten migration paths, and increase the effect of hydroxyl density

Active Publication Date: 2019-01-25
TAIYUAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there is a lack of compatibility between LTA-type molecular sieves and commonly used acidic zeolites in terms of structure and chemical composition. At the same time, in conventional hydrothermal synthesis systems, LTA-type molecular sieves are prone to undergo crystal transformation to form P-type zeolites.

Method used

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  • Core-shell type hydrogenation catalyst and preparation method thereof
  • Core-shell type hydrogenation catalyst and preparation method thereof
  • Core-shell type hydrogenation catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] Take 30.3mmol sodium metaaluminate, 24.6mmol sodium hydroxide, 11mmol fumed silica, add 19.8mL deionized water successively, stir at 60℃ for 3h, then add 0.24mmol Pt(NH 3 ) 4 Cl 2 , Continue to stir for 1h. Then it was put into a stainless steel reactor with PTFE lining, and reacted with dynamic hydrothermal crystallization at a constant temperature of 100°C for 24 hours. The obtained solid product was washed to neutrality, dried, calcined at 350℃ for 2h in air atmosphere, and then subjected to 10% H at 350℃ 2 / Ar was reduced for 2h to prepare Pt@LTA samples encapsulated with Pt metal clusters.

[0049] Take 2 g of the Pt@LTA sample prepared above, add 10 mL of ethanol and deionized water (1:1) to the mixture, and sonicate for 1 hour to obtain dispersion A.

[0050] Take 2.98mmol sodium metaaluminate, 1.22mmol sodium hydroxide, and 33.6mmol tetrapropylammonium hydroxide 25wt% aqueous solution, add 32mL deionized water and stir until clear, then add 55.4mmol ethyl orthosilica...

Embodiment 2

[0056] Take 30.3mmol sodium metaaluminate, 101.2mmol sodium hydroxide, 22mmol fumed silica, sequentially add 21.5mL deionized water, stir at 60℃ for 3h, add 0.12mmol [Pd(NH 2 CH 2 CH 2 NH 2 ) 2 ]Cl 2 , Continue to stir for 1h. Then it was put into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and reacted for 12 hours at a constant temperature of 100°C for dynamic hydrothermal crystallization. The obtained solid product was washed to neutrality, dried, calcined at 350℃ for 2h under air atmosphere, and then subjected to 10% H at 300℃ 2 / Ar reduction for 3h to prepare Pd@LTA samples encapsulated with Pd metal clusters.

[0057] Take 1.5 g of the Pd@LTA sample prepared above, add 10 mL of a mixture of ethanol and deionized water (1:1), and ultrasonicate for 1 h to obtain dispersion A.

[0058] Take 2.98mmol of sodium metaaluminate, 2.21mmol of sodium hydroxide, add 50.4mmol of tetrapropylammonium hydroxide 25wt% aqueous solution to 21mL of deionized water and...

Embodiment 3

[0062] Take 30.3mmol sodium metaaluminate, 63.4mmol sodium hydroxide, 18.4mmol fumed silica, sequentially add 22.8mL deionized water, stir at 60℃ for 3h, add 0.12mmol [Ir(NH 3 ) 5 Cl]Cl 2 , Continue to stir for 1h. Then it was put into a stainless steel reactor with PTFE lining, and reacted with dynamic hydrothermal crystallization at a constant temperature of 80°C for 24h. The obtained solid product was washed to neutrality, dried, calcined at 350℃ for 2h under air atmosphere, and then subjected to 10% H at 370℃ 2 / Ar was reduced for 2h, and Ir@LTA samples encapsulated with Ir nanoclusters were prepared.

[0063] Take 2.3 g of the Ir@LTA sample prepared above, add 10 mL of a mixture of ethanol and deionized water (1:1), and ultrasonicate for 1 hour to obtain dispersion A.

[0064] Take 2.98mmol of sodium metaaluminate, 2.9mmol of sodium hydroxide, add 60.1mmol of tetrapropylammonium hydroxide 25wt% aqueous solution to 44.3mL of deionized water and stir until clear, then add 66.8mm...

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Abstract

The invention discloses a core-shell type hydrogenation catalyst and a preparation method thereof. A core-layer structure of the core-shell type hydrogenation catalyst is an LTA molecular sieve, and anoble metal cluster is packaged into a hole cage; the noble metal cluster is formed by introducing a noble metal precursor into a synthesis system of the LTA molecular sieve, hydrothermally crystallizing in situ, roasting and reducing, and forming in the hole cage of the LTA molecular sieve; a shell-layer structure is a ZSM-5 zeolite molecular sieve, the LTA molecular sieve with the packaged noble metal cluster is added into a gel system for synthesis of the ZSM-5 zeolite molecular sieve, dried, and subjected to steam phase conversion reaction, and a ZSM-5 zeolite molecular sieve shell layeris formed on the surface of the LTA molecular sieve with the packaged noble metal cluster. The prepared core-shell type hydrogenation catalyst can be applied into the hydrogenation reaction of polycyclic aromatic hydrocarbon, the catalysis activity is high, and the anti-sulfur property is good.

Description

Technical field [0001] The invention relates to a hydrogenation catalyst, especially a catalyst for the hydrogenation reaction of fused ring aromatic hydrocarbons, and a preparation method of the catalyst. Background technique [0002] Crude oil has become increasingly heavy and deteriorated, and the content of fused-ring aromatics in diesel produced by catalytic cracking is getting higher and higher, which cannot meet the requirements of environmental protection and the automotive industry for indicators such as the content of aromatics and cetane number in diesel. Therefore, improving and upgrading the quality of catalytically cracked diesel oil is an important issue facing petroleum processing in the world. [0003] The deep hydrogenation of fused-ring aromatics can not only reduce the content of aromatics, but also increase the cetane number of diesel, which is an important way to upgrade heavy oil and diesel from low-quality FCC cracking. [0004] Catalysts made by loading sulf...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/85C07C5/10C07C13/50C07C5/11C07C13/48C10G45/54
CPCB01J29/005B01J29/44B01J29/85C07C5/10C07C5/11C07C2529/85C10G45/54C07C2602/28C07C13/50C07C13/48
Inventor 范彬彬路宁悦张雪莲闫晓亮李瑞丰
Owner TAIYUAN UNIV OF TECH
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