Preparation of core-shell catalyst of cyclohexene by efficient benzene hydrogenation

A catalyst and dual-function catalyst technology, applied in metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, hydrogenation to hydrocarbons, etc., to enhance stability, improve conversion, reduce mass transfer and transfer. The effect of thermal resistance

Pending Publication Date: 2019-05-24
FUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Therefore, the core-shell structure has good research significance and application prospects, but it is still a major challenge to develop a simple and general synthesis method for the core-shell structure to achieve precise control of shell thickness, uniformity, and functionality.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0020] The invention provides a method for preparing a (Ru / MeOx)@m-MeOx core-shell bifunctional catalyst, characterized in that the method comprises the following steps:

[0021] (1) Preparation of Ru / MeOx: According to the molar ratio of raw materials MeOx: RuCl 3 ·3H 2 O=60~90:1, MeOx was dried overnight in an oven at 60~100°C, and dispersed in RuCl under ultrasonic treatment 3 ·3H 2 O aqueous solution, then vigorously stirred for 2–10 h, the obtained suspension was separated by centrifugation, followed by washing, drying, and reduction to obtain Ru / MeOx particles;

[0022] (2) Preparation of Ru / MeOx@m-MeOx: Disperse Ru / MeOx in water to form a suspension A; dissolve the template in distilled water, then add HCl solution, and stir the mixture for 30-60 minutes to form a homogeneous solution B; add Ru / MeOx suspension A and (BuO) to solution B in sequence 4 Me, followed by stirring, filtering, washing, drying, and calcination to obtain Ru / MeOx@m-MeOx samples.

[0023] Acco...

Embodiment 1

[0034]This example is used to illustrate the preparation method of (Ru / MeOx)@m-MeOx core-shell bifunctional catalyst, including the following steps:

[0035] (1) Ru / ZrO 2 Preparation: According to the molar ratio of raw materials ZrO 2 : RuCl 3 ·3H 2 O=60:1, 5.85 g ZrO 2 Dry in an oven at 100 °C overnight and disperse in RuCl under sonication 3 ·3H 2 O aqueous solution (0.2082 g, 300 mL), then stirred vigorously for 3 h. The obtained suspension was separated by centrifugation, washed with deionized water until the AgNO 3 Reagent does not detect Cl - , and then dried in an air-circulating oven at 60 °C for 12 h. Subsequently, at 400 °C, the samples were heated in 10% H 2 (H 2 / N 2 =1:9, v / v) for 3 h, the heating rate was 5°C min -1 , to get ZrO 2 Loaded Ru particles;

[0036] (2) (Ru / ZrO 2 )@m-ZrO 2 Preparation: The molar composition of the liquid phase raw material is 1.0 CnTMAB: 15.0 HCl: 8.0 (BuO) 4 Zr: 680.0H 2 O. 3.74 g Ru / ZrO 2 Disperse in water to for...

Embodiment 2

[0039] This example is used to illustrate the preparation method of (Ru / MeOx)@m-MeOx core-shell bifunctional catalyst, including the following steps:

[0040] (1) Ru / ZrO 2 Preparation: According to the molar ratio of raw materials ZrO 2 : RuCl 3 ·3H 2 O=70:1, 5.85 g ZrO 2 Dry in an oven at 100 °C overnight and disperse in RuCl under sonication 3 ·3H 2 O aqueous solution (0.1816 g, 300 mL), then stirred vigorously for 3 h. The obtained suspension was separated by centrifugation, washed with deionized water until the AgNO 3 Reagent does not detect Cl - , and then dried in an air-circulating oven at 60 °C for 12 h. Subsequently, at 400 °C, the samples were heated in 10% H 2 (H 2 / N 2 =1:9, v / v) for 3 h, the heating rate was 5°C min -1 , to get ZrO 2 Loaded Ru particles;

[0041] (2) (Ru / ZrO 2 )@m-ZrO 2 Preparation: The molar composition of the liquid phase raw material is 1.0 CnTMAB: 15 HCl: 8.0 (BuO) 4 Zr: 680.0H 2 O. 3.74 g Ru / ZrO 2 Disperse in water to form...

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PUM

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Abstract

The invention discloses a preparation method of a bi-functional catalyst of a (Ru / MeOx)@MeOx core-shell structure. The method is characterized in that a center suitable for surface catalyzing is formed by core phase Ru / MeOx and shell phase m-MeOx. A ruthenium-based catalyst prepared by the method has high dispersing performance, so that benzene is dissociated and absorbed more easily at a lower temperature to improve the conversion rate of the benzene;the cyclohexene is allowed to be desorbed on a shell by a hydrophilic m-MeOx shell phase to prevent further hydrogenation and improve the selectivity of the cyclohexene, the loss of activated species can be reduced by the core-shell structure to allow the catalyst to be more stable, the mass transfer resistance can be reduced, the excellent composite performance can be applied to part of hydrogenation cyclohexene reaction of benzene, and extremely high selectivity and yield are obtained. The preparation method is simple, the conditions are mild, the repeating is easy, and the method is suitable for large-scale industrial production.

Description

technical field [0001] The present invention relates to the technical field of catalysts, specifically a kind of metal ruthenium as the core, and supports hydrophilic oxides (MeOx) on it to form dual active components, and then uses these hydrophilic oxides as Mesoporous nanoshell (m-MeOx), a preparation method of a catalyst forming a shell-core structure, is applied to the reaction of benzene partial hydrogenation to cyclohexene. Background technique [0002] Cyclohexene is a very important organic chemical raw material with active c=c double bonds, and can be widely used in polycycloolefin resins, rubber additives, high-octane gasoline stabilizers, nylon 6 and other fine chemical products production. Due to the wide range of uses of cyclohexene as a raw material, further development of more economical and green production routes of cyclohexene has been widely concerned. Benzene is cheap and abundant, and can be used to directly synthesize cyclohexene. The selective hydr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/46B01J23/62C07C5/11C07C13/20
Inventor 陈晓晖郑建伟黄清明胡晖
Owner FUZHOU UNIV
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