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Ru-based catalyst for preparing cyclohexene through partial hydrogenation of benzene and modification method of Ru-based catalyst

A ruthenium-based catalyst and cyclohexene technology, which is applied in the fields of chemical engineering and chemical catalysts, can solve the problems of high-yield data that are difficult to obtain repeated verification

Active Publication Date: 2016-06-15
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, it has to be pointed out that most of the high-yield data are difficult to be repeatedly verified even in the laboratory.

Method used

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  • Ru-based catalyst for preparing cyclohexene through partial hydrogenation of benzene and modification method of Ru-based catalyst
  • Ru-based catalyst for preparing cyclohexene through partial hydrogenation of benzene and modification method of Ru-based catalyst
  • Ru-based catalyst for preparing cyclohexene through partial hydrogenation of benzene and modification method of Ru-based catalyst

Examples

Experimental program
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Effect test

Embodiment 1

[0036] RuSiO 2 Preparation of core-shell catalysts

[0037] A certain amount of RuCl 3 ·3H 2 O was dissolved in 60ml of distilled water, and 15% NaOH solution was added under vigorous stirring, and left to stand for suction filtration after fully reacting. The resulting black solid was washed 3 times with distilled water and 3 times with 5% NaOH solution, then dispersed in 5% NaOH solution and transferred to an autoclave. Ru particles were obtained by raising the temperature to 150° C. for 3 h under a hydrogen partial pressure of 5 MPa and a stirring rate of 800 rpm. In a 250ml eggplant-shaped bottle, add 40ml of absolute ethanol, 5ml of distilled water, a certain amount of tetraethyl orthosilicate and 200ul of ammonia water, mix well and then add Ru particles. Magnetically stirred for 2 h, then washed twice with ethanol to obtain RuSiO 2 catalyst. The thickness of the surface silicon layer was adjusted by changing the amount of tetraethyl orthosilicate.

[0038] RuSiO ...

Embodiment 2

[0045] RuZnSiO 2 Preparation of core-shell catalysts

[0046] Weigh 1.66g of RuCl 3 ·3H 2 O was added to 150ml distilled water to prepare a solution. Weigh 10.08g of KOH and dissolve it in 100ml of deionized water, transfer it into a three-neck flask placed in a constant temperature water bath, and start stirring. The temperature of the constant temperature water bath was raised to 80°C, and the prepared RuCl 3 The solution was added to a three-necked flask. After the addition, stir at a constant temperature of 80°C for 1 hour, then stop stirring, continue to maintain a constant temperature of 80°C for about 1 hour, and then cool naturally. Wash the sediment with distilled water until neutral, along with 50ml benzene, 100ml distilled water, and 20g of ZnSO 4 ·7H 2 O was added to the autoclave. Then the RuZn alloy particles were obtained by reduction at 180°C, hydrogen partial pressure 5.0MPa and stirring rate 1000rpm for 8h. In a 250ml eggplant-shaped bottle, add 40ml...

Embodiment 3

[0050] RuBSiO 2 Preparation of core-shell catalysts

[0051] 50mL0.05mol / L of RuCl 3 With 25mL0.5mol / L NaBH 4 Restore drop by drop. Continue stirring for 10 min after the reduction is completed. RuB particles were obtained after standing, filtering, and washing with distilled water until neutral. In a 250ml eggplant-shaped bottle, add 40ml of absolute ethanol, 5ml of distilled water, a certain amount of ethyl orthosilicate and 200ul of ammonia water, mix well and add RuB particles. Magnetically stirred for 2 h, then washed twice with ethanol to obtain RuSiO 2 catalyst. The thickness of the surface silicon layer was adjusted by changing the amount of tetraethyl orthosilicate. According to the TEM results, RuBSiO 2 SiO on the surface of core-shell catalysts 2 The thickness is 1.0 nm.

[0052] RuBSiO 2 Catalyst Hydrogenation Characterization

[0053] Take 1gRuBSiO 2 Or RuB catalyst with equivalent active component quality, 17.25gZnSO 4 ·7H 2 O and 100ml of water we...

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Abstract

The invention relates to a Ru-based catalyst for preparing cyclohexene through partial hydrogenation of benzene and a modification method of the Ru-based catalyst. The Ru-based catalyst comprises Ru-based particles and a SiO2 layer, wherein the Ru-based particles are coated with the SiO2 layer, a core-shell catalyst is formed, and the thickness of the SiO2 layer is 0.5-2 nm; the Ru-based particles are the Ru-based catalyst. With the adoption of the Ru-based catalyst for preparing cyclohexene through partial hydrogenation of benzene and the modification method of the Ru-based catalyst, the condition that cyclohexene generated in the partial hydrogenation process of benzene is adsorbed to the surface of the catalyst again and is subjected to deep hydrogenation to generate cyclohexane is prevented on the basis of the difference of dissolution and diffusion properties of benzene and cyclohexene in a retained water membrane, the activity of the Ru-based catalyst before coated with SiO2 and the activity of the Ru-based catalyst after coated with SiO2 under the same hydrogenation condition are not remarkably influenced, the yield of a target product cyclohexene can be increased by 15%-20% or higher, and the Ru-based catalyst has a wider application range.

Description

technical field [0001] The invention relates to the field of chemistry and chemical engineering, in particular to the field of chemical catalysts, in particular to a ruthenium-based catalyst for partially hydrogenating benzene to cyclohexene and a modification method thereof. Background technique [0002] Cyclohexene is an important chemical raw material and intermediate, which can be used to synthesize important organic products such as lysine, cyclohexanol, and cyclohexanone. The main way to obtain cyclohexene is chemical synthesis. The partial hydrogenation of benzene uses benzene, which is easily obtained in industry, as the raw material, and obtains cyclohexene through partial hydrogenation, which has the advantages of less equipment investment, safety and stability, high carbon yield, environmental protection and energy saving. The hydrogenation of benzene to cyclohexene mainly includes complex catalysis, gas-phase catalysis and liquid-phase catalysis. Among them, th...

Claims

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Application Information

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IPC IPC(8): B01J23/46B01J23/60B01J35/00C07C5/11C07C13/20
CPCC07C5/11B01J23/462B01J23/60C07C2523/46C07C2523/60B01J35/398B01J35/393C07C13/20Y02P20/52
Inventor 袁佩青李艳辛双梅
Owner EAST CHINA UNIV OF SCI & TECH
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