Metal catalyst and its preparation method and its application in the selective hydrogenation of benzene to cyclohexene

A metal catalyst and catalyst technology, applied in the direction of hydrogenation to hydrocarbons, etc., can solve the problems of difficult separation of catalyst and product, expensive ruthenium catalyst, and reduced cyclohexene selectivity, etc., to achieve inhibition of coalescence, simple preparation process, and improved selectivity. sexual effect

Active Publication Date: 2018-06-22
SHANGHAI JIAO TONG UNIV
View PDF2 Cites 6 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the ruthenium catalyst produced by Asahi Kasei is expensive, and it is difficult to separate the nanoscale catalyst from the product
For this reason, domestic and international patent overwhelming majority all adopts Al O , SiO , ZrO , MCM-41, SBA-15 etc. various carriers to carry catalyst to reduce the cost of catalyst (CN 100496728 C, CN 1978053 B, CN103785477 A, CN 103721709 A, CN101219391 A, CN101549292 B, CN 102600888A), however, because the catalyst is loaded and exists in the nano-scale pores of the carrier, the reactant needs to diffuse into the carrier to react, and the resulting mass transfer problem is seriously reduced. The selectivity of cyclohexene limits the industrial application of supported catalysts
However, for unsupported catalysts, such as Asahi Kasei CN 1159269C, the precipitation method is used to prepare Ru-Zn alloys. The method has many steps, long cycle, low utilization rate of Zn salt, Zn raw material exceeds Ru, but Zn / Ru ratio in the catalyst is lower than 0.1

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Metal catalyst and its preparation method and its application in the selective hydrogenation of benzene to cyclohexene
  • Metal catalyst and its preparation method and its application in the selective hydrogenation of benzene to cyclohexene
  • Metal catalyst and its preparation method and its application in the selective hydrogenation of benzene to cyclohexene

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Weigh 0.5430g and 0.0395g of ruthenium acetylacetonate and zinc acetylacetonate respectively, add them into 80ml of diphenyl ether containing 40ml of oleamide, stir and dissolve, heat to 100°C, keep the temperature for 20min, and quickly inject 5.4mL of triethyl ether into the solution A THF solution of lithium borohydride (the concentration of lithium triethylborohydride is 1mol / L), the temperature was raised to 160°C under rapid stirring, and then slowly raised to 180°C, and after reflux for 30min, the reaction flask was removed from the heater. stop responding. After adding an appropriate amount of ethanol and centrifuging, the alloy catalyst with Ru-Zn was obtained, and the obtained catalyst was dispersed in hexane (all experiments were carried out under argon atmosphere).

[0030] figure 1 For the XRD picture of the sample prepared for this implementation, the diffraction peaks at the positions of about 38°, 44°, 58°, 69°, and 78° can be determined to be the 100, ...

Embodiment 2

[0032] Weigh 0.607g of ruthenium acetylacetonate and 0.0132g of zinc acetylacetonate respectively, add them into 100ml of diphenyl ether containing 50ml of oleamide, stir and dissolve, heat to 120°C, keep the temperature for 20min, and quickly inject triethyl hydroboration into the solution For lithium, the temperature was raised to 160°C under rapid stirring, and then slowly raised to 180°C. After reflux for 30 minutes, the reaction flask was removed from the heater to stop the reaction. After adding an appropriate amount of ethanol and centrifuging, the alloy catalyst with Ru-Zn was obtained, and the obtained catalyst was dispersed in hexane (all experiments were carried out under argon atmosphere).

[0033] The catalytic performance of the catalyst to catalyze the hydrogenation of benzene to cyclohexene at a reaction temperature of 140°C is shown in image 3 with Figure 4 ; Catalyst catalytic hydrogenation of benzene to cyclohexene life test when the reaction temperature ...

Embodiment 3

[0035] Weigh 0.575g of ruthenium acetylacetonate and 0.0265g of zinc acetylacetonate respectively, add them into 90ml of diphenyl ether containing 35ml of oleamide, stir and dissolve, heat to 140°C, keep the temperature for 20min, and quickly inject triethyl borohydrogenate into the solution For lithium, the temperature was raised to 180°C under rapid stirring, and then slowly raised to 220°C. After reflux for 30 minutes, the reaction flask was removed from the heater to stop the reaction. After adding an appropriate amount of ethanol and centrifuging, the alloy catalyst with Ru-Zn was obtained, and the obtained catalyst was dispersed in hexane (all experiments were carried out under argon atmosphere).

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

PropertyMeasurementUnit
particle diameteraaaaaaaaaa
Login to view more

Abstract

The invention relates to a metal catalyst and a preparation method as well as application on cyclohexane preparation by selective hydrogenation of benzene, wherein the Ru content is 85%-95% and the M content is 5%-15%. The preparation method comprises the following steps: (1) adding precursors including a ruthenium compound and a compound of a transition element M into diphenyl ether containing oleamide, stirring so as to obtain a solution A, and heating to 100-140 DEG C, keeping the temperature constant for 10-30 minutes; (2) injecting a strong reducing agent rapidly into the solution A, rising the temperature to 160-200 DEG C under rapid stirring, then rising to 180-220 DEG C slowly, backflowing for 30 minutes, and stopping heating and reaction; and (3) adding a dispersing agent, and carrying out centrifugal separation so as to obtain the alloy catalyst containing Ru-M. Compared with the prior art, the catalyst used in preparation of cyclohexane by selective hydrogenation of benzene is controllable in catalytic performance, and has high activity and high selectivity to cyclohexane.

Description

technical field [0001] The invention relates to a catalyst, in particular to a metal catalyst, a preparation method and an application in selective hydrogenation of benzene to prepare cyclohexene. Background technique [0002] Cyclohexene has active double bonds and is an important intermediate in organic synthesis. It is widely used in the production of fine chemicals such as adipic acid, nylon-6, and nylon-66. Cyclohexene and its downstream products have important industrial uses and broad market prospects. [0003] At present, nylon-6 and nylon-66 mainly use the route of complete hydrogenation of benzene, that is, the route of complete hydrogenation of benzene to produce cyclohexane, and oxidation of cyclohexane to produce cyclohexanol and cyclohexanone. Cyclohexane oxidation is a free radical reaction, prone to explosion, long process flow, low yield, high energy consumption and easy to cause environmental pollution. In contrast, the partial hydrogenation of benzene is...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/60B01J23/89C07C13/20C07C5/11
Inventor 刘河洲杜起段华南郭益平康红梅李华
Owner SHANGHAI JIAO TONG UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap