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A kind of preparation method that is used for phenol hydrogenation to prepare cyclohexanone catalyst

A cyclohexanone and catalyst technology, applied in the field of catalyst preparation, can solve the problems of affecting catalyst activity, surface palladium falling off, surface palladium content reduction, etc., and achieve the effect of improving catalytic hydrogenation activity, small ash content, and preventing direct reduction

Active Publication Date: 2020-12-22
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The traditional preparation method of palladium-carbon catalyst is impregnation adsorption method (US4394299). In the process of preparing palladium-carbon catalyst, it needs to be combined with stirring paddle for large-scale stirring to make the palladium solution evenly adsorbed on the activated carbon. However, for phenol Cyclohexanone palladium-carbon catalyst for hydrogen production, metal palladium is distributed in eggshell on the surface of the carrier, and the large-scale stirring process will easily cause the surface palladium to fall off, resulting in a decrease in the surface palladium content and affecting the activity of the catalyst

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Activated carbon pretreatment:

[0029] Weigh 100g of 4-8 mesh activated carbon, add 500mL of hydrochloric acid solution with a concentration of 0.1N, wash at 100°C for 4h, filter, and wash with water until neutral; add 200mL of triphenylphosphine solution with a concentration of 0.01N, mix well, and let stand at room temperature for 6h. Filter, wash and dry for later use.

[0030] Preparation of Palladium Carbon Catalyst:

[0031] Weigh 10g of pretreated activated carbon, ultrasonically spray and absorb a mixed solution containing 3mL of 20g / L palladium chloride and 2mL of hydrogen peroxide, add 20mL of water after standing for 1h, adjust pH=8 with sodium carbonate, add 10mL of NaHCO 3 , precipitated at 30°C for 24h, added 3mL of formaldehyde, reduced at 30°C for 8h, filtered, washed, and dried to obtain the palladium-carbon catalyst of this example.

[0032] The palladium-carbon catalyst obtained in this example has the following properties: the content of metal pal...

Embodiment 2

[0034] Weigh 100g of 4-8 mesh activated carbon, add 500mL of 0.5N hydrochloric acid solution, wash at 100°C for 4h, filter, and wash with water until neutral; add 200mL of 0.02N triphenylphosphorus solution, mix well, and let stand at room temperature for 5h. Filter, wash and dry for later use.

[0035] Preparation of Palladium Carbon Catalyst:

[0036] Weigh 10g of pretreated activated carbon, ultrasonically spray and absorb a mixed solution containing 2mL30g / L palladium chloride, 1.5mL hydrogen peroxide and 0.3mL sodium hypochlorite, add 20mL water after standing for 4 hours, adjust the pH=9 with sodium carbonate, add 10mLNaHCO 3 , Precipitate at 50°C for 24h, raise the temperature to 60°C, add 8mL formaldehyde for reduction for 6h, filter, wash, and dry to obtain the palladium-carbon catalyst of this example.

[0037] The palladium-carbon catalyst obtained in this example has the following properties: the content of metal palladium in the catalyst is 0.49%, and the cataly...

Embodiment 3

[0039] Activated carbon pretreatment:

[0040] Weigh 100g of 4-8 mesh activated carbon, add 500mL of 1N hydrochloric acid solution, wash at 80°C for 3h, filter, and wash with water until neutral; add 200mL of 0.1N tricyclohexylphosphine solution, mix well, let stand at room temperature for 5h, filter , washed and dried for later use.

[0041] Preparation of Palladium Carbon Catalyst:

[0042] Weigh 10g of pretreated activated carbon, ultrasonically spray and absorb a mixed solution containing 1.5mL 40g / L palladium chloride, 1.5mL hydrogen peroxide and 0.2mL sodium hypochlorite, add 20mL water after standing for 4 hours, adjust pH=9 with sodium carbonate, add 10mLNaHCO 3 , Precipitate at 50°C for 24h, raise the temperature to 60°C, add 8mlL formaldehyde for reduction for 6h, filter, wash, and dry to obtain the palladium-carbon catalyst of this example.

[0043] The palladium-carbon catalyst obtained in this example has the following properties: the content of metal palladium...

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PUM

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Abstract

A method for preparing a catalyst for hydrogenating phenol to produce cyclohexanone. After the activated carbon is treated with acid and chelating ligand, steps such as palladium adsorption, alkali precipitation, and reduction are performed to finally obtain the catalyst product. Its characteristic is that by pretreating activated carbon with chelating ligands, the electron-donating properties of the chelating ligands can be used to increase the electron density of Pd metal and improve its catalytic hydrogenation activity; by adding oxidants to the adsorption liquid, it can The metal palladium is evenly distributed on the outer surface of the activated carbon carrier to prevent the reducing groups on the surface of the activated carbon from directly reducing the palladium ions in the impregnation solution; through ultrasonic spray adsorption technology to load active components, the metal palladium can penetrate deep into the surface pores of the activated carbon, further The dispersion of Pd is improved, which is beneficial to the hydrogenation of phenol to cyclohexanone reaction.

Description

technical field [0001] The invention relates to a preparation method of a catalyst used in the hydrogenation process of various organic compounds, in particular to a preparation method of a catalyst capable of converting phenol into cyclohexanone. Background technique [0002] The activity, selectivity and stability of the catalyst for the hydrogenation of phenol to cyclohexanone have a great influence on its production cost, and the nature, structure and quantity of metal atoms on the catalyst surface are the key to determine the reaction activity and selectivity. In general, the hydrogenation activity of metal catalysts is related to the size of the metal area, and the size of the metal area is related to the grain size of the metal or the dispersion of the metal. It is reported that the supported Pd catalyst shows good activity and selectivity in the hydrogenation of phenol to cyclohexanone (GB1063357A). Since Pd is a noble metal, the dosage is generally small, so we use ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/24C07C45/00C07C49/403
CPCC07C45/006B01J31/2409B01J31/2414B01J37/16B01J37/343B01J2231/646B01J2531/824B01J35/397C07C49/403
Inventor 陈琛金汉强赵思远季峰崎孙盛凯杨忠林
Owner CHINA PETROLEUM & CHEM CORP