Supported copper-based catalyst preparation method and applications of supported copper-based catalyst in synthesis of ethylene glycol

A copper-based catalyst, supported technology, applied in the preparation of hydroxyl compounds, molecular sieve catalysts, chemical instruments and methods, etc., can solve the problems of high heat and power consumption, increased by-products, increased production costs, etc., to improve the activity of the reaction center , prolong catalyst life, improve synergistic effect

Active Publication Date: 2020-01-17
CHINA CATALYST HLDG CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, too high hydrogen-ester ratio also requires high performance of the circulating compressor, which will greatly increase the production cost
Patents CN101138730A and CN102463122A also disclose a Cu-Ag / SiO2 catalyst for oxalate hydrogenation, which are prepared by impregnation method and sol-gel method respectively. The preparation process of this type of catalyst is relatively complicated and the repeatability is not good , large metal grains and poor dispersion, it is difficult to achieve the desired effect in actual production
[0004] The reaction temperature and pressure of the above-mentioned catalysts are high, and the selectivity of ethylene glycol is low, which leads to high heat and power consumption and increased by-products. In addition, the copper-based catalysts are prone to grain agglomeration and deactivation, which makes the life of the catalyst difficult to meet the requirements of industrialization.

Method used

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  • Supported copper-based catalyst preparation method and applications of supported copper-based catalyst in synthesis of ethylene glycol
  • Supported copper-based catalyst preparation method and applications of supported copper-based catalyst in synthesis of ethylene glycol
  • Supported copper-based catalyst preparation method and applications of supported copper-based catalyst in synthesis of ethylene glycol

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] A preparation method of supported copper-based catalyst:

[0029] 1) Mix 20.0g of silicon mesoporous molecular sieve SBA-15 with 181.56ml of methanesulfonic acid (CH 3 SO 3 H) The solution was fully stirred and mixed at 60° C. for 2 hours, and then the solid was recovered by suction filtration, washed with deionized water to be close to neutral, and vacuum-dried at 80° C. for 12 hours to obtain a surface-modified silicon mesoporous molecular sieve sample.

[0030] 2) Add the surface-modified silicon mesoporous molecular sieve obtained in 1) and 413.34g of γ-methacryloxypropyltrimethoxysilane to 2375.78g of ethanol / water mixed solvent (80% ethanol content) at 60°C React for 6h, and filter the solid sample obtained after the reaction is completed;

[0031] 3) Mix the solid sample in 2) with 0.05954g of ammonium persulfate and 179.90g of acrylic acid in 326.15g of ethanol for graft copolymerization for 4 hours. After the reaction, the product is recovered by filtration, ...

Embodiment 2

[0034] A preparation method of supported copper-based catalyst:

[0035] 1) Mix 20.0g of silicon mesoporous molecular sieve MCM-41 and 443.82ml of β-naphthalenesulfonic acid (C10H8O3S) solution with a concentration of 0.90mol / L at 55°C for 4 hours, then recover the solid by suction filtration, and use deionized water Washing was close to neutrality, and vacuum drying was performed at 80°C for 16 hours to obtain a surface-modified silicon mesoporous molecular sieve sample.

[0036] 2) Add the surface-modified silicon mesoporous molecular sieve obtained in 1) and 394.73g of vinyltrimethoxysilane into 1289.64g of ethanol / water mixed solvent (71% ethanol content) to react at 60°C for 6h, and filter after the reaction is completed The solid sample obtained;

[0037] 3) Mix the solid sample in 2) with 0.4774g of potassium persulfate and 733.60g of methacrylic acid in 2522.93g of ethanol for graft copolymerization for 6 hours. After the reaction, the product is recovered by filtrati...

Embodiment 3

[0040] A preparation method of supported copper-based catalyst:

[0041] 1) Mix 20.0g of silicon mesoporous molecular sieve MSU-1 and 457.69ml of benzenesulfonic acid (C6H6O3S) solution with a concentration of 0.8mol / L at 60°C for 2 hours, then recover the solid by suction filtration, wash with deionized water close to Neutral, vacuum-dried at 80°C for 12 hours to obtain a surface-modified silicon mesoporous molecular sieve sample.

[0042] 2) Add the surface-modified silicon mesoporous molecular sieve obtained in 1) and 870.06g of methacryloxypropyltriethoxysilane to 1878.54g of ethanol / water mixed solvent (67% ethanol content) at 60°C React for 6h, and filter the solid sample obtained after the reaction is completed;

[0043] 3) Mix the solid sample in 2) with 0.1286g of azobisisobutyronitrile and 399.47g of phenylacrylic acid in 978.77g of ethanol for a graft copolymerization reaction for 4 hours. After the reaction, the product is recovered by filtration and fully washed ...

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Abstract

The invention discloses a supported copper-based catalyst preparation method and applications of the supported copper-based catalyst in synthesis of ethylene glycol. The method comprises: taking a silicon mesoporous molecular sieve, carrying out a reaction with sulfonic acid, carrying out a hydroxyl condensation reaction with a silane coupling agent, carrying out a graft copolymerization reactionon the obtained modified silicon mesoporous molecular sieve, an initiator and an acrylic acid compound, adding the obtained solid sample into an ethanol/aqueous solution mixed solvent of a soluble copper salt, carrying out a heating reflux reaction, filtering the obtained product, repeatedly washing with deionized water, drying, and roasting to obtain the modified silicon mesoporous molecular sieve supported copper-based catalyst. According to the invention, with the preparation method, the dispersity of the copper species in the final catalyst can be regulated, and the synergistic effect of monovalent copper and zero-valent copper can be improved, so that the high-dispersion supported nanometer copper catalyst is obtained; with the application of the catalyst in a reaction for synthesizing ethylene glycol through hydrogenating dimethyl oxalate, the conversion rate of dimethyl oxalate is more than 99.4%, and the selectivity of ethylene glycol is more than 96%; and the preparation process of the catalyst is simple, the cost is low, and the industrial application is easily achieved.

Description

technical field [0001] The invention relates to a method for preparing a supported copper-based catalyst and its application in synthesizing ethylene glycol, belonging to the technical field of catalytic chemical industry. Background technique [0002] The hydrogenation reaction of dimethyl oxalate (DMO) is the most critical step in the process of CO coupling synthesis of ethylene glycol. At the same time, in addition to the production of ethylene glycol, the hydrogenation reaction of dimethyl oxalate can also be used to produce methyl glycolate (MG) and ethanol, which are important components of the coal chemical industry chain. Since the 1970s, UCC Corporation of the United States and Ube Industries of Japan established the gas-phase catalytic synthesis of oxalate esters from synthesis gas at atmospheric pressure, and the research on the use of Cu-based catalysts for the gas-phase hydrogenation of oxalate esters to prepare ethylene glycol has also followed. developed. UC...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/03C07C29/149C07C31/20
CPCB01J29/0333C07C29/149B01J2229/186C07C31/202Y02P20/52
Inventor 王志光李进王贤彬王炳春
Owner CHINA CATALYST HLDG CO LTD
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