Hydrogenation catalyst and preparation method and application thereof

A technology of hydrogenation catalysts and additives, applied in chemical instruments and methods, preparation of organic compounds, metal/metal oxide/metal hydroxide catalysts, etc., can solve the problems of not reaching the industrialization level and high price, and achieve Increased unit activity, high selectivity, and high catalytic activity

Inactive Publication Date: 2020-08-25
XIAMEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to the high price of silver-based catalysts, people turn to the research of copper-based catalysts, but copper-based catalysts have strong hydrogenation activity, and loading them on common silica, molecular sieves and other carriers will cause excessive hydrogenation of dimethyl oxalate to ethyl alcohol. diol
[0006] Although it has been reported in the literature that copper-based catalysts can better control the hydrogenation of dimethyl oxalate to methyl glycolate when a modified composite oxide containing silica is used as a carrier, the conversion rate of dimethyl oxalate is between About 85%, the selectivity of methyl glycolate is about 83%, still at a low level, far from reaching the industrial level

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  • Hydrogenation catalyst and preparation method and application thereof
  • Hydrogenation catalyst and preparation method and application thereof

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preparation example Construction

[0041] When the preparation method is a chemical precipitation method, the preparation method of the metal oxide carrier preferably includes the following steps:

[0042] Perform primary mixing of soluble subgroup metal salts and polar solvents to obtain a mixed solution;

[0043] After the mixed solution and the precipitating agent are mixed in two stages, the metal oxide carrier is obtained by standing for aging and calcining in sequence.

[0044] In the present invention, the soluble subgroup metal salt and the polar solvent are mixed in one stage to obtain a mixed solution;

[0045] In the present invention, the soluble subgroup metal salt preferably includes a soluble subgroup inorganic metal salt and / or a soluble subgroup alkoxy metal salt; in the present invention, the soluble subgroup inorganic metal salt preferably includes Ce, Ti, Soluble inorganic metal salts of Zr and Zn, more preferably one or more of soluble nitrates, chlorides, sulfates and carbonates of Ce, Ti...

Embodiment 1

[0145] Mix 9.75g cerium nitrate and 50mL deionized water ultrasonically for 15min, the ultrasonic power is 40W, to obtain a mixed solution; add 4mol / L sodium hydroxide solution dropwise to the mixed solution, the dropping rate is 5 drops per second, in which hydrogen The molar ratio of sodium oxide and cerium nitrate is 3.0:1, stir evenly, transfer to a stainless steel hydrothermal kettle, heat at 150°C for 12h, leave it to age at room temperature for 2h, centrifuge the reacted mixed solution, and centrifuge the obtained product Washing was carried out sequentially, first washing twice with deionized water, then washing once with absolute ethanol, after washing until neutral, drying at 100°C for 12h, and then calcining at 500°C for 4h to obtain a cerium oxide carrier.

[0146] Mix 3.78g of copper nitrate trihydrate with 5mL of water to obtain an impregnating solution, immerse 4g of cerium oxide carrier in the impregnating solution for 12h, dry at 100°C for 12h, and then calcina...

Embodiment 2

[0149] 4.88g of cerium nitrate, 4.34g of zirconium oxychloride and 50mL of deionized water were ultrasonically mixed for 15min, and the ultrasonic power was 40W to obtain a mixed solution; the mixed solution was mixed with urea, wherein the moles of urea, cerium nitrate and zirconium oxychloride The ratio is 8:1:1; at 60°C, stir for 10 hours at a stirring speed of 500r / min, let it stand for aging at room temperature for 2 hours, then filter the mixed solution after the reaction, and wash the filtered product in turn until neutral. Drying at 100° C. for 12 hours, and then calcining at 500° C. for 4 hours to obtain a ceria-zirconia composite carrier.

[0150] Mix 3.78g of copper nitrate trihydrate with 5mL of water to obtain an impregnating solution, immerse 4g of cerium oxide-zirconia composite carrier in the impregnating solution for 12h, dry at 100°C for 12h, and then roast at 400°C for 4h; Hydrogenation catalyst precursor.

[0151] The hydrogenation catalyst precursor is p...

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Abstract

The invention relates to the technical field of catalysts, in particular to a hydrogenation catalyst and a preparation method and application thereof. The hydrogenation catalyst comprises a metal oxide carrier and an active component loaded on the metal oxide carrier, wherein the active component comprises a Cu elementary substance and/or an oxide of copper; the metal oxide carrier comprises a subgroup metal oxide or a subgroup composite metal oxide; the subgroup metal oxide comprises cerium oxide, titanium oxide, zirconium oxide or zinc oxide; the subgroup composite metal oxide comprises a composite oxide of two or more of cerium oxide, titanium oxide, zirconium oxide and zinc oxide. When the hydrogenation catalyst is used for catalyzing dimethyl oxalate hydrogenation to directly preparemethyl glycolate, the catalytic activity is high, the selectivity to methyl glycolate is high, and the stability of the structure and the performance of the hydrogenation catalyst in the long-term useprocess is high.

Description

technical field [0001] The invention relates to the technical field of catalysts, in particular to a hydrogenation catalyst and its preparation method and application. Background technique [0002] The oxalate ester method is the main method for indirect production of ethylene glycol from coal in my country. The main process is to first purify and separate the coal-to-synthesis gas. Esters are hydrogenated to yield products such as methyl glycolate and ethylene glycol. The whole reaction process has high atomic economy and is green and clean. Coal-to-methyl glycolate as an intermediate process of this route has also attracted more and more attention. The reason is that: on the one hand, it can solve the problem of overcapacity of coal-to-ethylene glycol; on the other hand, methyl glycolate is an important and expensive Chemical intermediates also urgently need to develop and supplement new routes. [0003] Methyl glycolate has become an important chemical raw material beca...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/72B01J23/78B01J23/80B01J23/83B01J35/10C07C67/31C07C69/675
CPCB01J23/002B01J23/72B01J23/78B01J23/80B01J23/83B01J35/1004C07C67/31C07C69/675
Inventor 段新平黄乐乐赵威袁友珠谢素原林海强
Owner XIAMEN UNIV
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