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Catalyst for hydrogenation of acetaldehyde, preparation method and application thereof

A technology for catalysts and acetaldehyde, applied in hydrogenolysis preparation, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc., can solve the problems of low catalyst acetaldehyde selectivity, high catalyst cost, and high cost , to achieve reliable repeatability, good thermal stability, and increase the effect of contact surface

Active Publication Date: 2019-10-18
PUJING CHEM IND SHA +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

CN104162446A discloses to have prepared Pt-Fe catalyst with equal volume impregnation method, and its mass content is respectively 2% and 15% of catalyst weight, and carrier is selected from silicon dioxide, MCM-41 molecular sieve or SBA-15 molecular sieve, when carrier is MCM At -41, under the conditions of 300°C, 0.1MPa, and a hydrogen-acid ratio of 10, the conversion rate of acetic acid is the highest 73.06%, and the acetaldehyde selectivity is 34.39%. The acetaldehyde selectivity of the catalyst is low, and the Pt is a noble metal, and the cost of the catalyst is high
[0005] In summary, the results of the existing literature show that the catalysts for the hydrogenation of acetic acid to acetaldehyde are mainly noble metal catalysts, which have high costs and low yields, and are not suitable for industrial production of acetaldehyde. Non-precious metal catalysts are beneficial to the industrial application of acetic acid hydrogenation to acetaldehyde technology

Method used

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  • Catalyst for hydrogenation of acetaldehyde, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] 25%Cu-5%Ni-5%P / SiO2 catalyst:

[0032] Dry the silica carrier at 110°C for 10 h, then weigh 20 g of the dried silica carrier, add it to 100 g of ethylene glycol monomethyl ether (EM), stir ultrasonically for 0.5 h, and then add 10 g of Hexamethyldisilazane (HMDS), the mixture was refluxed under nitrogen for 10h, then the mixture was washed with ethylene glycol monomethyl ether, and dried at 110°C for 24h to obtain a modified silica carrier . Dissolve 9.50g of copper nitrate in 20ml of deionized water, add 10g of modified silica carrier, stir ultrasonically for 2h, then stir and evaporate to dryness at 90°C, and then dry at 70°C for 8h, and the obtained solid is in Roast at 300°C for 6h to obtain solid A; prepare 0.1g / mL phosphoric acid aqueous solution, take 15.8mL, add solid A quickly, stir ultrasonically for 2h, then stir and evaporate to dryness at 80°C, and then dry at 100°C 6h, the obtained solid was roasted at 400°C for 5h to obtain solid B; 2.48g of nickel nitr...

Embodiment 2

[0043] 20%Fe-15%Zn-8%Al2O3 / TiO2 catalyst:

[0044] Titanium dioxide was dried at 80° C. for 24 h, then 15 g of dried titanium dioxide was weighed, added to 300 g of ethylene glycol monomethyl ether (EM), ultrasonically stirred for 1 h, and then 3 g of hexamethyldisilazane ( HMDS), the mixture was refluxed under argon for 4 h, then the mixture was washed with ethylene glycol monomethyl ether, and dried at 120° C. for 10 h to obtain modified titanium dioxide. Dissolve 14.43g of ferric nitrate in 30ml of deionized water, add 10g of modified titanium dioxide, stir ultrasonically for 0.5h, stir and evaporate to dryness at 70°C, and then dry at 50°C for 12h. Roast at ℃ for 8h to obtain solid A; prepare 0.2g / mL aluminum nitrate aqueous solution, take 16.7mL, add solid A quickly, stir ultrasonically for 1h, then stir and evaporate to dryness at 90℃, and then dry at 110℃ 4h, the obtained solid was roasted at 400°C for 6h to obtain solid B; 6.83g of zinc nitrate was dissolved in 20ml o...

Embodiment 3

[0049] 10%Mo-6%Co-3%B / SiO2 catalyst:

[0050] Dry the silica carrier at 100°C for 20 h, then weigh 15 g of the dried silica, add it to 100 g of ethylene glycol monomethyl ether (EM), stir ultrasonically for 1 h, and then add 6 g of hexamethyldisilazol Azane (HMDS), the mixture was refluxed under nitrogen for 4 h, then the mixture was washed with ethylene glycol monomethyl ether, and dried at 100° C. for 30 h to obtain a modified silica carrier. Dissolve 1.84g of ammonium molybdate in 15ml of deionized water, add 10g of modified silica, stir ultrasonically for 2 hours, evaporate to dryness with stirring at 80°C, then dry at 110°C for 4 hours, and dry the obtained solid at 450°C Roast at low temperature for 2 hours to obtain solid A; prepare 0.1g / mL boric acid aqueous solution, take 17.2mL, add solid A quickly, after ultrasonic stirring for 1 hour, stir and evaporate to dryness at 70°C, and then dry at 100°C for 6 hours, the obtained The solid was roasted at 350°C for 6 hours t...

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PUM

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Abstract

The invention relates to a catalyst for preparation of acetaldehyde through hydrogenation, and a preparation method and application thereof. The catalyst comprises an active metal, an auxiliary active component, a protective agent and a carrier in a mass ratio of (2-30): (1-20): (0.1-10): 100. Compared with the prior art, the catalyst provided by the invention is a non-noble metal catalyst which is good in activity and heat stability, low in cost, easy to reproduce and convenient for scale-up production and has been applied in the industry.

Description

technical field [0001] The invention relates to a hydrogenation catalyst, especially a catalyst for acid or ester hydrogenation to produce acetaldehyde and a preparation method thereof. Background technique [0002] Acetaldehyde is an important organic intermediate, which is mainly used in the fields of leather, medicine, papermaking and pesticides. Acetaldehyde is used in the manufacture of many products, including glyoxal, crotonaldehyde, chloral, pentaerythritol, vinyl acetate, and pyridines. The synthesis methods of acetaldehyde mainly include ethylene direct oxidation method (Wacker method), ethanol oxidation method, acetylene hydration method, ethanol dehydrogenation method and acetic acid hydrogenation method. The industry mainly adopts Wacker method and ethanol oxidation method to produce acetaldehyde, and the Wacker method is the most production route. However, the raw material of the Wacker method is ethylene, which belongs to the petroleum route. However, my cou...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J27/185B01J23/80B01J23/882B01J23/14B01J23/888B01J23/83B01J27/187B01J23/889B01J23/883C07C45/41C07C47/06
Inventor 闫理宾张博陈长军计扬鲁文质
Owner PUJING CHEM IND SHA
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