Ester hydrogenation catalyst and preparation method and application thereof

A catalyst, a technology for ester hydrogenation, applied in the preparation of carboxylate, chemical instruments and methods, preparation of hydroxyl compounds, etc., can solve the problems of insufficient sensitivity to nucleophilic attack, loss of carrier, slow process of gel formation, etc. The effect of high directional selectivity, improved activity and stability, and simple preparation process

Active Publication Date: 2017-10-31
PUJING CHEM IND SHA +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0002] In the ester hydrogenation series, the main research is to convert carboxylic acid esters into corresponding alcohols by catalytic hydrogenation, but because the carbonyl bond is not sensitive enough to nucleophilic attack, it is more difficult than the conversion of aldehydes and ketones into alcohols.
Traditional ester hydrogenation catalysts are mainly noble metals, such as ruthenium, rhodium, platinum, palladium, etc., which have high catalytic activity but relatively high cost of use. Non-noble metal catalysts mainly include copper, chromium, nickel, etc., but chromium will pollute the environment. Harmful to the human body, gradually eliminated
[0003] Catalysts for the hydrogenation of acetate to ethanol, in addition to Cu / Cr series catalysts, Cu / SiO 2 The series of catalysts are considered to be an ester hydrogenation catalyst with excellent reactivity, but the carrier SiO2 used in this series of catalysts 2 In the presence of alcohol, the performance is unstable, and it is very easy to undergo esterification reaction with alcohol to form silicate, thus, the carrier SiO 2 drain
CN102962071A discloses a catalyst for hydrogenation of acetate to ethanol and a preparation method thereof, which uses silicon oxide, aluminum oxide or SiO 2 -TiO 2 Composite oxide is used as a carrier, and the precursor solution of active elements is used to form a copper-containing gel, and then the gel is dried and roasted to obtain the final catalyst. Since the process of forming a gel from the catalyst precursor is slow, the catalyst preparation process is still relatively slow. slow
The currently used catalysts have the disadvantages of high catalytic hydrogenation reaction pressure and higher requirements for reaction equipment

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Weigh 5.7g of copper nitrate trihydrate and 0.30g of silver nitrate, add ethanol and water to make a solution, then add 7.31g of ammonia water, stir evenly, and prepare solution I for use. Mix 32g ethyl orthosilicate and 1.5g pseudo-boehmite evenly, and then add ethanol to form solution II. Slowly add solution I dropwise to solution II, stirring continuously while adding dropwise, and continue stirring for 2 h after the dropwise addition is completed. Then crystallize at 120°C for 24h, wash, dry, and finally calcinate at 450°C for 24h to obtain the target catalyst.

[0028] Press the target catalyst into tablets, crush and sieve, take 20-40 mesh catalyst and put 2g of the target catalyst into the catalyst bed, raise it from room temperature to 300°C under hydrogen atmosphere, keep it for 12h, then drop it to 240°C, and then pass through acetic acid Methyl ester undergoes ester hydrogenation reaction, and the space velocity of methyl acetate ester liquid is 1.0h -1 , t...

Embodiment 2

[0030] Weigh 9.45g of copper nitrate trihydrate and 0.542g of silver nitrate, add ethanol and water to make a solution, then add 11.52g of ammonia water, stir evenly, and prepare solution Ⅰ for use. Mix 32g ethyl orthosilicate and 3.0g pseudo-boehmite evenly, and then add ethanol to form solution II. Slowly add solution I dropwise to solution II, stirring continuously while adding dropwise, and continue stirring for 4 hours after the dropwise addition is completed. Then it was crystallized at 120°C for 24h, washed, dried, and finally calcined at 500°C for 24h to obtain the target catalyst.

[0031] The target catalyst was pressed, crushed, and sieved, and 2g of the target catalyst of 20-40 mesh was loaded into the catalyst bed. Under the conditions of 3.5MPa, liquid hourly space velocity 1.2h-1, and hydrogen-to-ester ratio of 150, dimethyl oxalate is used as raw material and methanol is used as solvent. The conversion rate of dimethyl oxalate is greater than 99.9%, and the s...

Embodiment 3

[0033]Weigh 1.89g of copper nitrate trihydrate and 1.16g of silver nitrate, add ethanol and water to make a solution, then add 1.65ml of hydrochloric acid with a concentration of 1mol / l and 3.47g of ammonia water, stir well, and prepare solution I for use. Mix 18g ethyl orthosilicate and 7.15g pseudo-boehmite evenly, then add ethanol to form solution II. Slowly add solution I dropwise to solution II, stirring continuously while adding dropwise, and continue stirring for 2 h after the dropwise addition is completed. Then it was crystallized at 120°C for 24h, washed, dried, and finally calcined at 500°C for 24h to obtain the target catalyst.

[0034] The target catalyst was pressed into tablets, crushed and sieved, and 2g of the 20-40 mesh catalyst was loaded into the catalyst bed, raised from room temperature to 260°C under a hydrogen atmosphere, kept at normal pressure for 10 hours, and then lowered to 200°C. Under the conditions of 2.5MPa, liquid hourly space velocity 1.0h-1...

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PUM

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Abstract

The invention relates to an ester hydrogenation catalyst and a preparation method and application thereof. The catalyst contains 5-30% (wt) of an active ingredient, 0.1-2.5% (wt) of an assistant and a carrier, wherein the active ingredient is a Cu-Ag alloy; the assistant includes one or more of B, C, N, F, Cl or Br; the carrier is a composite oxide of r-Al2O3 and SiO2, the mass ratio of Cu to Ag is (0.1-10):1 and the mass ratio of Al to Si in the carrier is (0.1-2):1. The catalyst is prepared by adopting a coprecipitation method, and is mainly applied to reaction of ester-hydrogenated alcohol. Compared with the prior art, the ester hydrogenation catalyst has the characteristics of high activity, high orientation selectivity and good stability, and is especially suitable for industrial application.

Description

technical field [0001] The invention relates to the technical field of catalyst synthesis, in particular to an ester hydrogenation catalyst and its preparation method and application. Background technique [0002] The main research in the ester hydrogenation series is the catalytic hydrogenation of carboxylic acid esters to the corresponding alcohols, but because the carbonyl bond is not sensitive enough to nucleophilic attack, it is more difficult than the conversion of aldehydes and ketones to alcohols. Traditional ester hydrogenation catalysts are mainly noble metals, such as ruthenium, rhodium, platinum, palladium, etc., which have high catalytic activity but relatively high cost of use. Non-noble metal catalysts mainly include copper, chromium, nickel, etc., but chromium will pollute the environment. Harmful to the human body and gradually eliminated. [0003] Catalysts for the hydrogenation of acetate to ethanol, in addition to Cu / Cr series catalysts, Cu / SiO 2 The se...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/89C07C29/149C07C31/08C07C31/20C07C67/31C07C69/675
CPCB01J23/8926C07C29/149C07C67/31C07C31/08C07C31/202C07C31/205C07C31/207C07C31/20C07C69/675
Inventor 骆念军贺俊
Owner PUJING CHEM IND SHA
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