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CN-121990887-A - Preparation method of ketol compound

CN121990887ACN 121990887 ACN121990887 ACN 121990887ACN-121990887-A

Abstract

The invention provides a method for preparing ketol compounds. The method comprises the step of carrying out dehydrogenation reaction on the diol compound shown in the formula 1 in the presence of a catalyst to generate the ketol compound shown in the formula 2, wherein the catalyst comprises a first active component, and the first active component comprises Cu and Ru. The method has the advantages of simple process, high product selectivity, high purity and simple post-treatment.

Inventors

  • WANG NING
  • WANG DEJU
  • REN JIE
  • QI SHENGDONG
  • WANG JIE

Assignees

  • 中石化（上海）石油化工研究院有限公司
  • 中国石油化工股份有限公司

Dates

Publication Date
20260508
Application Date
20241108

Claims (10)

  1. 1. A process for producing a ketol compound, which comprises subjecting a glycol compound represented by formula 1 to a dehydrogenation reaction in the presence of a catalyst to produce a ketol compound represented by formula 2; wherein the catalyst comprises a first active component comprising Cu and Ru; In the formulas 1 and 2, R 1 is selected from C1-C10 alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C3-C20 heteroaryl or a combination thereof, and R 2 is selected from hydrogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C3-C20 heteroaryl or a combination thereof.
  2. 2. The method according to claim 1, wherein in the first active component, the mass of Cu is 0.1% -99.9%, preferably 75% -99%, more preferably 90% -99% of the total mass of Cu and Ru; Optionally, the catalyst further comprises a second active component comprising one or more of Cr, fe, ni, zn, al, mo, ce, ag; Preferably, the mass ratio of the first active component to the second active component is (0.1-40): 0-30, more preferably (10-40): 0.1-30.
  3. 3. The method according to claim 1 or 2, wherein the catalyst further comprises a carrier supporting the active component; preferably, the carrier comprises one or more of alumina, silica, zirconia, molecular sieves, activated carbon; preferably, the loading amount of the first active component is 0.1wt% to 40wt%, more preferably 10wt% to 40wt%, and even more preferably 20wt% to 40wt%; Preferably, the loading of Cu in the catalyst is 10-30 wt%, more preferably 15-30 wt%; preferably, in the catalyst, the Ru loading amount is 0.1-5 wt%, more preferably 0.5-3 wt%; Preferably, the loading amount of the second active component is 0-30wt%.
  4. 4. The method of any of claims 1-3, wherein in formulas 1 and 2, R 1 is selected from the group consisting of C1-C6 alkyl, C3-C6 cycloalkyl, C6-C10 aryl, C3-C10 heteroaryl, or a combination thereof, R 2 is selected from the group consisting of hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C6-C10 aryl, C3-C10 heteroaryl, or a combination thereof; Preferably, R 1 is selected from C1-C6 alkyl, more preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl or hexyl, still more preferably methyl; Preferably, R 2 is selected from hydrogen or C1-C6 alkyl, more preferably hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl or hexyl, still more preferably hydrogen.
  5. 5. The method according to any one of claims 1 to 4, wherein the diol compound represented by formula 1 comprises 1, 2-propanediol, and the ketol compound represented by formula 2 comprises α -hydroxyacetone.
  6. 6. The method according to any one of claims 1 to 5, wherein the dehydrogenation reaction is carried out at a temperature of 200 ℃ to 350 ℃, preferably 260 ℃ to 300 ℃, and/or the dehydrogenation reaction is carried out at a pressure of 0.95atm to 1.05atm.
  7. 7. The method according to any one of claims 1 to 6, wherein the catalyst is subjected to reduction activation in a hydrogen atmosphere prior to the dehydrogenation reaction; Preferably, the reduction activation temperature is 200-400 ℃, and the reduction activation time is 1-6 h.
  8. 8. The method according to any one of claims 1 to 7, wherein the dehydrogenation reaction is carried out in a reactor, which is a fixed bed reactor, a fluidized bed reactor or a tank reactor; Preferably, the volume space velocity of the diol compound represented by formula 1 is 0.5h -1 ～15h -1 , preferably 1h -1 ～6h -1 , more preferably 1h -1 ～3h -1 .
  9. 9. The method according to any one of claims 1 to 8, further comprising a step of separating and purifying a product after the dehydrogenation reaction; Preferably, the separation and purification comprises rectification and purification; Preferably, the rectification and purification are carried out under the pressure condition of 0.95atm to 1.05atm or 1kPa to 10 kPa.
  10. 10. The method according to claim 9, wherein the rectification purification is carried out in a rectification column, which is a packed column or a tray column; Preferably, the rectification and purification are carried out under the pressure condition of 0.95atm to 1.05atm, the temperature of a reboiler at the bottom of a rectification tower is 140 ℃ to 180 ℃, the temperature of the top of the tower is 80 ℃ to 120 ℃, the reflux ratio is 1 to 10, preferably 2 to 6, or The rectification and purification are carried out under the pressure condition of 1kPa-10kPa, preferably 2kPa-6kPa, the temperature of a reboiler at the bottom of a rectifying tower is 90-160 ℃, the temperature of the top of the rectifying tower is 40-100 ℃, and the reflux ratio is 1-10, preferably 2-6.

Description

Preparation method of ketol compound Technical Field The invention relates to the technical field of chemical industry, in particular to a preparation method of ketol compounds. Background Alpha-hydroxy acetone, also called acetol, has a molecular formula of C 3H6O2, has hydroxyl and active unsaturated carbonyl, is an organic synthesis intermediate with high added value, is widely applied to pharmaceutical synthesis, textile manufacturing, cosmetic industry and food industry, and is mainly used for synthesizing 4-methylimidazole, methylglyoxal, pyruvic acid, lactic acid and the like. The main synthetic route of the alpha-hydroxyacetone comprises a1, 2-propanediol oxidation method, halogenated acetone esterification and hydrolysis, acetaldehyde and formaldehyde condensation, glycerol dehydration and the like. At present, the method for directly preparing the alpha-hydroxyacetone by taking the 1, 2-propanediol as the raw material is less, for example, an electrolytic silver catalyst is used for selective catalytic oxidation of the 1, 2-propanediol to co-produce the alpha-hydroxyacetone and methylglyoxal, the reaction temperature of the method is 300-500 ℃, a certain safety risk exists under the condition of an oxidant, the selectivity of the alpha-hydroxyacetone is only 36-39%, and the subsequent product separation flow is complex. CN110813364A uses a bimetallic nano catalyst to catalyze and oxidize 1, 2-propanediol to prepare pyruvic acid and hydroxy acetone, the catalyst cost is high, the selectivity of hydroxy acetone is lower than 70%, and the subsequent separation problem also exists. The method is characterized in that the alpha-hydroxyacetone is used for co-producing the alpha-hydroxyacetone, on one hand, the alpha-hydroxyacetone is not taken as a main target product, the selectivity of the alpha-hydroxyacetone is low, and on the other hand, the product components are complex, so that the subsequent separation process is complex and difficult, and the alpha-hydroxyacetone product with higher purity is difficult to obtain. CN109896941A uses vanadium-containing catalyst and uses carbohydrate as raw material to produce hydroxy acetone by catalytic hydrogenation, the cost of raw material is lower, but the yield of hydroxy acetone is only 4-35%, and the yield is lower, and at the same time, by-products such as methyl lactate, sorbitol and the like are produced. CN114315550a proposes a one-pot synthesis method of hydroxyacetone, the raw materials are acetone, alkali metal bromide, inorganic acid binding agent, phase transfer catalyst and hydrogen peroxide, and the hydroxyacetone with higher purity is obtained by extraction after reaction, but the method consumes larger solvent amount, has more complex extraction steps, and is not suitable for continuous production of alpha-hydroxyacetone. Therefore, it is necessary to improve the production process of α -hydroxyacetone to increase the yield of hydroxyacetone, reduce the production cost, avoid complicated post-treatment operations, and simplify the process flow. Disclosure of Invention In order to solve one of the technical problems in the prior art, the invention provides a preparation method of ketol compounds. The technical scheme of the invention is as follows: The invention provides a method for preparing ketol compounds, which comprises the steps of carrying out dehydrogenation reaction on glycol compounds shown in a formula 1 in the presence of a catalyst to generate ketol compounds shown in a formula 2; wherein the catalyst comprises a first active component comprising Cu and Ru; In the formulas 1 and 2, R 1 is selected from C1-C10 alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C3-C20 heteroaryl or a combination thereof, and R 2 is selected from hydrogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C3-C20 heteroaryl or a combination thereof. According to some embodiments of the invention, in formula 1 and formula 2, R 1 is selected from C1-C6 alkyl, C3-C6 cycloalkyl, C6-C10 aryl, C3-C10 heteroaryl, or a combination thereof. In some embodiments, R 1 is selected from C1-C6 alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, or hexyl. In some embodiments, R 1 is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or tert-butyl. In some embodiments, R 1 is selected from methyl or ethyl. In some embodiments, R 1 is methyl. According to some embodiments of the invention, in formula 1 and formula 2, R 2 is selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C6-C10 aryl, C3-C10 heteroaryl, or a combination thereof. In some embodiments, R 2 is selected from hydrogen or C1-C6 alkyl, such as hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, or hexyl. In some embodiments, R 2 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or tert-butyl. In some embodiments, R 2 is selected from hydrogen, methyl, or ethyl. In some embodiments, R 2 is hydrogen. According to som