WO2024066446A1 - Procédé de préparation d'un composé cyclohexanone par photocatalyse d'un composé phénolique issu de la biomasse - Google Patents

Procédé de préparation d'un composé cyclohexanone par photocatalyse d'un composé phénolique issu de la biomasse Download PDF

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Publication number
WO2024066446A1
WO2024066446A1 PCT/CN2023/098197 CN2023098197W WO2024066446A1 WO 2024066446 A1 WO2024066446 A1 WO 2024066446A1 CN 2023098197 W CN2023098197 W CN 2023098197W WO 2024066446 A1 WO2024066446 A1 WO 2024066446A1
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WIPO (PCT)
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photocatalyst
cyclohexanone
guaiacol
reactor
stirring
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PCT/CN2023/098197
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English (en)
Chinese (zh)
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林丽利
赵淑芳
陈翔翔
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浙江工业大学
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Publication of WO2024066446A1 publication Critical patent/WO2024066446A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/403—Saturated compounds containing a keto group being part of a ring of a six-membered ring

Definitions

  • the invention relates to the technical field of high-value utilization of biomass, and in particular to a method for preparing cyclohexanone compounds by photocatalysis of biomass phenolic compounds.
  • cyclohexanone is mainly used in the production of chemical intermediates such as caprolactam and adipic acid, while caprolactam and adipic acid are important monomers in the production of nylon 6 and nylon 66.
  • the main processes for producing cyclohexanone are phenol oxygenation (accounting for about 3%), cyclohexene hydration (accounting for about 4%), cyclohexane liquid phase oxidation (accounting for more than 90%) and phenol one-step hydrogenation.
  • phenol oxygenation ascending for about 3%
  • cyclohexene hydration ascending for about 4%
  • cyclohexane liquid phase oxidation accounting for more than 90%
  • phenol one-step hydrogenation Using photocatalytic oxidation with molecular oxygen as the oxidant, the process of selective oxidation of organic matter to produce cyclohexanone can also be achieved at room temperature or lower temperatures.
  • Biomass energy is an important part of renewable energy, and the development and utilization of biomass energy is of great significance to the development of world energy.
  • Lignin is one of the main components of woody biomass and is an amorphous aromatic polymer widely found in plants. Lignin can be selectively degraded under high temperature and catalyst to obtain a mixture rich in biomass phenolic compounds.
  • the biomass phenolic compound guaiacol (2-methoxyphenol, Guaiacol) is the most representative lignin depolymerization product and a renewable aromatic compound with high utilization value.
  • the chemical structure of guaiacol includes two oxygen-containing phenolic hydroxyl groups (Csp 2 OH) and phenolic methoxyl groups (Csp 2 OCH 3 ). Among them, the chemical bond energy of the methoxyl group is the weakest (247kJ/mol), and the bond energy of the CO bond between the aromatic benzene ring and the phenolic hydroxyl group is the strongest (414kJ/mol).
  • guaiacol can be directed to dissociate, and selectively breaking some of its chemical bonds can produce a variety of high value-added chemicals, such as catechol, phenol, anisole, cyclohexane, etc.
  • high value-added chemicals such as catechol, phenol, anisole, cyclohexane, etc.
  • due to the CO bond Due to the serious competitive hydrogenation reaction with CC on the benzene ring, the highly selective hydrogenolysis of guaiacol is very challenging.
  • the traditional thermal catalytic reaction has the following problems: first, the reaction temperature is relatively high, and the reaction occurs at above 240°C, and sometimes even as high as 450°C to occur; second, the reaction almost entirely requires H2 atmosphere conditions to occur, and the pressure during the reaction is relatively high, and sometimes the reaction pressure is as high as 65 bar to occur; third, while producing cyclohexanone, the reaction also generates some by-products such as methanol, cyclohexanol, and cyclohexane, which face the difficulty of separation and utilization of the by-products.
  • the present invention provides a method for preparing cyclohexanone compounds with high selectivity through photocatalysis of biomass phenolic compounds, thereby achieving high selectivity of cyclohexanone compounds.
  • a method for preparing cyclohexanone compounds from biomass phenolic compounds by photocatalysis comprising: adding a biomass phenolic compound represented by formula I, a photocatalyst and an aqueous solvent into a reactor, and performing a selective hydrogenation reaction at 150-180° C. under inert gas protection and light irradiation conditions to obtain a cyclohexanone compound represented by formula II;
  • the photocatalyst is composed of a carrier and nanometer-scale bimetallic alloy particles loaded on the carrier, the bimetallic alloy particles are selected from RuPd, PtPd, RhPd, RuRh, RuPt or RhPt, and the carrier is TiO 2 , At least one of CdS, Cu 2 O, CuO, Bi 2 O 3 , NiO, Cr 2 O 3 , Fe 3 O 4 , MoO 3 , ZnO, and MoS 2 , wherein the total loading amount of the bimetallic alloy relative to the carrier in the photocatalyst is 4.0 wt%-20.0 wt%, and the mass ratio of the two metals is 1-10:1-10;
  • R 1 is -H or -OCH 3
  • R 2 is -H, -CH 3 , -C 2 H 5 , -C 3 H 7 or -OCH 3 .
  • the biomass phenolic compounds of the present invention can be obtained by refining phenol-containing bio-oil obtained by depolymerization of lignin.
  • the carrier of the photocatalyst is TiO 2
  • the bimetallic alloy is RuPd alloy.
  • the total loading amount of the bimetallic alloy particles in the photocatalyst relative to the carrier is 5-10 wt %, most preferably 5 wt %.
  • the mass ratio of the two metals is 0.5-3:0.5-3, more preferably 2-3:2-3, most preferably 1:1.
  • the photocatalyst is prepared by the following method: uniformly dispersing the carrier in deionized water to obtain a slurry; adding the above slurry dropwise to an aqueous solution containing metal ions under stirring, and continuing to stir for 0.5-6h after the addition is complete; adding a sodium citrate protective agent, adding a reducing agent aqueous solution dropwise, and continuing to stir for 0.5-6h after the addition is complete; then after washing and drying, reducing at 50-500°C in a hydrogen atmosphere for 0.5-6h, and cooling to obtain the photocatalyst.
  • the reducing agent is sodium borohydride
  • the ratio of its molar amount to the total molar amount of metal ions is 20-1:1.
  • the ratio of the molar amount of sodium citrate to the total molar amount of metal ions is 20-1:1.
  • the aqueous solvent is water or a methanol aqueous solution with a volume concentration of 50-5%.
  • the aqueous solvent contains methanol, it is beneficial to increase the yield of cyclohexanone compounds.
  • the mass ratio of the biomass phenolic compound: the photocatalyst: the aqueous solvent is 100:1-25:500-5000, more preferably 100:20:5000.
  • the illumination is performed by visible light, ultraviolet light or infrared light.
  • xenon lamp illumination is selected.
  • the reaction is carried out under stirring at a stirring rate of 100-1200 r/min.
  • the reaction temperature of the selective hydrogenation reaction is 150°C.
  • the reaction time of the selective hydrogenation reaction is 0.5-20 h, more preferably 3-12 h, further preferably 3-6 h.
  • the present invention takes a sample and filters it, the filter cake is a catalyst, the catalyst is washed with water or ethanol and dried and can be recovered and reused, ethyl acetate is added to the filtrate for extraction, and after sufficient extraction, the upper organic phase is taken for gas chromatography analysis to calculate the conversion rate of biomass phenolic compounds and the selectivity of cyclohexanone compounds.
  • the preparation method of cyclohexanone compounds of the present invention takes guaiacol as a hydrogenation substrate and water as a solvent to prepare cyclohexanone as an example, and the reaction equation is as follows:
  • the present invention has the following beneficial effects: the method for preparing cyclohexanone compounds of the present invention reacts in a water-containing solvent under the conditions of photocatalysis and illumination, and uses hydrogen or H + generated by photocatalytic decomposition of water as a reducing agent to selectively hydrogenate biomass phenolic compounds to prepare cyclohexanone compounds.
  • This process is a water-phase photoreaction body that does not require additional hydrogen and reacts at medium-low temperature and normal pressure.
  • the system has mild reaction conditions, uses water as a solvent, is green and pollution-free, has a high conversion rate of biomass phenolic compounds, and has good selectivity for cyclohexanone compounds.
  • Figure 1 is a HR-TEM image of Ru 5 @TiO 2 , Pd 5 @TiO 2 , and Ru 2.5 Pd 2.5 @TiO 2 catalysts prepared in an embodiment of the present invention.
  • the particle size of RuPd metal in the RuPd@TiO 2 catalyst is 5-10 nm, and the size distribution is relatively uniform.
  • Figure 2 is an EDS-mapping diagram of the Ru 2.5 Pd 2.5 @TiO 2 catalyst prepared in an embodiment of the present invention. As can be seen from the figure, the distribution of the elements Ru and Pd on the metal particles in the Ru 2.5 Pd 2.5 @TiO 2 catalyst is consistent.
  • Figure 3 is an XPS graph of Ru 5 @TiO 2 , Pd 5 @TiO 2 , and Ru 2.5 Pd 2.5 @TiO 2 catalysts prepared in the examples of the present invention.
  • the Pd 3d peak of RuPd@TiO 2 is shifted toward the high binding energy direction
  • the Ru 5 @TiO 2 catalyst compared with the Ru 5 @TiO 2 catalyst, the Ru 3d peak is shifted toward the low binding energy direction.
  • the metal RuPd in RuPd@TiO 2 is an alloy, and Pd transfers electrons to Ru.
  • FIG. 4 is a gas chromatography analysis result of the organic phase obtained in Example 1 of the present invention.
  • guaiacol 0.5 g of guaiacol (0.004 mol), 0.1 g of the Ru 2.5 Pd 2.5 @TiO 2 photocatalyst prepared above, and 25 mL of H 2 O were added to the photocatalytic reactor, and the air in the reactor was replaced by nitrogen for 5 times. Then, magnetic stirring was performed at 150°C, the stirring speed was 1000 rpm, and the reaction time was 3 h. Then, a sample was taken and filtered, and the filter cake was used as the catalyst, which could be recycled. 15 mL of ethyl acetate was added to the filtrate, and after sufficient extraction, the upper organic phase was taken for gas chromatography analysis and calculation, and the conversion rate of guaiacol was 0%.
  • the method for preparing cyclohexanone defined in the present invention has higher conversion rate of guaiacol and selectivity of cyclohexanone than those in the comparative example.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de préparation d'un composé cyclohexanone par photocatalyse d'un composé phénolique issu de la biomasse, ledit procédé comprenant : l'ajout d'un composé phénolique issu de la biomasse, représenté par la formule I, d'un photocatalyseur et d'un solvant aqueux dans un réacteur, et la mise en oeuvre d'une réaction d'hydrogénation sélective à 150-180 °C sous atmosphère de gaz inerte dans des conditions d'éclairage pour obtenir un composé cyclohexanone représenté par la formule II. Le procédé offre des conditions de réaction modérées, utilise de l'eau en guise de solvant respectueux de l'environnement, permet d'obtenir de hauts taux de conversion de composés phénoliques de biomasse, et présente une bonne sélectivité pour les composés cyclohexanone.
PCT/CN2023/098197 2022-09-30 2023-06-05 Procédé de préparation d'un composé cyclohexanone par photocatalyse d'un composé phénolique issu de la biomasse WO2024066446A1 (fr)

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CN202211210256.6A CN115650829B (zh) 2022-09-30 2022-09-30 一种由生物质酚类化合物光催化制备环己酮类化合物的方法
CN202211210256.6 2022-09-30

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CN115650829B (zh) * 2022-09-30 2024-05-03 浙江工业大学 一种由生物质酚类化合物光催化制备环己酮类化合物的方法

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