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CN-121972202-A - Vanadium salt and carbon-based composite lignin depolymerization catalyst and application thereof

CN121972202ACN 121972202 ACN121972202 ACN 121972202ACN-121972202-A

Abstract

The invention belongs to the technical field of lignin depolymerization catalysts, and particularly relates to a vanadium salt and carbon-based composite lignin depolymerization catalyst and application thereof. The vanadium salt and carbon-based composite lignin depolymerization catalyst comprises vanadium salt and carbon-based. Wherein the mass ratio of the vanadium salt to the carbon base is 3.7-12.5:40. The vanadium salt is any one of vanadyl acetylacetonate, vanadyl sulfate, vanadyl oxalate, vanadyl triisopropoxide and ammonium metavanadate. The carbon base is biochar or activated carbon. The conversion rate of the 2-phenoxy-1-phenethyl alcohol in the vanadium salt and carbon-based lignin depolymerization catalyst reaches 100% at maximum under the synergistic effect of the vanadium salt and the activated carbon, the phenol yield reaches 68% at maximum, the methyl benzoate yield reaches 77% at maximum, and the catalyst has high lignin depolymerization catalytic activity and can efficiently catalyze lignin depolymerization reaction.

Inventors

  • ZHAO LI
  • Jiang Kechen
  • SHEN FEI
  • HUANG MEI
  • TIAN DONG
  • WU KAIKAI

Assignees

  • 四川农业大学

Dates

Publication Date
20260505
Application Date
20260127

Claims (10)

  1. 1. The catalyst for depolymerizing the vanadium salt and carbon-based composite lignin is characterized by being prepared by mixing vanadium salt and carbon-based; wherein the mass ratio of the vanadium salt to the carbon base is 3.7-12.5:40; the vanadium salt is any one of vanadium acetylacetonate, vanadyl sulfate, vanadyl oxalate, vanadyl triisopropoxide and ammonium metavanadate; the carbon base is biochar or activated carbon.
  2. 2. The vanadium salt and carbon-based composite lignin depolymerization catalyst according to claim 1, wherein the biochar is prepared by pyrolyzing wheat straw, rice straw, corn straw or rape straw at 300-600 ℃.
  3. 3. The vanadium salt and carbon-based composite lignin depolymerization catalyst of claim 1, wherein the activated carbon is any one of coal activated carbon, wood activated carbon, and fruit shell activated carbon.
  4. 4. The use of a vanadium salt and carbon-based composite lignin depolymerization catalyst according to claim 1, comprising the steps of: adding a vanadium salt and carbon-based composite lignin depolymerization catalyst, a solvent and lignin into a reaction kettle, sealing, stirring, replacing air in the reaction kettle with oxygen, oxidizing gas to a pressure of 0.1-1 MPa, reacting for 2-24 h at 80-180 ℃, and cooling to obtain the oxygen-containing aromatic compound.
  5. 5. The application of the vanadium salt and carbon-based composite lignin depolymerization catalyst according to claim 4, wherein the mass ratio of the vanadium salt and carbon-based composite lignin depolymerization catalyst to the solvent to lignin is 43.7-52.5:42.8:4000.
  6. 6. The use of a vanadium salt and carbon-based composite lignin depolymerization catalyst according to claim 4, wherein the oxygen pressure is 0.5MPa.
  7. 7. The application of the vanadium salt and carbon-based composite lignin depolymerization catalyst according to claim 4, wherein the reaction temperature is 100-180 ℃ and the reaction time is 4-24 hours.
  8. 8. The use of a vanadium salt and carbon-based composite lignin depolymerization catalyst according to claim 7 wherein the reaction temperature is 140 ℃.
  9. 9. The use of a vanadium salt and carbon-based composite lignin depolymerization catalyst according to claim 4, wherein the solvent is any one of methanol, ethanol, isopropanol, water, N-dimethylformamide and dimethyl sulfoxide.
  10. 10. The use of a vanadium salt and carbon-based composite lignin depolymerization catalyst according to claim 4, wherein the lignin is a β -O-4 model compound; The oxygen-containing aromatic compound is one or more of phenol, benzoic acid, methyl benzoate, 3, 4-dimethoxy methyl benzoate and methyl anisoate.

Description

Vanadium salt and carbon-based composite lignin depolymerization catalyst and application thereof Technical Field The invention belongs to the technical field of lignin depolymerization catalysts, and particularly relates to a vanadium salt and carbon-based composite lignin depolymerization catalyst and application thereof. Background The biomass reserves are rich, the carbon emission is low, and the biomass is clean energy. Among various biomass energy sources, lignocellulose biomass is most widely distributed and has the most abundant reserves. Wherein the lignin content in lignocellulose is inferior to cellulose. Lignin is the only renewable aromatic source in nature and has unique advantages in terms of conversion to high value-added oxygenated aromatics and other bulk chemicals. Lignin is formed by interconnecting a large number of aromatic structural units through CO and CC bonds, the C-C bonds can be selectively broken by a catalytic oxidation method, oxygen-containing groups and aromatic structures which are originally formed by the lignin are utilized to obtain the aromatic compound with oxygen-containing functional groups, and the core of oxidative depolymerization is to develop a catalyst capable of efficiently cutting off the chemical bonds. Currently, homogeneous catalysts are mostly metal complexes, which are difficult to separate after reaction. Heterogeneous catalytic systems generally have low catalytic efficiency and are difficult to achieve with high yields. Disclosure of Invention In order to solve the technical problems, the invention provides a vanadium salt and carbon-based composite lignin depolymerization catalyst and application thereof. The first object of the invention is to provide a vanadium salt and carbon-based composite lignin depolymerization catalyst, which is formed by mixing vanadium salt and carbon-based. Wherein the mass ratio of the vanadium salt to the carbon base is 3.7-12.5:40. The vanadium salt is any one of vanadyl acetylacetonate, vanadyl sulfate, vanadyl oxalate, vanadyl triisopropoxide and ammonium metavanadate. The carbon base is biochar or activated carbon. Preferably, the biochar is prepared by pyrolyzing wheat straw, rice straw, corn straw or rape straw at 300-600 ℃. Preferably, the preparation method of the biochar comprises the following steps: 1) And (5) air-drying, crushing and sieving the straw with a 50-mesh sieve to obtain straw particles. 2) 10G of straw particles are taken and placed in a tube furnace for inert roasting under nitrogen atmosphere. The temperature rising rate is 2-25 ℃ per minute, the roasting temperature is 200-1000 ℃ and the roasting time is 1-6 h. And after roasting, sieving with a 200-mesh sieve to obtain the biochar. Preferably, the straw is one of wheat straw, rice straw, corn straw and rape straw Preferably, the temperature rising rate is 5-10 ℃ per minute, the roasting temperature is 300-600 ℃ and the roasting time is 2-4 hours. Preferably, the activated carbon is one or more of coal activated carbon, wood activated carbon and shell activated carbon. The second object of the invention is to provide an application of a vanadium salt and carbon-based composite lignin depolymerization catalyst, comprising the following steps: Adding the vanadium salt, the carbon-based composite lignin depolymerization catalyst, the solvent and the lignin into a reaction kettle, sealing and stirring. And (3) replacing air in the reaction kettle with oxygen, oxygenating the air to a pressure of 0.1-1 MPa, reacting for 2-24 hours at 80-180 ℃, and cooling to obtain the oxygen-containing aromatic compound. Preferably, the mass ratio of the vanadium salt to the carbon-based composite lignin depolymerization catalyst to the solvent to lignin is 43.7-52.5:42.8:4000. Preferably, the oxygen pressure is 0.5MPa. Preferably, the reaction temperature is 100-180 ℃ and the reaction time is 4-24 hours. Preferably, the reaction temperature is 140 ℃. Preferably, the stirring speed is 700rpm. Preferably, the solvent is any one of methanol, ethanol, isopropanol, water, N-dimethylformamide and dimethyl sulfoxide. Preferably, the lignin is a beta-O-4 model compound. The oxygen-containing aromatic compound is one or more of phenol, benzoic acid, methyl benzoate, 3, 4-dimethyl methyl benzoate and methyl anisoate. Preferably, the β -O-4 model compound is 2-phenoxy-1-phenylethanol, 2- (4-methoxyphenoxy) -1-phenylethanol, 2- (3, 4-dimethoxyphenoxy) -1-phenylethanol, 2-phenoxy-1- (4-methoxyphenyl) ethanol, 2- (4-methoxyphenoxy) -1- (4-methoxyphenyl) ethanol or 2-phenoxy-1- (3, 4-dimethoxyphenyl) ethanol. Compared with the prior art, the invention has the following beneficial effects: 1. The vanadium salt and carbon-based composite lignin depolymerization catalyst comprises vanadium salt and carbon-based. Wherein the mass ratio of the vanadium salt to the carbon base is 3.7-12.5:40. The vanadium salt is any one of vanadyl acetylacetonate, vanadyl sulfate, vanadyl oxalate, v