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CN-122006711-A - Hydrodeoxygenation catalyst, preparation method and application thereof and preparation method of adipic acid

CN122006711ACN 122006711 ACN122006711 ACN 122006711ACN-122006711-A

Abstract

The invention relates to the field of biomass conversion, in particular to a hydrodeoxygenation catalyst, a preparation method and application thereof and a preparation method of adipic acid, wherein the catalyst comprises a bimetal composite oxide-carbon material composite carrier, and a first noble metal element and a second noble metal element on the composite carrier, wherein the first noble metal element is one or more of platinum, palladium, rhodium and gold, the second noble metal element is one or more of vanadium, molybdenum and rhenium, the bimetal composite oxide has a chemical composition shown as a formula M 2+ 1‑x M 3+ x O(OH) x , M 2+ is divalent metal for forming a laminate, M 3+ is trivalent metal for forming the laminate, x is the molar ratio of the trivalent metal to total metal, and x is in the range of 0.1-0.5.

Inventors

  • JING MENGMENG
  • YANG HEQIN
  • WANG CAN
  • JIA YINJUAN

Assignees

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

Dates

Publication Date
20260512
Application Date
20241111

Claims (10)

  1. 1. A hydrodeoxygenation catalyst is characterized by comprising a bimetallic composite oxide-carbon material composite carrier, and a first noble metal element and a second noble metal element on the composite carrier; The first noble metal is selected from one or more of platinum, palladium, rhodium and gold; the second noble metal is selected from one or more of vanadium, molybdenum and rhenium; The bimetal composite oxide is of a layered structure and has a chemical composition shown in a formula M 2+ 1-x M 3+ x O ( OH) x , wherein M 2+ is divalent metal for forming the laminate, M 3+ is trivalent metal for forming the laminate, x is the molar ratio of the trivalent metal to the total metal, and x has a value of 0.1-0.5.
  2. 2. The hydrodeoxygenation catalyst according to claim 1, wherein, The weight of the bimetal composite oxide is 10-50% of the total weight of the composite carrier, and/or The carbon material is 50-90wt% of the total weight of the composite carrier, and/or Based on the total weight of the catalyst, the content of the composite carrier is 91.5 to 98.95 percent by weight, the content of the first noble metal element is 0.05 to 0.5 percent by weight, the content of the second noble metal element is 1 to 8 percent by weight, and/or In the composite carrier, the bimetal composite oxide is a layered bimetal composite oxide.
  3. 3. The hydrodeoxygenation catalyst according to claim 1 or 2, wherein, The second noble metal is rhenium; Preferably, rhenium comprises three valence states +4, +6 and +7, the +4 valence content ratio is 28% -38%, the +6 valence content ratio is 20% -35%, and the +7 valence content ratio is 27% -52%.
  4. 4. The hydrodeoxygenation catalyst according to claim 1 or 2, wherein, The bi-metal composite oxide comprises a divalent metal selected from Ni, zn, cu, co or Mg, a trivalent metal selected from Al or Fe, and/or The carbon material is selected from one or more of porous carbon materials, preferably activated carbon.
  5. 5. The method for producing the hydrodeoxygenation catalyst according to any of claims 1 to 4, characterized in that the method comprises: (1) Contacting the mixed solution containing the M 2+ source, the M 3+ source and the carbon material with an alkali solution to obtain slurry, crystallizing, separating and drying to prepare a layered hydrotalcite-carbon material composite carrier; (2) And loading a first noble metal source and a second noble metal source to the layered hydrotalcite-carbon material composite carrier, and roasting and reducing the layered hydrotalcite-carbon material composite carrier, wherein the roasting condition comprises that the temperature is 250-450 ℃.
  6. 6. The preparation method according to claim 5, wherein, The step (1) also comprises the steps of adjusting the pH of the slurry to 10-14 before crystallization, and/or The concentration of metal ion in the mixed solution is 0.3-1.5M, and/or In the alkaline solution, the concentration of hydroxyl is 0.2-3M and/or the concentration of carbonate is 0-1.5M.
  7. 7. The process according to claim 5 or 6, wherein in the step (2), The calcination conditions include calcination in an inert gas atmosphere at 300-400 ℃ for 3-6 hours, and/or The reduction condition comprises that the reduction is carried out in the atmosphere containing reducing gas, the reduction temperature is 300-400 ℃, and the reduction time is 1-4h.
  8. 8. The process according to any one of claim 5 to 7, wherein, The M 2+ source is selected from soluble salts of divalent metals, and/or The source of M 3+ is selected from soluble salts of trivalent metals, and/or The alkali in the alkali solution is one or more of alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate and urea, and/or The first noble metal source is selected from soluble salts of the first noble metal, preferably one or more of chloroplatinic acid, chloropalladic acid, palladium nitrate, ammonium chloropalladite, rhodium chloride, and chloroauric acid, and/or The second noble metal source is selected from soluble salts of the second noble metal, preferably one or more of ammonium metavanadate, ammonium molybdate and ammonium perrhenate.
  9. 9. Use of the hydrodeoxygenation catalyst of any of claims 1-4 in the conversion of one or more of glucarate, glucarate salt, and glucarate.
  10. 10. A process for the preparation of adipic acid, the process comprising: Converting glucaric acid to adipic acid in the presence of a catalyst and hydrogen, the catalyst comprising the hydrodeoxygenation catalyst of any of claims 1-4; Preferably, the reaction conditions include a temperature of 80-140 ℃, and/or a pressure of 0.2-1.2MPa, and/or a time of 6-24 hours, and/or The catalyst is 5-20wt% of the mass of the glucaric acid; Preferably, the hydrogenation reaction is carried out in the presence of a liquid phase diluent, more preferably the liquid phase diluent is used in such an amount that the mass concentration of glucaric acid is 1-3wt%.

Description

Hydrodeoxygenation catalyst, preparation method and application thereof and preparation method of adipic acid Technical Field The invention relates to the field of biomass conversion, in particular to a hydrodeoxygenation catalyst, a preparation method and application thereof and a preparation method of adipic acid. Background Adipic acid is aliphatic alpha, omega-dibasic acid with the largest usage amount, and has wide application in the fields of high polymer materials, medicines, organic synthesis and the like. Currently, about 70% or more of adipic acid is used as a monomer for synthesizing nylon 6,6 and polymers such as polyurethane and dimethyl adipate. The current annual production is up to 300 tens of thousands of tons and increases year by year at a growth rate of 5%. The current industrial production method of adipic acid mainly adopts a nitric acid oxidation method which takes cyclohexane alcohol and cyclohexanone (KA oil) as raw materials, and in the production process, nitric acid has strong corrosiveness to reaction equipment, and a large amount of greenhouse gas N 2 O is generated, so that the environment is seriously polluted. Therefore, development of green adipic acid production process is increasingly important. Biomass materials have gained extensive attention and research in recent years as a renewable resource of abundant sources, with conversion. From saccharides, various green chemicals can be obtained by oxidation, hydrogenolysis, hydrogenation, and the like. CN102803195B provides a process for the chemical catalytic conversion of glucose sources into adipic acid products, but the reaction process requires the addition of halogen as an auxiliary agent, and the reaction temperature is required to be above 140 ℃. CN110872222A proposes that from potassium gluconate, d-glycosyl acid-1, 4;6,3 di-lactone is esterified, adipic acid is obtained through hydrogenolysis of a catalyst, and the catalyst directly adopts ammonium perrhenate, so that a recovery step is added. Disclosure of Invention Aiming at the problems existing in the prior art, the invention aims to provide a hydrodeoxygenation catalyst, a preparation method and application thereof and a preparation method of adipic acid, wherein the hydrodeoxygenation catalyst can effectively anchor noble metal active sites and promote catalytic activity, and the catalyst is used for preparing adipic acid from glucarate, glucaric acid, glucarate ester and the like, and has the advantages of high substrate conversion rate and high adipic acid yield. In order to achieve the above object, a first aspect of the present invention provides a hydrodeoxygenation catalyst comprising a bimetallic composite oxide-carbon material composite support and a first noble metal element and a second noble metal element on the composite support; The first noble metal is selected from one or more of platinum, palladium, rhodium and gold; the second noble metal is selected from one or more of vanadium, molybdenum and rhenium; The bimetal composite oxide is of a layered structure and has a chemical composition shown in a formula M 2+1-xM3+xO(OH)x, wherein M 2+ is divalent metal for forming the laminate, M 3+ is trivalent metal for forming the laminate, x is the molar ratio of the trivalent metal to the total metal, and the value of x is in the range of 0.1-0.5. In a second aspect, the present invention provides a method for preparing the hydrodeoxygenation catalyst according to the present invention, the method comprising: (1) Contacting the mixed solution containing the M 2+ source, the M 3+ source and the carbon material with an alkali solution to obtain slurry, crystallizing, separating and drying to prepare a layered hydrotalcite-carbon material composite carrier; (2) And loading a first noble metal source and a second noble metal source to the layered hydrotalcite-carbon material composite carrier, and roasting and reducing the layered hydrotalcite-carbon material composite carrier, wherein the roasting condition comprises that the temperature is 250-450 ℃. In a third aspect, the present invention provides the use of a hydrodeoxygenation catalyst according to the invention in the conversion of one or more of glucarate, glucarate and glucarate. In a fifth aspect, the present invention provides a process for the preparation of adipic acid, the process comprising: The glucaric acid is converted to adipic acid in the presence of a catalyst and hydrogen, the catalyst comprising the hydrodeoxygenation catalyst of the invention. Through the technical scheme, the hydrodeoxygenation catalyst disclosed by the invention can effectively anchor noble metal active sites and improve the catalytic activity. The hydrodeoxygenation catalyst is used for preparing adipic acid by hydrogenating glucaric acid and/or glucarate, and has the advantages of high substrate conversion rate and high adipic acid yield. Drawings FIG. 1 is an XRD spectrum of the catalyst prepared in example 1; F