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CN-117920176-B - Method for catalyzing and oxidizing cycloolefin

CN117920176BCN 117920176 BCN117920176 BCN 117920176BCN-117920176-B

Abstract

The invention relates to a method for catalytic oxidation of cycloolefin, which comprises the steps of enabling cycloolefin to contact with an oxidant for oxidation reaction in the presence of a catalyst containing a modified nano carbon-based material, wherein the modified nano carbon-based material is prepared by the steps of (1) placing graphite rods in a mixed solution containing starch and water, electrolyzing to obtain an electrolyzed starch mixed solution, (2) taking out solid matters in the electrolyzed starch mixed solution, and then roasting for 1-12h at 600-1500 ℃ in an anaerobic atmosphere to obtain a roasted nano carbon-based material, and (3) carrying out hydrothermal modification on the roasted nano carbon-based material under an alkaline condition. The method can realize the catalytic oxidation of cycloolefin under mild conditions, and obtain higher raw material conversion rate and product selectivity.

Inventors

  • SHI CHUNFENG
  • WANG XIAO
  • KANG ZHENHUI
  • HUANG HUI
  • LIU YANG
  • ZHOU BINJIE

Assignees

  • 中国石油化工股份有限公司
  • 中石化石油化工科学研究院有限公司

Dates

Publication Date
20260505
Application Date
20221014

Claims (20)

  1. 1. A method for catalytic oxidation of cycloolefin, characterized in that the method comprises the steps of contacting cycloolefin with an oxidant in the presence of a catalyst containing a modified nanocarbon-based material to perform an oxidation reaction; The modified nano carbon-based material is prepared by a method comprising the following steps: (1) Placing the graphite rod in a mixed solution containing starch and water, and electrolyzing to obtain an electrolyzed starch mixed solution; (2) Taking out solid matters in the electrolyzed starch mixed solution, and roasting for 1-12 hours at 600-1500 ℃ in an oxygen-free atmosphere to obtain a roasted nano carbon-based material; (3) And carrying out hydrothermal modification on the roasted nano carbon-based material under an alkaline condition.
  2. 2. The method of claim 1, wherein the modified nanocarbon-based material has an average particle diameter of 20-500nm.
  3. 3. The method according to claim 1, wherein in step (1), in the mixed liquid comprising starch and water, the weight ratio of the starch to the water is 1 (1-10); the electrolysis conditions include a voltage of 5-30V for 2-10 days.
  4. 4. The method of claim 1, wherein in step (1), the mixed liquor comprising starch and water contains an ammonia source.
  5. 5. The method of claim 4, wherein the ammonia source is selected from one or more of ammonia water, urea, and hydrazine hydrate.
  6. 6. The method according to claim 4, wherein the weight ratio of the starch to the ammonia source in terms of nitrogen-containing compounds in the mixed liquor is 100 (0.1-500).
  7. 7. The method according to claim 4, wherein the weight ratio of the starch to the ammonia source in terms of nitrogen-containing compounds in the mixed liquor is 100 (5-200).
  8. 8. The method according to claim 1, wherein step (2) comprises taking out solid matters in the electrolyzed starch mixed solution, and then carrying out the calcination under an oxygen-free atmosphere containing ammonia gas; The roasting conditions comprise 800-1200 ℃, 2-8 hours and 0.1-0.5MPa.
  9. 9. The method according to claim 8, wherein the molar fraction of the ammonia gas in the ammonia-containing oxygen-free atmosphere is 0.1 to 10mol%.
  10. 10. The method according to claim 8, wherein the mole fraction of the ammonia gas in the ammonia-containing oxygen-free atmosphere is 0.6 to 5mol%.
  11. 11. The method according to claim 1, wherein step (3) comprises mixing the calcined nanocarbon-based material with an alkaline aqueous solution, followed by the hydrothermal modification; the weight ratio of the calcined nano carbon-based material to water is 1 (1-10); The hydrothermal modification condition comprises the time of 2-24h and the temperature of 100-200 ℃.
  12. 12. The method of claim 11, wherein the basic aqueous solution is an aqueous solution containing an inorganic base; The aqueous solution containing inorganic alkali comprises one or more of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, calcium hydroxide aqueous solution and ammonia water.
  13. 13. The method according to claim 12, wherein the concentration of the inorganic base in the aqueous solution containing the inorganic base is 0.1 to 20% by weight.
  14. 14. The method according to claim 12, wherein the concentration of the inorganic base in the aqueous solution containing the inorganic base is 0.5 to 10% by weight.
  15. 15. The process according to claim 1, wherein the oxidation reaction conditions comprise a temperature of 30-150 ℃ for 0.1-12 hours and a pressure of 0.1-5.0MPa; The molar ratio of the cycloolefin to the oxidizing agent is 1 (0.1-10).
  16. 16. The method of claim 1, wherein the oxidizing agent is hydrogen peroxide and/or an organic peroxide; The cycloolefin is one or more of C6-C12 substituted or unsubstituted monocyclic olefin and C8-C16 substituted or unsubstituted bicyclic olefin; The substituent in the substituted monocyclic olefin is the same as or different from the substituent in the substituted bicyclic olefin, and each substituent is independently selected from one or more of halogen and alkyl with 1-5 carbon atoms.
  17. 17. The method of claim 1, wherein the oxidizing agent is hydrogen peroxide.
  18. 18. The process of claim 1, wherein the oxidation reaction is carried out in the presence of a solvent that is one of a C1-C6 saturated monohydric alcohol, a C3-C6 ketone, and a C2-C6 nitrile, or a combination of two or three thereof.
  19. 19. The method of claim 18, wherein the solvent is methanol, ethanol, isopropanol, acetone, butanone, or acetonitrile, or a combination of two or three thereof.
  20. 20. The method according to claim 1, wherein the catalyst is used in an amount of 20 to 2000mg based on 100mL of the cycloolefin based on the modified nanocarbon-based material contained in the catalyst.

Description

Method for catalyzing and oxidizing cycloolefin Technical Field The present disclosure relates to a method for catalytic oxidation of cycloolefins. Background The carbon-based material comprises carbon nano tube, active carbon, graphite, graphene, fullerene, carbon nano fiber, nano diamond and the like. The scientific research of nanocarbon catalysis began in the 90 s of the last century. Researches show that the surface chemical properties of the nano carbon material (mainly comprising nano carbon tubes and graphene) can be flexibly regulated and controlled, and the surface of the nano carbon material can be modified with functional groups containing hetero atoms such as oxygen, nitrogen and the like, so that the nano carbon material has certain acid-base properties and oxidation-reduction capability, and can be directly used as a catalyst material. The research and development of new catalytic materials related to carbon nano-tubes and other nano-carbon materials widens the application of the new catalytic materials in the fields of petrochemical industry, fine chemical industry and the like, and has profound theoretical significance and great potential application prospect. Disclosure of Invention The purpose of the present disclosure is to provide a method for catalytic oxidation of cycloolefin using nanocarbon-based material as catalyst, which can realize catalytic oxidation of cycloolefin under mild conditions and obtain higher conversion rate of raw material and selectivity of product. In order to achieve the above object, the present disclosure provides a method for catalytic oxidation of cycloolefin, comprising contacting cycloolefin with an oxidizing agent in the presence of a catalyst containing a modified nanocarbon-based material to perform an oxidation reaction; The modified nano carbon-based material is prepared by a method comprising the following steps: (1) Placing the graphite rod in a mixed solution containing starch and water, and electrolyzing to obtain an electrolyzed starch mixed solution; (2) Taking out solid matters in the electrolyzed starch mixed solution, and roasting for 1-12 hours at 600-1500 ℃ in an oxygen-free atmosphere to obtain a roasted nano carbon-based material; (3) And carrying out hydrothermal modification on the roasted nano carbon-based material under an alkaline condition. Optionally, the modified nanocarbon-based material has an average particle diameter of 20 to 500nm. Optionally, in the step (1), in the mixed liquid containing starch and water, the weight ratio of the starch to the water is 1 (1-10); the electrolysis conditions include a voltage of 5-30V for 2-10 days. Optionally, in step (1), the mixed liquor comprising starch and water contains an ammonia source; The ammonia source is selected from one or more of ammonia water, urea and hydrazine hydrate; Optionally, the weight ratio of the starch to the amount of the ammonia source calculated as nitrogen-containing compound in the mixed liquor is 100 (0.1-500), preferably 100 (5-200). Optionally, step (2) comprises removing solid matter from the electrolyzed starch mixture and then performing the calcination in an oxygen-free atmosphere containing ammonia gas; the roasting conditions comprise 800-1200 ℃, 2-8 hours and 0.1-0.5MPa of pressure; Alternatively, the molar fraction of ammonia in the ammonia-containing oxygen-free atmosphere is 0.1 to 10mol%, preferably 0.6 to 5mol%. Optionally, step (3) comprises mixing the calcined nanocarbon-based material with an alkaline aqueous solution and then performing the hydrothermal modification; the weight ratio of the calcined nano carbon-based material to water is 1 (1-10); The hydrothermal modification condition comprises 2-24h, 100-200deg.C; optionally, the alkaline aqueous solution is an aqueous solution containing an inorganic base; the aqueous solution containing inorganic alkali comprises one or more of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, calcium hydroxide aqueous solution and ammonia water; Alternatively, the concentration of the inorganic base in the aqueous solution containing the inorganic base is 0.1 to 20% by weight, preferably 0.5 to 10% by weight. Optionally, the oxidation reaction conditions comprise a temperature of 30-150 ℃ for 0.1-12 hours and a pressure of 0.1-5.0MPa; The molar ratio of the cycloolefin to the oxidizing agent is 1 (0.1-10). Optionally, the oxidizing agent is hydrogen peroxide and/or an organic peroxide, preferably hydrogen peroxide; The cycloolefin is one or more of C6-C12 substituted or unsubstituted monocyclic olefin and C8-C16 substituted or unsubstituted bicyclic olefin; The substituent in the substituted monocyclic olefin is the same as or different from the substituent in the substituted bicyclic olefin, and each substituent is independently selected from one or more of halogen and alkyl with 1-5 carbon atoms; Optionally, the oxidation reaction is carried out in the presence of a solvent whi