CN-121986092-A - Method for producing furan-based bis-hydroxymethyl compounds from mixtures comprising hydroxymethylfurfural and corresponding mixtures for use as intermediates

Abstract

Described herein is a process for the manufacture of furan-based bis-hydroxymethyl compounds from hydroxymethylfurfural, in particular from a mixture comprising hydroxymethylfurfural, and a reaction mixture comprising hydroxymethylfurfural as obtainable by said process, as well as the use of said reaction mixture in a hydrogenation process for the manufacture of 2, 5-bis (hydroxymethyl) furan and/or 2, 5-bis (hydroxymethyl) tetrahydrofuran.

Inventors

• S. Greisle
• A. KINDLER
• D. P. Kunsman Keitel
• C. Stoke
• P. MEYER
• B Thys Berg

Assignees

• 巴斯夫欧洲公司

Dates

Publication Date

20260505

Application Date

20240731

Priority Date

20230811

Claims (17)

1. 1. A method of making a furan-based bis-hydroxymethyl compound from hydroxymethylfurfural, the method comprising the steps of: S1) reacting hexoses in a reaction mixture further comprising an acid, water and an organic solvent, At a temperature in the range of 50 ℃ to 200 ℃, And removing water from the reaction mixture, Thereby forming the hydroxymethylfurfural which is then separated from the aqueous solution, S2) preferably substantially neutralising the reaction mixture from step S1) or substantially neutralising the acid component present in the reaction mixture from step S1), To obtain a substantially neutralized reaction mixture comprising hydroxymethylfurfural, And S3) bringing into contact The reaction mixture from step S1) comprising hydroxymethylfurfural Or a mixture comprising hydroxymethylfurfural derived or produced from the reaction mixture comprising hydroxymethylfurfural from step S1), Or (b) The substantially neutralized reaction mixture comprising hydroxymethylfurfural from step S2), Or a mixture comprising hydroxymethylfurfural derived or produced from the substantially neutralized reaction mixture comprising hydroxymethylfurfural from step S2), Subjecting to hydrogenation in the presence of a catalyst comprising ruthenium, comprising a temperature in the range of 50 ℃ to 150 ℃ and a hydrogen pressure in the range of 5 to 20 MPa, Thereby forming 2, 5-bis (hydroxymethyl) furan and/or 2, 5-bis (hydroxymethyl) tetrahydrofuran.
2. 2. The method according to claim 1, wherein in step S1) The hexose is selected from the group consisting of D-glucose, D-fructose, D-sucrose and mixtures thereof, Wherein preferably the hexose comprises or is D-fructose; And/or The organic solvent is selected from the group consisting of N-alkyl-2-pyrrolidone, preferably from the group consisting of N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, N-methylsuccinimide, 1, 3-dimethyl-2-imidazolidinone, dimethylformamide, dimethyl sulfoxide, N-dimethyl-lactamide, dimethylpropyleneurea and mixtures thereof, Wherein preferably the organic solvent is selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylsuccinimide, and mixtures thereof, Wherein more preferably the organic solvent comprises or is N-methyl-2-pyrrolidone; And/or The acid is selected from the group consisting of sulfuric acid, hydrochloric acid, hydrobromic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, camphorsulfonic acid and mixtures thereof, Wherein preferably the acid comprises or is sulfuric acid.
3. 3. A method according to any of the preceding claims, comprising the steps of: S1) reacting hexoses in a reaction mixture further comprising -An acid selected from the group consisting of sulfuric acid, hydrochloric acid, hydrobromic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, camphorsulfonic acid and mixtures thereof; wherein preferably the acid comprises or is sulfuric acid -Water and An organic solvent selected from the group consisting of N-alkyl-2-pyrrolidone, preferably selected from the group consisting of N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, N-methylsuccinimide, 1, 3-dimethyl-2-imidazolidinone, dimethylformamide, dimethyl sulfoxide, N-dimethyl-lactamide, dimethylpropyleneurea and mixtures thereof, Wherein preferably the organic solvent is selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylsuccinimide, and mixtures thereof, Wherein more preferably the organic solvent comprises or is N-methyl-2-pyrrolidone; At a temperature in the range of 50 ℃ to 200 ℃, And removing water from the reaction mixture, Thereby forming the hydroxymethylfurfural which is then separated from the aqueous solution, S2) substantially neutralising the reaction mixture from step S1) or substantially neutralising the acid component present in the reaction mixture from step S1) by adjusting the pH of the reaction mixture from step S1) to a value in the range of 6 to 8, To obtain a substantially neutralized reaction mixture comprising hydroxymethylfurfural, And S3) bringing into contact The reaction mixture from step S1) comprising hydroxymethylfurfural Or a mixture comprising hydroxymethylfurfural derived or produced from the reaction mixture comprising hydroxymethylfurfural from step S1), Or (b) The substantially neutralized reaction mixture comprising hydroxymethylfurfural from step S2), Or a mixture comprising hydroxymethylfurfural derived or produced from the substantially neutralized reaction mixture comprising hydroxymethylfurfural from step S2), Subjecting to hydrogenation in the presence of a catalyst comprising ruthenium, comprising a temperature in the range of 50 ℃ to 150 ℃ and a hydrogen pressure in the range of 5 to 20 MPa, Thereby forming 2, 5-bis (hydroxymethyl) furan and/or 2, 5-bis (hydroxymethyl) tetrahydrofuran.
4. 4. A method according to any of the preceding claims, wherein in step S1) -Removing water from the reaction mixture comprises distilling off water from the reaction mixture; And/or -The reaction is carried out for a period of time ranging from 3 to 8 hours, preferably from 4 to 7 hours; And/or The temperature comprises a temperature in the range of 60 ℃ to 190 ℃, preferably 80 ℃ to 180 ℃, more preferably 120 ℃ to 180 ℃, and even more preferably 140 ℃ to 180 ℃.
5. 5. A method according to any of the preceding claims, wherein the method comprises step S2), and wherein preferably in step S2) Substantially neutralizing the reaction mixture from step S1) or substantially neutralizing the acid component present in the reaction mixture from step S1) by adding 0.8 to 1.2 molar equivalents of base relative to the molar amount of acid present in the reaction mixture at the beginning of step S1), Wherein preferably the base is selected from the group consisting of alkali metal hydroxides, preferably aqueous alkali metal hydroxides, alkaline earth metal hydroxides, preferably aqueous alkaline earth metal hydroxides, and mixtures thereof, More preferably, the base is selected from the group consisting of sodium hydroxide, preferably aqueous sodium hydroxide, potassium hydroxide, preferably aqueous potassium hydroxide, and mixtures thereof; And/or Substantially neutralising the reaction mixture from step S1) by adjusting the pH of the reaction mixture from step S1) to a value in the range of 6 to 8, preferably 6.5 to 7.5, preferably by adding a base to the reaction mixture from step S1), Wherein preferably the base comprises or is selected from the group consisting of alkali metal hydroxides, preferably aqueous alkali metal hydroxides, alkaline earth metal hydroxides, preferably aqueous alkaline earth metal hydroxides, and mixtures thereof, More preferably, the base is selected from the group consisting of sodium hydroxide, preferably aqueous sodium hydroxide, potassium hydroxide, preferably aqueous potassium hydroxide, and mixtures thereof.
6. 6. A method according to any one of the preceding claims, wherein in step S3) the temperature comprises a temperature in the range of 60 to 150 ℃, preferably 60 to 140 ℃, more preferably 70 to 130 ℃.
7. 7. A process according to any one of the preceding claims, wherein in step S3) the ruthenium-containing catalyst comprises or is ruthenium carbon.
8. 8. The method according to claim 7, wherein in step S3) The hydrogenation is carried out for a period of time in the range of 5 to 30 hours, preferably 5 to 28 hours, and more preferably 5 to 26 hours; And/or The hydrogen pressure comprises or is a pressure in the range of 6 to 18 MPa, preferably 6 to 16 MPa, and more preferably 6 to 10 MPa; And/or -The concentration of hydroxymethylfurfural in the reaction mixture comprising hydroxymethylfurfural from step S1) is equal to or greater than 5 wt%, preferably equal to or greater than 10 wt%, Or the concentration of hydroxymethylfurfural in the substantially neutralized reaction mixture comprising hydroxymethylfurfural from step S2) is ≡5-wt-%, preferably ≡10-wt-%, relative to the total weight of the substantially neutralized reaction mixture comprising hydroxymethylfurfural from step S2), And/or -The concentration of hydroxymethylfurfural in the reaction mixture comprising hydroxymethylfurfural from step S1) is in the range of from ≡5 wt-% -25 wt-%, more preferably from ≡5 wt-% -20 wt-%, and even more preferably from ≡10 wt-% -20 wt-%; Or the concentration of hydroxymethylfurfural in the substantially neutralized reaction mixture comprising hydroxymethylfurfural from step S2) is in the range of from≥5 wt to≥25 wt-%, more preferably from≥5 wt to≥20 wt-%, and even more preferably from≥10 wt to≥20 wt-%, relative to the total weight of the substantially neutralized reaction mixture comprising hydroxymethylfurfural from step S2); And/or The temperature comprises a temperature in the range of 60 ℃ to 140 ℃, preferably 70 ℃ to 130 ℃, and more preferably 70 ℃ to 90 ℃.
9. 9. The process according to any one of claims 1 to 6, wherein in step S3) the ruthenium-comprising catalyst comprises or is ruthenium oxide hydroxide, preferably ruthenium oxide-III-hydroxide.
10. 10. The method according to claim 9, wherein in step S3) The hydrogenation is carried out for a period of time in the range of 8 to 24 hours, preferably 8 to 18 hours, and more preferably 10 to 14 hours; And/or The hydrogen pressure comprises a pressure in the range of 8 to 18 MPa, preferably 10 to 18 MPa, and more preferably 12 to 16 MPa; And/or The temperature comprises a temperature in the range of 70 ℃ to 140 ℃, preferably 80 ℃ to 120 ℃, and more preferably 90 ℃ to 110 ℃.
11. 11. A method according to any one of the preceding claims, wherein the method comprises the further step of: S4) separating 2, 5-bis (hydroxymethyl) furan and/or 2, 5-bis (hydroxymethyl) tetrahydrofuran, preferably from the reaction mixture received after step S3).
12. 12. The process of claim 11, wherein separating 2, 5-bis (hydroxymethyl) furan and/or 2, 5-bis (hydroxymethyl) tetrahydrofuran comprises separating by distillation or evaporation, Preferably comprising the step of fractional distillation or fractional evaporation, Wherein preferably the separation is carried out by evaporation or by fractional evaporation, including thin film evaporation.
13. 13. The process according to any one of claims 11 to 12, wherein the catalyst used in step S3) -Comprising or being ruthenium carbon, and step S3) is carried out as defined in claim 8, wherein in step S4) 2, 5-bis (hydroxymethyl) tetrahydrofuran is isolated; Or (b) -Comprising or being a ruthenium oxide hydroxide, preferably ruthenium oxide-III-hydroxide, and step S3) is performed as defined in claim 10, wherein in step S4) 2, 5-bis (hydroxymethyl) furan is isolated.
14. 14. A substantially neutralized reaction mixture comprising hydroxymethylfurfural, obtained or obtainable by the process according to any one of claims 1 to 5, preferably as obtained in or after step S1) of the process according to any one of claims 1 to 5, wherein preferably the reaction mixture has a pH in the range of 6 to 8.
15. 15. The substantially neutralized reaction mixture according to claim 14, wherein in the process according to any one of claims 1 to 5, the reaction mixture in step S1) further comprises as the organic solvent an organic solvent selected from the group consisting of N-alkyl-2-pyrrolidone, preferably selected from the group consisting of N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, N-methylsuccinimide, 1, 3-dimethyl-2-imidazolidinone, dimethylformamide, N-dimethylformamide, dimethylpropyleneurea and mixtures thereof, Wherein more preferably the organic solvent is selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylsuccinimide, and mixtures thereof, Wherein even more preferably the organic solvent comprises or is N-methyl-2-pyrrolidone.
16. 16. A substantially neutralized reaction mixture comprising hydroxymethylfurfural according to any one of claims 14 or 15, or as obtained or obtainable by a process according to any one of claims 1 to 5 Use in a hydrogenation process for the manufacture of 2, 5-bis (hydroxymethyl) furan and/or 2, 5-bis (hydroxymethyl) tetrahydrofuran.
17. 17. Use of ruthenium oxide hydroxide, preferably ruthenium oxide-III-hydroxide, as hydrogenation catalyst in a process for hydrogenating hydroxymethylfurfural.

Description

Method for producing furan-based bis-hydroxymethyl compounds from mixtures comprising hydroxymethylfurfural and corresponding mixtures for use as intermediates The present invention relates to a process for the manufacture of furan-based bis-hydroxymethyl compounds from hydroxymethylfurfural, in particular from a mixture comprising hydroxymethylfurfural, and to a reaction mixture comprising hydroxymethylfurfural as obtainable by the process according to the invention, and to the use of the reaction mixture in a hydrogenation process for the manufacture of 2, 5-bis (hydroxymethyl) furan and/or 2, 5-bis (hydroxymethyl) tetrahydrofuran. Aldehydes from renewable sources, like hydroxymethylfurfural ("HMF") or furfural, are important intermediates for the synthesis of mono-and di-functionalized alcohols, carboxylic acids, amines and other derivatives. Thus, convenient access to such aldehydes is of particular interest to the chemical industry. Unfortunately, HMF and furfural in particular are thermodynamically and chemically unstable and very sensitive compounds. Because the compounds are prone to the formation of humins (humins), their isolation is often difficult and is associated with high material losses and low yields. For example, 2, 5-bis (hydroxymethyl) furan and 2, 5-bis (hydroxymethyl) tetrahydrofuran are attractive starting compounds for producing a wide range of polymers, such as polyesters, polyester polyols, alcohol alkoxylates, and other valuable polymer structures. The polymeric structures have the advantage of being derived from renewable raw materials and are typically biodegradable, which makes them extremely valuable for sustainable future products or applications. In the literature, several publications have been directed to processes for the production of furan-based bis-hydroxymethyl compounds: In document CN 103804329A, a process for the direct synthesis of 2, 5-bis (hydroxymethyl) furan or 2, 5-bis (hydroxymethyl) tetrahydrofuran from hexoses using a catalyst is discussed. Document WO 2014/033289 relates to the production of hydroxymethylfurfural from fructose. S. Fulignati et al in APPLIED CATALYSIS A General [ applied catalysis A, general theory ],578 (2019) 122-133 report the hydrogenation of 2-hydroxymethylfurfural to furandiol using Ru/C as a catalyst. An integrated process for producing 2, 5-dimethylolfuran from fructose is discussed in P. Upare et al, GREEN CHEMISTRY [ Green chemistry ] 17/6 (2015) 3310-3313. An integrated process for the production of 2, 5-dimethylolfuran and its polymers from fructose is reported by P.Upeare et al in GREEN CHEMISTRY [ Green chemistry ] 20/4 (2018) 879-885. Document KR 2017 0031269A relates to a process for the selective hydrogenation of hydroxymethylfurfural using a ruthenium nanoparticle supported catalyst. Document DE 21 32 547 A1 relates to a process for hydrogenating aromatic compounds to the corresponding cycloaliphatic compounds, which process involves a catalyst comprising ruthenium oxide hydroxide. However, in view of the prior art, there remains a need for a simple, robust and efficient process for preparing furan-based bis-hydroxymethyl compounds from hydroxymethylfurfural, in particular 2, 5-bis (hydroxymethyl) furan and/or 2, 5-bis (hydroxymethyl) tetrahydrofuran. Accordingly, the main object of the present invention is to provide a process for the manufacture of furan-based bis-hydroxymethyl compounds, in particular 2, 5-bis (hydroxymethyl) furan and/or 2, 5-bis (hydroxymethyl) tetrahydrofuran, in high yields, while the process for the manufacture of said compounds should be particularly simple and robust. It is a further object of the present invention to provide a mixture comprising an intermediate or starting compound which can be used directly in a hydrogenation process for the manufacture of furan-based bis-hydroxymethyl compounds, in particular 2, 5-bis (hydroxymethyl) furan and/or 2, 5-bis (hydroxymethyl) tetrahydrofuran, wherein as little effort as possible is required to purify or isolate the intermediate or starting compound from the mixture. It has now been found that the main and other objects of the present invention can be achieved by a process for the manufacture of furan-based bis-hydroxymethyl compounds from hydroxymethylfurfural, comprising the steps of: S1) reacting hexoses in a reaction mixture further comprising an acid, water and an organic solvent, At a temperature in the range of 50 ℃ to 200 ℃, And removing water from the reaction mixture, Thereby forming the hydroxymethylfurfural which is then separated from the aqueous solution, S2) preferably substantially neutralising the reaction mixture from step S1) or substantially neutralising the acid component present in the reaction mixture from step S1) preferably by adjusting the pH of the reaction mixture from step S1) to a value in the range of 6 to 8, To obtain a substantially neutralized reaction mixture comprising hydroxymethylfurfural, And S3) bringing into