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KR-20260066087-A - Process for converting cellulose and/or starch or a source thereof to 5-(chloromethyl)furfural

KR20260066087AKR 20260066087 AKR20260066087 AKR 20260066087AKR-20260066087-A

Abstract

A method for converting a composition containing cellulose and/or starch into 5-(chloromethyl)furfural (CMF) through multiple extractions using aqueous hydrochloric acid and an organic extraction solvent. The method can be carried out in a batch-wise and continuous fashion.

Inventors

  • 부에노 모론 호르헤
  • 그뤼터 헤라르두스 요하네스 마리아
  • 파로디 아드리아노
  • 반 클링크 헤라르두스 페트루스 마리아

Assignees

  • 아반티움 놀리지 센터 비.브이.

Dates

Publication Date
20260512
Application Date
20240805
Priority Date
20230904

Claims (15)

  1. A method for producing 5-(chloromethyl)furfural from a composition comprising cellulose and/or starch, wherein the method comprises the following steps: a. A step of mixing the above composition containing cellulose and/or starch as follows: - Aqueous composition containing hydrochloric acid with an HCl concentration of 18-42%, - Part 1 of the organic extraction solvent, b. A step of reacting the above mixture at a temperature of 60-120°C for 10 minutes to 3 hours, c. A step of separating the organic fraction containing the organic extraction solvent and 5-(chloromethyl)furfural from the remainder containing hydrochloric acid and an aqueous fraction containing cellulose and/or starch, d. A step of adding an additional portion of an organic extraction solvent to the aqueous fraction obtained in step c, mixing, and reacting for 10 minutes to 2 hours at a temperature 5-25°C higher than the temperature at which step b was performed. e. A step of separating the organic liquid fraction containing the organic extraction solvent and 5-(chloromethyl)furfural from the remainder, A method characterized in that, wherein the organic extraction solvent is selected such that less than 2 g of extraction solvent is used per 100 mL of an aqueous HCl solution at 20°C, and further wherein the organic extraction solvent is additionally selected such that at least 5 g of 5-(chloromethyl)furfural can be dissolved per 100 mL of the organic extraction solvent at 20°C.
  2. In claim 1, A method in which the HCl concentration of the aqueous composition containing hydrochloric acid of step a is 19-40 wt%, preferably 30-39 wt%, and more preferably 35-39 wt%.
  3. In claim 1 or 2, A method in which the weight ratio of cellulose and/or starch to aqueous hydrochloric acid in step a is 1:2 to 1:50, and preferably 1:5 to 1:30, for the composition of cellulose and/or starch to aqueous HCl.
  4. In any one of claims 1 to 3, A method in which the reaction time of the mixture in step d is shorter than the reaction time in step b.
  5. In any one of claims 1 to 4, A method in which the reaction temperature of the mixture in step b is 70-110°C, preferably 75-100°C.
  6. In any one of claims 1 to 5, A method in which lithium chloride is not added to the reaction mixture of step a.
  7. A method for producing 5-(chloromethyl)furfural from a composition comprising cellulose and/or starch, wherein the method comprises the following steps: I. Step of feeding the following mixture to a Continuous Stirred Tank Reactor (CSTR): - Feed composition containing cellulose and/or starch, - Aqueous feed containing hydrochloric acid with an HCl concentration of 18-42%, - Feed containing an organic extraction solvent, II. A step of reacting the above mixture at a temperature of 60-120°C, wherein the average residence time in the CSTR is 10 minutes to 3 hours to produce an effluent, III. A step of supplying the effluent of the CSTR to a first continuous extraction unit to produce the following: - A first organic extraction fraction comprising an organic extraction solvent and 5-(chloromethyl)furfural, - Aqueous phase fraction containing hydrochloric acid and cellulose and/or starch and/or carbohydrate oligomers, The above continuous extraction device operates at a temperature of 60-120°C, and the average residence time in the continuous extraction device is 10 minutes to 2 hours, IV. A step of supplying the aqueous fraction obtained in Step III to a second continuous extraction device and supplying an organic extraction solvent to the second continuous extraction device to produce the following: - A second organic extraction fraction comprising an organic extraction solvent and 5-(chloromethyl)furfural, - Aqueous phase fraction containing hydrochloric acid, The second continuous extraction device operates at a temperature 5-25°C higher than the operating temperature of the first continuous extraction device and has an average residence time, V. A step of purifying and/or further reacting 5-(chloromethyl)furfural present in the first and/or second organic extract fraction, A method characterized in that, wherein the organic extraction solvent is selected such that less than 2 g of extraction solvent is used per 100 mL of an aqueous HCl solution at 20°C, and further wherein the organic extraction solvent is additionally selected such that at least 5 g of 5-(chloromethyl)furfural can be dissolved per 100 mL of the organic extraction solvent at 20°C.
  8. In claim 7, A method in which the HCl concentration of the aqueous feed containing hydrochloric acid of step I is 19-40 wt%, preferably 30-39 wt%, and more preferably 35-39 wt%.
  9. In claim 7 or 8, A method characterized in that, in step I, the weight ratio of the aqueous feed containing cellulose and/or starch to hydrochloric acid is 1:2 to 1:50, and preferably 1:5 to 1:30, of the aqueous feed containing cellulose and/or starch to hydrochloric acid.
  10. In any one of claims 7 to 9, A method in which the average residence time of the second continuous extraction device in step IV is equal to or shorter than the sum of the average residence time of the CSTR and the average residence time of the first extraction device, and more preferably at least 10% shorter.
  11. In any one of claims 7 to 10, A method in which the reaction temperature in step II of the above mixture is 70-110°C, preferably 75-100°C.
  12. In any one of claims 7 to 11, A method in which, in step I, the volume ratio of an aqueous feed containing an organic extraction solvent to hydrochloric acid is 0.5:1 to 20:1, preferably 1:1 to 10:1, and/or in step III, the volume ratio of an aqueous phase fraction containing an organic extraction solvent to hydrochloric acid is 0.5:1 to 20:1, preferably 1:1 to 10:1.
  13. In any one of claims 7 to 12, A method in which a first continuous extraction device and/or a second continuous extraction device is a column for reactive extraction.
  14. In any one of claims 1 to 13, A method characterized in that the organic extraction solvent comprises a halogenated aromatic solvent, diisopropyl ether, ethyl acetate, pentane, hexane, heptane, octane, decane, dodecane, cyclohexane, benzene, toluene, xylene, chloroform, 1,2-dichloroethane, carbon tetrachloride, trichloromethane, and mixtures thereof.
  15. As a method according to claim 14, A method in which a halogenated aromatic extraction solvent is selected from the group consisting of: mono-chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-trichlorobenzene, mono-fluorobenzene, o-difluorobenzene, m-difluorobenzene, p-difluorobenzene, 1,2,4-trifluorobenzene, 1,3-dichloro-2-fluorobenzene, fluorotoluene, chlorotoluene, and mixtures thereof.

Description

Process for converting cellulose and/or starch or a source thereof to 5-(chloromethyl)furfural The present invention relates to a method for converting a source containing cellulose and/or starch into 5-(chloromethyl)furfural (hereinafter "CMF"). The CMF thus obtained may be further processed, for example, into 5-(hydroxymethyl)furfural (HMF), 5-alkoxymethylfurfural, 5-(acetoxymethyl)furfural, methylfurfural, or separated as CMF. Compound 5-(chloromethyl)furfural (CMF) is a promising compound for two reasons. First, it can be produced by treating carbohydrate-containing biomass (e.g., compounds derived from renewable sources) with hydrochloric acid, and second, it can be converted into various other compounds, such as HMF (hydroxymethylfurfural) and MMF (methoxymethylfurfural), which can be readily used in the chemical industry. Therefore, CMF is a bio-based material that offers options for manufacturing other compounds. Patent application WO2019/149843 discloses a method for treating a solid lignocellulose material, such as wood chips, with strong hydrochloric acid. Such lignocellulose material comprises hemicellulose, cellulose, and lignin as the main fractions. In the method of the said patent application, substantially dried lignocellulose material is first reacted with hydrochloric acid at a concentration of 15 to 40% at room temperature to hydrolyze and remove hemicellulose from the lignocellulose material, and then the hemicellulose fraction is removed from the reactor. Subsequently, the remaining material is reacted with hydrochloric acid at a strength of 40 to 51% at room temperature to hydrolyze and remove the cellulose fraction from the reactor, leaving a solid lignin residue in the reactor. The method continues by heating the obtained cellulose hydrolysate (containing hydrochloric acid along with carbohydrates such as glucose and glucose oligomers) to produce 5-(chloromethyl)furfural (CMF). The CMF thus obtained can be extracted with a solvent. However, this method requires a very high concentration (40-51%) of hydrochloric acid, which is disadvantageous from a general methodological perspective because cellulose has high resistance to hydrolysis. H.H. Szmant et al. (J. Chem. Tech. Biotechnol., 1981, 31, 205-212) reported that fructose and high-fructose corn syrups could be converted into CMFs with a yield of 90-95% using 39% HCl. For glucose, the yield was lower (30-45%), and for corn starch, it was even lower (14-20%). Fructose and high-fructose corn syrups share the commonality of being used for high-value applications in the food industry or serving as relatively expensive carbohydrate sources. In the case of glucose and corn starch, the yields were too low to be commercially attractive. M. Mascal et al. (Angew. Chem. Int. Ed. 2008, 47, 1-4) disclosed that microcrystalline cellulose can be converted to CMF with a conversion degree of 80% in the presence of 5% lithium chloride. Although CMF was the major product (71%), other byproducts were also present in significant amounts. The extraction time required was 18 hours. Lithium chloride is known to promote hydrolysis by disrupting the crystallinity of cellulose material. While the conversion degree is acceptable, the long time required is not suitable for commercial purposes. Furthermore, while the essential addition of lithium chloride may be permissible for research purposes, it is not attractive for commercial purposes as it becomes another compound that must be recovered from the aqueous phase, purified, and reused. Additionally, the methods described in the aforementioned literature disclose methods that are suitable for conducting research but are not attractive for the commercial production of CMF. Therefore, there is a need for a method that can produce CMF or a solution containing CMF in good yield, preferably in a continuous manner, without incurring the disadvantages of the aforementioned prior art methods. Cellulose and/or starch are known to be relatively difficult to hydrolyze by hydrochloric acid. Therefore, converting them into CMFs with good yields is a difficult challenge. While not bound by theory, the macromolecules of glucose (cellulose and starch) appear to possess regions of different internal crystallinity: some regions are more difficult to hydrolyze than others, and the accessibility to acid in these different regions is also not uniform throughout the material. Surprisingly, it was found that by starting a reaction at a low or medium temperature to hydrolyze the most accessible and less crystalline region, and after removing most or all of the generated CMF (i.e., after performing the reaction and extraction), a second reaction/extraction is then applied at a higher temperature, preferably for a shorter time, to hydrolyze even the portion of cellulose/starch that appears more difficult to decompose and less accessible. This is particularly important for cellulose, but it also applies to starch. It is not desirable to