Composition for converting 5-halomethylfurfural into 5-acetoxymethylfurfural or 2,5-furandicarboxylic acid, and method for preparing 5-bromomethylfurfural or 2,5-furandicarboxylic acid by using same

Abstract

The present invention relates to a composition for converting a 5-halomethylfurfural into 5-acetoxymethylfurfural or 2,5-furandicarboxylic acid, and a method for preparing 5-bromomethylfurfural or 2,5-furandicarboxylic acid by using same. More specifically, the present invention relates to a composition and a method for directly converting a 5-halomethylfurfural into 5-acetoxymethylfurfural by using a composition comprising a 5-halomethylfurfural and potassium acetate, provides a method for selectively recovering 5-acetoxymethylfurfural from a mixed solution containing 5-acetoxymethylfurfural and a process for preparing 5-acetoxymethylfurfural or 2,5-furandicarboxylic acid, comprising same, and relates to a method enabling direct conversion into 2,5-furandicarboxylic acid by using, as a reactant, 5-bromomethylfurfural which is a specific 5-halomethylfurfural.

Description

Composition for converting 5-halomethylfurfural to 5-acetoxymethylfurfural or 2,5-furandicarboxylic acid and method for producing 5-bromomethylfurfural or 2,5-furandicarboxylic acid using the same

[0001] The present invention relates to a composition for converting 5-halomethylfurfural into 5-acetoxymethylfurfural or 2,5-furandicarboxylic acid, and a method for producing 5-bromomethylfurfural or 2,5-furandicarboxylic acid using the same.

[0002] More specifically, the invention relates to a composition and method for directly converting 5-halomethylfurfural into 5-acetoxymethylfurfural using a composition containing 5-halomethylfurfural and potassium acetate, a method for selectively recovering 5-acetoxymethylfurfural from a mixed solution containing 5-acetoxymethylfurfural, and a process for producing 5-acetoxymethylfurfural or 2,5-furandicarboxylic acid containing the same, and a method capable of direct conversion to 2,5-furandicarboxylic acid using 5-bromomethylfurfural, a specific 5-halomethylfurfural, as a reactant.

[0003] Global warming and abnormal climate phenomena occurring worldwide are attributed primarily to the rapid increase in atmospheric carbon dioxide concentrations resulting from the excessive use of fossil fuels since industrialization. Consequently, research and development efforts are ongoing to identify and utilize renewable and sustainable resources as alternatives to fossil fuel-derived resources, which are the cause of global warming.

[0004] Unlike fossil fuels, whose reserves are concentrated in certain regions, plant and woody biomass, which are abundant on Earth, contains polysaccharide components such as lignin, cellulose, and hemicellulose. Monosaccharides, including glucose, galactose, and fructose, can be recovered from these polysaccharides. Since monosaccharides contain highly reactive hydroxyl groups (-OH), research and development is underway to utilize them as chemical raw materials useful for industry and daily life through various chemical reactions, or to manufacture high-value-added compounds.

[0005] 5-hydroxymethylfurfural, produced from the dehydration reaction of the sugar component of a monosaccharide, is widely known as a platform compound that can be converted into furan compounds. The 5-hydroxymethylfurfural can be converted into various derivatives including 2,5-furandicarboxylic acid (FDCA), 2,5-furandimethanol (FDM), 5-ethoxymethylfurfural (EMF), etc.

[0006] In particular, 2,5-furandicarboxylic acid (FDCA) is attracting attention as a platform compound that can be used to manufacture bio-based plastics, including Polyethylene Furanoate (PEF), by replacing terephthalic acid (TPA), a petroleum-based chemical produced in the existing AMOCO process, and can also be biodegradable upon disposal, thereby reducing carbon emissions and minimizing environmental pollution.

[0007] However, there were problems with 5-hydroxymethylfurfural converted from sugars, such as being easily converted into levulinic acid and formic acid through dehydration reactions or forming humins through aldol condensation reactions. To solve this, a technique is known to obtain the final form of 5-halomethylfurfural by using a two-phase solution system in which the 5-hydroxymethylfurfural is converted into 5-halomethylfurfural (XMF) through a reaction with a halogen compound such as a chlorine compound or a bromine compound, and then extracted using an organic solvent.

[0008] For example, Korean Patent Publication No. 10-2023-0133784 (published September 19, 2023) discloses a method for producing 5-acetoxymethylfurfural by dispersing biomass-derived 5-halomethylfurfural (XMF) in an organic solvent and then contacting it with an ion exchange resin. However, since ion exchange resins are expensive and the cost of regenerating them is also high, there is a significant economic burden for applying this to large-scale processes, and there is also a limitation in that it involves the regeneration and disposal processes of the ion exchange resin after use.

[0009] Meanwhile, Korean Registered Patent Publication No. 10-1487171 (published on January 29, 2015) discloses a method for economically producing 5-acetoxymethylfurfural by dispersing biomass-derived 5-halomethylfurfural (XMF) in an organic solvent and then reacting it with alkylammonium acetate. However, the aforementioned patent document 2 requires the use of an acetate that is easily soluble in an organic solvent as both a catalyst and a reactant, and the acetate salts of alkali metals or alkaline earth metals mentioned as potentially usable in combination are merely referred to as substitutes that are introduced in large quantities instead of alkylammonium acetate because they are cheaper than the expensive alkylammonium acetate.

[0010] The aforementioned prior art has disadvantages such as the use of expensive ion exchange resins or the participation of many types of reactants in the reaction, so there is still a demand for a simple and economical manufacturing process for 5-acetoxymethylfurfural that does not have such disadvantages.

[0011] Furthermore, since the 5-acetoxymethylfurfural generated as described above is discharged mixed with reaction by-products after the reaction, it is necessary to separate 5-acetoxymethylfurfural from these mixtures to obtain it. However, not much research has been conducted on the above separation method, and the current practice is to simply separate it through distillation. However, simple distillation can result in excessive energy consumption, and there may also be issues with the denaturation of acetoxymethylfurfural due to high temperatures during separation; therefore, research on separate separation technologies is required.

[0012] In particular, since the by-products added vary depending on the method of producing 5-acetoxymethylfurfural, the method of separating / purifying 5-acetoxymethylfurfural may vary depending on the method of producing 5-acetoxymethylfurfural, so it is necessary to develop individual separation / purification technologies according to the method of producing 5-acetoxymethylfurfural.

[0013] Meanwhile, a non-patent document regarding a conventional FDCA manufacturing method (Heng Ban et al. Kinetics and Mechanism of Catalytic Oxidation of 5-Methylfurfural to 2,5-Furandicarboxylic Acid with Co / Mn / Br Catalyst. Industrial & Engineering Chemistry Research. 2019, 58, 41, 19009~19021) discloses a route for manufacturing FDCA by oxidizing 5-hydroxymethylfurfural (HMF) or methylfurfural (MF), which are widely known as platform compounds convertible into furan compounds. In addition to the above HMF, various methylfurfural derivatives such as 2,5-furandimethanol (FDM), 5-methoxymethylfurfural (MMF), and 5-ethoxymethylfurfural (EMF) can be used to convert to FDCA.

[0014] Nevertheless, continuous research and development is necessary given the increasing need for technology capable of overcoming global carbon neutrality regulations and manufacturing high-value-added platform compounds such as FDCA in an eco-friendly manner.

[0015] The present invention aims to provide a method for producing 5-acetoxymethylfurfural in a simple and high yield on a homogeneous substrate and a composition for the same, and to provide a process for producing 5-acetoxymethylfurfural from a sugar component using the composition.

[0016] In addition, the present invention aims to provide a method for selectively separating and recovering 5-acetoxymethylfurfural from a mixed solution containing 5-acetoxymethylfurfural, potassium halide, potassium acetate, and humin.

[0017] In addition, the present invention aims to provide a process for producing 5-acetoxymethylfurfural from sugars including the above separation method, and furthermore, a process for producing 2,5-furandicarboxylic acid (2,5-furandicarboxylic acid) in a simple and high yield.

[0018] In addition, the present invention aims to provide a composition and a method for producing 2,5-furandicarboxylic acid from sugar components contained in lignocellulosic biomass, wherein 5-bromomethylfurfural (BMF) is reacted to directly convert and produce 2,5-furandicarboxylic acid.

[0019] To solve the above problem, the present invention provides a reaction composition for converting 5-halomethylfurfural into 5-acetoxymethylfurfural, characterized by being composed of 5-halomethylfurfural and potassium acetate.

[0020] In the composition of the present invention, the potassium acetate / 5-halomethylfurfural molar ratio may be 1 to 2, and 5-halomethylfurfural may be a component derived from the dehydration reaction of a sugar component contained in biomass.

[0021] In addition, the present invention provides a method for producing 5-acetoxymethylfurfural, characterized by maintaining a mixture of 5-halomethylfurfural and potassium acetate (KOAc) within a predetermined temperature range so that the 5-halomethylfurfural is converted into 5-acetoxymethylfurfural.

[0022] In the method for producing 5-acetoxymethylfurfural of the present invention, the potassium acetate / 5-halomethylfurfural molar ratio in the mixture may be 1 to 2, the 5-halomethylfurfural may be a component derived from the dehydration reaction of a sugar component contained in biomass, and the predetermined temperature range may be a range selected from 25 ℃ to 150 ℃.

[0023] In addition, the present invention provides a process for producing 5-acetoxymethylfurfural from a sugar component, characterized by comprising: (a) a step of preparing a mixed solution in which an aqueous solution containing a sugar component, an acid component, and a halogen ion precursor and an extraction organic solvent are mixed in a reactor; (b) a step of performing a dehydration reaction by raising the temperature of the mixed solution and then separating it into an aqueous phase and an organic phase to recover the organic phase in which 5-halomethylfurfural is dissolved; (c) a step of obtaining a mixed solution composed of 5-halomethylfurfural and potassium acetate by adding potassium acetate to the organic phase in which 5-halomethylfurfural is dissolved and then removing the organic solvent through distillation; and (d) a step of producing 5-acetoxymethylfurfural by maintaining the mixed solution within a predetermined temperature range.

[0024] In the process of producing 5-acetoxymethylfurfural from a sugar component of the present invention, the sugar component of step (a) may be derived from biomass, the potassium acetate / 5-halomethylfurfural molar ratio of step (d) may be 1 to 2, and the temperature range may be selected from 25 to 150 ℃.

[0025] In addition, the present invention provides an extractant for selectively extracting 5-acetoxymethylfurfural, characterized by comprising an organic solvent having a relative polarity of 0.3 or less based on the polarity of water of 1, for selectively extracting 5-acetoxymethylfurfural from a mixed solution containing 5-acetoxymethylfurfural, potassium halide, potassium acetate, and humins.

[0026] In the present invention, the mixed solution may be the product of a reaction in which a solution composed of 5-halomethylfurfural and potassium acetate is heated to produce 5-acetoxymethylfurfural, and the organic solvent may be used in a molar amount of 5 to 100 times the molar amount of 5-acetoxymethylfurfural.

[0027] In addition, the present invention provides a method for selectively separating 5-acetoxymethylfurfural from a mixed solution comprising 5-acetoxymethylfurfural, potassium halide, potassium acetate, and humins, characterized by separating 5-acetoxymethylfurfural by adding an extractant containing an organic solvent having a relative polarity of 0.3 or less relative to the polarity of water of 1 to the mixed solution to selectively dissolve 5-acetoxymethylfurfural.

[0028] In the selective separation method of 5-acetoxymethylfurfural of the present invention, the mixed solution may be the product of a reaction in which a solution composed of 5-halomethylfurfural and potassium acetate is heated to produce 5-acetoxymethylfurfural, and the organic solvent may be used in a molar amount of 5 to 100 times the molar amount of 5-acetoxymethylfurfural.

[0029] In addition, the present invention comprises the steps of: (a) preparing a mixed solution in which an aqueous solution containing a sugar component, an acid component, and a halogen ion precursor is mixed with a first extraction solvent in a reactor; (b) performing a dehydration reaction by raising the temperature of the mixed solution, and then separating it into an aqueous phase and an organic phase to recover the organic phase in which 5-halomethylfurfural is dissolved; (c) obtaining a mixed solution composed of 5-halomethylfurfural and potassium acetate by adding potassium acetate to the organic phase in which 5-halomethylfurfural is dissolved and then removing the organic solvent through distillation; and (d) obtaining a reaction product containing 5-acetoxymethylfurfural by maintaining the mixed solution within a predetermined temperature range. and (e) a step of mixing a second extraction solvent into a reaction product solution containing the 5-acetoxymethylfurfural and selectively dissolving and recovering the 5-acetoxymethylfurfural with the second extraction solvent; the present invention provides a process for producing 5-acetoxymethylfurfural from a sugar component, characterized by comprising: (e) a second extraction solvent mixed with a reaction product solution containing the 5-acetoxymethylfurfural to selectively dissolve and recover the 5-acetoxymethylfurfural in the second extraction solvent.

[0030] In the process for producing 5-acetoxymethylfurfural from a sugar component of the present invention, the sugar component of step (a) may be derived from biomass, the first extraction solvent in step (a) and the second extraction solvent in step (e) may be one or more selected from organic solvents having a relative polarity of 0.3 or less based on the polarity of water 1, and the selective extraction in step (e) may be performed at 0 ℃ to 50 ℃.

[0031] In addition, the present invention comprises the steps of: (a) preparing a mixed solution comprising an aqueous solution containing a sugar component, an acid component, and a halogen ion precursor in a reactor; and a first extraction solvent; (b) performing a dehydration reaction by raising the temperature of the mixed solution, and then separating it into an aqueous phase and an organic phase to recover the organic phase in which 5-halomethylfurfural is dissolved; (c) obtaining a mixed solution composed of 5-halomethylfurfural and potassium acetate by adding potassium acetate to the organic phase in which 5-halomethylfurfural is dissolved and then removing the organic solvent through distillation; (d) obtaining a reaction product containing 5-acetoxymethylfurfural by maintaining the mixed solution within a predetermined temperature range; and (e) mixing a second extraction solvent into the reaction product solution containing 5-acetoxymethylfurfural to selectively dissolve and recover 5-acetoxymethylfurfural in the second extraction solvent. and (f) a step of obtaining 2,5-furandicarboxylic acid by oxidizing the recovered 5-acetoxymethylfurfural; the present invention provides a process for producing 2,5-furandicarboxylic acid from a sugar component, characterized by comprising: (f) a step of obtaining 2,5-furandicarboxylic acid by oxidizing the recovered 5-acetoxymethylfurfural.

[0032] In the process of producing 2,5-furandicarboxylic acid from the above sugar component, the first extraction solvent in step (a) and the second extraction solvent in step (e) may be one or more selected from organic solvents having a relative polarity of 0.3 or less based on the polarity of water 1.

[0033] In addition, the present invention can provide a composition for directly converting 5-bromomethylfurfural into 2,5-furandicarboxylic acid, characterized by comprising 5-bromomethylfurfural, acetic acid, and an oxidation catalyst.

[0034] As an example of the present invention, the 5-bromomethylfurfural may be a component derived from the dehydration reaction of a sugar component contained in biomass, and the oxidation catalyst may include cobalt (Co) and manganese (Mn).

[0035] In addition, the present invention can provide a method for directly converting 5-bromomethylfurfural to 2,5-furandicarboxylic acid.

[0036] The above method may be characterized by supplying 5-bromomethylfurfural (BMF) to an acetic acid solution containing an oxidation catalyst, and then reacting it under an oxidizing atmosphere to directly convert it into 2,5-furandicarboxylic acid.

[0037] The oxidation catalyst may include cobalt (Co) and manganese (Mn), and the precursors of the cobalt and manganese may each be selected from acetate salts, bromine salts, and mixtures thereof.

[0038] As an example of the present invention, the Co / Mn molar ratio of the catalyst may be 10 to 100.

[0039] The above 5-bromomethylfurfural solution may have a concentration of 5-bromomethylfurfural of 1 to 20 wt%.

[0040] The above oxidizing atmosphere can be formed by injecting O2 at a pressure of 2 to 20 bar, and the reaction can be carried out at a temperature of 100 to 180 ℃.

[0041] In addition, the present invention can provide a process for producing 2,5-furandicarboxylic acid from sugar components.

[0042] The manufacturing process of 2,5-furandicarboxylic acid according to the present invention may be characterized by comprising: (a) a step of preparing a mixed solution comprising an aqueous solution containing a sugar component, an acid component, and a bromide ion precursor; and an extraction organic solvent; (b) a step of performing a dehydration reaction by raising the temperature of the mixed solution, and then separating it into an aqueous phase and an organic phase to recover the organic phase in which 5-bromomethylfurfural is dissolved; (c) a step of removing the organic solvent by distilling the organic phase in which 5-bromomethylfurfural is dissolved, and then adding acetic acid to obtain an acetic acid solution in which 5-bromomethylfurfural is dissolved; and (d) a step of adding the acetic acid solution in which 5-bromomethylfurfural is dissolved to an aqueous solution in which a cobalt (Co) precursor and a manganese (Mn) precursor are dissolved in water, and then raising the temperature to perform a reaction to produce 2,5-furandicarboxylic acid.

[0043] The sugar component of step (a) above may be derived from lignocellulosic biomass.

[0044] The composition of the present invention, consisting of 5-halomethylfurfural and potassium acetate, has the advantage of being able to produce 5-acetoxymethylfurfural in a high yield in a simple and economical manner in a homogeneous phase.

[0045] In addition, the 5-acetoxymethylfurfural manufacturing process according to the present invention produces 5-acetoxymethylfurfural by utilizing sugars derived from biomass, which is a sustainable resource, so 5-acetoxymethylfurfural can be manufactured from sugars in a batch and is environmentally friendly.

[0046] According to another aspect of the present invention, only the 5-acetoxymethylfurfural component can be selectively recovered from a solution composed of acetoxymethylfurfural, potassium halide, potassium acetate, and humin using an extraction organic solvent.

[0047] In addition, an economical process can be provided to produce 2,5-furandicarboxylic acid in high yield by oxidizing 5-acetoxymethylfurfural or further the 5-acetoxymethylfurfural produced above.

[0048] In addition, the manufacturing process for 5-acetoxymethylfurfural or 2,5-furandicarboxylic acid is environmentally friendly because it uses sugars derived from biomass, a sustainable resource, as raw materials, and can provide an integrated process from sugar to final product.

[0049] According to another aspect of the present invention, there is an advantage in that 5-bromomethylfurfural can be directly converted and produced into 2,5-furandicarboxylic acid by reacting it, and since the 5-bromomethylfurfural can be produced from sugar components contained in lignocellulosic biomass, which is a sustainable resource, 2,5-furandicarboxylic acid can be produced in an environmentally friendly manner.

[0050] In addition, the reaction product, 2,5-furandicarboxylic acid, is in a solid crystalline state, so it is easy to separate from unreacted 5-bromomethylfurfural and by-products, which has the advantage of allowing the recovery of high-purity 2,5-furandicarboxylic acid.

[0051] FIGS. 1 and 2 show the 5-halomethylfurfural conversion rate and 5-acetoxymethylfurfural yield according to the methods of Example 1, Example 2, Comparative Example 1, and Comparative Example 2.

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by a skilled expert in the art to which this invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.

[0053] Throughout this specification, when a part is described as “comprising” a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0054] Hereinafter, we will examine the composition and method for manufacturing 5-acetoxymethylfurfural of the present invention.

[0055] The applicant has confirmed that in a reaction to convert 5-halomethylfurfural into 5-acetoxymethylfurfural, when potassium acetate is selected among acetate salts and the acetoxylation reaction is performed, the yield of 5-acetoxymethylfurfural is significantly improved even by a simple method, and accordingly, the composition for producing 5-acetoxymethylfurfural of the present invention may be characterized by being composed of 5-halomethylfurfural and potassium acetate.

[0056] In addition, unlike the heterogeneous derivatization reaction using an ion exchange resin as described in the aforementioned Korean Patent Publication No. 10-2023-0133784, the composition of the present invention allows potassium acetate, another reactant, to be dissolved and uniformly dispersed in 5-halomethylfurfural, which is both a solvent and a reactant in a liquid state, thereby enabling the production of 5-acetoxymethylfurfural in a homogeneous phase. This eliminates the need for expensive ion exchange resins and does not entail the regeneration and disposal processes of the ion exchange resins after use. Furthermore, since a reaction in a homogeneous liquid phase is possible, it has the advantage of being advantageous for establishing large-scale processes.

[0057] In the above composition, the potassium acetate / 5-halomethylfurfural molar ratio may be in the range of 1 to 2. If the molar ratio is less than 1, the amount of potassium acetate relative to 5-halomethylfurfural is small in terms of stoichiometry, so the conversion rate of 5-halomethylfurfural and the yield and conversion speed of 5-acetoxymethylfurfural may be lowered, and if the molar ratio is greater than 2, the effect of improving the yield and conversion speed of 5-acetoxymethylfurfural is negligible, while the excessive use of potassium acetate may lead to an increase in process costs.

[0058] The above 5-halomethylfurfural may be a component derived from the dehydration reaction of sugar components contained in biomass, for example, it may be a component produced by combining 5-hydroxymethylfurfural generated by the dehydration reaction of sugar components in an aqueous environment with a halogen ion.

[0059] In addition, the present invention provides a method for producing 5-acetoxymethylfurfural. The method for producing 5-acetoxymethylfurfural according to the present invention may be characterized by maintaining a reaction mixture composed of 5-halomethylfurfural and potassium acetate within a predetermined temperature range to perform a reaction that converts it into 5-acetoxymethylfurfural.

[0060] The above 5-halomethylfurfural is a reactant of a reaction that converts to 5-acetoxymethylfurfural, and may be a component derived from the dehydration reaction of a sugar component contained in biomass, for example, it may be a component produced by combining 5-hydroxymethylfurfural generated by the dehydration reaction of a sugar component in an aqueous environment with a halogen ion.

[0061] The heating above can be performed in a temperature range of 25 to 150 ℃, preferably 50 to 130 ℃. If the temperature is below 25 ℃, the yield and conversion rate of 5-acetoxymethylfurfural may be slowed down, and if it exceeds 150 ℃, 5-halomethylfurfural may be thermally decomposed.

[0062] Stirring may be performed to ensure uniform mixing of the reactants before or during heating the above reaction mixture, and there are no limitations on the stirring method, and a known stirring device may be used.

[0063] In addition, the present invention may provide a process for producing 5-acetoxymethylfurfural from a sugar component. The process for producing 5-acetoxymethylfurfural from the sugar component may be characterized by comprising: (a) a step of preparing a mixed solution in which an aqueous solution containing a sugar component, an acid component, and a halogen ion precursor and an extraction organic solvent are mixed in a reactor; (b) a step of increasing the temperature of the mixed solution to perform a dehydration reaction, and then separating it into an aqueous phase and an organic phase to recover the organic phase in which 5-halomethylfurfural is dissolved; (c) a step of obtaining a mixed solution composed of 5-halomethylfurfural and potassium acetate by adding potassium acetate to the organic phase in which 5-halomethylfurfural is dissolved and then removing the organic solvent through distillation; and (d) a step of producing 5-acetoxymethylfurfural by maintaining the mixed solution within a predetermined temperature range.

[0064] Step (a) above is a step of preparing a two-phase mixed solution comprising a sugar component, an aqueous acid solution that induces a dehydration reaction of the sugar component, and a halogen ion precursor as a halogen source for 5-halomethylfurfural, and also an extraction organic solvent for easily extracting 5-halomethylfurfural.

[0065] The sugar component of step (a) above is a raw material component that can be converted into 5-hydroxymethylfurfural through a dehydration reaction, and may be derived from biomass, and may be one or more of, for example, monosaccharides including glucose, fructose, and galactose; disaccharides including maltose, sucrose, and lactose; polysaccharides including starch including hexoses, cellulose, and hemicellulose; and preferably one or more of glucose and cellulose. The concentration of the sugar component may be in the range of 0.01 to 30 wt%.

[0066] The above acid component is intended to induce a dehydration reaction of the above sugar component and may be selected from inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, hydrofluoric acid, boric acid, and organic acids such as acetic acid, lactic acid, olsalic acid, salicylic acid, and pyruvate, but preferably one or more selected from sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, etc., and more preferably may be sulfuric acid.

[0067] The above halogen ion precursor is not limited to any material capable of generating a halogen ion that produces 5-halomethylfurfural by ion-exchanging with the proton of 5-hydroxymethylfurfural, which is produced by dehydrating a sugar component by an acid component.

[0068] The above halogen is one or more selected from chlorine, bromine, and iodine, and the above halogen precursor is, for example, chlorine (Cl2), lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), rubidium chloride (RbCl), cesium chloride (CsBr), calcium chloride (CaCl2), magnesium chloride (MgCl2), strontium chloride (SrCl2), barium chloride (BaCl2), hydrogen chloride (HCl), zinc chloride (ZnCl2), aluminum chloride (AlCl3); Bromine (Br2), lithium bromide (LiBr), sodium bromide (NaBr), potassium bromide (KBr), rubidium bromide (RbBr), cesium bromide (CsBr), calcium bromide (CaBr2), magnesium bromide (MgBr2), strontium bromide (SrBr2), barium bromide (BaBr2), hydrogen bromide (HBr), zinc bromide (ZnBr2), aluminum bromide (AlBr3); It may be selected from iodine (Br2), lithium iodide (LiI), sodium iodide (NaI), potassium iodide (KI), rubidium iodide (RbI), cesium iodide (CsI), calcium iodide (CaI2), magnesium iodide (MgI2), strontium iodide (SrI2), barium iodide (BaI2), hydrogen iodide (HI), zinc iodide (ZnI2), aluminum iodide (AlI3), etc.

[0069] The above extraction organic solvent is a solvent used to extract 5-hydroxymethylfurfural after converting it into halogen-bound 5-halomethylfurfural in order to prevent 5-hydroxymethylfurfural obtained from biomass from being converted into levulinic acid, etc., and it is preferable to use one having a relative polarity of 0.3 or less based on the polarity of water of 1.

[0070] Examples of the above-mentioned extraction organic solvents may include one or more of toluene, xylene, chlorobenzene, cyclohexane, pentane, hexane, heptane, methyl t-butyl ether, diethylamine, dioxane, and N,N-dimethylaniline, and preferably, one or more of toluene, xylene, and chlorobenzene may be used from the perspective of environmental hazards and solvent recovery.

[0071] In the mixed two-phase solution obtained by the above organic solvent and aqueous solution, the volume ratio of the organic phase to the aqueous phase may be in the range of 2 to 10.

[0072] Step (b) above is a step in which a dehydration reaction is performed on the sugar component in the two-phase mixed solution of Step (a) to finally produce 5-halomethylfurfural via 5-hydroxymethylfurfural, the produced 5-halomethylfurfural is dissolved in an extractive organic solvent and moves from the aqueous phase to the organic phase, and the organic phase is recovered through phase separation.

[0073] The reaction in step (b) above is not limited to this but may be operated at a temperature in the range of 80°C to 160°C and may be operated under reflux conditions of an organic solvent at atmospheric pressure. If the temperature is below 80°C, there may be a problem with the dehydration reaction rate being negligible, and if the temperature is above 160°C, there may be a problem with the over-decomposition reaction being promoted. In addition, in step (b) above, stirring may be performed on the two-phase solution to expand the interface where the dehydration reaction occurs in order to improve the reaction rate and yield.

[0074] Step (c) above is a step of obtaining a mixed solution of 5-halomethylfurfural and potassium acetate by performing distillation to remove the extraction organic solvent contained in the organic phase in which 5-halomethylfurfural is dissolved. The potassium acetate introduced in step (c) contributes to suppressing the decomposition of 5-halomethylfurfural or the occurrence of side reactions during distillation by neutralizing hygroscopic and acidic byproducts to prevent the decomposition of 5-halomethylfurfural.

[0075] The above distillation is not limited thereto, but preferably may be accompanied by a heating step under vacuum at a reaction temperature below the boiling point of the organic solvent, and the heating may be performed in the range of 50°C to 100°C. When performed in the above temperature range, the use of excessive energy or the thermal decomposition of 5-halomethylfurfural can be reduced and the organic solvent can be removed.

[0076] Step (d) above is a step in which a reaction is performed to produce 5-acetoxymethylfurfural by maintaining the mixed solution, from which the extraction organic solvent has been removed in Step (c), at a predetermined temperature, so that the halogen ions of 5-halomethylfurfural are exchanged with the acetate ions of potassium acetate.

[0077] The potassium acetate / 5-halomethylfurfural molar ratio in step (d) may be 1 to 2. When within this range, it is desirable in terms of improving the yield and conversion rate of 5-acetoxymethylfurfural.

[0078] Step (d) above can be performed in the range of 25 ℃ to 150 ℃, preferably 50 ℃ to 130 ℃. If the temperature is below 25 ℃, the yield and conversion rate of 5-acetoxymethylfurfural may be slowed, and if it is above 150 ℃, 5-halomethylfurfural may be thermally decomposed.

[0079] As an example of the present invention, following step (d) above, a known method for selectively extracting and recovering 5-acetoxymethylfurfural may be performed without limitation.

[0080] In addition, the present invention can provide an extractant and a method for selectively dissolving and separating 5-acetoxymethylfurfural.

[0081] The extractant according to the present invention selectively dissolves and separates 5-acetoxymethylfurfural from a mixed solution containing 5-acetoxymethylfurfural, potassium halide, potassium acetate, and humin, and it is preferable to use one having a relative polarity of 0.3 or less based on the polarity of water of 1.

[0082] Examples of the above-mentioned extraction organic solvents include, but are not limited to, one or more organic solvents selected from toluene, xylene, chlorobenzene, cyclohexane, pentane, hexane, heptane, alkyl ether, diethylamine, dioxane, and N,N-dimethylaniline, and preferably, it is suitable to use an alkyl ether-based organic solvent with a low boiling point that facilitates the recovery of the organic solvent after extraction.

[0083] At this time, the organic solvent may be used in a range of 5 to 100 moles per mole of the 5-acetoxymethylfurfural, preferably 10 to 50 moles. If the organic solvent is used in an amount less than 5 moles, the extraction of 5-acetoxymethylfurfural may be insufficient or it may be difficult to separate the organic solvent from the insoluble precipitate, and if it is used in an amount greater than 100 moles, economic efficiency may be reduced because excessive energy must be used to recover the 5-acetoxymethylfurfural from the organic solvent.

[0084] In addition, the above mixed solution may be characterized as being a reaction product of a reaction in which 5-halomethylfurfural is converted into 5-acetoxymethylfurfural by heating a composition consisting of 5-halomethylfurfural and potassium acetate.

[0085] In the above composition, the molar ratio of potassium acetate / 5-halomethylfurfural may be in the range of 1 to 2. If the molar ratio is less than 1, the amount of potassium acetate relative to 5-halomethylfurfural is small in terms of stoichiometry, so the conversion rate of 5-halomethylfurfural and the yield and conversion speed of 5-acetoxymethylfurfural may be lowered, and if the molar ratio is greater than 2, the effect of improving the yield and conversion speed of 5-acetoxymethylfurfural is negligible, while the excessive use of potassium acetate may lead to an increase in process costs.

[0086] The above 5-halomethylfurfural may be a component derived from the dehydration reaction of sugar components contained in biomass, for example, it may be a component produced by combining 5-hydroxymethylfurfural generated by the dehydration reaction of sugar components in an aqueous environment with a halogen ion.

[0087] In addition, the present invention provides a method for selectively separating 5-acetoxymethylfurfural from a mixed solution comprising 5-acetoxymethylfurfural, potassium halide, potassium acetate, and humins, characterized by separating 5-acetoxymethylfurfural by adding an extractant containing one or more organic solvents selected from organic solvents having a relative polarity of 0.3 or less based on the polarity of water of 1 to the mixed solution, thereby allowing 5-acetoxymethylfurfural to be selectively dissolved in the extractant.

[0088] Organic solvents having a relative polarity of 0.3 or less based on the polarity of water 1 may include, but are not limited to, toluene, xylene, chlorobenzene, cyclohexane, pentane, hexane, heptane, alkyl ether, diethylamine, dioxane, N,N-dimethylaniline, etc.

[0089] In the selective separation method of 5-acetoxymethylfurfural of the present invention, the content of the organic solvent introduced can be used in a molar amount of 5 to 100 times, preferably 10 to 50 times, the molar amount per mole of 5-acetoxymethylfurfural.

[0090] After adding the above organic solvent, stirring may be performed to promote the dissolution extraction of 5-acetoxymethylfurfural, and after adding the above extractant, stirring may be performed to expand the interface where extraction occurs in order to improve extraction efficiency. The stirring is not limited to any commonly used stirring means, and for example, a stirrer, ultrasound, etc. may be used.

[0091] In addition, after the addition of the extractant, selective dissolution of 5-acetoxymethylfurfural by the extractant can be performed in the range of 0 ℃ to 50 ℃. If the temperature is below 0 ℃, the extraction of 5-acetoxymethylfurfural may be insufficient, and if it exceeds 50 ℃, potassium halides, potassium acetate, and humins may also be dissolved in addition to 5-acetoxymethylfurfural.

[0092] In addition, the present invention provides a process for producing 5-acetoxymethylfurfural from a sugar component including the method for selectively separating 5-acetoxymethylfurfural.

[0093] The process for producing 5-acetoxymethylfurfural according to the present invention comprises: (a) a step of preparing a mixed solution in which an aqueous solution containing a sugar component, an acid component, and a halogen ion precursor is mixed with a first organic solvent in a reactor; (b) a step of performing a dehydration reaction by raising the temperature of the mixed solution, and then separating it into an aqueous phase and an organic phase to recover the organic phase in which 5-halomethylfurfural is dissolved; (c) a step of obtaining a mixed solution composed of 5-halomethylfurfural and potassium acetate by adding potassium acetate to the organic phase in which 5-halomethylfurfural is dissolved and then removing the organic solvent through distillation; and (d) a step of obtaining a reaction product containing 5-acetoxymethylfurfural by maintaining the mixed solution within a predetermined temperature range. and (e) a step of mixing a second organic solvent into a reaction product solution containing 5-acetoxymethylfurfural to selectively dissolve and recover 5-acetoxymethylfurfural in the second organic solvent; may be characterized by including.

[0094] Step (a) above is a step of preparing a two-phase mixed solution comprising a sugar component, an aqueous acid solution that induces a dehydration reaction of the sugar component, and a halogen ion precursor as a halogen source of 5-halomethylfurfural, and also a first organic solvent for easily extracting 5-halomethylfurfural.

[0095] The sugar component of step (a) above is a raw material component that can be converted into 5-hydroxymethylfurfural through a dehydration reaction, and may be derived from biomass, and may be one or more of, for example, monosaccharides including glucose, fructose, and galactose; disaccharides including maltose, sucrose, and lactose; polysaccharides including starch including hexoses, cellulose, and hemicellulose; and preferably one or more of glucose and cellulose. The concentration of the sugar component may be in the range of 0.01 to 30 wt%.

[0096] The above acid component is intended to induce a dehydration reaction of the above sugar component and may be selected from inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, hydrofluoric acid, boric acid, and organic acids such as acetic acid, lactic acid, olsalic acid, salicylic acid, and pyruvate, but preferably one or more selected from sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, etc., and more preferably may be sulfuric acid.

[0097] The above halogen ion precursor is not limited to any material capable of generating a halogen ion that produces 5-halomethylfurfural by ion-exchanging with the proton of 5-hydroxymethylfurfural, which is produced by dehydrating a sugar component by an acid component. The above halogen is one or more selected from chlorine, bromine, and iodine, and the above halogen precursor is, for example, chlorine (Cl2), lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), rubidium chloride (RbCl), cesium chloride (CsBr), calcium chloride (CaCl2), magnesium chloride (MgCl2), strontium chloride (SrCl2), barium chloride (BaCl2), hydrogen chloride (HCl), zinc chloride (ZnCl2), aluminum chloride (AlCl3), bromine (Br2), lithium bromide (LiBr), sodium bromide (NaBr), potassium bromide (KBr), rubidium bromide (RbBr), cesium bromide (CsBr), calcium bromide (CaBr2), magnesium bromide (MgBr2), strontium bromide (SrBr2), barium bromide (BaBr2). It may be selected from hydrogen bromide (HBr), zinc bromide (ZnBr2), aluminum bromide (AlBr3); iodine (Br2), lithium iodide (LiI), sodium iodide (NaI), potassium iodide (KI), rubidium iodide (RbI), cesium iodide (CsI), calcium iodide (CaI2), magnesium iodide (MgI2), strontium iodide (SrI2), barium iodide (BaI2), hydrogen iodide (HI), zinc iodide (ZnI2), aluminum iodide (AlI3), etc.

[0098] The above first organic solvent is an organic solvent that converts 5-hydroxymethylfurfural obtained from biomass into 5-halomethylfurfural bound to a halogen and then extracts it, in order to prevent 5-hydroxymethylfurfural obtained from biomass from being converted into levulinic acid, etc., and it is preferable to use one having a relative polarity of 0.3 or less based on the polarity of water of 1.

[0099] Examples of the first organic solvent mentioned above may include one or more of toluene, xylene, chlorobenzene, cyclohexane, pentane, hexane, heptane, methyl t-butyl ether, diethylamine, dioxane, and N,N-dimethylaniline, and preferably, one or more of toluene, xylene, and chlorobenzene may be used from the perspective of environmental hazards and solvent recovery.

[0100] In the mixed two-phase solution obtained by the first organic solvent and the aqueous solution, the volume ratio of the organic phase to the aqueous phase may be in the range of 2 to 10.

[0101] Step (b) above is a step in which a dehydration reaction is performed on the sugar component in the two-phase mixed solution of Step (a) to finally produce 5-halomethylfurfural via 5-hydroxymethylfurfural, the produced 5-halomethylfurfural is dissolved in a first organic solvent and moves from the aqueous phase to the organic phase, and the organic phase is recovered through phase separation.

[0102] The reaction in step (b) above is not limited thereto but can be operated in a range of 80°C to 160°C and can be operated under reflux conditions of the first organic solvent at atmospheric pressure. If the temperature is below 80°C, there is a problem that the dehydration reaction rate is negligible, and if the temperature is above 160°C, there is a problem that the over-decomposition reaction is promoted. In addition, in step (b) above, stirring may be performed on the two-phase solution to expand the interface where the dehydration reaction occurs in order to improve the reaction rate and yield.

[0103] Step (c) above is a step of adding potassium acetate to an organic phase in which 5-halomethylfurfural is dissolved, and performing distillation to remove the included first organic solvent to obtain a mixed solution of 5-halomethylfurfural and potassium acetate. The potassium acetate added in step (c) contributes to suppressing the decomposition of 5-halomethylfurfural or side reactions during distillation by neutralizing hygroscopic and acidic byproducts to prevent the decomposition of 5-halomethylfurfural. The amount of potassium acetate added may be such that the potassium acetate / 5-halomethylfurfural molar ratio is in the range of 1 to 2. If the above molar ratio is less than 1, the amount of potassium acetate relative to 5-halomethylfurfural is small in terms of stoichiometry, so the conversion rate of 5-halomethylfurfural and the yield and conversion speed of 5-acetoxymethylfurfural may be lowered, and if the above molar ratio is greater than 2, the effect of improving the yield and conversion speed of 5-acetoxymethylfurfural is negligible, while the excessive use of potassium acetate may lead to an increase in process costs.

[0104] The above distillation is not limited thereto, but preferably may be accompanied by a heating step under vacuum, and the heating may be performed in the range of 50°C to 100°C. When performed in the above temperature range, excessive energy use or thermal decomposition of 5-halomethylfurfural can be reduced and organic solvents can be removed.

[0105] Step (d) above is a step in which a reaction is performed to produce 5-acetoxymethylfurfural by maintaining the mixed solution, from which the first organic solvent has been removed in Step (c), at a predetermined temperature, so that the halogen ions of 5-halomethylfurfural are exchanged with the acetate ions of potassium acetate.

[0106] Step (d) above can be performed in the range of 25 ℃ to 150 ℃, preferably 50 ℃ to 130 ℃. If the temperature is below 25 ℃, the yield and conversion rate of 5-acetoxymethylfurfural may be slowed down, and if it is above 150 ℃, 5-halomethylfurfural may be thermally decomposed, so it is desirable to perform it within the above temperature range in terms of yield.

[0107] Step (e) is a step of mixing a second organic solvent with the reaction product solution produced in Step (d) to selectively dissolve and recover 5-acetoxymethylfurfural in the second organic solvent phase. In addition to 5-acetoxymethylfurfural, the reaction product solution may contain unreacted potassium acetate (KOAc), potassium halides as reaction products, and humins as reaction by-products. Since these act as impurities that reduce reaction efficiency when proceeding with the subsequent reaction to produce 2,5-furandicarboxylic acid using 5-acetoxymethylfurfural, only 5-acetoxymethylfurfural must be separated and purified using the second organic solvent.

[0108] The second organic solvent used above has a relative polarity of 0.3 or less based on the polarity of water (1), and is one or more selected from toluene, xylene, chlorobenzene, cyclohexane, pentane, hexane, heptane, alkyl ether, diethylamine, dioxane, and N,N-dimethylaniline, and may be the same as or different from the first organic solvent.

[0109] (e) The amount of the second organic solvent added in step (e) can be used in the range of 5 to 100 moles per mole of 5-acetoxymethylfurfural, preferably 10 to 50 moles. If the organic solvent is used in an amount less than 5 moles, the extraction of 5-acetoxymethylfurfural may be insufficient or it may be difficult to separate the organic solvent from the insoluble precipitate, and if it is used in an amount greater than 100 moles, there is a problem that excessive energy must be used to recover 5-acetoxymethylfurfural from the organic solvent.

[0110] After adding the above organic solvent, stirring may be performed to expand the interface where extraction occurs in order to improve extraction efficiency. The stirring is not limited to any commonly used stirring means, and for example, a stirrer, ultrasound, etc., may be used.

[0111] In addition, after the addition of the extractant, selective dissolution of 5-acetoxymethylfurfural by the extractant can be performed in the range of 0°C to 50°C. If the temperature is below 0°C, the extraction of 5-acetoxymethylfurfural may be insufficient, and if it exceeds 50°C, potassium halides, potassium acetate, and humins may also be dissolved in addition to 5-acetoxymethylfurfural.

[0112] The organic solvent removed in steps (c) and (e) above can be recovered and reused.

[0113] In addition, the present invention provides a process for producing 2,5-furandicarboxylic acid from a sugar component, comprising: (a) a step of preparing a mixed solution in which an aqueous solution containing a sugar component, an acid component, and a halogen ion precursor in a reactor; and a first organic solvent are mixed; (b) a step of increasing the temperature of the mixed solution to perform a dehydration reaction, and then separating it into an aqueous phase and an organic phase to recover the organic phase in which 5-halomethylfurfural is dissolved; (c) a step of obtaining a mixed solution composed of 5-halomethylfurfural and potassium acetate by adding potassium acetate to the organic phase in which 5-halomethylfurfural is dissolved and then removing the organic solvent through distillation; and (d) a step of obtaining a reaction product containing 5-acetoxymethylfurfural by maintaining the mixed solution within a predetermined temperature range. (e) a step of mixing a second organic solvent with a reaction product solution containing the 5-acetoxymethylfurfural to selectively dissolve and recover the 5-acetoxymethylfurfural in the second organic solvent; and (f) a step of oxidizing the recovered 5-acetoxymethylfurfural to obtain 2,5-furandicarboxylic acid; the present invention provides a process for producing 2,5-furandicarboxylic acid from a sugar component, characterized by comprising: (e) a step of mixing a second organic solvent with the reaction product solution containing the 5-acetoxymethylfurfural to selectively dissolve and recover the 5-acetoxymethylfurfural in the second organic solvent; and (f) a step of oxidizing the recovered 5-acetoxymethylfurfural to obtain 2,5-furandicarboxylic acid.

[0114] The process for producing 2,5-furandicarboxylic acid from the sugar component of the present invention is identical to steps (a) to (e) of the process for producing 5-acetoxymethylfurfural, and step (f) is further added as a step of producing 2,5-furandicarboxylic acid by oxidizing the 5-acetoxymethylfurfural recovered in step (e).

[0115] (f) The oxidation process in step (f) can use a conventional process, and 2,5-furandicarboxylic acid can be produced through a known AMOCO process.

[0116] In addition, the present invention provides a composition and a method for directly converting 5-bromomethylfurfural to 2,5-furandicarboxylic acid.

[0117] As a composition for preparing 2,5-furandicarboxylic acid according to the present invention, the composition may be characterized by comprising 5-bromomethylfurfural, acetic acid, and an oxidation catalyst.

[0118] The 5-bromomethylfurfural included in the above composition is a reactant, and the 5-bromomethylfurfural may be a component derived from the dehydration reaction of a sugar component contained in biomass, for example, it may be a component produced by combining 5-hydroxymethylfurfural generated by the dehydration reaction of a sugar component in an aqueous environment with a bromide ion.

[0119] In addition, as an example of the present invention, the oxidation catalyst may include cobalt (Co) and manganese (Mn). The type of precursor is not limited as long as the cobalt (Co) and manganese (Mn) can be dissolved in acetic acid to provide cobalt ions and manganese ions, but may be, for example, any one selected from acetate salts, bromine salts, and mixtures thereof, and preferably may be an acetate salt.

[0120] In addition, the present invention may also provide a method for directly converting the 5-bromomethylfurfural into 2,5-furandicarboxylic acid.

[0121] Since the above method shares technical features with a composition that directly converts 5-bromomethylfurfural to 2,5-furandicarboxylic acid, overlapping descriptions may be omitted.

[0122] The method for directly converting the above 5-bromomethylfurfural into 2,5-furandicarboxylic acid may be characterized by supplying 5-bromomethylfurfural (BMF) to an acetic acid solution containing an oxidation catalyst, and then reacting it under an oxidizing atmosphere to directly convert it into 2,5-furandicarboxylic acid.

[0123] The cobalt (Co) and manganese (Mn) constituting the above oxidation catalyst are capable of dissolving in acetic acid to provide cobalt ions and manganese ions, and the type of precursor is not limited, but preferably, it may be any one selected from acetate salts, bromine salts, and mixtures thereof, and preferably, it may be an acetate salt.

[0124] As an example of the present invention, the Co / Mn molar ratio of the oxidation catalyst may be 10 to 100, preferably 40 to 100. If the molar ratio is less than 10, the effect of increasing the FDCA yield is negligible, but there may be a problem in that an additional purification process is required to separate solid FDCA and metal oxide after the reaction because manganese is added in excess of what is necessary in the oxidation reaction and metal oxide is formed. If the molar ratio is greater than 100, the amount of Mn added is reduced compared to Co, so the catalytic reaction rate decreases, and as a result, the rate of FDCA production decreases significantly, which may lead to a problem of reduced FDCA productivity.

[0125] The above 5-bromomethylfurfural solution may have a concentration of 5-bromomethylfurfural of 1 to 20 wt%, preferably 5 to 20 wt%. If the concentration is less than 1 wt%, there may be a problem with reduced FDCA productivity and economic efficiency due to the use of low-concentration raw materials, and if it exceeds 20 wt%, there may be a problem with reduced FDCA yield due to excessive accumulation of Br ions generated from BMF, which lowers the catalytic activity for the oxidation reaction.

[0126] As an example of the present invention, the oxidizing atmosphere may be formed by injecting O2 at a pressure of 2 to 20 bar, preferably 5 to 15 bar. If the pressure is less than 2 bar, the oxidation reaction to FDCA is not completed due to incomplete oxidation of BMF, and there may be a problem of excessive generation of intermediate oxidation products as byproducts. If the pressure is greater than 20 bar, there may be a problem of reduced FDCA yield and increased byproduct generation due to excessive oxidation.

[0127] In another example of the present invention, the reaction may be carried out at a temperature of 100 to 180 ℃, preferably 100 to 150 ℃. If the temperature is below 100 ℃, there is a problem that the reaction temperature is insufficient to carry out the oxidation reaction of BMF, so FDCA is not produced, and if it is above 180 ℃, there is a problem that BMF and FDCA are over-decomposed due to the excessive reaction temperature, which increases the production of by-products such as humin, and consequently lowers the FDCA yield and purity.

[0128] Stirring may be performed to ensure uniform mixing of the reactants before or during heating the above reaction mixture, and there are no limitations on the stirring method, and a known stirring device may be used.

[0129] As an example of the present invention, known separation and purification methods may be performed to recover and purify the 2,5-furandicarboxylic acid produced through the above reaction, and examples include extraction, filtration, crystallization, and phase separation.

[0130] In addition, the present invention may provide a process for producing 2,5-furandicarboxylic acid from a sugar component. Since the process for producing 2,5-furandicarboxylic acid from a sugar component of the present invention shares technical features with the method for directly converting 5-bromomethylfurfural into 2,5-furandicarboxylic acid, duplicate descriptions are omitted.

[0131] A process for producing 2,5-furandicarboxylic acid from the above sugar component may be characterized by comprising: (a) a step of preparing a mixed solution comprising an aqueous solution containing a sugar component, an acid component, and a bromide ion precursor; and an extraction organic solvent; (b) a step of performing a dehydration reaction by raising the temperature of the mixed solution, and then separating it into an aqueous phase and an organic phase to recover the organic phase in which 5-bromomethylfurfural is dissolved; (c) a step of removing the organic solvent by distilling the organic phase in which 5-bromomethylfurfural is dissolved, and then adding acetic acid to obtain an acetic acid solution in which 5-bromomethylfurfural is dissolved; and (d) a step of adding the acetic acid solution in which 5-bromomethylfurfural is dissolved to an aqueous solution in which a cobalt (Co) precursor and a manganese (Mn) precursor are dissolved in water, and then raising the temperature to perform a reaction to produce 2,5-furandicarboxylic acid.

[0132] Step (a) above is a step of preparing a two-phase mixed solution comprising a sugar component, an aqueous acid solution that induces a dehydration reaction of the sugar component, a bromide ion precursor as a bromine source (Br source) for 5-bromomethylfurfural, and an extraction organic solvent for easily extracting 5-bromomethylfurfural.

[0133] The sugar component of step (a) above is a raw material component that can be converted into 5-hydroxymethylfurfural through a dehydration reaction, and may be derived from lignocellulosic biomass, and may be one or more of, for example, monosaccharides including glucose, fructose, and galactose; disaccharides including maltose, sucrose, and lactose; polysaccharides including starch including hexoses, cellulose, and hemicellulose; and preferably one or more of glucose and cellulose. The concentration of the sugar component may be in the range of 0.01 to 30 wt%.

[0134] The above acid component is intended to induce a dehydration reaction of the above sugar component and may be selected from inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, phosphoric acid, hydrofluoric acid, boric acid, and organic acids such as acetic acid, lactic acid, olsalic acid, salicylic acid, and pyruvate, but preferably one or more selected from sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, etc., and more preferably may be sulfuric acid.

[0135] The above-mentioned bromide ion precursor is not limited to any substance capable of generating bromide ions that produce 5-bromomethylfurfural by ion-exchanging with the protons of 5-hydroxymethylfurfural, which are produced when a sugar component is dehydrated by an acid component.

[0136] The above-mentioned bromide ion precursor may be selected from, for example, bromine (Br2), lithium bromide (LiBr), sodium bromide (NaBr), potassium bromide (KBr), rubidium bromide (RbBr), cesium bromide (CsBr), calcium bromide (CaBr2), magnesium bromide (MgBr2), strontium bromide (SrBr2), barium bromide (BaBr2), hydrogen bromide (HBr), zinc bromide (ZnBr2), aluminum bromide (AlBr3), etc.

[0137] The above extraction organic solvent is a solvent used to extract 5-hydroxymethylfurfural after converting it into bromomethylfurfural with bromine bonds, in order to prevent 5-hydroxymethylfurfural obtained from lignocellulosic biomass from being converted into byproducts such as levulinic acid, and it is preferable to use one having a relative polarity of 0.3 or less based on the polarity of water of 1.

[0138] Examples of the above-mentioned extraction organic solvents may include one or more of toluene, xylene, chlorobenzene, cyclohexane, pentane, hexane, heptane, methyl t-butyl ether, diethylamine, dioxane, and N,N-dimethylaniline, and preferably, one or more of toluene, xylene, and chlorobenzene may be used from the perspective of environmental hazards and solvent recovery.

[0139] In the mixed two-phase solution obtained by the above-mentioned extraction organic solvent and aqueous solution, the volume ratio of the organic phase to the aqueous phase may be in the range of 2 to 10.

[0140] Step (b) above is a step in which a dehydration reaction is performed on the sugar component in the two-phase mixed solution of Step (a) to finally produce 5-bromomethylfurfural via 5-hydroxymethylfurfural, the produced 5-bromomethylfurfural is dissolved in an extractive organic solvent and moves from the aqueous phase to the organic phase, and the organic phase is recovered through phase separation.

[0141] The reaction in step (b) above is not limited thereto but may be operated at a temperature in the range of 80°C to 160°C and may be operated under reflux conditions of an organic solvent at atmospheric pressure. If the temperature is below 80°C, there is a problem that the dehydration reaction rate is negligible, and if the temperature is above 160°C, there is a problem that the over-decomposition reaction is promoted. In addition, in step (b) above, stirring may be performed on the two-phase solution to expand the interface where the dehydration reaction occurs in order to improve the reaction rate and yield.

[0142] Step (c) above is a step of removing the organic solvent by distilling the organic phase in which 5-bromomethylfurfural is dissolved, and then adding acetic acid to obtain an acetic acid solution in which 5-bromomethylfurfural is dissolved.

[0143] As an example of the present invention, potassium acetate may be added before the distillation of step (c), and potassium acetate can contribute to preventing the decomposition of 5-bromomethylfurfural or side reactions during distillation by neutralizing hygroscopic and acidic byproducts and preventing the decomposition of 5-bromomethylfurfural.

[0144] The above distillation is not limited thereto, but preferably may be accompanied by a heating step under vacuum at a reaction temperature below the boiling point of the extracting organic solvent, and said heating may be performed in the range of 50 ℃ to 100 ℃. When performed in the above temperature range, excessive energy use or thermal decomposition of 5-bromomethylfurfural can be reduced and the organic solvent can be removed.

[0145] Step (d) above is a step in which an acetic acid solution containing 5-bromomethylfurfural, from which the extraction organic solvent has been removed in Step (c), is added to an aqueous solution in which a cobalt (Co) precursor and a manganese (Mn) precursor are dissolved in water, and after injecting oxygen, the temperature is raised to perform a reaction to produce 2,5-furandicarboxylic acid.

[0146] The reaction of step (d) above can be carried out in the range of 100 to 180 ℃, preferably 100 to 150 ℃. If the temperature is below 100 ℃, there is a problem that the reaction temperature is insufficient to carry out the oxidation reaction of BMF, so FDCA is not produced, and if it is above 180 ℃, there is a problem that BMF and FDCA are over-decomposed due to the excessive reaction temperature, which increases the production of by-products such as humin, and consequently lowers the FDCA yield and purity.

[0147] As an example of the present invention, following step (d) above, a known method for selectively extracting and recovering 2,5-furandicarboxylic acid may be performed without limitation.

[0148]

[0149] Hereinafter, preferred embodiments of the present invention will be examined. For reference, the following embodiments are provided to illustrate one or more preferred embodiments of the present invention, but the present invention is not limited to such embodiments. A number of modifications falling within the scope of the present invention may be made to the following embodiments.

[0150] <Example 1>

[0151] A mixture of 20.0 g of cellulose and 100 mL of a 67 wt% aqueous sulfuric acid solution was stirred at room temperature for 1 hour in a 2-liter 3-neck flask equipped with a condenser to obtain an aqueous cellulose solution. Subsequently, a two-phase solution to which 68 g of KBr and 800 mL of toluene were additionally added was heated to 110 °C, the boiling point of toluene, while stirring to perform a dehydration reaction. After a specific reaction time, the reaction flask was placed in a cold water bath at 0 °C to rapidly cool it, and the toluene layer was separated from the water layer.

[0152] The above toluene layer was transferred to a 1-liter round-bottom flask, and potassium acetate equivalent to 1.5 times the molar amount of 5-bromomethylfurfural present in the toluene layer was added. Then, the round-bottom flask was placed in a 90°C hot water bath and heated while stirring, and then toluene was separated by vacuum distillation (90°C, < 200 mmHg). The homogeneous mixture of non-volatile 5-bromomethylfurfural and potassium acetate in the round-bottom flask was reacted at 90°C while stirring for 15 minutes starting from the point when the toluene was completely distilled. To quantitatively analyze 5-acetoxymethylfurfural produced by the reaction of 5-bromomethylfurfural and potassium acetate, toluene was added to the reactants over time after the reaction to dissolve the 5-bromomethylfurfural and 5-acetoxymethylfurfural, and then quantified using a DB-624UI column and GC analysis equipped with FID. As a result, the 5-bromomethylfurfural conversion rate and 5-acetoxymethylfurfural yield are shown in Figure 1.

[0153]

[0154] <Example 2>

[0155] A mixture of 20.0 g of cellulose and 100 mL of a 67 wt% aqueous sulfuric acid solution was stirred at room temperature for 1 hour in a 2-liter 3-neck flask equipped with a condenser to obtain an aqueous cellulose solution. Subsequently, a two-phase solution to which 70 g of KCl and 800 mL of toluene were additionally added was heated to 110 °C, the boiling point of toluene, while stirring to perform a dehydration reaction. After a specific reaction time, the reaction flask was rapidly cooled by placing it in a cold water bath at 0 °C, and the toluene layer was separated from the water layer.

[0156] The above toluene layer was transferred to a 1-liter round-bottom flask, and potassium acetate equivalent to 1.5 times the molar amount of 5-chloromethylfurfural present in the toluene layer was added. Then, the round-bottom flask was placed in an oil bath at 90°C and heated while stirring, and toluene was separated by vacuum distillation (90°C, < 200 mmHg). The homogeneous mixture of non-volatile 5-chloromethylfurfural and potassium acetate in the round-bottom flask was reacted at 120°C while stirring for 30 minutes starting from the point when the toluene was completely distilled. To quantitatively analyze 5-acetoxymethylfurfural produced by the reaction of 5-chloromethylfurfural and potassium acetate, toluene was added to the reactants over time after the reaction to dissolve the 5-chloromethylfurfural and 5-acetoxymethylfurfural, and then quantified using a DB-624UI column and GC analysis equipped with FID. As a result, the 5-chloromethylfurfural conversion rate and 5-acetoxymethylfurfural yield are shown in Figure 2.

[0157]

[0158] <Comparative Example 1>

[0159] The same method as in Example 1 was used, except that sodium acetate (NaOAc) was added in equal molar amounts instead of potassium acetate (KOAc) and the reaction was carried out for 30 minutes, and the resulting 5-bromomethylfurfural conversion rate and 5-acetoxymethylfurfural yield are shown in Figure 1.

[0160]

[0161] <Comparative Example 2>

[0162] The procedure was carried out in the same manner as in Example 2, except that sodium acetate (NaOAc) was added in equal molar amounts instead of potassium acetate (KOAc), and the resulting 5-chloromethylfurfural conversion rate and 5-acetoxymethylfurfural yield are shown in Figure 2.

[0163]

[0164] Referring to Figures 1 and 2, Examples 1 and 2, which used potassium acetate as the acetate ion source, showed significantly higher reaction activity compared to Comparative Examples 1 and 2, which used sodium acetate. From this, it can be seen that in the reaction in which 5-halomethylfurfural is directly reacted with an acetate salt to form 5-acetoxymethylfurfural, high-yield conversion or production of acetoxymethylfurfural is possible when potassium acetate is used as the acetate salt.

[0165]

[0166] <Example 3>

[0167] 131.5 g of toluene, equivalent to 50 times the molar amount of AMF, was added to 11.6 g of the reaction product obtained in Example 1 above, stirred at 200 rpm for 30 minutes, and then allowed to stand to separate into two phases consisting of a liquid phase and a solid phase. The upper phase was filtered to recover a toluene layer in which AMF was selectively dissolved. The recovered toluene layer was subjected to vacuum distillation (75°C, <250 mmHg) to completely distill the toluene and recover AMF.

[0168]

[0169] <Example 4>

[0170] A layer of diethyl ether in which AMF was selectively dissolved was obtained by performing the same procedure as in Example 3, except that diethyl ether was used instead of toluene in the product after the reaction. The recovered diethyl ether layer was subjected to vacuum distillation (30°C, < 500 mmHg) to completely distill the diethyl ether and recover AMF.

[0171]

[0172] <Comparative Example 3>

[0173] In Example 3 above, acetic acid was added instead of toluene to the product after the reaction, and an unfiltered mixture was obtained.

[0174]

[0175] <Comparative Example 4>

[0176] In Example 3 above, acetic acid was added to the product after the reaction instead of toluene, and then filtered to obtain a mixture.

[0177]

[0178] <Comparative Example 5>

[0179] In Example 3 above, acetic acid was added to the product after reaction instead of toluene, and the mixture was filtered to obtain a mixture, and activated carbon (10 wt%) was added to the mixture, stirred at 200 rpm for 30 minutes, and then filtered to obtain a mixture from which humin was removed.

[0180]

[0181] <Example 5>

[0182] 5-1. Manufacture of AMF from CMF

[0183] A mixture of 20.0 g of cellulose and 100 mL of a 67 wt% aqueous sulfuric acid solution was stirred at room temperature for 1 hour in a 2-liter 3-neck flask equipped with a condenser to obtain an aqueous cellulose solution. Subsequently, a two-phase solution to which 70 g of KCl and 800 mL of toluene were additionally added was heated to 110 °C, the boiling point of toluene, while stirring to perform a dehydration reaction. After a specific reaction time, the reaction flask was rapidly cooled by placing it in a cold water bath at 0 °C, and the toluene layer was separated from the water layer. The above toluene layer was transferred to a 1-liter round-bottom flask, and potassium acetate equivalent to 1.5 times the molar amount of 5-chloromethylfurfural present in the toluene layer was added. Then, the round-bottom flask was placed in an oil bath at 90°C and heated while stirring, and toluene was separated by vacuum distillation (90°C, <200 mmHg). The homogeneous mixture of non-volatile 5-chloromethylfurfural and potassium acetate in the round-bottom flask was reacted at 120°C while stirring for 30 minutes starting from the point when the toluene was completely distilled.

[0184] As a result, a reaction product mixed with AMF was obtained. The reaction product was analyzed using GC, HPLC, and IC and found to contain 44.1 wt% AMF, 28.8 wt% KOAc, 12.0 wt% KCl, and 15.1 wt% Humin.

[0185] 5-2. Selective Recovery of AMF

[0186] 124.5 g of toluene, equivalent to 50 times the molar amount of AMF, was added to 10.3 g of the reaction product obtained in 3-1 above, stirred at 200 rpm for 30 minutes, and then allowed to stand to separate into two phases consisting of a liquid phase and a solid phase. This was filtered to recover the toluene layer in which AMF was selectively dissolved. The recovered toluene layer was subjected to vacuum distillation (75°C, <250 mmHg) to completely distill the toluene and recover AMF.

[0187]

[0188] <Example 6>

[0189] A diethyl ether layer in which AMF was selectively dissolved was obtained by performing the same procedure as in Example 5-2 above, except that diethyl ether was used instead of toluene in the product after the reaction. The recovered diethyl ether layer was subjected to vacuum distillation (30°C, < 500 mmHg) to completely distill the diethyl ether and recover AMF.

[0190]

[0191] <Comparative Example 6>

[0192] In Example 5-2 above, acetic acid was added instead of toluene to the product after the reaction, and an unfiltered mixture was obtained.

[0193]

[0194] <Comparative Example 7>

[0195] In Example 5-2 above, a mixture was obtained by adding acetic acid instead of toluene to the product after the reaction and then filtering it.

[0196]

[0197] <Comparative Example 8>

[0198] In Example 5-2 above, acetic acid was added to the product after reaction instead of toluene, and the mixture was filtered to obtain a mixture, and activated carbon (10 wt%) was added to this, stirred at 200 rpm for 30 minutes, and then filtered to obtain a mixture from which humin was removed.

[0199]

[0200] <Experimental Example>

[0201] Experiments were conducted to synthesize 2,5-furandicarboxylic acid (FDCA) using 5-acetoxymethylfurfural obtained in Examples 3 to 6 and Comparative Examples 3 to 8, and the suitability of the 5-acetoxymethylfurfural obtained in the Examples and Comparative Examples as a raw material for synthesizing 2,5-furandicarboxylic acid (FDCA) was examined.

[0202] The above 2,5-furandicarboxylic acid production reaction was carried out as follows.

[0203] An acetic acid solution (10 g) containing water (2 wt%) and a catalyst composed of Co(CH3COO)2·4H2O, Mn(CH3COO)2·4H2O, and HBr (molar ratio Co / Mn / Br = 1 / 0.025 / 1.350) was added to a semi-batch type 50 ml zirconium reactor, oxygen was injected at a pressure of 5 bar, and the temperature was raised to 120 ℃. Once the reaction temperature was maintained at 120 ℃, a reaction solution of 5-acetoxymethylfurfural dissolved in the acetic acid reaction solvent at a concentration of 5 wt% was injected into the reactor using a liquid transfer pump at a rate of 0.33 cc / min for 30 minutes to carry out the oxidation reaction of 5-acetoxymethylfurfural. After a predetermined reaction time, the reactor was cooled to room temperature, and the reaction product was filtered to recover the solids. The recovered 2,5-furandicarboxylic acid solid was washed with acetic acid and distilled water, dried in an oven at 65°C, and weighed to determine the yield of 2,5-furandicarboxylic acid, and the values ​​are shown in Table 1.

[0204] Classification AMF Use of Raw Material Extractor Type of Extractor FDCA Yield (%) Experiment 1 Reagent Grade AMF × -76 Experiment 2 Example 3 ○ Toluene 70 Experiment 3 Example 4 ○ Diethyl Ether 75 Experiment 4 Comparative Example 3 × -0 Experiment 5 Comparative Example 4 × -38 Experiment 6 Comparative Example 5 × -48 Experiment 7 Example 5 ○ Toluene 72 Experiment 8 Example 6 ○ Diethyl Ether 76 Experiment 9 Comparative Example 6 × -0 Experiment 10 Comparative Example 7 × -35 Experiment 11 Comparative Example 8 × -51

[0205] As shown in Table 1 above, when a reaction to produce 2,5-furandicarboxylic acid was performed using 5-acetoxymethylfurfural obtained by the separation and purification of the present invention, 2,5-furandicarboxylic acid could be obtained with a higher yield compared to 5-acetoxymethylfurfural obtained by Comparative Examples 3 to 8, and in particular, when diethyl ether was used as an extractant, 2,5-furandicarboxylic acid could be obtained to an amount almost identical to that obtained when commercially available pure 5-acetoxymethylfurfural was used as a raw material.

[0206]

[0207] <Example 7: Prepared by direct conversion of 5-bromomethylfurfural to 2,5-furandicarboxylic acid>

[0208] The reaction for the production of 2,5-furandicarboxylic acid from 5-bromomethylfurfural was carried out as follows. An acetic acid solution (10 g) containing water (5 wt%) and a catalyst composed of Co(CH3COO)2·4H2O and Mn(CH3COO)2·4H2O (molar ratio Co / Mn = 1 / 0.025) was added to a semi-batch type 50 ml zirconium reactor, oxygen was injected at a pressure of 8 bar, and the temperature was raised to 120 ℃. Once the reaction temperature was maintained at 120 ℃, a reaction solution of 5-bromomethylfurfural dissolved in the acetic acid reaction solvent at a concentration of 5 wt% was injected into the reactor using a liquid transfer pump at a rate of 0.33 cc / min for 30 minutes to carry out the oxidation reaction of 5-bromomethylfurfural. After a specific reaction time, the reactor was cooled to room temperature, and the reaction product was filtered to recover the solids. The recovered 2,5-furandicarboxylic acid solid was washed with acetic acid and distilled water, dried in an oven at 65°C, and weighed to determine the yield of 2,5-furandicarboxylic acid, and the values ​​are shown in Table 2.

[0209]

[0210] <Comparative Example 9: Prepared by converting 5-chloromethylfurfural to 2,5-furandicarboxylic acid>

[0211] The same method as in Example 7 was performed except that an equal amount of 5-chloromethylfurfural (CMF) was supplied as a reactant, and the yield of 2,5-furandicarboxylic acid was measured and the values ​​are shown in Table 2.

[0212] Classification Reactant Catalyst Reaction Temperature (°C) Conversion Rate (%) FDCA Yield (%) Example 7 BMF Co / Mn (Molar Ratio = 1 / 0.025) 120 100 42 Comparative Example 9 CMF 1000

[0213] Referring to Table 2 above, it was confirmed that in Comparative Example 9, which used 5-chloromethylfurfural (CMF) instead of 5-bromomethylfurfural (BMF) as the reactant, the product was not converted to FDCA, and only byproducts such as 5-methylfurfural, 5-hydroxyfurfural (HMF), 5-acetoxyfurfural (AMF), levulinic acid, formic acid, CO, CO2, and humins were produced. In other words, it was found that direct conversion to FDCA is possible only when BMF is selectively used among the halomethylfurfurals obtained during the process of producing perural from lignocellulosic biomass.

[0214]

[0215] Although the present invention has been described above with reference to embodiments described in the specification or illustrated in the attached drawings, this is merely illustrative, and those skilled in the art will understand that various modifications and equivalent alternative embodiments are possible therefrom. Accordingly, the technical scope of protection of the present invention should be determined by the following claims.

[0216]

[0217] The present invention relates to a composition for directly converting 5-halomethylfurfural to 5-acetoxymethylfurfural, a conversion method, a method for selectively recovering 5-acetoxymethylfurfural from a mixed solution containing 5-acetoxymethylfurfural, a process for producing 5-acetoxymethylfurfural or 2,5-furandicarboxylic acid containing the same, and a composition and method for directly converting 5-bromomethylfurfural to 2,5-furandicarboxylic acid. Since it can be usefully employed in the field of technology for producing eco-friendly platform compounds and polymer monomers that replace petroleum-based chemicals in bioplastics or fine chemical industries, it has industrial applicability.

Claims

As a composition for the preparation of 1,5-acetoxymethylfurfural, A composition for producing 5-acetoxymethylfurfural, characterized in that the above composition consists of 5-halomethylfurfural and potassium acetate.

2. In Paragraph 1, A composition for producing 5-acetoxymethylfurfural, characterized in that the above 5-halomethylfurfural is a component derived from the dehydration reaction of a sugar component contained in biomass.

3. In Paragraph 1, A composition for producing 5-acetoxymethylfurfural, characterized in that the potassium acetate / 5-halomethylfurfural molar ratio is 1 to 2. In a method for manufacturing 4,5-acetoxymethylfurfural, A method for producing 5-acetoxymethylfurfural, characterized by maintaining a mixture of 5-halomethylfurfural and potassium acetate (KOAc) within a predetermined temperature range to convert 5-halomethylfurfural into 5-acetoxymethylfurfural.

5. In Paragraph 4, A method for producing 5-acetoxymethylfurfural, characterized in that the above 5-halomethylfurfural is a component derived from the dehydration reaction of a sugar component contained in biomass.

6. In Paragraph 4, A method for producing 5-acetoxymethylfurfural, characterized in that the above-mentioned predetermined temperature range is a range selected from 25 ℃ to 150 ℃.

7. In a process for producing 5-acetoxymethylfurfural from sugar components, (a) A step of preparing a mixed solution comprising an aqueous solution containing a sugar component, an acid component, and a halogen ion precursor in a reactor; and an extraction organic solvent; (b) a step of heating the above mixed solution to perform a dehydration reaction, then separating it into an aqueous phase and an organic phase to recover the organic phase in which 5-halomethylfurfural is dissolved; (c) a step of obtaining a mixed solution composed of 5-halomethylfurfural and potassium acetate by adding potassium acetate to the organic phase in which the 5-halomethylfurfural is dissolved and then removing the organic solvent through distillation; and (d) a step of producing 5-acetoxymethylfurfural by maintaining the above mixed solution within a predetermined temperature range; characterized by comprising a process for producing 5-acetoxymethylfurfural from a sugar component.

8. In Paragraph 7, A process for producing 5-acetoxymethylfurfural from a sugar component, characterized in that the sugar component of step (a) above is derived from biomass.

9. In Paragraph 7, A process for producing 5-acetoxymethylfurfural from a sugar component, characterized in that the potassium acetate / 5-halomethylfurfural molar ratio in step (d) above is 1 to 2.

10. In Paragraph 7, A process for producing 5-acetoxymethylfurfural from a sugar component, characterized in that the temperature range of step (d) above is selected from a range of 25 ℃ to 150 ℃. An extractant for selectively extracting 5-acetoxymethylfurfural from a mixed solution containing 11,5-acetoxymethylfurfural, potassium halide, potassium acetate, and humins, characterized by comprising an organic solvent having a relative polarity of 0.3 or less based on the polarity of water of 1.

12. In Paragraph 11, An extractant for selectively extracting 5-acetoxymethylfurfural, characterized in that the above mixed solution is a product of a reaction in which a solution composed of 5-halomethylfurfural and potassium acetate is heated to produce 5-acetoxymethylfurfural.

13. In Paragraph 11, An extractant for selectively extracting 5-acetoxymethylfurfural, characterized in that the above organic solvent is used in a molar amount of 5 to 100 times the molar amount of 5-acetoxymethylfurfural. A method for selectively separating 5-acetoxymethylfurfural from a mixed solution containing 14,5-acetoxymethylfurfural, potassium halide, potassium acetate, and humins, wherein A method for selectively separating 5-acetoxymethylfurfural from a mixed solution, characterized by separating 5-acetoxymethylfurfural by adding an extractant containing an organic solvent having a relative polarity of 0.3 or less based on the polarity of water of 1 to the mixed solution to selectively dissolve 5-acetoxymethylfurfural.

15. In Paragraph 14, A method for selectively separating acetoxymethylfurfural from a mixed solution, characterized in that the above mixed solution is a product of a reaction in which a solution composed of 5-halomethylfurfural and potassium acetate is heated to produce 5-acetoxymethylfurfural.

16. In Paragraph 14, A method for selectively separating acetoxymethylfurfural from a mixed solution, characterized in that the above organic solvent is used in a molar amount of 5 to 100 times the molar amount of 5-acetoxymethylfurfural.

17. In a process for producing 5-acetoxymethylfurfural from sugar components, (a) A step of preparing a mixed solution comprising an aqueous solution containing a sugar component, an acid component, and a halogen ion precursor in a reactor; and a first extraction solvent; (b) a step of heating the above mixed solution to perform a dehydration reaction, then separating it into an aqueous phase and an organic phase to recover the organic phase in which 5-halomethylfurfural is dissolved; (c) a step of obtaining a mixed solution composed of 5-halomethylfurfural and potassium acetate by adding potassium acetate to the organic phase in which the 5-halomethylfurfural is dissolved and then removing the organic solvent through distillation; (d) a step of obtaining a reaction product containing 5-acetoxymethylfurfural by maintaining the above mixed solution within a predetermined temperature range; and (e) a step of mixing a second extraction solvent into a reaction product solution containing the above-mentioned 5-acetoxymethylfurfural to selectively dissolve and recover the 5-acetoxymethylfurfural in the second extraction solvent; characterized by comprising a process for producing 5-acetoxymethylfurfural from a sugar component.

18. In Paragraph 17, A process for producing 5-acetoxymethylfurfural from a sugar component, characterized in that the sugar component of step (a) above is derived from biomass.

19. In Paragraph 17, A process for producing 5-acetoxymethylfurfural from a sugar component, characterized in that the first extraction solvent in step (a) and the second extraction solvent in step (e) are one or more selected from organic solvents having a relative polarity of 0.3 or less based on the polarity of water of 1.

20. In Paragraph 17, A process for producing 5-acetoxymethylfurfural from a sugar component, characterized in that the selective extraction in step (e) above is performed at 0 ℃ to 50 ℃.

21. In a process for producing 2,5-furandicarboxylic acid from sugar components, (a) A step of preparing a mixed solution comprising an aqueous solution containing a sugar component, an acid component, and a halogen ion precursor in a reactor; and a first extraction solvent; (b) a step of heating the above mixed solution to perform a dehydration reaction, then separating it into an aqueous phase and an organic phase to recover the organic phase in which 5-halomethylfurfural is dissolved; (c) a step of obtaining a mixed solution composed of 5-halomethylfurfural and potassium acetate by adding potassium acetate to the organic phase in which the 5-halomethylfurfural is dissolved and then removing the organic solvent through distillation; (d) a step of obtaining a reaction product containing 5-acetoxymethylfurfural by maintaining the above mixed solution within a predetermined temperature range; (e) a step of mixing a second extraction solvent into the reaction product solution containing the 5-acetoxymethylfurfural to selectively dissolve and recover the 5-acetoxymethylfurfural in the second extraction solvent; and (f) a step of obtaining 2,5-furandicarboxylic acid by oxidizing recovered 5-acetoxymethylfurfural; characterized by comprising a process for producing 2,5-furandicarboxylic acid from a sugar component.

22. In Paragraph 21, A process for producing 5-acetoxymethylfurfural from a sugar component, characterized in that the first extraction solvent in step (a) and the second extraction solvent in step (e) are one or more selected from organic solvents having a relative polarity of 0.3 or less based on the polarity of water of 1. As a composition for the preparation of 23,2,5-furandicarboxylic acid, A composition for directly converting 5-bromomethylfurfural into 2,5-furandicarboxylic acid, characterized by comprising 5-bromomethylfurfural, acetic acid, and an oxidation catalyst.

24. In Paragraph 23, A composition for directly converting 5-bromomethylfurfural into 2,5-furandicarboxylic acid, characterized in that the above 5-bromomethylfurfural is a component derived from the dehydration reaction of a sugar component contained in biomass.

25. In Paragraph 23, A composition for directly converting 5-bromomethylfurfural to 2,5-furandicarboxylic acid, characterized in that the oxidation catalyst comprises cobalt (Co) and manganese (Mn).

26. A method for directly converting 5-bromomethylfurfural into 2,5-furandicarboxylic acid, characterized by supplying 5-bromomethylfurfural (BMF) to an acetic acid solution containing an oxidation catalyst and then reacting it under an oxidizing atmosphere to directly convert it into 2,5-furandicarboxylic acid.

27. In Paragraph 26, A method for directly converting 5-bromomethylfurfural to 2,5-furandicarboxylic acid, characterized in that the oxidation catalyst comprises cobalt (Co) and manganese (Mn).

28. In Paragraph 27, A method for directly converting 5-bromomethylfurfural to 2,5-furandicarboxylic acid, characterized in that the precursors of cobalt (Co) and manganese (Mn) are each selected from acetate salts, bromine salts, and mixtures thereof.

29. In Paragraph 27, A method for directly converting 5-bromomethylfurfural to 2,5-furandicarboxylic acid, characterized in that the Co / Mn molar ratio of the oxidation catalyst is 10 to 100.

30. In Paragraph 26, A method for directly converting 5-bromomethylfurfural to 2,5-furandicarboxylic acid, characterized in that the above 5-bromomethylfurfural solution has a concentration of 1 to 20 wt% of 5-bromomethylfurfural.

31. In Paragraph 26, A method for directly converting 5-bromomethylfurfural to 2,5-furandicarboxylic acid, characterized in that the above-mentioned oxidizing atmosphere is formed by injecting O2 at a pressure of 2 to 20 bar.

32. In Paragraph 26, A method for directly converting 5-bromomethylfurfural to 2,5-furandicarboxylic acid, characterized in that the above reaction is carried out at a temperature of 100 to 180 ℃.

33. In a process for producing 2,5-furandicarboxylic acid from sugar components, (a) A mixed solution comprising an aqueous solution containing a sugar component, an acid component, and a bromide ion precursor; and an extraction organic solvent; (b) a step of heating the above mixed solution to perform a dehydration reaction, then separating it into an aqueous phase and an organic phase to recover the organic phase in which 5-bromomethylfurfural is dissolved; (c) a step of distilling the organic phase in which the 5-bromomethylfurfural is dissolved to remove the extraction organic solvent, and then adding acetic acid to obtain an acetic acid solution in which the 5-bromomethylfurfural is dissolved; and (d) a step of adding an acetic acid solution in which the 5-bromomethylfurfural is dissolved to an aqueous solution in which a cobalt (Co) precursor and a manganese (Mn) precursor are dissolved in water, and then increasing the temperature to produce 2,5-furandicarboxylic acid, wherein the reaction is performed; characterized by comprising: a step of producing 2,5-furandicarboxylic acid from a sugar component.

34. In Paragraph 33, A process for producing 2,5-furandicarboxylic acid from a sugar component, characterized in that the sugar component of step (a) above is derived from lignocellulosic biomass.

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