Catalyst comprising metal nitrate and ionic liquid, and method for producing hmf derived from glucose and hfcs using same

Abstract

A catalyst comprising a metal nitrate and an ionic liquid, and a method for producing 5-hydroxymethylfurfural derived from glucose and high-fructose corn syrup using the same are provided. The invention relates to a catalyst for producing 5-hydroxymethylfurfural (HMF) comprising a metal nitrate or its hydrate; and a nitrate-based ionic liquid; and provides a method for designing a non-halogenated metal-ionic liquid combination catalyst system capable of selectively synthesizing HMF from glucose and HFCS.

Description

Technology Field

[0001] The present invention relates to a catalyst comprising a metal nitrate and an ionic liquid, and a method for producing 5-hydroxymethylfurfural derived from glucose and high-fructose corn syrup using the same. Background Technology

[0002] With growing interest in biodegradable bioplastic production technologies, the technology for producing monomers for bioplastics synthesized from biomass, a sustainable energy resource, is critical. Hydrogenated Membrane (HMF), a biomass conversion derivative synthesized through glucose isomerization and dehydration reactions, serves as a base material capable of generating FDCA, a monomer for the bioplastic polyethylene furandicarboxylate (PEF). As a material that can replace conventional petroleum-based plastic polyethylene terephthalate (PET), it can be utilized in various chemical industries. Furthermore, producing HMF from low-cost raw materials such as high-fructose corn syrup (HFCS), rather than from expensive refined materials like crystalline glucose or crystalline fructose, is an essential technology as it reduces raw material costs and ensures price competitiveness. The production of HMF from HFCS can expand the market size of the bioplastic industry by reducing process costs, not only from a technical perspective but also from an economic one.

[0003] Meanwhile, 5-hydroxymethylfurfural (HMF) is gaining attention as a bio-based platform chemical that serves as a precursor for the synthesis of furan-2,5-dicarboxylic acid (FDCA), which can replace terephthalic acid (TPA), a petroleum-based chemical. However, existing acid catalysts used in HMF synthesis have technical limitations in terms of low synthesis yield, selectivity, process stability, and economic feasibility. Therefore, there is a need to develop new catalyst technologies that increase HMF synthesis yield and selectivity by limiting the generation of byproducts, while also enhancing process stability. Prior art literature

[0004] Korean Patent Publication No. 10-2016-0111954 The problem to be solved

[0005] The objective of the present invention is to solve the aforementioned problems by optimizing a catalyst system combining a metal nitrate-based catalyst and an ionic liquid to provide a catalyst with the best performance.

[0006] In addition, this is applied to the HMF production reaction to provide HMF with high selectivity from glucose and HFCS. means of solving the problem

[0007] According to one aspect of the present invention, a catalyst for producing 5-hydroxymethylfurfural (HMF) is provided, comprising a metal nitrate or its hydrate; and a nitrate-based ionic liquid.

[0008] In addition, the above catalyst can produce 5-hydroxymethylfurfural from one or more selected from the group consisting of glucose and high fructose corn syrup (HFCS).

[0009] In addition, the metal nitrate can be represented by Chemical Formula 1.

[0010] [Chemical Formula 1]

[0011] M(NO3)x

[0012] M is Cr, Al, Ga, In, Cu, Fe, Mn, Co, Ni, Zn, Mg, Ca, La, Ce or Sm, and

[0013] X is any one of integers from 1 to 4.

[0014] In addition, the hydrates of the metal nitrates are Cr(NO3)3·9H2O, Al(NO3)3·9H2O, Ga(NO3)3·xH2O (where x is an integer from 1 to 10). It may include one or more selected from the group consisting of and In(NO3)3·xH2O (where x is an integer from 1 to 10).

[0015] In addition, the above nitrate-based ionic liquid may include a compound represented by structural formula 1.

[0016] [Structural Formula 1]

[0017]

[0018] In the above structural formula 1,

[0019] R 1 It is a hydrogen atom or a C1 to C15 alkyl group, and

[0020] R 2 is a hydrogen atom or a C1 to C9 alkyl group.

[0021] Also, R 1 is a C1 to C10 alkyl group, and R 2 It can be a hydrogen atom or a methyl group.

[0022] In addition, the nitrate-based ionic liquid comprises 1-methylimidazolium nitrate ([MIM]NO3), 1-ethyl-3-methylimidazolium nitrate ([EMIM]NO3), 1-butyl-3-methylimidazolium nitrate ([BMIM]NO3) and 1-decyl-3-methylimidazolium nitrate ([C10 It may include one or more types selected from the group consisting of [MIM]NO3).

[0023] In addition, the catalyst may include a combination catalyst of In(NO3)3·xH2O (where x is an integer from 1 to 10) and [EMIM]NO3.

[0024] According to another aspect of the present invention, a method for producing 5-hydroxymethylfurfural is provided, comprising the step of reacting a reactant comprising one or more selected from the group consisting of glucose and high fructose corn syrup (HFCS) in the presence of a catalyst and a solvent to produce 5-hydroxymethylfurfural.

[0025] In addition, the solvent may include one or more selected from the group consisting of dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), acetonitrile, toluene, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, ethyl acetate, hexane, benzene, 1,4-dioxane, diethyl ether, chloroform, dichloromethane, water (H2O), methyl isobutyl ketone (MIBK), methyl t-butyl ether (MTBE), dimethyl ether (DME), dimethyl carbonate (DMC), and dimethoxyethane.

[0026] In addition, the above reaction may be carried out at 80 to 150 ℃.

[0027] In addition, the catalyst comprises a metal nitrate or its hydrate; and a nitrate-based ionic liquid; and can produce 5-hydroxymethylfurfural (HMF).

[0028] In addition, the metal nitrate can be represented by Chemical Formula 1.

[0029] [Chemical Formula 1]

[0030] M(NO3)x

[0031] M is Cr, Al, Ga, In, Cu, Fe, Mn, Co, Ni, Zn, Mg, Ca, La, Ce or Sm, and

[0032] X is any one of integers from 1 to 4.

[0033] In addition, the hydrates of the metal nitrates are Cr(NO3)3·9H2O, Al(NO3)3·9H2O, Ga(NO3)3·xH2O (where x is an integer from 1 to 10). and In(NO3)3·xH2O (where x may include one or more selected from the group consisting of integers from 1 to 10.

[0034] In addition, the above nitrate-based ionic liquid may include a compound represented by structural formula 1.

[0035] [Structural Formula 1]

[0036]

[0037] In the above structural formula 1,

[0038] R 1 It is a hydrogen atom or a C1 to C15 alkyl group, and

[0039] R 2 is a hydrogen atom or a C1 to C9 alkyl group.

[0040] Also, R 1 is a C1 to C10 alkyl group, and R 2 It can be a hydrogen atom or a methyl group.

[0041] In addition, the nitrate-based ionic liquid comprises 1-methylimidazolium nitrate ([MIM]NO3), 1-ethyl-3-methylimidazolium nitrate ([EMIM]NO3), 1-butyl-3-methylimidazolium nitrate ([BMIM]NO3) and 1-decyl-3-methylimidazolium nitrate ([C 10 It may include one or more types selected from the group consisting of [MIM]NO3). Effects of the invention

[0042] The present invention can provide a method for designing a non-halogenated metal-ionic liquid combination catalyst system capable of selectively synthesizing HMF from glucose and HFCS.

[0043] In addition, the development of non-halogenated catalysts with excellent stability can resolve the problems of corrosiveness and catalyst toxicity that may occur during the bioplastic monomer production process. Brief explanation of the drawing

[0044] These drawings are for reference to explain exemplary embodiments of the present invention, and therefore, the technical concept of the present invention should not be interpreted as being limited to the attached drawings. Figure 1 is a flowchart illustrating the method for reusing the catalyst of the present invention. Figure 2 shows the catalyst separation and HMF extraction process of the present invention. FIG. 3 shows the glucose conversion rate (%), HMF selectivity (%), and fructose selectivity (%) according to Examples 1-1 to 4-4 of the present invention. Figure 4 shows the glucose conversion rate (%), HMF selectivity (%), and fructose selectivity (%) under conditions without a catalyst (Comparative Example 1) and conditions using only an acid catalyst (Comparative Examples 2 to 4). FIG. 5 shows the glucose conversion rate (%), HMF selectivity (%), and fructose selectivity (%) of the catalyst in Example 2-4 of the present invention (In(NO3)3·xH2O (where x is an integer from 1 to 10)-[EMIM]NO3) and the recycled catalyst in Example 2-4 of the present invention (Recycled In(NO3)3·xH2O (where x is an integer from 1 to 10)-[EMIM]NO3). Figure 6 shows the HFCS conversion rate (%), glucose conversion rate (%), fructose conversion rate (%), and HMF selectivity (%) according to the catalysts of Examples 2-1 to 2-4 of the present invention. Figure 7 shows the HFCS conversion rate (%), glucose conversion rate (%), fructose conversion rate (%), and HMF selectivity (%) according to the amount of DMSO used. Figure 8 shows the glucose conversion rate (%), fructose conversion rate (%), and HMF selectivity (%) according to the mixing ratio of glucose and fructose. Specific details for implementing the invention

[0045] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings so that those skilled in the art can easily implement the present invention.

[0046] However, the following description is not intended to limit the present invention to specific embodiments, and detailed descriptions of related prior art are omitted if it is determined that such detailed descriptions could obscure the essence of the present invention.

[0047] The terms used herein are merely for describing specific embodiments and are not intended to limit the invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, terms such as "comprising" or "having" are intended to indicate the presence of the features, numbers, steps, actions, components, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, or combinations thereof.

[0048] Additionally, terms including ordinal numbers, such as "first," "second," etc., used below may be used to describe various components, but said components are not limited by said terms. These terms are used solely for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be named the second component, and similarly, the second component may be named the first component.

[0049] Furthermore, when it is stated that a component is "formed" or "laminated" on another component, it should be understood that while it may be formed or laminated by being directly attached to the entire surface or one surface of the other component, there may also be other components present in between.

[0050] Hereinafter, a catalyst comprising a metal nitrate and an ionic liquid, and a method for producing 5-hydroxymethylfurfural derived from glucose and high-fructose corn syrup using the same will be described in detail. However, this is presented as an example and is not intended to limit the present invention, and the present invention is defined only by the scope of the claims set forth below.

[0052] The present invention provides a catalyst for producing 5-hydroxymethylfurfural (HMF), comprising a metal nitrate or its hydrate; and a nitrate-based ionic liquid.

[0053] In addition, the above catalyst can produce 5-hydroxymethylfurfural from one or more selected from the group consisting of glucose and high fructose corn syrup (HFCS).

[0054] In addition, the metal nitrate can be represented by Chemical Formula 1.

[0055] [Chemical Formula 1]

[0056] M(NO3)x

[0057] M is Cr, Al, Ga, In, Cu, Fe, Mn, Co, Ni, Zn, Mg, Ca, La, Ce or Sm, and

[0058] X is any one of integers from 1 to 4.

[0059] In addition, the hydrates of the metal nitrates are Cr(NO3)3·9H2O, Al(NO3)3·9H2O, Ga(NO3)3·xH2O (where x is an integer from 1 to 10). It may include one or more selected from the group consisting of and In(NO3)3·xH2O (where x is an integer from 1 to 10).

[0060] In addition, the above nitrate-based ionic liquid may include a compound represented by structural formula 1.

[0061] [Structural Formula 1]

[0062]

[0063] In the above structural formula 1,

[0064] R 1 It is a hydrogen atom or a C1 to C15 alkyl group, and

[0065] R 2 is a hydrogen atom or a C1 to C9 alkyl group.

[0066] Also, R 1 is a C1 to C10 alkyl group, and R 2 It can be a hydrogen atom or a methyl group.

[0067] In addition, the nitrate-based ionic liquid comprises 1-methylimidazolium nitrate ([MIM]NO3), 1-ethyl-3-methylimidazolium nitrate ([EMIM]NO3), 1-butyl-3-methylimidazolium nitrate ([BMIM]NO3) and 1-decyl-3-methylimidazolium nitrate ([C 10 It may include one or more types selected from the group consisting of [MIM]NO3).

[0068] In addition, the catalyst may include a combination catalyst of In(NO3)3·xH2O (where x is an integer from 1 to 10) and [EMIM]NO3.

[0069] According to another aspect of the present invention, a method for preparing a catalyst is provided, comprising: (1) a step of preparing a metal nitrate or its hydrate; (2) a step of preparing an ionic liquid; and (3) a step of mixing the metal nitrate or its hydrate and the ionic liquid.

[0070] Additionally, the above step (2) may include: (2-1) a step of adding an alkylimidazole precursor to a solvent; (2-2) a step of adding a nitrate and stirring; and (2-3) a step of drying in a rotary evaporator.

[0071] Additionally, the above step (2-2) may be performed at a temperature of -10 to 30°C. If the above step (2-2) is performed at a temperature below -10°C, it is not desirable because it is lower than the freezing point of water used as a solvent, and if it is performed at a temperature above 30°C, it is not desirable because high-temperature exothermic reaction may occur.

[0072] Additionally, the above step (2-3) may be performed at a temperature of 50 to 90°C. If the above step (2-3) is performed at a temperature below 50°C, it is not desirable because water evaporation is difficult, and if it is performed at a temperature above 90°C, it is not desirable because the ionic liquid may evaporate along with the water due to rapid water evaporation when using a rotary evaporator.

[0073] According to another aspect of the present invention, a method for producing 5-hydroxymethylfurfural is provided, comprising the step of reacting a reactant comprising one or more selected from the group consisting of glucose and high fructose corn syrup (HFCS) in the presence of a catalyst and a solvent to produce 5-hydroxymethylfurfural.

[0074] In addition, the solvent may include one or more selected from the group consisting of dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), acetonitrile, toluene, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, ethyl acetate, hexane, benzene, 1,4-dioxane, diethyl ether, chloroform, dichloromethane, water (H2O), methyl isobutyl ketone (MIBK), methyl t-butyl ether (MTBE), dimethyl ether (DME), dimethyl carbonate (DMC), and dimethoxyethane.

[0075] In addition, the above reaction may be carried out for 5 to 200 minutes. If the above reaction is carried out for less than 5 minutes, it is undesirable because the efficiency of producing 5-hydroxymethylfurfural is low due to insufficient reaction time, and if it is carried out for more than 200 minutes, it is undesirable because the selectivity of 5-hydroxymethylfurfural is low and side reactions may occur.

[0076] In addition, the above reaction may be carried out at a temperature of 80 to 150 ℃. If the above reaction is carried out at a temperature below 80 ℃, it is undesirable because the conversion rate of glucose is too low and the efficiency of producing 5-hydroxymethylfurfural is low, and if it is carried out at a temperature above 150 ℃, it is undesirable because the selectivity of 5-hydroxymethylfurfural is low and side reactions may occur.

[0077] In addition, the catalyst comprises a metal nitrate or its hydrate; and a nitrate-based ionic liquid; and can produce 5-hydroxymethylfurfural (HMF).

[0078] In addition, 1 to 30 parts by weight of a metal nitrate or its hydrate may be included with respect to 100 parts by weight of the glucose. If the metal nitrate or its hydrate is less than 1 part by weight with respect to 100 parts by weight of the glucose, it is undesirable because the amount of catalyst is insufficient to activate the glucose, and if it exceeds 30 parts by weight, it is undesirable because an unnecessarily large amount of catalyst is consumed for the catalytic conversion of glucose.

[0079] In addition, 1 to 50 parts by weight of an ionic liquid may be included for every 100 parts by weight of the glucose. If the ionic liquid is less than 1 part by weight for every 100 parts by weight of the glucose, it is undesirable because the amount of catalyst is insufficient to activate the glucose, and if it exceeds 50 parts by weight, it is undesirable because an unnecessarily large amount of catalyst is consumed for the catalytic conversion of glucose.

[0080] In addition, the metal nitrate can be represented by Chemical Formula 1.

[0081] [Chemical Formula 1]

[0082] M(NO3)x

[0083] M is Cr, Al, Ga, In, Cu, Fe, Mn, Co, Ni, Zn, Mg, Ca, La, Ce or Sm, and

[0084] X is any one of integers from 1 to 4.

[0085] In addition, the hydrates of the metal nitrates are Cr(NO3)3·9H2O, Al(NO3)3·9H2O, Ga(NO3)3·xH2O (where x is an integer from 1 to 10). It may include one or more selected from the group consisting of and In(NO3)3·xH2O (where x is an integer from 1 to 10).

[0086] In addition, the above nitrate-based ionic liquid may include a compound represented by structural formula 1.

[0087] [Structural Formula 1]

[0088]

[0089] In the above structural formula 1,

[0090] R 1 It is a hydrogen atom or a C1 to C15 alkyl group, and

[0091] R 2 is a hydrogen atom or a C1 to C9 alkyl group.

[0092] Also, R 1 is a C1 to C10 alkyl group, and R 2 It can be a hydrogen atom or a methyl group.

[0093] In addition, the nitrate-based ionic liquid comprises 1-methylimidazolium nitrate ([MIM]NO3), 1-ethyl-3-methylimidazolium nitrate ([EMIM]NO3), 1-butyl-3-methylimidazolium nitrate ([BMIM]NO3) and 1-decyl-3-methylimidazolium nitrate ([C 10 It may include one or more types selected from the group consisting of [MIM]NO3).

[0094] FIG. 1 is a flowchart showing the method for reusing the catalyst of the present invention, and FIG. 2 shows the catalyst separation and HMF extraction process of the present invention.

[0095] Referring to FIGS. 1 and 2, a method for reusing a catalyst is provided, comprising the steps of: separating a solid metal nitrate or its hydrate; extracting HMF present in the liquid phase with diethyl ether to separate it from a DMSO (ionic liquid) layer; adding water to completely dissolve the ionic liquid to remove humin in the DMSO layer, then adding activated carbon (activated charcoal) and stirring to adsorb humin; removing the activated carbon after humin adsorption; and separating the ionic liquid by evaporating water.

[0096] In addition, the step of separating the metal nitrate or its hydrate may use filter paper.

[0097] In addition, the hydrate of the metal nitrate may include one or more selected from the group consisting of Cr(NO3)3·9H2O, Al(NO3)3·9H2O, Ga(NO3)3·xH2O (where x is an integer from 1 to 10), In(NO3)3·xH2O (where x is an integer from 1 to 10), Cu(NO3)2·2.5H2O, Fe(NO3)3·6H2O, Mn(NO3)2·4H2O, Co(NO3)2·6H2O, Ni(NO3)2·6H2O, Zn(NO3)2·6H2O, Mg(NO3)2·6H2O, Ca(NO3)2·4H2O, La(NO3)3·6H2O, Ce(NO3)3·6H2O, and Sm(NO3)3·6H2O.

[0098] In addition, the activated carbon may comprise 1 to 30 parts by weight for every 100 parts by weight of the catalyst. If the activated carbon is less than 1 part by weight for every 100 parts by weight of the catalyst, it is not desirable because it cannot sufficiently adsorb humin, and if it exceeds 30 parts by weight, it is not desirable because an unnecessarily large amount of activated carbon is consumed.

[0099] In addition, the step of adsorbing the humin may be performed for 5 to 24 hours. If the step of adsorbing the humin is performed for less than 5 hours, it is not desirable because the humin is not sufficiently adsorbed, and if it is performed for more than 24 hours, it is not desirable because an unnecessarily large amount of time is consumed.

[0100] In addition, the step of removing the activated carbon can be performed by syringe filtering.

[0101] In addition, the above ionic liquid is 1-methylimidazolium nitrate ([MIM]NO3), [EMIM]NO3, [BMIM]NO 3,1-Butyl-3-methylimidazolium nitrate ([BMIM]NO3) and 1-decyl-3-methylimidazolium nitrate ([C 10 It may include one or more types selected from the group consisting of [MIM]NO3).

[0102] [Example]

[0103] Hereinafter, preferred embodiments of the present invention will be described. However, this is for illustrative purposes only and does not limit the scope of the present invention.

[0104] Preparation Example: Preparation of Ionic Liquids

[0105] Preparation Example 1: [MIM]NO 3 manufacturing

[0106] 1-Methylimidazole (0.05 mol) and water (10 mL) were placed in a round-bottom flask. The flask was then stored in an ice bath to maintain the temperature between 0 and 3 °C. HNO3 60% (0.083 mol) was added dropwise to the side wall of the round-bottom flask while vigorously stirring. Subsequently, the mixture was stirred for an additional 1 hour at 0 °C, followed by stirring at room temperature for 1 day. The resulting ionic liquid was dried under reduced pressure in a rotary evaporator at 60 °C for 1 hour to finally produce [MIM]NO3.

[0107] Preparation Example 2: [EMIM]NO 3

[0108] [EMIM]NO3(TCI, E0775, 143314-14-1) was used.

[0109] Preparation Example 3: [BMIM]NO 3

[0110] [BMIM]NO3(TCI, B5103, 179075-88-8) was used.

[0111] Preparation Example 4: [C 10 MIM]NO 3 manufacturing

[0112] 1-decyl-3-methylimidazolium chloride (0.05 mol) and AgNO3 (0.05 mol) were dissolved in 30 ml of water. The mixture was stirred at room temperature for 12 hours. The resulting powder (AgCl) was filtered through Celite and washed with water. The filtered ionic liquid solution was filtered again through a hydrophilic syringe filter to remove the remaining AgCl powder. The ionic liquid solution was then dried in a rotary evaporator at 60 °C under reduced pressure for 2 hours to finally [C 10 MIM]NO3 was manufactured.

[0113] Example: Catalyst comprising a hydrate-ionic liquid of a metal nitrate

[0114] Example 1: M(NO 3 ) 3 ·xH 2 O-[MIM]NO 3 catalyst (xH, unless specifically stated otherwise in the present invention) 2 x of O is any integer from 1 to 10)

[0115] Example 1-1: Cr(NO 3 ) 3 ·9H 2 O-[MIM]NO 3

[0116] Cr(NO3)3·9H2O-[MIM]NO3 was prepared by mixing 1 g (5.55 mmol) of glucose, 1.67 mmol of the ionic liquid [MIM]NO3 according to Preparation Example 1, and 1.11 mmol of Cr(NO3)3·9H2O in 10 mL of DMSO solvent in a high pressure flask and reacting for 2 hours at 120 °C by installing an oil bath in a heating stirrer equipped with a temperature control device.

[0117] Examples 1-2: Al(NO 3 ) 3·9H 2 O-[MIM]NO 3

[0118] An Al(NO3)3·9H2O-[MIM]NO3 catalyst was prepared in the same manner as in Example 1-1, except that Al(NO3)3·9H2O was used as the metal nitrate precursor instead of Cr(NO3)3·9H2O.

[0119] Examples 1-3: Ga(NO 3 ) 3 ·xH 2 O-[MIM]NO 3

[0120] A Ga(NO3)3·xH2O-[MIM]NO3 catalyst was prepared in the same manner as in Example 1-1, except that Ga(NO3)3·xH2O was used instead of Cr(NO3)3·9H2O as the metal nitrate precursor.

[0121] Examples 1-4: In(NO 3 ) 3 ·xH 2 O-[MIM]NO 3

[0122] An In(NO3)3·xH2O-[MIM]NO3 catalyst was prepared in the same manner as in Example 1-1, except that In(NO3)3·xH2O was used as the metal nitrate precursor instead of Cr(NO3)3·9H2O.

[0123] Example 2: M(NO 3 ) 3 ·xH 2 O-[EMIM]NO 3 catalyst

[0124] Example 2-1: Cr(NO 3 ) 3 ·9H 2 O-[EMIM]NO3

[0125] Cr(NO3)3·9H2O-[EMIM]NO3 was prepared in the same manner as in Example 1-1, except that [EMIM]NO3 prepared in Preparation Example 2 was used instead of [MIM]NO3 prepared in Preparation Example 1.

[0126] Example 2-2: Al(NO 3 ) 3 ·9H 2 O-[EMIM]NO 3

[0127] Al(NO3)3·9H2O-[EMIM]NO3 was prepared in the same manner as in Examples 1-2, except that [EMIM]NO3 prepared in Preparation Example 2 was used instead of [MIM]NO3 prepared in Preparation Example 1.

[0128] Example 2-3: Ga(NO 3 ) 3 ·xH 2 O-[EMIM]NO 3

[0129] Ga(NO3)3·xH2O-[EMIM]NO3 was prepared in the same manner as in Examples 1-3, except that [EMIM]NO3 prepared in Preparation Example 2 was used instead of [MIM]NO3 prepared in Preparation Example 1.

[0130] Examples 2-4: In(NO 3 ) 3 ·xH 2 O-[EMIM]NO 3

[0131] In(NO3)3·xH2O-[EMIM]NO3 was prepared in the same manner as in Examples 1-4, except that [EMIM]NO3 prepared in Preparation Example 2 was used instead of [MIM]NO3 prepared in Preparation Example 1.

[0132] Example 3: M(NO 3 ) 3 ·xH 2 O-[BMIM]NO 3 catalyst

[0133] Example 3-1: Cr(NO 3 ) 3 ·9H 2 O-[BMIM]NO 3

[0134] Cr(NO3)3·9H2O-[BMIM]NO3 was prepared in the same manner as in Example 1-1, except that [BMIM]NO3 prepared in Preparation Example 3 was used instead of [MIM]NO3 prepared in Preparation Example 1.

[0135] Example 3-2: Al(NO 3 ) 3 ·9H 2 O-[BMIM]NO 3

[0136] Al(NO3)3·9H2O-[BMIM]NO3 was prepared in the same manner as in Examples 1-2, except that [BMIM]NO3 prepared in Preparation Example 3 was used instead of [MIM]NO3 prepared in Preparation Example 1.

[0137] Example 3-3: Ga(NO 3 ) 3 ·xH 2 O-[BMIM]NO 3

[0138] Ga(NO3)3·xH2O-[BMIM]NO3 was prepared in the same manner as in Examples 1-3, except that [BMIM]NO3 prepared in Preparation Example 3 was used instead of [MIM]NO3 prepared in Preparation Example 1.

[0139] Examples 3-4: In(NO3 ) 3 ·xH 2 O-[BMIM]NO 3

[0140] In(NO3)3·xH2O-[BMIM]NO3 was prepared in the same manner as in Examples 1-4, except that [BMIM]NO3 prepared in Preparation Example 3 was used instead of [MIM]NO3 prepared in Preparation Example 1.

[0141] Example 4: M(NO 3 ) 3 ·xH 2 O-[C 10 MIM]NO 3 catalyst

[0142] Example 4-1: Cr(NO 3 ) 3 ·9H 2 O-[C 10 MIM]NO 3

[0143] Instead of using [MIM]NO3 prepared in Preparation Example 1, [C prepared in Preparation Example 4 10 Except for using [MIM]NO3, the same method as in Example 1-1 was used for Cr(NO3)3·9H2O-[C 10 MIM]NO3 was manufactured.

[0144] Example 4-2: Al(NO 3 ) 3 ·9H 2 O-[C 10 MIM]NO 3

[0145] Instead of using [MIM]NO3 prepared in Preparation Example 1, [C prepared in Preparation Example 4 10Except for using [MIM]NO3, the same method as in Examples 1-2 was used for Al(NO3)3·9H2O-[C 10 MIM]NO3 was manufactured.

[0146] Example 4-3: Ga(NO 3 ) 3 ·xH 2 O-[C 10 MIM]NO 3

[0147] Instead of using [MIM]NO3 prepared in Preparation Example 1, [C prepared in Preparation Example 4 10 Except for using [MIM]NO3, the same method as in Examples 1-3 was used for Ga(NO3)3·xH2O-[C 10 MIM]NO3 was manufactured.

[0148] Example 4-4: In(NO 3 ) 3 ·xH 2 O-[C 10 MIM]NO 3

[0149] Instead of using [MIM]NO3 prepared in Preparation Example 1, [C prepared in Preparation Example 4 10 Except for using [MIM]NO3, the same method as in Examples 1-4 was used for In(NO3)3·xH2O-[C 10 MIM]NO3 was manufactured.

[0150] Comparative Example 1: No catalyst prepared

[0151] The catalyst was not manufactured.

[0152] Comparative Example 2: HCl catalyst

[0153] HCl (36%, 0.51 g) was prepared as an acid catalyst.

[0154] Comparative Example 3: HNO 3 catalyst

[0155] HNO3 (60%, 0.52 g) was prepared as an acid catalyst.

[0156] Comparative Example 4: H 2 SO 4 catalyst

[0157] H2SO4 (95%, 0.52 g) was prepared as an acid catalyst.

[0158] Table 1 below summarizes the conditions in the manufacturing process of Comparative Examples 1 to 4 and Examples 1-1 to 4-4 of the present invention.

[0159] division ionic liquid metal nitrate precursor catalyst Example 1-1 [MIM]NO3 Cr(NO3)3·9H2O Cr(NO3)3·9H2O-[MIM]NO3 Examples 1-2 [MIM]NO3 Al(NO3)3·9H2O Al(NO3)3·9H2O-[MIM]NO3 Examples 1-3 [MIM]NO3 Ga(NO3)3·xH2O Ga(NO3)3·xH2O-[MIM]NO3 Examples 1-4 [MIM]NO3 In(NO3)3·xH2O In(NO3)3·xH2O-[MIM]NO3 Example 2-1 [EMIM]NO3 Cr(NO3)3·9H2O Cr(NO3)3·9H2O-[MIM]NO3 Example 2-2 [EMIM]NO3 Al(NO3)3·9H2O Al(NO3)3·9H2O-[MIM]NO3 Examples 2-3 [EMIM]NO3 Ga(NO3)3·xH2O Ga(NO3)3·xH2O-[MIM]NO3 Examples 2-4 [EMIM]NO3 In(NO3)3·xH2O In(NO3)3·xH2O-[MIM]NO3 Example 3-1 [BMIM]NO3 Cr(NO3)3·9H2O Cr(NO3)3·9H2O-[MIM]NO3 Example 3-2 [BMIM]NO3 Al(NO3)3·9H2O Al(NO3)3·9H2O-[MIM]NO3 Example 3-3 [BMIM]NO3 Ga(NO3)3·xH2O Ga(NO3)3·xH2O-[MIM]NO3 Examples 3-4 [BMIM]NO3 In(NO3)3·xH2O In(NO3)3·xH2O-[MIM]NO3 Example 4-1 [W 10 ME]NO3 Cr(NO3)3·9H2O Cr(NO3)3·9H2O-[MIM]NO3 Example 4-2 [W 10 ME]NO3 Al(NO3)3·9H2O Al(NO3)3·9H2O-[MIM]NO3 Example 4-3 [W 10 ME]NO3 Ga(NO3)3·xH2O Ga(NO3)3·xH2O-[MIM]NO3 Examples 4-4 [W 10 ME]NO3 In(NO3)3·xH2O In(NO3)3·xH2O-[MIM]NO3 Comparative Example 1 - - - Comparative Example 2 - - HCl Comparative Example 3 - - HNO3 Comparative Example 4 - - H2SO4

[0160] [Test Example]

[0161] Test Example 1: Confirmation of glucose conversion rate (%), HMF selectivity (%), and fructose selectivity (%) of Examples 1-1 to 4-4 of the present invention

[0162] FIG. 3 shows the glucose conversion rate (%), HMF selectivity (%), and fructose selectivity (%) according to Examples 1-1 to 4-4 of the present invention.

[0163] HMF selectivity (% selectivity), fructose selectivity (% selectivity), glucose conversion (% conversion) and HFCS conversion (% conversion) were calculated using Equations 1 to 6 below.

[0165] 5-HMF Yield (%) = (1)

[0167] Fructose Yield (%) = (2)

[0169] Glucose conversion (%) = (3)

[0171] HMF Selectivity (%) = (4)

[0173] Fructose Selectivity (%) = (5)

[0175] HFCS Conversion (%) = (6)

[0177] Table 2 summarizes the catalyst screening data for the HMF production reaction for metal nitrate hydrate-nitrate-based ionic liquid catalyst combinations according to Examples 1-1 to 4-4 of the present invention.

[0178] division catalyst Glucose %Conversion HMF %Selectivity Fructose %Selectivity Example 1-1 Cr(NO3)3·9H2O-[MIM]NO3 95.37 44.93 12.16 Examples 1-2 Al(NO3)3·9H2O-[MIM]NO3 97.22 49.34 7.19 Examples 1-3 Ga(NO3)3·xH2O-[MIM]NO3 99.61 41.88 5.99 Examples 1-4 In(NO3)3·xH2O-[MIM]NO3 96.97 72.53 0 Example 2-1 Cr(NO3)3·9H2O-[EMIM]NO3 92.61 46.14 18.96 Example 2-2 Al(NO3)3·9H2O-[EMIM]NO3 93.30 28.89 12.64 Examples 2-3 Ga(NO3)3·xH2O-[EMIM]NO3 100 46.19 4.40 Examples 2-4 In(NO3)3·xH2O-[EMIM]NO3 97.20 83.38 5.78 Example 3-1 Cr(NO3)3·9H2O-[BMIM]NO3 94.56 45.64 13.45 Example 3-2 Al(NO3)3·9H2O-[BMIM]NO3 90.84 28.66 15.06 Example 3-3 Ga(NO3)3·xH2O-[BMIM]NO3 98.71 44.23 6.94 Examples 3-4 In(NO3)3·xH2O-[BMIM]NO3 93.94 72.49 5.32 Example 4-1 Cr(NO3)3·9H2O-[C 10 [MIM]NO3 70.28 65.81 0 Example 4-2 Al(NO3)3·9H2O-[C 10 [MIM]NO3 97.91 63.34 0 Example 4-3 Ga(NO3)3·xH2O-[C 10 [MIM]NO3 94.01 74.21 0 Examples 4-4 In(NO3)3·xH2O-[C 10 [MIM]NO3 95.83 70.63 0

[0179] Referring to FIG. 3 and Table 2, the hydrates of metal nitrates Cr(NO3)3·9H2O, Al(NO3)3·9H2O, Ga(NO3)3·xH2O, and In(NO3)3·xH2O, and the nitrate-based ionic liquids [MIM]NO3, [EMIM]NO3, [BMIM]NO3, and [C 10 A glucose conversion reaction was performed using a non-halogen catalyst combination of [MIM]NO3. The In(NO3)3·xH2O-[EMIM]NO3 combination exhibited the highest HMF selectivity at 82.61%. Furthermore, among non-halogen catalyst combinations, even when using the same ionic liquid, the combination catalysts containing In(NO3)3·xH2O—In(NO3)3·xH2O-[MIM]NO3, In(NO3)3·xH2O-[EMIM]NO3, and In(NO3)3·xH2O-[BMIM]NO3—showed high HMF selectivity compared to other metals, with values ​​of 72.53%, 83.38%, and 72.49%, respectively.

[0180] Test Example 2: Confirmation of glucose conversion rate (%), HMF selectivity (%), and fructose selectivity (%) of Comparative Examples 1 to 4

[0181] Figure 4 shows the glucose conversion rate (%), HMF selectivity (%), and fructose selectivity (%) under conditions without a catalyst (Comparative Example 1) and conditions using only an acid catalyst (Comparative Examples 2 to 4).

[0182] Table 3 summarizes the glucose conversion rate (%), HMF selectivity (%), and fructose selectivity (%) of Comparative Examples 1 to 4.

[0183] division Glucose %Conversion HMF %Selectivity Fructose %Selectivity Comparative Example 1 6.41 0 0 Comparative Example 2 98.11 7.47 2.47 Comparative Example 3 86.68 0 12.94 Comparative Example 4 89.59 21.44 17.57

[0184] Referring to Figure 4 and Table 3, Comparative Example 1, which did not use a catalyst, and Comparative Examples 2, 3, and 4, which used only an acid catalyst, showed no HMF selectivity or significantly low HMF selectivity. When a metal-based catalyst is used, an isomerization reaction occurs in glucose to form fructose, and HMF can be produced through the dehydration reaction of fructose. Therefore, it was confirmed that the use of a metal-based catalyst (Lewis acid) is important for HMF production.

[0185] Test Example 3: HMF production reaction using recycled catalyst

[0186] Figure 5 shows the glucose conversion rate (%), HMF selectivity (%), and fructose selectivity (%) of the catalyst in Example 2-4 of the present invention (In(NO3)3·xH2O-[EMIM]NO3) and the recycled catalyst in Example 2-4 of the present invention (Recycled In(NO3)3·xH2O-[EMIM]NO3).

[0187] Table 4 summarizes the reaction data for HMF production according to the catalysts of Example 2-4 of the present invention (In(NO3)3·xH2O-[EMIM]NO3) and the recycled Example 2-4 of the present invention (Recycled In(NO3)3·xH2O-[EMIM]NO3).

[0188] catalyst Glucose %Conversion HMF %Selectivity Fructose %Selectivity In(NO3)3·xH2O-[EMIM]NO3 99.16 82.61 7.14 Recycled In(NO3)3·xH2O-[EMIM]NO3 88.90 66.35 5.92

[0189] Referring to Figure 5 and Table 4, it can be seen that the In(NO3)3·xH2O-[EMIM]NO3 catalyst can be separated from the produced HMF. In addition, since HMF can be produced even using a recycled catalyst, it was confirmed that the In(NO3)3·xH2O-[EMIM]NO3 catalyst can be recycled.

[0190] Test Example 4: HMF production reaction using high fructose corn syrup (HFCS)

[0191] Figure 6 shows the HFCS conversion rate (%), glucose conversion rate (%), fructose conversion rate (%), and HMF selectivity (%) according to the catalysts of Examples 2-1 to 2-4 of the present invention.

[0192] The test conditions involved mixing HFCS (1 g, composition of HFCS: 30 wt% of water, 42 wt% of fructose, 0.28 wt% of glucose), In(NO3)3·xH2O (1.11 mmol), [EMIM]NO3 (1.67 mmol), and DMSO, and stirring at 120 ℃ for 2 hours.

[0193] Table 5 summarizes the data showing the conversion rates of HFCS, glucose, and fructose and the selectivity of HMF according to the catalysts of Examples 2-1 to 2-4 of the present invention.

[0194] catalyst HFCS %Conversion Glucose %Conversion Fructose %Conversion HMF %Selectivity Cr(NO3)3·9H2O-[EMIM]NO3 97.51 93.77 99.99 55.01 Al(NO3)3·9H2O-[EMIM]NO3 98.91 97.77 99.99 25.35 Ga(NO3)3·xH2O-[EMIM]NO3 100 100 99.99 47.27 In(NO3)3·xH2O-[EMIM]NO3 96.47 91.19 99.99 64.97

[0195] * Represents the conversion rates of glucose and fructose, respectively, contained in HFCS.

[0196] Referring to Figure 6 and Table 5, it was confirmed that HMF can be produced from HFCS when using the M(NO3)3·xH2O-[EMIM]NO3 catalyst.

[0197] Test Example 5: HFCS conversion rate and HMF production reaction according to DMSO usage

[0198] Figure 7 shows the HFCS conversion rate (%), glucose conversion rate (%), fructose conversion rate (%), and HMF selectivity (%) according to the amount of DMSO used.

[0199] The test conditions involved mixing HFCS (1 g, composition of HFCS: 30 wt% of water, 42 wt% of fructose, 0.28 wt% of glucose), In(NO3)3·xH2O (1.11 mmol), [EMIM]NO3 (1.67 mmol), and DMSO, and stirring at 120 ℃ for 2 hours.

[0200] Table 6 summarizes the conversion rates of HFCS, glucose, and fructose and the selectivity of HMF according to the amount of DMSO used.

[0201] Amount of DMSO (mL) HFCS %Conversion Glucose %Conversion Fructose %Conversion HMF %Selectivity 1 99.95 99.87 99.99 33.19 2 91.36 78.89 99.68 52.35 3 93.91 84.77 99.99 69.31 4 91.31 78.28 99.99 71.67 5 99.57 98.93 99.99 72.70 6 88.60 71.51 99.99 63.11 7 94.89 87.21 99.99 64.86 8 97.92 94.81 99.99 66.60 9 99.36 98.39 99.99 69.35 10 96.47 91.19 99.99 64.97

[0202] * Represents the conversion rates of glucose and fructose, respectively, contained in HFCS.

[0203] Referring to Figure 7 and Table 6, the HFCS conversion reaction was carried out using a non-halogen catalyst combination of metal nitrate hydrates Cr(NO3)3·9H2O, Al(NO3)3·9H2O, Ga(NO3)3·xH2O, and In(NO3)3·xH2O, and the nitrate-based ionic liquid [EMIM]NO3. As a result, the In(NO3)3·xH2O-[EMIM]NO3 combination of Examples 2-4 exhibited the highest HMF selectivity at 64.97%. To determine the optimal amount of DMSO to use while performing the HFCS conversion reaction with the In(NO3)3·xH2O-[EMIM]NO3 catalyst, the amount of DMSO was adjusted from 1 mL to 10 mL; when 5 mL of DMSO was used, the highest HMF selectivity of 72.7% was observed, along with a high conversion rate of HFCS.

[0204] Test Example 6: HMF production reaction according to the mixing ratio of glucose and fructose

[0205] Figure 8 shows the glucose conversion rate (%), fructose conversion rate (%), and HMF selectivity (%) according to the mixing ratio of glucose and fructose.

[0206] The test conditions involved mixing Glucose (0 g to 10 g), Fructose (10 g to 0 g), In(NO3)3·xH2O (1.11 mmol), [EMIM]NO3 (1.67 mmol), and DMSO (10 mL), and stirring at 120 ℃ for 2 hours.

[0207] Table 7 summarizes the glucose and fructose conversion rates and HMF selectivity according to the mixing ratio of glucose and fructose.

[0208] Glucose:Fructose Glucose %Conversion Fructose %Conversion HMF %Selectivity 0:10 89.89 100 1:9 62.99 99.99 69.81 2:8 89.99 99.99 70.27 3:7 75.27 99.99 67.64 4:6 83.10 99.99 68.88 5:5 91.17 99.99 70.14 6:4 89.16 99.99 70.97 7:3 92.88 95.83 74.84 8:2 97.32 81.01 79.59 9:1 97.86 92.29 80.41 10:0 97.20 83.37

[0209] *total amount of sugar (glucose+fructose): 5.55 mmol

[0210] Referring to Figure 8 and Table 7, the HMF selectivity according to the mixing ratio of glucose and fructose was determined using the In(NO3)3·xH2O-[EMIM]NO3 combination catalyst. The highest HMF selectivity of 80.41% was observed under the condition where glucose and fructose were mixed in a 9:1 ratio.

[0211] The scope of the present invention is defined by the claims set forth below rather than by the detailed description above, and all modifications or variations derived from the meaning and scope of the claims and equivalent concepts thereof should be interpreted as being included within the scope of the present invention.

Claims

Claim 1 A catalyst comprising a metal nitrate or its hydrate; and a nitrate-based ionic liquid; wherein the catalyst comprises a combination catalyst of In(NO3)3·xH2O (where x is an integer from 1 to 10) and 1-Ethyl-3-methylimidazolium nitrate ([EMIM]NO3), and a catalyst for producing 5-hydroxymethylfurfural (HMF). Claim 2 A catalyst according to claim 1, characterized in that the catalyst is for producing 5-hydroxymethylfurfural from one or more selected from the group consisting of glucose and corn syrup. Claim 3 delete Claim 4 delete Claim 5 delete Claim 6 delete Claim 7 delete Claim 8 delete Claim 9 A method for producing 5-hydroxymethylfurfural, comprising the step of reacting a reactant containing one or more selected from the group consisting of glucose and corn syrup in the presence of a catalyst and a solvent according to claim 1 to produce 5-hydroxymethylfurfural. Claim 10 A method for producing 5-hydroxymethylfurfural according to claim 9, characterized in that the solvent comprises one or more selected from the group consisting of dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), acetonitrile, toluene, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, ethyl acetate, hexane, benzene, 1,4-dioxane, diethyl ether, chloroform, dichloromethane, water (H2O), methyl isobutyl ketone (MIBK), methyl t-butyl ether (MTBE), dimethyl ether (DME), dimethyl carbonate (DMC), and dimethoxyethane. Claim 11 A method for producing 5-hydroxymethylfurfural according to claim 9, characterized in that the above reaction is carried out at 80 to 150 ℃. Claim 12 delete Claim 13 delete Claim 14 delete Claim 15 delete Claim 16 delete Claim 17 delete

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