Metal nitrate hydrate catalyst and method for preparing 5-hydroxymethylfurfural using same

Abstract

The present invention relates to a metal nitrate hydrate catalyst and a method for preparing 5-hydroxymethylfurfural, using same and, more specifically, may provide: a catalyst which comprises a metal nitrate hydrate and is to prepare 5-hydroxymethylfurfural (HMF) from at least one selected from the group consisting of monosaccharides and disaccharides; and a method for preparing 5-hydroxymethylfurfural (HMF), the method comprising (a) a step of preparing 5-HMF by reaction in the presence of the catalyst from a sugar comprising at least one selected from the group consisting of monosaccharides and disaccharides. The present invention provides high 5-HMF yield and selectivity, biological and process stability, and economic efficiency by using inexpensive monosaccharides and / or disaccharides.

Description

Metal nitrate hydrate catalyst and method for producing hydroxymethylfurfural using the same

[0001] The present invention relates to a metal nitrate hydrate catalyst and a method for producing hydroxymethylfurfural using the same.

[0002] Hydroxymethylfurfural (HMF) is attracting attention as a bio-based platform material capable of producing furan-2,5-dicarboxylic acid (FDCA), the monomer for the bioplastic polyethylene furandicarboxylate (PEF). It can replace the existing petroleum-based plastic polyethylene terephthalate (PET) and can be utilized in various chemical industries. However, the scale of raw material production is small compared to the volume of bioplastic products produced, necessitating the development of monomer production technologies derived from biomass, a sustainable energy resource. Conventional chromium-based and halogen-based catalysts used in HMF synthesis suffer from technical limitations in terms of low synthesis yield, selectivity, process stability, and economic feasibility. Therefore, the development of novel catalyst technologies that can increase HMF synthesis yield and selectivity while also enhancing process stability is essential. With growing interest in biomass-derived bioplastic production technologies, the conversion of lignocellulosic biomass, a globally abundant raw material, is gaining importance.

[0003] Therefore, it is necessary to develop a method for producing HMF that can secure price competitiveness by reducing the cost of raw materials by producing HMF from low-cost sugars or mixed sugars rather than refined raw materials such as high-cost crystalline glucose or crystalline fructose.

[0004] An object of the present invention is to provide a catalyst comprising a metal nitrate hydrate and for producing HMF from monosaccharides and / or disaccharides.

[0005] In addition, it is an object of the present invention to provide a catalyst having high yield and selectivity of HMF and excellent biological stability and process stability.

[0006] In addition, an object of the present invention is to provide a method for producing HMF with high conversion rate and selectivity from monosaccharides and / or disaccharides using the above catalyst.

[0007] In addition, it is an object of the present invention to provide an economical method for producing HMF using inexpensive monosaccharides and disaccharides.

[0008] According to one aspect of the present invention, a catalyst is provided for producing hydroxymethylfurfural (HMF, 5-hydroxymethylfurfural) from at least one selected from the group consisting of monosaccharides and disaccharides, and comprising a metal nitrate hydrate.

[0009] In addition, the catalyst may be for producing hydroxymethylfurfural (HMF, 5-hydroxymethylfurfural) from one selected from the group consisting of monosaccharides and disaccharides, or two or more selected from the group consisting of monosaccharides and disaccharides.

[0010] Additionally, the catalyst may be for producing hydroxymethylfurfural (HMF, 5-hydroxymethylfurfural) from two or more selected from the group consisting of monosaccharides and disaccharides.

[0011] Additionally, the catalyst may be a non-halogen catalyst.

[0012] In addition, the metal nitrate hydrate includes at least one selected from the group consisting of In(NO3)3·xH2O, Al(NO3)3·xH2O, Ga(NO3)3·xH2O, Mg(NO3)2·xH2O, Ca(NO3)2·xH2O, La(NO3)3·xH2O, Ce(NO3)3·xH2O, Sm(NO3)3·xH2O, Zn(NO3)2·xH2O, Cu(NO3)2·xH2O, Ni(NO3)2·xH2O, Co(NO3)2·xH2O, Fe(NO3)3·xH2O, Mn(NO3)2·xH2O, and Cr(NO3)3·xH2O, wherein x may be 1≤x≤30.

[0013] In addition, the monosaccharides and disaccharides may include at least one selected from the group consisting of glucose, fructose, mannose, sucrose, galactose, lactose, maltose, and trehalose.

[0014] Additionally, the monosaccharides and disaccharides may include at least one selected from the group consisting of glucose, fructose, mannose, and sucrose.

[0015] According to another aspect of the present invention, a method for producing hydroxymethylfurfural is provided, comprising the step (a) of producing hydroxymethylfurfural (HMF, 5-hydroxymethylfurfural) by reacting a sugar comprising at least one selected from the group consisting of monosaccharides and disaccharides in the presence of a catalyst.

[0016] In addition, the sugar comprises glucose, and the catalyst comprises at least one selected from the group consisting of In(NO3)3·xH2O, Al(NO3)3·xH2O, Ga(NO3)3·xH2O, Mg(NO3)2·xH2O, Ca(NO3)2·xH2O, La(NO3)3·xH2O, Ce(NO3)3·xH2O, Sm(NO3)3·xH2O, Zn(NO3)2·xH2O, Cu(NO3)2·xH2O, Ni(NO3)2·xH2O, Co(NO3)2·xH2O, Fe(NO3)3·xH2O, Mn(NO3)2·xH2O, and Cr(NO3)3·xH2O, wherein x may be 1≤x≤30.

[0017] In addition, the sugar may include fructose, and the catalyst may include In(NO3)3·xH2O, wherein x may be 1≤x≤30.

[0018] In addition, the sugar contains mannose, and the catalyst is Cr(NO3) 3· xH2O, Al(NO3) 3·X H2O, Ga(NO3) 3· xH2O and In(NO3) 3·X Contains at least one selected from the group consisting of H2O, wherein x may be 1≤x≤30.

[0019] In addition, the sugar contains sucrose, and the catalyst is In(NO3) 3·X Contains H2O, where x can be 1≤x≤30.

[0020] In addition, the sugar includes two or more selected from the group consisting of glucose, fructose, mannose, sucrose, galactose, lactose, maltose, and trehalose, and the catalyst includes In(NO3)3·xH2O, wherein x may be 1≤x≤30.

[0021] In addition, the sugar may include glucose and fructose, and the catalyst may include In(NO3)3·xH2O, wherein x may be 1≤x≤30.

[0022] Additionally, the above step (a) can be performed using a solvent.

[0023] In addition, the solvent may include at least one selected from the group consisting of dimethyl sulfoxide (DMSO), ethanol (EtOH), 2-propanol (IPA), methanol (MeOH), acetonitrile (MeCN), dimethoxyethane (DME), ethyl acetate (EA), tetrahydrofuran (THF), methyl isobutyl ketone (MIBK), dimethyl carbonate (DMC), tert-butyl methyl ether (MTBE), and water (H2O).

[0024] Additionally, step (a) can be performed at 50 to 200°C.

[0025] According to another aspect of the present invention, hydroxymethylfurfural manufactured according to the above method for manufacturing hydroxymethylfurfural is provided.

[0026] The present invention can provide a catalyst comprising a metal nitrate hydrate and for producing HMF from monosaccharides and / or disaccharides.

[0027] In addition, the present invention can provide a catalyst having high yield and selectivity of HMF and excellent biological stability and process stability.

[0028] In addition, the present invention can provide a method for producing HMF with high conversion rate and selectivity from monosaccharides and / or disaccharides using the catalyst.

[0029] In addition, the present invention can provide an economical method for producing HMF using inexpensive monosaccharides and / or disaccharides.

[0030] These drawings are for reference in explaining exemplary embodiments of the present invention, and therefore, the technical idea of ​​the present invention should not be interpreted as being limited to the attached drawings.

[0031] Figure 1 is a graph showing the glucose conversion efficiency, HMF selectivity, and fructose selectivity according to various types of metal nitrate hydrate-based catalysts.

[0032] Figure 2 is a graph showing the glucose conversion efficiency, HMF selectivity, fructose selectivity, mannose selectivity, trehalose selectivity, and fructose dimer selectivity according to Al, Ga, and In-based metal complexes and metal oxide catalysts.

[0033] Figure 3 is a graph showing fructose conversion efficiency, HMF selectivity, and glucose selectivity according to various types of metal nitrate hydrate-based catalysts.

[0034] Figure 4 is a graph showing mannose conversion efficiency, HMF selectivity, and glucose selectivity according to various types of metal nitrate hydrate-based catalysts.

[0035] Figure 5 is a graph showing sucrose conversion efficiency, HMF selectivity, glucose selectivity, and fructose selectivity according to various types of metal nitrate hydrate-based catalysts.

[0036] Figure 6 is a graph showing glucose conversion efficiency, HMF selectivity, and fructose selectivity according to various types of organic solvents.

[0037] Figure 7 is a graph showing total sugar conversion efficiency, glucose conversion efficiency, fructose conversion efficiency, HMF selectivity, mannose selectivity, trehalose selectivity, and fructose dimer selectivity according to the mixing ratio of glucose and fructose.

[0038] Figure 8 is a graph showing the glucose conversion efficiency, HMF selectivity, fructose selectivity, and fructose dimer selectivity according to the recycled In(NO3)3·14.4H2O catalyst.

[0039] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings so that a person having ordinary skill in the art to which the present invention pertains can easily practice the invention.

[0040] However, the following description is not intended to limit the present invention to a specific embodiment, and when explaining the present invention, if it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description is omitted.

[0041] The terminology used herein is for the purpose of describing specific embodiments only and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, the terms "comprises" or "has" and the like are intended to indicate the presence of a feature, number, step, operation, component, or combination thereof described in the specification, but should be understood to not preclude the presence or addition of one or more other features, numbers, steps, operations, components, or combinations thereof.

[0042] Additionally, terms including ordinal numbers, such as "first," "second," etc., which will be used hereinafter, may be used to describe various components, but these components are not limited by these terms. These terms are used solely to distinguish one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.

[0043] Additionally, when it is said that a component is "formed on" or "laminated on" another component, it should be understood that it may be formed or laminated directly on the entire surface or one side of the other component, but there may also be other components present in between.

[0044] Hereinafter, a metal nitrate hydrate catalyst and a method for producing hydroxymethylfurfural using the catalyst will be described in detail. However, this is provided as an example and the present invention is not limited thereto. The present invention is defined solely by the scope of the claims set forth below.

[0045] According to one aspect of the present invention, a catalyst is provided for producing hydroxymethylfurfural (HMF, 5-hydroxymethylfurfural) from at least one selected from the group consisting of monosaccharides and disaccharides, and comprising a metal nitrate hydrate.

[0046] In addition, the catalyst may be for producing hydroxymethylfurfural (HMF, 5-hydroxymethylfurfural) from one selected from the group consisting of monosaccharides and disaccharides, or two or more selected from the group consisting of monosaccharides and disaccharides.

[0047] Additionally, the catalyst may be for producing hydroxymethylfurfural (HMF, 5-hydroxymethylfurfural) from two or more selected from the group consisting of monosaccharides and disaccharides.

[0048] Additionally, the catalyst may be a non-halogen catalyst.

[0049] In addition, the metal nitrate hydrate includes at least one selected from the group consisting of In(NO3)3·xH2O, Al(NO3)3·xH2O, Ga(NO3)3·xH2O, Mg(NO3)2·xH2O, Ca(NO3)2·xH2O, La(NO3)3·xH2O, Ce(NO3)3·xH2O, Sm(NO3)3·xH2O, Zn(NO3)2·xH2O, Cu(NO3)2·xH2O, Ni(NO3)2·xH2O, Co(NO3)2·xH2O, Fe(NO3)3·xH2O, Mn(NO3)2·xH2O, and Cr(NO3)3·xH2O, wherein x may be 1≤x≤30.

[0050] In addition, the monosaccharides and disaccharides may include at least one selected from the group consisting of glucose, fructose, mannose, sucrose, galactose, lactose, maltose, and trehalose.

[0051] Additionally, the monosaccharides and disaccharides may include at least one selected from the group consisting of glucose, fructose, mannose, and sucrose.

[0052] According to another aspect of the present invention, a method for producing hydroxymethylfurfural is provided, comprising the step (a) of producing hydroxymethylfurfural (HMF, 5-hydroxymethylfurfural) by reacting a sugar comprising at least one selected from the group consisting of monosaccharides and disaccharides in the presence of a catalyst.

[0053] In addition, the sugar comprises glucose, and the catalyst comprises at least one selected from the group consisting of In(NO3)3·xH2O, Al(NO3)3·xH2O, Ga(NO3)3·xH2O, Mg(NO3)2·xH2O, Ca(NO3)2·xH2O, La(NO3)3·xH2O, Ce(NO3)3·xH2O, Sm(NO3)3·xH2O, Zn(NO3)2·xH2O, Cu(NO3)2·xH2O, Ni(NO3)2·xH2O, Co(NO3)2·xH2O, Fe(NO3)3·xH2O, Mn(NO3)2·xH2O, and Cr(NO3)3·xH2O, wherein x may be 1≤x≤30.

[0054] In addition, the sugar may include fructose, and the catalyst may include In(NO3)3·xH2O, wherein x may be 1≤x≤30.

[0055] In addition, the sugar contains mannose, and the catalyst is Cr(NO3) 3· xH2O, Al(NO3) 3·X H2O, Ga(NO3) 3· xH2O and In(NO3) 3·X Contains at least one selected from the group consisting of H2O, wherein x may be 1≤x≤30.

[0056] In addition, the sugar contains sucrose, and the catalyst is In(NO3) 3·X Contains H2O, where x can be 1≤x≤30.

[0057] In addition, the sugar includes two or more selected from the group consisting of glucose, fructose, mannose, sucrose, galactose, lactose, maltose, and trehalose, and the catalyst includes In(NO3)3·xH2O, wherein x may be 1≤x≤30.

[0058] In addition, the sugar may include glucose and fructose, and the catalyst may include In(NO3)3·xH2O, wherein x may be 1≤x≤30.

[0059] Additionally, the above step (a) can be performed using a solvent.

[0060] In addition, the solvent may include at least one selected from the group consisting of dimethyl sulfoxide (DMSO), ethanol (EtOH), 2-propanol (IPA), methanol (MeOH), acetonitrile (MeCN), dimethoxyethane (DME), ethyl acetate (EA), tetrahydrofuran (THF), methyl isobutyl ketone (MIBK), dimethyl carbonate (DMC), tert-butyl methyl ether (MTBE), and water (H2O).

[0061] Additionally, step (a) may be performed at 50 to 200°C. Here, if the temperature is lower than 50°C, the conversion efficiency of glucose decreases, which is not preferable, and if it exceeds 200°C, the selectivity for hydroxymethylfurfural production decreases due to rapid conversion of glucose, which is not preferable.

[0062] According to another aspect of the present invention, hydroxymethylfurfural manufactured according to the above method for manufacturing hydroxymethylfurfural is provided.

[0063] Hereinafter, the present invention will be described in more detail with examples. However, these examples are provided for illustrative purposes only and are not intended to limit the scope of the present invention.

[0064] [Example]

[0065] 1. Calculation method

[0066]

[0067] 2. Evaluation of catalytic properties of glucose conversion reaction

[0068] 2-1. Results of HMF production reaction using various metal nitrate hydrate-based catalysts

[0069] Glucose conversion HMF production reactions were performed using various metal nitrate hydrate-based catalysts at 120°C for 2 hours using 27.75 mmol of glucose, 5.55 mmol of metal nitrate hydrate, and 50 mL of DMSO as a solvent, and the resulting glucose conversion efficiency (%), HMF selectivity (%), and fructose selectivity (%) were calculated and presented in Table 1 and Fig. 1. Referring to Table 1 and Fig. 1, among the metal nitrate hydrate catalysts, Cr(NO3)3·9H2O, Al(NO3)3·9H2O, Ga(NO3)3·26.8H2O, and In(NO3)3·14.4H2O showed high HMF selectivities of 59.54%, 69.51%, 57.46%, and 84.58%, respectively, compared to the other metal nitrate hydrate catalysts.

[0070] catalystGlucoseConversion (%)HMFSelectivity (%)FructoseSelectivity (%)No catalyst12.500Cr(NO3)3·9H2O98.1159.546.95Mn(NO3)2·4H2O8.91035.83Fe(NO3)3·6H2O61.042.052.80Co(NO3)2·6H 2O14.123.3457.18Ni(NO3)2·6H2O23.286.5811.55Cu(NO3)2·2.5H2O71.885.862.15Zn(NO3)2·6H2O24.7929.5710.73Al( NO3)3·9H2O99.8169.513.88Ga(NO3)3·26.8H2O10057.462.45In(NO3)3·14.4H2O99.1284.582.7Mg(NO3)2·6H2O11.1601 0.38Ca(NO3)2·4H2O5.48021.62La(NO3)3·6H2O12.24016.75Ce(NO3)3·6H2O10.64039.12Sm(NO3)3·6H2O16.351.3227.81

[0071] 2-2. Results of HMF production reactions using various metal complexes and metal oxide catalysts based on Al, Ga, and In.

[0072] Based on the Group 13 metals with high HMF selectivity, such as Al(NO3)3·9H2O, Ga(NO3)3·26.8H2O, and In(NO3)3·14.4H2O in the above 2-1, the glucose conversion reaction according to the metal complexes and metal oxides based on nitrate, chloride, sulfate, and phosphate was performed using 27.75 mmol of glucose, 5.55 mmol of metal complexes and metal oxides, and 50 mL of DMSO as a solvent, and the results are shown in Table 2 and Fig. 2 below. Referring to Table 2 and Fig. 2, as a result of screening the metal complex and metal oxide catalysts, the metal nitrate catalysts Al(NO3)3·9H2O, Ga(NO3)3·26.8H2O, and In(NO3)3·14.4H2O showed the best results in terms of HMF selectivity, glucose conversion efficiency, and catalyst stability. Among chloride metal catalysts, when GaCl3 catalyst was used, the selectivity for HMF was higher at 67.24% than that of Ga(NO3)3·26.8H2O catalyst. However, since GaCl3 is highly reactive toward moisture, it is difficult to perform the reaction under ambient conditions. On the other hand, metal sulfate catalysts and metal phosphate catalysts showed low HMF selectivity although they are less reactive toward moisture than chloride metal catalysts.

[0073] catalystGlucoseConversion (%)HMFSelectivity (%)FructoseSelectivity (%)Mannose Selectivity (%)Trehalose Selectivity (%)Fructose dimer Selectivity(%)Al(NO3)3·9H2O99.8169.513.02000.60Ga(NO3)3·26.8H2O10057.462.48000.44In(NO3)3·14.4H2O99.1284 .582.70001.26AlCl395.1043.96006.080GaCl399.4767.241.57000.76InCl379.0642.667.502.4702.90Al2(SO4)3·14.3H2O 94.5534.371.950.9900Ga2(SO4)3·10.3H2O99.1920.243.680.1900In2(SO4)3·10.5H2O77.2532.710000AlPO412.5700000In PO428.96038.17000Al2O326.7511.270040.070Ga2O339.330.410044.500In2O335.5200041.290In(CH3COO)395.2303.35000

[0074] 3. Results of fructose conversion to HMF production reaction using various metal nitrate hydrate-based catalysts.

[0075] When fructose instead of glucose was selected as a substrate, the HMF production reaction using a metal nitrate hydrate catalyst was performed at 120°C for 2 hours using 27.75 mmol of fructose, 5.55 mmol of metal nitrate hydrate, and 50 mL of DMSO as a solvent, and the results are shown in Table 3 and Fig. 3. As can be seen in Table 3 and Fig. 3, fructose showed a high HMF selectivity of 74.16% even in the absence of a catalyst. In the fructose conversion experiment using a metal nitrate hydrate catalyst, the selectivity for HMF was very high at 90.89% when In(NO3)3·14.4H2O was used as a catalyst.

[0076] catalystFructoseConversion (%)HMFSelectivity (%)GlucoseSelectivity (%)No catalyst87.674.160Cr(NO3)3·9H2O95.2570.560.54Mn(NO3)2·4H2O80.2469.050.47Fe(NO3)3·6H2O98.4451.600Co(NO3)2 ·6H2O94.5271.300.38Ni(NO3)2·6H2O97.9477.750.77Cu(NO3)2·2.5H2O97.9464.350Zn(NO3)2·6H2O95.4367.240.96Al(NO3) )3·9H2O96.2072.130.14Ga(NO3)3·26.8H2O96.8053.270In(NO3)3·14.4H2O91.2090.890Mg(NO3)2·6H2O79.5669.230.14Ca( NO3)2·4H2O72.4968.130.21La(NO3)3·6H2O93.4877.590.26Ce(NO3)3·6H2O94.0674.910.13Sm(NO3)3·6H2O94.1668.030.40

[0077] 4. Results of mannose conversion HMF production reaction using various metal nitrate hydrate-based catalysts

[0078] The HMF production reaction according to various metal nitrate hydrate catalysts was performed at 120℃ for 2 hours using 27.75 mmol of mannose, 5.55 mmol of metal nitrate hydrate, and 50 mL of DMSO as a solvent, with mannose as a substrate, and the results are shown in Table 4 and Fig. 4. Referring to Table 4 and Fig. 4, the results showed that when Cr(NO3)3·9H2O, Al(NO3)3·9H2O, Ga(NO3)3·26.8H2O, and In(NO3)3·14.4H2O were used as catalysts, the mannose conversion efficiency was close to 100%. In addition, high HMF selectivities of 57.02%, 67.68%, 47.01%, and 84.93% were observed.

[0079] catalystMannoseConversion (%)HMFSelectivity (%)GlucoseSelectivity (%)No catalyst30.8000Cr(NO3)3·9H2O99.7457.020.84Mn(NO3)2·4H2O8.5700Fe(NO3)3·6H2O69.325.900Co(NO3)2 ·6H2O19.5715.900Ni(NO3)2·6H2O24.8321.950.61Cu(NO3)2·2.5H2O79.6913.350Zn(NO3)2·6H2O38.3841.270 .40Al(NO3)3·9H2O10067.680.21Ga(NO3)3·26.8H2O10047.010In(NO3)3·14.4H2O10084.930Mg(NO3)2·6H2O0 .5500Ca(NO3)2·4H2O4.5100La(NO3)3·6H2O8.100.300Ce(NO3)3·6H2O15.444.080Sm(NO3)3·6H2O26.6916.080

[0080] 5. Results of sucrose conversion HMF production reaction using various metal nitrate hydrate-based catalysts.

[0081] Sucrose, a 1:1 combination of glucose and fructose, was selected as a substrate, and the HMF production reaction according to various metal nitrate hydrate catalysts was performed at 120°C for 2 hours using 27.75 mmol of sucrose, 5.55 mmol of metal nitrate hydrate, and 50 mL of DMSO as a solvent, and the results are shown in Table 5 and Fig. 5. Referring to Table 5 and Fig. 5, except for Cr(NO3)3·9H2O, Al(NO3)3·9H2O, Ga(NO3)3·26.8H2O, and In(NO3)3·14.4H2O, the remaining metal nitrate hydrate catalysts showed high conversion efficiency of fructose after sucrose was hydrolyzed into glucose and fructose, but low conversion efficiency of glucose, which can be confirmed through the high selectivity for glucose. That is, Cr(NO3)3·9H2O, Al(NO3)3·9H2O, Ga(NO3)3·26.8H2O, and In(NO3)3·14.4H2O catalysts have superior glucose conversion efficiencies compared to other metals. In the evaluation of catalyst characteristics according to various substrates such as glucose, fructose, mannose, and sucrose, the In(NO3)3·14.4H2O catalyst has higher HMF selectivity compared to other metals.

[0082] catalystSucroseConversion (%)HMFSelectivity (%)GlucoseSelectivity (%)Fructose Selectivity (%)No catalyst97.1472.5891.4310.20Cr(NO3)3·9H2O98.74121.455.168.94Mn(N O3)2·4H2O97.8447.8986.5024.11Fe(NO3)3·6H2O97.8456.1948.062.08Co(N O3)2·6H2O95.4878.0184.513.08Ni(NO3)2·6H2O94.8285.1374.190Cu(NO3) 2·2.5H2O95.0569.4537.621.67Zn(NO3)2·6H2O95.2076.3175.192.06Al(NO3 )3·9H2O99.10130.332.266.94Ga(NO3)3·26.8H2O99.3083.170.155.06In(N O3)3·14.4H2O98.43163.432.641.79Mg(NO3)2·6H2O98.0864.9485.7910.81C a(NO3)2·4H2O97.8847.9586.7725.42La(NO3)3·6H2O97.8964.5985.8310.7 8Ce(NO3)3·6H2O98.0466.9284.937.76Sm(NO3)3·6H2O98.1673.2283.933.06

[0083] 6. Results of Glucose Conversion HMF Production Reactions According to Various Organic Solvents

[0084] Glucose conversion HMF production reactions were performed at 120°C for 2 hours using 27.75 mmol of glucose, 5.55 mmol of In(NO3)3·14.4H2O, and 50 mL of DMSO as a solvent, and the results are shown in Table 6 and Fig. 6. Referring to Table 6 and Fig. 6, when DMSO was used as a reaction solvent, the highest HMF selectivity of 84.58% was observed. It can be confirmed that other solvents except water showed high glucose conversion efficiencies of over 60%, while the selectivity for HMF was very low at less than 2%.

[0085] SolventGlucoseConversion (%)HMFSelectivity (%)Fructose Selectivity (%)Dimethyl sulfoxide (DMSO)99.1284.582.7Acetonitrile (MeCN)91.7400Ethanol (EtOH)74.511.527.51Methanol (MEOH)67.78018.182-propanol (IPA)88.510.282.85Ethyl acetate (EA)97.7701.43Water (H2O)13.48049.73

[0086] 7. Results of HMF production reaction of glucose and fructose mixture conversion according to the mixing ratio of glucose and fructose

[0087] A glucose and fructose mixture conversion HMF production reaction was performed at 90°C for 2 hours using 27.75 mmol of a glucose and fructose mixture, 5.55 mmol of In(NO3)3·14.4H2O, and 50 mL of DMSO as a solvent, depending on the mixing ratio of glucose and fructose, and the results are shown in Table 7 and Fig. 7 below. Referring to Table 7 and Fig. 7, as the ratio of glucose increases, the total sugar conversion efficiency decreases, while the selectivity of HMF tends to be maintained at about 70%.

[0088] Glucose:FructoseSugar Conversion (%)Glucose Conversion (%)Fructose Conversion (%)HMF Selectivity (%)Mannose Selectivity (%)Trehalose Selectivity (%)Fructose dimer Selectivity (%)0:1097.98097.9962.469.3109.701:977.19086.6068.232.85012.002:872.120.2490.0977.882.24 011.973:768.7316.0791.3567.932.0709.034:662.9618.4992.6169.391.9907.425:552.9517.1888.7 961.882.0006.696:445.8716.0690.5967.691.0405.627:337.6316.8686.2372.921.1004.948:233.3020.2485.5365.550.931.812.159:123.9619.2866.4666.481.1313.24010:027.8827.88039.61016.850

[0089] 8. Results of Glucose Conversion HMF Production Reaction According to the Number of Catalyst Recycles

[0090] The extraction of In(NO3)3·14.4H2O used after the glucose conversion reaction and the generated HMF follows the following process. First, the solid In(NO3)3·14.4H2O is separated using centrifugation. Then, the separated In(NO3)3·14.4H2O is washed more than 5 times using centrifugation using clean DMSO, and is further washed until the DMSO layer becomes clear. The HMF present in the liquid phase is extracted with diethyl ether and separated from the DMSO (ionic liquid) layer, and the In(NO3)3·14.4H2O thus washed is recycled without additional drying.

[0091] The glucose conversion HMF production reaction was performed at 120℃ for 2 hours using 27.75 mmol of glucose, 5.55 mmol of In(NO3)3·14.4H2O, and 50 mL of DMSO as the solvent with one recycling of the above method, depending on the number of recycling of the In(NO3)3·14.4H2O catalyst, and the results are shown in Table 8 and Fig. 8 below. Referring to Table 8 and Fig. 8, it can be confirmed that the recycled In(NO3)3·14.4H2O shows a high HMF selectivity of over 70% even after being recycled three times. In addition, it can be seen that In(NO3)3·14.4H2O acts as a homogeneous catalyst that dissolves at high temperatures and shows high catalytic efficiency, whereas it acts as a heterogeneous catalyst that can be reused because it precipitates as a crystalline solid at room temperature.

[0092] Cycle numberGlucoseConversion (%)HMFSelectivity (%)Fructose Selectivity (%)Mannose Selectivity (%)Fructose dimer Selectivity (%)0 / Fresh In(NO3)3·14.4H2O99.1284.582.701.26199.7181.562.3202.00298.4382.322.1502.16397.1077.701.8702.08

[0093] Hereinafter, preferred embodiments of the present invention have been described. However, those skilled in the art will appreciate that various modifications and changes to the present invention may be made by adding, changing, deleting, or adding components, without departing from the spirit of the present invention as set forth in the claims, and such modifications and changes are also included within the scope of the present invention. For example, each component described as a single component may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form. The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims

1. Contains metal nitrate hydrate, For producing hydroxymethylfurfural (HMF, 5-hydroxymethylfurfural) from at least one selected from the group consisting of monosaccharides and disaccharides. catalyst.

2. In paragraph 1, A catalyst characterized in that the catalyst is for producing hydroxymethylfurfural (HMF, 5-hydroxymethylfurfural) from one selected from the group consisting of monosaccharides and disaccharides, or two or more selected from the group consisting of monosaccharides and disaccharides.

3. In paragraph 1, A catalyst characterized in that the catalyst is for producing hydroxymethylfurfural (HMF, 5-hydroxymethylfurfural) from two or more selected from the group consisting of monosaccharides and disaccharides.

4. In paragraph 1, A catalyst characterized in that the above catalyst is a non-halogen catalyst.

5. In paragraph 1, A catalyst characterized in that the metal nitrate hydrate comprises at least one selected from the group consisting of In(NO3)3·xH2O, Al(NO3)3·xH2O, Ga(NO3)3·xH2O, Mg(NO3)2·xH2O, Ca(NO3)2·xH2O, La(NO3)3·xH2O, Ce(NO3)3·xH2O, Sm(NO3)3·xH2O, Zn(NO3)2·xH2O, Cu(NO3)2·xH2O, Ni(NO3)2·xH2O, Co(NO3)2·xH2O, Fe(NO3)3·xH2O, Mn(NO3)2·xH2O, and Cr(NO3)3·xH2O, wherein x is 1≤x≤30.

6. In paragraph 1, A catalyst characterized in that the monosaccharides and disaccharides include at least one selected from the group consisting of glucose, fructose, mannose, sucrose, galactose, lactose, maltose, and trehalose.

7. In paragraph 1, A catalyst characterized in that the above monosaccharides and disaccharides include at least one selected from the group consisting of glucose, fructose, mannose, and sucrose.

8. A method for producing hydroxymethylfurfural, comprising the step (a) of producing hydroxymethylfurfural (HMF, 5-hydroxymethylfurfural) by reacting a sugar comprising at least one selected from the group consisting of monosaccharides and disaccharides in the presence of a catalyst.

9. In paragraph 8, The above sugar contains glucose, A method for producing hydroxymethylfurfural, characterized in that the catalyst comprises at least one selected from the group consisting of In(NO3)3·xH2O, Al(NO3)3·xH2O, Ga(NO3)3·xH2O, Mg(NO3)2·xH2O, Ca(NO3)2·xH2O, La(NO3)3·xH2O, Ce(NO3)3·xH2O, Sm(NO3)3·xH2O, Zn(NO3)2·xH2O, Cu(NO3)2·xH2O, Ni(NO3)2·xH2O, Co(NO3)2·xH2O, Fe(NO3)3·xH2O, Mn(NO3)2·xH2O, and Cr(NO3)3·xH2O, wherein x is 1≤x≤30.

10. In paragraph 8, The above sugar contains fructose, A method for producing hydroxymethylfurfural, characterized in that the catalyst comprises In(NO3)3·xH2O, wherein x is 1≤x≤30.

11. In paragraph 8, The above sugar contains mannose, A method for producing hydroxymethylfurfural, characterized in that the catalyst comprises at least one selected from the group consisting of Cr(NO3)3·xH2O, Al(NO3)3·xH2O, Ga(NO3)3·xH2O, and In(NO3)3·xH2O, wherein x is 1≤x≤30.

12. In paragraph 8, The above sugar contains sucrose, A method for producing hydroxymethylfurfural, characterized in that the catalyst comprises In(NO3)3·xH2O, wherein x is 1≤x≤30.

13. In paragraph 8, The above sugar comprises two or more selected from the group consisting of glucose, fructose, mannose, sucrose, galactose, lactose, maltose, and trehalose, A method for producing hydroxymethylfurfural, characterized in that the catalyst comprises In(NO3)3·xH2O, wherein x is 1≤x≤30.

14. In paragraph 13, The above sugars include glucose and fructose, A method for producing hydroxymethylfurfural, characterized in that the catalyst comprises In(NO3)3·xH2O, wherein x is 1≤x≤30.

15. In paragraph 8, A method for producing hydroxymethylfurfural, characterized in that the above step (a) is performed using a solvent.

16. In paragraph 15, A method for producing hydroxymethylfurfural, characterized in that the solvent comprises at least one selected from the group consisting of dimethyl sulfoxide (DMSO), ethanol (EtOH), 2-propanol (IPA), methanol (MeOH), acetonitrile (MeCN), dimethoxyethane (DME), ethyl acetate (EA), tetrahydrofuran (THF), methyl isobutyl ketone (MIBK), dimethyl carbonate (DMC), tert-butyl methyl ether (MTBE), and water (H2O).

17. In paragraph 8, A method for producing hydroxymethylfurfural, characterized in that step (a) is performed at 50 to 200°C.

18. Hydroxymethylfurfural manufactured according to the manufacturing method of hydroxymethylfurfural according to Article 8.

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