KR20150065630A - Method for preparing 5-hydroxymethyl-2-furfural using metal triflate catalysts under biomass-derived ethylene glycol based solvent condition - Google Patents

Abstract

Provided is a method for preparing 5-hydroxymethyl-2-furfural usingmetal triflate catalysts under biomass-derived ethylene glycol based solvent, the method which uses straight or ring ethylene glycol-based compounds as solvent, and comprises the step of preparing 5-hydroxymethyl-2-furfural, from fructose, using metal trifalte catalysts. According to this invention, dependency on oil can be reduced and suitable measures can thus be taken for greenhouse gas regulations. Also, 5-hydroxymethyl-2-furfural can be prepared from fructose at a high yield; and after the reaction, solvent and catalysts can be efficiently managed and reused.

Description

METHOD FOR PREPARING 5-HYDROXYMETHYL-2-FURFURAL USING METAL TRIFLATE CATALYSTS UNDER BIOMASS-DERIVED ETHYLENE GLYCOL BASED SOLVENT USING METALLIC TRIFLATE CATALYST IN AN ETHYLENE GLYCOL SOLVENT FROM BIOMASS CONDITION}

The present invention relates to a process for producing 5-hydroxymethyl-2-furfural, and more particularly to a process for producing 5-hydroxymethyl-2-furfural from a fructose by using an ethylene glycol solvent derived from biomass and a metal triflate catalyst, Hydroxymethyl-2-furfural, a platform compound of biochemicals.

Limited oil reserves will inevitably be depleted at some point, and the surge in oil demand due to the growth of emerging economies is creating an imbalance in market supply and demand, leading to an era of high oil prices. Moreover, irreversible greenhouse gases arising from the indiscriminate use of oil are causing serious environmental problems such as global warming.

Already, countries around the world are making efforts to replace petroleum resources through renewable and sustainable biomass. Biofuels such as bioethanol and biodiesel, and bioplastic monomers such as lactic acid and propanediol, To replace transportation fuels or petrochemicals.

As a part of this effort, recently, a substance that has been attracting attention is 5-hydroxymethyl-2-furfural (HMF), which is a furan compound converted from biomass-derived carbohydrates.

HMF can be converted to 2,5-furan dicarboxylic acid (FDCA) through an oxidation process. FDCA is widely used in PET (poly (ethylene terephthalate)), Is known as a substitute for terephthalic acid (TPA). PET is obtained through condensation polymerization using ethylene glycol (EG) and terephthalic acid (TPA) as monomers. To produce biomass-based PET, ethylene glycol (EG) , But terephthalic acid (TPA) is not yet available on the basis of biomass.

In recent years, HMF has attracted much attention as a key intermediate of bioplastics and biofuels, and many studies have been conducted to mass produce them, but the process for industrial mass production has yet to be developed.

The most excellent solvent in the conversion method that can efficiently obtain HMF from fructose is known as dimethyl sulfoxide (DMSO). This is because HMF can be obtained in an excellent yield from fructose when heated at 80 to 150 ° C. for 1 to 2 hours under acidic conditions using DMSO as a solvent. However, since DMSO has a boiling point of 189 캜 which is very high, it is difficult to remove by distillation, and it is difficult to obtain HMF using a direct extraction method from DMSO because of its characteristic of being mixed with most of the solvents.

In order to solve such problems, an attempt has been made to extract HMF as a product in real time by carrying out a conversion reaction on a two-component system using DMSO and other solvents (GW Huber, JN Chheda, CJ Barrett, JA Dumesic, 2005, 308, 1446), there was a limitation in completely extracting HMF from DMSO, and there was a problem that the solvent could not be reused.

In order to replace DMSO, DMF with low boiling point (GA Halliday, RJ Young, VV Grushin, Org. Lett. 2003, 5, 2003) Zhao, JE Holladay, H. Brown, ZC Zhang, Science, 2007, 316, 1597). However, DMF still has a high boiling point (153 캜), and ionic liquids have economic problems in industrial mass production processes due to their high price.

In addition, inorganic acid catalysts such as sulfuric acid and hydrochloric acid which can be used in the dehydration reaction are difficult to purify the catalyst remaining in the solution after the reaction, and there are problems in the process such as generation of a large amount of high concentration wastewater. Environmentally friendly catalytic process technology is required.

It is an object of the present invention to solve the above-described problems of the prior art, and it is an object of the present invention to provide a process for producing a biomass-derived non-petroleum solvent which can reduce dependency of petroleum in the chemical industry, - < / RTI > furfural.

In addition, the product can be obtained in high yield from fructose, and after the reaction is completed, the solvent and metal triflate catalyst can be efficiently separated and reused, and the drying process of fructose can be omitted, Hydroxymethyl-2-furfural. ≪ / RTI >

In order to accomplish the above object of the present invention, there is provided a process for producing 5-hydroxymethyl-5-hydroxymethyl- -2-furfural, comprising the step of preparing 5-hydroxymethyl-2-furfural.

The linear ethylene glycol compound may be a compound represented by the following structural formula (1).

[Structural formula 1]

In the above formula 1,

R ¹ and R ² may be the same or different from each other, R ¹ and R ² are each independently a C 1 to C 6 alkyl group,

m is an integer of 1 to 6;

According to an embodiment of the present invention, preferably,

R ¹ and R ² may be the same or different from each other, R ¹ and R ² are each independently a methyl group or an ethyl group, and m may be an integer of 1 to 4.

The cyclic ethylene glycol compound may be a compound represented by the following structural formula (2).

[Structural formula 2]

In the above formula 2,

n is an integer of 1 to 6;

According to another embodiment of the present invention, preferably,

and n may be an integer of 1 to 3.

The linear or cyclic ethylene glycol compound may be prepared from ethanol obtained by fermentation of biomass.

Wherein the linear or cyclic ethylene glycol compound is selected from the group consisting of 1,4-dioxane, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. These solvents may be used alone or in combination of two or more.

In the step of preparing 5-hydroxymethyl-2-furfural, the fructose is provided in the form of a syrup containing the fructose and water, and the content of the fructose 100 May be 10 to 50 parts by weight based on the weight parts.

The metal of the metal triflate catalyst may be one selected from the group consisting of transition elements, lanthanide elements, Group 2 elements, Group 13 elements and Group 15 elements.

The metal of the metal triflate catalyst may be one selected from the group consisting of a transition element, a lanthanide element and a group 15 element.

The transition element may be one selected from the group consisting of Sc, Y, La, Zn, Cu, Pd, Pt, Ag, Ti, Mn, Fe, Co and Ni.

The Group 15 element may be Bi.

The lanthanide element may be one selected from the group consisting of Yb, Nd, Dy, Lu, Gd and Tb.

The metal triflate catalyst is scandium triflate (Sc (OTf) _3), ytterbium triflate (Yb (OTf) _3), bismuth triflate (Bi (OTf) _3), niobium triflate (Nd (OTf) ₃₎ , dysprosium triflate (Dy (OTf) _3), yttrium triflate (Y (OTf) _3), lanthanum triflate (La (OTf) _3), zinc triflate (Zn (OTf) _2), calcium triflate ( Ca (OTf) _3), magnesium triflate (Mg (OTf) _2), copper triflate (Cu (OTf) may be at least one member selected from the group consisting of _2), and aluminum triflate (Al (OTf) ₃₎ .

The step of preparing 5-hydroxymethyl-2-furfural from the fructose may be carried out at a temperature of 80 to 150 ° C.

After the step of preparing 5-hydroxymethyl-2-furfural from the fructose, the solvent and the metal triflate catalyst may be separated to reuse the metal triflate catalyst.

The process for producing 5-hydroxymethyl-2-furfural of the present invention can reduce the dependence of petroleum in the chemical industry and cope with greenhouse gas regulations by using biomass-derived nonstoichiometric solvent. Further, the product, 5-hydroxymethyl-2-furfural, can be obtained in high yield from fructose, and after the reaction is completed, the solvent and the metal triflate catalyst can be efficiently separated and reused .

Fig. 1 shows the HPLC after preparation of 5-hydroxymethyl-2-furfural according to Example 1. Fig.

Hereinafter, embodiments and examples of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention.

It is to be understood, however, that the following description is not intended to limit the invention to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises ", or" having ", and the like, specify that the presence of stated features, integers, steps, operations, elements, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

As used herein, unless otherwise defined, the term "alkyl group" means a straight, branched or cyclic aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" which does not contain any double or triple bonds.

As used herein, unless otherwise defined, the term "alkyl group" means a straight, branched or cyclic aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" which does not contain any double or triple bonds.

The alkyl group may be an "unsaturated alkyl group" comprising at least one double bond or triple bond.

The alkyl group may be a C1 to C6 alkyl group, preferably a C1 to C3 alkyl group.

For example, the C1 to C4 alkyl groups may have 1 to 4 carbon atoms in the alkyl chain, i.e., the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, Indicating that they are selected from the group.

Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, ethenyl group, Butyl group, cyclopentyl group, cyclohexyl group, and the like.

The process for preparing 5-hydroxymethyl-2-furfural (HMF) of the present invention uses a metal triflate catalyst in a linear or cyclic ethylene glycol-based solvent To conduct dehydration reaction of fructose to prepare 5-hydroxymethyl-2-furfural.

The linear ethylene glycol-based compound solvent may be a compound represented by the following structural formula (1).

[Structural formula 1]

In the above formula 1,

R ¹ and R ² may be the same or different from each other, R ¹ and R ² are each independently a C 1 to C 6 alkyl group,

m is an integer of 1 to 6;

As shown in the structural formula 1, the linear ethylene glycol compound solvent may be repeated as a unit molecule, and the terminal hydroxyl group may have a molecular structure protected in an alkyl ether form.

The number of repeating units (m) of ethylene glycol may be 1 to 6, preferably 1 to 4. If m is larger than 6, the yield of 5-hydroxymethyl-2-furfural may be lowered, and after the reaction is completed, separation of the solvent is difficult and reuse may not be possible.

In addition, when the number of carbon atoms of the alkyl group (R ¹ and R ² ) is increased, the hydrophobicity is increased and the compatibility with fructose is lowered, so that the yield of 5-hydroxymethyl-2-furfural can be lowered.

R ¹ and R ² may be the same or different from each other, and R ¹ and R ² are each independently a C ¹ to C 6 alkyl group, more preferably, R ¹ and R ² may be the same or different from each other, and R ¹ and R ² each independently may be a methyl group or an ethyl group.

The cyclic ethylene glycol compound solvent may be a compound represented by the following structural formula (2).

[Structural formula 2]

In the above formula 2,

n is an integer of 1 to 6;

The cyclic ethylene glycol compound solvent may be a cyclic molecular structure in which ethylene glycol is repeated as a unit molecule, as shown in the structural formula (2).

The repeating number (n) of ethylene glycol is preferably 1 to 6, more preferably 1 to 3. If n is 6 or more, it may be chemically unstable for use as a solvent.

The linear or cyclic ethylene glycol-based compound solvent can be prepared from ethanol obtained by fermentation of biomass. The schematic mechanism of the production of the ethylene glycol-based compound solvent is shown in the following reaction formula (1).

 [Reaction Scheme 1]

Thus, since the ethylene glycol-based compound solvent can be produced from industrially produced bio-ethanol, the manufacturing cost can be reduced and the dependence on the oil can be reduced.

The linear or cyclic biomass-derived ethylene glycol-based compound solvent may be 1,4-dioxane, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.

The metal triplate is a compound in which metal cation and triflate (OTf) anions are present in the form of a salt, and has high solubility in water and excellent dewatering performance even under the presence of a large amount of water.

The metal contained in the metal triflate catalyst is preferably a transition element, a lanthanide element, a group II element, a group 13 element, and a group 15 element. More preferably, it may be a transition element, a lanthanide element, or a Group 15 element.

More specifically, it is preferable to use Sc, Y, La, Cu, Zn, Pd, Pt, Ag, Ti, Mn, Fe, Co, Ni or the like as the transition element. La and Cu can be used.

It is preferable to use Yb, Nd, Dy, Lu, Gd, Tb or the like as the lanthanide element, more preferably Yb, Nd or Dy.

It is preferable that Bi is used as the Group 15 element.

The metal triflate catalyst is scandium triflate (Sc (OTf) _3), ytterbium triflate (Yb (OTf) _3), bismuth triflate (Bi (OTf) _3), niobium triflate (Nd (OTf) ₃₎ , dysprosium triflate (Dy (OTf) _3), yttrium triflate (Y (OTf) _3), lanthanum triflate (La (OTf) _3), zinc triflate (Zn (OTf) _2), calcium triflate ( Ca (OTf) _3), magnesium triflate (Mg (OTf) _2), copper triflate (Cu (OTf) _2), aluminum triflate (Al (OTf) _3), etc. can be applied to the triflate of different metals , Scandium triflate (Sc (OTf) ₃ ), ytterbium triflate (Yb (OTf) ₃ ), and bismuth triflate (Bi (OTf) ₃ ).

The fructose is preferably used in the form of a syrup containing water and fructose.

At this time, the water content is preferably 10 to 50 parts by weight, more preferably 20 to 30 parts by weight, based on 100 parts by weight of fructose.

Since the ethylene glycol-based compound solvent used in the present invention can be completely mixed with water, it is not necessary to use fructose in powder form, and it can be used in a form mixed with water. Therefore, no separate fructose drying process is required.

In the dehydration reaction, the reaction temperature is preferably 80 to 150 ° C. If the reaction temperature is lower than 80 ° C, the reaction rate may be lowered. If the reaction temperature is higher than 150 ° C, the production of by-products may be increased.

The reaction time may vary depending on the reaction temperature. The reaction time is long when the reaction temperature is low, and the reaction time is relatively short when the reaction temperature is high. Specifically, when the reaction temperature is 120 ° C, the reaction time may be 0.5 to 9 hours, preferably 1 to 6 hours, and more preferably 2 to 4 hours. When the reaction temperature is lower than 120 ° C, the reaction time is relatively long, and when the reaction temperature is higher than 120 ° C, the reaction time can be relatively short.

The reaction pressure can be easily and economically advantageous because the reaction can proceed at atmospheric pressure at the reaction temperature below the boiling point of the reaction solvent. Since the pressure in the reactor increases due to the vapor pressure at the reaction temperature higher than the boiling point of the reaction solvent, a reaction device capable of withstanding the pressurized condition is required, but the reaction time can be reduced as described above. Therefore, the reaction pressure and the reaction temperature can be appropriately adjusted according to the situation.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided to further understand the present invention, and the present invention is not limited by the examples.

[Example]

Example  One

(150 mmol, weight ratio of water: 25%) and Sc (OTf) ₃ (1: 1) were added to a 38 mL thick glass walled pressure tubular reactor (25.5 mm of OD and 20.3 cm of length) equipped with a Teflon screw cap. mol%), and the reaction was carried out using 1,4-dioxane (3 mL) as an ethylene glycol solvent. The reaction mixture was heated to 120 < 0 > C and stirred at 700 rpm for 3 hours. After completion of the reaction, the reaction solution was cooled at room temperature, diluted 100 times with distilled water, and subjected to HPLC analysis. The results are shown in FIG. As a result of analysis, it was confirmed that 78% of HMF was produced, and it was confirmed that the product prepared according to Example 1 was HMF through comparison with an authentic sample on HPLC.

Example  2

(150 mmol, weight ratio of water: 25%) and Bi (OTf) ₃ (1: 1) were added to a 38 mL thick glass walled pressure tubular reactor (25.5 mm of OD and 20.3 cm of length) equipped with a Teflon screw cap. mol%), and the reaction was carried out using 1,4-dioxane (3 mL) as an ethylene glycol solvent. The reaction mixture was heated to 120 < 0 > C and stirred at 700 rpm for 1 hour. After completion of the reaction, the reaction mixture was cooled at room temperature, diluted 100 times with distilled water and subjected to HPLC analysis. As a result, it was confirmed that 65% of HMF was produced.

Example  3

(150 mmol, weight ratio of water: 25%) and Yb (OTf) ₃ (1: 1) were added to a 38 mL thick glass walled pressure tubular reactor (25.5 mm of OD and 20.3 cm of length) equipped with a Teflon screw cap. mol%), and the reaction was carried out using 1,4-dioxane (3 mL) as an ethylene glycol solvent. The reaction mixture was heated to 120 < 0 > C and stirred at 700 rpm for 6 hours. After completion of the reaction, the reaction mixture was cooled at room temperature, diluted 100 times with distilled water and subjected to HPLC analysis. As a result, it was confirmed that 55% of HMF was produced.

Example  4

(150 mmol, weight ratio of water: 25%) and Sc (OTf) ₃ (1: 1) were added to a 38 mL thick glass walled pressure tubular reactor (25.5 mm of OD and 20.3 cm of length) equipped with a Teflon screw cap. mol%), and the reaction was carried out using an ethylene glycol-based solvent, monoethylene glycol dimethyl ether (3 mL). The reaction mixture was heated to 120 < 0 > C and stirred at 700 rpm for 6 hours. After completion of the reaction, the reaction mixture was cooled at room temperature, diluted 100 times with distilled water, and analyzed by HPLC. As a result, it was confirmed that 47% of HMF was produced.

Example  5

(150 mmol, weight ratio of water: 25%) and Yb (OTf) ₃ (1: 1) were added to a 38 mL thick glass walled pressure tubular reactor (25.5 mm of OD and 20.3 cm of length) equipped with a Teflon screw cap. mol%), and the reaction was carried out using an ethylene glycol-based solvent, monoethylene glycol dimethyl ether (3 mL). The reaction mixture was heated to 120 < 0 > C and stirred at 700 rpm for 6 hours. After completion of the reaction, the reaction mixture was cooled at room temperature and diluted 100 times with distilled water, and analyzed by HPLC. As a result, it was confirmed that 41% of HMF was produced.

Example  6

(150 mmol, weight ratio of water: 25%) and Sc (OTf) ₃ (1: 1) were added to a 38 mL thick glass walled pressure tubular reactor (25.5 mm of OD and 20.3 cm of length) equipped with a Teflon screw cap. mol%), and the reaction was carried out using ethylene glycol solvent diethylene glycol dimethyl ether (3 mL). The reaction mixture was heated to 120 < 0 > C and stirred at 700 rpm for 6 hours. After completion of the reaction, the reaction mixture was cooled at room temperature, diluted 100 times with distilled water and subjected to HPLC analysis. As a result, 49% of HMF was produced.

Example  7

(150 mmol, weight ratio of water: 25%) and Yb (OTf) ₃ (1: 1) were added to a 38 mL thick glass walled pressure tubular reactor (25.5 mm of OD and 20.3 cm of length) equipped with a Teflon screw cap. mol%), and the reaction was carried out using ethylene glycol solvent diethylene glycol dimethyl ether (3 mL). The reaction mixture was heated to 120 < 0 > C and stirred at 700 rpm for 6 hours. After completion of the reaction, the reaction mixture was cooled at room temperature, diluted 100 times with distilled water and subjected to HPLC analysis. As a result, it was confirmed that 43% of HMF was produced.

Example  8

(150 mmol, weight ratio of water: 25%) and Sc (OTf) ₃ (1: 1) were added to a 38 mL thick glass walled pressure tubular reactor (25.5 mm of OD and 20.3 cm of length) equipped with a Teflon screw cap. mol%), and the reaction was carried out using triethylene glycol dimethyl ether (3 mL) as an ethylene glycol solvent. The reaction mixture was heated to 120 < 0 > C and stirred at 700 rpm for 6 hours. After completion of the reaction, the reaction mixture was cooled at room temperature, diluted 100 times with distilled water, and analyzed by HPLC. As a result, it was confirmed that 47% of HMF was produced.

Example  9

(150 mmol, weight ratio of water: 25%) and Yb (OTf) ₃ (1: 1) were added to a 38 mL thick glass walled pressure tubular reactor (25.5 mm of OD and 20.3 cm of length) equipped with a Teflon screw cap. mol%), and the reaction was carried out using triethylene glycol dimethyl ether (3 mL) as an ethylene glycol solvent. The reaction mixture was heated to 120 < 0 > C and stirred at 700 rpm for 6 hours. After completion of the reaction, the reaction mixture was cooled at room temperature, diluted 100 times with distilled water, and analyzed by HPLC. As a result, it was confirmed that 47% of HMF was produced.

Example  10

(150 mmol, weight ratio of water: 25%) and Sc (OTf) ₃ (1: 1) were added to a 38 mL thick glass walled pressure tubular reactor (25.5 mm of OD and 20.3 cm of length) equipped with a Teflon screw cap. mol%), and the reaction was carried out using tetraethylene glycol dimethyl ether (3 mL) as an ethylene glycol solvent. The reaction mixture was heated to 120 < 0 > C and stirred at 700 rpm for 6 hours. After completion of the reaction, the reaction mixture was cooled at room temperature, diluted 100 times with distilled water and subjected to HPLC analysis. As a result, it was confirmed that 57% of HMF was produced.

Example  11

(150 mmol, weight ratio of water: 25%) and Yb (OTf) ₃ (1: 1) were added to a 38 mL thick glass walled pressure tubular reactor (25.5 mm of OD and 20.3 cm of length) equipped with a Teflon screw cap. mol%), and the reaction was carried out using tetraethylene glycol dimethyl ether (3 mL) as an ethylene glycol solvent. The reaction mixture was heated to 120 < 0 > C and stirred at 700 rpm for 6 hours. After completion of the reaction, the reaction mixture was cooled at room temperature, diluted 100 times with distilled water and subjected to HPLC analysis. As a result, it was confirmed that 62% of HMF was produced.

Example  12

After separating the mixture by adding ethyl acetate and distilled water to the remaining reaction mixture, residual Sc (OTf) _{3 was added} to the water layer, And then separated and recovered by distillation and drying.

HMF was prepared in the same manner as in Example 1 except that Sc (OTf) ₃ and 1,4-dioxane were recovered and recovered. After completion of the reaction, the reaction mixture was diluted 100 times with distilled water and subjected to HPLC analysis. As a result, it was confirmed that 75% of HMF was produced.

Comparative Example  One

Sc (OTf) ₃ HMF was produced in the same manner as in Example 1, except that Zeolite beta was used instead of the catalyst and the R-value (weight of catalyst / weight of fructose as a substrate) was 1 and the reaction time was 6 hours , And the analysis showed that 24% of HMF was produced.

Comparative Example  2

Sc (OTf) ₃ HMF was prepared and analyzed by HPLC in the same manner as in Example 1, except that Zeolite Υ (R-value = 1) was used instead of the catalyst. As a result, it was confirmed that 45% of HMF was produced.

Comparative Example  3

Sc (OTf) ₃ HMF was prepared and analyzed by HPLC in the same manner as in Example 1 except that Nafion (R-value = 1) was used instead of the catalyst and the reaction time was changed to 2 hours. As a result, 63% Respectively.

The HMF production conditions and yields of Examples 1 to 12 and Comparative Examples 1 to 3 are summarized in Table 1 below.

division menstruum catalyst Reaction temperature (캜) Reaction time (h) HMF yield (%) Kinds usage
(Compared to Fructose) Example 1 1,4-dioxane Sc (OTf) ₃ 1 mol% 120 3 78 Example 2 1,4-dioxane Bi (OTf) ₃ 1 mol% 120 One 65 Example 3 1,4-dioxane Yb (OTf) ₃ 1 mol% 120 6 55 Example 4 monoethylene glycol dimethyl ether Sc (OTf) ₃ 1 mol% 120 6 47 Example 5 monoethylene glycol dimethyl ether Yb (OTf) ₃ 1 mol% 120 6 41 Example 6 diethylene glycol dimethyl ether Sc (OTf) ₃ 1 mol% 120 6 49 Example 7 diethylene glycol dimethyl ether Yb (OTf) ₃ 1 mol% 120 6 43 Example 8 triethylene glycol dimethyl ether Sc (OTf) ₃ 1 mol% 120 6 47 Example 9 triethylene glycol dimethyl ether Yb (OTf) ₃ 1 mol% 120 6 47 Example 10 tetraethylene glycol dimethyl ether Sc (OTf) ₃ 1 mol% 120 6 57 Example 11 tetraethylene glycol dimethyl ether Yb (OTf) ₃ 1 mol% 120 6 62 Example 12 1,4-dioxane Sc (OTf) ₃ 1 mol% 120 3 75 Comparative Example 1 1,4-dioxane Zeolite beta * R-Value = 1 120 6 24 Comparative Example 2 1,4-dioxane Zeolite Υ * R-Value = 1 120 3 45 Comparative Example 3 1,4-dioxane Nafion * R-Value = 1 120 2 63

* R-value = weight of catalyst / weight ratio of fructose, substrate

According to Table 1, Examples 1 to 12 of the present invention show that 5-hydroxymethyl-2-furfural is produced with higher or similar yields even with a relatively small amount of catalyst as compared with Comparative Examples 1 to 3 It can be seen that

The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.

Claims (9)

A process for preparing 5-hydroxymethyl-2-furfural from fructose under a metal triflate catalyst using a linear ethylene glycol-based compound represented by the following structural formula 1 as a solvent ≪ / RTI >
The metal triflate catalyst is scandium triflate (Sc (OTf) _3), ytterbium triflate (Yb (OTf) _3), niobium triflate (Nd (OTf) _3), dysprosium triflate (Dy (OTf) ₃₎ , yttrium triflate (Y (OTf) _3), lanthanum triflate (La (OTf) _3), zinc triflate (Zn (OTf) _2), and copper triflate from the group consisting of (Cu (OTf) ₂₎ Gt; 5-hydroxymethyl-2-furfural < / RTI >
[Structural formula 1]

In the above formula 1,
R ¹ and R ² may be the same or different from each other, R ¹ and R ² are each independently a C 1 to C 6 alkyl group,
m is an integer of 1 to 6; Hydroxymethyl-2-furfural from fructose under a metal triflate catalyst using an ethylene glycol-based compound represented by the following structural formula 2 as a solvent Comprising the steps of:
Wherein the metal triflate catalyst is bismuth triflate (Bi (OTf) ₃ ).
[Structural formula 2]

In the above formula 2,
n is an integer of 1 to 6; The method according to claim 1,
R ¹ and R ² may be the same or different from each other, R ¹ and R ² are each independently a methyl group or an ethyl group, and m is an integer of from 1 to 4, to prepare 5-hydroxymethyl-2-furfural Way. 3. The method of claim 2,
and n is an integer of 1 to 3. 5. A process for producing 5-hydroxymethyl-2-furfural according to claim 1, 3. The method according to claim 1 or 2,
Wherein the linear or cyclic ethylene glycol compound is prepared from ethanol obtained by fermentation of biomass. 3. The method according to claim 1 or 2,
Wherein the linear ethylene glycol compound is selected from the group consisting of monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene Tetraethylene glycol dimethyl ether, and the like.
Wherein the cyclic ethylene glycol-based compound is 1,4-dioxane. 3. The method according to claim 1 or 2,
In the step of preparing 5-hydroxymethyl-2-furfural, the fructose is provided in the form of a syrup containing the fructose and water, and the content of the fructose 100 To 10 parts by weight based on 100 parts by weight of the total amount of the hydroxymethyl-2-furfural. 3. The method according to claim 1 or 2,
Wherein the step of preparing 5-hydroxymethyl-2-furfural from the fructose is carried out at a temperature of 80 to 150 ° C. 3. The method according to claim 1 or 2,
Hydroxymethyl-2-furfural from the fructose, followed by separation of the solvent and the metal triflate catalyst to reuse the metal triflate catalyst. ≪ / RTI >

Images