WO2019039705A1 - Method for separating 5-hydroxymethyl-2-furfural and dimethyl sulfoxide in preparation process for 5-hydroxymethyl-2-furfural - Google Patents

Abstract

The present invention relates to a method for separating 5-hydroxymethyl-2-furfural (HMF) and dimethyl sulfoxide (DMSO), the method comprising the steps of: (a) preparing a mixture solution comprising HMF and DMSO; and (b) mixing an organic solvent and water with the mixture solution to prepare a layer separation solution in which an aqueous layer comprising the DMSO and an organic layer comprising the HMF are layer-separated, wherein the organic solvent comprises a first organic solvent comprising an aprotic nonpolar organic solvent and a second organic solvent comprising an aprotic polar organic solvent. According to the present invention, a dimethyl sulfoxide solvent and 5-hydroxymethyl-2-furfural can be effectively separated after the termination of a preparation reaction for 5-hydroxymethyl-2-furfural using dimethyl sulfoxide solvent.

Description

A method for separating 5-hydroxymethyl-2-furfural and dimethylsulfoxide in a process for producing 5-hydroxymethyl-2-furfural

The present invention relates to a process for the separation of 5-hydroxymethyl-2-furfural and dimethylsulfoxide in the process for the production of 5-hydroxymethyl-2-furfural.

With the recent depletion of limited petroleum resources, the need for alternative resources continues to increase. As a result, the replacement of petroleum resources with sustainable biomass resources is becoming increasingly important. Among them, 2,5-furan dicarboxylic acid (FDCA), which is a biomass-derived compound, is in the spotlight. 2,5-furan dicarboxylic acid is widely used in food, It can be used as a substitute for terephthalic acid (TPA), which is a monomer of polyethylene terephthalate (PET), which is being used, thus enabling the production of PET based on biomass.

The biggest obstacle to the use of 2,5-furan dicarboxylic acid in PET production is the formation of 5-Hydroxymethyl-2-furfural, a precursor of 2,5-furan dicarboxylic acid , HMF). The 2,5-furan dicarboxylic acid can be converted via an oxidation process of 5-hydroxymethyl-2-furfural. However, there has been no development of a mass production process for converting 3 water molecules into 5-hydroxymethyl-2-furfural by dehydrogenation in fructose.

Of the currently developed methods for producing 5-hydroxymethyl-2-furfural, an effective and economical method is to convert fructose obtained from carbohydrate-based biomass into ion exchange resin catalysts in a dimethylsulfoxide (DMSO) To obtain 5-hydroxymethyl-2-furfural.

However, since dimethylsulfoxide has a high boiling point, it is difficult to separate through distillation, and it is difficult to recover 5-hydroxymethyl-2-furfural in a dimethylsulfoxide solvent because it is mixed with most of the solvents.

An object of the present invention to solve the above problems is to provide a separation method for efficiently separating dimethylsulfoxide and 5-hydroxymethyl-2-furfural from a mixture of 5-hydroxymethyl-2-furfural and dimethylsulfoxide .

Another object of the present invention is to provide a process for the production of 5-hydroxymethyl-2-furfural using a dimethylsulfoxide solvent, which can effectively separate the dimethylsulfoxide solvent and 5-hydroxymethyl-2-furfural To provide a separation method.

According to one aspect of the present invention, there is provided a pharmaceutical composition comprising (a) 5-hydroxymethyl-2-furfural (HMF) and dimethyl sulfoxide (DMSO) Preparing a mixed solution; And

(b) mixing an organic solvent and water with the mixed solution to prepare a layer separation solution layered with an aqueous solution containing DMSO and an organic layer containing HMF; Lt; / RTI >

Wherein the organic solvent comprises a first organic solvent comprising an aprotic nonpolar organic solvent and a second organic solvent comprising an aprotic polar organic solvent, A method of separating DMSO is provided.

Further, the separation method may further include (c) after step (b), separating the aqueous solution layer from the layer separation solution to obtain the organic layer.

Further, the separation method may further include (d) after step (c), removing the organic solvent from the organic layer to obtain the HMF.

Also, the first organic solvent may have a dipole moment D of 0 or more and less than 1.0D (0 < dipole moment &lt; 1.0).

Also, the first organic solvent may have a dipole moment D of 0.05 to 0.5D (0.05 dipole moment? 0.5).

The first organic solvent may have a solubility in H ₂ O (g / 100 g) of 0 to 0.2.

The first organic solvent may be at least one selected from the group consisting of an aliphatic hydrocarbon compound, an alicyclic hydrocarbon compound, and an aromatic hydrocarbon compound.

The aliphatic hydrocarbon compound may be at least one selected from the group consisting of pentane, hexane (HX) and heptane,

Wherein the alicyclic hydrocarbon compound is at least one selected from the group consisting of cyclopentane and cyclohexane,

The aromatic hydrocarbon compound may be at least one selected from the group consisting of benzene, toluene (TOL) and xylene.

Also, the second organic solvent may have a dipole moment (D) of 1 to 3 D.

In addition, the second organic solvent may have a dipole moment (D) of 1.5 to 3 D.

The second organic solvent may have a solubility in H ₂ O (g / 100 g) of 0 to 10.0.

The second organic solvent may be at least one selected from the group consisting of a halogen-based hydrocarbon compound, an ester-based hydrocarbon compound, a ketone-based hydrocarbon compound, and an ether-based hydrocarbon compound.

The halogen-based hydrocarbon compound is at least one selected from the group consisting of chloroform (CF), dichloromethane (DCM) and 1,2-dichloroethane (DCE)

Wherein the ester-based hydrocarbon compound is at least one selected from the group consisting of ethyl acetate (EA), methyl acetate and ethyl benzoate,

Wherein the ketone-based hydrocarbon compound is at least one selected from the group consisting of methyl isobutyl ketone (MIBK) and 3-pentanone,

The ether-based hydrocarbon compound may be at least one selected from the group consisting of diethyl ether (DEE) and methyltit-butyl ether (MTBE).

The organic solvent may have a volume ratio of the first organic solvent to the second organic solvent of 0.1: 9.9 to 5.0: 5.0 (v: v).

The organic solvent may have a volume ratio of the first organic solvent and the second organic solvent of 0.3: 9.7 to 3.0: 7.0 (v: v).

The organic solvent may have a volume ratio of the first organic solvent to the second organic solvent of 0.5: 9.5 to 1.5: 8.5 (v: v).

The organic solvent and water may also have a volume ratio of 5: 5 to 9: 1 (v: v).

The volume ratio of the mixed solution and the organic solvent may be 1: 1 to 1:10 (v: v).

In addition, step (a) may be a step of preparing the mixed solution by preparing the HMF by using an anion exchange resin and a cation exchange resin in the DMSO solvent.

Also, step (a) may be a step of preparing the mixed solution by preparing the HMF using a cation exchange resin in the DMSO solvent.

The present invention can provide a separation method that effectively separates dimethylsulfoxide and 5-hydroxymethyl-2-furfural in a mixture of 5-hydroxymethyl-2-furfural and dimethylsulfoxide.

The present invention also relates to a process for the production of 5-hydroxymethyl-2-furfural using a dimethylsulfoxide solvent. After completion of the reaction, a step of separating the dimethylsulfoxide solvent and 5-hydroxymethyl-2-furfural Method can be provided.

FIG. 1 is a diagram showing a process of separating HMF prepared from a hexane-containing compound under DMSO solvent from DMSO using a mixed extraction vessel solvent as a schematic diagram of the present invention.

FIG. 2 is a correction graph showing the correlation between the HMF / DMSO region ratio and the HMF / DMSO molar ratio, which are used to obtain HMF and DMSO present in the water layer and the organic layer, respectively.

The invention is capable of various modifications and may have various embodiments, and particular embodiments are exemplified and will be described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific 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.

Furthermore, terms including an ordinal number such as first, second, etc. to be used below can be used to describe various elements, but the constituent elements are not limited by the terms. The terms are used only 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 referred to as a second component, and similarly, the second component may also be referred to as a first component.

Also, when an element is referred to as being " formed " or " laminated " on another element, it may be directly attached or laminated to the front surface or one surface of the other element, It will be appreciated that other components may be present in the &lt; / RTI &gt;

The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Hereinafter, a method for separating 5-hydroxymethyl-2-furfural (HMF) from dimethyl sulfoxide (DMSO) will be described.

According to one aspect of the present invention, there is provided a process for preparing a mixed solution comprising (a) 5-hydroxymethyl-2-furfural (HMF) and dimethyl sulfoxide (DMSO) ; And (b) mixing an organic solvent and water with the mixed solution to prepare a layer separation solution layered with an aqueous solution layer containing DMSO and an organic layer containing HMF; Wherein the organic solvent comprises a first organic solvent comprising an aprotic nonpolar organic solvent and a second organic solvent comprising an aprotic polar organic solvent, A method of separating HMF and DMSO can be provided.

In addition, step (a) may be a step of preparing the mixed solution by preparing the HMF by using an anion exchange resin and a cation exchange resin in the DMSO solvent.

Also, step (a) may be a step of preparing the mixed solution by preparing the HMF using a cation exchange resin in the DMSO solvent.

There are two types of structural isomers of ketone and aldose in the hexacyano compound.

As used herein, the term &quot; aldose-type hexadecane compound &quot; means aldose, a monosaccharide containing one aldehyde per mole, and means a sugar having six carbons.

The aldose-type hexacarbonyl compound may be an aldose-type glucose, an aldose-type galactose, a sugar compound including an aldose-type glucose or an aldose-type galactose.

The term &quot; 5-hydroxymethyl-2-furfural (HMF) &quot; used in the present invention means a monosaccharide containing one ketone per mole of the ketose-type hexacosaccharide compound.

The ketose and aldose can be classified according to the position of the carbonyl group as shown in the following Chemical Formula 1, wherein ketose is a ketone compound in which a carbonyl group exists at the C2 position, and aldose is an aldehyde compound in which a carbonyl group exists at the C1 position.

In addition, the hexacyano compound exists in an equilibrium relationship between the linear structure and the ring structure according to the pH condition. At this time, the ketose has a pentagonal ring structure as shown in Formula 1, and aldose is a hexagonal ring Structure.

The anion exchange resin is a polystyrene-based bead-like resin having a quaternary ammonium or tertiary amine functional group at the terminal thereof, and the counter ion is substituted with bicarbonate or aluminate, . For this purpose, the anion exchange resin should be thoroughly washed with saturated sodium bicarbonate or saturated sodium aluminate before use.

The cation exchange resin is a polystyrene-based bead-like resin having a sulfonic acid functional group at the terminal, and the counter ion is substituted with a proton to have strong acidity. For this, the cation exchange resin should be thoroughly washed with aqueous hydrochloric acid solution before use.

Further, the separation method may further include (c) after step (b), separating the aqueous solution layer from the layer separation solution to obtain the organic layer.

Further, the separation method may further include (d) after step (c), removing the organic solvent from the organic layer to obtain the HMF.

Also, the first organic solvent may have a dipole moment D of 0 or more and less than 1.0 D (0 dipole moment <1.0), preferably 0.05 to 0.5 D (0.5 dipole moment? 0.5) . Here, if the dipole moment of the first organic solvent is 1.0D or more, DMSO can not migrate to the organic solvent layer, which is not preferable.

The first organic solvent may have a solubility in H ₂ O (g / 100 g) of 0 to 0.2. If the solubility of the first organic solvent in water is more than 0.2, it is not preferable because DMSO can migrate to the organic solvent layer.

The first organic solvent may be a hydrocarbon-based aliphatic compound such as pentane, hexane (HX) or heptane, a hydrocarbon-based alicyclic compound such as cyclopentane or cyclohexane, a hydrocarbon such as benzene, toluene (TOL) And aromatic compounds of the above-mentioned type.

Also, the second organic solvent may have a dipole moment (D) of 1 to 3, preferably 1.5 to 3. If the dipole moment of the second organic solvent is less than 1.0D, HMF can not be efficiently extracted into the organic layer, which is undesirable. If the molecular weight exceeds 3 D, DMSO can not be transferred to the organic layer.

The second organic solvent may have a solubility in H ₂ O (g / 100 g) of 0 to 10.0. Here, if the solubility of the second organic solvent in water is more than 10.0, it is not preferable because the effective phase separation is not performed and the extraction efficiency for HMF is lowered.

The second organic solvent may be a halogen-based compound such as chloroform (CF), dichloromethane (DCM) or 1,2-dichloroethane (DCE), an ester such as ethyl acetate (EA), methyl acetate, ethyl benzoate Based compounds such as methyl isobutyl ketone (MIBK) and 3-pentanone, and ether compounds such as diethyl ether (DEE) and methyl tert-butyl ether (MTBE) .

The organic solvent may have a volume ratio of the first organic solvent to the second organic solvent of 0.1: 9.9 to 5.0: 5.0 (v: v), preferably 0.3: 9.7 to 3.0: 7.0 (v: v) And preferably 0.5: 9.5 to 1.5: 8.5 (v: v). If the volume ratio is less than 0.1: 9.9, DMSO can not be transferred to the organic layer, and if it is more than 5.0: 5.0, HMF can not be efficiently extracted.

The organic solvent and water may also have a volume ratio of 5: 5 to 9: 1 (v: v). If the volume ratio is less than 5: 5, HMF can not be efficiently extracted, which is undesirable. When the volume ratio is more than 9: 1, DMSO can not migrate to the organic layer.

The volume ratio of the mixed solution and the organic solvent may be 1: 1 to 1:10 (v: v). If the volume ratio is less than 1: 1, it is not preferable because effective phase separation can not be achieved. If the volume ratio is more than 1:10, it is not preferable because of an increase in the cost of the extraction process.

[Example]

Hereinafter, preferred embodiments of the present invention will be described. However, this is for the purpose of illustration only and is not intended to limit the scope of the present invention

Use single extraction organic solvent

PREPARATION EXAMPLE 1

First, a screening operation was performed to compare the performance of the extraction vessel solvent for separating HMF and DMSO. For this purpose, a standard solution having a molar ratio of DMSO: HMF of 80:20 was prepared and used for screening. The organic layer and water layer were used in a volume ratio of 5 times the standard solution. The molar ratios of HMF and DMSO present in the organic layer and the water layer were obtained by converting the ratio of the area represented by HPLC to the molar ratio using the ratio of HMF and DMSO in FIG. 2. The ratio of HMF and DMSO Mol.

5 ml of dichloromethane (DCM) as an extraction solvent was added to 1 ml of a standard solution of DMSO + HMF (80:20, mol%), and 5 ml of the same amount of water as the extraction solvent was added and stirred. After the stirring, an organic layer (lower layer, only the halogen-free organic solvent is the upper layer) containing 5-hydroxymethyl-2-furfural separated by layer separation was obtained, and an aqueous layer containing dimethylsulfoxide And the halogen-based organic solvent was the lower layer). After separating the water layer from the organic layer, the amount of DMSO and HMF present in each layer was measured by HPLC analysis, and the results as shown in Table 1 were obtained.

Preliminary Example 2

Except that chloroform (CF) was added in place of dichloromethane (DCM).

Preliminary Example 3

Except that 1,2-dichloroethane (DCE) was added instead of dichloromethane (DCM).

Preliminary Example 4

Except that diethyl ether (DEE) was added in place of dichloromethane (DCM).

Preliminary Example 5

Except that methyltit-butyl ether (MTBE) was added instead of dichloromethane (DCM).

Preliminary Example 6

The procedure of Example 1 was repeated except that ethyl acetate (EA) was added instead of dichloromethane (DCM).

Preliminary Example 7

Except that methyl isobutyl ketone (MIBK) was added in place of dichloromethane (DCM).

Preliminary Example 8

The procedure of Example 1 was repeated except that toluene (TOL) was added instead of dichloromethane (DCM).

PREPARATION EXAMPLE 9

Except that hexane (HX) was added instead of dichloromethane (DCM).

	Extracted organic solvent	DMSO (mol%)		HMF (mol%)
		Water layer	Organic layer	Water layer	Organic layer
PREPARATION EXAMPLE 1	DCM	53.9	26.1	4.4	15.6
Preliminary Example 2	CF	63.6	16.4	5.7	14.3
Preliminary Example 3	DCE	72.7	7.3	6.5	13.5
Preliminary Example 4	DEE	74.1	5.9	7.6	12.4
Preliminary Example 5	MTBE	79.2	0.8	8.5	11.5
Preliminary Example 6	EA	75.0	5.0	4.9	15.1
Preliminary Example 7	MIBK	74.3	5.7	5.4	14.6
Preliminary Example 8	TOL	79.4	0.6	8.8	11.2
PREPARATION EXAMPLE 9	HX	79.9	0.1	19.9	0.1

In Table 1, DMSO mol% (organic layer) + DMSO mol% (water layer) + HMF mol% (organic layer) + HMF mol% (water layer) = 100 mol%.

Use mixed extraction organic solvent

Example 1-1

Except that dichloromethane (DCM) and dichloromethane (DCM) were mixed at a volume ratio of 1: 1 instead of dichloromethane (DCM) and hexane (HX) as a mixture extraction solvent. The amounts of DMSO and HMF present in each layer were measured by HPLC analysis and the results are shown in Table 1.

Examples 1-2

Except that dichloromethane (DCM) was added instead of chloroform (CF) and hexane (HX) as a mixed extraction solvent at a volume ratio of 1: 1.

Example 1-3

Except that dichloromethane (DCM) was added instead of diethyl ether (DEE) + hexane (HX) as a mixed extraction solvent at a volume ratio of 1: 1.

Examples 1-4

Except that methyltit-butyl ether (MTBE) + hexane (HX), which is a mixed extraction solvent, was added at a volume ratio of 1: 1 instead of adding dichloromethane (DCM) .

Examples 1-5

Except that dichloromethane (DCM) was added instead of ethyl acetate (EA) and hexane (HX) in a volume ratio of 1: 1.

Examples 1-6

Except that methyl isobutyl ketone (MIBK) and hexane (HX) were added in a volume ratio of 1: 1 instead of adding dichloromethane (DCM).

Examples 1-7

Except that dichloromethane (DCM) was added instead of toluene (TOL) and hexane (HX) at a volume ratio of 1: 1.

	Extracted organic solvent	Composition (v: v)	DMSO (mol%)		HMF (mol%)
			Water layer	Organic layer	Water layer	Organic layer
Example 1-1	DCM: HX	1: 1	69.0	11.0	8.0	12.0
Examples 1-2	CF: HX	1: 1	79.5	0.5	9.1	10.9
Example 1-3	DEE: HX	1: 1	79.6	0.4	9.4	10.6
Examples 1-4	MTBE: HX	1: 1	79.7	0.3	9.0	11.0
Examples 1-5	EA: HX	1: 1	78.6	1.4	5.2	14.8
Examples 1-6	MIBK: HX	1: 1	79.0	1.0	8.5	11.5
Examples 1-7	TOL: HX	1: 1	67.5	12.5	8.1	11.9

Effect of mixed extraction organic solvent composition

Example 2-1

5 ml of ethyl acetate and hexane (volume: 2.5 ml each) were added to 1 ml of the standard solvent DMSO + HMF (80:20, mol%) as an extraction solvent and a volume of water 5 ml was added and stirred.

After stirring, the organic layer (upper layer) containing 5-hydroxymethyl-2-furfural was separated to obtain a water layer (lower layer) containing dimethylsulfoxide. The water layer was separated from the organic layer, and the amounts of DMSO and HMF present in each layer were measured by HPLC analysis. The water layer was further extracted with 5 ml of fresh extraction solvent (2.5 ml each of ethyl acetate and hexane), and the amount of DMSO and HMF present in each layer was measured by HPLC analysis for each extraction. The results are shown in Table 3.

Example 2-2

Ethyl acetate and hexane were added at a volume ratio of 1: 2 instead of 1: 1 by volume ratio.

Example 2-3

Ethyl acetate and hexane were added in a volume ratio of 1: 3 instead of 1: 1 in volume ratio.

Examples 2-4

Ethyl acetate and hexane were added in a volume ratio of 1: 4 instead of 1: 1 by volume ratio.

Example 2-5

Ethyl acetate and hexane were added in a volume ratio of 1: 5 instead of 1: 1 by volume ratio.

	Extracted organic solvent		DMSO (mol%)		HMF (mol%)
	Composition (v: v)	Extraction order	Water layer	Organic layer	Water layer	Organic layer
Example 2-1	HX + EA (1: 1)	1 st	79.6	0.4	8.4	11.6
	HX + EA (1: 1)	2 nd	79.6	0.4	7.4	12.6
	HX + EA (1: 1)	3 rd	79.5	0.5	6.2	13.8
Example 2-2	HX + EA (1: 2)	1 st	79.6	0.4	7.7	12.3
	HX + EA (1: 2)	2 nd	79.5	0.5	5.9	14.1
	HX + EA (1: 2)	3 rd	79.5	0.5	4.4	15.6
Example 2-3	HX + EA (1: 3)	1 st	78.7	1.3	7.0	13.0
	HX + EA (1: 3)	2 nd	78.6	1.4	4.8	15.2
	HX + EA (1: 3)	3 rd	78.5	1.5	3.0	17.0
Examples 2-4	HX + EA (1: 4)	1 st	78.8	1.2	6.5	13.5
	HX + EA (1: 4)	2 nd	78.5	1.5	4.4	15.6
	HX + EA (1: 4)	3 rd	78.3	1.7	3.2	16.8
Example 2-5	HX + EA (1: 5)	1 st	79.6	0.4	7.3	12.7
	HX + EA (1: 5)	2 nd	79.4	0.6	4.1	15.9
	HX + EA (1: 5)	3 rd	79.4	0.6	2.2	17.8

Example 3-1

5 ml of methyl isobutyl ketone and hexane (volume: 2.5 ml each of methyl isobutyl ketone and hexane) having a volume ratio of 1: 1 as an extraction solvent was added to 1 ml of a standard solution of DMSO + HMF (80:20, mol%), 5 ml of a volume of water was added and stirred.

After stirring, the organic layer (upper layer) containing 5-hydroxymethyl-2-furfural was separated to obtain a water layer (lower layer) containing dimethylsulfoxide. The water layer was separated from the organic layer, and the amounts of DMSO and HMF present in each layer were measured by HPLC analysis. The water layer was further extracted with 5 ml of fresh extraction solvent (2.5 ml each of methyl isobutyl ketone and hexane), and the amount of DMSO and HMF present in each layer was measured by HPLC analysis for each extraction Respectively. The results are shown in Table 4. &lt; tb &gt; &lt; TABLE &gt;

Example 3-2

Except that methyl isobutyl ketone (MIBK) and hexane were added at a volume ratio of 1: 2 instead of 1: 1 at a volume ratio.

Example 3-3

Except that methyl isobutyl ketone (MIBK) and hexane were added at a volume ratio of 1: 3 instead of 1: 1 at a volume ratio.

Example 3-4

Methyl isobutyl ketone (MIBK) and hexane at a volume ratio of 1: 4 instead of 1: 1 at a volume ratio.

Example 3-5

Except that methyl isobutyl ketone (MIBK) and hexane were added at a volume ratio of 1: 5 instead of 1: 1 at a volume ratio.

Examples 3-6

Except that methyl isobutyl ketone (MIBK) and hexane were added at a volume ratio of 1: 6 instead of 1: 1 at a volume ratio.

Examples 3-7

Except that methyl isobutyl ketone (MIBK) and hexane were added at a volume ratio of 1: 7 instead of 1: 1 at a volume ratio.

Examples 3-8

Except that methyl isobutyl ketone (MIBK) and hexane were added at a volume ratio of 1: 8 instead of 1: 1 at a volume ratio.

Examples 3-9

Except that methyl isobutyl ketone (MIBK) and hexane were added at a volume ratio of 1: 9 instead of 1: 1 at a volume ratio.

Example  3-10

Except that methyl isobutyl ketone (MIBK) and hexane were added at a volume ratio of 1: 10 instead of 1: 1 at a volume ratio.

	Extracted organic solvent		DMSO (mol%)		HMF (mol%)
	Furtherance	Extraction order	Water layer	Organic layer	Water layer	Organic layer
Example 3-1	HX + MIBK (1: 1)	1 st	79.7	0.3	9.0	11.0
	HX + MIBK (1: 1)	2 nd	79.7	0.3	7.5	12.5
	HX + MIBK (1: 1)	3 rd	79.7	0.3	6.7	13.3
Example 3-2	HX + MIBK (1: 2)	1 st	79.8	0.2	7.9	12.1
	HX + MIBK (1: 2)	2 nd	79.8	0.2	6.1	13.9
	HX + MIBK (1: 2)	3 rd	79.8	0.2	4.8	15.2
Example 3-3	HX + MIBK (1: 3)	1 st	79.7	0.3	7.4	12.6
	HX + MIBK (1: 3)	2 nd	79.7	0.3	4.0	16.0
	HX + MIBK (1: 3)	3 rd	79.7	0.3	3.8	16.2
Example 3-4	HX + MIBK (1: 4)	1 st	79.9	0.1	6.9	13.1
	HX + MIBK (1: 4)	2 nd	79.9	0.1	4.9	15.1
	HX + MIBK (1: 4)	3 rd	79.8	0.2	3.4	16.6
Example 3-5	HX + MIBK (1: 5)	1 st	79.8	0.2	6.7	13.3
	HX + MIBK (1: 5)	2 nd	79.8	0.2	4.5	15.5
	HX + MIBK (1: 5)	3 rd	79.8	0.2	3.1	16.9
Examples 3-6	HX + MIBK (1: 6)	1 st	79.9	0.1	6.6	13.4
	HX + MIBK (1: 6)	2 nd	79.9	0.1	4.3	15.7
	HX + MIBK (1: 6)	3 rd	79.8	0.2	2.9	17.1
Examples 3-7	HX + MIBK (1: 7)	1 st	79.7	0.3	6.4	13.6
	HX + MIBK (1: 7)	2 nd	79.7	0.3	4.1	15.9
	HX + MIBK (1: 7)	3 rd	79.7	0.3	2.8	17.2
Examples 3-8	HX + MIBK (1: 8)	1 st	79.9	0.1	6.3	13.7
	HX + MIBK (1: 8)	2 nd	79.9	0.1	3.8	16.2
	HX + MIBK (1: 8)	3 rd	79.9	0.1	2.7	17.3
Examples 3-9	HX + MIBK (1: 9)	1 st	79.9	0.1	6.2	13.8
	HX + MIBK (1: 9)	2 nd	79.9	0.1	3.7	16.3
	HX + MIBK (1: 9)	3 rd	79.9	0.1	2.6	17.4
Examples 3-10	HX + MIBK (1:10)	1 st	79.8	0.2	6.8	13.2
	HX + MIBK (1:10)	2 nd	79.7	0.3	3.9	16.1
	HX + MIBK (1:10)	3 rd	79.7	0.3	2.2	17.8

Production Example 1

Fructose corn syrup (glucose: fructose = 2: 8, mol%) containing fructose, which is a ketose-type hexabody compound converted from glucose, which is an aldoose-type hexabody compound, was dissolved in DMSO as a solvent The HMF synthesis reaction was carried out using the continuous reaction equipment. First, the raw material solution of 20% (w / w) high fructose corn syrup was dissolved in DMSO, and glass beads and glass fiber were sequentially placed in a column type reactor (ID = 1.77 cm), filled with Amberlyst-15 as a heterogeneous acid catalyst Glass fiber and glass beads were put in order. The height of Amberlyst-15 was about 10 cm. An electric furnace was operated to adjust the temperature of the reactor to 100 ° C or 110 ° C, and then the raw material solution was flowed at a specified flow rate. At this time, the WHSV was set to 1. The reaction mixture from the reactor was analyzed by HPLC to examine the separation performance of DMSO and HMF after extraction.

Example 4

1.25 l of a mixed solvent of EA / HX (4: 1) as an extraction solvent was added to 250 ml of the HMF solution prepared in Preparation Example 1, and 1.25 l of the same volume of water as the extraction solvent was added and stirred. After stirring, the organic layer (upper layer) containing 5-hydroxymethyl-2-furfural was separated to obtain a water layer (lower layer) containing dimethylsulfoxide. The water layer was separated from the organic layer, and the organic solvent of the organic layer was distilled to obtain 14.0 g of pure HMF.

[Test Example]

Test Example: Analysis of yield of dimethylsulfoxide and hydroxymethyl-2-furfural

Extraction using water and one-component organic solvent

As shown in Table 1, the extraction performance of HMF was good, but MMSK, DEE, EA, DCM, and DCE were extracted with a considerable amount of DMSO, and HX was not extracted into the organic layer of DXO, I did not. In addition, MTBE does not have excellent extraction performance, but DMSO is not extracted into organic layer. HMF extraction was repeated three times using MTBE as an extraction solvent in the screening solvent. HMF with 94% purity was obtained at 80% recovery after three times of repeated extraction.

Extraction using water and binary organic solvent

As shown in Table 2, dual-solvent extraction was performed using HX, which can not extract DMSO and HMF at all, as a co-solvent. EA / HX, and MIBK / HX dual solvent systems.

Referring to Table 3, extraction was carried out with various compositions of EA / HX dual solvent. Three consecutive extractions with EA / HX (1: 5) dual solvent were carried out to obtain HMF of 97% purity at 89% recovery.

Referring to Table 4, extraction was carried out with various compositions of MIBK / HX dual solvent. MIBK / HX (1:10) three solvent extraction with dual solvent gave 98% purity HMF at 89% recovery.

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.

The present invention can provide a separation method that effectively separates dimethylsulfoxide and 5-hydroxymethyl-2-furfural in a mixture of 5-hydroxymethyl-2-furfural and dimethylsulfoxide.

The present invention also relates to a process for the production of 5-hydroxymethyl-2-furfural using a dimethylsulfoxide solvent. After completion of the reaction, a step of separating the dimethylsulfoxide solvent and 5-hydroxymethyl-2-furfural Method can be provided.

Claims (20)

1. (a) preparing a mixed solution comprising 5-hydroxymethyl-2-furfural (HMF) and dimethyl sulfoxide (DMSO); And

   (b) mixing an organic solvent and water with the mixed solution to prepare a layer separation solution layered with an aqueous solution containing DMSO and an organic layer containing HMF; Lt; / RTI &gt;

   Wherein the organic solvent comprises a first organic solvent comprising an aprotic nonpolar organic solvent and a second organic solvent comprising an aprotic polar organic solvent, DMSO.
2. 2. The method of claim 1, wherein said separating method is performed after step (b)

   (c) separating the aqueous solution layer from the layer separation solution to obtain the organic layer.
3. 3. The method of claim 2, wherein the separation method is performed after step (c)

   (d) removing the organic solvent from the organic layer to obtain the HMF.
4. The method according to claim 1,

   Wherein the first organic solvent has a dipole moment D of 0 or more and less than 1.0D (0 < dipole moment &lt; 1.0).
5. 5. The method of claim 4,

   Wherein the first organic solvent has a dipole moment (D) of 0.05 to 0.5D (0.05 &lt; dipole moment &lt; = 0.50).
6. The method according to claim 1,

   Wherein the first organic solvent has a Solubility in H ₂ O (g / 100 g) of 0 to 0.2.
7. The method according to claim 1,

   Wherein the first organic solvent is at least one selected from the group consisting of an aliphatic hydrocarbon compound, an alicyclic hydrocarbon compound, and an aromatic hydrocarbon compound.
8. The method according to claim 1,

   Wherein the aliphatic hydrocarbon compound is at least one selected from the group consisting of pentane, hexane (HX) and heptane,

   Wherein the alicyclic hydrocarbon compound is at least one selected from the group consisting of cyclopentane and cyclohexane,

   Wherein the aromatic hydrocarbon compound is at least one selected from the group consisting of benzene, toluene (TOL) and xylene.
9. The method according to claim 1,

   Wherein the second organic solvent has a dipole moment (D) of 1 to 3 D.
10. 10. The method of claim 9,

    Wherein the second organic solvent has a dipole moment (D) of 1.5 to 3 D.
11. The method according to claim 1,

    Wherein the second organic solvent has a solubility in water (H ₂ O, g / 100 g) of 0 to 10.0.
12. The method according to claim 1,

    Wherein the second organic solvent is at least one selected from the group consisting of a halogen-based hydrocarbon compound, an ester-based hydrocarbon compound, a ketone-based hydrocarbon compound, and an ether-based hydrocarbon compound.
13. The method according to claim 1,

    Wherein the halogen-based hydrocarbon compound is at least one selected from the group consisting of chloroform (CF), dichloromethane (DCM) and 1,2-dichloroethane (DCE)

    Wherein the ester-based hydrocarbon compound is at least one selected from the group consisting of ethyl acetate (EA), methyl acetate and ethyl benzoate,

    Wherein the ketone-based hydrocarbon compound is at least one selected from the group consisting of methyl isobutyl ketone (MIBK) and 3-pentanone,

    Wherein the ether-based hydrocarbon compound is at least one selected from the group consisting of diethyl ether (DEE) and methyltit-butyl ether (MTBE).
14. The method according to claim 1,

    Wherein the organic solvent has a volume ratio of the first organic solvent to the second organic solvent of 0.1: 9.9 to 5.0: 5.0 (v: v).
15. The method according to claim 1,

    Wherein the organic solvent has a volume ratio of the first organic solvent to the second organic solvent of 0.3: 9.7 to 3.0: 7.0 (v: v).
16. 16. The method of claim 15,

    Wherein the organic solvent has a volume ratio of the first organic solvent to the second organic solvent of 0.5: 9.5 to 1.5: 8.5 (v: v).
17. The method according to claim 1,

    Wherein the water and the organic solvent have a volume ratio of 5: 5 to 9: 1 (v: v).
18. The method according to claim 1,

    Wherein the mixed solution and the organic solvent have a volume ratio of 1: 1 to 1:10 (v: v).
19. The method according to claim 1,

    Wherein the step (a) is a step of preparing the mixed solution by preparing the HMF by using an anion exchange resin and a cation exchange resin in the DMSO solvent, and separating the HMF and DMSO .
20. The method according to claim 1,

    Wherein the step (a) is a step of preparing the mixed solution by preparing the HMF by using a cation exchange resin in the presence of fructose in the DMSO solvent.

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