KR20110079484A - Methods for production of hydroxymethylfurfural using starch or raw plant extract - Google Patents

Abstract

PURPOSE: A method for preparing hydroxymethylfurfural is provided to lower production cost and to enhance production efficiency without a special chemical process. CONSTITUTION: A method for preparing hydroxymethylfurfural comprises: a step of mixing ionic liquid, organic solvent catalyst, and metal catalyst to form a first mixture; a step of reacting the first mixture at 100-150°C for 5-20 minutes; a step of adding acid catalyst and starch to form a reactant; and a step of heating the reactant at 100-120°C for 50-100 minutes. The starch is soluble starch, corn starch, wheat starch, rice starch, potato starch, sweet potato starch, or acorn starch. The acid catalyst is oxalic acid, phosphoric acid, sulpheric acid, or hydrochloric acid. The organic solvent catalyst is ethyl acetate or maleic acid.

Description

Methods for production of hydroxymethylfurfural using starch or raw plant extract}

The present invention relates to a process for producing hydroxymethylfurfural.

Hydroxymethylfurfural (5-hydroxymethyl-2-furaldehyde, HMF) is a compound mainly used as a precursor of other useful compounds, for example. It is a cyclic compound of high importance as a precursor compound for the synthesis of medicinal compounds, thermo-resistant polymers compounds and complex macrocycles (ARKRVOC 2001 (10: 17-54)).

Recent reports indicate that hydroxymethylfurfural has been approved by the Food and Drug Administration (FDA) for the treatment of sickle cell disease. Currently, a pharmaceutical company (Xechem International, Inc) The company is expected to develop hydroxymethylfurfural demand in the future as it plans to develop and market it as a drug for treating anemia. In addition, HMF exhibits anti-tyrosinase activity, which inhibits tyrosinase activity, and can be used as a non-toxic food additive to increase food shelf life (Phytotherapy Research, 2004, 18: 841). -844), which can be used as a cosmetic ingredient with skin whitening efficacy and as a raw material of dimethylfuran (DMF), which is highly regarded as energy efficiency as a future liquid biofuel material, It can also be used as a raw material for various carbohydrate derivatives, and a recent paper (Analytical and Bioanalytical Chemistry, 2007, 387: 2801-2814) reported that hydroxymethylfurfural can be developed as an anticancer agent. The potential value of hydroxymethylfurfural is therefore very high.

Due to such various efficacy and usefulness, researches on the synthesis of hydroxymethylfurfural have been conducted for a long time. For the production of hydroxymethylfurfural, refined carbohydrates such as glucose and fructose are used as raw materials. The pretreatment process for refining these carbohydrates is complicated and expensive, and the yield is very low and efficient compared to expensive raw material costs. There is a problem in that mass production is not achieved industrially, but mainly produced only for experiments in the current laboratory.

On the other hand, in recent years, there are two phenomena which are most importantly required in chemical processes for synthesizing materials. The first is a chemical process that minimizes greenhouse gas emissions to prevent global warming, and the second is to develop sustainable renewable resources for fossil fuel depletion. It is to develop process technology that can synthesize material by using.

Therefore, in the present invention, a more complicated process, which is essential for synthesizing hydroxymethylfurfural, that is, a pretreatment process for producing a raw material of hydroxymethylfurfural and a process for synthesizing hydroxymethylfurfural, are simplified. This will reduce greenhouse gas emissions associated with chemical processes, develop new and renewable resources to produce hydroxymethylfurfural continuously and produce competitively priced products. Hydroxymethylfurfural through raw material production costs will achieve mass production.

The present inventors use renewable carbohydrate resources, which are not refined carbohydrates such as glucose and fructose, which are used as raw materials for the synthesis of hydroxymethylfurfural. While trying to develop a method that can be used, according to the production method of the present invention confirmed that it is possible to synthesize a large amount of hydroxymethylfurfural by using starch or plant biomass as a raw material without undergoing a pretreatment step, and completed the present invention. It was.

The present invention

It provides a method for producing hydroxymethylfurfural comprising heating a reaction mixture containing starch, an ionic liquid, an acid catalyst and an organic solvent catalyst.

Also,

Mixing an ionic liquid, an organic solvent catalyst, and a metal catalyst to form a primary mixture;

Reacting the primary mixture at 100 to 150 ° C. for 5 to 20 minutes;

Adding an acid catalyst and starch to the reactants to form a reaction mixture; And

It provides a method for producing hydroxymethylfurfural comprising the step of heating the reaction mixture.

Also,

It provides a method for producing hydroxymethylfurfural comprising heating a reaction mixture containing a plant biological extract, an ionic liquid and an organic solvent catalyst.

Also,

Mixing the ionic liquid and the metal catalyst to form a primary mixture;

Reacting the primary mixture at 100 to 150 ° C. for 5 to 20 minutes;

Adding a plant biological extract and an organic solvent catalyst to the reactants to form a reaction mixture; And

It provides a method for producing hydroxymethylfurfural comprising the step of heating the reaction mixture.

The production method of hydroxymethylfurfural of the present invention can reduce the production cost by using starch or plant biomass as a raw material, and increase the production efficiency of hydroxymethylfurfural because it uses a simple heating process without a special chemical process. In addition to reducing gas emissions, which is a problem in chemical processes, it is useful for the mass production of hydroxymethylfurfural, which has high industrial and economic value. In addition, the present invention provides a base technology for mass production of hydroxymethylfurfural, which is highly regarded for its industrial and economic value, and thus, DMF for next-generation liquid bioenergy as well as related industries such as medicine, food, and cosmetics. The present invention may be utilized as a raw material for producing.

1 is a graph showing the yield of HMF according to the concentration and the reaction time of the hydrochloric acid solution used as an acid catalyst in the synthesis of HMF from the starch of the present invention.
Figure 2 is a graph showing the yield of HMF with the addition of chromium chloride used as a metal catalyst in the synthesis of HMF from the starch of the present invention.
3 is a graph showing the yield of HMF according to the concentration of ethyl acetate used as the organic solvent catalyst in the synthesis of HMF from the starch of the present invention.
Figure 4 is a graph showing the yield of HMF according to the reaction time in the synthesis of HMF from the plant biological extract of the present invention. (GR; Pork Potato, CR; Chicory, PT; Potato, SP; Sweet Potato, AC; Acorn, KR; Root Root, MR; Cassava)
5 is a graph showing the yield of HMF according to the addition of metal catalysts in the synthesis of HMF from the plant biological extract of the present invention.
Figure 6 is a graph showing the yield of HMF according to the addition of CrF ₃ concentration in the synthesis of HMF from the tapioca biological extract of the present invention.
Figure 7 is a graph showing the yield of HMF according to the concentration of plant biomass in the synthesis of HMF from the plant biological extract of the present invention.
8 is a graph showing the yield of HMF according to the concentration of ethyl acetate used as the organic solvent catalyst in the synthesis of HMF from the plant biological extract of the present invention according to the concentration.

The present invention

It provides a method for producing hydroxymethylfurfural comprising heating a reaction mixture containing starch, an ionic liquid, an acid catalyst and an organic solvent catalyst.

Also,

Mixing an ionic liquid, an organic solvent catalyst, and a metal catalyst to form a primary mixture;

Reacting the primary mixture at 100 to 150 ° C. for 5 to 20 minutes;

Adding an acid catalyst and starch to the reactants to form a reaction mixture; And

It provides a method for producing hydroxymethylfurfural comprising the step of heating the reaction mixture.

In the step of heating the reaction mixture of the present invention, the reaction mixture may be heated at 100 to 150 ° C. for 30 to 120 minutes, and more preferably at 100 to 120 ° C. for 50 to 100 minutes.

Starch of the present invention can be used as a starch itself or in the form of a solution. When used in the form of a solution, the concentration of the solution may be 1 to 90% concentration, preferably 5 to 20% concentration.

The starch of the present invention may be a starch separated from various plant species, and any starch derived from chemical synthesis, biotechnological synthesis, etc. may be used, and the type thereof is not limited.

In one embodiment of the present invention, the starch is one selected from the group consisting of soluble starch, corn starch, wheat starch, rice starch, potato starch, sweet potato starch, tapioca starch, tapioca starch, acorn starch and starch starch. It may be more than, preferably tapioca starch.

The 'soluble starch' refers to a substance that is initially produced when acid, alkali and amylase are applied to starch grass, and has a property of being dissolved in warm water.

Ionic liquid of the present invention is 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium tetraborate (1-ethyl-3-methylimidazolium tetraborate ), 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium chloride, 1-butyl- 3-methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium bromide, 1-octyl-3-methylimidazolium chloride (1-octyl- 3-methylimidazolium chloride) and 1-octyl-3-methylimidazolium bromide (1-octyl-3-methylimidazolium bromide) It may be one or more, preferably 1-octyl-3-methylimidazolium chloride (abbreviated as '[OMIM] Cl').

Acid catalyst of the present invention may be one selected from the group consisting of oxalic acid (Oxalic acid), phosphoric acid (Phophoric acid), sulfuric acid (Sulpheric acid) and hydrochloric acid (Hydrochloric acid), preferably may be hydrochloric acid. When hydrochloric acid is used as the acid catalyst of the present invention, it may be used at a concentration of 0.1M to 1M, preferably 0.3M to 0.5M.

The organic solvent catalyst of the present invention may be ethyl acetate (male acetate) or maleic acid (maleic acid), preferably ethyl acetate. When ethyl acetate is used as the organic solvent catalyst of the present invention, it may be used at a concentration of 5 to 30%, preferably at a concentration of 5 to 20%.

The metal catalyst of the present invention is zinc chloride (ZnCl ₂ ), chromium chloride (CrCl ₂ ), chromium chloride (CrCl ₃ ), chromium bromide (CrBr ₃ ), chromium fluoride (CrF ₃ ), zeolite, chloride It may be at least one selected from the group consisting of cobalt (CoCl ₂ ), nickel chloride (NiCl ₂ ) and magnesium chloride (MgCl ₂ ).

Also preferably, chromium chloride (CrCl ₂ ) is added alone, chromium fluoride (CrF ₃ ) is added alone, chromium chloride (CrCl ₂ ) and chromium chloride (CrCl ₃ ) are added together, and chromium chloride (CrCl ₃ ) is added. ₂ ) mixed addition of chromium bromide (CrBr ₃ ), mixed addition of chromium chloride II (CrCl ₂ ) and chromium bromide (CrBr ₃ ), mixed addition of chromium chloride III (CrCl ₃ ) and chromium fluoride (CrF ₃ ) or It may be a mixed addition of chromium bromide (CrBr ₃ ) and chromium fluoride (CrF ₃ ).

The metal catalyst of the present invention is preferably added at a concentration of 1 to 5% based on the total volume of the reaction mixture of the present invention.

The invention also

It provides a method for producing hydroxymethylfurfural comprising heating a reaction mixture containing a plant biological extract, an ionic liquid and an organic solvent catalyst.

The invention also

Mixing the ionic liquid and the metal catalyst to form a primary mixture;

Reacting the primary mixture at 100 to 150 ° C. for 5 to 20 minutes;

Adding a plant biological extract and an organic solvent catalyst to the reactants to form a reaction mixture; And

It provides a method for producing hydroxymethylfurfural comprising the step of heating the reaction mixture.

The reaction mixture heating is preferably heated at 100 to 150 ℃ for 30 to 120 minutes, more preferably at 100 to 120 ℃ for 50 to 100 minutes.

Extracting method of the plant biological extracts used in the present invention can be extracted using an extraction method that is generally performed in the art, such extraction methods include hot water extraction, cold water extraction, solvent extraction, ultrasonic extraction, supercritical extraction, etc. .

Specifically, for example, the plant biological extract may be extracted by drying the plant living body in powder form and then applying heat thereto, or extracting the plant living body in powder form and adding the extraction solvent to obtain the extract. Can be.

In one embodiment of the present invention, the plant biological extract may be dried and pulverized and then dried to form a plant biomass, followed by adding the pulverized dry powder to an acidic extraction solvent and reacting to separate the extract. The acidic extraction solvent may be one selected from the group consisting of oxalic acid, phosphoric acid, sulfuric acid, and hydrochloric acid, preferably hydrochloric acid at a concentration of 0.3M to 0.5M. This is good. In addition, the extraction temperature may be a temperature of 60 to 100 ℃, preferably 70 to 80 ℃. The extraction time may be 60 minutes to 180 minutes, preferably 100 minutes to 150 minutes.

In the present invention, the "plant biomass" refers to a plant that can be used as biomass.

In the present invention, the "plant biological extract" means an extract obtained by extracting the plant biomass.

The plant biomass used in the present invention is not particularly limited in kind, but may be at least one selected from the group consisting of pork potatoes, chicory, potatoes, sweet potatoes, acorns, wild roots and cassava (manioc), preferably May be a pig potato.

Ionic liquid of the present invention is 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium tetraborate (1-ethyl-3-methylimidazolium tetraborate ), 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium chloride, 1-butyl- 3-methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium bromide, 1-octyl-3-methylimidazolium chloride (1-octyl- 3-methylimidazolium chloride) and 1-octyl-3-methylimidazolium bromide (1-octyl-3-methylimidazolium bromide) It may be one or more, preferably 1-octyl-3-methylimidazolium chloride (abbreviated as '[OMIM] Cl').

The organic solvent catalyst of the present invention may be ethyl acetate (male acetate) or maleic acid (maleic acid), preferably ethyl acetate. When ethyl acetate is used as the organic solvent catalyst of the present invention, it may be used at a concentration of 5 to 30%, preferably at a concentration of 5 to 20%.

The metal catalyst of the present invention is zinc chloride (ZnCl ₂ ), chromium chloride (CrCl ₂ ), chromium chloride (CrCl ₃ ), chromium bromide (CrBr ₃ ), chromium fluoride (CrF ₃ ), zeolite, chloride It may be at least one selected from the group consisting of cobalt (CoCl ₂ ), nickel chloride (NiCl ₂ ) and magnesium chloride (MgCl ₂ ).

Also preferably, chromium chloride (CrCl ₂ ) is added alone, chromium fluoride (CrF ₃ ) is added alone, chromium chloride (CrCl ₂ ) and chromium chloride (CrCl ₃ ) are added together, and chromium chloride (CrCl ₃ ) is added. ₂ ) mixed addition of chromium bromide (CrBr ₃ ), mixed addition of chromium chloride II (CrCl ₂ ) and chromium bromide (CrBr ₃ ), mixed addition of chromium chloride III (CrCl ₃ ) and chromium fluoride (CrF ₃ ), It may be a mixed addition of chromium bromide (CrBr ₃ ) and chromium fluoride (CrF ₃ ).

The metal catalyst of the present invention is preferably added at a concentration of 1 to 5% based on the total volume of the reaction mixture of the present invention.

In one embodiment of the present invention, the metal catalyst of the present invention may be in the form of chromium fluoride (CrF3) alone at a concentration of 1% based on the total reaction mixture volume.

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various forms, and only the embodiments are intended to complete the disclosure of the present invention, and the general knowledge in the technical field to which the present invention pertains. It is provided to fully convey the scope of the invention to those skilled in the art, and the present invention is defined only by the scope of the claims.

< Example >

Hydroxymethylfurfural  ( HMF ) And sugar analysis

Analysis of HMF and sugars was quantified by high performance liquid chromatograpy (HPLC). For their analysis, the Waters HPLC system, Waters autosampler and Waters refractometer were used. HMF quantification was performed at 320 nm using a Waters XBridge C18 reversed phase column (4.6 mm x 150 mm, 5). A gradient mobile phase was used and the flow rate was 0.7 mL / min. Gradient conditions are as follows: 2 minutes on 100% water, first transition state and 8 minutes on gradient of 80% water and 20% methanol, second transition state and finally 20 minutes on 100% water. For quantification of sugar, YMC-Pack Polyamine II column (4.6mm x 250mm, S-5, 12nm, Japan) was used and mobile phase (75:25, acetonitrile: water) was used at a flow rate of 1ml / min. .

Statistical processing

All measurements were calculated as the average of at least 4 independent responses and expressed as standard deviation. Regarding the relative HMF yield, the reaction was carried out for 60 minutes in a solvent mixture containing 10 g soluble starch containing 4 g [OMIM] Cl and 5 ml of 0.3 M hydrochloric acid added with 1 ml ethyl acetate and chromium chloride (CrCl ₂ ). The HMF yield obtained was used as a control.

Example 1 Synthesis of Hydroxymethylfurfural ( HMF) from Starch

Example 1 -1: Effect of hydrochloric acid concentration and reaction time

Soluble starch was investigated in relation to two variables, hydrochloric acid and reaction time in the presence of [OMIM] Cl solvent. (Soluble starch (Yakuri Pure Chemicals Co. Ltd.), [OMIM] Cl (Merck), hydrochloric acid (Junsei Chemical Co. Ltd.))

1 g of soluble starch was added to a 10 ml mixture containing 5 ml of hydrochloric acid solution (0.0M, 0.1M, 0.3M and 0.5M), 1 ml of ethyl acetate, and 4 g of [OMIM] Cl, followed by a heating mantle. The reaction was stirred at 120 ° C. for 0 minutes to 120 minutes. Samples were taken every 30 minutes of reaction time to analyze the content of hydroxymethylfurfural.

As a result, as shown in Figure 1, the lower the hydrochloric acid concentration tended to longer reaction time, the overall reaction time effective for the synthesis of HMF was found to be 50 minutes to 120 minutes, 0.3M and 1M hydrochloric acid solution The highest HMF yield was obtained when 60 minutes were reacted, especially when 90 minutes were reacted in 0.5M hydrochloric acid solution.

Example 1 -2: Investigation of the influence of the metal catalyst

In order to evaluate the yield of HMF with addition of the metal catalyst, it was carried out in two groups.

Group 1 (without chromium chloride) added 1 g of soluble starch to a 10 ml mixture containing 5 ml of hydrochloric acid solution (0.0M, 0.3M, 0.5M and 1.0M), 1 ml of ethyl acetate and 4 g of [OMIM] Cl. The reaction was stirred at 120 ° C. for 0 to 120 minutes on a heating mantle. Samples were taken every 30 minutes of reaction time to analyze the content of HMF.

In the second group (adding chromium chloride), a mixture of 4 g of [OMIM] Cl, 1 ml of ethyl acetate and 0.2 g of chromium chloride (CrCl ₂ ) was pre-reacted at 120 to 10 minutes, followed by hydrochloric acid solution (0.0M, 0.3M, 0.5M and 1.0M) 5ml and 1g of soluble starch were added and then reacted with stirring at 120 ° C. for 0 to 120 minutes. Samples were taken every 30 minutes of reaction time to analyze the content of HMF.

As a result, as shown in Figure 2, the overall treatment of the addition of chromium chloride treatment group was confirmed that the yield of HMF about twice or more than the addition of the treatment group, in particular 0.3M and 0.5M of the chromium chloride addition treatment group In the experiment with hydrochloric acid solution of HMF yield was much higher. In addition, the results of analysis by reaction time showed that the yield of HMF was almost the same in 0.3 M hydrochloric acid solution at 60 and 90 minutes, and the highest yield of HMF was observed at 60 M reaction time in 0.5 M hydrochloric acid solution. . Therefore, in order to synthesize HMF from starch efficiently, it was confirmed that it is most effective to add chromium chloride by adjusting the concentration of hydrochloric acid solution from 0.3M to 0.5M.

Example 1 -3: Investigation of the influence of organic solvent catalyst concentration

In order to evaluate the yield of HMF according to the addition of the organic solvent catalyst, ethyl acetate (etrhyl acetate) was used as the organic solvent catalyst, the concentration of ethyl acetate was 0%, 5%, 10%, 15%, 20%, 25% and The experiment was performed at 30%. A mixture of 1 g of soluble starch, 5 ml of 0.3 M hydrochloric acid solution, chromium chloride and [OMIM] Cl was used, with as little as the amount of ethyl acetate added on a 5 g weight basis for [OMIM] Cl.

As a result, as shown in Figure 3, it was confirmed that the highest HMF obtained in the treated group added at 10% ethyl acetate concentration, the yield tends to gradually decrease at higher concentrations.

Example 1 -4: investigation of the effect of starch concentration

Four different starch concentrations (5, 10, 15 and 20%) were used to evaluate the synthetic yield of HMF according to the starch concentration.

First, starch was added to 0.3M and 0.5M hydrochloric acid solution to prepare starch solutions of each concentration of 5%, 10%, 15% and 20% (w / v).

To this end, it was divided into two groups according to the molarity of the hydrochloric acid solution.

Group 1 (using 0.3 M hydrochloric acid solution) is a starch solution prepared by using 0.3 M hydrochloric acid solution as a solvent in a mixture of [OMIM] Cl 4 g, ethyl acetate 1 ml, and 0.2 g chromium chloride (CrCl 2). After the addition, the reaction was stirred at 120 to 0 to 120 minutes on a heating mantle. Samples were taken every 30 minutes of reaction time to analyze the content of HMF.

Group 2 (using 0.5 M hydrochloric acid solution) was prepared by mixing starch solution prepared using 0.5 M hydrochloric acid solution as a solvent in a mixture of 4 g of [OMIM] Cl, 1 ml of ethyl acetate, and 0.2 g of chromium chloride (CrCl2). After addition, the reaction was allowed to stir at 120 to 0 minutes for 120 minutes on a heating mantle. Samples were taken every 30 minutes of reaction time to analyze the content of HMF.

Comparison of production of HMF by reaction time according to starch concentration and hydrochloric acid concentration (unit: wt%) 0.3 M hydrochloric acid (HCl) 0.5 M hydrochloric acid (HCl) Starch
(%) Response time (minutes) Response time (minutes) 30 60 90 120 30 60 90 120 5 - 64.0 ± 2.2 61.2 ± 4.3 46.1 ± 8.6 10.2 ± 4.2 64.0 ± 3.7 54.0 ± 9.1 39.2 ± 8.1 10 19.4 ± 4.7 63.1 ± 6.1 58.0 ± 2.3 40.5 ± 7.8 13.5 ± 5.7 59.5 ± 4.9 56.2 ± 2.8 36.3 ± 3.8 15 12.7 ± 6.1 55.2 ± 4.1 48.8 ± 2.4 46.3 ± 3.8 8.0 ± 4.9 50.5 ± 3.4 46.9 ± 4.4 41.7 ± 5.7 20 7.3 ± 3.9 40.8 ± 6.7 48.1 ± 3.4 36.8 ± 3.3 8.8 ± 4.1 44.0 ± 3.6 38.3 ± 3.8 34.0 ± 5.2

As a result, as shown in Table 1, the yields of the highest HMF (64.0 ± 3.7 and 64.0 ± 2.2% by weight) of all treatment groups were reacted for 60 minutes in a mixture to which 5% soluble starch was added. One case was confirmed. Overall, the higher the starch concentration, and the longer the reaction time, the more the 60 minutes or more, the yield of HMF tended to decrease. Another characteristic of this experiment is that the difference in HMF yields between the two hydrochloric acid solution concentrations (0.3M and 0.5M) was not significantly different, whereas the 0.3M treatment group with 20% starch added allowed 90 minutes of reaction. When the highest yield of HMF was obtained. As a result of these experiments, it was estimated that the reaction time should be extended to 90 minutes or more in the 0.3M hydrochloric acid treatment group when the starch concentration was high (more than 20%).

Example 1 -5: Investigation of starch type effect

Starch derived from 8 kinds of plants (corn, wheat, rice, potato, sweet potato, tapioca, acorn, and root root) was used to compare the yield of HMF according to the types of starch, and the method was the same as in Example 1-4. Only the type of starch is used instead of the concentration of starch. (Wako Pure Chemical Industries, Ltd.), Wheat (SIgma), Rice (Sigma), Potato (Junsei Chemical Co. Ltd.), Sweet Potato (Wako Pure Chemical Industries, Ltd.), Tapioca (Sold by a domestic alcohol company Acorn (Ecoforest), 칡 (Jecheon Institute of Agricultural Technology)

To the 10 ml mixture containing 5 ml of hydrochloric acid solution, 1 ml of ethyl acetate and 4 g of [OMIM] Cl, 1 g of starch of each type was added, and the mixture was stirred on a heating mantle at 120 ° C. for 0 to 120 minutes. I was. Samples were taken every 30 minutes of reaction time to analyze the content of hydroxymethylfurfural.

Effect of Hydrochloric Acid Concentration and Reaction Time on HMF Yield from Starch by Plant Type (Unit: wt%) 0.3 M hydrochloric acid (HCl) 0.5 M hydrochloric acid (HCl) Starch
Kinds Response time (minutes) Response time (minutes) 30 60 90 120 30 60 90 120 corn - 49.5 ± 9.8 47.0 ± 4.5 38.1 ± 6.8 13.0 ± 5.8 63.5 ± 2.4 54.0 ± 3.6 40.7 ± 5.4 wheat 19.0 ± 4.4 65.5 ± 3.7 57.0 ± 3.1 43.9 ± 5.8 9.5 ± 3.9 54.5 ± 3.9 53.1 ± 2.2 42.7 ± 4.1 rice - 64.0 ± 2.2 62.0 ± 2.8 46.8 ± 7.6 12.0 ± 4.6 57.8 ± 2.6 52.0 ± 3.4 39.5 ± 3.9 potato 3.3 ± 1.9 52.1 ± 3.9 48.5 ± 5.2 36.2 ± 6.8 7.0 ± 3.9 62.0 ± 3.2 53.5 ± 2.5 39.8 ± 7.1 sweet potato 6.2 ± 3.2 56.0 ± 2.9 50.5 ± 4.6 41.2 ± 5.9 12.5 ± 3.9 66.5 ± 5.1 51.5 ± 6.7 42.0 ± 5.8 tapioca 8.0 ± 3.8 62.5 ± 2.7 56.5 ± 4.9 42.1 ± 8.1 10.1 ± 5.5 73.0 ± 3.8 61.1 ± 4.2 44.5 ± 6.8 Acorn 4.5 ± 2.1 54.5 ± 3.1 50.2 ± 4.3 36.3 ± 3.3 9.5 ± 4.6 58.5 ± 3.2 55.0 ± 4.6 39.5 ± 8.2 칡 7.5 ± 3.2 55.2 ± 2.8 48.5 ± 3.4 38.8 ± 4.6 12.2 ± 4.4 63.5 ± 3.6 54.1 ± 8.2 38.8 ± 6.1

As a result, as shown in Table 2, the highest measured starch yield of HMF showed a yield of 73.0 ± 3.8% by weight as tapioca (in 0.5M hydrochloric acid 60 minutes reaction time treatment group).

Example 2 Synthesis of Hydroxymethylfurfural ( HMF) from Plant Biotic Extracts

Example 2 -1: plant living body Biomass  Ready

The biomass of the plant used was 60-degree Celsius for pig, potato, chicory, potato (potato tuber), sweet potato, acorn (acorn), kudzu and cassava (manioc). After drying at 65 ° C., the mixture was pulverized with a grinder to prepare a powder.

Example 2 -2: proper extraction temperature and extraction time of plant biological extract

10% (w / v) of plant biopowder powder was added to 0.5M hydrochloric acid solution, followed by reaction at 60 ° C and 80 ° C for 0-3 hours, followed by centrifugation at 13500 × g for 60 minutes to extract the supernatant. It was used for the synthesis of HMF.

Comparison of HMF Yield with Extraction Temperature and Extraction Time by Type of Plant Biomass (Unit: wt%) 60 ℃ 80 ℃ Biomass
Kinds Extraction time (hour) Extraction time (hour) 0 One 2 3 0 One 2 3 Pork Potato - 19.5 ± 2.8 24.0 ± 4.5 27.1 ± 1.8 - 43.5 ± 2.4 44.0 ± 5.6 40.7 ± 5.4 Chicory - 16.5 ± 3.7 21.0 ± 3.1 23.9 ± 3.8 - 36.5 ± 3.9 34.1 ± 4.2 32.7 ± 4.1 potato - 10.0 ± 2.2 12.0 ± 2.8 14.8 ± 2.6 - 17.8 ± 2.6 16.0 ± 3.4 14.5 ± 1.9 sweet potato - 12.1 ± 3.9 14.5 ± 3.2 15.2 ± 1.8 - 15.0 ± 3.2 14.5 ± 2.5 13.8 ± 3.1 Acorn - 10.0 ± 2.9 14.5 ± 1.6 17.2 ± 2.9 - 16.5 ± 5.1 16.5 ± 3.7 13.0 ± 2.8 Root Root - 2.5 ± 0.7 6.5 ± 2.9 8.1 ± 1.1 - 11.0 ± 3.8 11.1 ± 1.2 10.5 ± 1.8 cassava - 10.5 ± 3.1 15.2 ± 3.3 15.3 ± 1.3 - 17.5 ± 3.2 16.0 ± 1.6 15.5 ± 1.2

As a result, as shown in Table 3, the yield of HMF was much higher than the extract extracted at 80 ℃ Celsius compared to the extraction of 60 ℃ Celsius. In particular, potato pigs and chicory yields were nearly twice as high as those at 60 ° C. According to the results of analyzing the yield of HMF by the extraction time of the extract, the highest yield of HMF was measured in the extraction time range of 1 to 2 hours, which is the titration of all plant biomass used in this experiment. It was supported by the fact that extraction time.

Example 2 -3: investigation of the influence of the appropriate reaction temperature

This experiment was carried out to select the appropriate reaction time for each biobiomass of plants used as experimental materials.

[OMIM] Cl 4g, Ethyl Acetate 1ml And 5 ml of each plant biological extract, extracted from each plant biomass, was added to the mixture of 0.2 g of chromium chloride and reacted at 120 ° C. for 30 minutes to 120 minutes.

As a result, as shown in FIG. 4, it was found that the yield of most plant biomass HMF was the highest at a reaction time of 60 minutes (average of about 22.4 mg / ml of each extract).

Example 2 -4: Investigation of the influence of hydrochloric acid concentration and metal catalyst

In order to compare the effects of hydrochloric acid and chromium chloride on the synthesis of HMF from plant biomass, two groups were added: chromium chloride addition and no treatment in the hydrochloric acid solution (0.0M, 0.3M, 0.5M, 1.0M HCl). The experiment was carried out in portions.

Group 1 (without chromium chloride) consists of a mixture of 4 g of [OMIM] Cl, 1 ml of ethyl acetate, and 5 ml of each plant biological extract (extracted from 7 different plant biomass using concentration hydrochloric acid solution). The reaction was stirred at 120 ° C. for 60 minutes on a heating mantle.

Group 2 (with chromium chloride) consists of 4 g of [OMIM] Cl and chromium chloride (CrCl ₂ ) After 0.2 g of the mixture was pre-reacted at 120 ° C. for 15 minutes, 5 ml of each plant bio extract (extracted from 7 kinds of plant biomass using concentration hydrochloric acid solution) and 1 ml of ethyl acetate were added. The reaction was stirred at 120 ° C. for 60 minutes.

Effect of Hydrochloric Acid Concentration and Chromium Chloride on HMF Yield by Type of Plant Biomass (Unit: mg / ml Extract) metal
Catalyst Biomass
Kinds Hydrochloric Acid Concentration (M) 0.0 0.3 0.5 1.0 Chromium chloride
No addition Pork Potato - 37.9 ± 3.5 40.6 ± 4.1 25.6 ± 3.8 Chicory - 28.1 ± 3.8 31.5 ± 3.7 28.6 ± 4.1 potato - 15.3 ± 2.9 16.0 ± 4.0 13.8 ± 1.8 sweet potato - 14.3 ± 8.1 14.7 ± 2.7 12.5 ± 3.9 Acorn - 11.6 ± 4.8 12.6 ± 3.9 11.6 ± 2.4 Root Root - - - 5.7 ± 2.8 cassava - 15.4 ± 3.8 14.0 ± 6.1 13.2 ± 2.8 Chromium chloride
adding Pork Potato 8.4 ± 5.8 49.1 ± 5.4 64.5 ± 3.5 49.4 ± 3.9 Chicory 7.5 ± 3.6 46.0 ± 4.8 50.2 ± 5.1 39.4 ± 3.3 potato - 40.6 ± 2.9 61.4 ± 5.8 37.6 ± 4.1 sweet potato - 42.0 ± 3.5 61.4 ± 4.4 35.0 ± 3.7 Acorn - 45.4 ± 4.2 63.6 ± 7.2 34.6 ± 2.8 Root Root - 10.5 ± 2.3 11.4 ± 3.8 9.8 ± 3.3 cassava - 46.7 ± 6.8 55.3 ± 6.3 42.7 ± 5.8

As a result, as shown in Table 4, it was confirmed that the synthesis of HMF in the chromium chloride addition treatment group is almost three times higher. Particularly, the concentration of HMF was the highest in the 0.5 M treatment group, and the yield of HMF decreased by about half. From the results obtained in this experiment, it was found that the addition of chromium chloride and the use of 0.5 M hydrochloric acid solution increased the HMF synthesis efficiency, depending on the type of plant.

Example 2 -5: Halogen chrome  Investigation of the Effect of Metal Catalysts

In order to compare the effects on the synthesis of HMF according to the type of halogen chrome metal catalysts, the types of metal catalysts (CrCl ₂ , CrCl ₃ , CrBr ₃ , CrF ₃ , CrCl ₂ + CrCl ₃ , CrCl ₂ + CrBr ₃ , CrCl ₂ + CrF ₃ , CrCl ₃ + CrBr ₃ , CrCl ₃ + CrF ₃ , CrBr ₃ + CrF ₃ ) was performed according to the addition. CrCl ₂ (97% anhydrous), CrCl ₃ (99.5%, 6H2O), CrBr ₃ (crystalline, 6H2O) and CrF ₃ (98%, hydrate) used above were purchased from Alfa Aesar, Mass., USA. Was used.

First, 10% (w / v) dried acorn biopowder powder was added to 0.3 M hydrochloric acid solution and reacted at 80 degrees Celsius for 2 hours, followed by centrifugation at 13500 × g for 60 minutes to extract the supernatant.

[OMIM] Cl 4g and 0.2g of the halogen chromium metal catalysts of each type were mixed (0.1g of each catalyst in the case of two mixed metal catalysts), pre-reacted for 120 to 15 minutes, and then the acorn biomass was extracted. 5 ml of extract and 1 ml of ethyl acetate were added, followed by reaction with stirring. After the reaction, samples were taken at 60 and 90 minutes to analyze the content of HMF.

As a result, as shown in FIG. 5, the highest HMF yield (58.7 + 1.3dwt%) was observed when the overall reaction was carried out by adding a mixed catalyst of CrCl ₂ and CrCl ₃ or a mixed catalyst of CrBr ₃ and CrF ₃ for 90 minutes. . In addition, CrCl ₂ showed the highest HMF yield as a single catalyst, whereas CrF ₃ alone showed the lowest HMF yield.

Example 2 -6: CrF ₃ Investigation of the effects of different concentrations of

To compare the effect of HF on the synthesis of CrF ₃ catalyst by the concentration of CrF ₃ catalyst, tapioca (cassava) biopowder was used, and the mass ratio of the reaction mixture volume was 0.05% to 2%. The experiment was performed by adding CrF ₃ . The CrF ₃ (98%, hydrate) used was purchased from Alfa Aesar, Mass., USA.

First, 10% (w / v) dried tapioca biopowder powder was added to 0.3 M hydrochloric acid solution and reacted at 80 degrees Celsius for 2 hours, followed by centrifugation at 13500 × g for 60 minutes to extract the supernatant.

[OMIM] Cl 4g and CrF ₃ (0.05g, 0.1g, 0.15g, 2g) were mixed and pre-reacted at 120 to 15 minutes, and then 5ml of the extracted tapioca extract and 1ml of ethyl acetate were added and stirred. Reacted. After the reaction, samples were taken at 60 and 90 minutes to analyze the content of HMF. (The concentration of CrF ₃ is CrF ₃ to be mixed, based on the total reaction mixture volume Based on mass)

As a result, as shown in FIG. 6, the highest HMF yield (64.5 + 2.3 dwt%) was observed when reacting for 90 minutes by adding CrF 3 at a concentration of 1%. In Example 2-5, when CrF ₃ was added at a concentration of 2% based on the total reaction mixture, it showed the lowest HMF yield compared to other metal catalysts. It was found that the highest HMF yield was obtained (about 10% higher than other catalysts) compared to the catalyst. Since CrF _{3 as} a metal catalyst is cheaper than other metal catalysts, it is meaningful to obtain a high yield of HMF industrially by using a concentration of 1% of the present metal catalyst.

Example 2 -7: plant living body Biomass  Investigate impact by concentration

Acorn was used as a plant biomass to evaluate the yield of HMF according to the plant biomass concentration, and 10%, 15%, 20%, 25%, 30 was added by adding dried acorn biopowder to 0.3M hydrochloric acid solution. The effect on the yield of HMF at each concentration of%, 40%, 45% and 50% (w / v) was evaluated.

First, acorn dry powder was added to 0.3M hydrochloric acid solution to prepare 10%, 15%, 20%, 25%, 30%, 40%, 45%, and 50% (w / v) acorn biological solution. The acorn biological solution for each concentration was reacted at 80 ° C. for 2 hours, followed by centrifugation to extract the supernatant, thereby preparing acorn extract for each concentration.

[OMIM] Cl 4g, CrBr3 0.1g and CrF3 0.1g were mixed and pre-reacted at 120 ° C. for 15 minutes, and then 5 ml of acorn extracts and 1 ml of ethyl acetate for each concentration were added and reacted with stirring. 90 minutes after the reaction, a sample was taken and analyzed for HMF content. In order to compare relative HMF yield, the acorn bioextract extracted with acorn solution at a concentration of 10% (w / v) was evaluated based on the HMF yield of 1 as a reference.

As a result, as shown in Figure 7, the acorn extract extracted using a solution of a concentration of 15% (w / v) showed a relatively high HMF yield.

Example 2 -8: Investigation of the influence of organic solvent catalyst concentration

In order to evaluate the yield of HMF according to the addition of the organic solvent catalyst, ethyl acetate (etrhyl acetate) was used as the organic solvent catalyst, the concentration of ethyl acetate was 0%, 5%, 10%, 15%, 20%, 25% and The experiment was performed at 30%.

A mixture of 5 ml of acorn biological extract, chromium chloride and [OMIM] Cl was used, and in the case of [OMIM] Cl, as little as the amount of ethyl acetate added based on the weight of 5 g.

As a result, as shown in Figure 8, it was confirmed that the highest HMF obtained in the treatment group added 10% ethyl acetate concentration.

GR; Pork Potato, CR; Chicory, PT; Potato, SP; Sweet potato, AC; Acorns, KR; Rootroot, MR; cassava

Claims (24)

A method for producing hydroxymethylfurfural comprising heating a reaction mixture containing starch, an ionic liquid, an acid catalyst and an organic solvent catalyst.
Mixing an ionic liquid, an organic solvent catalyst, and a metal catalyst to form a primary mixture;
Reacting the primary mixture at 100 to 150 ° C. for 5 to 20 minutes;
Adding an acid catalyst and starch to the reactants to form a reaction mixture; And
Method for producing hydroxymethylfurfural comprising the step of heating the reaction mixture.
The method according to claim 1 or 2,
Heating the reaction mixture is a method for producing hydroxymethylfurfural, characterized in that for heating 50 to 100 minutes at 100 to 120 ℃.
The method according to claim 1 or 2,
The starch is hydroxy starch, corn starch, wheat starch, rice starch, potato starch, sweet potato starch, tapioca (cassava starch), acorn starch and hydroxy starch, characterized in that at least one selected from the group consisting of Method of producing methylfurfural.
The method according to claim 1 or 2,
The ionic liquid is 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium tetraborate, 1-ethyl-3-methylimidazolium tetraborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium chloride, 1-butyl-3- Methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium chloride (1-butyl-3-methylimidazolium bromide) 1-hexyl-3-methylimidazolium chloride), 1-hexyl-3-methylimidazolium bromide, 1-octyl-3-methylimidazolium chloride (1-octyl-3- methylimidazolium chloride) and 1-octyl-3-methylimidazolium bromide (1-octyl-3-methylimidazolium bromide) Method of hydroxymethyl furfural, characterized in that the merchant production.
The method according to claim 1 or 2,
The acid catalyst is oxalic acid (Oxalic acid), phosphoric acid (Phophoric acid), sulfuric acid (Sulpheric acid) and hydrochloric acid (Hydrochloric acid) is a production method of hydroxymethylfurfural, characterized in that one selected from the group consisting of.
The method according to claim 1 or 2,
The acid catalyst is a method for producing hydroxymethylfurfural, characterized in that the hydrochloric acid of 0.3M to 0.5M concentration.
The method according to claim 1 or 2,
Wherein the organic solvent catalyst is ethyl acetate or maleic acid.
The method according to claim 1 or 2,
The organic solvent catalyst is hydroxymethylfurfural production method, characterized in that the ethyl acetate of 5 to 20% concentration based on the total reaction mixture volume.
The method of claim 2,
The metal catalyst is zinc chloride (ZnCl ₂ ), chromium chloride II (CrCl ₂ ), chromium chloride (CrCl ₃ ), chromium bromide (CrBr ₃ ), chromium fluoride (CrF ₃ ), zeolite, cobalt chloride ( CoCl ₂ ), nickel chloride (NiCl ₂ ) and magnesium chloride (MgCl ₂ ) The production method of hydroxymethylfurfural, characterized in that at least one selected from the group consisting of.
The method of claim 2,
The metal catalyst is chromium chloride (CrCl ₂ ) alone, chromium fluoride (CrF ₃ ) alone, chromium chloride (CrCl ₂ ) and chromium chloride (CrCl ₃ ) mixed form, chromium chloride (CrCl ₂ ) And mixed forms of chromium bromide (CrBr ₃ ), mixed forms of chromium chloride II (CrCl ₂ ) and chromium bromide (CrBr ₃ ), mixed forms of chromium chloride (CrCl ₃ ) and chromium fluoride (CrF ₃ ) or chromium bromide A process for producing hydroxymethylfurfural, characterized in that it is a mixed form of (CrBr ₃ ) and chromium fluoride (CrF ₃ ).
A method for producing hydroxymethylfurfural comprising heating a reaction mixture containing a plant biological extract, an ionic liquid and an organic solvent catalyst.
Mixing the ionic liquid and the metal catalyst to form a primary mixture;
Reacting the primary mixture at 100 to 150 ° C. for 5 to 20 minutes;
Adding a plant biological extract and an organic solvent catalyst to the reactants to form a reaction mixture; And
Method for producing hydroxymethylfurfural comprising the step of heating the reaction mixture.
The method according to claim 12 or 13,
Heating the reaction mixture is a method for producing hydroxymethylfurfural, characterized in that for heating 50 to 100 minutes at 100 to 120 ℃.
The method according to claim 12 or 13,
The plant bio extract is obtained by adding a plant biobiomass dry powder to an acidic extraction solvent and reacting at 60 to 80 ° C. for 30 minutes to 3 hours, followed by centrifugation to extract the supernatant. Process for the production of oxymethylfurfural.
16. The method of claim 15,
The plant biomass is a method of producing hydroxymethylfurfural, characterized in that one species selected from the group consisting of pork potato, chicory, potatoes, sweet potatoes, acorns, chopped root and cassava (manioc).
16. The method of claim 15,
The acidic extraction solvent is oxalic acid (Oxalic acid), phosphoric acid (Phophoric acid), sulfuric acid (Sulpheric acid) and hydrochloric acid (Hydrochloric acid) production method of hydroxymethylfurfural, characterized in that one selected from the group consisting of.
16. The method of claim 15,
The acidic extraction solvent is a method for producing hydroxymethylfurfural, characterized in that the hydrochloric acid of 0.3M to 0.5M concentration.
The method according to claim 12 or 13,
The ionic liquid is 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium tetraborate, 1-ethyl-3-methylimidazolium tetraborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium chloride, 1-butyl-3- Methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium chloride (1-butyl-3-methylimidazolium bromide) 1-hexyl-3-methylimidazolium chloride), 1-hexyl-3-methylimidazolium bromide, 1-octyl-3-methylimidazolium chloride (1-octyl-3- methylimidazolium chloride) and 1-octyl-3-methylimidazolium bromide (1-octyl-3-methylimidazolium bromide) Method of hydroxymethyl furfural, characterized in that the merchant production.
The method according to claim 12 or 13,
The organic solvent catalyst is ethyl acetate or maleic acid (maleic acid), characterized in that the production method of hydroxymethylfurfural.
The method according to claim 12 or 13,
The organic solvent catalyst is hydroxymethylfurfural production method, characterized in that the ethyl acetate of 5 to 20% concentration based on the total reaction mixture volume.
The method of claim 13,
The metal catalyst is zinc chloride (ZnCl ₂ ), chromium chloride (CrCl ₂ ), chromium chloride (CrCl ₃ ), chromium bromide (CrBr ₃ ), chromium fluoride (CrF ₃ ), zeolite, cobalt chloride ( CoCl ₂ ), nickel chloride (NiCl ₂ ) and magnesium chloride (MgCl ₂ ) The production method of hydroxymethylfurfural, characterized in that at least one selected from the group consisting of.
The method of claim 13,
The metal catalyst is chromium chloride (CrCl ₂ ) alone, chromium fluoride (CrF ₃ ) alone, chromium chloride (CrCl ₂ ) and chromium chloride (CrCl ₃ ) mixed form, chromium chloride (CrCl ₂ ) And mixed forms of chromium bromide (CrBr ₃ ), mixed forms of chromium chloride II (CrCl ₂ ) and chromium bromide (CrBr ₃ ), mixed forms of chromium chloride (CrCl ₃ ) and chromium fluoride (CrF ₃ ) or chromium bromide A process for producing hydroxymethylfurfural, characterized in that it is a mixed form of (CrBr ₃ ) and chromium fluoride (CrF ₃ ).
The method of claim 13,
The metal catalyst is a method of producing hydroxymethylfurfural, characterized in that the chromium fluoride (CrF3) in the form of 1% based on the total reaction mixture volume.

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