KR101130215B1 - Production process of 5-hydroxymethyl-2-furaldehyde from raw biomass using the same - Google Patents

Abstract

The present invention relates to a process technology for efficiently producing 5-hydroxymethyl-2-furaldehyde (HMF) using biobiomass. In particular, the present invention relates to a method of producing a large amount of HMF under an appropriate reaction temperature after mixing a grape juice obtained from a living body of grape fruit and various kinds of solvents and catalysts or mixing a solvent and a catalyst alone with grape juice. . According to the present invention, it is very useful for the production of dimethylfuran (DMF), which is highly available as an alternative bioenergy for fossil fuels, and for industrial fields related to the synthesis of pharmaceuticals, food, cosmetics, fine chemicals and petroleum-derived compounds. HMF can be mass produced.

Biobiomass, HMF

Description

PRODUCTION PROCESS OF 5-HYDROXYMETHYL-2-FURALDEHYDE FROM RAW BIOMASS USING THE SAME}

The present invention relates to a process for producing 5-hydroxymethyl-2-furaldehyde (HMF) with high efficiency by using biomass containing a large amount of sugar compounds as a substrate material. Specifically, the high efficiency production technology of HMF which provides the reaction conditions with the optimum combination ratio according to the type of grape juice liquid, ionic liquid solvent, and / or catalyst prepared by using grape as a material as bio biomass. It is about.

Synthesis of 5-hydroxymethyl-2-furaldehyde (hereinafter referred to as 'HMF') mainly consists of sugar compounds as the main raw material and high temperature dehydration using acid catalyst. Has been produced. Related research has a long history of research that has been conducted by many researchers since the late 1800's and continues to this day, but the production of HMF in large quantities is judged to be of low economic value and thus has little economic value. There has been little progress in industrialization research (Lewkowski, J. ARKIVOC, 1, (ARKAT-USA; ISSN1424-6376), pp.17-54, 2001; Website; www.arkat-usa.org/home.aspx?). VIEW-MANUSCRIPT & MSID = 403).

Recently, however, the results of a significant improvement in the production process of HMF have been reported by US researchers, who have found that efficient production of HMF using fructose and glucose as substrate materials. Published research reports on HMF production processes (Y. Rom, JN Chheda, JA Dumesic, Science 312, 1933-1937, 2006; H. Zhao, JE Holladay, HB Brown, ZC Zhang, Science 316, 1597-1600). , 2007; Rom, CJ Barrett, ZY Liu, JA Dumesic, Nature 447, 982-986, 2007).

In particular, studies conducted by Zhao et al. (H. Zhao, JE Holladay, HB Brown, ZC Zhang, Science 316, 1597-1600, 2007) efficiently produce HMF by properly combining catalysts and liquid solvents that have not been tried until now. HMF production process was suggested to prepare a place for mass production of HMF. In particular, HMF is the next-generation alternative liquid fuel for fossil fuels and is not only an intermediate raw material that is essential for the production of high potential dimethylfuran (DMF) (Rom, CJ Barrett, ZY Liu, JA Dumesic, Nature 447, 982- 986, 2007), medicines (O. Abdulmalik, MK Safo, et al. Britsh J. Haematology 128, 552-561, 2005; VK Sharma, J. Choi, N. Sharma et al. Phytotherapy Research 18, 841-844, 2004) and are very useful intermediate chemicals as raw materials for petrochemical products (Lewkowski, J. ARKIVOC, 1, (ARKAT-USA; ISSN1424-6376), pp.17-54, 2001; Website; www. arkat-usa.org/home.aspx?VIEW-MANUSCRIPT & MSID = 403).

        The production of HMF is produced by chemical process using sugar compound as raw material, and it has to go through several stages, and the conversion to HMF is very low as 2-10%. In addition, since various by-products are also produced in the process, high-cost separation and purification costs are required to separate and purify the synthesized HMF, so these disadvantages become a factor to increase the production cost of HMF.

      Thus, breakthrough HMF production techniques to address these shortcomings have been reported by two US teams as described above (Science, 2007, 316: 1597-1600; Science, 2006, 312: 1933-1937). The use of the two-phase system, metal chloride catalyst and liquid ionic solvent developed by the company not only significantly increased the production of HMF, but also significantly reduced the time required for separation and purification of the produced HMF. Nevertheless, the high cost of production was pointed out as a problem. In addition, due to the disadvantage of using a large number of harmful substances caused in the production process, there is a need to develop a technology that can produce HMF at a more eco-friendly and low-cost production cost.

       Therefore, it is considered that the development of a technology that can produce HMF in a more environmentally friendly and low-cost way with little by-products generated in the production process of HMF is very important industrially.

This HMF is not only essential as a raw material for DMF, the next generation biofuel, but also used as a raw material for pharmaceuticals (Anti-sickling agent: British J. of Haematology, 2005, 128: 552-561)) and various petrochemicals. Because it is a very important compound that can be used (ARKIVOC, 2001; ARKAT-USA; ISSN 1424-6376, (i), pp. 17-54), the development of technologies that produce HMF efficiently has a high value added industrially. to be.

     As mentioned above, HMF is a very useful material industrially as a compound having various efficacy. At present, HMF is mainly produced through chemical synthesis process (ARKRVOC 2001 (10: 17-54), but such chemical synthesis process of HMF is not only complicated but also very expensive to purify HMF after production. .

Therefore, researches are currently being actively conducted to solve these problems, and in particular, development of next-generation alternative fuels is considered an important future industrial technology in preparation for depletion of chemical fuels. In particular, since the biobiomass presented in the present invention does not have a concern of exhaustion, the establishment of such a technology is an important technology development field in addition to the development of technology capable of producing HMF with high yield by using HMF in a more economical and simple process. have.

In order to meet the above-described technology development, an object of the present invention is to provide a technique capable of economically and easily producing high yields of HMF by directly using biomass, in particular, grape organisms.

That is, an object of the present invention is to efficiently prepare HMF by using a biobiomass preparation method and a liquid ion solvent and a catalyst alone, or by appropriately combining the liquid ion solvent and a catalyst with different reaction temperatures and reaction times. It is to provide a process technology related to the reaction process conditions and the method to produce.

According to the present invention,

Preparing a juice of biomass for synthesizing 5-hydroxymethyl-2-furalaldehyde from biomass;

Wherein the living body is at least one plant selected from grape berries consisting of Vitis; And

Reacting the juice of the biomass biomass under a reaction temperature of 80-120 ° C. for 1-9 hours to synthesize 5-hydroxymethyl-2-furaldehyde; Provided is a method for synthesizing 5-hydroxymethyl-2-furalaldehyde using a biobiomass consisting of high efficiency.

      As described above, the final object of the present invention is to provide a reaction process technology for efficiently synthesizing highly industrially useful HMF using bio-biomass. To this end, a method of preparing grape juice used as a raw material as a biomass and a reaction temperature condition for efficiently synthesizing HMF using the grape juice prepared by this method, types of catalysts, addition methods thereof, and ion solvents The HMF is synthesized to the maximum by appropriately adjusting the selection of and the combination of the catalyst and the conditions of the reaction process such as reaction time and reaction temperature. Therefore, the technology regarding the reaction process conditions and the method of the reaction process should be developed first. The present inventors have persistently searched for such reaction process conditions and reaction process methods, and completed the present invention.

First, a method for preparing biomass used as a raw material in the present invention will be described.

The biobiomass usable in the present invention may be a plant biomaterial including all grapes capable of synthesizing HMF, and may be a biobiomass of a plant selected from plant biobiomass containing a large amount of fructose, glucose and sucrose. . For example, it may be a biobiomass selected from biobiomass of plants belonging to Vitaceae including grapes (Vinis vinifera), which is the material of the present experiment. In a preferred specific example of the present invention, the fruit of grapes can be used.

The grape fruit may be fully matured from the medium size or more or fully mature grape fruit, but it is preferable to use enough mature grape fruit to obtain the best HMF production effect. In addition, the grape fruit may be used as it is or by removing the skin. In a preferred specific example of the present invention, for the sake of easy production and high yield of HMF, the above-mentioned grape fruit is pulverized in a pulverizer, and then it is preferable to use the juice solution.

In addition, the present invention is to maximize the production of HMF by performing a variety of reaction conditions, such as the mixing ratio of the juice solution and solvent prepared from grape biomass, the type of solvent and catalyst used, the addition ratio of the catalyst, the reaction temperature and reaction time, etc. Provides a description of the reaction process.

In the present invention, acid catalysts used in the synthesis of HMF are generally added with various kinds of acid catalysts commonly used. Acid catalysts commonly used in the synthesis of HMF include oxalic acid, phosphoric acid, sulfuric acid, hydrochloric acid, zinc chloride (ZnCl ₂ ), zeolite, and the like. It may be at least one selected from the group of acid catalysts, and preferably a hydrochloric acid catalyst may be used.

Considering the proper amount of hydrochloric acid catalyst for efficiently synthesizing HMF from the juice of the grape biomass, the concentration is preferably 0.05 M to 1 M based on the molarity (M) of hydrochloric acid, more preferably 0.1 It is good that it is 0.5M.

In specific examples of the reaction conditions of the reaction solution containing the hydrochloric acid catalyst, the reaction temperature and reaction time may be adjusted to induce the synthesis of HMF. In order to enhance the synthesis efficiency of HMF, the reaction temperature may be added in the range of 60-150 ° C., and the reaction time is sufficient in the range of 1-10 hours for each temperature. Preferably it is reacted for 4-8 hours at a reaction temperature of 80-120 ℃.

In one specific example of the present invention, in order to synthesize HMF production more efficiently, a metal catalyst may be further added to the juice of the grape biomass. The metal additive added may be any conventional metal catalyst added to promote the synthesis of HMF, for example aluminum chloride (AlCl ₃ ), zinc chloride (ZnCl ₂ ), magnesium chloride (MgCl ₂ ), chromium chloride Group consisting of (CrCl ₂ ), cobalt chloride (CoCl ₂ ), nickel chloride (NiCl ₂ ), iron chloride (FeCl ₂ ), copper chloride (CuCl ₂ ), manganese chloride (MnCl ₂ ) and platinum chloride ((PtCl ₂ ) The amount of the at least one metal catalyst is added in an amount of 0.01-1 g per 10 millimeters (mL) of grape juice based on the weight, and reacted for 1-9 hours at a reaction temperature of 80-120 ° C. Preferably, 0.1-0.5 g is added and reacted for 1-8 hours under a reaction temperature of 100-120 ° C.

In one specific example of the present invention, in order to further increase the amount of HMF synthesized, Ionic liquid may be further added to the juice of the grape biomass. The added liquid ion solvent may be any conventional liquid ion solvent added to increase the amount of HMF synthesized, for example 1-ethyl-3-methylimidazolium bromide (1-ethyl-3-methylimidazolium bromide ), 1-ethyl-3-methylimidazolium tetraborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium bromide (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) and the like may be one or more selected from the group consisting of. The amount of the at least one liquid ion solvent added is 10% (mL) to 80% (mL) based on the volume of grape juice and 90-10% based on the weight of the liquid ion solvent (g). The reaction can be carried out for 1-9 hours, preferably 10-60% (mL) based on the volume of the grape juice and 90-40% by weight (g) of the liquid ion solvent are mixed with each other under a reaction temperature of 100-120 ° C. Reaction for -7 hours is good considering efficiency and economics.

In order to increase the amount of HMF synthesized compared to the above-described method of HMF, hydrochloric acid catalyst, liquid ionic solvent and metal chloride catalyst may be properly mixed with the juice of grape biomass, and reacted for 1 hour or more at an appropriate reaction temperature. .

To this end, 0.1-1 g of the metal catalyst is prepared by mixing 10-90% (mL) of the juice solution of grape biomass containing the acid catalyst and 10-90% (g) of the liquid ion solvent by weight. It can be reacted at a reaction temperature of 80-120 ℃ for 1-9 hours after the addition, more preferably 30-60% (mL) and the liquid ion solvent weight based on the volume of grape juice solution containing 0.1-1 mol hydrochloric acid (G) 70-40% of each other is mixed with the above-mentioned metal chlorides by adding 0.1-1 g per 10 milliliters (mL) of the mixture of the reaction solution (grape juice containing hydrochloric acid + liquid ion solvent) to 80-100. It is preferable to react for 1-7 hours under the reaction temperature of ° C.

According to the present invention, in providing a reaction process technology for synthesizing HMF using grapes, a biobiomass that has never been attempted, it is much simpler than the technology produced by the conventional reaction process, and the production efficiency of HMF is also high. Not only can high and low cost HMF be produced, but HMF can also be produced in a more environmentally friendly way. In particular, HMF is an important compound that is used as a precursor for synthesizing pharmaceuticals, petroleum products and other fine compounds as well as future petroleum substitute biofuels, but the biggest problem was that the production cost is high. It has the advantage to do it.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are only for illustrating the present invention, the scope of the present invention is not limited by these examples. In addition, the numerical values shown in the following examples represent the average value of the values obtained by performing five times each.

Example 1 Preparation of Grape Biomass

Commercial grapes were purchased to remove the skins of the grapes, and then pulverized for 2-3 minutes in a fruit mixer, followed by extracting the juice solution using three layers of 200 mesh nylon mesh. The extracted juice solution was centrifuged at 9000 × g for 20 minutes to freeze the supernatant at −80 ° C. to prepare a material of grape biomass.

Example 2: Optimization of Reaction Temperature Conditions

10 mL of the biomass juice solution of the grapes prepared above was added to a 25 mL flask vessel and then reacted at 80 ° C., 100 ° C. and 120 ° C. for 9 hours. During the reaction, the reactants were collected at 1 hour intervals and used as samples for measuring the synthesized HMF yield. The results are shown in FIG. 1.

Example 3: Optimization of Acid Catalyst Concentration

Biomass juice of grapes prepared in Example 1 was prepared by adjusting the concentration of four hydrochloric acid (HCl), that is, 0.1 mol, 0.3 mol, 0.5 mol and 1 mol concentration. 10 mL of the biomass juice of grapes prepared at each hydrochloric acid concentration was placed in a 25 mL flask container, and then reacted for 9 hours at 100 degrees Celsius. The reaction samples were collected at an hourly interval to produce the amount of HMF synthesized at each hour. It measured, and the result is shown in FIG.

Example 4 Preparation and Reaction Temperature of Liquid Ion Solvent

Three kinds of liquid ionic solvents in order to examine and compare the kinds of solvents on the synthesis of HMF and the effect of reaction temperature for each solvent on the synthesis of HMF; 1-ethyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium chloride, and 1-octyl-3- 5 g of each methyl imidazolium chloride (1-octyl-3-methylimidazolium chloride) was mixed with 5 mL of grape biomass juice containing 0.3 mol hydrochloric acid and reacted for 9 hours at 80, 100 and 120 degrees Celsius, respectively. Each reaction temperature was collected at 1 hour intervals to measure the amount of HMF synthesized.

Example 5: Preparation of Catalyst

Five kinds of catalysts were used to compare and examine the effect of the catalyst on the synthesis of HMF. The five species of the catalyst used is a chloride, chromium (CrCl _2), cobalt chloride _{(CoCl 2? 6H 2 O)} , nickel chloride _{(NiCl 2? 6H 2 O)} , zinc chloride (ZnCl ₂₎ and magnesium chloride (MgCl ₂₎ To 10 mL of the grape biomass juice solution, 0.2 g of chromium chloride, 0.3 g of cobalt chloride, 0.3 g of nickel chloride, 0.2 g of zinc chloride, and 0.2 g of magnesium chloride were respectively added and reacted at 100 degrees Celsius for 9 hours. The reactants were collected at intervals of 1 hour for each catalyst to measure the amount of HMF synthesized.

Example 6 Preparation of Mixing Ratio of Acid Catalyst, Liquid Ion Solvent and Catalyst

In order to explore the reaction process for inducing the maximum amount of HMF synthesis from the grape biomass juice solution, 5 g of each of the three liquid ions used in Example 4 were taken, and the five catalysts used in Example 5 were used for each liquid ion solvent. After reacting at 100 ° C. for 10 minutes, 5 mL of grape biomass juice solution containing 0.3 mol hydrochloric acid was added and reacted for 9 hours. The reactants were collected at 1 hour intervals for each treatment. The amount of production was measured, respectively, and the comprehensive experimental results are summarized in Table 1 and Table 2, respectively.

Example 7: Analysis of amount of HMF synthesis in the reactants

After diluting each of the reactant samples synthesized in Examples 1 to 6 by 100 times (10 microliters of reactant sample and 990 microliters of pure water), the obtained reactant samples were filtered through a microfilter (0.2 micrometer, Satorius), followed by HPLC. The amount of HMF synthesized was analyzed using (High performance liquid chromatography; Waters).

The analysis conditions of the HPLC analyzer were as follows: The measurement column (XBridge, Waters) was used as a C ₁₈ reverse phase column. The rate of flow rate was fixed at 0.7 milliliters per minute (0.7 mL / min), and HMF was analyzed by a mixing gradient of methanol and water. Gradient conditions are 2 minutes in 100% water, 1 minute transition state, 8 minutes in 80% water and 20% water mixed state, 1 minute in the second transition state, 5 minutes in 20% water and 80% methanol mixed state, and Finally, HPLC analysis was performed for 20 minutes in 100% water.

The results of HMF synthesis in each of the reactants thus obtained are shown in Tables 1 to 2 together. Specifically, Table 1 shows the reaction mixture of the three liquid ion solvents and the grape juice solution having four concentrations of hydrochloric acid in the present invention were reacted at 80 ° C., 100 ° C. and 120 ° C. for 4 hours, respectively. Table 2 shows the production amount of HMF, and Table 2 shows the addition of five metal chloride catalysts to the reaction mixture of the three liquid ion solvents and the grape juice solution having a 0.3 mol hydrochloric acid concentration. Table showing the production of HMF synthesized in the reaction reacted for 1 hour to 9 hours at, shows a comprehensive experimental results for the synthesis of HMF.

<Abbreviation in table>

[OMIM] Cl; 1-octyl-3-methylimidazolium chloride

[HMIM] Cl; 1-hexyl-3-methylimidazolium chloride

[EMIM] Cl; 1-ethyl-3-methylimidazolium chloride

In Tables 1, 2, Figures 1 and 2 above As shown, in order to synthesize high-efficiency HMF from grape biomass, the selection of biomass and the preparation of materials, the addition of acid catalyst at the appropriate concentration according to the reaction temperature, the selection of liquid ion solvent and the appropriate mixing concentration are important variables. The most efficient method of HMF synthesis is 3-5 hours at 100 ° C in a reaction mixture of 0.22 g of chromium chloride (CrCl ₂ ) in a mixture of 50% (volume) ionic liquid and 50% (weight) grape biomass juice. It was found that the most amount of HMF can be synthesized during the reaction at 120 ° C. or 1-2 hours at 120 ° C., but the HMF synthesis amount can be obtained without the addition of a metal chloride catalyst as shown in Table 1.

FIG. 1 is a graph comparing the amount of HMF synthesized in a reaction product in which 10 milliliters of grape juice solution containing 0.3 mol of hydrochloric acid was reacted at 80 ° C., 100 ° C. and 120 ° C. for 1 hour to 8 hours.

Figure 2 is a graph comparing the production of HMF synthesized in the reactants reacted from the grape juice with four hydrochloric acid concentrations carried out in the present invention at 100 ℃ 1 hour to 9 hours, respectively.

Claims (7)

A first step of preparing a juice of a bio-biomass selected from grape fruit of Vitis; And A second step of synthesizing 5-hydroxymethyl-2-furaldehyde by reacting the juice of the biomass under a reaction temperature of 80-120 ° C. for 1-9 hours; A high-efficiency synthesis method of 5-hydroxymethyl-2-furalde using a biobiomass consisting of. delete The method of claim 1, In addition to the second step, 1-ethyl-3-methylimidazolium bromide and 1-ethyl-3-methylimidazolium tetraborate , 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium chloride, 1-butyl-3 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 octyl-3-methylimidazolium chloride) and 1-octyl-3-methylimidazolium bromide (1-octyl-3-methylimidazolium bromide) And at least one liquid ion solvent selected in a weight ratio of 1: 1-10 with the grape biomass juice solution. The method of claim 3, The liquid ion solvent is 1-ethyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium chloride, and 1-ethyl-3-methylimidazolium chloride. -Octyl-3-methylimidazolium chloride (1-octyl-3-methylimidazolium chloride) The synthesis method characterized in that at least one member selected from the group consisting of. The method of claim 3, In addition to the second step, chromium chloride (CrCl ₂ ), cobalt chloride (CoCl ₂ ~ 6H ₂ O), nickel chloride (NiCl ₂ ~ 6H ₂ O), zinc chloride (ZnCl ₂ ) and magnesium chloride (MgCl ₂ ) Synthesis method characterized in that the synthesis by further adding 0.05-0.5g of at least one catalyst selected from the group. The method according to claim 1 or 3, In the second step, a reaction product containing 0.22 g of chromium chloride (CrCl ₂ ) or zinc chloride (ZnCl ₂ ) in a mixture of 50% by weight of the biomass juice solution and 50% by volume of the liquid ion solution was reacted at 100 ° C. for 3-5 hours. Synthesis method characterized in that. The method according to claim 1 or 3, In the second step, a reaction product of 0.22 g of chromium chloride (CrCl ₂ ) or zinc chloride (ZnCl ₂ ) was added to a mixed solution of 50% by weight of grape biomass juice solution and 50% by volume of liquid ion solution at 120 ° C. for 1-2 hours. A reaction method characterized in that the reaction.

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