WO2013002397A1 - Procédé de production d'un composé de furfural, et appareil afférent compound - Google Patents

Procédé de production d'un composé de furfural, et appareil afférent compound Download PDF

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WO2013002397A1
WO2013002397A1 PCT/JP2012/066796 JP2012066796W WO2013002397A1 WO 2013002397 A1 WO2013002397 A1 WO 2013002397A1 JP 2012066796 W JP2012066796 W JP 2012066796W WO 2013002397 A1 WO2013002397 A1 WO 2013002397A1
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reaction
furfurals
tank
organic solvent
hmf
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PCT/JP2012/066796
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Japanese (ja)
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文人 川嶋
昌敏 森田
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国立大学法人愛媛大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom

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  • the present invention relates to a method for producing furfurals from sugars and a production apparatus for furfurals.
  • Furfurals such as 5-hydroxymethylfurfural (hereinafter also referred to as HMF) produced from saccharides can be used in the fields of plastics and pharmaceuticals as industrial raw materials.
  • HMF 5-hydroxymethylfurfural
  • HMF can be generated with high selectivity from glucose by dehydration reaction in the presence of a chromium catalyst in a high boiling point organic solvent or ionic liquid.
  • a chromium catalyst in a high boiling point organic solvent or ionic liquid.
  • Japanese Patent Application Laid-Open No. 2007-269766 reports that HMF can be generated with high selectivity by reacting sugars in water in a high-temperature and high-pressure subcritical or supercritical state for a short time.
  • Japanese Patent Application Laid-Open No. 2010-248113 discloses a method for synthesizing an HMF reactant from a saccharide in a reaction system with a small amount of catalyst added in a short time and continuously in a high yield and high selectivity.
  • JP-A-58-79988 discloses a process for producing 5-halomethylfurfural by acid decomposition of a saccharide with a water-organic solvent-magnesium halide system.
  • An object of the present invention is to produce a furfural that can be effectively used as an industrial raw material from a saccharide with a high reaction efficiency under mild conditions, and to provide a production method that can be used on an industrial scale. Moreover, it aims at providing the manufacturing apparatus of furfural which can manufacture furfural easily from saccharides.
  • the aqueous solution is a method for producing a furfural according to ⁇ 1> or ⁇ 2>, further including an acid catalyst.
  • ⁇ 4> The method for producing furfurals according to any one of ⁇ 1> to ⁇ 3>, wherein an organic solvent is further allowed to coexist in a reaction system for performing the dehydration reaction.
  • the present invention provides an aqueous solution containing saccharides, water, magnesium sulfate, and an acid catalyst from the viewpoint of producing furfurals in a high yield under mild reaction conditions (eg, 160 ° C. or lower), organic A method for producing furfurals in which a dehydration reaction of the saccharide is performed in the presence of a solvent is preferable.
  • the reaction system is the method for producing furfurals according to ⁇ 4>, wherein the dehydration reaction is performed in a two-layer system including an aqueous layer and an organic layer.
  • ⁇ 6> The method for producing a furfural according to ⁇ 4> or ⁇ 5>, wherein the organic solvent is an aliphatic alcohol or an aliphatic ketone compound.
  • ⁇ 7> The method for producing a furfural according to any one of ⁇ 1> to ⁇ 6>, wherein the furfural is 5-hydroxymethylfurfural.
  • a reaction vessel containing an organic solvent, saccharides, water, and magnesium sulfate, and performing a dehydration reaction of the saccharides in a two-layer system of an aqueous layer and an organic layer, and the reaction vessel and the first flow path A first supply tank for supplying the sugar and the water to the reaction tank; and a first supply tank for supplying the organic solvent to the reaction tank connected to the reaction tank through a second flow path. It is a manufacturing apparatus of furfurals which has 2 supply tanks, and the organic layer accommodation tank which accommodates the organic layer containing the furfurals isolate
  • the organic layer storage tank further includes an organic solvent separator, ⁇ 8> having a fourth flow path that connects the organic layer storage tank and the second supply tank and supplies the organic solvent separated from the organic solvent separator to the second supply tank. It is a manufacturing apparatus of the described furfurals.
  • ⁇ 10> The above ⁇ 8> further comprising a fifth flow path for connecting the reaction tank and the first supply tank and supplying the water layer separated from the reaction tank to the first supply tank. Or it is a manufacturing apparatus of the furfurals as described in said ⁇ 9>.
  • the furfural production apparatus which can manufacture furfurals easily from saccharides can be provided.
  • FIG. 1 is a schematic view of the furfural production apparatus of the present invention.
  • FIG. 2 is a diagram showing the relationship between the reaction time and the amount of HMF produced.
  • FIG. 3 is a diagram showing the relationship between the reaction time and the amount of HMF produced.
  • FIG. 4 is a diagram showing the relationship between the reaction time and the amount of HMF produced.
  • FIG. 5 is a diagram showing the relationship between the reaction time and the amount of HMF produced.
  • FIG. 6 is a diagram showing the relationship between the reaction time and the amount of HMF produced.
  • FIG. 7 is a diagram showing the relationship between the reaction time and the amount of HMF produced.
  • FIG. 8 is a diagram showing the relationship between the reaction time and the amount of HMF produced.
  • FIG. 1 is a schematic view of the furfural production apparatus of the present invention.
  • FIG. 2 is a diagram showing the relationship between the reaction time and the amount of HMF produced.
  • FIG. 3 is a diagram showing the relationship between the reaction time and the amount of
  • FIG. 9 is a diagram showing the relationship between the reaction time and the amount of HMF produced.
  • FIG. 10 is a diagram showing the relationship between the reaction time and the amount of HMF produced.
  • FIG. 11 is a diagram showing the relationship between the reaction time and the amount of HMF produced.
  • FIG. 12 is a diagram showing the relationship between the reaction time and the amount of HMF produced.
  • FIG. 13 is a diagram showing the relationship between the reaction time and the amount of HMF produced.
  • FIG. 14 is a diagram showing the relationship between the number of reactions and the amount of HMF produced.
  • FIG. 15 is a diagram showing the relationship between the reaction time and the amount of HMF produced.
  • FIG. 16 is a diagram showing the relationship between the reaction time and the amount of HMF produced.
  • FIG. 17 is a diagram showing the relationship between the number of reactions and the amount of HMF produced.
  • the method disclosed in J. AM. CHEM. SOC. 2009, 131, 1979-1985, Japanese Patent Application Laid-Open No. 2007-269766, and Japanese Patent Application Laid-Open No. 2010-248113 uses a supercritical fluid or the like. Because the reaction requires special reaction conditions and severe conditions of high temperature and pressure, the reaction process is complicated. On the other hand, the manufacturing method of the furfurals of this invention can manufacture furfurals by dehydration reaction of saccharides by making magnesium sulfate exist in the aqueous solution containing saccharides and water. Therefore, the dehydration reaction is not performed under special reaction conditions using a subcritical fluid or supercritical fluid in a high temperature and high pressure state as a reaction solvent.
  • furfurals it is possible to produce furfurals under mild conditions, not under high-temperature and high-pressure harsh conditions, and further, furfurals can be produced without going through complicated production processes. Can be manufactured.
  • furfurals can be obtained in the presence of water and magnesium sulfate without using an organic solvent, there is no problem of post-treatment with a high boiling point organic solvent or a chromium catalyst.
  • magnesium halide which is one of the halides
  • 5-halomethylfurfural which is a halogenated furfural. That is, since magnesium halide is decomposed to produce 5-halomethylfurfural, it is necessary to add magnesium halide each time 5-halomethylfurfural is produced.
  • magnesium sulfate used for the dehydration reaction of saccharides is a catalyst, and thus has only an action of promoting the dehydration reaction. Magnesium sulfate itself becomes a part of the obtained furfurals. There is no disassembly.
  • the furfurals can be produced again by re-introducing the saccharide as a raw material into the reaction vessel. .
  • the presence of an organic solvent is essential, and a large amount of acid is required for the substrate, such as using sulfuric acid at a high concentration such as 70% or 98%. Therefore, after the reaction, drainage treatment of the organic solvent and post-treatment such as acid neutralization are required. Furthermore, in the present invention, in order to improve the yield of furfurals, it is possible to optionally add an acid or an organic solvent to the reaction system. Small amount is enough. Details of the type and amount of the organic solvent will be described later.
  • furfurals produced by the method for producing furfurals of the present invention vary depending on the type of saccharide that undergoes a dehydration reaction (dehydration decomposition reaction).
  • dehydration decomposition reaction For example, 5-hydroxymethylfurfural (HMF), furfural, 5- Examples include hydroxyethyl furfural, 5-methyl furfural, 5-ethyl furfural, 5-n-propyl furfural, 5-iso, propyl furfural, 5-n-butyl furfural, 5-t-butyl furfural.
  • HMF is one of the 12 core chemical raw materials selected by the US Department of Energy's Department of Energy (DOE) Biomass program (2004) and is the main source of future biorefinery produced from sugars. It is attracting attention as a raw material.
  • Fatty acid derivatives obtained from HMF are diphenolic acid as a polymer raw material, succinic acid as a food additive and polymer raw material, methyltetrahydrofuran as a fuel additive, and a physiologically active substance in addition to levulinic acid (levulinic acid). Examples include aminolevulinic acid. Similarly, formic acid (formic acid) obtained from HMF is used as a preservative, antibacterial agent, organic synthetic raw material and the like.
  • furfurals can be synthesized from glucose, mannose, cellobiose and the like in one step, and the reaction environment is a simple reaction in an aqueous solution to which a certain metal salt is added. It is a system. Therefore, the method for producing furfurals of the present invention is an environmentally friendly method for producing furfural.
  • HMF generation scheme of HMF is shown below for glucose as an example.
  • various saccharides such as monosaccharides can be dehydrated in an aqueous solution in the presence of magnesium sulfate, and furfurals represented by HMF can be selectively synthesized in a one-step reaction.
  • magnesium sulfate By using magnesium sulfate in the production method of furfurals of the present invention, the above one-stage reaction for obtaining furfurals can be effectively promoted. Furthermore, since magnesium sulfate is present in a dissolved or suspended state in an aqueous solution, when the furfurals are separated from the reaction system after completion of the reaction using an organic solvent, the production process is less likely to occur. This is also advantageous from the viewpoint of efficiency.
  • saccharide used as the raw material examples include monosaccharides, disaccharides, and polysaccharides.
  • monosaccharides include glucose, mannose, galactose, and fructose.
  • disaccharide examples include cellobiose, saccharose, maltose and the like.
  • polysaccharide examples include cellulose.
  • One type of saccharide may be used alone, or a plurality of types may be mixed and used. Among these, from the viewpoint of reaction yield, monosaccharides or disaccharides are preferable, and glucose, mannose, and cellobiose are more preferable.
  • the aqueous solution preferably further contains an acid catalyst.
  • the amount of the acid catalyst with respect to the water constituting the aqueous solution may be small, for example, a small amount such that 1 mL of low concentration sulfuric acid of 0.5% by mass or less is used with respect to 25 mg of saccharide. Specific preferred amounts of the acid catalyst will be described later.
  • the presence of the acid catalyst in the aqueous solution can further increase the yield of furfurals.
  • the acid catalyst that can be used in the present invention is not particularly limited, and either a homogeneous acid catalyst or a heterogeneous acid catalyst can be used.
  • the homogeneous acid catalyst examples include sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid, trifluoroacetic acid and the like.
  • the heterogeneous acid catalyst examples include solid acids such as ion exchange resins and niobic acid.
  • One kind of acid catalyst may be used alone, or a plurality of kinds may be mixed and used.
  • the acid catalyst is preferably a homogeneous acid catalyst, more preferably an inorganic acid such as sulfuric acid, phosphoric acid, hydrochloric acid, and acetic acid, and more preferably sulfuric acid.
  • reaction conditions for the dehydration reaction of saccharides will be described. As described above, this reaction is performed in an aqueous solution containing at least saccharide and water in the presence of magnesium sulfate.
  • the amount of saccharide in the aqueous solution is preferably 1 to 30 parts by mass, more preferably 5 to 15 parts by mass with respect to 100 parts by mass of water.
  • the amount of magnesium sulfate in the aqueous solution is preferably 3 to 30 parts by mass, more preferably 10 to 25 parts by mass with respect to 100 parts by mass of water.
  • the amount of the acid catalyst added to the aqueous solution is not particularly limited, but is preferably 0.1 to 10 parts by weight, preferably 0.1 to 3.5 parts by weight with respect to 100 parts by weight of water. Is more preferable.
  • reaction temperature of this reaction is not particularly limited, but is preferably 100 ° C to 300 ° C, more preferably 130 ° C to 260 ° C.
  • reaction temperature By allowing an organic solvent to further exist in the reaction system for the dehydration reaction, the reaction can be carried out at a lower reaction temperature (for example, 160 ° C. or lower).
  • reaction time Although reaction time changes with reaction temperature, it is preferable that it is 10 minutes or more from a viewpoint of improving the yield of furfurals. On the other hand, from the viewpoint of preventing excessive decomposition of the produced furfurals, for example, it is preferably 30 minutes or less in a reaction at 200 ° C., and preferably 400 minutes or less in a reaction at 150 ° C., for example.
  • an organic solvent be further present in the reaction system for dehydrating saccharides in addition to the aqueous solution described above in which magnesium sulfate is present.
  • the amount of the organic solvent may be small and used to facilitate separation of furfurals. Specific preferred amounts of the organic solvent will be described later.
  • the dehydration reaction can be performed in a two-layer system including an aqueous layer containing an aqueous solution and an organic layer containing an organic solvent.
  • the generated furfurals can be extracted into the organic layer, and not only it becomes easy to collect the furfurals, but also the decomposition of the furfurals produced by the dehydration reaction can be prevented, and the reaction efficiency is further increased. It becomes possible.
  • the organic solvent is not particularly limited as long as it is a water-insoluble organic solvent that can separate the reaction system of the dehydration reaction into an aqueous layer and an organic layer, and even if it is an aliphatic hydrocarbon compound, aromatic carbonization is possible. It may be a hydrogen compound.
  • Examples of the aliphatic hydrocarbon compound include linear, branched, or cyclic aliphatic alcohols having 4 to 10 carbon atoms (for example, 1-butanol, 2-butanol, 4-methyl-2-pentanol, 1 -Hexanol, 2-ethyl-1-hexanol, 1-octanol, decanol, etc.), aliphatic ketone compounds having 6 to 12 carbon atoms (for example, methyl isobutyl ketone [MIBK], 2,4-dimethyl-3) -Pentanone, 5-methyl-2-hexanone, heptyl isobutyl ketone) and the like.
  • Examples of the aromatic hydrocarbon compound include toluene, benzene, cresol and the like.
  • One kind of organic solvent may be used alone, or a plurality of kinds may be mixed and used.
  • aliphatic hydrocarbon compounds are preferable, aliphatic alcohols having 4 to 8 carbon atoms or aliphatic ketone compounds having 6 to 7 carbon atoms are more preferable, MIBK, 2,4-dimethyl-3-pentanone, 5- More preferred are methyl-2-hexanone, 2-butanol, 4-methyl-2-pentanol, 1-hexanol, 2-ethyl-1-hexanol, and 1-octanol.
  • the amount of the organic solvent is preferably 50 parts by volume to 1200 parts by volume with respect to 100 parts by volume of water contained in the reaction system of the dehydration reaction (more specifically, a reaction vessel for performing the dehydration reaction of saccharides). More preferred is 800 parts by volume.
  • the apparatus used in the present invention may be in the form of a tank type or a tube type, and may be a batch type reaction apparatus that obtains a reaction product every time or continuously obtains a reaction product. It may be a type reactor.
  • a type reactor In particular, when producing furfurals using an organic solvent, it is preferable to produce the furfurals using the furfural production apparatus of the present invention described below.
  • the furfural production apparatus of the present invention includes an organic solvent, a saccharide, water, and magnesium sulfate, a reaction tank for performing a dehydration reaction of the saccharide in a two-layer system of an aqueous layer and an organic layer, and the reaction tank And a first supply tank for supplying the saccharide and the water to the reaction tank, and the reaction tank and the second flow path.
  • the production apparatus for furfurals has the above configuration.
  • Saccharides can be dehydrated smoothly, and the produced furfurals can be easily separated.
  • the furfurals produced as a result of the dehydration reaction move from the aqueous layer to the organic layer. Therefore, the furfural in the organic layer can be easily taken out from the organic layer storage tank by separating the organic layer containing the furfurals from the water tank and storing the organic layer in the organic layer storage tank.
  • Magnesium sulfate may be put in the reaction tank in advance or in the first supply tank. The first flow path, the second flow path, and the third flow path smoothly move the liquid or solid between the reaction tank and the first or second supply tank or the organic layer storage tank. In order to carry out, you may provide drive devices, such as a liquid feeding pump.
  • the furfural production apparatus of the present invention preferably further has the following configuration. That is, the organic layer storage tank further includes an organic solvent separator, connects the organic layer storage tank and the second supply tank, and removes the organic solvent separated from the organic solvent separator. It is preferable to have the 4th flow path supplied to 2 supply tanks.
  • the organic layer storage tank has an organic solvent separator such as a distillation apparatus, the organic solvent can be separated from the organic layer discharged from the reaction tank, and the separated organic solvent is removed through the fourth flow path. It can be returned to the second supply tank.
  • the organic layer storage tank and the organic solvent separator may be connected to each other, or the organic layer storage tank may also serve as the organic solvent separator.
  • the furfural production apparatus of the present invention preferably further has the following configuration. That is, it is preferable to have a fifth flow path that connects the reaction tank and the first supply tank and supplies the water layer separated from the reaction tank to the first supply tank. After performing the dehydration reaction in the reaction vessel, magnesium sulfate and water remain in the reaction vessel. Magnesium sulfate used in the present invention is excellent in durability and can be repeatedly used for dehydration reaction of saccharides.
  • the saccharide dehydration reaction can be continued without re-adding water and magnesium sulfate.
  • FIG. 1 is a schematic view showing a flow reactor.
  • a sugar aqueous solution tank (first supply tank) 1 for supplying sugar and water to the reaction tank and an organic solvent tank (second supply tank) 2 for supplying organic solvent to the reaction tank are respectively provided with a liquid feed pump 3.
  • the aqueous solution of sugar and the organic solvent are subjected to a production reaction of furfurals via lines (first flow path and second flow path) connecting the flow rates of the sugar solution and the organic solvent independently of each other.
  • Magnesium sulfate may be added to the sugar aqueous solution tank 1 or to the reaction tank 4.
  • a thermostat (not shown) is provided outside the reaction tank 4 so as to keep the reaction tank 4 at a predetermined temperature.
  • the dehydration reaction of sugar into furfurals is performed in the aqueous layer 5 of the reaction tank 4, and the generated furfurals are extracted into an organic solvent and moved to the organic layer 6.
  • An organic solvent separator 7 such as a distillation apparatus is provided downstream of the reaction tank 4 via a line (third flow path) to separate the furfurals from the organic solvent.
  • the separated organic solvent is returned to the organic solvent tank 2 via a line (fourth flow path).
  • the produced furfurals are discharged out of the system as crude furfurals 9.
  • the aqueous layer of the reaction tank 4 is returned to the sugar aqueous solution tank 1 through a line (fifth flow path), and is added to the sugar and then recycled.
  • the stirring means 8 may be provided in the reaction tank 4.
  • Example 1 D-glucose 25 mg, 0.368% sulfuric acid aqueous solution 1 mL [that is, the amount of water is 0.99632 mL (0.999632 g)] and magnesium sulfate 50 mg are put in a glass reaction tube and sealed, and the reaction temperature is 200 ° C. A decomposition reaction (dehydration reaction) of D-glucose was performed. After a predetermined time elapsed, the reaction tube was cooled to room temperature, and then the reaction solution was taken out from the reaction tube.
  • FIG. 2 shows the relationship between the reaction time and the reaction yield, and the relationship between the reaction time and the residual rate of D-glucose.
  • the horizontal axis represents the reaction time [min] and the vertical axis represents the yield [%].
  • Example 2 The D-glucose decomposition reaction was carried out under the same conditions as in Example 1 except that the concentration of sulfuric acid was 0%, that is, 1 mL of water was used instead of 1 mL of 0.368% sulfuric acid aqueous solution. A summary of the results is shown in FIG.
  • FIG. 3 shows that HMF can be produced with a yield of about 20% even without an acid catalyst.
  • Example 3 The decomposition reaction of D-mannose was carried out under the same conditions as in Example 1 except that the same amount of D-mannose was used instead of D-glucose. A summary of the results is shown in FIG.
  • FIG. 6 shows that D-mannose is decomposed in the same manner as D-glucose, and HMF can be produced in a yield of about 40% at the maximum.
  • Example 4 Cellobiose was decomposed under the same conditions as in Example 1 except that the same amount of cellobiose was used instead of D-glucose. A summary of the results is shown in FIG.
  • FIG. 8 indicates that the disaccharide cellobiose is decomposed into glucose and that HMF can be produced in a maximum yield of about 36%. From this result, it was suggested that the hydrolysis reaction of the polysaccharide to a monosaccharide also proceeds under the conditions of the present invention, and that HMF can be produced from the produced monosaccharide.
  • FIG. 9 shows that although cellobiose was rapidly decomposed into glucose, the yield of HMF was as low as that of Comparative Example 1, and the generated HMF was decomposed as the reaction time passed. became.
  • Example 5 D-glucose 125 mg, 0.368% sulfuric acid aqueous solution 5 mL [that is, the amount of water is 4.9816 mL (4.9816 g)], 2-butanol (2-BuOH) 8 mL and magnesium sulfate 1000 mg are placed in a glass reaction tube. The mixture was sealed, and D-glucose was decomposed at a reaction temperature of 150 ° C. while stirring the reaction tube. After a predetermined time elapsed, the reaction tube was cooled to room temperature, and then the organic layer and the aqueous layer were respectively taken out from the reaction tube.
  • the reaction yield is a percentage of the amount of HMF produced in the experiment with respect to the amount of HMF produced when all the D-glucose is converted to HMF. What put together the result about an organic layer and a water layer is shown in FIG.10 and FIG.11, respectively.
  • the pressure of the reaction system of the dehydration reaction when the vapor pressure is calculated in a two-phase system of water and 1-butanol, as shown in Table 1, it is about 1.0 MPa at 160 ° C. and about 2.6 MPa at 200 ° C. It becomes. Therefore, it can be seen that the reaction environment of the reaction system in Example 5 is not an excessively pressurized state but a mild reaction state. In the reaction system of Example 6 described later using MIBK as the organic solvent, it is considered that the numerical values are comparable.
  • Example 6 D-glucose 150 mg, 0.368% sulfuric acid aqueous solution 1.5 mL [(ie, the amount of water is 1.4945 mL (1.4945 g)], methyl isobutyl ketone (MIBK) 7.5 mL and magnesium sulfate 300 mg
  • the reaction tube was sealed and sealed, and D-glucose was decomposed at a reaction temperature of 160 ° C. while stirring the reaction tube (first reaction) After a predetermined time, the reaction tube was cooled to room temperature. Then, the organic layer and the aqueous layer were respectively taken out from the reaction tube.
  • MIBK methyl isobutyl ketone
  • reaction yield is a percentage of the amount of HMF produced in the experiment with respect to the amount of HMF produced when all the D-glucose is converted to HMF. What put together the result about an organic layer and a water layer is shown in FIG.12 and FIG.13, respectively.
  • Example 6 150 mg of D-glucose as a raw material was again added to the aqueous solution that was the aqueous layer after use, and the obtained aqueous solution was sealed together with 7.5 mL of MIBK in a glass reaction tube. While stirring the aqueous solution and the organic solvent in the reaction tube, the decomposition reaction of D-glucose was carried out at a reaction temperature of 160 ° C. (second reaction). As in the first reaction, the reaction solution was neutralized, the solid content was removed by centrifugation, and the amount of HMF produced and the amount of D-glucose in the supernatant were quantified by HPLC. For the organic layer, the solid content was removed by centrifugation, and the amount of HMF produced and the amount of D-glucose in the supernatant were quantified by HPLC.
  • FIG. 14 shows the yield of HMF in each reaction number from the first reaction to the fourth reaction in Example 6.
  • the horizontal axis represents the number of reactions
  • the vertical axis represents the yield [%].
  • Example 6 was performed as follows. In the decomposition reaction of Example 6, the reaction temperature, MIBK / water ratio, sulfuric acid concentration, magnesium sulfate concentration, and D-glucose concentration were carried out with the numerical values shown in Table 3. As a result, HMF was obtained with the yield shown in Table 3. It was. Table 3 also shows data of Example 6 (first reaction) for comparison. In Table 3, Example 6 and Example 11 are repeatedly shown for numerical comparison.
  • the ratio of MIBK to sulfuric acid aqueous solution (MIBK / water ratio) is based on volume, and the concentration of sulfuric acid [%] is the mass ratio to the mass of water, the concentration of magnesium sulfate [%], and The concentration [%] of D-glucose represents the mass ratio with respect to the mass of the sulfuric acid aqueous solution.
  • Example 23 to Example 29 Next, in Example 6 (first reaction), the organic solvent MIBK was changed to various organic solvents shown in Table 4, and the D-glucose dehydration reaction in Examples 23 to 29 was performed. Went. Specifically, it was performed as follows.
  • Example 30 In Example 1, D-glucose was dehydrated in the same manner except that the reaction temperature was changed from 200 ° C. to 180 ° C. After a predetermined time elapsed, the reaction tube was cooled to room temperature, and then the reaction solution was taken out from the reaction tube. After neutralizing the reaction solution, the solid content was removed by centrifugation, and the amount of HMF produced and the amount of D-glucose in the supernatant were quantified by high performance liquid chromatography (HPLC).
  • FIG. 15 shows the relationship between the reaction time and the reaction yield, and the relationship between the reaction time and the residual rate of D-glucose.
  • Example 30 In Example 30, instead of 50 mg of magnesium sulfate, 50 mg of magnesium sulfate and an equimolar amount of magnesium chloride (MgCl 2 ; Comparative Example 6) or 50 mg of magnesium sulfate and an equivalent amount of magnesium iodide (MgI 2 ; Comparative Example 7) The production of furfurals was attempted in the same manner except that was used.
  • FIG. 16 (Comparative Example 6) and FIG. 17 (Comparative Example 7) show the relationship between the reaction time and the reaction yield, and the relationship between the reaction time and the residual rate of D-glucose.
  • furfurals are produced under mild conditions of 200 ° C. or less and without complicated processes by using water, magnesium sulfate and saccharides. You can see that
  • the furfurals obtained by the method for producing furfurals of the present invention are useful as raw materials for various chemical products and pharmaceuticals.

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Abstract

Cette invention concerne un procédé de production d'un composé de furfural comprenant la mise en œuvre d'une réaction de déshydratation d'un saccharide dans une solution aqueuse comprenant le saccharide et de l'eau en présence de sulfate de magnésium.
PCT/JP2012/066796 2011-06-29 2012-06-29 Procédé de production d'un composé de furfural, et appareil afférent compound WO2013002397A1 (fr)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
WO2017170503A1 (fr) * 2016-04-01 2017-10-05 三菱化学株式会社 Procédé de production de furfural
JP2018118945A (ja) * 2017-01-27 2018-08-02 三菱ケミカル株式会社 フルフラールの製造方法
JP2021525732A (ja) * 2018-05-29 2021-09-27 ズートツッカー アーゲー 塩と酸との混合物により触媒されるｈｍｆの製造
WO2022230769A1 (fr) * 2021-04-30 2022-11-03 三菱ケミカル株式会社 Procédé de fabrication de dérivé de furane contenant un ５－hydroxyméthylfurfural （５－ｈｍｆ）, dérivé de furane, solution contenant ce dérivé de furane, et procédé de fabrication d'acide furanedicarboxylique ou d'ester d'acide furanedicarboxylique

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WO2017170503A1 (fr) * 2016-04-01 2017-10-05 三菱化学株式会社 Procédé de production de furfural
JP2017186308A (ja) * 2016-04-01 2017-10-12 三菱ケミカル株式会社 フルフラールの製造方法
US10844030B2 (en) 2016-04-01 2020-11-24 Mitsubishi Chemical Corporation Method for producing furfural
JP2018118945A (ja) * 2017-01-27 2018-08-02 三菱ケミカル株式会社 フルフラールの製造方法
JP2021525732A (ja) * 2018-05-29 2021-09-27 ズートツッカー アーゲー 塩と酸との混合物により触媒されるｈｍｆの製造
JP7410058B2 (ja) 2018-05-29 2024-01-09 ズートツッカー アーゲー 塩と酸との混合物により触媒されるｈｍｆの製造
WO2022230769A1 (fr) * 2021-04-30 2022-11-03 三菱ケミカル株式会社 Procédé de fabrication de dérivé de furane contenant un ５－hydroxyméthylfurfural （５－ｈｍｆ）, dérivé de furane, solution contenant ce dérivé de furane, et procédé de fabrication d'acide furanedicarboxylique ou d'ester d'acide furanedicarboxylique

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