JP5369349B2 - Process for producing 5-hydroxymethyl-2-furfurylaldehyde and apparatus therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for continuously synthesizing a HMF reaction product from a saccharide in a reaction system containing a fine amount of a catalyst in a short time in a high yield and in a high selection rate, to provide a reaction product therefrom, and to provide an apparatus therefor. <P>SOLUTION: There are provided the method for continuously producing an HMF reaction product from a saccharide in a high yield in a high selection rate at a high speed, comprising introducing a catalyst in a fine amount of &le;1 mol%, a substrate and a reaction solvent into a flow type high temperature high pressure apparatus using a semi-critical fluid or super critical fluid as the reaction solvent at a pressure of 0.1 to 40 MPa at a temperature of 100 to 400&deg;C, and changing the various conditions such as temperature, pressure and catalyst; the reaction product therefrom; and the apparatus therefor. According to the method, a synthesis process not needing an organic solvent can be attained. Therefore, a HMF reaction product free from the residue of the organic solvent, not injurious to living bodies, and high in safety can be provided. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

The present invention relates to the production how the 5-hydroxymethyl-2-furfuryl aldehyde (HMF), more particularly a water or acetic acid mixed solvent thereof in the high-temperature high-pressure state as the reaction solvent, in one step, The present invention relates to a method for manufacturing HMF. The present invention, acetic acid, and their mixed solvent reaction medium, the temperature 100 to 19 0 ° C., a pressure 0.1 to 5 MPa of water or acetic acid, as a mixed solvent thereof reaction solvent, a trace amount of a reduced amount of catalyst in the catalyst, the HMF from saccharides, in a single step and in a short time, there is provided a way to continuously synthesized.

  HMF is used as a sickle cell disease treatment (2007 US FDA approved) and has multifaceted pharmacological action like nicotinic acid and anticoagulant action on blood and blood vessels, metabolic syndrome, hypertension, diabetes, arteries It is suggested that it is effective as a preventive and food for sclerosis and economy syndrome. In addition, as a C6 biorefinery basic material, it is expected to be applied to PET substitute polymer materials, chemical products, fuels, etc. It has not only high functionality but also high added value compared to sugar of raw materials and substrates. Therefore, it is important in the pharmaceutical and food fields.

  Conventionally, various methods for synthesizing HMF from saccharides using a catalyst having a dehydrating action in an organic solvent have been reported (see Non-Patent Document 1). In general, using an organic solvent that dissolves sugar, such as DMSO, using an ion exchange resin or a Lewis acid (for example, Non-Patent Document 2), using D-glucose as a raw material, the HMF is about 90%. There are numerous reports that can be obtained at a rate. However, when used for pharmaceuticals and foods, it is necessary to completely remove the remaining organic solvent, and such a separation operation is difficult in terms of cost.

  On the other hand, when water is used as a solvent, there are few reports, but the yield tends to be lower than when using an organic solvent. Generally, in water at a temperature of 200 ° C. or less, the reactivity is low, so the yield is low. In water at a temperature of 200 ° C. or more, the reactivity is improved, but the yield is about 58% ( FIG. 1).

  Recently, HMF was 30% from D-glucose, 40% from D-sucrose, D-fructose under subcritical water conditions at 240 ° C. adjusted to pH 2 with phosphoric acid using a batch-type apparatus, with a reaction time of 120 seconds. However, in this method, a large amount of phosphoric acid as much as 2 mol equivalent to saccharide is required (Non-patent Document 3).

  Also, the conversion rate from D-glucose was determined by using a flow-type high-temperature and high-pressure water apparatus at a temperature of 300 ° C., 20 MPa, and a residence time of 15 seconds using 5.5 mol equivalent of acetic anhydride as a dehydrating agent with respect to saccharides. There is a method of obtaining HMF with 74%, HMF selectivity 63%, and yield 47%, but in this case as well, a large amount of acetic anhydride is required (Patent Document 3). Accordingly, there is currently no method for synthesizing HMF from saccharides with a small amount of catalyst in a high yield.

  Regarding the post-treatment after the reaction, in the usual synthesis of HMF in a catalyst / organic solvent, a neutralizing agent is added to the reaction mixture as a dehydrating agent, and after neutralization, an extraction solvent and water or a saturated saline solution are added to separate the components. The solvent layer is then dried, solvent removed, distilled or rectified to obtain the desired product. In addition to water, the water layer contains catalyst, organic solvent, acetic acid, substrate, and product. Contains complex mixtures of products, by-products and minerals.

  Here, when the separation of the catalyst from the aqueous layer is easy, it is recovered and regenerated and reused, but when the separation is difficult, it is discarded and disposed as it is (FIG. 2). As in the case of HMF synthesis in high-temperature and high-pressure water, if the water layer does not contain an organic solvent and contains only water, a trace amount of catalyst, and a product, only the trace amount of catalyst is separated. It is possible to separate into water and product. This means that the water can be regenerated and is an environmental load reduction type process as compared with the normal method (FIG. 3).

  As described above, in the conventional method, in the case of HMF synthesis, a large amount of catalyst and organic solvent are required. Therefore, in the separation operation after the reaction, it is necessary to remove a large amount of catalyst and organic solvent in terms of product quality. The water layer after the separation operation tends to be waste, and causes a problem of waste liquid. Furthermore, a higher degree of separation of a large amount of catalyst / organic solvent is required in consideration of the influence on the environment and harmfulness to living bodies and the safety of foods and pharmaceuticals that are orally administered by humans.

  The cost required for advanced separation is similar to that of the synthesis operation, and it is desirable not to use a large amount of catalyst or organic solvent. In view of the above, in this technical field, continuous synthesis of HMF that is simple, low-cost, environmental load-reduction-type synthesis process, easy to perform separation operation and capable of high-level separation, and no catalyst or organic solvent remains. There was a strong demand for the establishment of a new HMF synthesis method that would enable this.

Japanese Patent Laid-Open No. 2005-200321 JP-A-2005-232116 JP 2007-269766 A

J. et al. Lewkowski, ARKIVOC, 2001, (i), 17-54. K. Seri, Y .; Inoue, H.C. Ishida, Chem. Lett. , 2000, 22 F. S. Asghari and H.H. Yoshida, Ind. Eng. Chem. Res. , 2006, 45, 2163-2173

Under such circumstances, in view of the prior art, the present inventors have developed a new synthesis method capable of continuously synthesizing the HMF by a simple high-speed synthesis process that is low in cost and friendly to the environment. As a result of intensive research with the goal of developing, as a result of using subcritical water as a reaction solvent, it was found that a small amount of catalyst can be added from saccharides to synthesize HMF, and the present invention has been completed. . The present invention is, from sugars, the addition of small amount of catalyst, under reaction conditions of a short time HMF, it is an object to provide a way to continuously synthesized.

The present invention for solving the above-described problems comprises the following technical means.
(1) The most sugars in the reaction system with the addition of sulfuric acid as 1 mole percent of the traces of catalyst A method of synthesizing HMF reaction from saccharide as substrate, using a subcritical flow body as a reaction solvent, Without using an organic solvent, by introducing a substrate and a reaction solvent into a flow-type high-temperature and high-pressure apparatus and carrying out a synthesis reaction at a temperature of 190 ° C. or less and a pressure of 0.1 MPa or more, a one- step synthesis reaction from sugar A method for producing an HMF reactant, which comprises selectively synthesizing an HMF reactant.
( 2 ) The method for producing an HMF reaction product according to (2), wherein the saccharide is D-glucose .
(3) Temperature 100 ~ 190 ° C., the production method of (1) or (2) HMF reaction product according to use subcritical flow body pressure 0.1 to 5 MPa as the reaction solvent.
(4) as a subcritical flow body, water, according to any one of acetic acid, and the use of other inorganic or organic solvents, or a mixed solvent of an inorganic solvent and an organic solvent (1) of (3) HMF A method for producing a reactant.
(5) 0.2 to 0.8 manufacturing method of HMF reaction product according to any one of the the use of catalysts of mole% traces from (1) (4).
( 6 ) The method for producing an HMF reactant according to any one of ( 1 ) to ( 5 ), wherein the synthesis reaction is performed by changing the reaction time in a range of 20 seconds to 2.9 minutes.

The present invention for solving the above problems, a reaction system with the addition of 1 mol% or less of the traces of the catalyst, a method of synthesizing HMF from saccharides, using subcritical flow body of the high-temperature high-pressure state as a reaction solvent, An HMF reactant obtained by introducing a substrate and a reaction solvent into a flow-type high-temperature and high-pressure apparatus without using an organic solvent, and selectively synthesizing an HMF reactant by a one- step synthesis reaction from a saccharide. Manufacturing method.

The method comprises (1) saccharide, Oh with D- glucose Rukoto, (2) Temperature 100 to 19 0 ° C., the use of subcritical flow body pressure 0.1 to 5 MPa as the reaction solvent, (3 ) as a subcritical flow body, water, acetic acid, other inorganic solvent or a mixed solvent of an organic or inorganic solvent and an organic solvent, (4) 0.2 to 0.8 mol% of trace the use of catalysts, and the preferred embodiment that, to carry out the synthesis reaction by changing the range of 20 seconds to 2.9 minutes between (5) anti-latency time.

Further, in the present invention , a water feed pump for feeding water, a water heating coil, a high-temperature high-pressure flow cell, a reactant feed pump for feeding a substrate, a furnace body, and a reactant for introducing the reactant into the furnace body inlet, effluent line for discharging the reaction solution, HMF synthesis apparatus characterized in that it comprises a back pressure valve for setting a cooling flange and pressure Ru preferably used.

Next, the present invention will be described in more detail.
In the present invention, as shown in Chemical Formula 2, HMF can be selectively and continuously synthesized from a saccharide of Chemical Formula 1 in a one-step reaction process with a small amount of catalyst added and a short reaction time. It is a feature. In the present invention, as the reaction solvent, temperature 100 to 19 0 ° C., subcritical flow of pressure 0.1 to 5 MPa is we used. Further, reaction conditions, for example, preferably a temperature 180 to 19 0 ° C., pressure 0.1 MPa, the reaction time 20 seconds to 3 minutes, is adjusted to.

Here, as the saccharide, monosaccharides, disaccharides such can be mentioned, for example, as a monosaccharide, glucose, full Rukuto scan, disk Carreau scan can be cited as disaccharide.

In the present invention, the substrate and the reaction solvent are introduced into a reaction vessel, and the synthesis reaction is carried out for a predetermined reaction time. Thus, as the reactor, for example, Ru can be used continuous type flow through type high-temperature high-pressure reactor.

In the method of the present invention, as the reaction solvent, for example, subcritical flow body is used in a high-temperature and high-pressure state. Specifically, as the subcritical fluid, subcritical water (100 ° C. or higher, 0.1 MPa), the subcritical methanol (100 ° C. or higher, more 0.1 MPa) are exemplified.

As the sub supercritical fluid, the good suitable, subcritical water (180- 19 0 ℃, 0.1MPa) is used.

As the reaction solvent, Ru can include organic and inorganic solvents other than those described above in any proportion. Specifically, for example, a reaction solution containing acetone, acetonitrile, tetrahydrofuran or the like as an organic solvent and acetic acid, ammonia or the like as an inorganic solvent can be substituted.

In the present invention, as the catalyst, it is possible to use sulfuric acid. Further, the catalyst, 1 mol% relative to the substrate (0.01 eq) following trace amounts employed.

In the present invention, the composition of the reaction solvent for the subcritical flow body, the temperature and pressure conditions, the type and amount of the substrate, by adjusting the reaction time, the short time, efficiently, to synthesize a reaction product Can do. In the present invention, for example, a predetermined reaction product is synthesized by introducing a substrate and a reaction solvent into a flow-type high-temperature and high-pressure apparatus and changing the reaction time in a range of 20 seconds to 2.9 minutes. Can do. The reaction conditions can be appropriately set depending on the starting material used, the type of the desired reaction product, and the like.

  In the method of the present invention, the synthesis of HMF from saccharides, which has been conventionally carried out in the presence of a large amount of catalyst, can be carried out continuously at a high speed by reducing the amount of catalyst by adding a small amount of catalyst. The required process can be made more efficient. Further, in the method of the present invention, since a conventionally used catalyst is not used at all, there is no need for post-treatment / disposal such as neutralization treatment and detoxification treatment of the solution after the reaction, and environmental load reduction can be achieved. .

  Further, after the reaction, since only a small amount of catalyst is separated, there is no need to separate and recover the organic solvent, and product separation becomes easy. According to the present invention, the yield is 47% when the substrate is D-glucose and the yield is 58% when D-sucrose is used. In the case of D-fructose, the yield of HMF is 70%. The synthesis method of the present invention makes it possible to produce HMF that can be used in flavors, pharmaceuticals, and foods efficiently, in large quantities, and continuously at high speed.

  Conventionally, various examples of performing HMF synthesis using subcritical fluids and supercritical fluids have been reported. However, there is no example demonstrating that HMF can be synthesized in a high yield by a subcritical water process by adding a small amount of a catalyst from saccharides. For the first time have proved its effectiveness. Moreover, the HMF synthesized from the saccharides in the conventional method had a problem of remaining catalyst and organic solvent, but the reaction product synthesized from the saccharides in the present invention has no remaining catalyst and organic solvent. The HMF reactant of the present invention has advantages over conventional products.

In the present invention, the fine amount of catalyst conditions, in order to realize a synthesis reaction of HMF from sugars, for example, a solution of a substrate beforehand solvent was fed, high-temperature high-pressure reaction course subcritical flow body It is also possible to use a flow-type high-temperature high-pressure infrared spectroscopic in-situ measurement apparatus (FIG. 5) that is observed by infrared spectroscopic analysis using an infrared flow cell (FIG. 4).

However, the high temperature and high pressure infrared flow cell and replaced with no window high temperature and high pressure flow cell (Fig. 6), to the flow of the subcritical fluid directly in contact reacting reactant flow, is better to piping arrangement, the hot A problem such as a leak in the vicinity of the cell window in the high-pressure infrared flow cell does not occur, and the synthesis can be performed in a short time at a higher flow rate. For these reasons, an apparatus equipped with this windowless high-temperature and high-pressure flow cell was used in Examples described later.

  Here, the windowless high-temperature high-pressure flow cell main body (FIG. 6) is attached so that, for example, a commercially available SUS316 cloth 1 is threaded and fixed to a temperature sensor sheath (12 in FIG. 7) described below. Without measuring the temperature of the furnace body atmosphere, the position of the temperature sensor is adjusted so as to indicate the cell temperature, and screwed with the sheath fixing screw and the male screw 3. The pipe 4 of SUS316 is connected to the cross 1 with a taper screw 2 with a one-ring ferrule on the cross 1. Of course, the cloth 1 can also be used as a tee by closing one flow path with an end screw.

  FIG. 7 is a reactor body portion of a flow-type high temperature / high pressure reactor equipped with a windowless high temperature / high pressure flow cell, which is a main body of the reactor. If this is installed in the shaded position of the flow-type high-temperature and high-pressure fluid in-situ infrared spectrometer of Fig. 5, the infrared spectroscopy cannot be measured, but the subcritical / supercritical fluid contact type with variable temperature, pressure and flow rate. It can be used as a synthesis reaction apparatus. In this case, the reaction is observed by collecting the discharged aqueous solution, performing quantification from a calibration curve using a pure product by GC-FID, and performing qualitative analysis by GC / MS. In addition, quantitative and qualitative analysis is performed by NMR.

  Hereinafter, with reference to FIG. 7, water is fed from the water feed pump 5, and after passing through the cooling flange 8, is sent to the furnace body 13. After that, it passes through the water heating coil 9 and is introduced into a high temperature / high pressure flow cell 14 supported and fixed to a temperature sensor sheath 12 in which the temperature sensor 11 is inserted in a high temperature / high pressure state. On the other hand, the reactant is fed from the reactant feed pump 6, passes through the cooling flange 8, and then sent to the furnace body 13. After passing through the coiled reactant introduction tube 10, it is introduced into a high-temperature and high-pressure flow cell 14 fixed to the temperature sensor sheath 12.

  Further, the washing water is fed by the washing water feeding pump 7, passes through the solvent introduction pipe 16, is introduced into the tee 18, and is used for washing. The solution that has passed through the high-temperature and high-pressure flow cell passes through the discharge pipe 17, passes through the cooling flange 8, and passes outside the furnace body while being air-cooled. Thereafter, the discharged liquid from the back pressure valve 19 that has set the pressure is collected and used as a sample.

  Here, in order to eliminate the influence of heating of the effluent containing the reactants and products, rapid heating is performed, the piping of the coiled reactant introduction line 10 and the discharge pipe 17 is made as short as possible, and the water heating coil It is desirable to make 9 as long as possible. The present invention is not limited to these, and any reaction apparatus having the same effect as these can be used in the same manner.

In general, when synthesizing HMF, the conventional method requires an acid / base catalyst in addition to the aprotic organic solvent. When used in foods and pharmaceuticals, the removal of the remaining organic solvent and catalyst is a great effort. In addition to affecting the environment, it has problems such as being harmful to living bodies. The present invention is a catalyst and a saccharide traces, only the process using water, there is provided a way of synthesizing HMF, not only medicines and food, it is also applicable to chemicals synthesis, the HMF It enables efficient production and supply in a short time.

The present invention has the following effects.
(1) HMF can be synthesized continuously at a high speed with a small amount of catalyst in which the amount of catalyst is reduced from saccharides.
(2) A synthesis process that does not require an organic solvent can be realized.
(3) Therefore, it is possible to provide a highly safe HMF reactant that has no residual organic solvent and is not harmful to the living body.
(4) As a new mass production process of HMF useful as pharmaceuticals and foods, it is possible to provide a new production technology that can replace the existing production process.

The HMF synthesis using a catalyst and an organic solvent is shown. The post-process flowchart of the HMF synthesis | combination using a catalyst and an organic solvent is shown. The post-process flowchart of the HMF synthesis | combination using an aqueous solvent is shown. 1 shows a high temperature high pressure infrared flow cell. 1 shows a flow-type high-temperature and high-pressure fluid in-situ infrared spectrometer used in the examples. 1 shows a high temperature and high pressure flow cell without a window. The main part of the flow-type high temperature / high pressure reactor used in the examples is shown. The temperature effect in HMF synthesis is shown. The pressure dependence in HMF synthesis is shown. The sulfuric acid amount dependence in HMF synthesis is shown.

  EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Examples.

Example 1-5
In this example, using the flow-type high-temperature and high-pressure reactor shown in FIG. 7, the synthesis conditions were a temperature of 25 to 300 ° C., a pressure of 0.1 to 5 MPa, and a residence time of 20 seconds to 3 minutes. 7 is set to a predetermined temperature and a predetermined pressure, and the flow rate of the water feed pump 5 or the reactant feed pump 6 or the length of the coiled reactant introduction pipe 10 is set. To adjust the residence time. Pure water was sent to a high-temperature and high-pressure water supply device at a flow rate of 5.0 ml / min to obtain high-temperature and high-pressure water (subcritical water).

  Thereafter, a reaction mixture in which a small amount of catalyst of 1 mol% or less of the substrate and propionic acid as an internal standard (5 mol% of the substrate) was added to the saturated sugar aqueous solution was fed from the reactant feed pump 6. After feeding the reaction mixture, 2 ml of the discharged aqueous solution 20 minutes after the back pressure valve 19 was collected. When the internal volume of the pipe from the reaction tee to the back pressure valve outlet was the reaction volume, the reaction time was 20 seconds to 3 minutes. The composition of the recovered aqueous solution was determined by GC / MS analyzer (Hewlett Packard HP6890, column HP-5, inlet temperature 150 ° C., initial column temperature 60 ° C. (holding time 2 minutes), heating rate 10 ° C./min. The final column temperature was 250 ° C. (retention time 2 minutes).

  The obtained mass spectrum was confirmed by the Willy database with a coincidence of 90% or more. In addition, quantification and qualitativeness in the presence of commercially available reagents are as follows: with propionic acid as an internal standard, GC-FID (Agilent GC6890, column DB-WAX, inlet temperature 230 ° C., split ratio 5.61, initial column temperature 50 C. (retention time 0.5 minutes), temperature increase rate 20 ° C./minute, final column temperature 230 ° C. (retention time 20 minutes)).

  140 ° C, 160 ° C, 180 ° C, 190 ° C, 200 ° C under constant conditions of D-glucose aqueous solution (0.101M) to which 0.40 mol% sulfuric acid was added, pressure 0.1 MPa, residence time 2.9 minutes The temperature dependence of was investigated. As a result, the yields of HMF were 5%, 17%, 42%, 52%, and 50%, respectively, and the optimum was 190 ° C. (FIG. 8).

Example 6
In the same manner as in Example 1-5, a D-glucose aqueous solution (0.195 M) to which 0.62 mol% of sulfuric acid was added, a pressure of 0.1 MPa, a residence time of 2.9 minutes, and a temperature of 190 ° C. The yield was examined. As a result, the yield of HMF was 64% (FIG. 8).

Example 7-9
In the same manner as in Example 1-5, in the flow-type high-temperature and high-pressure reactor (FIG. 7), a short coiled reactant introduction tube 10 was installed, and D-glucose aqueous solution (0 195M), pressure 0.1 MPa, residence time 2.9 minutes, and temperature dependence was studied at 265 ° C., 285 ° C., and 300 ° C. As a result, the yields of HMF were 31%, 45%, and 48%, respectively, and although the reaction temperature was increased as compared with Example 1-5, the yield was not improved (FIG. 8). ).

Examples 10-13
In the same manner as in Example 1-5, a D-glucose aqueous solution (0.195 M) to which 0.69 mol% of sulfuric acid was added, a pressure of 0.1 MPa, a residence time of 2.9 minutes, a constant temperature of 120 ° C., 140 ° C. The temperature dependence of ° C, 160 ° C and 180 ° C was examined. As a result, the yields of HMF were 10%, 18%, 28% and 59%, respectively, and 180 ° C. was optimal (FIG. 8). In addition, at 190 degreeC and 200 degreeC, obstruction | occlusion occurred and the result was not obtained.

Examples 14-17
In the same manner as in Example 1-5, a D-glucose aqueous solution (0.195 M) to which 1.0 mol% of sulfuric acid was added, pressure 0.1 MPa, residence time 2.9 minutes, 120 ° C., 160 ° C. The temperature dependence of ° C, 170 ° C and 180 ° C was examined. As a result, the yields of HMF were 7%, 32%, 36%, and 50%, respectively, and 180 ° C. was optimal (FIG. 8). In addition, at 190 degreeC and 200 degreeC, obstruction | occlusion occurred and the result was not obtained.

Examples 18-20
In the same manner as in Example 1-5, D-glucose aqueous solution (0.101M) to which 0.4 mol% of sulfuric acid was added, temperature 190 ° C, residence time 2.9 minutes, 0.1 MPa, 2 MPa The pressure dependence was examined at 5 MPa. As a result, the yields of HMF were 52%, 49%, and 43%, respectively, and 0.1 MPa was optimal (FIG. 9).

Examples 21-23
In the same manner as in Example 1-5, sulfuric acid 0.4 mol%, 0.69 mol%, 1 mol under constant conditions of D-glucose aqueous solution (0.195 M), temperature 160 ° C. and residence time 2.9 minutes %, The dependence on catalyst amount was examined. As a result, the yields of HMF were 17%, 28%, and 32%, respectively, and 1 mol% was optimal (FIG. 10).

Examples 24-26
In the same manner as in Example 1-5, sulfuric acid 0.4 mol%, 0.69 mol%, 1 mol under constant conditions of D-glucose aqueous solution (0.195 M), temperature 180 ° C. and residence time 2.9 minutes. %, The dependence on catalyst amount was examined. As a result, the yields of HMF were 42%, 59%, and 50%, respectively, and 0.69 mol% was optimal (FIG. 10). Therefore, HMF synthesis was possible with a small amount of catalyst of 1 mol% or less.

  From the above examples, it was revealed that HMF can be synthesized in good yield using high-temperature and high-pressure water as a reaction solvent.

As described above in detail, the present invention is, as a reaction solvent a high-temperature, high-pressure fluid, from sugars, reduces the amount of catalyst, a trace amount of catalyst, without the use of organic solvents, relates to how to synthesize HMF There, in the conventional method, synthesis of HMF from sugars, the catalyst was added to the organic solvent, it was necessary to carry out the reaction for several hours, by using a subcritical flow body shown in the present invention, substantially It became possible to synthesize HMF continuously at high speed and in a short time without using any catalyst and without using an organic solvent. This brings about the merit that HMF useful as a fragrance, a medicine, and a food can be continuously produced in a short time in a large amount. From these facts, it is possible to reduce the initial cost and running cost of the process by simplifying the synthesis and separation process of HMF, and further, the post-treatment of the neutralization treatment is unnecessary, and the environment is harmonized. Mold production is possible. INDUSTRIAL APPLICABILITY The present invention is useful as a new mass production process for HMF useful as pharmaceuticals and foods, which can replace existing production processes.

1 Tee or cloth (one side opening φ4mm threaded)
2 φ4mm × 5.0mmL hexagon taper screw 3 Male screw with one ring ferrule 4 SUS316 piping 5 Water feed pump 6 Reactant feed pump 7 Washing water feed pump 8 Cooling flange (cooling water circulates)
9 Water heating coil 10 Coiled reactant introduction tube 11 Temperature sensor 12 Temperature sensor sheath 13 Furnace body 14 High-temperature and high-pressure flow cell (Tee type for normal temperature rise, cross type for rapid temperature rise)
15 ZnSe window 16 Solvent introduction pipe 17 Discharge pipe 18 Tee 19 Back pressure valve 21 Aqueous solution 22 Washing water 23 Aqueous solution pump 24 Cleaning pure water feed pump 25 Furnace heating system 26 Furnace 27 High-temperature high-pressure infrared flow cell 28 Cooling water (inlet) )
29 Cooling water (exit)
30 Back pressure valve 31 Discharged aqueous solution receiver 32 Movable mirror 33 Movable mirror 34 Interferometer 35 Light source 36 Infrared laser 37 MCT light receiver 38 TGS light receiver 39 Analysis monitor 40 Reactant liquid feed pump 41 Substrate liquid feed pump 42 Water liquid feed pump 43 Reaction tee 44 Piping 45 Mixing tee 46 Discharge piping 47 Cooler 48 Back pressure valve 49 Collection container 50 Temperature sensor 51 Temperature sensor

Claims (6)

A most methods of synthesizing HMF reaction from saccharide sugars in the reaction system with the addition of sulfuric acid as a mole% of the traces of the catalyst as a substrate, using a subcritical flow body as a reaction solvent, an organic solvent without using, in the flow type high-temperature high-pressure device, and the introduction of substrates and reaction solvent, temperature 190 ° C. or less, by carrying out the synthesis reaction in the above pressure 0.1 MPa, in the synthesis reaction of one step from sugars, HMF reaction Is selectively synthesized. A method for producing an HMF reactant. The method for producing an HMF reaction product according to claim 2, wherein the saccharide is D-glucose . Temperature 100 ~ 190 ° C., the manufacturing method according to claim 1 or 2 HMF reactants described using the subcritical flow body pressure 0.1 to 5 MPa as the reaction solvent. As a subcritical flow body, water, acetic acid, and a manufacturing method of HMF reaction product according to any one of claims 1 to 3, using other inorganic or organic solvents, or a mixed solvent of an inorganic solvent and an organic solvent. Method of manufacturing HMF reaction product according to any one of claims 1 to 4 for use 0.2-0.8 mole% of traces of catalysts. The method for producing an HMF reactant according to any one of claims 1 to 5 , wherein the synthesis reaction is carried out by changing the reaction time in a range of 20 seconds to 2.9 minutes.