2,5-furandicarboxylic acid continuous production device and continuous production method for 2,5-furandicarboxylic acid

Abstract

Embodiments of the present invention may provide a continuous manufacturing system for 2,5-furandicarboxylic acid, comprising: a raw material supply unit that supplies an aqueous solution of 5-hydroxymethylfurfural and an aqueous solution of a base, respectively; a micro-mixing unit that mixes the aqueous solution of 5-hydroxymethylfurfural (HMF) and the aqueous solution of a base, respectively supplied from the raw material supply unit, to form a raw material mixture; an electrochemical reaction unit that synthesizes 2,5-furandicarboxylic acid by passing the raw material mixture introduced from the mixing unit in a single pass; and a product storage unit that stores the product discharged from the electrochemical reaction unit.

Description

Technology Field

[0001] The embodiments of the present invention relate to a continuous manufacturing system capable of continuously producing electrochemical 2,5-furandicarboxylic acid and a method for manufacturing the same, specifically to a continuous flow reaction system for separating and mixing raw materials for the production of 2,5-furandicarboxylic acid and a method for continuously producing high-purity 2,5-furandicarboxylic acid. Background Technology

[0003] The consumption of petroleum-derived plastics is continuously increasing, and carbon dioxide emissions from plastic production amount to approximately 1.7 gigatons, accounting for 15% of global carbon dioxide emissions. Consequently, there is a growing demand for CO2-free plastics composed of biomass-derived chemicals as an alternative to petroleum-derived plastics. Polyethylene furanoate (PEF) is one of the plant-based plastics and is attracting attention as a substitute for PET, which is manufactured from petroleum-derived compounds. Polyethylene furanoate (PEF) is one of the bio-based plastics receiving significant attention due to its high mechanical strength, excellent heat resistance, and superior O2 and CO2 gas barrier properties. 2,5-furandicarboxylic acid (FDCA), a monomer of PEF plastic, can be synthesized through the oxidation reaction of 5-hydroxymethylfurfural (HMF), which is generated through the strong acid saccharification of cellulose.

[0004] Generally, the oxidation of HMF is carried out under high temperature (~140°C) and high pressure (~40 bar) conditions using chemical oxidizers (O2 and air) and precious metal catalysts (Pt, Pd, Au, and Ru). However, this conventional method suffers from high energy consumption. In particular, as the proportion of power generation from new and renewable energy sources has recently increased, there is a growing need to develop electrochemical production methods that allow the generated electrical energy to be used directly in the target chemical reaction without the need to convert electricity into heat or pressure.

[0005] To solve the above problems, the applicant filed domestic patents (KR10-2021-0148900) and (KR10-2022-0128697) related to a catalyst electrode for efficiently producing 2,5-furandicarboxylic acid (FDCA).

[0006] However, in batch-type reaction systems, a strong basic solution (0.1 M KOH, pH 13) in which the reactant 5-hydroxymethylfurfural is dissolved is injected into the reactor to carry out the reaction, and there is a need to solve the problem that the reactant (including intermediate reactants) that remains unconverted to FDCA during the reaction time (several hours) continuously degrades and changes into polymer impurities depending on the exposure time to the basic solution. In addition, due to the problem of pH decreasing during the reaction, a strong basic aqueous solution (4 M KOH) must be continuously injected for the reaction, and there is a need to solve the problem of accelerated deterioration of the reactant caused by this. The problem to be solved

[0007] In an embodiment of the present invention, we aim to provide a continuous manufacturing system for 2,5-furandicarboxylic acid that can minimize material loss due to degradation and improve material stability by shortening the reaction time, and a method for continuously manufacturing high-purity 2,5-furandicarboxylic acid. means of solving the problem

[0009] A continuous manufacturing system for 2,5-furandicarboxylic acid according to one embodiment of the present invention may include: a raw material supply unit that supplies an aqueous solution of 5-hydroxymethylfurfural and an aqueous solution of a base, respectively; a micro-mixing unit that mixes the aqueous solution of 5-hydroxymethylfurfural (HMF) and the aqueous solution of a base, respectively supplied from the raw material supply unit, to form a raw material mixture; an electrochemical reaction unit that synthesizes 2,5-furandicarboxylic acid by passing the raw material mixture introduced from the mixing unit in a single pass; and a product storage unit that stores the product discharged from the electrochemical reaction unit.

[0010] The electrochemical reaction unit may include: a first electrode plate and a second electrode plate positioned facing each other; a membrane positioned between the first electrode plate and the second electrode plate; an oxidation electrode and a reduction electrode positioned facing each other on both sides of the membrane; an oxidation electrode flow path positioned between the first electrode plate and the oxidation electrode; and a reduction electrode flow path positioned between the second electrode plate and the reduction electrode.

[0011] The above oxidation electrode channel and the above reduction electrode channel may be a grid-type channel with a grid formed therein or a bulk-type channel without a grid formed therein.

[0012] The above grid-type channel may be a lattice-type channel with a straight grid formed therein or a zigzag-type channel with a zigzag grid formed therein.

[0013] The above oxidation electrode flow path is a grid-type flow path in which a grid is formed, and the reduction electrode flow path may be a bulk-type flow path in which a grid is not formed.

[0014] A method for the continuous production of 2,5-furandicarboxylic acid according to one embodiment of the present invention may include the steps of: supplying an aqueous solution of 5-hydroxymethylfurfural (HMF) and an aqueous solution of a base to a micro-mixing unit, respectively; mixing the supplied aqueous solution of 5-hydroxymethylfurfural (HMF) and the aqueous solution of the base in the micro-mixing unit to form a raw material mixture; and supplying the raw material mixture to an electrochemical reaction unit to synthesize 2,5-furandicarboxylic acid while passing it through in a single pass.

[0015] The above-mentioned mixed 5-hydroxymethylfurfural (HMF) aqueous solution and base aqueous solution are supplied to an electrochemical reaction unit, and the time for passing through in a single pass may be in the range of 1 minute to 5 minutes.

[0016] In the step of supplying the above 5-hydroxymethylfurfural (HMF) aqueous solution and the base aqueous solution to a micro-mixing unit, the ratio of the flow rate of the 5-hydroxymethylfurfural (HMF) aqueous solution to the flow rate of the base aqueous solution (5-hydroxymethylfurfural (HMF) flow rate : base aqueous solution flow rate) may be in the range of 1:0.5 to 1:2.

[0017] In the step of supplying the above 5-hydroxymethylfurfural (HMF) aqueous solution and the base aqueous solution to a micro-mixing unit, the above 5-hydroxymethylfurfural (HMF) aqueous solution and the base aqueous solution may be supplied at a flow rate in the range of 0.5 ml / min to 5 ml / min.

[0018] In the step of supplying the above 5-hydroxymethylfurfural (HMF) aqueous solution and the base aqueous solution to a micro-mixing unit, the concentration of the above 5-hydroxymethylfurfural (HMF) aqueous solution may be in the range of 0.5 wt% to 2.0 wt%.

[0019] In the step of mixing the supplied 5-hydroxymethylfurfural (HMF) aqueous solution and base aqueous solution in a micro-mixing unit to form a raw material mixture, the residence time of the 5-hydroxymethylfurfural (HMF) aqueous solution and base aqueous solution in the micro-mixing unit may be in the range of 0.5 seconds to 10 seconds. Effects of the invention

[0021] A continuous manufacturing system for producing 2,5-furandicarboxylic acid according to one embodiment of the present invention has the advantage of being able to produce 2,5-furandicarboxylic acid with very low impurity content and high purity by minimizing material loss due to degradation.

[0022] A continuous manufacturing system for 2,5-furandicarboxylic acid according to one embodiment of the present invention has the advantage of ensuring chemical stability of the material during the reaction process and producing high-quality 2,5-furandicarboxylic acid by supplying raw materials in a separate mixing manner.

[0023] A method for producing 2,5-furandicarboxylic acid according to one embodiment of the present invention has the advantage of being able to shorten the reaction time and continuously produce 2,5-furandicarboxylic acid of high purity, thereby improving the efficiency of the entire process. Brief explanation of the drawing

[0025] FIG. 1 schematically illustrates a continuous manufacturing system for 2,5-furandicarboxylic acid according to one embodiment of the present invention. FIG. 2 schematically shows the structure of a micro-mixing section according to one embodiment of the present invention. FIG. 3 schematically shows an electrochemical reaction section applied to a continuous flow reaction system for the production of 2,5-furandicarboxylic acid according to one embodiment of the present invention. FIG. 4 schematically shows an electrode flow path according to one embodiment of the present invention. Figure 5 shows the generated current according to various combinations of reduction electrode channels and oxidation electrode channels and the applied voltage. Figure 6 shows a lab-scale continuous production system for 2,5-furandicarboxylic acid. Figure 7 shows the change in current according to reaction time when the manufacturing system of Figure 6 is used. Figure 8 schematically shows an FDCA manufacturing system using a conventional batch-type reactor. Figure 9 shows the change in current according to reaction time when the manufacturing system of Figure 8 is used. Figure 10 shows the change in the concentration of the substance over time in Comparative Example 1. Specific details for implementing the invention

[0026] The technical terms used herein are for the reference of specific embodiments only and are not intended to limit the invention. The singular forms used herein include plural forms unless phrases clearly indicate otherwise. As used in the specification, the meaning of "comprising" specifies certain characteristics, areas, integers, steps, actions, elements, and / or components, and does not exclude the presence or addition of other characteristics, areas, integers, steps, actions, elements, and / or components.

[0027] Unless otherwise defined, all terms used herein, including technical and scientific terms, have the same meaning as generally understood by those skilled in the art to which this invention pertains. Terms defined in commonly used dictionaries are further interpreted to have meanings consistent with relevant technical literature and the present disclosure, and are not interpreted in an ideal or highly formal sense unless otherwise defined.

[0028] Terms such as first, second, and third are used to describe various parts, components, regions, layers, and / or sections, but are not limited thereto. These terms are used solely to distinguish one part, component, region, layer, or section from another part, component, region, layer, or section. Accordingly, the first component, part, region, layer, or section described below may be referred to as the second component, part, region, layer, or section without departing from the scope of the present invention.

[0029] In the description of the present invention, the reactants may be raw materials, products, or a mixture thereof.

[0030] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention, and the present invention is defined only by the scope of the claims set forth below.

[0031] One embodiment of the present invention can provide a continuous production system for 2,5-furandicarboxylic acid.

[0032] FIG. 1 schematically illustrates a continuous manufacturing system for 2,5-furandicarboxylic acid according to one embodiment of the present invention.

[0033] Referring to FIG. 1, a continuous manufacturing system for 2,5-furandicarboxylic acid according to one embodiment of the present invention may include: a raw material supply unit that supplies an aqueous solution of 5-hydroxymethylfurfural (HMF) and an aqueous solution of a base, respectively; a micro-mixing unit (200) that mixes the aqueous solution of 5-hydroxymethylfurfural (HMF) and the aqueous solution of a base, respectively supplied from the raw material supply unit, to form a raw material mixture; an electrochemical reaction unit (300) that synthesizes 2,5-furandicarboxylic acid by passing the raw material mixture introduced from the mixing unit (200) through a single pass; and a product storage unit (400) that stores the product discharged from the electrochemical reaction unit.

[0034] First, the raw material supply unit may include an HMF supply unit (110) that supplies a 5-hydroxymethylfurfural (HMF) aqueous solution and a base supply unit (120) that supplies a base aqueous solution. Each supply unit is a device capable of continuously supplying raw material from a raw material storage tank to a downstream micro-mixing unit (200), and may be a peristaltic pump. The raw material supply unit is not particularly limited as long as it can continuously supply the raw material at the supply rate intended in the present invention. In the present invention, the HMF supply unit (110) and the base supply unit (120) can supply the HMF aqueous solution and the base aqueous solution at a supply rate in the range of 0.5 ml / min to 5 ml / min. When the supply rate of the raw material from the HMF supply unit (110) and the base supply unit (120) is within the above range, the residence time range of the reactant in the electrochemical reaction unit intended in the present invention can be satisfied, thereby preventing or reducing the deterioration of HMF and having the advantage of improving the conversion rate of HMF and the yield of FDCA.

[0035] Although not shown in the drawing, a storage tank for storing an aqueous solution of 5-hydroxymethylfurfural (HMF) and an aqueous solution of a base, respectively, may be provided.

[0036] It includes a micro-mixing section (200) into which an aqueous HMF solution and an aqueous base solution supplied through the HMF supply section (110) and the base supply section (120), respectively, are introduced.

[0037] Referring to the structure of the micro-mixing section (200) schematically illustrated according to one embodiment of the present invention in FIG. 2, an HMF aqueous solution and a base aqueous solution are introduced into the micro-mixing section (200) through the HMF inlet (210) and the base inlet (220), respectively, and are supplied to the downstream electrochemical reaction section (300) through the mixture outlet (230). The angle (θ) between the flow direction of the HMF aqueous solution introduced through the HMF inlet (210) and the flow direction of the mixture discharged through the mixture outlet (230) may be 90° or greater and less than 180°. Meanwhile, based on the flow direction of the mixture discharged through the mixture outlet (230), the HMF aqueous solution and the base aqueous solution may be introduced at the same angle. This is advantageous for the HMF aqueous solution and the base aqueous solution to be introduced into the micro-mixing section (200) and form a uniform mixture in a short period of time.

[0039] An electrochemical reaction section (300) is located at the rear end of the micro-mixing section (200).

[0040] FIG. 3 schematically illustrates an electrochemical reaction section applied to a continuous flow reaction system for producing 2,5-furandicarboxylic acid according to an embodiment of the present invention. Referring to FIG. 3, an electrochemical reaction section (300) according to an embodiment of the present invention comprises: a first electrode plate (341) and a second electrode plate (342) positioned facing each other at both ends; a membrane (340) positioned between the first electrode plate (341) and the second electrode plate (342); an oxidation electrode (331) and a reduction electrode (332) positioned facing each other on both sides of the membrane (340); an oxidation electrode flow path (321) positioned between the first electrode plate (341) and the oxidation electrode (331); and a reduction electrode flow path (322) positioned between the second electrode plate (342) and the reduction electrode (332).

[0041] The first electrode plate (341) and the second electrode plate (342) are conductive electrode plates that serve to carry current for an electrochemical reaction, and include a gold-coated bronze (brass) electrode plate (351, 352) and an end plate (311, 312) which is a metal housing made of nickel-coated stainless steel (SUS316L) to protect it, and may include a catalyst as needed. The material is not particularly limited as long as it can carry the desired current in the present invention. Meanwhile, the first electrode plate (341) and the second electrode plate (342) regulate the electric voltage and current applied by the power supply unit (500).

[0042] The membrane (340) is an ion-conducting membrane, and an anion-conducting membrane or a cation-conducting membrane may be used.

[0043] The oxidation electrode (331) and the reduction electrode (332) may be metal electrodes comprising one or more selected from nickel, copper, or (other metal catalysts), and the area is 1 cm² 2 up to 150 cm 2 It may be a range, specifically 5 cm 2 to 100 cm 2 It can be a range.

[0045] An oxidation electrode channel (321) located between the first electrode plate (341) and the oxidation electrode (331) can provide a path through which a raw material mixture formed by mixing an aqueous solution of 5-hydroxymethylfurfural (HMF) supplied from the micro-mixing unit (200) and an aqueous solution of a base passes. As the raw material mixture passes through the oxidation electrode channel (321), it undergoes an electrochemical reaction to produce 2,5-furandicarboxylic acid, and the 2,5-furandicarboxylic acid discharged from the electrochemical reaction unit (300) can be stored in a product storage unit (400).

[0046] The reduction electrode channel (322) located between the second electrode plate (342) and the reduction electrode (332) can provide a path for water, humidified air, or an aqueous base solution to pass through, and water can be electrolyzed to generate hydrogen as it passes through the reduction electrode channel (322).

[0048] The electrode channel (320), that is, the oxidation electrode channel (321) and the reduction electrode channel (322), may be a plate with a hole formed in the center. The water or raw material mixture may perform an electrochemical reaction while passing through the hole. At this time, the thickness of the plate may be in the range of 0.5 cm to 1 cm to minimize electrical resistance as a path for transmitting current to the oxidation electrode (331) and the reduction electrode (332), and the material of the plate may be one or more selected from nickel and titanium.

[0049] Meanwhile, one or more grids may be formed in the hole. Specifically, reactants passing through the electrode channel (320) may be separated by the grids and pass through. Referring to the schematic diagram of the electrode channel (320) according to one embodiment of the present invention shown in FIG. 4, FIG. 4(a) and FIG. 4(b) schematically show a grid-type channel in which a grid is formed in the hole, and FIG. 4(c) shows an N-type channel, which is a bulk (None) type channel in which no grid is formed. Specifically, FIG. 4(a) shows a P-type channel, which is a parallel electrode channel in which a grid-shaped grid is formed, and FIG. 4(b) shows an S-type channel, which is a serpentine electrode channel in which a zigzag-shaped grid is formed.

[0050] The oxidation electrode channel (321) and the reduction electrode channel (322) can be used in a selective combination of the above-mentioned grid type channel and bulk type channel, and specifically, the reduction electrode channel (322) may be of the bulk type and the oxidation electrode channel (321) may be of the grid type channel.

[0051] The spacing between the grids may be in the range of 2 mm to 5 mm. When the grid spacing is in the above range, there is an advantage that the reactant can pass through smoothly and the flow rate of the aqueous solution can be easily controlled.

[0053] Another embodiment of the present invention is a method for the continuous production of 2,5-furandicarboxylic acid, which may include the steps of: supplying an aqueous solution of 5-hydroxymethylfurfural (HMF) and an aqueous solution of a base to a micro-mixing unit, respectively; mixing the supplied aqueous solution of 5-hydroxymethylfurfural (HMF) and the aqueous solution of the base in the micro-mixing unit to form a raw material mixture; and supplying the raw material mixture to an electrochemical reaction unit to synthesize 2,5-furandicarboxylic acid while passing it in a single pass.

[0054] The above 5-hydroxymethylfurfural (HMF) aqueous solution may be prepared by storing it in a separate container. Meanwhile, the above 5-hydroxymethylfurfural (HMF) aqueous solution may be an aqueous solution with a concentration in the range of 0.5 wt% to 5.0 wt%, specifically an aqueous solution with a concentration in the range of 0.5 wt% to 2.0 wt%, and more specifically an aqueous solution with a concentration in the range of 0.5 wt% to 1.2 wt%, in which case the pH value may be about 7.

[0055] The above-mentioned aqueous base solution may be prepared by storing it in a separate container. The above-mentioned aqueous base solution may be one or more selected from potassium hydroxide (KOH) aqueous solution, sodium hydroxide (NaOH) aqueous solution, lithium hydroxide (LiOH) aqueous solution, and cesium hydroxide (CsOH) aqueous solution, and the pH value of the aqueous base solution may be approximately 14.

[0056] The above 5-hydroxymethylfurfural (HMF) aqueous solution and base aqueous solution can be supplied continuously by a pump and can be supplied at a supply rate in the range of 0.5 ml / min to 5.0 ml / min. Meanwhile, the above 5-hydroxymethylfurfural (HMF) aqueous solution and base aqueous solution can be supplied at the same supply rate. This is advantageous for the above 5-hydroxymethylfurfural (HMF) aqueous solution and base aqueous solution to be uniformly mixed in a short time in the micro-mixing section.

[0057] The above 5-hydroxymethylfurfural (HMF) aqueous solution and base aqueous solution are each supplied to a micro-mixing section and then mixed to form a raw material mixture. The ratio of the flow rate of the 5-hydroxymethylfurfural (HMF) aqueous solution to the flow rate of the base aqueous solution (5-hydroxymethylfurfural (HMF) flow rate : base aqueous solution flow rate) may be in the range of 0.5 to 1:2, and specifically 1:1. Meanwhile, the residence time of the raw material mixture in the micro-mixing section may be in the range of 0.5 seconds to 10 seconds. When the residence time is within the above range, the 5-hydroxymethylfurfural (HMF) aqueous solution and base aqueous solution are uniformly mixed, which is advantageous for reducing the overall process time.

[0058] The raw material mixture formed in the micro-mixing section above can be introduced into the electrochemical reaction section at a flow rate ranging from 1 ml / min to 10 ml / min. When the flow rate of the raw material mixture is within the above range, it is advantageous for improving the conversion rate of HMF and the yield of FDCA.

[0059] As the above raw material mixture passes through the electrochemical reaction unit, an electrochemical reaction occurs, converting HMF into FDCA. At this time, the time the raw material mixture passes through the electrochemical reaction unit may be in the range of 0.5 minutes to 5 minutes, specifically in the range of 1 minute to 4 minutes. When the time the raw material mixture passes through the electrochemical reaction unit, that is, the residence time in the electrochemical reaction unit, is within the above range, it is advantageous to minimize the degradation of HMF and improve the yield of FDCA. If the residence time in the electrochemical reaction unit is less than 1 minute, there is a problem that the conversion yield of HMF to FDCA is low, and if the residence time exceeds 5 minutes, there is a problem that the generation of impurities increases due to the degradation of HMF.

[0060] Meanwhile, the output of the power applied to the electrochemical reaction unit may be 5W to 60W. Specifically, the applied voltage may be 2.0V to 3.0V, and more specifically, 2.0V to 2.6V. In addition, the current may be 5A to 20A, and specifically, 6.5A to 20A.

[0062] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention, and the present invention is defined only by the scope of the claims set forth below.

[0064] (Test Example 1: Comparison of generated current according to Euro combinations by type)

[0065] The reduction electrode channel (322) and the oxidation electrode channel (321) were arbitrarily combined among the aforementioned N-type, P-type, and S-type channels, and the 2,5-furandicarboxylic acid production current of the electrochemical reactor according to the applied voltage was compared.

[0066] Specifically, the voltage was applied in the range of 1.6V to 2.4V using a constant voltage test method, and the current value was obtained by measuring it for 5 to 10 minutes.

[0067] FIG. 5 shows the generated current according to various combinations of the reduction electrode channel (322) and the oxidation electrode channel (321) and the applied voltage. Referring to FIG. 5, it was found that when the reduction electrode channel (negative channel in FIG. 5) is N-type and the oxidation electrode channel (positive channel in FIG. 5) is P-type, the generated current is high regardless of changes in the applied voltage. In addition, various combinations including S-type for the oxidation electrode channel (positive channel in FIG. 5) are disclosed.

[0069] (Test Example 2: Comparison of generated current over time)

[0070] Figure 6 shows a lab-scale continuous production system for 2,5-furandicarboxylic acid.

[0071] When an FDCA conversion experiment was performed using a 1.26 wt% HMF aqueous solution and a 1M KOH aqueous solution as raw materials using the FDCA continuous manufacturing system of Fig. 6, the change in current according to reaction time was observed and summarized in Fig. 7.

[0072] Referring to Fig. 7, it can be seen that an aqueous HMF solution and an aqueous KOH solution are mixed separately, and a reaction product of a constant concentration is continuously supplied to the continuous flow reaction device according to the present invention, that is, the electrochemical reaction part, and the FDCA generation current is maintained at an almost constant level without significant change over time.

[0074] (Comparative Example 1: Preparation of FDCA using a batch-type reactor)

[0075] When an FDCA conversion experiment was performed using a batch-type reactor as illustrated in Fig. 8, with 1.26 wt% HMF aqueous solution and 4M KOH aqueous solution as raw materials, the change in current over time was observed, and the results are shown in Fig. 9.

[0076] Referring to Figure 9, it is shown that the current decreases with reaction time in the batch reactor, which is attributed to the decrease in the reactants contained in the batch reactor. Additionally, it can be observed that the current fluctuates with the addition of KOH to resolve the problem of pH reduction, and it is believed that impurities are generated due to the spontaneous deterioration of the reactants caused by the high pH of 4M KOH during this process.

[0077] In addition, Figure 10 shows the changes in the concentration of HMF and various intermediate products in the aqueous solution over time when the pH in Comparative Example 1 was set to 7, 9, 12, 13, and 14.

[0078] Referring to Figure 10(a), it can be seen that the decrease in HMF concentration in the aqueous solution increases as time progresses as the pH increases, and no decrease in concentration was observed when the pH was 12 or lower.

[0079] Figure 10(b) shows the change in concentration of various intermediate products over time under conditions of pH 13. Referring to Figure 10(b), it was found that not only the reaction raw material HMF but also the intermediate products generated during the reaction process were unstable in the same basic environment. In particular, it was found that dipomilfuran (DFF) deteriorated nearly six times faster than HMF, and such deterioration can form polymeric impurities.

[0080] Table 1 below shows the results of HMF degradation rate and FDCA yield according to reaction time under conditions of pH 13 in Comparative Example 1.

[0081] Reaction time HMF Degradation Rate (%) Theoretical maximum FDCA yield (%) 0 0 100 10 min 0.3 99.7 30 min 1 99 1 hour 2 98 5 hours 10 90 10 hours 20 80

[0082] Referring to Table 1, it is believed that the HMF degradation rate increases with reaction time, and the theoretical FDCA yield decreases.

[0083] The above HMF degradation rate is the initial concentration of HMF contained in an aqueous solution of pH 13 (C OConcentration of HMF (C) after ) and time (t) t Using ), HMF degradation rate (%) = ((CO-C t It was calculated as ) / C0) X 100. The theoretical maximum yield of FDCA is the residual HMF concentration (C) remaining in the aqueous solution without degradation. t Using ), the theoretical maximum FDCA yield (%) = C t It was calculated as / C0X 100.

[0084] Meanwhile, the HMF conversion rate (%) is the concentration of HMF consumed after the reaction process (C0-C0) out of the initial HMF concentration (C0) in the electrochemical reactor. t ) ratio, and ((C0-C t It was calculated as ) / C0) X 100. The FDCA yield (%) is the FDCA concentration produced after the reaction (C) divided by the initial HMF concentration (C0). FDCA ) ratio, and (C FDCA It was calculated as / C0) X 100.

[0086] (Experimental Example: Preparation of FDCA using the continuous reactor of the present invention)

[0087] The lab-scale FDCA continuous manufacturing system of Fig. 6 was used, and experiments were conducted for more than 40 hours using 1.26 wt% HMF solution and 1M KOH solution as raw materials.

[0088] A 1.26 wt% HMF solution and a 1M KOH solution were each supplied and mixed in a micromixer, and then supplied to an electrochemical reaction section and passed through to perform the FDCA conversion reaction.

[0089] The product discharged from the electrochemical reaction unit was collected and analyzed using High-Performance Liquid Chromatograph, and the HMF conversion rate and FDCA yield were calculated using the method described above.

[0090] The size of the oxidation electrode and the reduction electrode is 100 cm each. 2The experimental conditions and results for each experiment using a phosphorus reactor are summarized in Table 2 below.

[0092] No. HMF concentration (wt%) KOH concentration (M) Applied voltage (V) Current (A) Flow rate (mL / min) Time of stay (min) HMF Conversion Rate (%) FDCA Yield (%) Example 1 1.2 1.0 2.0 7.0 1.0 2.0 99.0 95.8 Example 2 1.2 1.0 2.2 10.0 1.0 2.0 99.8 99.3 Example 3 1.2 1.0 2.2 10.0 2.0 1.0 99.4 97.0 Example 4 1.2 1.0 2.4 10.0 0.5 4.0 99.9 99.2 Example 5 0.6 1.0 2.2 6.5 1.0 2.0 99.6 98.0 Example 6 1.2 1.0 2.6 20.0 1.0 2.0 99.6 97.8 Comparative Example 1 0.2 1.0 2.0 4.7 2.0 1.0 91.7 84.1 Comparative Example 2 0.6 1.0 2.0 2.0 1.0 2.0 98.8 90.2 Comparative Example 3 0.6 1.0 2.0 2.0 2.0 1.0 87.1 79.0 Comparative Example 5 1.2 1.0 1.6 0.5 1.0 2.0 98.7 92.6 Comparative Example 6 2.5 1.0 2.0 3.5 1.0 2.0 99.3 93.5 Comparative Example 7 2.5 1.0 2.2 3.6 1.0 2.0 99.1 83.7 Comparative Example 8 2.5 1.0 2.4 3.8 1.0 2.0 97.3 72.7 Comparative Example 9 1.2 1.0 2.2 10.0 4.0 0.5 98.0 95.3 Comparative Example 10 1.2 1.0 2.2 10.0 10 0.2 85.2 72.7 Comparative Example 11 1.2 1.0 2.2 10.0 20 0.1 65.5 53.3 Comparative Example 12 1.2 1.0 2.2 10.0 40 0.05 56.7 42.1

[0094] Referring to Table 2 above, in the case of Examples 1 to 6, where the residence time of the reactant in the electrochemical reaction section is 1 minute to 5 minutes, the concentration of the raw material HMF is in the range of 0.5 wt% to 2.0 wt%, and the applied power output is in the range of 10 W to 60 W, it can be confirmed that the conversion rate of the raw material HMF is 99% or higher and the FDCA yield is 95% or higher.

[0096] The present invention is not limited to the above embodiments and can be manufactured in various different forms, and those skilled in the art will understand that the invention can be implemented in other specific forms without changing the technical concept or essential features of the invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. Explanation of the symbols

[0098] 100: Raw Material Supply Unit 110: HMF supply unit 120: Base supply unit 200: Micro-mixing section 300: Electrochemical reaction unit 400: Storage section 500: Power supply unit 331: Oxidation electrode (anode) 332: Reduction electrode (cathode) 320: Electrode path 321: Oxidation electrode flow path 322: Reduction electrode flow path 340: Membrane 341: 1st Plate 342: Second Play 311, 312: End plate 351, 352: Bronze (brass) plates

Claims

Claim 1 A raw material supply unit that supplies an aqueous solution of 5-hydroxymethylfurfural and an aqueous solution of a base, respectively; a micro-mixing unit that mixes the aqueous solution of 5-hydroxymethylfurfural (HMF) and the aqueous solution of a base, respectively supplied from the raw material supply unit, to form a raw material mixture; an electrochemical reaction unit that synthesizes 2,5-furandicarboxylic acid by passing the raw material mixture introduced from the mixing unit in a single pass; and a product storage unit that stores a product discharged from the electrochemical reaction unit; wherein the electrochemical reaction unit comprises: a first electrode plate and a second electrode plate positioned facing each other; a membrane positioned between the first electrode plate and the second electrode plate; an oxidation electrode and a reduction electrode positioned facing each other on both sides of the membrane; and an oxidation electrode flow path positioned between the first electrode plate and the oxidation electrode. A continuous manufacturing system for 2,5-furandicarboxylic acid, comprising: a reduction electrode channel located between the second electrode plate and the reduction electrode; wherein the 5-hydroxymethylfurfural (HMF) aqueous solution and the base aqueous solution are supplied at a flow rate in the range of 0.5 mL / min to 2 mL / min, the voltage applied to the electrochemical reaction unit is 2.0V to 3.0V, the time for the raw material mixture to be supplied to the electrochemical reaction unit and pass through in a single pass is in the range of 1 minute to 5 minutes, the oxidation electrode channel and the reduction electrode channel are plates in the range of 0.5 cm to 1 cm in thickness with a hole formed in the center, the oxidation electrode channel is a grid-type channel with a grid formed therein, and the reduction electrode channel is a bulk-type channel without a grid formed therein. Claim 2 A continuous manufacturing system for 2,5-furandicarboxylic acid, wherein, in claim 1, the grid-type flow path is a lattice-type flow path in which a straight grid is formed or a zigzag-type flow path in which a zigzag grid is formed. Claim 3 A continuous manufacturing system for 2,5-furandicarboxylic acid, wherein the grid-type flow path is a lattice-type flow path in which a straight grid is formed. Claim 4 The method comprises the steps of: supplying an aqueous solution of 5-hydroxymethylfurfural (HMF) and an aqueous solution of a base to a micro-mixing section, respectively; mixing the supplied aqueous solution of 5-hydroxymethylfurfural (HMF) and the aqueous solution of the base in the micro-mixing section to form a raw material mixture; and supplying the raw material mixture to an electrochemical reaction section to synthesize 2,5-furandicarboxylic acid while passing through in a single pass; wherein the electrochemical reaction section comprises: a first electrode plate and a second electrode plate positioned facing each other; a membrane positioned between the first electrode plate and the second electrode plate; an oxidation electrode and a reduction electrode positioned facing each other on both sides of the membrane; and an oxidation electrode flow path positioned between the first electrode plate and the oxidation electrode. A method for the continuous production of 5-furandicarboxylic acid (2,5-furandicarboxylic acid), comprising: a reduction electrode channel located between the second electrode plate and the reduction electrode; wherein the 5-hydroxymethylfurfural (HMF) aqueous solution and the base aqueous solution are supplied at a flow rate in the range of 0.5 mL / min to 2 mL / min, the voltage applied to the electrochemical reaction unit is 2.0V to 3.0V, the time for the raw material mixture to be supplied to the electrochemical reaction unit and pass through in a single pass is in the range of 1 minute to 5 minutes, the oxidation electrode channel and the reduction electrode channel are plates in the range of 0.5 cm to 1 cm in thickness with a hole formed in the center, the oxidation electrode channel is a grid-type channel with a grid formed therein, and the reduction electrode channel is a bulk-type channel without a grid formed therein. Claim 5 A method for the continuous production of 2,5-furandicarboxylic acid, wherein, in paragraph 4, the grid-type flow path is a lattice-type flow path in which a straight grid is formed or a zigzag-type flow path in which a zigzag grid is formed. Claim 6 A method for the continuous production of 2,5-furandicarboxylic acid, wherein, in paragraph 4, the grid-type flow path is a lattice-type flow path in which a straight grid is formed. Claim 7 delete Claim 8 A continuous method for producing 2,5-furandicarboxylic acid, wherein, in the step of supplying the aqueous solution of 5-hydroxymethylfurfural (HMF) and the aqueous solution of a base to a micro-mixing unit, the ratio of the flow rate of the aqueous solution of 5-hydroxymethylfurfural (HMF) to the flow rate of the aqueous solution of the base (5-hydroxymethylfurfural (HMF) flow rate : aqueous solution of the base flow rate) is in the range of 1:0.5 to 1:

2. Claim 9 delete Claim 10 A continuous method for producing 2,5-furandicarboxylic acid, wherein, in the step of supplying the aqueous solution of 5-hydroxymethylfurfural (HMF) and the aqueous solution of a base to a micro-mixing unit, the concentration of the aqueous solution of 5-hydroxymethylfurfural (HMF) is in the range of 0.5 wt% to 2.0 wt%. Claim 11 A continuous method for producing 2,5-furandicarboxylic acid, wherein, in the step of mixing the supplied aqueous solution of 5-hydroxymethylfurfural (HMF) and the aqueous solution of a base in a micro-mixing section to form a raw material mixture, the residence time of the aqueous solution of 5-hydroxymethylfurfural (HMF) and the aqueous solution of the base in the micro-mixing section is in the range of 0.5 seconds to 10 seconds.

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