KR20190083546A - Electrochemical hydrogenation reactor and method of hydrogenation using the same - Google Patents

Abstract

An electrochemical hydrogenation reactor of the present invention is provided with a positive electrode chamber and a negative electrode chamber on each side of a solid polymer electrolyte membrane. Hydrogen is supplied to the positive electrode chamber, and unsaturated organic compounds are supplied to the negative electrode chamber, and the hydrogen is decomposed into protons and electrons in the negative electrode chamber, and then moved to the negative electrode chamber to react with the unsaturated organic compound to produce a saturated organic compound.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochemical hydrogenation reactor and a method for producing the hydrogenation reactor using the same,

The present invention relates to an electrochemical hydrogenation reactor, and more particularly, to an electrochemical hydrogenation reactor in which hydrogen is decomposed into protons and electrons in an anode chamber and then moved to a cathode chamber to react with an unsaturated organic compound to produce a saturated organic compound . The present invention also relates to a method for producing a hydride using the above-described electrochemical hydrogenation reactor.

New and renewable energy is actively introduced for the purpose of CO ₂ reduction at home and abroad. However, renewable energy such as wind power generation and photovoltaic power generation are irregular in electric power generation, and inconsistency between electric power demand and electric power generation is very problematic. As an alternative to this, it is possible to control instantaneous energy storage and output by a device such as a conventional battery, but it is difficult to apply because of a large cost due to seasonal factors (summer and winter) and long-distance energy transmission.

Therefore, an energy carrier capable of storing electric power obtained from these renewable energy for a long time or transporting it to a remote place is considered. Energy carriers include liquid hydrogen (or compressed hydrogen), ammonia (ammonia), and liquid organic hydrogen carriers (LOHC). At present, the hydrogen carrier has a disadvantage in that it requires a special tank for transportation and storage since it is a gas at room temperature and atmospheric pressure (low weight energy and low volume energy density). On the other hand, LOHC is liquid carrier at normal temperature and pressure, is similar to petroleum and has good physical properties, and is a hydrogen carrier that has advantages of easy transportation using existing infrastructure. Representative LOHCs include benzene, naphthalene, toluene, N-ethylcarbazole, and pyridine.

Chemical reaction methods and electrochemical synthesis methods have been proposed as methods for producing hydrides such as methylcyclohexane, which is a hydride of toluene, one of the LOHCs.

The chemical reaction method is a method of producing methylcyclohexane by reacting hydrogen and toluene produced by hydrotreatment using renewable energy in a hydrogenation reactor at high temperature and high pressure (Patent Document 1, Patent Document 2). The advantage of such a chemical reaction method is high utilization because it uses hydrogen produced by various methods such as reforming method or electrolysis method.

The electrochemical synthesis method is a method of directly adding hydrogen electrochemically. Unlike the chemical reaction method operated at a high temperature and a high pressure, it operates at room temperature and atmospheric pressure, has high efficiency, and is excellent in followability against stoppage of the apparatus.

In relation to the electrochemical synthesis method, Patent Document 3 discloses an electrolytic cell for reducing an organic compound having an unsaturated bond. Patent Literatures 4, 5, 6, and 7 disclose that hydrogen is obtained in the oxidation reaction of water and toluene and hydrogen And is generally disclosed in a reduction method of reacting. However, it is difficult to commercialize an electrolytic cell for producing a saturated hydrogenated organic compound by electrolyzing an unsaturated liquid organic compound using a conventional method.

On the other hand, in Patent Documents 4, 5, 6, and 7, water is supplied to the anode chamber to decompose water into hydrogen ions, electrons, and oxygen by the anode catalyst, and hydrogen ions move through the solid polymer electrolyte membrane to the cathode chamber , And the principle of supplying hydrogen by reacting with electrons moved through an external circuit is used (see Fig. 1 (A)).

However, Patent Documents 4, 5, 6 and 7 have problems in practical use due to the following reasons.

First, the oxygen and water supplied to the anode chamber are diffused into the cathode chamber, and the oxygen diffused into the cathode chamber reacts with the saturated hydrogenated organics produced in the cathode chamber to oxidize to produce byproducts. There is a problem of lowering.

Secondly, since it can be applied only by electrolysis of water, the electrolysis hydrogenation process can not be used for hydrogen or the like in the gas reforming reaction. In addition, it is not applicable to a conventional electrolysis process.

The low - temperature water electrolysis cell uses a membrane electrode assembly with a solid polymer electrolyte membrane and an electrode bonded together, and supplies hydrogen and oxygen to the anode as a raw material. Such a cell structure is presumed to be applicable to electrolytic cells of organic hydrides, but the components (eg, electrodes and supports) are optimized to provide a large amount of water as a raw material, so improvement is required for manufacturing LOHC Do.

In a low temperature type fuel cell, a membrane electrode assembly formed by bonding a solid polymer electrolyte membrane and an electrode is used, and hydrogen and oxygen are supplied to obtain electric power. Such a cell structure can also be applied to an electrolytic cell of an organic hydride, but the component is optimized to supply a gas raw material, and improvement is required for use of the LOHC.

Japanese Laid-Open Patent Application No. 2011-207641 Japanese Patent No. 4907210 PCT Publication No. 2012-091128 Korean National Publication No. 10-2017-0085591 Korea Publication No. 10-2017-0063694 Korea Publication No. 10-2013-0037649 Korea Publication No. 10-2017-0012199

Accordingly, the present invention has been developed in order to solve the problems of the prior art as described above, and it is an object of the present invention to provide an electric field generating apparatus, which is capable of generating electricity by reacting with an unsaturated organic compound, A chemical hydrogenation reactor and a method for producing a hydride using the same.

In order to achieve the above object, the present invention provides an electrochemical hydrogenation reactor comprising an anode chamber and a cathode chamber on both sides of a solid polymer electrolyte membrane, wherein hydrogen is supplied to the anode chamber, The hydrogen is decomposed into protons and electrons in the anode chamber and then moved to the cathode chamber to react with the unsaturated organic compound to generate a saturated organic compound.

According to the present invention, the unsaturated organic compound is toluene, and the saturated organic compound is methylcyclohexane.

In addition, according to the present invention, a reaction layer and a diffusion layer, in which an electrochemical oxidation reaction and a reduction reaction are performed, are sequentially formed on both sides of the solid polymer electrolyte membrane to form a membrane electrode assembly.

Further, according to the present invention, the solid polymer electrolyte membrane is a material of a fluorine-based polymer membrane type or a hydrocarbon-based polymer membrane type and has a thickness of 5 to 300 μm.

According to the present invention, the reaction layer includes a catalyst and a carrier for supporting the catalyst to increase the reaction surface area of the catalyst, wherein the catalyst has a particle diameter of 0.001 to 0.1 탆, and the particle diameter of the carrier is 10 To 1,000 nm.

Further, according to the present invention, the diffusion layer is made of carbon or a metal, and has a thickness of 0.1 to 2 mm and an aperture ratio of 30 to 70%.

In order to accomplish the above object, the present invention provides a method for producing a hydride, wherein a saturated organic compound is produced using the electrochemical hydrogenation reactor configured as described above.

Further, according to the present invention, the purity of the supplied hydrogen is 90% or more and the relative humidity is 10% or more.

According to the present invention, the supplied current is 0.01 A / cm ² to 2.0 A / cm ² per unit area, and the operating temperature is 10 ° C to 100 ° C.

Also, according to the present invention, the pressure of the supplied hydrogen is 0.1 bar to 350 bar.

In this invention, hydrogen is decomposed into protons and electrons in an anode chamber and then transferred to a cathode chamber to react with an unsaturated organic compound to produce a saturated organic compound. In the hydrogenation reaction, electricity which can be operated at room temperature and atmospheric pressure Since the chemical method is used, there is an advantage in that the operationality at the time of operation and stop of operation is excellent.

Further, unlike the method in which water is electrolyzed at the anode and used for hydrogenation at the cathode, since the method uses hydrogen at the anode and hydrogenation at the cathode, it is possible to operate at a low power and dramatically reduce the operation cost There are advantages.

Further, since the present invention uses hydrogen for electrochemical reactions, it is possible to use hydrogen obtained irrespective of the hydrogen production method (the reforming method or the electrolysis solution method).

1 is a conceptual diagram of an electrochemical hydrogenation reactor according to the prior art and the present invention,
2 is a structural view of a membrane electrode assembly applied to the electrochemical hydrogenation reactor of the present invention,
3 is a structural view of an electrochemical cell used as an electrochemical hydrogenation reactor of the present invention,
4 is a structural view of an electrochemical stack used as an electrochemical hydrogenation reactor of the present invention,
FIGS. 5 and 6 are graphs of voltage-current density and hydrogenation for the comparative examples and the embodiments tested by applying the electrochemical hydrogenation reactor according to the prior art and the present invention, respectively.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of an electrochemical hydrogenation reactor and a method for producing a hydride using the same according to the present invention will be described in detail with reference to the accompanying drawings.

Hereinafter, in this embodiment, a method of reducing methylcyclohexane (MCH) as a saturated organic compound with toluene (TL) as an unsaturated organic compound will be described as an example.

FIG. 1 (a) is a conceptual view of an electrochemical hydrogenation reactor according to the prior art (Patent Documents 4 to 7), and FIG. 1 (b) is a conceptual diagram of an electrochemical hydrogenation reactor according to the present invention.

As shown in FIG. 1, the electrochemical hydrogenation reactor is composed of anodes 110 and 140, solid polymer electrolyte membranes 120 and 150, and cathodes 130 and 160.

Conventionally, water (H ₂ O) is supplied to the anode chamber as shown in FIG. 1 (a), and water is decomposed into oxygen, proton and electrons in the anode 110. At this time, the anode electrode reaction is a reaction in which water is decomposed. Theoretically, the anode electrode reaction is operated at about 1.9 V due to the voltage of 1.23 V, usually the catalyst overvoltage.

1 ( _b ), hydrogen (H ₂ ) is supplied to the anode 140, hydrogen is decomposed into protons and electrons, and the electrons are transferred to the cathode 160, So that the reaction takes place. That is, the present invention is configured so that a hydrogen reaction (oxidation reaction) occurs at the anode and a reaction (hydrogenation reaction, reduction reaction) occurs at the anode. At this time, the theoretical electrode reaction is 0V, and the actual operation is about 0.4V in consideration of the overvoltage and the like, so that the operation energy can be drastically reduced in comparison with the operation method of the conventional technology.

In addition, the electrochemical hydrogenation reactor of the present invention has the following other features in comparison with the prior art. FIG Conventionally decomposes in water (H ₂ O) The electrodes in the anode 110 is decomposed into oxygen, protons, electrons, these oxygen, water (H ₂ O) and from the anode chamber, as shown in (a) of the first ( O ₂ ) passes through the solid polyelectrolyte membrane 120, water is an impurity of the cathode product, and oxygen reacts with toluene (TL) or methylcyclohexane (MCH) to decompose these substances, I have a problem. However, since the present invention does not diffuse impurities in the reaction of supplying hydrogen to the anode chamber, a high-efficiency product can be obtained.

This invention is also advantageous in terms of electrochemical reaction stability. If reactants such as H ₂ and O ₂ react in the same anode chamber and reach the concentration range of 4% ~ 75% which is the explosion limit of hydrogen, explosion reaction may occur due to internal ignition sources such as sparks. However, this invention has an advantage of high stability in handling hydrogen because H ₂ gas close to 100% of high purity is supplied to the anode chamber and reacted. On the other hand, LOHC species as reactants in the cathode chamber are known as stable compounds which do not cause explosion or combustion reaction within the reaction range.

2 is a structural view of a membrane electrode assembly 200 applied to the electrochemical hydrogenation reactor of the present invention.

As shown in FIG. 2, a membrane electrode assembly (hereinafter referred to as "MEA") is the most important component of the electrochemical cell. The MEA may be one in which the reaction layers 204 and 208 where an electrochemical oxidation reaction and a reduction reaction take place are integrated with a solid polymer electrolyte membrane 206 (hereinafter referred to as "PEM "), Means that the diffusion layers 202 and 210 are integrated with the reaction layers 204 and 208 and the PEM 206 in the reduction reaction.

Hereinafter, the first electrochemical reaction layer 204 where oxidation occurs and the second electrochemical reaction layer 208 where the reduction reaction takes place will be described. When an electric current is applied to the first electrochemical reaction layer 204, Reduction reaction occurs at the same time.

When hydrogen (H ₂ ) is supplied to the first electrochemical reaction layer 204 through the first diffusion layer 202, hydrogen is supplied to the first electrochemical catalyst 212 (oxidation catalyst, cathode active material, or hydrogen gas decomposition electrode) To electrons (e ^- ) and hydrogen ions (H ⁺ ) (proton) (see Scheme 1). At this time, the hydrogen ion H ⁺ passes through the PEM 206 by the electric field to move to the second electrochemical catalyst 216 (the reducing catalyst, the anode active material, or the hydrogen gas generating electrode), and the electron e ^- Is transferred from the first electrochemical catalyst 212 to the second electrochemical catalyst 216 via the first diffusion layer 202, the external circuit (not shown), and the second diffusion layer 210.

In the second electrochemical catalyst 216, hydrogen ions (H ⁺ ) and electrons (e ^- ) migrated in the first electrochemical catalyst 212 and toluene (TL in FIG. 2) supplied from the outside react with each other to form methylcyclohexane (MCH) is generated (see Scheme 2).

The electrochemical reactions occurring in the first electrochemical catalyst 212 and the second electrochemical catalyst 216 are expressed by the following reaction formulas 1, 2 and 3, respectively.

[Reaction Scheme 1]

3H ₂ ? 6H ⁺ + 6e ^- (anode)

[Reaction Scheme 2]

TL (toluene) + 6H ⁺ + 6e ^- → MCH (methylcyclohexane)

[Reaction Scheme 3]

3H ₂ + TL (toluene) → MCH (methylcyclohexane)

Hereinafter, components applied to the electrochemical cell of the present invention will be described.

The PEM 206 has a sulfonic acid ion exchanger which is excellent in oxidative reaction and long-term use stability against organic compounds (TL and MCH) and excellent in hydrogen ion (proton or H ⁺ ) conductivity, It is necessary to be able to suppress mixing or diffusion of the actual substance (TL, MCH). For example, Nafion (registered trademark) of DuPont, Flemion (registered trademark) of Asahi Glass Co., Ltd., Aciplex (Ashiflex, registered trademark) of Asahi Kasei Co., And Gore Select (registered trademark) may be used. Examples of hydrocarbon-based polymer membranes include sulfonated polyether ketone, sulfonated polyether sulfone, sulfonated polyether ether sulfone, sulfonated polysulfide, sulfonated polyphenylene .

The thickness of the PEM is preferably 5 to 300 mu m, particularly preferably 20 to 170 mu m. If the thickness of the PEM is less than 5 mu m, cross leakage (migration of the product from the cathode chamber to the anode chamber) tends to occur. If the thickness of the PEM is greater than 300 mu m, proton resistance increases, not.

The first and second electrochemical catalysts 212 and 216 may be formed of any one of platinum group metals such as platinum, palladium, ruthenium, iridium, rhodium and osmium as well as iron, lead, copper, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium, Aluminum, etc., alloys thereof, oxides, double oxides and the like can be used. In order to enable the electrode reaction to be efficiently and stably used for a long period of time with excellent electrode reactivity, platinum, palladium, rhodium, ruthenium and iridium Or a metal or an oxide selected from the group consisting of a metal and an oxide.

If the particle diameter of the first and second electrochemical catalysts 212 and 216 is too large, the activity of the catalyst is deteriorated. If the particle size is too small, the stability of the catalyst is lowered. Therefore, the particle size is preferably 0.001 to 0.1 mu m, Is 1 to 50 nm.

As the carrier (or carrier) 214 or 218 for supporting the catalyst in order to enlarge the reaction surface area of the catalyst, an electron conductive particle type is preferable and a metal oxide including titanium, carbon black, graphite, graphite, activated carbon, carbon It is preferable to use fibers, carbon nanotubes, and fullerene. If the diameter of the support is too small, it is difficult to form an electron conductive pathway of the generated electron. If the diameter is too large, the gas diffusion property to the electrode catalyst layer formed on the support may decrease, Since the utilization factor is lowered, the particle diameter is preferably 10 to 1,000 nm, more preferably 10 to 100 nm.

The first and second diffusion layers 202 and 210 may be made of a carbon material or a metal material. The first and second diffusion layers 202 and 210 may be made of cloth, paper, sintered fiber, or the like. The first diffusion layer 202 is preferably a carbon-based material having a surface coated with a hydrophobic material such as polytetrafluoroethylene (PTFE) and having excellent corrosion resistance against hydrogen in order to smooth the gas fluid flow. The second diffusion layer 210 is not limited to the material. It is preferable that the first and second diffusion layers 202 and 210 have a thickness of 0.1 to 2 mm and an aperture ratio of about 30 to 70% in order to promote gas diffusion.

The manufacturing process of the MEA 200 includes a catalyst synthesis process, a catalyst ink production process, a catalyst ink transfer process, and a thermo compression process (a process of forming the transferred catalyst ink on the PEM or the diffusion layer).

In the catalyst synthesis step, commercially available particles may be used for the catalyst and the carrier, but they may be synthesized according to known methods and used. For example, the synthesis may employ a wet method in which a reducing agent is mixed with an aqueous solution that dissolves catalyst metal ions, or a dry method such as a vapor deposition sputter may be employed.

The catalyst ink manufacturing process is a process in which the catalysts 212 and 216 and the carriers 214 and 218 obtained in the catalyst synthesis process are formed so that the catalyst can be easily formed in the PEM 206 or the diffusion layers 202 and 210, Ionomer, Nafion (registered trademark) dispersion.

The catalytic ink for the first electrochemical reaction layer 204 includes a first electrochemical catalyst 212, a carrier 214, a polymer electrolyte ionomer, a solvent and a hydrophobic resin, and the second electrochemical reaction layer 208 The catalyst ink includes a second electrochemical catalyst 216, a carrier 218, a polymer electrolyte ionomer, a solvent, and a hydrophobic resin. The hydrophobic resin (fluorine-based polymer component) is a gas-permeable material, and the particle diameter of the powder is preferably 0.005 to 10 mu m. In the case of the anode catalyst (the first electrochemical catalyst 212) used in the first electrochemical reaction layer 204 or the reduction catalyst (the second electrochemical catalyst 216) used in the hydrogenation reaction of toluene, Is not less than 0.01 mg / cm ^{2 and not} more than 10 mg / cm ² . This is because the reaction efficiency is lowered when the concentration is less than 0.01 mg / cm ² , and the facility cost of the electrochemical reaction cell is increased when the concentration exceeds 10 mg / cm ² .

The catalyst ink transferring step is a step of transferring the catalyst ink prepared under the above conditions to a transfer paper (e.g., Teflon sheet or polyimide sheet) to leave the main catalyst component and remove the solvent component. This transfer process may be omitted if the catalyst ink is sprayed directly onto the PEM or the diffusion layer.

The thermocompression process is a process of transferring a catalyst layer formed on a transfer sheet to a film or a diffusion layer through thermal and pressure bonding. As the processing apparatus, a known apparatus such as a hot press or a hot roller can be used. The pressing conditions are preferably room temperature to 360 DEG C and a pressure of 0.1 to 5 MPa.

FIG. 3 is an electrochemical cell used as an electrochemical hydrogenation reactor of the present invention, which is a structural view of an electrochemical cell 300 having a membrane electrode assembly shown in FIG. 2, and FIG. 4 is an electrochemical hydrogenation reactor 3 is a structural view of an electrochemical stack 400 in which a plurality of unit electrochemical cells shown in Fig. 3 are stacked. Fig.

3, the electrochemical cell 300 includes a first end plate 302, a first insulating plate 304, a first current supply plate 306, a first electrochemical reaction chamber frame The first electrochemical reaction chamber 310, the MEA 200, the second electrochemical reaction chamber 312, the second electrochemical reaction chamber frame 314, the second current supply plate 316, A second insulation plate 318 and a second end plate 320. The DC power supply unit includes a DC power supply unit 324 for supplying current to the electrochemical cell.

(See (a) of FIG. 3) for supplying and discharging respective reactants or products is formed in the first electrochemical reaction chamber 310 (anode chamber) and the second electrochemical reaction chamber 312 (cathode chamber) And has a function of mechanically supporting the MEA 200 and an electrical connection function with the adjacent unit cells.

The first end plate 302 and the second end plate 320 provide a passage (not shown) function of bolt / nut fastening holes (not shown), reactants and products for assembling the unit electrochemical cell, The first current plate 304 and the second insulation plate 318 are electrically connected to each other between the first end plate 302 and the first current supply plate 306 and between the second end plate 320 and the second current supply plate 316, And the first current supply plate 306 and the second current supply plate 316 are connected to the power conversion device 324 to supply the required current to the electrochemical cell 300.

In the case where the first electrochemical catalyst 212 is located in the first electrochemical reaction chamber 310 and oxidation reaction occurs, it becomes a space for the movement of hydrogen as a reactant, In the second electrochemical reaction chamber 312 located on the opposite side of the chemical reaction chamber 310, toluene is supplied and a space for externally discharging methylcyclohexane by the reduction reaction is provided.

The first electrochemical reaction chamber 310 is shielded from the outside by the first electrochemical reaction chamber frame 308 and the second electrochemical reaction chamber 312 is blocked by the second electrochemical reaction chamber frame 314 from the outside . A gasket (or packing) 322 is provided between the MEA 200 and the first electrochemical reaction chamber frame 308 and the second electrochemical reaction chamber frame 314 to prevent external leakage of reactants and products .

The first electrochemical reaction chamber frame 308, the second electrochemical reaction chamber frame 314 and the gasket 322 among the constituent elements of the electrochemical cell 300 are connected through an electrochemical cell to the inlet (Shown by a dotted line in FIG. 3 (A)) is formed in the first electrochemical reaction chamber frame 308 and the second electrochemical reaction chamber frame 314. The flow path

In order to obtain a desired amount of product, a plurality of unit electrochemical cells are required. At this time, an aggregate of two or more stacked electrochemical cells can be formed into an electrochemical stack 400 (see FIG. 4).

The operation method of the electrochemical cell is described below.

(Hydrogen) is supplied to the lower portion of the first electrochemical reaction chamber 310 of the electrochemical cell 300 and the reactant 2 (toluene) is supplied to the second electrochemical reaction chamber 312 as in the example of FIG. As shown in FIG. At this time, the purity of the supplied hydrogen is not limited, but preferably 90% or more. The supply relative humidity of hydrogen is 10% or more. This is because when the concentration is less than 10%, the proton conductivity of the PEM is lowered and the performance is lowered.

The current supplied to the first electrochemical reaction layer 204 and the second electrochemical reaction layer 208 is preferably from 0.01 A / cm ² to 2.0 A / cm ² per unit area. This is because there is a problem that the area of the electrolysis reaction is increased at 0.01 A / cm < ² > or below, which increases the investment cost. When the cell density exceeds 2.0 A / cm < ² >, the durability of the components of the electrolytic cell .

The operating temperature of the electrolytic cell is suitably from 10 캜 to 100 캜, more preferably from 50 캜 to 80 캜. This is because the proton transfer resistance is increased at a temperature of less than 10 DEG C, and the durability of the electrolytic cell component becomes a problem at more than 100 DEG C.

The hydrogen pressure supplied to the electrolysis cell is suitably from 0.1 bar to 350 bar. This is because the electrolysis efficiency is reduced due to the reverse diffusion of the cathode chamber when the pressure is less than 0.1 bar, and the durability of the components of the electrolysis cell is problematic when the pressure exceeds 350 bar.

<Examples>

Hereinafter, embodiments of the present invention will be described in detail, but these embodiments are merely examples for explaining the present invention, and the present invention is not limited at all.

Example 1 Hydrogenation of Toluene (Product Methyl Cyclohexane)

MEA (200) to Nafion 117 perfluorocarbon sulfonic acid-based film (thickness 170) with a first electrochemical reaction layer 204 (anode catalyst, Pt / C carrier (Tanaka Precious metals industry) 0.5mg / cm ² and the second electrochemical reaction layer 208 (anode catalyst, Pt-Ru / C carrier (Tanaka precious metals industry)) 0.5mg / cm ^2, a first diffusion layer (202, carbon paper), and the second diffusion layer (210, sintered titanium fiber opening ratio 80 %, Thickness 0.2 mm, manufactured by Deutsche Industries, Germany). The area (electrochemical reaction area) of the MEA 200 was 25 cm ² .

Hydrogen having a relative humidity of 100% was supplied to the lower portion of the first electrochemical reaction chamber (anode chamber) of the electrochemical cell 300, and toluene was supplied to the lower portion of the second electrochemical reaction chamber (cathode chamber) Supply. The current supplied to the electrochemical cell 300 was 1 A / cm ² , the temperature was 80 ° C, and the hydrogen supply pressure was 5 bar.

The performance was evaluated by evaluating the voltage-current performance of the electrochemical cell (Example 1 in FIG. 4) and by measuring the weight change rate of the product methylcyclohexane (Example 1 in FIG. 5).

Example 2 N-ethylcarbazole hydrogenation (product C ₁₄ H ₂₅ N (3-butyladamantan-1-amine))

The MEA was constructed in the same manner as the MEA 200 of Example 1.

Hydrogen having a relative humidity of 100% is supplied to the lower portion of the first electrochemical reaction chamber 310 (anode chamber) of the electrochemical cell 300, and N- Ethylcarbazole (N-ethylcarbazole). The current supplied to the electrochemical cell 300, the temperature, and the hydrogen supply pressure were the same as those in Example 1.

Performance is the voltage of the electrochemical cells, the current performance evaluation (the embodiment of Figure 4, Example 2), and the product, _{C 14 H 25 N (3-} butyladamantan-1-amine) by weight of the rate of change of (the embodiment of Figure 5 2) And the hydrogenation amount was measured.

&Lt; Comparative Example 1 > Hydrogenation of toluene (product methylcyclohexane)

Water is supplied to the lower part of the first electrochemical reaction chamber 310 (anode chamber) of the electrochemical cell 300 using the MEA 200 of the first embodiment, and the second electrochemical reaction chamber 312 (cathode chamber) Toluene was fed to the bottom of the reactor.

The current supplied to the electrochemical cell 300 was 1 A / cm ² , the temperature was 80 ° C, and the hydrogen supply pressure was 5 bar.

The performance was evaluated by evaluating the voltage-current performance of the electrochemical cell (Comparative Example 1 in Fig. 4) and by measuring the weight change rate of methylcyclohexane (Comparative Example 1 in Fig. 5) as a product.

<Experimental Results>

It was confirmed that the hydrochemical hydrogenation reactor according to the present invention remarkably improved the hydrogenation amount and the electricity consumption amount. Further, it was confirmed that the electrochemical hydrogenation reactor according to the present invention can be effectively used for the hydrogenation reaction irrespective of the substance to be hydrogenated.

The present invention is not limited to the above-described embodiments, and it is possible to add various modifications such as design changes based on knowledge of those skilled in the art, and embodiments in which such modifications are added are also included in the scope of the present invention.

110, 140: anode 120, 150: solid polymer electrolyte membrane
130, 160: cathode

Claims (10)

An anode chamber and a cathode chamber on both sides of the solid polymer electrolyte membrane,
Wherein hydrogen is supplied to the anode chamber and an unsaturated organic compound is supplied to the cathode chamber so that the hydrogen is decomposed into protons and electrons in the anode chamber and moves to the cathode chamber to react with the unsaturated organic compound to form a saturated organic compound Wherein the hydrocracking reaction is carried out in the presence of a catalyst. The method according to claim 1,
Wherein the unsaturated organic compound is toluene, and the saturated organic compound is methylcyclohexane. The method according to claim 1,
Wherein a membrane electrode assembly is formed by sequentially forming a reaction layer and a diffusion layer on both sides of the solid polymer electrolyte membrane where an electrochemical oxidation reaction and a reduction reaction occur. The method of claim 3,
Wherein the solid polymer electrolyte membrane is a fluorine-based polymer membrane type or a hydrocarbon-based polymer membrane type material and has a thickness of 5 to 300 탆. The method of claim 3,
Wherein the reaction layer comprises a catalyst and a carrier for supporting the catalyst to increase the reaction surface area of the catalyst,
Wherein the catalyst has a particle diameter of 0.001 to 0.1 mu m and a particle diameter of the carrier is 10 to 1,000 nm. The method of claim 3,
Wherein the diffusion layer is made of carbon or metal and has a thickness of 0.1 to 2 mm and an opening ratio of 30 to 70%. A method for producing a hydride, characterized in that a saturated organic compound is produced using the electrochemical hydrogenation reactor according to any one of claims 1 to 6. The method of claim 7,
Wherein the purity of the supplied hydrogen is 90% or more and the relative humidity is 10% or more. The method of claim 7,
Wherein the supplied current is 0.01 A / cm ² to 2.0 A / cm ² per unit area, and the operating temperature is 10 ° C to 100 ° C. The method of claim 7,
Wherein the pressure of the supplied hydrogen is 0.1 bar to 350 bar.

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