KR101695622B1 - Method for electrochemical ammonia synthesis using alcohol-based electrolyte - Google Patents

Method for electrochemical ammonia synthesis using alcohol-based electrolyte Download PDF

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KR101695622B1
KR101695622B1 KR1020150157383A KR20150157383A KR101695622B1 KR 101695622 B1 KR101695622 B1 KR 101695622B1 KR 1020150157383 A KR1020150157383 A KR 1020150157383A KR 20150157383 A KR20150157383 A KR 20150157383A KR 101695622 B1 KR101695622 B1 KR 101695622B1
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electrode
ammonia
alcohol
reducing
reducing electrode
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윤형철
유충열
김종남
한상섭
한종인
김귀용
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한국에너지기술연구원
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C25B11/035—
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features

Abstract

The present invention relates to an ammonia synthesis method and, more specifically, to an electrochemical ammonia synthesis method using an alcohol-based electrolyte. According to the ammonia synthesis method, an alcohol-based electrolyte is used, so solubility of nitrogen participating in a reaction is increased. Moreover, production yield of ammonia and current efficiency are improved.

Description

TECHNICAL FIELD The present invention relates to an electrochemical ammonia synthesis method using an alcohol-based electrolyte,

The present invention relates to a method for synthesizing ammonia, and more particularly, to a method for synthesizing electrochemical ammonia using an alcohol-based electrolyte.

Ammonia is a hydrogen and nitrogen compound with the formula NH 3 and exists in a gaseous state with a stimulant odor at room temperature. It is contained in a small amount in the atmosphere, is contained in a small amount in natural water, and may be generated in the process of decomposing nitrogen organic matter of bacteria in the soil. Ammonia is used as a raw material for various chemical industries, for the production of ammonia water, and as a solvent for ionic substances.

Recently, the frequency of use of renewable energy has been increasing to meet the depletion of petroleum resources and the achievement of the greenhouse reduction target in response to climate change. New and renewable energy has a problem of local ubiquity and intermittency, and storage and transportation means are essential. As an energy carrier to solve these problems, ammonia has attracted attention as well as hydrogen. Although there is a limit to the storage and transportation of hydrogen, since ammonia is in a liquid state at a room temperature of 8.5 atm, it is advantageous in that it is easier to store and transport than hydrogen.

The most common method of producing ammonia is carried out at high pressure (~ 200 bar), high temperature (~ 400 ° C) in the presence of iron or ruthenium catalyst in the Harber-Bosch process synthesized from hydrogen and nitrogen, This reaction consumes an enormous amount of energy of about 34.4 GJ / ton NH 3 and has the problem of emitting a large amount of greenhouse gas of 1.8 ton CO2 / ton NH 3 due to the fossil fuel used for supplying this energy .

(Formula 1)

N 2 + 3H 2 - > 2NH 3 + 92.2 kJ

In order to overcome the problem of the Harbor-Bosch process, an electrochemical ammonia synthesis method using an ion conductive oxide electrolyte has been proposed, and an electrochemical ammonia synthesis method using electrolytes using water and nitrogen as raw materials has been actively studied (Marnellos et al). The electrolytic cell based on the water-based electrolyte in the electrochemical ammonia synthesis method is subjected to a series of processes as shown in the following Chemical Formula 2, wherein a reaction in which water is decomposed into hydrogen ions and electrons (2-1) And a reaction (2-2) in which electrons reduce nitrogen molecules to generate ammonia. The final product of this ammonia electrochemical synthesis is ammonia and oxygen only, so there is no carbon emission.

(2)

Oxide reaction: 3H 2 O → 6H + + 3 / 2O 2 + 6e - (2-1)

Reduced Polar Reaction: N 2 + 6H + + 6e - ? 2NH 3 (2-2)

In the electrochemical ammonia synthesis reaction, the main limiting reaction is the step of reducing the reducing polar phase of the nitrogen molecule to ammonia, which results from the strong triple bond of the nitrogen molecule. In the case of using water - based electrolyte, the reduction reaction is often a hydrogen generation reaction instead of the nitrogen reduction reaction. Indeed, current efficiency is known to be less than 1% when using a water-based system (R. Lan et al.).

European Patent No. 972855 relates to an ammonia synthesis apparatus, which discloses an ammonia synthesis apparatus for synthesizing ammonia by using a flat proton-conductive solid oxide as an electrolyte and applying an external current. However, the use of a solid oxide electrolyte requires a high-temperature operating condition, which is a temperature at which ammonia can be decomposed into hydrogen and nitrogen gas, which makes it difficult to obtain a high yield. In addition, there is a disadvantage in that a complicated step such as powder synthesis, sintering, and catalyst application must be performed during the production of an oxide electrolyte and a sealing material which requires a high temperature heat treatment must be used.

Therefore, there is a need for an energy-friendly ammonia synthesis method that has higher yield and lower manufacturing cost.

European Patent No. 972855

 Marnellos et al., &Quot; Ammonia Synthesis at Atmospheric Pressure ", Science, 98 (1998) 282  R. Lan et al., &Quot; Synthesis of ammonia directly from air and water at ambient temperature and pressure ", Scientific Reports, 3: 1145 (2013) 1

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide a method for synthesizing electrochemical ammonia using an alcohol-based electrolyte.

The present inventors have found that synthesis of ammonia by an electrochemical ammonia synthesis apparatus using an alcohol-based electrolyte improves production yield and current efficiency, and thus the present invention has been accomplished.

The present invention relates to a method for synthesizing electrochemical ammonia using an alcohol-based electrolyte, comprising the steps of: generating electrons and hydrogen ions at an oxidizing electrode portion including an oxidizing electrode and an oxidizing electrode; Passing the hydrogen ion through a cation conductive membrane which is in contact with the oxidation electrode and separates the oxidized electrode portion and the reducing electrode portion; The hydrogen ions having passed through the cation conductive membrane reach a reducing electrode portion including a reducing electrode liquid, a reducing electrode and a nitrogen supplying portion; And reducing the nitrogen molecules in the reducing electrode to produce ammonia, wherein the reducing electrode solution is an alcohol-based electrolyte, and the electrolyte is selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, lithium chloride, and lithium perchlorate And a monohydric alcohol having 1 to 8 carbon atoms, wherein the alcohol-based electrolyte is a mixture solution of at least one selected from the group consisting of the monohydric alcohol having 1 to 8 carbon atoms and the monohydric alcohol having 1 to 8 carbon atoms.

The oxidation electrode and the reducing electrode are porous metals and the metal is selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn Y, Zr, Nb, Mo, The present invention provides a method for synthesizing electrochemical ammonia using an alcohol-based electrolyte, which is at least one selected from the group consisting of Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt and Au. do.

The present invention also relates to a process for the production of electrochemical ammonia synthesis using an alcohol-based electrolyte, wherein the oxidant solution contains a hydrogen ion donor and the hydrogen ion donor is at least one selected from the group consisting of water, hydrogen gas, hydrogen sulfide, methane, ≪ / RTI >

The present invention also provides a method for synthesizing electrochemical ammonia using an alcohol-based electrolyte, wherein the nitrogen supply unit supplies nitrogen gas to the reduction electrode at a flow rate of 50 to 200 sccm.

The present invention also provides a method for synthesizing electrochemical ammonia using an alcohol-based electrolyte, wherein the alcohol is propan-2-ol.

The electrochemical ammonia synthesis method using the alcohol-based electrolyte of the present invention has an effect of improving the yield of ammonia production and the current efficiency by increasing the solubility of nitrogen involved in the reaction by using an electrolyte based on alcohol.

1 is a schematic view showing an electrochemical ammonia synthesis apparatus using an alcohol-based electrolyte according to an embodiment of the present invention.
FIG. 2 is a graph showing the amount of current, the amount of ammonia produced, and the current measured in the synthesis of ammonia by an electrochemical ammonia synthesizer using an alcohol-based electrolyte according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

In one aspect, the present invention provides a method for synthesizing electrochemical ammonia using an alcohol-based electrolyte, the method comprising the steps of: generating electrons and hydrogen ions at an oxidizing electrode comprising an oxidant electrode and an oxidizing electrode; Passing the hydrogen ion through a cation conductive membrane which is in contact with the oxidation electrode and separates the oxidized electrode portion and the reducing electrode portion; The hydrogen ions having passed through the cation conductive membrane reach a reducing electrode portion including a reducing electrode liquid, a reducing electrode and a nitrogen supplying portion; And reducing ions of hydrogen and electrons in the reducing electrode to produce ammonia, wherein the reducing electrode solution is an alcohol-based electrolyte, wherein the electrolyte is a primary alcohol having 1 to 20 carbon atoms or a primary alcohol having 1 to 20 carbon atoms Polyhydric alcohols; And a mixed solution of at least one selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, lithium chloride, lithium perchlorate, and the like, is an electrochemical ammonia synthesis method using an alcohol-based electrolyte.

The theoretical electrochemical potential (NH 2 + 6H + + 6e - → 2NH 3 ) in which ammonia is generated by the reaction of hydrogen ions and nitrogen generated during the electrolysis of water is 0.057 V compared to the standard hydrogen electrode potential (SHE) It is very similar to 0 V, the hydrogen reduction potential. Therefore, an electrolyte-based electrochemical ammonia synthesis method capable of generating a large amount of hydrogen ions is excellent in energy efficiency. However, in the electrochemical ammonia synthesis method using the aqueous electrolyte, hydrogen gas is generated when the hydrogen ion is reduced. That is, the ammonia synthesis reaction and the hydrogen gas generation reaction occur, and the ammonia synthesis yield is affected. Therefore, the present invention increases the solubility of ammonia by increasing the solubility of nitrogen by using the electrolyte of the reducing electrode as an alcohol base.

1 is a schematic view showing an ammonia synthesis apparatus using an alcohol-based electrolyte of the present invention. In the above synthesizing apparatus, the oxidizing electrode portion 10 and the reducing electrode portion 20 are partitioned by the cation conductive membrane 30, and the cation conductive membrane 30 is in contact with the oxidizing electrode 102. The oxidizing electrode unit 10 includes an oxidizing electrode 101 and an oxidizing electrode 102. The reducing electrode unit 20 includes a reducing electrode 202, a reducing electrode solution 201 and a nitrogen supplying unit 203, The electrode 102 and the reducing electrode 202 are electrically connected. In the nitrogen supply unit 203, nitrogen is supplied to the reducing electrode liquid 201, and the supplied nitrogen is reduced at the reducing electrode 202 by hydrogen ions and electrons and synthesized into ammonia. Since the ammonia synthesis method of the present invention can synthesize ammonia at room temperature and atmospheric pressure, it is more economical than a synthesis method requiring a high temperature condition such as a Harber-Bosch method or a synthesis method using a solid oxide electrolyte, which is a conventional synthesis method.

The cation conductive film 30 is positioned in contact with the oxidizing electrode 102 of the oxidizing electrode 10 and contacts the reducing electrode liquid 201 of the reducing electrode 20. And is made of a porous material capable of moving hydrogen ions, and the porosity thereof is preferably 10 to 50%. If the porosity of the cationic electrodepositable film is more than 50%, the electrolytic efficiency may decrease due to migration of the oxidant solution from the oxidized electrode portion to the reducing electrode portion. If the porosity is less than 10%, current conduction is difficult , And the migration rate of hydrogen ions is lowered. The cationic conductive membrane is a solid polymer electrolyte having a thickness of 50 to 200 μm and anions can not move along the inside thereof, while cationic hydrogen ions must be movable. The proton conductive membrane may be formed of an ion transport group such as sulfonic acid, carboxylic acid, and phosphoric acid so that cations can be selectively transferred to a polymer of a hydrocarbon or fluorocarbon type. phosphoric acidic groups, and in one embodiment, Nafion ( TM ).

The oxidized pole portion is a section where hydrogen ions are generated, and the hydrogen ion donor contained in the oxidized electrode solution is electrolyzed in the oxidized electrode to provide hydrogen ions. In one embodiment, the donor of the hydrogen ion is at least one member selected from the group consisting of water, hydrogen, hydrogen sulfide, methane and alcohol, and is preferably water. The above-mentioned oxidant electrode solution is an aqueous solution containing at least one ion-transferring material selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, lithium chloride and lithium perchlorate. Hydrogen ions generated by oxidizing hydrogen gas in the oxidizing electrode of the oxidizing electrode part pass through the cation conducting membrane and move to the reducing electrode part. At the reducing electrode of the reducing electrode, hydrogen ions and electrons are reduced to nitrogen and synthesized as ammonia, where the reducing electrode solution of the reducing electrode is an alcohol-based electrolyte. The reduction of the amount of alcohol to water makes it possible to increase the final ammonia synthesis yield by increasing the solubility of nitrogen to 10 to 50 times that of water, thereby decreasing the amount of current required for electrolysis and increasing the current efficiency. The alcohols used in the synthesis method of the present invention are monohydric alcohols having 1 to 8 carbon atoms such as methanol, ethanol, propan-2-ol, propan-2-ol, butan- Cyclohexanol, benzyl alcohol and menthol, and preferably propan-2-ol. The nitrogen is supplied from the nitrogen supply portion of the reducing electrode. In one embodiment, the reducing electrode solution of the reducing electrode includes at least one ion transferring material selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, lithium chloride and lithium perchlorate. In one embodiment, the nitrogen supply unit supplies nitrogen gas to the reduction electrode at a rate of 50 to 200 sccm. When the supply rate is less than 50 sccm, the efficiency of ammonia synthesis is decreased due to a low nitrogen supply rate in the reducing electrode. When the supply rate is more than 200 sccm, the reduction amount of the reducing electrode is increased.

The oxidizing electrode and the reducing electrode of the present invention are porous metals and the metal is selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn Y, Zr, Nb, Mo, Ru, An oxide or a nitride selected from the group consisting of Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt and Au. In the method for synthesizing ammonia according to the present invention, it is preferable to provide a tank for supplying the oxidizing electrode liquid and the reducing electrode liquid to the oxidizing electrode and the reducing electrode, respectively, and circulating the respective electrolytes. The tank is connected to the circulation line, and the electrolytic solution discharged from the oxidizing electrode and the reducing electrode is electrolyzed while circulating through the tank to each part.

All technical terms used in the present invention are used in the sense that they are generally understood by those of ordinary skill in the relevant field of the present invention unless otherwise defined. The contents of all publications referred to herein are incorporated herein by reference.

Hereinafter, embodiments are provided to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited to the following examples.

Example  1. Electrochemical ammonia synthesis using an alcohol-based electrolyte

In order to synthesize ammonia by using alcohol electrolyte, a 0.1 M lithium chloride aqueous solution was used as an oxidizing electrode solution. A platinum plate was used for the oxidizing electrode and porous nickel was used for the reducing electrode. The CMX of Neosepta Co., Ltd. was used as the cationic conductive membrane. An aqueous solution containing 0.1 M of lithium chloride as a comparative example was prepared. In Experimental Example 1 and Experimental Example 2, propan-2-ol Were prepared. A voltage of 1.5 V was applied to the reduction electrode of the comparative example at a rate of 100 sccm for electrolysis for 10 hours. While nitrogen was injected at a rate of 100 sccm into the reducing electrode of Experimental Example 1, In Experimental Example 2, 2.0 V voltage was applied while nitrogen was injected into the reducing electrode at a rate of 100 sccm, and electrolysis was performed for 10 hours each. The amount of current, the amount of ammonia produced, and the current efficiency of Comparative Example, Experimental Examples 1 and 2 were measured for 10 hours during which electrolysis was performed. The results are shown in Table 1 and FIG.

[Table 1]

Figure 112015109362472-pat00001

Referring to FIG. 2, when water was used as an electrolyte, current flowed higher than when propan-2-ol was used as an electrolyte. Propane-2-ol was used as the electrolyte, the current flow was lower in both the voltage of 1.5 V and 2.0 V than in the case of using water as the electrolyte. However, when the voltage of 1.5 V was applied to the synthesis of ammonia using propan-2-ol, the amount of ammonia synthesis was twice as much as that of water. Also, the efficiency of propane-2-ol as an electrolyte was 32 times higher than that of using water as an electrolyte. This is because the alcohol has higher solubility of nitrogen than water and it is considered to be suitable for the synthesis of ammonia by suppressing the hydrogen generation reaction occurring in the aqueous electrolyte. Therefore, the ammonia synthesis method of the present invention enables the synthesis of ammonia at a low temperature by using an alcohol-based electrolyte, and a higher ammonia synthesis yield can be obtained.

10. Oxide electrode
20. Reduction pole
30. Cationic Conductive Film
101. Oxide solution
102. Electrode electrode
201. Reduction amount
202. Reduced electrode
203. Nitrogen supply

Claims (5)

As an electrochemical ammonia synthesis method using an alcohol-based electrolyte,
The method includes the steps of generating electrons and hydrogen ions at an oxidized portion including an oxidant electrode and an oxidizing electrode;
Passing the hydrogen ion through a cation conductive membrane which is in contact with the oxidation electrode and separates the oxidized electrode portion and the reducing electrode portion;
The hydrogen ions having passed through the cation conductive membrane reach a reducing electrode portion including a reducing electrode liquid, a reducing electrode and a nitrogen supplying portion; And
And reducing ions of hydrogen ions and electrons in the reducing electrode to produce ammonia,
Wherein the oxidizing electrode is a platinum plate, the reducing electrode is porous nickel,
The above-mentioned oxidant solution is a lithium chloride aqueous solution,
The reducing electrode solution is a propan-2-ol solution to which lithium chloride is added,
Wherein the nitrogen supply unit supplies nitrogen gas to the reducing electrode,
A Method for the Synthesis of Electrochemical Ammonia Using an Alcohol - based Electrolyte.
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Cited By (5)

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KR101863208B1 (en) 2017-03-20 2018-05-31 한국에너지기술연구원 Method for ammonia synthesis using lithium super ionic conductor
WO2019182207A1 (en) * 2018-03-23 2019-09-26 한국에너지기술연구원 Lithium superionic conductor-based ammonia synthesis method
JP2020533491A (en) * 2017-09-08 2020-11-19 ハスコリ・アイランズ Production of electrolytic ammonia using transition metal oxide catalysts
KR20220094663A (en) * 2020-12-29 2022-07-06 한국에너지기술연구원 Electrochemical ammonia synthesis method using nitrogen nanobubble sparger and electrochemical ammonia synthesis apparatus
WO2023096042A1 (en) * 2021-11-25 2023-06-01 한국과학기술연구원 Electrochemical water treatment apparatus for recovering high-concentration ammonia nitrogen

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JP2006045652A (en) * 2004-08-09 2006-02-16 Kenichi Machida Hydrogen production apparatus, ammonia production apparatus, hydrogen production method and ammonia production method
JP2014040336A (en) * 2012-08-21 2014-03-06 Nagoya Institute Of Technology Method for producing ammonia and apparatus for producing ammonia
KR101470929B1 (en) * 2013-09-11 2014-12-09 한국에너지기술연구원 Electrochemical Module for Ammonia Synthesis Using Catalytic Electrode of Metal Nitride, Fabrication Method thereof and Ammonia Synthesis Method using the same

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EP0972855A1 (en) 1998-07-03 2000-01-19 Foundation for Research and Technology Hellas, Chemical Process, Engineering Research Institute Method and apparatus for ammonia synthesis at atmospheric pressure
JP2006045652A (en) * 2004-08-09 2006-02-16 Kenichi Machida Hydrogen production apparatus, ammonia production apparatus, hydrogen production method and ammonia production method
JP2014040336A (en) * 2012-08-21 2014-03-06 Nagoya Institute Of Technology Method for producing ammonia and apparatus for producing ammonia
KR101470929B1 (en) * 2013-09-11 2014-12-09 한국에너지기술연구원 Electrochemical Module for Ammonia Synthesis Using Catalytic Electrode of Metal Nitride, Fabrication Method thereof and Ammonia Synthesis Method using the same

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101863208B1 (en) 2017-03-20 2018-05-31 한국에너지기술연구원 Method for ammonia synthesis using lithium super ionic conductor
JP2020533491A (en) * 2017-09-08 2020-11-19 ハスコリ・アイランズ Production of electrolytic ammonia using transition metal oxide catalysts
JP7204755B2 (en) 2017-09-08 2023-01-16 ハスコリ・アイランズ Electrolytic ammonia production using transition metal oxide catalysts
WO2019182207A1 (en) * 2018-03-23 2019-09-26 한국에너지기술연구원 Lithium superionic conductor-based ammonia synthesis method
KR20190111480A (en) * 2018-03-23 2019-10-02 한국에너지기술연구원 Method for ammonia synthesis using lithium super ionic conductor
KR102128228B1 (en) 2018-03-23 2020-06-30 한국에너지기술연구원 Method for ammonia synthesis using lithium super ionic conductor
KR20220094663A (en) * 2020-12-29 2022-07-06 한국에너지기술연구원 Electrochemical ammonia synthesis method using nitrogen nanobubble sparger and electrochemical ammonia synthesis apparatus
KR102510919B1 (en) * 2020-12-29 2023-03-16 한국에너지기술연구원 Electrochemical ammonia synthesis method using nitrogen nanobubble sparger and electrochemical ammonia synthesis apparatus
WO2023096042A1 (en) * 2021-11-25 2023-06-01 한국과학기술연구원 Electrochemical water treatment apparatus for recovering high-concentration ammonia nitrogen

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