KR102244158B1 - Electrochemical system for producing ammonium nitrate from nitrogen oxides and preparation method thereof - Google Patents

Abstract

An ammonium ion production apparatus including a cathode electrode, an anode electrode, a reference electrode, an electrolyte including a metal complex compound, and a nitrogen oxide injection port in which a reduction reaction of the complex between the nitrogen oxide and the metal complex compound occurs; And an apparatus for producing nitrate ions including a cathode electrode, an anode electrode in which an oxidation reaction of nitrogen oxide occurs, a reference electrode, an electrolyte, and a nitrogen oxide injection port. The apparatus for producing ammonium nitrate provided in one aspect of the present invention produces ammonium ions by electrochemically reducing nitrogen oxides under conditions of room temperature and pressure, but has an effect of producing ammonium ions with high selectivity. In addition, nitrate ions are produced by oxidizing nitrogen oxide electrochemically, but there is an effect of producing nitrate ions with high selectivity. That is, there is an effect of overcoming the low temperature selectivity and high cost of commercially available denitrification technologies and enabling the production of high value-added materials. In addition, the phenomenon that the metal complex compound used in the process is oxidized by oxygen and loses its adsorption properties can be overcome by maintaining an electrochemical reducing atmosphere.

Description

Electrochemical reactor and manufacturing method for producing ammonium nitrate from nitrogen oxide {ELECTROCHEMICAL SYSTEM FOR PRODUCING AMMONIUM NITRATE FROM NITROGEN OXIDES AND PREPARATION METHOD THEREOF}

It relates to an electrochemical reactor for producing ammonium nitrate from nitrogen oxides and a method for producing ammonium nitrate from nitrogen oxides.

_{Nitric Oxide (NO) is a type of nitrogen oxide (NO X} ) that is generally generated by oxidation of nitrogen in the combustion process, and itself causes respiratory-related diseases. It is a representative air pollutant that causes various environmental problems such as particulate matter, photochemical smog, acid rain and ozone depletion. In particular, in countries that are rapidly growing economically, such as China and India, large amounts of nitrogen oxides are emitted due to excessive industrial activities, causing fine dust to directly affect neighboring countries. Secondary fine dust can be generated through a variety of causative substances, but it is reported that nitrogen oxides and sulfur oxides account for the largest proportion of more than 65% of the exhaust gas emitted from industrial activities. Due to its high water solubility and chemical reactivity, the treatment of sulfur oxides can be easily treated with high treatment efficiency by sedimenting them as solids like the Limestone process, whereas in the case of nitrogen oxides, nitrogen monoxide has little water solubility and thus cannot be treated in water. And, high-temperature reaction and use of expensive noble metal catalysts and reducing agents are indispensable.

Commercially available nitrogen oxide removal technologies include Selective catalytic reduction (SCR), Non-selective catalytic reduction (NSCR), Lean NO _X trap (LNT), and exhaust. There is an Exhaust Gas Recirculation (EGR), and the technologies currently being developed include an electron beam, a corona discharge, a biological treatment process (BioDeNO _X ), and a solid oxide electrolysis device. Among them _{, the most widely used technology in terms of DeNO X} efficiency is a selective reduction catalyst device or a large-scale emission point source such as the energy industry including power plants, the petrochemical industry, and the manufacturing industry such as the steel industry in terms of securing space. It is mainly used and has high-temperature operating conditions, and the cost of the catalyst and reducing agent used. In recent years, the price of catalyst and the size of the reactor have been improved through the improvement, and thus it is partially applied to mobile pollutants such as vehicles and ships using diesel, but there is a difficulty in technical application due to the lack of physical space.

On the other hand, nitrogen monoxide (NO, Nitric Oxide), which accounts for about 95% of nitrogen oxides, can be oxidized or reduced by exchanging electrons, that is, it has electrochemical activity, which supplies external electrical energy and converts it into a nitrogen compound that is harmless to the environment. This suggests that this is possible. When the NOx is oxidized, nitrite ions (NO ₂ ^-), nitrate ion (NO ₃ ^-) in a conversion and for reducing, in a switchable product is nitrous oxide (N ₂ O), nitrogen (N _2), hydroxide There are amine (NH ₂ OH), hydrazine (N ₂ H ₄ ), and ammonia (NH ₃ ), and nitrogen monoxide is converted to a specific nitrogen compound, for example, through optimization according to variables such as electrochemical reaction catalyst, electrolyte, and electrical energy input. For example, it can be selectively converted into useful compounds such as nitric acid and ammonia, which can be said to have an economic advantage compared to conventional denitrification technology that simply treats with nitrogen in terms of production of high value-added substances. On the other hand, ammonium nitrate is produced by reacting nitric acid and ammonia. More than 90% of nitric acid and ammonia produced worldwide has a very high commercial value in that it is used for the production of ammonium nitrate for agricultural fertilizer production.

In the case of nitric acid, it is produced through the Ostwald process, where ammonia is oxidized under high temperature conditions to convert it to nitrogen monoxide (NO), and then nitric acid is finally produced through an oxidation tower to nitrogen dioxide and a suction tower. After all, for the production of nitric acid, the Habor process of converting hydrogen and nitrogen into ammonia under conditions of high temperature of 500 degrees or higher and high pressure of 12 to 25 MPa must be preceded, so energy consumption is very high. On the other hand, the manufacturing process of nitric acid through electrochemical oxidation of nitrogen monoxide does not require the most energy consuming step in the Oswald process, that is, the process of oxidizing ammonia to nitrogen monoxide is not necessary, and it is possible to produce nitric acid at room temperature only with external electric energy. There is an advantage to be able to.

On the other hand, in the case of ammonia, most of the production is being used for the production of ammonium nitrate, but in recent years, due to the safety and storage properties of ammonia, various studies to use it as a carrier of hydrogen, which is in the spotlight as a next-generation transport fuel, have received a lot of investment and are proceeding And when commercialization is reached, demand is expected to increase exponentially.

In the case of the currently commercialized ammonia production process, the Haber process, in order to break the triple bond of nitrogen, it is operated at a high temperature of 500 degrees or higher and a high pressure of 15 to 25 MPa, and hydrogen must be supplied as a precursor. There is a big drawback in energy and cost consumption. To replace this, a study on the electrochemical process of producing ammonia by electrochemically reducing nitrogen and adding hydrogen ions, similarly, a study on producing ammonia using solar energy, and direct ammonia as a fuel. Research on fuel cells to be used is actively being conducted around the world.

The production of ammonia through electrochemical nitrogen reduction is advantageous in that it is easy to operate at room temperature and pressure compared to the harbor process, and uses nitrogen and pure water in the atmosphere as precursors, but most of the electric energy supplied is Since it is consumed as a side reaction, that is, a hydrogen generation reaction rather than generation, the conversion efficiency is very low, less than 3% based on an aqueous reaction, making it difficult to commercialize.

For example, Korean Patent Registration No. 10-1767894 is an invention related to a nitrogen circulation type nitrogen oxide treatment system and method, specifically, a nitrogen circulation type nitrogen oxide treatment system using an ammonia synthesis cell, and the nitrogen oxide treatment The system includes an exhaust gas supply line for supplying exhaust gas including _{NO x} and SO _{x to a desulfurizer;} A processing gas supply line for supplying the processing gas _{from which SO x} has been removed through the desulfurization unit _{to the NO x scrubber;} A processing gas discharge line for absorbing _{NO x} in the processing gas using an absorbent in the NO _{x scrubber and discharging the remaining gas; A NO x} absorption solution supply line for supplying the absorption solution absorbing NO _x from the NO _{x scrubber to the NO x} and absorbent separation device; And the NO _x and NO _x from the absorbent, but a separate separator supply ammonia synthetic cell, and comprises a NO _x supply line for supplying via the concentrator, wherein the ammonia synthesis cell is oxygen-ion conductive film; And two electrodes coated on both surfaces of the oxygen ion conductive film, wherein the electrodes are electrically connected, and a nitrogen circulating nitrogen oxide treatment system is disclosed. However, since the above technology uses pure nitrogen oxide as a raw material in the reduction process for ammonia production, there is a problem in that a high temperature environment must be maintained for high selectivity.

In addition, Korean Patent Application Publication No. 10-2017-0021713 is an invention related to an electrolysis device for trapping nitrogen compounds using iron-ethylenediamine tetraacetic acid, and specifically, an electrolysis device for trapping nitrogen compounds comprising the following configuration: ( a) a reactor body containing a compound of a divalent metal ion and a chelating agent therein; (b) anode and cathode; (c) a collection tube for collecting nitrogen compounds, including the anode therein; (d) a gas inlet for supplying a source gas containing a nitrogen compound to the reactor body; And (e) discloses a discharge port for discharging the gas is collected in the inside of the reactor and the nitrogen compound has been removed. However, the above technology only uses a chelating agent to adsorb the nitrogen compound, and only recovers the nitrogen compound through the oxidation reaction of the anode electrode after adsorption. There is not.

In addition, Korean Patent Registration No. 10-1773969 relates to an electrochemical reaction cell for improving a reduction reaction, and includes (a) a polymer electrolyte membrane; (b) a cathode electrode in which a first gas diffusion layer and a first catalyst layer are sequentially stacked on one surface of the electrolyte membrane; (c) a membrane electrode assembly including an anode electrode in which a second catalyst layer and a second gas diffusion layer are sequentially stacked on the other surface of the electrolyte membrane; (d) a cathode electrolyte solution stacked on the first catalyst layer and in which the reactive body and the reactive body are mixed is supplied to the first catalyst layer along a separate flow path, and the cathode electrolyte solution comprises the first catalyst layer and the first gas. A first distribution plate that penetrates and diffuses through the diffusion layer to form a three-phase interface by meeting the reactive body in the first catalyst layer contacting the flow path through which the reactive body is supplied; Disclosed is an electrochemical reaction cell comprising: (e) a second distribution plate stacked on the second gas diffusion layer to supply an anode electrolyte solution to the second gas diffusion layer. As an example, as an electrochemical reaction cell for reducing nitrogen monoxide, there is a disclosure that the _{reaction gas is nitrogen monoxide (NO) and nitric acid (HNO 3 ) remains after the reaction, but nitric acid (HNO 3} ) is only an electrolyte solution, The process of obtaining nitrate ions with high selectivity by oxidizing nitrogen oxides has not been disclosed.

However, ammonium nitrate (NH ₄ NO ₃ ) is a raw material responsible for more than 90% of the production of nitric acid and ammonia, and if ammonium nitrate can be produced, the production of high value-added nitric acid and ammonia will be facilitated. In addition, ammonium nitrate is used as a very important fertilizer, and it is easy to handle and inexpensive, so it is also used as an explosive material, and it is also used as a coolant.

Accordingly, there has been a need for research on a system and a manufacturing method capable of producing ammonium nitrate by producing ammonium ions and nitrate ions with high selectivity while performing the reaction at room temperature and pressure conditions.

Korean Patent Registration No. 10-1767894 Republic of Korea Patent Publication No. 10-2017-0021713 Korean Patent Registration No. 10-1773969

An object of the present invention is to provide an electrochemical reaction apparatus and a method for producing ammonium nitrate from nitrogen oxide by producing ammonium ions and nitrate ions with high selectivity while performing a reaction at room temperature and pressure conditions.

In order to achieve the above object, in one aspect of the present invention

An ammonium ion production apparatus including a cathode electrode, an anode electrode, a reference electrode, an electrolyte including a metal complex compound, and a nitrogen oxide injection port in which a reduction reaction of the complex between the nitrogen oxide and the metal complex compound occurs; And

There is provided an ammonium nitrate production apparatus including a cathode electrode, an anode electrode in which an oxidation reaction of nitrogen oxide occurs, a reference electrode, an electrolyte, and an apparatus for producing nitrate ions including a nitrogen oxide injection port.

In addition, in another aspect of the present invention

Introducing nitrogen oxide into an ammonium ion production apparatus including a cathode electrode, an anode electrode, a reference electrode, an electrolyte including a metal complex compound, and a nitrogen oxide injection port in which a reduction reaction of the complex between the nitrogen oxide and the metal complex compound occurs; Forming a complex between the introduced nitrogen oxide and a metal complex compound in the electrolyte; And performing an electrochemical reduction reaction on the formed complex to produce ammonium ions;

Introducing nitrogen oxide into a nitrate ion production apparatus including a cathode electrode, an anode electrode in which an oxidation reaction of nitrogen oxide occurs, a reference electrode, an electrolyte, and a nitrogen oxide injection port; Producing nitrate ions by performing an electrochemical oxidation reaction on the introduced nitrogen oxide; And

A method for producing ammonium nitrate from nitrogen oxides comprising; generating ammonium nitrate from the generated ammonium ions and nitrate ions is provided.

The apparatus for producing ammonium nitrate provided in one aspect of the present invention produces ammonium ions by electrochemically reducing nitrogen oxides under conditions of room temperature and pressure, but has an effect of producing ammonium ions with high selectivity. In addition, nitrate ions are produced by oxidizing nitrogen oxide electrochemically, but there is an effect of producing nitrate ions with high selectivity. That is, there is an effect of overcoming the low temperature selectivity and high cost of commercially available denitrification technologies and enabling the production of high value-added materials. In addition, the phenomenon that the metal complex compound used in the process is oxidized by oxygen and loses its adsorption properties can be overcome by maintaining an electrochemical reducing atmosphere.

1 is a schematic diagram showing an example of an apparatus for producing ammonium nitrate;
2 is a schematic diagram showing an example of an ammonium ion production apparatus;
3 is a schematic diagram showing an example of an apparatus for producing nitrate ions;
Figure 4 is a graph of performing the linear sweep current method for the ammonium ion production apparatus according to an experimental example of the present invention;
5 is a graph of a linear sweeping current method performed on an apparatus for producing nitrate ions according to an experimental example of the present invention;
6 is a graph showing a constant potential method with respect to an apparatus for producing ammonium ions according to an experimental example of the present invention;
7 is a graph showing a constant potential method with respect to the apparatus for producing nitrate ions according to an experimental example of the present invention;
8 is a graph showing conversion efficiency to hydrogen and ammonium ions in an ammonium ion production apparatus according to an experimental example of the present invention;
9 is a graph showing the conversion efficiency of nitrate ions and nitrite ions in a nitrate ion production apparatus according to an experimental example of the present invention;
10 is a graph showing the production rate of ammonium ions in the ammonium ion production apparatus according to an experimental example of the present invention;
11 is a graph showing the production rate of nitrate ions in the nitrate ion production apparatus according to an experiment of the present invention;
12 is a graph showing denitrification efficiency in an ammonium ion production apparatus according to an experiment of the present invention;
13 is a graph showing the denitration efficiency in the nitrate ion production apparatus according to an experiment of the present invention.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by an expert skilled in the art to which the present invention belongs. In general, the nomenclature used in this specification is well known and commonly used in the art. An object of the present invention is to provide a production apparatus capable of producing ammonium nitrate by selectively converting nitrogen oxides, particularly nitrogen monoxide, into ammonium ions and nitrate ions.

To this end, the present inventors have provided an electrochemical ammonium ion production apparatus and a cathode electrode including a cathode electrode, an anode electrode, a reference electrode, an electrolyte including a metal complex compound, and a nitrogen oxide injection port in which a reduction reaction of a complex between nitrogen oxide and a metal complex compound occurs, An ammonium nitrate production apparatus (see FIG. 1) including an electrochemical nitrate ion production apparatus including an anode electrode, a reference electrode, an electrolyte, and a nitrogen oxide injection port in which an oxidation reaction of nitrogen oxide occurs was developed.

Ammonium ion-producing device is provided in one aspect of the present invention, ammonium ion (NH ₄ ^+), or can refer to a device for producing the ammonia (NH _3), nitrate ion production apparatus nitrate ion (NO ₃ ^-), or nitric acid (HNO ₃ ) It may mean an apparatus for manufacturing.

At this time, an example of an apparatus for producing ammonium nitrate is schematically shown in FIGS. 1 to 3,

Hereinafter, the ammonium nitrate production apparatus 1000 provided in one aspect of the present invention will be described in detail for each configuration with reference to the schematic diagrams of FIGS. 1 to 3.

At this time, the nitrogen oxide used as a raw material for the ammonium nitrate production apparatus 1000 provided in an aspect of the present invention may be nitrogen monoxide in that nitrogen monoxide accounts for about 95% of the nitrogen oxide.

In addition, the ammonium nitrate manufacturing apparatus 1000 provided in one aspect of the present invention includes an ammonium ion manufacturing apparatus 100. The ammonium ion manufacturing apparatus includes an anode electrolyte chamber 112 containing an electrolyte, an anode cell 110 including an anode electrode 113 and an outer wall 111 of the anode 111 formed in the anode electrolyte chamber, and contains a metal complex compound. The cathode electrolyte chamber 122 containing the containing electrolyte, the cathode electrode 121 formed in the cathode electrolyte chamber, the reference electrode 123 formed in the cathode electrolyte chamber, and a nitrogen oxide injection port for supplying nitrogen oxide to the cathode electrolyte chamber ( 125) and a cathode cell 120 including a cathode outer wall 124, and an ion exchange membrane 130 formed between the anode cell and the cathode cell. In addition, the ammonium ion manufacturing apparatus may include an ammonium ion outlet 126 for discharging ammonium ions generated in the cathode cell.

The metal forming the metal complex in the electrochemical ammonium ion production apparatus 100 may be a divalent metal such as iron, magnesium, potassium, zinc or chromium, and the ions of this metal combine with the complex to form a compound. , This compound serves, for example, to selectively adsorb nitrogen monoxide in the liquid phase. The use of iron or magnesium may be considered in that the affinity with nitrogen monoxide is excellent, and in particular, the use of iron ions may be considered.

The complex compound forming the metal complex in the electrochemical ammonium ion production apparatus 100 is the group consisting of ethylenediamine tetraacetic acid (EDTA), 1,2 cyclohexanediamine tetraacetic acid (CyDTA), and nitrotrisodium acetate (NTA). One kind of salt selected from can be used. A complex compound is a compound that combines with a metal to form a metal complex, and can be used without limitation as a compound that performs such a function, but the use of EDTA can be considered in that the reaction rate is fast and the reaction with various metals is possible. have.

In the electrochemical ammonium ion manufacturing apparatus 100, the anode electrode 113 may be made of a wide variety of metals and non-metals, and in detail, at least one conductive metal selected from graphite, platinum, titanium, nickel, and gold and platinum , Ruthenium, osmium, palladium, iridium, carbon, it may be characterized in that it is composed of a mixture or oxide of one or more selected from a transition metal. The electrode material of the anode electrode can be used without any special restrictions, but it is preferable to use iron, aluminum, copper, silver, nickel, etc., in the form of oxides, which can spontaneously proceed with the oxidation reaction when electric energy is introduced into the electrode material of the anode. Do. Most preferably, a platinum electrode or an insoluble electrode (Dimensional stable anode, DSA) may be used.

In addition, in the electrochemical ammonium ion production apparatus 100, the cathode electrode 121 undergoes a reduction reaction of the complex between the nitrogen oxide and the metal complex compound in the electrolyte as in the following reaction equation, and iron, glassy carbon (GC). ), aluminum, copper, silver, nickel, platinum, oxides thereof, and one or more selected from the group consisting of alloys thereof can be used, and according to the experimental results, the speed of producing ammonium ions is very fast. You may consider using silver in.

At this time, it is preferable that the voltage applied to the cathode electrode 121 in the electrochemical ammonium ion production apparatus 100 is in the range of -0.1 V to -0.6 V compared to the hydrogen reference electrode, and is in the range of -0.2 V to -0.5 V. More preferably, it is more preferably in the range of -0.3 V to -0.4 V. If the voltage applied to the cathode electrode in the electrochemical ammonium ion production apparatus is -0.1 V or less compared to the hydrogen reference electrode, it is preferable in that the activation energy required for the reaction can be satisfied and ammonium ion production is possible, and -0.6 When a voltage of V or higher is applied, it is preferable in that the current efficiency of the generated ammonium is increased by suppressing the competition reaction due to the generation of hydrogen.

In addition, the pH of the electrolyte included in the electrochemical ammonium ion production apparatus 100 may be maintained in a neutral range of 6 to 8. In terms of the production of ammonium ions, maintaining the pH of the electrolyte in the neutral range as described above is preferable in terms of selectivity and stability of the complex compound.

The electrochemical ammonium ion manufacturing apparatus 100 includes a reference electrode 123, and the reference electrode may be, for example, an Ag/AgCl electrode.

The electrochemical ammonium ion manufacturing apparatus 100 includes an electrolyte, and the electrolyte includes a metal complex compound for forming a complex.

The electrochemical ammonium ion manufacturing apparatus 100 includes a nitrogen oxide inlet 125 for supplying nitrogen oxide as a raw material into the system, and nitrogen oxide as a raw material is supplied into the system through the inlet, and a metal complex compound A metal complex compound and a complex are formed in the containing electrolyte, and reduction proceeds on the cathode electrode 121.

For example, when a metal chelate (M ^II C) is used as a liquid adsorbent for selective adsorption of nitrogen monoxide, the reaction equation is as follows.

M ^Ⅱ C (aq) + NO (g) -> M ^Ⅱ C-NO (aq) [Scheme 1]

The chemical reaction is carried out in the cathode cell 120 of FIG. 2 of the electrochemical ammonium production apparatus 100 provided in the present invention, and when a potential difference is applied by an external power source, water is oxidized in the anode cell 110 to cause oxygen molecules and Hydrogen ions and electrons are generated, and at the same time, in the cathode cell, M ^II C-NO to which nitrogen monoxide is adsorbed receives electrons to cause a reduction reaction and can be converted into various products.

^{M Ⅲ C (aq) + e} - -> M Ⅱ C (aq) [ Scheme 2]

^{2M Ⅱ C-NO (aq)} + 2e - + 2H + -> 2M Ⅱ C + N 2 O (g) + H 2 O [ Reaction Scheme 3]

^{2M Ⅱ C-NO (aq)} + 4e - + 4H + -> 2M Ⅱ C + N 2 (g) + 2H 2 O [ Reaction Scheme 4]

^{M Ⅱ C-NO (aq)} + 3e - + 4H + -> M Ⅱ C + NH 3 OH + (aq) [ Scheme 5]

^{M Ⅱ C-NO (aq)} + 5e - + 6H + -> M Ⅱ C + NH 4 + (aq) + H 2 O [ Reaction Scheme 6]

^{First, M Ⅲ} C, which is oxidized by exposure to oxygen, ^{can be reduced to M Ⅱ} C, a form that can selectively adsorb nitrogen monoxide by receiving electrons from the cathode (Scheme 2), respectively, 2 electrons, 4 electrons, 3 It can be converted into nitrous oxide (Scheme 3), nitrogen (Scheme 4), hydroxyl ammonium (Scheme 5), and ammonium (Scheme 6) according to the electron and 5 electron reactions.

On the other hand, under the overvoltage condition of a certain potential difference or more, a hydrogen generation reaction (Scheme 7) occurs competitively with the reduction reaction of nitrogen monoxide provided in one aspect of the present invention, and this It lowers the Faraday efficiency.

2H ⁺ + 2e ^-- > H ₂ (g) [Scheme 7]

The gaseous nitrogen monoxide supplied through the nitrogen oxide inlet 125 of FIG. 2 in the ammonium ion production apparatus 100 ^{is adsorbed to the metal-chelate (M II} C) aqueous solution of the electrolyte contained in the cathode cell 120 to be liquid. When a potential difference is applied by an external power source, water decomposition occurs in the anode electrode 113 and is converted into oxygen molecules, hydrogen ions, and electrons, and M ^{II in the cathode electrode (working electrode 121) inside the cathode cell.} C-NO is reduced and converted into various nitrogen compounds. At this time, the gaseous nitrogen compound is discharged through the gas outlet and is analyzed by gas chromatography, and the nitrogen compound in the solution remaining inside the cathode cell is analyzed by ion chromatography through sampling after reaction, and the current for gaseous and liquid products Efficiency can be obtained. The reaction may be carried out in a continuous manner instead of a batch type, and the hydrogen gas generated by the side reaction is discharged together with the gaseous nitrogen compound, and separation/capture is possible if necessary.

In the ammonium ion production apparatus 100, the concentration of the metal complex compound in the electrolyte is not particularly limited in use, but it may be considered to use 0.01 M to 0.5 M. If the concentration of the metal complex compound is 0.01 M or more, the amount of adsorption of the raw material is sufficient and suitable for industrial use. If the concentration is less than 0.5 M, the metal complex compound is not formed and is precipitated in the form of iron oxide, contaminating the electrode and electrolyte. It can prevent sticking to the reactor wall.

In addition, the ammonium nitrate manufacturing apparatus 1000 provided in one aspect of the present invention includes a nitrate ion manufacturing apparatus 200. The nitrate ion manufacturing apparatus supplies nitrogen oxide to an anode electrolyte chamber 214 containing an electrolyte, an anode electrode 212 formed in the anode electrolyte chamber, a reference electrode 213 formed in the anode electrolyte chamber, and an anode electrolyte chamber. A cathode electrolyte chamber 222 including an anode cell 210 including a nitrogen oxide injection hole 215 and an anode outer wall 211 and including an electrolyte, a cathode electrode 221 formed in the cathode electrolyte chamber, and an outer wall of the cathode It includes a cathode cell 220 including 223, and includes an ion exchange membrane 230 formed between the anode cell and the cathode cell. In addition, the nitrate ion manufacturing apparatus may include a nitrate ion outlet 216 for discharging nitrate ions generated in the anode cell.

The anode electrode 212 of the electrochemical nitrate ion manufacturing apparatus 200 may include a gas diffusion layer 212a. There is an advantage of maximizing selectivity of a specific product by adjusting the ratio of the catalyst and the strength of the applied voltage according to the desired purpose including the gas diffusion layer.

Meanwhile, in the electrochemical nitrate ion manufacturing apparatus 200, the cathode electrode 221 may be made of a wide variety of metals and non-metals, and specifically, 1 selected from the group consisting of graphite, platinum, titanium, nickel, and gold. It may be considered to be composed of a mixture or oxide of at least one kind selected from the group consisting of more than one kind of conductive metal and platinum, ruthenium, osmium, palladium, iridium, carbon, and transition metal. The electrode material of the cathode electrode can be used without any particular limitation, but it is recommended to use iron, aluminum, copper, silver, nickel, etc., in the form of oxides, which can spontaneously undergo oxidation reactions when electric energy is introduced as the electrode material of the cathode. Can be considered. It is possible to consider using a platinum electrode or an insoluble electrode (Dimensional Stable Anode, DSA).

The electrochemical nitrate ion manufacturing apparatus 200 may include a reference electrode 213, and, for example, a hydrogen electrode or an Ag/AgCl electrode, and a reference electrode used in other general electrochemical systems may be used. It can be operated without electrodes.

The electrochemical nitrate ion manufacturing apparatus 200 includes an electrolyte, and an electrolyte used in a general electrochemical system may be used without limitation.

The electrochemical nitrate ion manufacturing apparatus 200 includes a nitrogen oxide injection port 215 communicating with an anode electrode including the gas diffusion layer 212a. The nitrogen oxide supplied through the inlet is supplied to the anode electrode through the gas diffusion layer, and the oxidation reaction proceeds in the nitrate ion production apparatus.

In the electrochemical nitrate ion production apparatus 200, the anode electrode 212 may further include a catalyst layer 212b. The catalyst layer may be a carbon catalyst layer of nanoparticles. In the oxidation reaction at the anode electrode, the carbon catalyst layer increases the conductivity by mixing with other metal catalysts or directly oxidizes nitrogen oxides as a catalyst. At this time, the metal catalysts to be mixed include iron (Fe), nickel (Ni), copper (Cu), silver (Ag), zinc (Zn), gold (Au), platinum (Pt), iridium (Ir), and rudenium. (Ru), cobalt (Co), lead (Pb), cadmium (Cd), tungsten (W), mercury (Hg), titanium (Ti), vanadium (V), and oxides thereof (MO _x ) can be used. .

At this time, the potential difference applied to the anode electrode 212 in the electrochemical nitrate ion production apparatus 200 is preferably in the range of 1.1 V to 3.0 V compared to the hydrogen reference electrode, and more preferably in the range of 1.4 V to 1.8 V. And, it is preferably 1.4 V to 1.7 V, more preferably 1.5 V to 1.6 V. If the voltage applied to the anode electrode in the electrochemical nitrate ion production apparatus is 1.1 V or more compared to the hydrogen reference electrode, it is preferable in that it can satisfy the activation energy required for the conversion reaction of nitrogen monoxide, so that nitrate ions can be produced. When a voltage of 3.0 V or less is applied, the oxygen generation reaction by water electrolysis or the oxidation reaction of the carbon catalyst layer itself is suppressed, thereby increasing the current efficiency for the products generated by conversion of nitrogen monoxide.

In the anode electrode 212 of the nitrate ion manufacturing apparatus 200, for example, the following oxidation reaction proceeds to generate nitrate ions or nitrite ions.

_{NO + H 2 O -> NO} 2 - + 2H + + e - ... … … … … … … (Scheme 8)

_{NO + 2H 2 O -> NO} 3 - + 4H + + 3e - ... … … … … … … (Scheme 9)

In addition, in the cathode electrode 221 of the nitrate ion production apparatus 200, for example, the following water decomposition reaction proceeds.

^{_{2H 2 O + 2e - ->}} H 2 + 2OH - ... … … … … … … … … (Scheme 10)

Ammonium nitrate manufacturing device 1000 is provided in one aspect of the present invention, ammonium ion (NH ₄ ⁺⁾ and nitrate ions in the oxides of nitrogen in particular, nitrogen monoxide using a specific electrode and the specific potential condition of nitrogen (NO ₃ ^-) It may be characterized in that it comprises a means for selectively converting. Here has a selective means is experimentally ammonium ion (NH ₄ ⁺⁾ and nitrate ions (NO ₃ ^-) means that the current efficiency of the conversion to the 95% or more.

In addition, in another aspect of the present invention

Introducing nitrogen oxide into an ammonium ion production apparatus including a cathode electrode, an anode electrode, a reference electrode, an electrolyte including a metal complex compound, and a nitrogen oxide injection port in which a reduction reaction of the complex between the nitrogen oxide and the metal complex compound occurs; Forming a complex between the introduced nitrogen oxide and a metal complex compound in the electrolyte; And performing an electrochemical reduction reaction on the formed complex to produce ammonium ions;

Introducing nitrogen oxide into a nitrate ion production apparatus including a cathode electrode, an anode electrode in which an oxidation reaction of nitrogen oxide occurs, a reference electrode, an electrolyte, and a nitrogen oxide injection port; Producing nitrate ions by performing an electrochemical oxidation reaction on the introduced nitrogen oxide; And

A method for producing ammonium nitrate from nitrogen oxides comprising; generating ammonium nitrate from the generated ammonium ions and nitrate ions is provided.

Hereinafter, a method for producing ammonium nitrate from nitrogen oxide provided in another aspect of the present invention will be described in detail for each step.

First, the method for producing ammonium nitrate from nitrogen oxide provided in another aspect of the present invention includes a cathode electrode, an anode electrode, a reference electrode, an electrolyte including a metal complex compound, and a nitrogen oxide injection port in which a reduction reaction of the complex between the nitrogen oxide and the metal complex compound occurs. Introducing nitrogen oxides into an ammonium ion production apparatus comprising a; Forming a complex between the introduced nitrogen oxide and a metal complex compound in the electrolyte; And performing an electrochemical reduction reaction on the formed complex to produce ammonium ions.

The first step of the ammonium ion manufacturing method is a step of introducing nitrogen oxide as a raw material into the ammonium ion manufacturing apparatus 100, wherein the nitrogen oxide may be nitrogen monoxide, for example, through the inlet 125 of nitrogen oxide. It is introduced into the ammonium ion production apparatus and reacts with the metal complex compound in the electrolyte.

As described above, the nitrogen oxide introduced into the ammonium ion production apparatus reacts with the metal complex compound in the electrolyte to form a complex. At this time, the concentration of the metal complex compound in the electrolyte may be adjusted in the range of 10 mM to 500 mM. If the concentration of the metal complex compound is 10 mM or more, the amount of adsorption of the raw material is sufficient and suitable for industrial use. If the concentration is less than 500 mM, the metal complex compound does not form and precipitates in the form of iron oxide, contaminating the electrode and electrolyte. It can prevent sticking to the reactor wall.

The pH of the electrolyte used in the ammonium ion production method may be in a neutral range of 6 to 8. Adjusting the pH of the electrolyte may be necessary for the selectivity of ammonia, and in consideration of the high selectivity of ammonium ions under neutral conditions, the pH range may be adjusted to the above range.

The method for preparing ammonium ions includes the step of performing an electrical reduction reaction on the formed complex after the complex is formed, through which nitrogen oxide is electrochemically reduced in the complex state to form ammonium ions.

On the other hand, in the ammonium ion manufacturing method, the voltage applied to the cathode electrode 121 is preferably in the range of -0.1 V to -0.6 V compared to the hydrogen reference electrode, more preferably -0.2 V to -0.5 V, and -0.3 It is more preferably in the range of V to -0.4 V. If the voltage applied to the cathode electrode in the electrochemical ammonium ion production apparatus is -0.1 V or less compared to the hydrogen reference electrode, it is preferable in that the activation energy required for the reaction can be satisfied and ammonium ion production is possible, and -0.6 When a voltage higher than V is applied, it is preferable in that the current efficiency of the generated ammonium is increased by suppressing the competition reaction due to the generation of hydrogen.

The method for preparing the ammonium ion is a method performed at room temperature and pressure. In the conventional ammonia production process, the reaction was carried out under high temperature and high pressure conditions to increase the selectivity of ammonia, but the ammonium nitrate production method provided in one aspect of the present invention can obtain excellent ammonia selectivity even at room temperature and atmospheric pressure conditions. There is an advantage.

In the method for producing ammonium ions, a reduction reaction proceeds in a state in which a raw material and a metal complex compound form a complex as described above. As the raw material forms a complex with the metal complex compound, the amount of the raw material involved in the reduction reaction increases, thereby increasing productivity.

Next, the method for producing ammonium nitrate from nitrogen oxide provided in another aspect of the present invention is a nitrate ion production apparatus including a cathode electrode, an anode electrode in which an oxidation reaction of nitrogen oxide occurs, a reference electrode, an electrolyte, and a nitrogen oxide injection port. Introducing an oxide; And performing an electrochemical oxidation reaction on the introduced nitrogen oxide to produce nitrate ions.

The first step of the nitrate ion manufacturing method is a step of introducing nitrogen oxide as a raw material into the ammonium ion manufacturing apparatus 200, wherein the nitrogen oxide may be nitrogen monoxide.

In this case, the nitrate ion manufacturing method may include supplying nitrogen oxide to the gas diffusion layer 212a of the anode electrode 212, through which nitrogen oxide is supplied to the gas diffusion layer along the nitrogen oxide inlet 215 Thus, it is finally removed through an oxidation reaction on the anode electrode as shown in the following reaction equation. In the case of including the gas diffusion layer as described above, in the method for producing nitrate ions, nitrogen oxide is introduced to the anode electrode through the gas diffusion layer, thereby increasing the concentration of usable reactants around the electrode, thereby maximizing the denitration efficiency.

In the nitrate ion manufacturing method, the anode electrode 212 may further include a catalyst layer 212b. The catalyst layer may be a carbon catalyst layer of nanoparticles. In the oxidation reaction at the anode electrode, the carbon catalyst layer increases the conductivity by mixing with other metal catalysts or directly oxidizes nitrogen oxides as a catalyst. At this time, the metal catalysts to be mixed include iron (Fe), nickel (Ni), copper (Cu), silver (Ag), zinc (Zn), gold (Au), platinum (Pt), iridium (Ir), and rudenium. (Ru), cobalt (Co), lead (Pb), cadmium (Cd), tungsten (W), mercury (Hg), titanium (Ti), vanadium (V) and oxides thereof (MO _X ) can be used. .

At this time, the potential difference applied to the anode electrode 212 in the nitrate ion manufacturing method is preferably in the range of 1.1 V to 3.0 V, more preferably in the range of 1.4 V to 1.8 V, and more preferably in the range of 1.4 V to 1.8 V, compared to the hydrogen reference electrode. It is preferably 1.7 V, and more preferably 1.5 V to 1.6 V. If the voltage applied to the anode electrode in the electrochemical nitrate ion production apparatus is 1.1 V or more compared to the hydrogen reference electrode, it is preferable in that it can satisfy the activation energy required for the conversion reaction of nitrogen monoxide, so that nitrate ions can be produced. When a voltage of 3.0 V or less is applied, the oxygen generation reaction by water electrolysis or the oxidation reaction of the carbon catalyst layer itself is suppressed, thereby increasing the current efficiency for the products generated by conversion of nitrogen monoxide.

The method for producing nitrate ions includes performing an electrical oxidation reaction on the introduced nitrogen oxide. The electrical oxidation reaction for nitrogen oxides in the nitrate ion production method of the present invention may be carried out by the following reaction equation.

_{NO + H 2 O -> NO} 2 - + 2H + + e - ... … … … … … … (Scheme 8)

_{NO + 2H 2 O -> NO} 3 - + 4H + + 3e - ... … … … … … (Scheme 9)

During the above reaction, nitrate ions may be selectively produced by controlling the type of the catalyst layer and the potential applied to the anode electrode.

Next, the method for producing ammonium nitrate from nitrogen oxide provided in another aspect of the present invention includes the step of producing ammonium nitrate from the produced ammonium ions and nitrate ions.

The step of producing the ammonium nitrate is carried out by a reaction of a general ammonium ion and a nitrate ion. The pH of the electrolyte in the ammonium ion manufacturing apparatus may be changed to basic by the ammonium ion manufacturing method, and the electrolyte pH of the nitrate ion manufacturing apparatus may be changed to acidic by the nitrate ion manufacturing method. Can be obtained.

The system and the manufacturing method according to the present invention have the advantage of being able to manufacture high value-added ammonium nitrate by using nitrogen oxide, which is an air pollutant, particularly nitrogen monoxide, which accounts for about 95% thereof. In particular, many parts of air pollutants are nitrogen oxides and sulfur oxides, and while sulfur oxides can be easily separated and removed, it is difficult to easily separate and remove nitrogen oxides. The present invention is characterized in that the nitrogen oxide, which is difficult to remove, is used as a raw material. In addition, despite the process at room temperature and pressure, side reactions are suppressed, and there is a feature of the invention in that the selectivity for ammonium ions and nitrate ions is high.

Hereinafter, the present invention will be described in more detail through experimental examples. These experimental examples are for illustrative purposes only, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not construed as being limited by these experimental examples.

<Experimental Example 1> Analysis of the ammonium ion production device and the nitrate ion production device according to the linear sweeping current method

First, an apparatus for producing ammonium ions shown in the schematic diagram of FIG. 2 was constructed. Specifically, the electrolysis device for ammonium ion production is composed of an anode outer wall, an anode PEEK cell, a cathode PEEK cell, and a cathode outer wall, with an electrolyte inlet above the anode PEEK cell, and an electrolyte inlet and gas discharge line above the cathode PEEK cell. , There is a gas injection line into which a gas diffuser made of quartz material can be inserted downward, and an Ag/AgCl reference electrode (electrode pore 2 mm) insertion hole on the side. A 2 cm * 5 cm platinum electrode was inserted between the anode outer wall and the anode PEEK cell as the counter electrode, and a 2.5 cm * 2.5 cm glassy carbon electrode was sandwiched between the cathode PEEK cell and the cathode outer wall as the working electrode. 0.5 M Phosphate Buffer was used as an electrolyte toward the cathode PEEK cell, and 1.5 mL of electrolyte was injected into the anode PEEK cell and the cathode PEEK cell, respectively, during the electrochemical reaction for nitrogen oxide conversion. For the electrochemical reaction of nitrogen monoxide proposed in the present invention, a time-varying current method was performed using a Potentiostat, an electrochemical analyzer, and a gaseous product was analyzed by connecting the gas discharge line of the cathode PEEK cell to gas chromatography. In the case of the liquid product, after performing the time-varying current method, the electrolyte of the cathode PEEK cell was sampled and analyzed by ion chromatography. The selectivity, ammonium ion current density, and denitrification rate for the product were calculated based on the analysis result of the product and the current density recorded in the time vs. amperometric method.

Next, an apparatus for producing nitrate ions shown in the schematic diagram of FIG. 3 was constructed. Specifically, the electrolysis device for the manufacture of nitrate ions is composed of an anode outer wall, an anode PEEK cell, a cathode PEEK cell, and a cathode gas injection cell, and an electrolyte injection port above the anode PEEK cell is an electrolyte injection port and a gas discharge line above the cathode PEEK cell. There is an Ag/AgCl reference electrode (electrode pore 2 mm) insertion hole on the side. There is a gas injection line above the cathode gas injection cell, and when gas is supplied, a 2.5 cm * 2.5 cm gas diffusion electrode (cathode including a carbon/iron mixed catalyst layer and a gas diffusion layer) located between the cathode PEEK cell and the outer wall of the cathode is provided. The gas diffuses through and passes through, and goes out to the gas outlet of the cathode PEEK cell. A platinum electrode of 2 cm * 5 cm was sandwiched between the anode outer wall and the anode PEEK cell as a counter electrode. As an electrolyte, 0.5 M Phosphate Buffer was used, and 1.5 mL of electrolyte was injected into the anode PEEK cell and the cathode PEEK cell, respectively, during the electrochemical reaction for nitrogen oxide conversion. For the electrochemical reaction of nitrogen monoxide proposed in the present invention, a time-varying current method was performed using a Potentiostat, an electrochemical analyzer, and a gaseous product was analyzed by connecting the gas discharge line of the cathode PEEK cell to gas chromatography. In the case of the liquid product, after performing the time-varying current method, the electrolyte of the cathode PEEK cell was sampled and analyzed by ion chromatography. The selectivity, ammonium ion current density, and denitrification rate for the product were calculated based on the analysis results of the product and the current density recorded in the time versus current method.

For such a device, in the ammonium ion production device for ammonium production by supplying 1% nitrogen monoxide gas at a flow rate of 5 mL/min, the production of nitrate ions is performed under a voltage condition of +0.2 V to -0.5 V compared to the hydrogen reference electrode. In the nitrate ion production apparatus for, the linear sweeping current method was performed under a voltage condition of +1.1 V to +2.2 V compared to the hydrogen reference electrode, and the results are shown in FIGS. 4 and 5.

In the case of the ammonium ion production apparatus, the current density curve by the linear-vnegative current method showed a big difference between the supply of argon gas and the supply of nitrogen monoxide gas. Under the conditions, a current according to voltage is generated from about -0.2 V compared to the hydrogen reference electrode, and it can be seen that as the overvoltage increases, the amount of nitrogen monoxide that is electrochemically reduced also increases (FIG. 4). Likewise, in the case of the nitrate ion manufacturing apparatus, the difference in the current density curve under argon and nitrogen monoxide conditions is a result of the oxidation reaction of nitrogen monoxide, and it can be seen that the amount of nitrogen monoxide to be oxidized increases as the overvoltage increases ( Fig. 5).

<Experimental Example 2> Analysis of an ammonium ion production device and a nitrate ion production device according to a constant potential method

For the device of Experimental Example 1, in the case of the ammonium ion production device, 1% nitrogen monoxide gas was supplied at 5 mL/min, and in the voltage range of -0.13 V to -0.44 V compared to the hydrogen reference electrode, in the case of the nitrate ion production device 1 % Nitrogen monoxide was supplied at 5 mL/min, and the constant potential method was performed in a voltage range of 1.26 V to 1.67 V compared to the hydrogen reference electrode, respectively, and the results are shown in FIGS. 6 and 7.

In the case of the ammonium ion manufacturing apparatus, it can be seen that the reduction current increases with an increase in overpotential (FIG. 6), and in the case of the nitrate ion manufacturing apparatus, it can be seen that the oxidation current increases as the overvoltage increases (FIG. 7). .

<Experimental Example 3> Analysis of the selectivity of the ammonium ion production device and the nitrate ion production device

For the apparatus of Experimental Example 1, the current density obtained from the constant potential method performed in Experimental Example 2 and the current efficiency of the convertible products were calculated based on the analysis results of gas chromatography and ion chromatography. The results are shown in FIGS. 8 and 9.

In the case of the ammonium ion production apparatus, ammonium ions were selectively generated up to -0.3 V compared to the hydrogen reference electrode, and when a voltage lower than that is applied, it competes with the hydrogen generation reaction, but the ammonium generation reaction is dominant up to -0.4 V. It was confirmed that the hydrogen generation reaction dominated at a voltage of 0.45 V or less (FIG. 8).

On the other hand, in the case of the nitrate ion manufacturing apparatus, when a voltage of 1.25 V or less compared to the hydrogen reference electrode is applied, nitrite ions are the main product of the oxidation reaction, but when a voltage of 1.25 V or more is applied, it is confirmed that nitrate ions are selectively generated. (Fig. 9).

<Experimental Example 4> Analysis of the production rate of the ammonium ion production device and the nitrate ion production device

For the apparatus of Experimental Example 1, the production rate of ammonium ions according to the potential difference in voltage conditions of -0.13 V to -0.44 V compared to the hydrogen reference electrode and the nitrate ions according to the potential difference in voltage conditions of 1.26 V to 1.67 V compared to the hydrogen reference electrode. The production rate was calculated, and the results are shown in FIGS. 10 and 11. The production rate of ammonium is obtained by multiplying the ammonium-current efficiency obtained by multiplying the total current density obtained by the constant potential method and the ammonium selectivity calculated in Experimental Example 3 based on the results of gas chromatography and ion chromatography analysis, and multiplied by the reaction time (3600 seconds). After finding the amount of charge that flowed for 1 hour, divide it by the Faraday constant (96485.3399 C/mole electrons) and the number of electrons required for ammonium generation (5), and convert the electrode area (cm ² → m ² ) to finally NH ₄ ⁺ mole/ It was calculated in units of ^{m 2 /hr.} Likewise, the production rate of nitrate ions was calculated by multiplying the total current density obtained by the constant potential method and the nitrate ion selectivity calculated in Experimental Example 3 based on the results of gas chromatography and ion chromatography, and the reaction time (3600). Sec) to find the amount of charge that has flowed for 1 hour, divide it by the Faraday constant (96485.3399 C/mole electrons) and the number of electrons required for nitrate ion generation (3), and convert the electrode area (cm ² → m ² ) to finally NO ₃ ^-It was calculated in units of mole/m ^{2 /hr.}

In the ammonium ion production device, the ammonium ion production rate is excellent at -0.3 V to -0.5 V compared to the hydrogen reference electrode, and in particular, it can be seen that the fastest ammonium ion production rate is shown around -0.38 V. In the nitrate ion production device, 1.4 It can be seen that the production rate of nitrate ions is excellent at V to 1.7 V, and in particular, the production rate of nitrate ions is the fastest around 1.57 V.

<Experimental Example 5> Analysis of denitrification efficiency of the ammonium ion production device and the nitrate ion production device

For the apparatus of Experimental Example 1, the denitration rate was calculated based on the result of calculating the concentration of the generated nitrogen compound, and the results are shown in FIGS. 12 and 13. First, in the ammonium ion production apparatus, ^{it was calculated how quickly 50 mM Fe II} EDTANO used in the experiment was removed through the constant potential method. As calculated by Experimental Example 4, in the ammonium ion production apparatus, the production rates of all products that can be produced at the reduction potential such as nitrous oxide, nitrogen, and hydroxyl ammonium were calculated, and the sum of them became the removal rate of nitrogen monoxide. In the case of the nitrate ion production apparatus, the production rates of nitrate ions and nitrite ions were summed and calculated as the nitrogen monoxide removal rate, and the results are shown in FIGS. 12 and 13.

It can be seen that in the ammonium ion manufacturing apparatus, the denitrification rate increases as the potential difference increases, and then decreases again after showing the highest value near -0.38 V. It can be seen that after showing the highest efficiency in, it decreases again.

1000: ammonium nitrate manufacturing apparatus
100: ammonium ion production device
110: anode cell
111: anode outer wall
112: anode electrolyte chamber
113: anode electrode
120: cathode cell
121: cathode electrode
122: cathode electrolyte chamber
123: reference electrode
124: cathode outer wall
125: nitrogen oxide supply port
126: outlet
130: ion exchange membrane
200: nitrate ion manufacturing apparatus
210: anode cell
211: anode outer wall
212: anode electrode
212a: gas diffusion layer
212b: catalyst layer
213: reference electrode
214: anode electrolyte chamber
215: nitrogen oxide supply port
216: outlet
220: cathode cell
221: cathode electrode
222: cathode electrolyte chamber
223: cathode outer wall
230: ion exchange membrane

Claims (12)

An ammonium ion production apparatus including a cathode electrode, an anode electrode, a reference electrode, an electrolyte including a metal complex compound, and a nitrogen monoxide injection port in which a reduction reaction of a complex between nitrogen monoxide and a metal complex compound occurs; And
A cathode electrode, an anode electrode in which an oxidation reaction of nitrogen monoxide occurs, a reference electrode, an electrolyte, and an apparatus for producing nitrate ions including a nitrogen monoxide injection port;
The potential difference applied to the cathode electrode in the ammonium ion production apparatus is in the range of -0.1 V to -0.4 V compared to the hydrogen reference electrode,
Ammonium nitrate production apparatus, characterized in that the potential difference applied to the anode electrode in the nitrate ion production apparatus is in the range of 1.25 V to 3.0 V compared to the hydrogen reference electrode.
The method of claim 1,
In the ammonium ion production apparatus, the metal of the metal complex is a divalent metal, and the complex is ethylenediamine tetraacetic acid (EDTA), 1,2 cyclohexanediamine tetraacetic acid (CyDTA), and nitrotrisodium acetate (NTA). An apparatus for producing ammonium nitrate, characterized in that it is one salt selected from the group consisting of.
The method of claim 1,
In the ammonium ion manufacturing apparatus, the material of the cathode electrode is at least one selected from the group consisting of iron, glassy carbon (GC), aluminum, copper, silver, nickel, platinum, oxides thereof, and alloys thereof. An apparatus for producing ammonium nitrate, characterized in that.
The method of claim 1,
The ammonium nitrate production device, characterized in that the pH of the electrolyte in the ammonium ion production device is maintained in the range of 6 to 8.
delete delete The method of claim 1,
The apparatus for producing nitrate ions is an apparatus for producing ammonium nitrate, characterized in that the anode electrode includes a gas diffusion layer.
The method of claim 1,
The apparatus for producing ammonium nitrate, wherein the apparatus for producing nitrate ions comprises a catalyst layer on an anode electrode.
Introducing nitrogen monoxide into an ammonium ion production apparatus including a cathode electrode, an anode electrode, a reference electrode, an electrolyte including a metal complex compound, and a nitrogen monoxide injection port in which a reduction reaction of the complex between nitrogen monoxide and the metal complex compound occurs; Forming a complex between the introduced nitrogen monoxide and a metal complex compound in the electrolyte; And performing an electrochemical reduction reaction on the formed complex to produce ammonium ions;
Introducing nitrogen monoxide into a nitrate ion production apparatus including a cathode electrode, an anode electrode in which an oxidation reaction of nitrogen monoxide occurs, a reference electrode, an electrolyte, and a nitrogen monoxide injection port; Producing nitrate ions by performing an electrochemical oxidation reaction on the introduced nitrogen monoxide; And
A method for producing ammonium nitrate from nitrogen monoxide comprising; generating ammonium nitrate from the generated ammonium ions and nitrate ions,
In the step of preparing the ammonium ion, the electrochemical reduction reaction is performed at a potential difference of -0.1 V to -0.4 V compared to the hydrogen reference electrode,
In the step of preparing the nitrate ion, the electrochemical oxidation reaction is performed at a potential difference of 1.25 V to 3.0 V compared to the hydrogen reference electrode.
The method of claim 9,
The method for producing ammonium nitrate from nitrogen monoxide, characterized in that the concentration of the metal complex compound in the step of preparing the ammonium ion is 10 mM to 500 mM.
delete The method of claim 9,
The method for producing ammonium nitrate from nitrogen monoxide, characterized in that the pH of the electrolyte included in the ammonium ion production apparatus is maintained in the range of 6 to 8 in the step of preparing the ammonium ions.

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