KR101392828B1 - Ammonia fabrication method - Google Patents

Abstract

The present invention relates to a method for producing ammonia, wherein the ammonia is produced from water vapor and nitrogen gas supplied together, while carrying out a reforming process of hydrocarbon based fuel gas through a ion-conducting gas separation membrane by receiving oxygen absorbed in the reforming process of hydrocarbon based fuel gas from water vapor supplied to the opposite side to the side to which the hydrocarbon based fuel gas of the gas separation membrane is supplied through an ion permeation method. The method of the present invention comprises: a step of supplying hydrocarbon based fuel gas, while maintaining the temperature of 500°C to 700°C in a device for producing ammonia of which an inner space is divided into a first space and a second space by a gas separation membrane, which is a border, to allow one side of the gas separation membrane to contact with the first space; a step of supplying water vapor (H_2O) and nitrogen (N_2) gas with the pressure of 1 to 10 atm to allow the other side of the gas separation membrane to contact with the second space; a step of obtaining synthesis gas, which is a reaction product generated in the first space; and a step of obtaining ammonia which is produced in the second space. The method for producing ammonia of the present invention can produce ammonia from water vapor and nitrogen without electric energy supplied from outside as well as has an advantage of reforming hydrocarbon based fuel gas at the same time.

Description

Ammonia Fabrication Method [0002]

The present invention relates to a method for producing ammonia, and more particularly, to a method for producing ammonia, in which ammonia is synthesized at the same time as a hydrocarbon-based fuel gas is reformed using a gas separation membrane.

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. The molecular structure of ammonia has three hydrogen atoms that can form an equilateral triangle having one side of 0.163 nm, and the nitrogen atom is floating at 0.038 nm from the center of the equilateral triangle. There is a pair of unshared electron pairs in the nitrogen atom that makes up ammonia, so that ammonia can act as a proton acceptor, that is, a base. The dipole moment of ammonia becomes nonzero with a triangular-pyramidal molecular structure, and ammonia becomes a polar substance. The ammonia has a hydrogen bond, the length of the NH bond in the ammonia molecule is 0.1014 nm, and the bonding angle of HNH is 107 °.

Ammonia is used as a material for synthetic fertilizers. Nitrogen is one of the essential elements for plant growth. Naturally, some bacteria in soil cause nitrogen fixation that fixes nitrogen in the air as a nitrogen compound, which allows plants to absorb nitrogen. Ammonia contained in the fertilizer acts as a nitrogen source to the soil, allowing the crop to supply rich nitrogen, resulting in increased crop production. The nitrogen is fixed in the air by the harbor method to synthesize ammonia to make urea fertilizer.

Ammonium nitrate, ammonium nitrate with the formula NH ₄ NO ₃ is relatively safe even at about 200 ° C, but it acts as a powerful oxidant when it is accompanied by fuel such as petroleum. Bombs produced using this property of ammonium nitrate are called "fertilizer bombs" and ammonia is used as a raw material for explosives. In addition to its use as a raw material for synthesis of ammonium salts, nitric acid and urea, ammonia is used as a raw material for various chemical industries, for the production of ammonia water, and as a solvent for ionic substances.

The most common method for producing ammonia is a synthesis process using hydrogen and nitrogen. In the presence of a catalyst, one nitrogen molecule and three hydrogen molecules combine to form two ammonia molecules, generating heat of 100 kJ.

N ₂ + 3H ₂ -> 2NH ₃ + 100 kJ

U.S. Patent No. 7,811,442 discloses a method for producing electrochemical ammonia using water and nitrogen at atmospheric pressure. The disclosed contents are ammonia synthesis using a hydrogen cation electrolyte. Ni and Pd for the electrolytic solution electrode body and Co and Ru for the nitrogen decomposition electrode body have been proposed. Electrochemical ammonia production using water and nitrogen at atmospheric pressure has been widely used for hydrogen cations and oxygen anion electrolyte membranes [A. Skrodra, M. Stoukides, Solid State Ionics, 2009, 180, 1332], molten salts [T. Murakami et al., Electrochimica Acta, 2005, 50, 5234).

U. S. Patent No. 2007/0207351 discloses a method for storing ammonia and an electric energy production method using stored ammonia. There have been proposed methods for storing ammonia by using a salt and discharging ammonia from a salt when electric energy is needed and directly producing ammonia fuel cell or ammonia by injecting hydrogen produced in the existing fuel cell system .

However, since electrochemical ammonia production through water and nitrogen is a method of using electricity, there is a problem that an additional electric energy is consumed and the manufacturing cost of ammonia increases. Therefore, there is a need for a more energy-friendly method of producing ammonia.

SUMMARY OF THE INVENTION The present invention has been conceived to solve the problems of the prior art described above, and it is an object of the present invention to provide a reforming method for reforming a hydrocarbon-based fuel gas reforming process through a gas separation membrane, The present invention also provides a method for producing ammonia by synthesizing ammonia from water vapor and nitrogen gas supplied together.

In order to solve the above-described problems, the inventors of the present invention conducted a hydrocarbon-based fuel gas reforming process through a gas separation membrane, and found that the oxygen absorbed in the hydrocarbon-based fuel gas reforming process is reacted against the surface of the gas- It was found that ammonia can be synthesized from water vapor and nitrogen gas supplied together by receiving the water vapor supplied to the surface through the ion permeation system, thereby completing the present invention.

The present invention relates to a method of manufacturing an ammonia production apparatus in which the temperature of an ammonia production apparatus in which an inner space is divided into a first space and a second space with a boundary of a gas separation membrane is maintained at 500 ° C to 700 ° C, Supplying a hydrocarbon-based fuel gas so as to contact the one surface; Supplying water vapor (H ₂ O) and nitrogen (N ₂ ) gas at a pressure of 1 atm to 10 atm so as to be in contact with the other surface of the gas separation membrane in a second space of the manufacturing apparatus; Obtaining a synthesis gas which is a reactant generated in the first space; And obtaining ammonia produced in the second space.

The present invention also provides a method for producing ammonia, wherein the gas separation membrane is an ion-electron mixed conducting membrane.

The present invention also provides a method for producing ammonia, wherein the ion-electron mixed conducting membrane is composed of a single phase of perovskite.

The present invention is also characterized in that the ion-electron mixed conducting film comprises an electron conductive metal phase selected from silver (Ag), palladium (Pd), gold (Au) or platinum (Pt); And yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScSZ), Sm-doped ceria (SDC), gadolinium-doped ceria (GDC) or LaGaO3 The present invention provides a method for producing ammonia, which is a complex comprising an ion conductive fluorite phase.

The present invention is also characterized in that the ion-electron mixed conduction film comprises a dense structure of a perovskite system or a spinel system, an electron conductive oxide; And yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScSZ), Sm-doped ceria (SDC), gadolinium-doped ceria (GDC) or LaGaO3 The present invention provides a method for producing ammonia, which is a complex comprising an ion conductive fluorite phase.

The present invention also relates to a method of manufacturing an ammonia producing apparatus in which the temperature of the ammonia producing apparatus in which the inner space is divided into the first space and the second space by the boundary of the gas separating membrane module is maintained at 500 캜 to 700 캜, Supplying hydrocarbonaceous fuel gas so as to contact one surface of the membrane module; Supplying water vapor (H ₂ O) and nitrogen (N ₂ ) gas at a pressure of 1 atm to 10 atm so as to be in contact with the other surface of the gas separation membrane module in a second space of the manufacturing apparatus; Obtaining a synthesis gas which is a reactant generated in the first space; And obtaining ammonia produced in the second space.

The gas separation membrane module of the present invention may further comprise: a porous conductive support; A plurality of gas separation membranes formed in contact with the upper surface of the porous conductive support and separated from each other; A connection member which is in contact with the outer surface of the porous support and is disposed between the gas separation membranes separated from each other and in contact with the respective gas separation membranes; And a porous electrode active layer contacting the upper surfaces of the plurality of gas separation membranes and the support, wherein the porous electrode active layer is energized with the porous conductive support through a connecting material.

The present invention is also characterized in that the gas separation membrane comprises at least one of yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScSZ), gadolinia doped-ceria (GDC) Wherein the ammonia comprises at least one material selected from the group consisting of Smaria doped-Ceria, and Lanthanum gallates.

The present invention also provides a method for producing ammonia, wherein the porous conductive support and the porous electrode active layer are selected from a porous metal, a cermet, and an electron conductive metal oxide.

The present invention also provides a method for producing ammonia, wherein the porous metal is selected from nickel, nickel alloys, and iron-based alloys.

The present invention also relates to a cermet according to the invention, wherein the cermet is a composite of a porous metal and a gas separation membrane material, wherein the porous metal is selected from nickel, a nickel alloy, and an iron-based alloy, the gas separation membrane comprising yttria-stabilized zirconia zirconia, YSZ, scandia-stabilized zirconia (ScSZ), gadolinia doped-ceria (GDC), Smaria doped-Ceria, and lanthanum gallates. Wherein the at least one material is selected from the group consisting of:

The present invention also provides a method for producing ammonia, wherein the linking material is a metal or a dense structure of an electron conductive metal oxide.

The present invention also provides a method for producing ammonia, wherein the metal is selected from silver (Ag), palladium (Pd), gold (Au), and platinum (Pt).

The present invention also provides a method of manufacturing a semiconductor device, wherein the electron conductive metal oxide is selected from the group consisting of perovskite series, lanthanum strontium ferrite (LSF), lanthanum strontium manganite (LSM), lanthanum strontium cobaltate LSC, lanthanum strontium chromite (LSCr), lanthanum strontium cobalt ferrite (LSCF), spinel oxide manganese ferrite (MnFe ₂ O ₄ ), and nickel ferrite (NiFe ₂ O ₄ ) Wherein the ammonia is at least one selected from the group consisting of ammonia and ammonia.

The present invention also provides a method for producing ammonia, wherein the hydrocarbon-based fuel gas is at least one selected from the group consisting of methane, methanol, ethanol, propane and butane.

The present invention has an advantage that ammonia can be produced from water vapor and nitrogen without using external electric energy, and also the hydrocarbon fuel gas can be reformed at the same time.

1 is a schematic diagram showing a process for producing electrochemical ammonia using oxygen ion conduction or proton conduction.
2 is a conceptual diagram showing a methane reforming process and ammonia production process using a mixed conductive or composite oxygen separator.
3 is a conceptual diagram showing a methane reforming process and an ammonia production process using an ion conductive membrane module.

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

A separation membrane is a material having a function of selectively restricting the movement of a substance between two phases. With the recent demand for high-purity and high-quality products due to the advancement and diversification of industries, the separation process is recognized as a very important process. Therefore, not only industrial fields such as chemical industry, food industry and pharmaceutical industry, but also medical, biochemical and environmental fields It is becoming an important research subject.

Gas separation using membranes proceeds by selective gas permeation principle for membranes. That is, when the gas mixture contacts the surface of the membrane, the gas component dissolves and diffuses into the membrane, where the solubility and permeability of each gas component are different for the membrane material. The propulsive force for gas separation is the partial pressure difference for the particular gas component applied across the membrane. In particular, the membrane separation process using a separation membrane has been widely used in various fields because it has no phase change and energy consumption is low.

The present invention provides a method for producing ammonia using a mixed conducting gas separation membrane and a gas separation membrane module. The gas separation membrane module may be a mixed conducting or composite separating membrane. The gas separation membrane module may include a porous electrically conductive oxide (for example, perovskite or spinel) or a metal membrane on both sides of a dense fluorite ion- And the electrically conductive films located on both sides of the conductive film are electrically connected. The gas separation membrane module includes a porous conductive support, a plurality of mutually separated gas separation membranes formed on the upper surface of the porous conductive support, a connection member positioned between the gas separation membranes, and a porous electrode activation layer disposed on the gas separation membrane and the connection member.

1 shows a process for producing electrochemical ammonia by applying external electric power to an ion conductive gas separation membrane. Proton, which is an oxygen ion or a hydrogen ion, moves through the ion conductive gas separation membrane and electrons are supplied through an external power source. The proton transmittance, which is an oxygen ion or a hydrogen ion, is precisely controlled by current supply, and oxygen or hydrogen can move in either direction irrespective of the partial pressure of oxygen or hydrogen gas located in both directions of the separation membrane.

1 (a) shows a porous electrode active layer on both sides of an oxygen separation membrane. Electrons are supplied to a porous electrode active layer through which water vapor is supplied, and oxygen separated from water vapor is converted into an anion to pass through the ion conductive separator. Separated from the power source, the oxygen in the water vapor supplied from the power source is ionized. After passing through the separation membrane, the electrode active layer located on the opposite side of the surface to which the water vapor is supplied is separated into oxygen gas, oxygen is separated, and the remaining hydrogen reacts with nitrogen Ammonia. The reaction formula for supplying steam and nitrogen to the oxygen separation membrane and synthesizing ammonia using the power source is as follows.

3H ₂ O + N ₂ - > 2NH _{3 +} (3/2) O ₂

In FIG. 1 (b), the porous electrode active layer is present on both sides of the hydrogen separation membrane, and electrons are separated from hydrogen by the power source in the porous electrode active layer to which water vapor is supplied, so that a proton, which is a hydrogen ion, permeates the ion conductive separator. The hydrogen of the water vapor supplied from the power source is ionized and passes through the separation membrane and is synthesized as ammonia in contact with electrons and nitrogen gas in the electrode active layer located on the opposite side of the surface to which the water vapor is supplied. The reaction scheme for supplying ammonia with water vapor and nitrogen to the hydrogen separation membrane is as follows.

^{6H + + N2 + 6e - -} > 2NH 3

2 shows a structure for producing ammonia from water vapor and nitrogen using a reforming reaction of a hydrocarbon-based fuel gas through a mixed conducting or composite oxygen separating membrane (3). The ion-permeable ceramics membrane for oxygen permeation is largely classified into a pure oxygen ion conducting membrane and a mixed ionic-electronic conducting membrane (MIEC). The pure oxygen ion conductive membrane requires an external power source and an electrode to supply the current and the oxygen ion permeation amount is precisely controlled by the current supply and the oxygen can move in either direction irrespective of the partial pressure of oxygen placed in both directions of the membrane . In contrast, the ion-electron mixed conducting membrane transmits oxygen ions and electrons by the pressure difference of oxygen without external power supply. The ion-electron mixed conducting membrane mainly consists of a single-phase ion-electron mixed conducting membrane composed of a single phase of perovskite, which permeates both oxygen ions and electrons, and a two- Phase mixed ion-exchange membrane, wherein the double phase ion-electron mixed conduction film permeates (5) an electron-conductive oxide material or a metal phase and an ion that permeates electrons (5) ) Fluorite phase or a fluorite phase.

The dual phase ion-electron mixed conducting membrane has a fluorosilicic oxide which inherently has strong stability against acidic or reducing gases. The double phase ion-electron mixed conductive film may be formed of a metal phase selected from silver (Ag), palladium (Pd), gold (Au) or platinum (Pt), yttria- doped ceria (SDC), or gadolinium-doped ceria (GDC), LaGaO3, and the like.

In addition, a complex of a fluorite phase or a fluorite phase which transmits an electron conductive oxide (for example, a perovskite system or a spinel system) and ions in the double phase ion-electron mixed conductive film may be a dense complex having electron conductivity Sintering is essential for the production of a separator of the form.

In the process of producing ammonia from water and nitrogen using the reforming reaction of hydrocarbon-based fuel gas such as methane, methanol, ethanol, propane or butane through the mixed conducting or composite separating membrane, the hydrocarbon-based fuel gas is a reducing gas, Thereby giving a driving force for moving oxygen from the opposite electrode. When the hydrocarbon-based fuel supplied to the reforming gas when water vapor on the other side electrode with a separator (H ₂ O) and nitrogen (N ₂₎ gas, the ammonia is synthesized from nitrogen and hydrogen is an out oxygen out of the residual water from the reaction.

In this case, since the electric energy is not used, not only the production cost of ammonia can be lowered but also synthesis gas (for example, H ₂ + CO) can be produced simultaneously by reforming hydrocarbon fuel gas. Therefore, it is a method that can simultaneously realize modification of hydrocarbon fuel gas and ammonia production. The synthesized gas thus prepared can be obtained through a collecting process known to a person skilled in the art.

In one embodiment of the present invention, the hydrocarbon-based fuel gas reforming and ammonia production using the mixed conducting or composite separating membrane is performed at a temperature of 500 ° C to 700 ° C in the space where the separation membrane belongs, and the supply pressure of the steam and nitrogen is about 10 atmospheric pressure is required, and the fuel gas, methane, methanol, ethanol, propane or butane, is supplied at normal pressure. The produced ammonia can be collected by any of the ammonia collection processes known to those skilled in the art. In one embodiment of the present invention, ammonia is collected using water to obtain ammonia water.

FIG. 3 is a cross-sectional view of a membrane module for ammonia production, in which a porous membrane electrode assembly and an electrode active layer are located on a top surface of a membrane electrode assembly and a connecting member. The module comprises a porous conductive support (10), a plurality of ion conductive gas separation membranes (20) formed in contact with the upper surface of the porous conductive support and separated from each other, an ion conductive A connecting member (30) positioned between the gas separating membranes so as to be in contact with the respective gas separating membranes; And a porous electrode active layer (40) in contact with the upper surfaces of the plurality of ion conductive gas separation membranes and the support, wherein the porous electrode active layer is energized with the porous conductive support through a connection material.

The porous conductive support 10 forms a frame of the module and is composed of an electrically conductive material since electrons and ions flow. The porous conductive support used in one embodiment of the present invention is composed of a porous metal, a cermet or an electron conductive metal oxide which is a porous metal and an oxygen separation membrane material composite.

The porous metal is selected from nickel, a nickel alloy, and an iron-based alloy. Cermet, which is a porous metal and an oxygen separation membrane material composite, is a porous metal selected from the group consisting of nickel, nickel alloy, and iron-based alloy, yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia Scandium Phosphorus (ScSZ), gadolinia doped-ceria (GDC), Smaria doped-Ceria, and lanthanum gallates. And the compressive strength.

When the gas such as methane is supplied to the cermet electrode in the natural gas reforming process including methane (CH ₄ ), the cermet is reformed into synthesizers H ₂ and CO by the permeation of oxygen.

In one embodiment of the present invention, the connecting material is a metal or a dense electron conductive metal oxide, and the metal is selected from among silver (Ag), palladium (Pd), gold (Au) and platinum do.

The electron conductive metal oxide may include a perovskite type lanthanum strontium ferrite (LSF), a lanthanum strontium manganite (LSM), a lanthanum strontium cobaltate (LSC) Lanthanum strontium chromite (LSCr), lanthanum strontium cobalt ferrite (LSCF), spinel oxide (MnFe ₂ O ₄ ), nickel ferrite (NiFe ₂ O ₄ ) And a high porosity and an excellent compressive strength.

In one embodiment of the present invention, the gas separation membrane 20 is an oxygen separation membrane, and the oxygen separation membrane is formed of yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScSZ) And one or more materials selected from the group consisting of gadolinia doped-ceria (GDC), Smaria doped-Ceria, and lanthanum gallates.

The porous electrode active layer 40, which is a catalyst layer formed on the gas separation membrane 20 and the connecting material 30, is electrically connected to the support 10 through the connection material. The support 10 and the porous electrode active layer 40 are made of a material selected from a porous metal, a cermet, and an electron conductive metal oxide having a porous structure.

In an embodiment of the present invention, the hydrocarbon-based fuel gas reforming and the ammonia production using the oxygen separation membrane module are performed at a temperature of 500 ° C. to 700 ° C. and a supply pressure of the steam and nitrogen of about 10 Atmospheric pressure conditions are required, and the fuel gas, methane, methanol, ethanol, propane or butane, is supplied at normal pressure. The produced ammonia can be collected by any of the ammonia collection processes known to those skilled in the art. In one embodiment of the present invention, ammonia is collected using water to obtain ammonia water.

In the production of ammonia using the membrane module, since hydrocarbon fuel gas, methane, methanol, ethanol, propane or butane, is a reducing gas, it induces a difference in oxygen partial pressure and gives driving force to move oxygen from the opposite electrode. When the water vapor (H ₂ O) and nitrogen (N ₂ ) gas are supplied to the opposite electrode in the reforming of the natural gas using the membrane module, oxygen in the water vapor escapes and the remaining hydrogen reacts with nitrogen to synthesize ammonia. For this, the temperature of the module is maintained at 500 ° C to 700 ° C, and the steam and nitrogen supply pressure maintains a constant pressure value between normal pressure and 10 atmospheres. The oxygen ion permeates the oxygen separation membrane in the form of oxygen ions, which are anions, in the porous electrode active layer having a high oxygen partial pressure state and in the direction of the support having a low oxygen partial pressure state, and the electrons are transmitted through the coupling material to the support layer and the porous electrode active layer (52). ≪ / RTI > In this way, the gas separator module selectively transmits oxygen through the exchange of oxygen ions through the conductive gas separation membrane and the exchange reaction of electrons by the coupling material.

In one embodiment of the present invention, hydrocarbon fuel gas such as methanol, ethanol, propane, and butane, as well as methane, which is a reducing gas, can be used in the cermet using the porous conductive support as the cermet of the gas separation membrane module. This is because, for example, in the case of the NiO-YSZ composite, the reducing gas is supplied so that the NiO is reduced to Ni, thereby maintaining the thermometry.

The porous electrode active layer has an ionization reaction of oxygen molecules (O ₂ + 4e ^- → 2O < ^{2 &} gt ^; ), and maintains the porous structure so that water vapor diffuses to the electrolyte surface and ionizes.

The hydrocarbon-based fuel gas is supplied to the cermet portion and nitrogen gas is supplied together with water vapor to the porous electrode active layer located on the cermet base on the basis of the gas separation membrane to allow oxygen to separate and pass through the gas separation membrane, Hydrogen reacts with the supplied nitrogen gas to synthesize ammonia. That is, the hydrocarbon-based fuel gas such as methane gas is modified in the support and ammonia is synthesized in the porous electrode active layer. The synthesized ammonia can be collected by any of the ammonia collection processes known to those skilled in the art. In one embodiment of the present invention, ammonia is collected using water to obtain ammonia water.

The hydrocarbon-based fuel gas reforming in the support of the gas separation membrane module and the synthesis of ammonia in the porous electrode active layer can be carried out not only when the support and the porous electrode active layer are cermets, but also when diffusion of fuel gas, steam and nitrogen gas such as porous metal and electron conductive metal oxide It is also possible to increase the speed of the porous layer.

3. Mixed conducting or composite oxygen separator
10. Porous conductive support 20. Ion conductive gas separation membrane
30. Connecting material 40. Porous electrode active layer
51. Oxygen ion flow 52. Oxygen separator electron flow

Claims (15)

The temperature of the ammonia production apparatus in which the inner space is divided into the first space and the second space by the boundary of the gas separation membrane is maintained at 500 ° C. to 700 ° C. and the first space of the production apparatus is brought into contact with one surface of the gas separation membrane Supplying a hydrocarbon-based fuel gas;
Supplying water vapor (H ₂ O) and nitrogen (N ₂ ) gas at a pressure of 1 atm to 10 atm so as to be in contact with the other surface of the gas separation membrane in a second space of the manufacturing apparatus;
Obtaining a synthesis gas which is a reactant generated in the first space; And
And obtaining ammonia produced in said second space.
Ammonia.
The method according to claim 1,
Wherein the gas separation membrane is an ion-electron mixed conducting membrane,
Ammonia.
3. The method of claim 2,
Wherein the ion-electron mixed conducting film is made of a perovskite single phase,
Ammonia.
3. The method of claim 2,
The ion-electron mixed conduction film may be formed by,
An electron conductive metal phase selected from silver (Ag), palladium (Pd), gold (Au) or platinum (Pt); And
Ions selected from yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScSZ), Sm-doped ceria (SDC), gadolinium-doped ceria (GDC) A composite comprising a conductive fluorite phase,
Ammonia.
3. The method of claim 2,
The ion-electron mixed conduction film may be formed by,
An electron conductive oxide having a dense structure perovskite system or spinel system; And
Ions selected from yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScSZ), Sm-doped ceria (SDC), gadolinium-doped ceria (GDC) A composite comprising a conductive fluorite phase,
Ammonia.
The temperature of the ammonia production apparatus in which the inner space is divided into the first space and the second space by the boundary of the gas separation membrane module is maintained at 500 ° C. to 700 ° C. and the first space of the gas separation membrane module Supplying a hydrocarbon-based fuel gas such that the hydrocarbon-based fuel gas is in contact therewith;
Supplying water vapor (H ₂ O) and nitrogen (N ₂ ) gas at a pressure of 1 atm to 10 atm so as to be in contact with the other surface of the gas separation membrane module in a second space of the manufacturing apparatus;
Obtaining a synthesis gas which is a reactant generated in the first space; And
And obtaining ammonia produced in said second space.
Ammonia.
The method according to claim 6,
In the gas separation membrane module,
A porous conductive support;
A plurality of gas separation membranes formed in contact with the upper surface of the porous conductive support and separated from each other;
A connection member which is in contact with the outer surface of the porous support and is disposed between the gas separation membranes separated from each other and in contact with the respective gas separation membranes; And
And a porous electrode active layer contacting the upper surfaces of the plurality of gas separation membranes and the support, wherein the porous electrode active layer is electrically connected to the porous conductive support through a connection material,
Ammonia.
8. The method of claim 7,
The gas separation membrane may include at least one of yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScSZ), gadolinia doped-ceria (GDC), Smaria doped -Ceria), and lanthanum gallates.
Ammonia.
8. The method of claim 7,
Wherein the porous conductive support and the porous electrode active layer are selected from a porous metal, a cermet, and an electron conductive metal oxide.
Ammonia.
10. The method of claim 9,
Wherein the porous metal is selected from nickel, a nickel alloy, and an iron-
Ammonia.
10. The method of claim 9,
The cermet is a composite of a porous metal and a gas separation membrane material,
The porous metal is selected from nickel, a nickel alloy, and an iron-based alloy,
The gas separation membrane may include at least one of yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScSZ), gadolinia doped-ceria (GDC), Smaria doped -Ceria), and lanthanum gallates.
Ammonia.
8. The method of claim 7,
Wherein the linking material is a metal or a dense structure of an electron conductive metal oxide,
Ammonia.
13. The method of claim 12,
Wherein the metal is selected from silver (Ag), palladium (Pd), gold (Au), and platinum (Pt)
Ammonia.
The method according to claim 9 or 12,
The electron conductive metal oxide may be at least one selected from the group consisting of perovskite type lanthanum strontium ferrite (LSF), lanthanum strontium manganite (LSM), lanthanum strontium cobaltate (LSC), lanthanum strontium At least one selected from the group consisting of Lanthanum strontium Chromite (LSCr), Lanthanum strontium cobalt ferrite (LSCF), spinel oxide (MnFe ₂ O ₄ ), and nickel ferrite (NiFe ₂ O ₄ ) ,
Ammonia.
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