WO2014168377A1 - Plate-type module of gas separation film and method for manufacturing same - Google Patents

Abstract

The present invention relates to a plate-type module structure for connecting and extending a support layer, which exchanges gas ions by using an ion-conductive separation film and is formed from a dense-structure electronic-conductive material, or a unit short circuit separation film for selectively passing a gas through an electron exchange reaction by the film. The present invention has the advantage of: obtaining remarkable chemical and mechanical durability by using a fluorite-based ion-conductive film which is stable at high temperatures, specifically, within a CO₂ and H₂O atmosphere; and manufacturing a pure gas at a low cost since gas can be passed by using an internal circuit without applying a voltage from the outside. In addition, the present invention enables a compact separation film module for manufacturing a gas by stacking plate-type films to be easily formed, and the separation film module to be manufactured by using a tape casting method, and thereby simplifying a manufacturing process.

Description

Gas separation membrane plate module and manufacturing method

The present invention relates to a gas separation membrane plate module structure for connecting and expanding a unit short-circuit membrane through which gas is permeated through exchange of gas ions through a gas separation membrane and exchange of electrons by a support layer or membrane made of an electron conductive material. .

Ion-permeable ceramic membrane membranes for gas permeation are largely divided into pure gas ion conductive membranes and mixed ionic-electronic conducting (MIEC) membranes. Pure gas ion conductive membranes require an external power source and electrodes to supply current, and the gas ion permeation rate is precisely controlled by the current supply, and the gas can move in any direction regardless of the partial pressure of oxygen located in both directions of the membrane. have. In contrast, the ion-electron mixed conductive film transmits gas ions and electrons by the pressure difference of the gas without supplying external power. The ion-electron mixed conductive film mainly consists of a Perovskite single phase, which transmits both gas ions and electrons, and two different electron and gas ions. There is a dual phase ion-electron mixed conducting film which respectively transmits into a phase, and the dual phase ion-electron mixed conducting film has an electron conducting oxide material or a metal phase and a fluorite structure or fluorite which transmits electrons. It includes a fluorite phase.

The perovskite constituting the single-phase ion-electron mixed conductive film is formed of oxides of the gas and perovskite in the presence of an acidic or reducing gas such as CO ₂ , H ₂ S, H ₂ O, or CH ₄ . It is chemically unstable because the reaction destroys the perovskite structure. That is, most of the mixed conducting oxides are difficult to be used in actual process conditions because they have a problem of decomposing in the form of carbonate or hydroxide in the presence of CO ₂ or H ₂ O.

The dual phase ion-electron mixed conductive film has a fluorspar structure oxide which has inherently strong stability to the acidic or reducing gas. The dual phase ion-electron mixed conductive film is a metal phase selected from silver (Ag), palladium (Pd), gold (Au), or platinum (Pt), and yttria-stabilized zirconia (YSZ) and scandia stabilized zirconia. (scandia-stabilized zirconia, ScSZ), samarium implanted ceria (Sm-doped ceria, SDC), or gadolinium implanted ceria (Gd-doped ceria, GDC), LaGaO ₃ and the like. Since the metal phase and the ion conducting phase must have a path connected across the membrane, a large amount of expensive metals are required, as well as a conductivity problem according to the manufacturing method, thereby lowering the gas ion permeability.

In addition, in the dual phase ion-electron mixed conductive film, a complex of an electron conductive oxide (eg, perovskite-based or spinel-based) and a fluorite structure or a fluorite phase that transmits ions is a dense complex having electron conductivity. Sintering is essential to make the separator in the form. However, when sintering, the problem of two materials reacting is inevitable, which leads to low gas ion permeability. That is, this method forms an insulating layer at the interface by the reaction between the two materials during the sintering process to produce a dense gas separation membrane, there is a problem that the gas permeability is lowered (see Non-Patent Document 1).

Accordingly, there is a need for a new separator that balances chemical stability and gas ion permeability. To solve this problem, an ion conductive ceramic separator with an external short circuit has been developed. The porous electrically conductive metal film is coated on both sides of the dense fluorite phase conductive film and the wires are connected to both metal films to the outside, so that the gas ion conduction through the ceramic separator and the electron conduction through the wire (Galvanic method) It occurs as a short circuit membrane.

The externally connected wire serves as a metal paste such as silver (Ag) for sealing between two different gases separated by the ceramic separator coated with the metal membrane instead of electrically contacting the metal coated on both ends of the ceramic separator. can do. However, conventional membranes with external short circuits are limited to thinner materials because they are ion-conductive ceramic supports. In addition, if the large area is increased, the conduction path of the electrons is increased, and thus the resistance is increased, so that high transmittance cannot be obtained. Since a metal such as Ag, Pt, and Au must be used as the conductive sealing material, manufacturing cost increases. Therefore, there is a need to develop a technology capable of realizing a short-circuit separation membrane having a low manufacturing cost while reducing the thickness of the ion conductive membrane.

Until now, the concept of a modular modular membrane has not been reported, and the conventional technology is based on a plate-shaped structure in constructing a module, and in the case of the Galvanic method, a separate electric energy is consumed because voltage must be applied from the outside. There is a problem that the oxygen production cost is high. In the case of the cylindrical membrane disclosed in US Pat. No. 6,565,632, since the membrane area is small in the unit volume, there is a problem in that the equipment cost occupied by the gas production equipment increases when a large area and a large capacity gas production module is to be manufactured.

U.S. Pat.No. 7,556,676 also discloses a technique for mixed oxygen ion conductive gas separation membranes. The gas separation membrane is composed of an electronic phase, an ionic phase, and a porous support layer, and the ion phase and the electronic phase have a constant size, thereby limiting miniaturization.

In consideration of these problems, a technical development of a gas separation membrane module having a more compact structure is required.

[Preceding technical literature]

[Patent Documents]

(0001) United States Patent US 7,556,676

(0002) United States Patent US 6,565,632

[Non-Patent Documents]

(0001) Kharton et al., “Oxygen transport in Ce _0.8 Gd _0.2O2 d-based composite membranes”, Solid State Ionics, 160 (2003), 247

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and selectively transmits gas through exchange of gas ions through an ion conductive gas separation membrane and exchange of electrons by a support layer or membrane made of an electron conductive material. Provides a plate-like module structure for connecting and expanding unit short-circuit separators.

In order to solve the above problems, the present inventors connect a unit short-circuit separator which selectively permeates gas through the exchange of gas ions using an ion conductive separator and the exchange of electrons by a support layer or membrane made of a dense structure electron conductive material. And to find a plate-like module structure for expansion, to complete the present invention.

The present invention includes a support made of a plate-shaped dense structure electronic conductive material having a plurality of holes; A plurality of plate-type gas separation membranes which cover each space formed by the plurality of holes in contact with an upper surface of the support and are separated from each other; An upper porous electrode active layer coated on the plate-type gas separation membrane and the support; And a lower porous electrode active layer disposed in contact with a lower surface of the plate-type gas separation membrane and an upper surface of the cogwheel inner surface of the support, wherein the upper porous electrode active layer is energized to the lower porous electrode active layer through a support layer. To provide.

The present invention also comprises a gas separation membrane formed with a plurality of co-gyu; A membrane made of a plurality of plate-shaped dense structure electronic conductive materials which cover each space formed by the plurality of holes in contact with an upper surface of the separator and are separated from each other; An upper porous electrode active layer coated on an upper surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact; And a lower porous electrode active layer coated on a lower surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact, wherein the upper porous electrode active layer is energized to the lower porous electrode active layer through a membrane made of an electronic conductive material. Provides a plate module.

The present invention also provides a plurality of bands are ion-conductive gas separation membrane in the form of being arranged parallel to each other spaced at regular intervals; A membrane made of a dense structured electronically conductive material having a parallel band shape and covering each space formed by the gap to be in contact with an upper surface of the separator and separated from each other; An upper porous electrode active layer coated on an upper surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact; And a lower porous electrode active layer coated on a lower surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact, wherein the upper porous electrode active layer is energized to the lower porous electrode active layer through a membrane made of an electronic conductive material. Provides a plate module.

The present invention also provides a gas separation membrane plate module, wherein the electron conductive material is selected from cermet, electron conductive metal oxide, and ion conductive electrolyte material-electroconductive metal oxide composite.

The present invention also, the cermet is a composite of an ion conductive electrolyte material and one selected from nickel, nickel alloy, and iron-based alloy, the ion conductive electrolyte material is yttria-stabilized zirconia (YSZ), Scandia stabilized zirconia (scandia-stabilized zirconia, ScSZ), gd doped-ceria (GDC), samarium injected ceria (Sm doped-Ceria), lanthanum gallates, SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O _{7 It} is made of at least one material, the ion conductive electrolyte material included in the cermet, the gas separation membrane, the same material as the gas separation membrane, Provides a plate module.

The present invention, the electron conductive metal oxide, strontium titanium ferrite (SrTi _1-x Fe _x O _3-δ , STF), lanthanum strontium ferrite (LSF), lanthanum strontium manganite (Lanthanum strontium Manganite, LSM), lanthanum strontium cobalt tight (lanthanum strontium Cobatite, LSC), lanthanum strontium chromite (lanthanum strontium chromite, LSCr), lanthanum strontium cobalt ferrite (lanthanum strontium cobalt ferrite, LSCF) , manganese ferrite (MnFe ₂ O _4), and At least one selected from nickel ferrite (NiFe ₂ O ₄ ), and the ion conductive electrolyte material-electroconductive metal oxide composite is composed of an ion conductive electrolyte material and the electron conductive metal oxide, and in the composite, the ion conductive electrolyte material The volume ratio of 20 to 80%, the ion conductive electrolyte material, yttria stabilized zirconia (ytt ria-stabilized zirconia (YSZ), scandia-stabilized zirconia (SCSZ), gadolinia doped-ceria (GDC), Smaria doped-Ceria, lanthanum gallate gallates) at least one selected from SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O ₇ , and the ion conductive electrolyte material included in the composite is Provided is a gas separation membrane plate module, which is the same material as the gas separation membrane.

The present invention, the gas separation membrane is a hydrogen separation membrane or oxygen separation membrane having a thickness of 50 to 500μm, the oxygen separation membrane is yttria-stabilized zirconia (YSZ), Scandia-stabilized zirconia (ScZ) , Gadolinium implanted ceria (Gd doped-ceria, GDC), samarium implanted ceria (Sm doped-Ceria), and lanthanum gallates (Lanthanum gallates) of one or more materials selected from, the hydrogen separation membrane is SrCeO ₃ , BaCeO _It provides a gas separation membrane plate module consisting of one or more materials selected from ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O ₇ .

In another aspect, the porous electrode active layer is selected from a porous metal, a porous cermet, and a porous electron conductive metal oxide, and the porous metal is one selected from nickel, a nickel alloy, and an iron-based alloy. To provide.

The present invention, the electron conductive metal oxide, strontium titanium ferrite (SrTi _1-x Fe _x O _3-δ , STF), lanthanum strontium ferrite (LSF), lanthanum strontium manganite (Lanthanum strontium Manganite, LSM), lanthanum strontium cobalt tight (lanthanum strontium Cobatite, LSC), lanthanum strontium chromite (lanthanum strontium chromite, LSCr), lanthanum strontium cobalt ferrite (lanthanum strontium cobalt ferrite, LSCF) , manganese ferrite (MnFe ₂ O _4), and Provided is a gas separation membrane plate module, which is at least one selected from nickel ferrite (NiFe ₂ O ₄ ).

The present invention also, the cermet is a composite of an ion conductive electrolyte material and one selected from nickel, nickel alloy, and iron-based alloy, the ion conductive electrolyte material is yttria-stabilized zirconia (YSZ), Scandia stabilized zirconia (scandia-stabilized zirconia, ScSZ), gd doped-ceria (GDC), samarium injected ceria (Sm doped-Ceria), lanthanum gallates, SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O _{7 It} is made of at least one material, the ion conductive electrolyte material included in the cermet, the gas separation membrane, the same material as the gas separation membrane, Provides a plate module.

The present invention also provides a method for manufacturing a support tape made of a plurality of porous plate-shaped electronically conductive materials using a tape casting process; Stacking a plurality of gas separator membrane tapes on a support tape made of the plate-shaped dense structure electronic conductive material such that each of the gas separator membranes is separated from each other; Co-sintering the gas separation membrane tape and the support tape made of the plate-shaped dense structure electronic conductive material at 1200 to 1500 ° C. for densification after the laminating step; And coating a porous electrode active layer on an upper surface of the gas separation membrane covering the cavity and an upper surface of the support and an upper surface of the gas separation membrane exposed to the inside of the cavity and an upper surface of the inner surface of the cavity. Provide a method.

The present invention also provides a method of manufacturing a gas separation membrane tape having a plurality of coarse particles using a tape casting process; Covering the plurality of holes with a membrane tape made of a plurality of densely structured electronically conductive materials, and laminating them on the upper surface of the gas separation membrane tape such that the films made of the electronically conductive materials are separated from each other; Co-sintering the gas separation membrane tape and the membrane tape made of the electronic conductive material at 1200 to 1500 ° C. for densification after the laminating; And coating a porous electrode active layer on an upper surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact, and a lower surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact. To provide.

The present invention also provides a method for manufacturing a plurality of strip-shaped gas separator tapes using a tape casting process; The plurality of gas separation membranes are spaced at regular intervals and arranged in parallel to each other, and each of the spaces formed by the gaps is covered with a membrane tape made of a dense structure of an electron conductive material, and the membrane tapes made of the electronic conductive materials Stacking on the upper surface of the gas separation membrane tape to be separated and positioned; Simultaneously sintering the gas separation membrane tape and the membrane tape made of the electronic conductive material at 1200 to 1500 ° C. for densification after the laminating; And coating a porous electrode active layer on an upper surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact, and a lower surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact. To provide.

The present invention also provides a gas separation membrane plate module, wherein the electron conductive material is selected from cermet, electron conductive metal oxide, and ion conductive electrolyte material-electroconductive metal oxide composite.

The present invention also, the cermet is a composite of an ion conductive electrolyte material and one selected from nickel, nickel alloy, and iron-based alloy, the ion conductive electrolyte material is yttria-stabilized zirconia (YSZ), Scandia stabilized zirconia (scandia-stabilized zirconia, ScSZ), gd doped-ceria (GDC), samarium injected ceria (Sm doped-Ceria), lanthanum gallates, SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O _{7 It} is made of at least one material, the ion conductive electrolyte material included in the cermet, the gas separation membrane, the same material as the gas separation membrane, It provides a method of manufacturing a plate module.

The present invention, the electron conductive metal oxide, strontium titanium ferrite (SrTi _1-x Fe _x O _3-δ , STF), lanthanum strontium ferrite (LSF), lanthanum strontium manganite (Lanthanum strontium Manganite, LSM), lanthanum strontium cobalt tight (lanthanum strontium Cobatite, LSC), lanthanum strontium chromite (lanthanum strontium chromite, LSCr), lanthanum strontium cobalt ferrite (lanthanum strontium cobalt ferrite, LSCF) , manganese ferrite (MnFe ₂ O _4), and At least one selected from nickel ferrite (NiFe ₂ O ₄ ), and the ion conductive electrolyte material-electroconductive metal oxide composite is composed of an ion conductive electrolyte material and the electron conductive metal oxide, and in the composite, the ion conductive electrolyte material The volume ratio of 20 to 80%, the ion conductive electrolyte material, yttria stabilized zirconia (ytt ria-stabilized zirconia (YSZ), scandia-stabilized zirconia (SCSZ), gadolinia doped-ceria (GDC), Smaria doped-Ceria, lanthanum gallate gallates) at least one selected from SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O ₇ , and the ion conductive electrolyte material included in the composite is Provided is a method for producing a gas separation membrane plate module, which is the same material as the gas separation membrane.

The present invention, the gas separation membrane is a hydrogen separation membrane or oxygen separation membrane having a thickness of 50 to 500μm, the oxygen separation membrane is yttria-stabilized zirconia (YSZ), Scandia-stabilized zirconia (ScZ) , Gadolinium implanted ceria (Gd doped-ceria, GDC), samarium implanted ceria (Sm doped-Ceria), and lanthanum gallates (Lanthanum gallates) of one or more materials selected from, the hydrogen separation membrane is SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O ₇ Provides a method for producing a gas separation membrane plate module consisting of one or more materials selected from.

In another aspect, the porous electrode active layer is selected from a porous metal, a porous cermet, and a porous electron conductive metal oxide, and the porous metal is one selected from nickel, a nickel alloy, and an iron-based alloy. It provides a method of manufacturing.

The present invention, the electron conductive metal oxide, strontium titanium ferrite (SrTi _1-x Fe _x O _3-δ , STF), lanthanum strontium ferrite (LSF), lanthanum strontium manganite (Lanthanum strontium Manganite, LSM), lanthanum strontium cobalt tight (lanthanum strontium Cobatite, LSC), lanthanum strontium chromite (lanthanum strontium chromite, LSCr), lanthanum strontium cobalt ferrite (lanthanum strontium cobalt ferrite, LSCF) , manganese ferrite (MnFe ₂ O _4), and Provided is a method of manufacturing a gas separation membrane plate module, which is at least one selected from nickel ferrite (NiFe ₂ O ₄ ).

The present invention also, the cermet is a composite of an ion conductive electrolyte material and one selected from nickel, nickel alloy, and iron-based alloy, the ion conductive electrolyte material is yttria-stabilized zirconia (YSZ), Scandia stabilized zirconia (scandia-stabilized zirconia, ScSZ), gd doped-ceria (GDC), samarium injected ceria (Sm doped-Ceria), lanthanum gallates, SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O _{7 It} is made of at least one material, the ion conductive electrolyte material included in the cermet, the gas separation membrane, the same material as the gas separation membrane, It provides a method of manufacturing a plate module.

In another aspect, the present invention, the inner space is divided into a first space and a second space bordering the gas separation membrane plate module, the electrode active layer of the first space of the hydrocarbon reformer is cermet, lanthanum strontium chromit (LSCr) Or lanthanum strontium titanate (LSTi), and supplying a hydrocarbon-based fuel gas to be in contact with the surface of the first space of the reformer while maintaining the temperature at 500 to 900 ° C. ; And it provides a hydrocarbon reforming method comprising the step of obtaining a synthesis gas in the first space and the second space, or the first space.

The present invention also relates to the hydrocarbon reforming method, before the step of obtaining the syngas, the air (air) at a pressure of 1 to 10 atm so as to contact the other surface of the membrane module in the second space of the reformer. It further provides a hydrocarbon reforming method, further comprising the step of feeding.

The present invention also provides a hydrocarbon reforming method wherein the hydrocarbon is methane gas (CH ₄ ) and the synthesis gas obtained in the first space is hydrogen (H ₂ ) and carbon monoxide (CO).

In another aspect, the hydrocarbon is methane gas (CH ₄ ) is a mixture of carbon monoxide (CO) and hydrogen (H ₂ ), the synthesis gas obtained in the first space is carbon monoxide (CO), in the second space The syngas obtained is hydrogen (H ₂ ).

In another aspect, the hydrocarbon is a mixture of carbon dioxide (CO ₂ ), water vapor (H ₂ O) and nitrogen (N ₂ ), the synthesis gas obtained in the first space is hydrogen (H ₂ ), carbon monoxide ( CO) and ammonia (NH ₃ ), and the synthesis gas obtained in the second space is carbon monoxide (CO) and hydrogen (H ₂ ).

The present invention can secure excellent chemical and mechanical durability by using a fluorite-based ion conductive membrane which is chemically stable at high temperature, especially in a CO ₂ , H ₂ O atmosphere, and can be applied to an internal circuit without applying a voltage from the outside. By gas permeation occurs there is an advantage that can produce a pure gas at a low cost. In addition, by separating and sintering the gas separation membrane in which ions move and the electron conductive support or membrane in which electrons move, there is an advantage of avoiding a problem of a decrease in permeability caused by the reaction of two materials during sintering in the case of a composite.

By stacking the plate-shaped membrane, it is easy to construct a compact gas-producing membrane module, and it is possible to reduce the thickness of the electrolyte, which is a characteristic of the plate-shaped structure, and thus to have a high transmittance, and the support and the electrolyte can be manufactured by a tape casting method. There is an advantage that the manufacturing process is simple.

1 is a schematic diagram illustrating an oxygen separation process as an example of a gas separation process using an ion conductive separator.

2 is a schematic diagram showing (a) a pure gas conductive separator with an external power source, (b) a mixed conductive separator, (c) a dual phase separator, and (d) a short circuit separator to be.

3 is a schematic view showing a cross-sectional structure of a first plate-shaped module according to an embodiment of the present invention.

Figure 4a is a schematic diagram showing the oxygen ion and electron transfer mechanism in the first plate-shaped module using an oxygen separation membrane according to an embodiment of the present invention.

Figure 4b is a schematic diagram showing the hydrogen ion and electron transfer mechanism in the first plate-type module using a hydrogen separation membrane according to an embodiment of the present invention.

5A is a unit module of the first plate-shaped module according to an embodiment of the present invention.

5B is a schematic diagram illustrating a module in which unit modules of a first plate module according to an embodiment of the present invention are connected in series.

6 is a schematic view showing a second plate-shaped module according to an embodiment of the present invention.

7 is a real picture of the third plate-shaped module according to an embodiment of the present invention.

Figure 8a is a schematic diagram showing the oxygen ion and electron transfer mechanism of the second plate-type module and the third plate-type module using an oxygen separation membrane as a gas separation membrane according to an embodiment of the present invention.

8B is a schematic diagram illustrating hydrogen ions and electron transfer mechanisms of the second and third plate modules using the hydrogen separation membrane as a gas separation membrane according to one embodiment of the present invention.

9 is a schematic diagram of methane gas reforming of the second plate-type module and the third plate-type module using an oxygen separation membrane as a gas separation membrane according to one embodiment of the present invention.

10 is a schematic diagram illustrating a multiple coupling reaction of a second plate-type module and a third plate-type module using an oxygen separation membrane as a gas separation membrane according to an embodiment of the present invention.

11 is a schematic diagram showing a methane gas reforming process of the second plate-type module and the third plate-type module using a hydrogen separation membrane as a gas separation membrane according to an embodiment of the present invention.

12 is a real picture of a third plate-shaped module using an oxygen separation membrane according to an embodiment of the present invention.

Figure 13 shows the oxygen permeability according to the temperature of the second plate-type module using the oxygen separation membrane according to an embodiment of the present invention.

Figure 14 shows the oxygen permeability according to the temperature of the third plate-shaped module using an oxygen separation membrane according to an embodiment of the present invention.

Prior to the description of the invention, the terms or words used in the specification and claims described below should not be construed as limiting in their usual or dictionary meanings. Therefore, the embodiments described in the specification and the drawings shown in the drawings are only one of the most preferred embodiments of the present invention and do not represent all of the technical idea of the present invention, various modifications that can be replaced at the time of the present application It should be understood that there may be equivalents and variations.

In one aspect the present application relates to a gas separation membrane plate module. In one embodiment of the present invention, the gas separation membrane plate module includes a support made of a plate-shaped dense structure electronic conductive material having a plurality of holes; A plurality of plate-type gas separation membranes which cover each space formed by the plurality of holes in contact with an upper surface of the support and are separated from each other; An upper porous electrode active layer coated on the plate-type gas separation membrane and the support; And a lower porous electrode active layer disposed in contact with a lower surface of the plate-type gas separation membrane and an upper surface of the cogwheel inner surface of the support, wherein the upper porous electrode active layer is energized to the lower porous electrode active layer through a support layer. Hereinafter, referred to as a first plate-shaped module.

In another embodiment of the present invention, the gas separation membrane plate module includes a gas separation membrane in which a plurality of holes are formed; A membrane made of a plurality of plate-shaped dense structure electronic conductive materials which cover each space formed by the plurality of holes in contact with an upper surface of the separator and are separated from each other; An upper porous electrode active layer coated on an upper surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact; And a lower porous electrode active layer coated on a lower surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact, wherein the upper porous electrode active layer is energized to the lower porous electrode active layer through a membrane made of an electronic conductive material. Plate-shaped module, hereinafter referred to as second plate-shaped module.

In another embodiment of the present invention, the gas separation membrane plate module includes an ion conductive gas separation membrane having a plurality of bands spaced at regular intervals and arranged in parallel with each other; A membrane made of a dense structured electronically conductive material having a parallel band shape and covering each space formed by the gap to be in contact with an upper surface of the separator and separated from each other; An upper porous electrode active layer coated on an upper surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact; And a lower porous electrode active layer coated on a lower surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact, wherein the upper porous electrode active layer is energized to the lower porous electrode active layer through a membrane made of an electronic conductive material. Plate-shaped module, hereinafter referred to as third plate-shaped module.

The separator may be defined as an interphase of a material having a function of selectively restricting the movement of a material between two phases. As high purity and high quality products are required due to the recent advancement and diversification of the industry, the separation process is recognized as a very important process, and not only in the industrial fields such as chemical industry, food industry, and pharmaceutical industry, but also in the medical, biochemical and environmental fields. It is becoming an important research subject.

Gas separation using membranes is driven by the selective gas permeation principle to the membranes. That is, when the gas mixture comes into contact with the membrane surface, 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 driving force for gas separation is the partial pressure difference for the particular gas component across the membrane. In particular, membrane separation process using membrane is widely applied in all fields because of the advantages of no phase change and low energy consumption.

According to the present invention, a porous electrically conductive oxide (for example, perovskite-based or spinel-based) or a porous metal membrane is disposed on both surfaces of a dense fluorite phase ion conductive membrane, and an electrically conductive membrane positioned on both sides of the conductive membrane has a dense structure. A gas separator plate-shaped module is electrically connected through a support.

1 illustrates an oxygen separation process as an example of a gas separation process using an ion conductive membrane, in which oxygen is anion in the air supply side, penetrates the ion conductive membrane, and electrons move together, but at a high pressure and a high temperature. The concept of an oxygen separator using a perovskite separator is used to provide the energy required for separation. Oxygen mixture gas at high temperature and high pressure is ionized and passed through the membrane to release electrons, which are separated into oxygen gas, and electrons move in the opposite direction to oxygen ions.

2 illustrates an oxygen separation membrane structure as an example of various types of gas separation membrane structures. Each gas separation membrane structure is distinguished from each other based on technical characteristics depending on how the transmission of ions and electrons, in particular, the transmission of electrons occurs. 2A illustrates a pure oxygen separation membrane requiring an external power supply and an electrode for supplying current. The oxygen ion permeation rate in the pure oxygen separation membrane is precisely controlled by the current supply, and oxygen can move in any direction regardless of the oxygen partial pressure located in both directions of the membrane. FIG. 2 (b) shows a single phase ion-electron mixed conductive film mainly composed of a Perovskite single phase and transmitting oxygen ions and electrons. FIG. 2C shows a dual phase ion-electron mixed conductive film that transmits electrons and oxygen ions to two different phases, respectively. FIG. 2 (d) is an ion conductive ceramic separator with a short circuit for implementing a new separator that balances chemical stability and oxygen ion permeability. The present invention relates to an electrode-supported short-circuit separator module for oxygen separation using the short circuit separator shown in FIG.

Since the prior art (d) is an ion conductive membrane support, there is a limit to thinning the thickness of this material (typically: 300 μm to 1 mm), which makes it difficult to obtain high oxygen permeability, and it is necessary to use a metal such as Ag, Pt, Au as a conductive sealing material. There is a problem that the manufacturing cost increases. In addition, when the large area is increased, the conduction path of the electrons is increased to increase the resistance, and thus high transmittance is hardly obtained.

The common rule of the present invention means a hole which is drilled or dug out. A plate-like structure in which a plurality of holes is formed has a shape, for example, a window frame. In the present invention, the first plate-shaped module and the second plate-shaped module includes a flat support having a plurality of holes formed thereon.

Figure 3 shows a cross-sectional structure of a first plate-shaped module made using a support made of a dense structure electronic conductive material of the present invention. The first plate module includes a support 10 made of a plate-shaped dense structure electronic conductive material having a plurality of holes; A plurality of plate-type gas separation membranes 20 which are in contact with the upper surface of the support and cover each space formed by the plurality of holes and are separated from each other; An upper porous electrode active layer 30 coated on the plate-type gas separation membrane and the support; And a lower porous electrode active layer 40 positioned in contact with a lower surface of the plate-type gas separation membrane and an upper surface of the common inner surface of the support, wherein the upper porous electrode active layer is energized to the lower porous electrode active layer through the support layer. The support 10 made of the plate-shaped dense structure of the electronic conductive material forms a frame of the module and connects two or more unit modules, and thus is formed of an electrically conductive material.

Figure 4a schematically shows an oxygen separation process of the first plate-shaped module using a gas separation membrane as an oxygen separation membrane. Oxygen ions permeate the oxygen separation membrane in the form of oxygen ions as anions in the upper direction of the plate-shaped module under low oxygen partial pressure at the lower part of the plate-shaped module with high oxygen partial pressure, and electrons are the upper porous electrode active layer and the catalyst layer through the support. Between the lower porous electrode active layer flows in a direction from the top to the bottom in the direction opposite to the oxygen ion (52). When the gas mixture containing oxygen is placed under the plate-shaped module, the gas mixture reaches the oxygen separation membrane through the lower porous electrode active layer, and oxygen in the oxygen separation membrane obtains electrons to become oxygen ions. Oxygen ions penetrate the oxygen separation membrane to reach the porous electrode active layer, which is the catalyst layer, and release electrons. At this time, the electrons separated from the oxygen ions move in the opposite direction from the oxygen ion from the upper porous electrode active layer to the lower porous electrode active layer through the support. In one embodiment of the present invention it is possible to obtain a high transmittance by setting the ion conductive oxygen separation membrane thickness less than 200μm.

Figure 4b schematically shows a hydrogen separation process of the first plate-shaped module using a gas separation membrane as a hydrogen separation membrane. Hydrogen ions permeate the hydrogen separation membrane in the form of hydrogen ions, which are cations, from the lower part of the plate-shaped module under high hydrogen partial pressure to the upper part of the plate-shaped module with high partial pressure of electrons. Between the upper porous electrode active layer flows in a direction from the bottom of the plate-shaped module in the same direction as hydrogen ions toward the top (62). When the gas mixture containing hydrogen is placed under the plate-shaped module, the gas mixture reaches the hydrogen separation membrane through the lower porous electrode activity, and hydrogen in the hydrogen separation membrane loses electrons to become hydrogen ions. At this time, the electrons separated from the hydrogen ions flow in the same direction as the hydrogen ions to the upper porous electrode active layer through the support. When hydrogen ions penetrate the hydrogen separation membrane and reach the porous electrode active layer, which is a catalyst layer, electrons are obtained to form hydrogen gas. In one embodiment of the present invention it is possible to obtain a high transmittance by setting the ion conductive hydrogen separation membrane thickness less than 150μm. The cermet separates hydrogen from gases such as CH ₄ and CO.

As described above, oxygen or protons are selectively permeated through the exchange of oxygen ions or protons through the proton conductive membrane, which is oxygen ions or hydrogen ions, and the exchange of electrons by the support layer. In one embodiment of the present invention, in the case of using a cermet, it is necessary to inject a reducing gas such as methane, carbon monoxide, hydrogen molecules. This is because, for example, in the case of NiO-YSZ composite, when the reducing gas is injected, NiO is reduced to Ni, so the cermet form is maintained.

In one embodiment of the present invention, the gas mixture uses synthetic air containing 300 to 500 ppm of carbon dioxide, atmospheric air, or process gas.

The oxygen or hydrogen separation as described above occurs through the unit module (Fig. 5a) of the first plate-shaped module, the unit ion-wide support gas separation membrane plate module is connected to each other (Fig. 5b) to increase the area of the entire oxygen or hydrogen separation membrane. You lose. If the electron conduction support having a plurality of porosity is used, a large area is possible, and the size and thickness of the ion permeable membrane can be adjusted according to the size of the porosity. In addition, it is possible to form a compact membrane module by connecting them in series.

6 is a schematic view of a second plate-shaped module structure using the separator of the present invention. The module comprises a gas separation membrane 20 formed with a plurality of holes; A membrane (10) formed of a plurality of dense structure electronic conductive materials disposed in contact with and covering each space formed by the plurality of holes in contact with an upper surface of the separator; An upper porous electrode active layer 30 coated on an upper surface of the gas separation membrane structure in which the membrane made of the electronic conductive material contacts; And a lower porous electrode active layer 40 coated on a lower surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact, wherein the upper porous electrode active layer is energized to the lower porous electrode active layer through the membrane made of the electronic conductive material. . In one embodiment of the present invention, the gas separation membrane 20 and / or the membrane 100 made of the dense structure electronic conductive material is flat.

7 is a schematic diagram of a third plate-shaped module structure using the separator of the present invention. The module includes an ion conductive gas separation membrane 20 in which a plurality of bands are spaced at regular intervals and arranged in parallel with each other; A membrane (100) formed of a dense structure of a conductive electronic material in the form of parallel bands which cover each space formed by the gap in contact with an upper surface of the separator and are separated from each other; An upper porous electrode active layer 30 coated on an upper surface of the gas separation membrane structure in which the membrane made of the electronic conductive material contacts; And a lower porous electrode active layer 40 coated on a lower surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact, wherein the upper porous electrode active layer is energized to the lower porous electrode active layer through the membrane made of the electronic conductive material. . When the membrane formed of the band-shaped electron conductive material is positioned in the space between the strip-shaped gas separation membranes arranged in parallel and viewed from above, the membrane and the gas separation membrane of the band-shaped electron conductive material are exposed.

The second plate-type module and the third plate-type module are classified according to the shape of the gas separation membrane, and the gas separation membranes of the second plate-type module and the third plate-type module are located in the separation membrane as both modules serve as frames of the module, A membrane made of a conductive material is positioned in such a structure as to cover the gas separation membrane in the gap between the gas separation membranes used in the second plate-shaped module, for example, or the parallel gas separation membrane in the third plate-shaped module. An electrode active layer is coated on the upper and lower portions of the plate-type structure formed by the gas separation membrane and the electron conductive membrane.

The membrane of the support of the first plate-shaped module, the second plate-shaped module and the third plate-shaped module of the present invention is an electrically conductive material, and in one embodiment of the present invention, the electronically conductive material is a cermet that is a gas separation membrane material composite. , An electron conductive metal oxide, and an ion conductive electrolyte material-electroconductive metal oxide composite. The cermet is a composite of an ion conductive electrolyte material with one selected from nickel, nickel alloys, and iron-based alloys, and the ion conductive electrolyte material is yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia , ScSZ), Gd doped-ceria (GDC), Samarium infused Ceria (Sm doped-Ceria), Lanthanum gallates, SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O _{7 It} is made of one or more materials selected from, the ion conductive electrolyte material contained in the cermet is the same material as the gas separation membrane. In one embodiment of the present invention, the cermet forms a dense structure by performing a sintering process formed of a composite at a high temperature of 1200 to 1500 ° C. In one embodiment of the invention the nickel alloy is Inconel (Inconel), the Inconel is nickel mainly 15% chromium, 6-7% iron, 2.5% titanium, less than 1% aluminum manganese • Heat-resistant alloy with silicon added.

In one embodiment of the present invention, the electron conductive metal oxide is a perovskite-based, strontium titanium ferrite (SrTi _1-x Fe _x O _3-δ , STF), lanthanum strontium ferrite (LSF), lanthanum Lanthanum strontium Manganite (LSM), Lanthanum strontium Cobatite (LSC), Lanthanum strontium Chromite (LSCr), Lanthanum strontium cobalt ferrite (LantCF) Oxides include manganese ferrite (MnFe ₂ O ₄ ), nickel ferrite (NiFe ₂ O ₄ ), and the like, and in one embodiment of the present invention, are sintered at a high temperature of 1200 to 1500 ° C. to form a dense structure.

Further, in one embodiment of the present invention, the ion conductive electrolyte material forming the ion conductive electrolyte material-electroconductive metal oxide composite is selected from an oxygen separation membrane or a hydrogen separation membrane material. The oxygen separation membrane material is yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (SCSZ), gd-doped ceria (GDC), samarium injection ceria (Sm -doped Ceria), and Lanthanum gallates, and the hydrogen separation membrane material is Perovskite-based SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , or Pyrochlore-based La ₂ Zr ₂ O ₇ , La ₂ Ce ₂ O _{7 It} is selected from. An ion conductive electrolyte material selected from the oxygen separation membrane material or the hydrogen separation membrane material is complexed with the electron conductive metal oxide.

When the ion conductive electrolyte material and the electron conductive metal oxide form a composite, one component occupies 20 to 80% by volume, in order to ensure conductivity. In one embodiment of the present invention, the volume ratio of the ion conductive electrolyte material and the electron conductive metal oxide is 50%. The composite as described above has a stable structure due to a small difference between the separation coefficient and the thermal expansion coefficient, and is advantageous in controlling the shrinkage rate in the sintering process during manufacture, thereby improving productivity.

In particular, when the ion conductive electrolyte material-electroconductive metal oxide composite is selected as the support and the membrane material, the ion conductive electrolyte material may be the same material as the gas separation membrane material. The thermal expansion coefficient difference can be minimized.

FIG. 8A illustrates an oxygen separation process of the second and third plate modules using the oxygen separation membrane as a gas separation membrane. Oxygen ions penetrate the oxygen separation membrane in the form of oxygen ions as anions from the lower part of the module under high oxygen partial pressure to the upper part of the lower oxygen partial pressure in the form of anion, and the electrons are the upper porous electrode active layer and the catalyst layer through the conductive membrane. Between the lower porous electrode active layer flows in a direction from the top to the bottom opposite to the oxygen ion (52). When the gas mixture containing oxygen is placed in the lower part of the module, the gas mixture reaches the oxygen separation membrane through the lower porous electrode active layer, and oxygen in the oxygen separation membrane obtains electrons to become oxygen ions. Oxygen ions penetrate the oxygen separation membrane to reach the porous electrode active layer, which is the catalyst layer, and deliver electrons. At this time, electrons separated from the oxygen ion are transferred from the upper porous electrode active layer to the lower porous electrode active layer in the opposite direction to the oxygen ion through the membrane made of an electron conductive material. Move.

8b schematically illustrates a hydrogen separation process of the second plate-type module and the third plate-type module using the hydrogen separation membrane as a gas separation membrane. Hydrogen ions permeate the hydrogen separation membrane in the form of hydrogen ions, which are cations, from the lower portion of the module under high hydrogen partial pressure to the upper portion of the module under high hydrogen partial pressure, and the electrons pass through the lower porous electrode active layer through a membrane made of an electron conductive material. Between the upper porous electrode active layer, which is a catalyst layer, flows in a direction from the bottom of the module toward the top in the same direction as hydrogen ions (62). When the gas mixture containing hydrogen is placed in the lower part of the module, the gas mixture reaches the hydrogen separation membrane through the lower porous electrode activity, and hydrogen in the hydrogen separation membrane loses electrons to become hydrogen ions. In this case, the electrons separated from the hydrogen ions flow in the same direction as the hydrogen ions to the upper porous electrode active layer through the film made of the electron conductive material. When hydrogen ions penetrate the hydrogen separation membrane and reach the porous electrode active layer, which is a catalyst layer, electrons are obtained to form hydrogen gas. In an embodiment of the present invention, a high transmittance may be obtained by setting the thickness of the ion conductive hydrogen separation membrane in the range of 50 to 300 μm.

In one embodiment of the present invention, the gas mixture uses synthetic air containing 300 to 500 ppm of carbon dioxide, atmospheric air, or process gas.

The gas separation membrane used in the first plate module, the second plate module and the third plate module of the present invention may be, for example, a material for transferring hydrogen or oxygen ions, and the gas separation membrane may have a hydrogen separation membrane or oxygen having a thickness of 50 to 500 μm. Separation membrane, the oxygen separation membrane is yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (SCSZ), gadolinium injection ceria (Gd doped-ceria (GDC), samarium injection ceria (Sm doped-Ceria), and lanthanum gallates (Lanthanum gallates) and one or more materials selected from, the hydrogen separation membrane SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and It consists of one or more materials selected from La ₂ Ce ₂ O ₇ .

The electrode active layer used in the first plate-shaped module, the second plate-shaped module and the third plate-shaped module of the present invention may be formed on the support 10, the gas separation membrane 20, and the upper surface of the support in the case of the first plate module (see FIG. 3). The upper porous electrode active layer 30, which is a catalyst layer, is electrically connected to the lower porous electrode active layer 40 positioned in contact with the lower surface of the plate-type gas separation membrane and the upper inner surface of the common substrate through the support. In the case of the second plate-shaped module (see FIG. 6), the upper porous electrode activity 30 coated on the upper surface of the gas separation membrane 20 structure in which the membrane 100 made of the plate-shaped electronic conductive material is in contact with the electronic conductive material. The membrane made of the electronic conductive material is electrically connected to the lower porous electrode active layer 40 coated on the lower surface of the gas separation membrane structure in contact with the membrane. In the case of the third plate module (see FIG. 7), the upper porous electrode active layer 30 coated on the upper surface of the gas separation membrane 20 structure in which the membrane 100 made of a band-shaped electronic conductive material is in contact with the electronic conductive material. The membrane made of the electronic conductive material is electrically connected to the lower porous electrode active layer 40 coated on the lower surface of the gas separation membrane structure in contact with the membrane.

In one embodiment of the present invention, the electrode active layer of the first plate-shaped module, the second plate-shaped module and the third plate-shaped module is selected from a porous metal, a porous cermet, and a porous electron conductive metal oxide, and the porous metal is Nickel, nickel alloys, and iron-based alloys. The electron conductive metal oxide may include strontium titanium ferrite (SrTi _1-x Fe _x O _3-δ , STF), lanthanum strontium ferrite (LSF), lanthanum strontium manganite (LSM), and lanthanum strontium manganite. cobalt tight (lanthanum strontium Cobatite, LSC), lanthanum strontium chromite (lanthanum strontium chromite, LSCr), lanthanum strontium cobalt ferrite (lanthanum strontium cobalt ferrite, LSCF) , manganese ferrite (MnFe ₂ O _4), and nickel ferrite (NiFe ₂ O ₄ ) is one or more selected from. The cermet is a composite of an ion conductive electrolyte material with one selected from nickel, nickel alloys, and iron-based alloys, and the ion conductive electrolyte material is yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia , ScSZ), Gd doped-ceria (GDC), Samarium-infused Ceria (Sm doped-Ceria), Lanthanum gallates, SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O _{7 It} is made of one or more materials selected from, the ion conductive electrolyte material contained in the cermet is the same material as the gas separation membrane.

The first plate-type module, the second plate-type module and the third plate-type module can be formed in a membrane structure having a large area by connecting a single gas separation membrane module in series. In addition, it is possible to secure a mechanically stable structure due to the support made of the electronic conductive material of the first plate-shaped module or the gas separation membrane support of the second plate-shaped module. Electron conduction in the permeation mechanism is controlled by adjusting the spacing and width of the separator made of the electronic conductive material in the first plate-shaped module and the membrane made of the electronic conductive material in the second plate-shaped module. It can be easily changed to achieve optimum oxygen or hydrogen permeation conditions. In addition, even in the third plate module having the same gas separation mechanism as the second plate module, it is possible to easily control the width and spacing of the band-shaped separator and the electron conductive membrane to achieve electron conduction and optimum oxygen or hydrogen permeation conditions.

Oxygen or hydrogen separation using the plate-shaped module (first plate module, second plate module and third plate module) of the present invention as described above occurs in the entire gas separation membrane located in the module, thereby increasing the area of the oxygen or hydrogen separation membrane. Can be. In addition, it is possible to form a compact membrane module by connecting them in series.

In another aspect, the present invention relates to a method for producing a gas separation membrane plate module described above. The method is a manufacturing method of the first plate-shaped module, the second plate-shaped module and the third plate-shaped module, the manufacturing method of the first plate-shaped module is a plate-shaped porous electronic conductivity having a plurality of holes using a tape casting process Preparing a support tape made of a material; Stacking a plurality of gas separator membrane tapes on a support tape made of the plate-shaped dense structure electronic conductive material such that each of the gas separator membranes is separated from each other; Co-sintering the gas separation membrane tape and the support tape made of the plate-shaped dense structure electronic conductive material at 1200 to 1500 ° C. for densification after the laminating step; And coating a porous electrode active layer on the upper surface of the gas separation membrane covering the cavity and the upper surface of the support and the lower surface of the gas separation membrane exposed inside the cavity and on the inner side of the cavity.

The manufacturing method of the second plate-shaped module comprises the steps of manufacturing a gas separation membrane tape (tape) having a plurality of common rules using a tape casting (Tape Casting) process; Covering the plurality of holes with a membrane tape made of a plurality of densely structured electronically conductive materials, and laminating them on the upper surface of the gas separation membrane tape such that the films made of the electronically conductive materials are separated from each other; Co-sintering the gas separation membrane tape and the membrane tape made of the electronic conductive material at 1200 to 1500 ° C. for densification after the laminating; And coating a porous electrode active layer on an upper surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact, and a lower surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact.

The method of manufacturing the third plate-shaped module may include manufacturing a plurality of strip-shaped gas separation membrane tapes by using a tape casting process; The plurality of gas separation membranes are spaced at regular intervals and arranged in parallel to each other, and each of the spaces formed by the gaps is covered with a membrane tape made of a dense structure of an electron conductive material, and the membrane tapes made of the electronic conductive materials Stacking on the upper surface of the gas separation membrane tape to be separated and positioned; Simultaneously sintering the gas separation membrane tape and the membrane tape made of the electronic conductive material at 1200 to 1500 ° C. for densification after the laminating; And coating a porous electrode active layer on an upper surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact, and a lower surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact.

Electrode active layer formed on the plate-like module ionization reaction of oxygen molecules at the surface ^{_{(O 2 + 4e - → 2O}} 2-) and gas-forming reaction of the hydrogen ions ^{(2H + + 2e - → H} 2) so that the coating can take place Oxygen gas can diffuse and ionize to the surface of the electrolyte and maintain a porous structure so that hydrogen ions can combine with electrons to become a gas. In one embodiment of the present invention, dip-coating, screein print, or CVD method is used for coating the gas separation membrane and the porous electrode active layer.

The material used for the support, the gas separation membrane and the porous electrode active layer of the first plate-shaped module is formed by using the above-described materials of the first plate-shaped module, and also the gas separation membrane and the dense structure conductivity of the second plate-shaped module and the third plate-shaped module. The materials used for the membrane and the electroactive layer are formed using the materials of the second plate-shaped module and the third plate-shaped module described above.

In another aspect, the present invention relates to a hydrocarbon reforming method using the above-described gas separation membrane plate module. The method divides an internal space into a first space and a second space by using a first plate module, a second plate module, and a third plate module, which are gas separation membrane plate modules, as a boundary between a module selected from the gas separation membrane plate modules. The electrode active layer in the first space of the high hydrocarbon reformer is one selected from cermet, lanthanum strontium chromit (LSCr) or lanthanum strontium titanate (LSTi), and the temperature is 500 to 900 ° C. Supplying a hydrocarbon-based fuel gas in contact with the surface of the first space of the reformer; And obtaining a synthesis gas in the first space and the second space, or the first space.

In one embodiment of the present invention, the hydrocarbon reforming method, before the step of obtaining the synthesis gas, the air (air) in the second space of the reforming device to contact with the other surface of the membrane module 1 to 10 atm Supplying at a pressure may be further included. The porous electrode active layer of the gas separation membrane plate module of the present invention during hydrocarbon modification is an electrode active layer made of one material selected from cermet, lanthanum strontium chromit (LSCr), or lanthanum strontium titanate (LSTi). Use

9 is a schematic diagram related to methane gas reforming using an oxygen separation membrane as a gas separation membrane of a second plate module or a third plate module. In one embodiment of the present invention, the hydrocarbon-based fuel gas is methane (CH ₄ ) and is supplied at atmospheric pressure. Since the hydrocarbon-based fuel gas is a reducing gas, it causes an oxygen partial pressure difference to impart a driving force to move oxygen from the opposite electrode. Therefore, oxygen passes through the separator in the form of ions, and electrons flow from the lower porous electrode active layer 40 to the upper porous electrode active layer 30 through the conductive membrane. When the hydrocarbon is reformed using the membrane, oxygen is released from the air supplied to the second space in which the opposite electrode is located, and nitrogen remains. In this case, since the electrical energy is not used, the production cost of the synthesis gas (eg, H ₂ + CO) can be reduced by reforming the hydrocarbon-based fuel gas. The prepared synthetic gas can be obtained through a collection process known to those skilled in the art in the first space. In the case of the first plate-shaped module, a support made of an electronic conductive material replaces the role of the conductive film of the second plate-shaped module or the third plate-shaped module, and electrons flow from the lower porous electrode active layer to the upper electrode active layer through the electronic conductive support.

10 is a schematic diagram illustrating a multiple coupling reaction in a plate module using an oxygen separation membrane as a gas separation membrane of a second plate module or a third plate module. When reforming the hydrocarbon using the plate-shaped module, when gas such as CO ₂ , H ₂ O, or N ₂ is injected into the upper electrode active layer 30, oxygen is released to the lower electrode active layer 40 simultaneously with CO, H ₂ , and NH _3. Reducing gas production, such as these, is possible. In the hydrocarbon reforming using the membrane module, the fuel gas, methane, is a reducing gas, which induces an oxygen partial pressure difference, thereby providing driving force for moving oxygen on the opposite side. Oxygen ions pass through the oxygen separation membrane in the form of oxygen ions from the porous electrode active layer in the high oxygen partial pressure state to the opposite electrode active layer in the low oxygen partial pressure state, and electrons pass through the membrane made of an electron conductive material between the gas separation membrane layers. Flows in the opposite direction.

 In the case of the first plate-shaped module, a support made of an electronic conductive material replaces the role of the conductive film of the second plate-shaped module or the third plate-shaped module, and the oxygen ions are lowered in the porous electrode active layer due to the oxygen partial pressure difference. The oxygen separation membrane penetrates toward the opposite electrode active layer in the partial pressure of oxygen in the form of oxygen ions as anions. However, electrons flow through the support and in the opposite direction to oxygen ions.

As described above, the gas separation membrane module selectively transmits oxygen through the exchange of oxygen ions through the conductive gas separation membrane and the exchange of electrons by the connecting material. Membranes using existing mixed conducting materials or composites of ionic and hydrogen ion conductive oxides are difficult to realize under the above conditions due to decomposition or phase change in reducing gas atmosphere.

In one embodiment of the present invention, the hydrocarbon reforming and the multiple coupling reaction using the oxygen separation membrane module have a temperature of 500 to 900 ° C. in the space to which the separation membrane module belongs, and the supply pressure of the water vapor and nitrogen ranges from normal pressure to about 10 atmospheres. Phosphorus condition is required, and the fuel gas methane is supplied at atmospheric pressure. The ammonia produced in the multiple coupling reaction may be collected by applying any of the ammonia collection processes known to those skilled in the art.

In one embodiment of the present invention, when the lower electrode active layer of the gas separation membrane module uses a cermet, a hydrocarbon-based fuel gas such as methanol, ethanol, propane, butane, as well as methane, which is a reducing gas, may be used for the cermet. This is because, for example, in the case of NiO-YSZ composite, when the reducing gas is supplied, NiO is reduced to Ni, so the cermet form is maintained.

11 is a schematic diagram illustrating a methane gas reforming process in a first plate-type module and a second plate-type module using a hydrogen separation membrane as a gas separation membrane. In an embodiment of the present invention, the first space is supplied with methane gas which is a hydrocarbon mixed with hydrogen and carbon monoxide. Under the above conditions, hydrogen passes through the hydrogen ion conductive separator in the form of hydrogen ions from the first space under the module where the lower electrode active layer having the high partial pressure of hydrogen is located to the second upper space of the module with low hydrogen partial pressure, and the electrons are made of an electron conductive material. It flows from the bottom of the module toward the top through the membrane formed in the same direction as the hydrogen ions. When the hydrocarbon mixture containing hydrogen is placed in the lower part of the module, the gas mixture reaches the hydrogen ion conductive separator through the electrode active layer located in the first space, and the hydrogen in the hydrogen ion conductive separator loses electrons to become hydrogen ions. At this time, the electrons separated from the hydrogen ions flow in the same direction as the hydrogen ions to the porous electrode active layer through the conductive membrane. When hydrogen ions penetrate the hydrogen ion conductive membrane and reach the porous electrode active layer, which is a catalyst layer, electrons are obtained to form a hydrogen gas. In the case of the first plate-shaped module, a support made of an electronic conductive material replaces the role of the conductive film of the second plate-shaped module or the third plate-shaped module, and electrons flow through the electronic conductive support, and the second plate-shaped module or the third plate-shaped module It flows in the same direction as the hydrogen ions transmitted through the hydrogen separation membrane as shown. The prepared hydrogen may be collected by applying any of the hydrogen collection processes known to those skilled in the art. In addition, the carbon monoxide remains in the first space, and also known carbon monoxide capture process can be collected by applying any known to those skilled in the art.

Hereinafter, examples are provided to help understand the present invention. However, the following examples are provided only to more easily understand the present invention, and the present invention is not limited to the following examples.

Example

Example 1 Fabrication of a Second Plate-Module Module Using an Oxygen Separation Membrane and Oxygen Permeability According to Temperature

As an ion conductive gas separation membrane, a Gd-doped ceria (Cd _0.9 Gd _0.1 O _2-δ ) tape having a thickness of 50 μm, which is an oxygen ion permeable membrane, was prepared. In order to minimize the difference in Thermal Expansion Coefficient (TEC), a plurality of dense electron conductive membrane tapes used a gadoline-infused ceria-lanthanum strontium cobalt ferrite (GDC-LSCF) composite, and the volume ratio of the composites was Ce _0.9. 80 vol% Gd _0.1 O _{2-δ and} 20 vol% lanthanum strontium cobalt ferrite (LSCF) were laminated. Sintering was carried out at 1350 ° C. for 5 hours for densification. After sintering, lanthanum strontium cobalt was selected as the electron conductive porous coating layer and coated using a screen printing method, and heat-treated at 1000 ° C. for 3 hours to bond the coating layers. As a result of measuring the oxygen permeability according to the temperature after fabrication of the module (FIG. 13), high oxygen permeability of 0.3 cc / cm ² min or more was confirmed at 750 ° C. FIG.

Example 2 Preparation of Third Plate Module Using Oxygen Separation Membrane and Oxygen Permeability According to Temperature

A band of gadolinium-implanted ceria (Gd doped-ceria, Ce _0.9 Gd _0.1 O _2-δ ) tape having a thickness of 100 μm, which is an oxygen ion permeable membrane, was prepared as an ion conductive gas separation membrane. In order to minimize the difference in Thermal Expansion Coefficient (TEC), a plurality of dense band-type electroconductive membrane tapes used a gadolinium-infused ceria-lanthanum strontium manganite (GDC-LSM) composite, and the volume ratio of each composite component was Ce. _The stack was selected at _0.9 Gd _0.1 O _2-δ 80 vol% and lanthanum strontium manganite (LSM) 20 vol%. Sintering was carried out at 1350 ° C. for 5 hours for densification. After sintering, lanthanum strontium cobalt was selected as an electrode active layer and coated on the top and bottom using a screen printing method, and heat-treated at 1000 ° C. for 3 hours for bonding of the coating layer, as shown in FIG. 12. And a large area rectangular gas separation membrane module (5.5 cm × 5.5 cm) was produced.

14 shows the results of measuring oxygen permeability according to temperature after fabrication of the module. Measurement was made at 700 to 850 ° C. and oxygen permeability increased with increasing temperature. High oxygen permeability of 0.5 cc / cm ² min or more was confirmed at 700 ° C.

Although the exemplary embodiments of the present application have been described in detail above, the scope of the present application is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to.

All technical terms used in the present invention, unless defined otherwise, are used in the meaning as commonly understood by those skilled in the art in the related field of the present invention. The contents of all publications described herein by reference are incorporated into the present invention.

[Description of the code]

10. Support made of plate-shaped electronic conductive material

20. Gas separation membrane

30. Upper porous electrode active layer

40. Lower porous electrode active layer

51. Oxygen Ion Flow

52. Oxygen Separator Electron Flow

61. Hydrogen Ion Flow

62. Hydrogen Separator Electron Flow

100. Membrane made of dense structure electronic conductive material

Claims (25)

A support made of a plate-shaped dense structure electronic conductive material having a plurality of holes formed therein; A plurality of plate-type gas separation membranes which cover each space formed by the plurality of holes in contact with an upper surface of the support and are separated from each other; An upper porous electrode active layer coated on the plate-type gas separation membrane and the support; And A lower porous electrode active layer disposed in contact with a lower surface of the plate-type gas separation membrane and an upper surface of a common inner surface of the support; The upper porous electrode active layer is energized to the lower porous electrode active layer through a support layer, Gas separation membrane plate module. A gas separation membrane in which a plurality of voids are formed; A membrane made of a plurality of plate-shaped dense structure electronic conductive materials which cover each space formed by the plurality of holes in contact with an upper surface of the separator and are separated from each other; An upper porous electrode active layer coated on an upper surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact; And A lower porous electrode active layer coated on a lower surface of the gas separation membrane structure in which the membrane made of the electronic conductive material contacts; The upper porous electrode active layer is energized to the lower porous electrode active layer through a film made of an electron conductive material, Gas separation membrane plate module. An ion conductive gas separation membrane having a plurality of bands spaced at regular intervals and arranged in parallel with each other; A membrane made of a dense structured electronically conductive material having a parallel band shape and covering each space formed by the gap to be in contact with an upper surface of the separator and separated from each other; An upper porous electrode active layer coated on an upper surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact; And A lower porous electrode active layer coated on a lower surface of the gas separation membrane structure in which the membrane made of the electronic conductive material contacts; The upper porous electrode active layer is energized to the lower porous electrode active layer through a film made of an electron conductive material, Gas separation membrane plate module. The method according to any one of claims 1 to 3, The electron conductive material is selected from cermet, electron conductive metal oxide, and ion conductive electrolyte material-electroconductive metal oxide composite, Gas separation membrane plate module. The method of claim 4, wherein The cermet is a composite of an ion conductive electrolyte material and one selected from nickel, nickel alloys, and iron-based alloys, The ion conductive electrolyte material is yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScZ), gadolinium implanted ceria (Gd doped-ceria (GDC), samarium implanted ceria (Sm doped) -Ceria), lanthanum gallates, SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O ₇ , The ion conductive electrolyte material included in the cermet is the same material as the gas separation membrane, Gas separation membrane plate module. The method of claim 4, wherein The electron conductive metal oxide may include strontium titanium ferrite (SrTi _1-x Fe _x O _3-δ , STF), lanthanum strontium ferrite (LSF), lanthanum strontium manganite (LSM), and lanthanum strontium manganite. cobalt tight (lanthanum strontium Cobatite, LSC), lanthanum strontium chromite (lanthanum strontium chromite, LSCr), lanthanum strontium cobalt ferrite (lanthanum strontium cobalt ferrite, LSCF) , manganese ferrite (MnFe ₂ O _4), and nickel ferrite (NiFe ₂ O ₄ ) is one or more selected from, The ion conductive electrolyte material-electroconductive metal oxide composite is composed of an ion conductive electrolyte material and the electron conductive metal oxide, and the volume ratio of the ion conductive electrolyte material in the composite is 20 to 80%, The ion conductive electrolyte materials include yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (SCSZ), gadolinia doped-ceria (GDC), samarium injection ceria. (Smaria doped-Ceria), Lanthanum gallates SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O ₇ The ion conductive electrolyte material included in the composite is the same material as the gas separation membrane, Gas separation membrane plate module. The method according to any one of claims 1 to 3, The gas separation membrane is a hydrogen separation membrane or oxygen separation membrane having a thickness of 50 to 500μm, The oxygen separation membrane is yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (SCSZ), gadolinium injection ceria (Gd doped-ceria (GDC), samarium injection ceria (Sm doped-Ceria) ), And lanthanum gallates; The hydrogen separation membrane is made of one or more materials selected from SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O ₇ , Gas separation membrane plate module. The method according to any one of claims 1 to 3, The porous electrode active layer is selected from a porous metal, porous cermet, and porous electron conductive metal oxide, The porous metal is one selected from nickel, nickel alloys, and iron-based alloys, Gas separation membrane plate module. The method of claim 8, The electron conductive metal oxide may include strontium titanium ferrite (SrTi _1-x Fe _x O _3-δ , STF), lanthanum strontium ferrite (LSF), lanthanum strontium manganite (LSM), and lanthanum strontium manganite. cobalt tight (lanthanum strontium Cobatite, LSC), lanthanum strontium chromite (lanthanum strontium chromite, LSCr), lanthanum strontium cobalt ferrite (lanthanum strontium cobalt ferrite, LSCF) , manganese ferrite (MnFe ₂ O _4), and nickel ferrite (NiFe ₂ One or more selected from O ₄ ), Gas separation membrane plate module. The method of claim 8, The cermet is a composite of an ion conductive electrolyte material and one selected from nickel, nickel alloys, and iron-based alloys, The ion conductive electrolyte material is yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScZ), gadolinium implanted ceria (Gd doped-ceria (GDC), samarium implanted ceria (Sm doped) -Ceria), lanthanum gallates, SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O ₇ , The ion conductive electrolyte material included in the cermet is the same material as the gas separation membrane, Gas separation membrane plate module. Preparing a support tape made of a plate-shaped dense structure electronic conductive material having a plurality of holes using a tape casting process; Stacking a plurality of gas separator membrane tapes on a support tape made of the plate-shaped dense structure electronic conductive material such that each of the gas separator membranes is separated from each other; Co-sintering the gas separation membrane tape and the support tape made of the plate-shaped porous electronic conductive material at 1200 to 1500 ° C. for densification after the laminating step; And And coating a porous electrode active layer on an upper surface of the gas separation membrane covering the cavity and an upper surface of the support and an upper surface of the gas separation membrane exposed to the inside of the cavity and an inner surface of the cavity. Method for producing a gas separation membrane plate module. Manufacturing a plurality of gas separator membrane tapes using a tape casting process; Covering the plurality of holes with a membrane tape made of a plurality of densely structured electronically conductive materials, and laminating them on the upper surface of the gas separation membrane tape such that the films made of the electronically conductive materials are separated from each other; Co-sintering the gas separation membrane tape and the membrane tape made of the electronic conductive material at 1200 to 1500 ° C. for densification after the laminating; And Coating a porous electrode active layer on an upper surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact, and a lower surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact; Method for producing a gas separation membrane plate module. Manufacturing a plurality of strip-shaped gas separator tapes using a tape casting process; The plurality of gas separation membranes are spaced at regular intervals and arranged in parallel to each other, and each of the spaces formed by the gaps is covered with a membrane tape made of a dense structure of an electron conductive material, and the membrane tapes made of the electronic conductive materials Stacking on the upper surface of the gas separation membrane tape to be separated and positioned; Simultaneously sintering the gas separation membrane tape and the membrane tape made of the electronic conductive material at 1200 to 1500 ° C. for densification after the laminating; And Coating a porous electrode active layer on an upper surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact, and a lower surface of the gas separation membrane structure in which the membrane made of the electronic conductive material is in contact; Method for producing a gas separation membrane plate module. The method according to any one of claims 11 to 13, The electron conductive material is selected from cermet, electron conductive metal oxide, and ion conductive electrolyte material-electroconductive metal oxide composite, Method for producing a gas separation membrane plate module. The method of claim 14, The cermet is a composite of an ion conductive electrolyte material and one selected from nickel, nickel alloys, and iron-based alloys, The ion conductive electrolyte material is yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScZ), gadolinium implanted ceria (Gd doped-ceria (GDC), samarium implanted ceria (Sm doped) -Ceria), lanthanum gallates, SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O ₇ , The ion conductive electrolyte material included in the cermet is the same material as the gas separation membrane, Method for producing a gas separation membrane plate module. The method of claim 14, The electron conductive metal oxide may include strontium titanium ferrite (SrTi _1-x Fe _x O _3-δ , STF), lanthanum strontium ferrite (LSF), lanthanum strontium manganite (LSM), and lanthanum strontium manganite. cobalt tight (lanthanum strontium Cobatite, LSC), lanthanum strontium chromite (lanthanum strontium chromite, LSCr), lanthanum strontium cobalt ferrite (lanthanum strontium cobalt ferrite, LSCF) , manganese ferrite (MnFe ₂ O _4), and nickel ferrite (NiFe ₂ O ₄ ) is one or more selected from, The ion conductive electrolyte material-electroconductive metal oxide composite is composed of an ion conductive electrolyte material and the electron conductive metal oxide, and the volume ratio of the ion conductive electrolyte material in the composite is 20 to 80%, The ion conductive electrolyte materials include yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (SCSZ), gadolinia doped-ceria (GDC), samarium injection ceria. (Smaria doped-Ceria), Lanthanum gallates SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O ₇ The ion conductive electrolyte material included in the composite is the same material as the gas separation membrane, Method for producing a gas separation membrane plate module. The method according to any one of claims 11 to 13, The gas separation membrane is a hydrogen separation membrane or oxygen separation membrane having a thickness of 50 to 500μm, The oxygen separation membrane is yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (SCSZ), gadolinium injection ceria (Gd doped-ceria (GDC), samarium injection ceria (Sm doped-Ceria) ), And lanthanum gallates; The hydrogen separation membrane is made of one or more materials selected from SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O ₇ , Method for producing a gas separation membrane plate module. The method according to any one of claims 11 to 13, The porous electrode active layer is selected from a porous metal, porous cermet, and porous electron conductive metal oxide, The porous metal is one selected from nickel, nickel alloys, and iron-based alloys, Method for producing a gas separation membrane plate module. The method of claim 18, The electron conductive metal oxide may include strontium titanium ferrite (SrTi _1-x Fe _x O _3-δ , STF), lanthanum strontium ferrite (LSF), lanthanum strontium manganite (LSM), and lanthanum strontium manganite. cobalt tight (lanthanum strontium Cobatite, LSC), lanthanum strontium chromite (lanthanum strontium chromite, LSCr), lanthanum strontium cobalt ferrite (lanthanum strontium cobalt ferrite, LSCF) , manganese ferrite (MnFe ₂ O _4), and nickel ferrite (NiFe ₂ One or more selected from O ₄ ), Method for producing a gas separation membrane plate module. The method of claim 18, The cermet is a composite of an ion conductive electrolyte material and one selected from nickel, nickel alloys, and iron-based alloys, The ion conductive electrolyte material is yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScZ), gadolinium implanted ceria (Gd doped-ceria (GDC), samarium implanted ceria (Sm doped) -Ceria), lanthanum gallates, SrCeO ₃ , BaCeO ₃ , BaZrO ₃ , CaZrO ₃ , SrZrO ₃ , La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O ₇ , The ion conductive electrolyte material included in the cermet is the same material as the gas separation membrane, Method for producing a gas separation membrane plate module. The method according to any one of claims 1 to 3, The inner space is divided into a first space and a second space on the basis of the gas separation membrane plate module, and the electrode active layer of the first space of the hydrocarbon reformer is cermet, lanthanum strontium chromit (LSCr) or lanthanum strontium tita Supplying a hydrocarbon-based fuel gas so as to be in contact with the surface of the first space of the reformer while the temperature is maintained at 500 to 900 ° C., selected from lanthanum strontium titanate (LSTi); And Obtaining syngas in the first space and the second space, or the first space, Hydrocarbon reforming method. The method of claim 21, The hydrocarbon reforming method may further include supplying air at a pressure of 1 atm to 10 atm so as to contact the other side of the membrane module in the second space of the reformer before the syngas is obtained. Included, Hydrocarbon reforming method. The method of claim 21, The hydrocarbon is methane gas (CH ₄ ), the synthesis gas obtained in the first space is hydrogen (H ₂ ) and carbon monoxide (CO), Hydrocarbon reforming method. The method of claim 21, The hydrocarbon is methane gas (CH ₄ ) mixed with carbon monoxide (CO) and hydrogen (H ₂ ), The syngas obtained in the first space is carbon monoxide (CO), Synthetic gas obtained in the second space is hydrogen (H ₂ ), Hydrocarbon reforming method. The method of claim 21, The hydrocarbon is a gas in which carbon dioxide (CO ₂ ), water vapor (H ₂ O) and nitrogen (N ₂ ) are mixed. Synthesis gas obtained in the first space is hydrogen (H ₂ ), carbon monoxide (CO) and ammonia (NH ₃ ), Syngas obtained in the second space is carbon monoxide (CO) and hydrogen (H ₂ ), Hydrocarbon reforming method.

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