WO2019156313A1

WO2019156313A1 - Ceramic oxygen separator module and manufacturing method therefor

Info

Publication number: WO2019156313A1
Application number: PCT/KR2018/013446
Authority: WO
Inventors: 유지행; 윤경식; 이대근; 김현진; 나범탁; 박종혁; 강은정
Original assignee: 한국에너지기술연구원
Priority date: 2018-02-12
Filing date: 2018-11-07
Publication date: 2019-08-15
Also published as: KR20190097357A; KR102020778B1

Abstract

The present invention relates to a thin ceramic oxygen separator having enhanced durability by using a compact support layer in which a plurality of flow channels are formed vertically. A ceramic oxygen separator module of the present invention can effectively support an oxygen permeable membrane composed of a thin membrane layer and an active layer by using the compact support layer in which a plurality of flow channels are formed vertically, and can effectively collect the permeated oxygen without the interruption of oxygen flow by utilizing an oxygen collection space inside. Furthermore, a support structure is inserted into an inner space of a gas channel layer, thereby enhancing the durability of the module.

Description

Ceramic Oxygen Membrane Module and Manufacturing Method Thereof

The present invention relates to a gas separation membrane module and a method for manufacturing the same, and more particularly, to a module including a thin ceramic oxygen separation membrane layer having improved durability using a dense support layer having a plurality of flow paths vertically formed and a method of manufacturing the same. .

Recently, as interest in the environment and energy has increased, research on oxygen separation membranes has been actively conducted. The oxygen separation membrane extracts only pure oxygen from the air, and is widely used in ammonia synthesis, other synthetic chemical industries, metallurgy, metal welding and cutting. Oxygen separation using a separation membrane includes a separation method using a ceramic separation membrane and a polymer separation membrane. Among the membrane separation methods, the hollow fiber membrane (HFM) using polysulfone and polyimide-based polymers (Journal of Membrane Science, 1, 99108, 1976) has low oxygen production cost, but the concentration of oxygen produced is 30 to The disadvantage is as low as 40%. In general, the polymer membrane separation membrane cannot be applied to separate oxygen from the hot mixed gas due to the low thermal durability. In the oxygen separation method using a ceramic separator, oxygen is selectively bound to the oxygen separator to separate oxygen ions and electrons. The separated oxygen ions and the electrons are moved through the oxygen separation membrane, respectively, and the transferred oxygen ions and the electrons are combined again with oxygen molecules so that the oxygen molecules are released to the outside of the oxygen separation membrane. The ceramic separator can be driven at high temperatures, making it particularly suitable for high temperature processes.

Ceramic membranes are classified 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.

Since the two-phase mixed conductive film of the perovskite / fluorite structure has to be electrically shorted at both ends of the membrane, the perovskite, which is an electron conductive phase, should be connected to each other in the separator. In the conventional method, an oxygen separation membrane was manufactured by mechanically mixing and sintering at least 15-30 vol% or more of perovskite powder with fluorite powder to make an electrical short. This method has a problem in that when the mechanically mixed perovskite / fluorite powder is sintered at a high temperature, the fluorite phase reacts with the perovskite phase to produce a secondary phase that lowers oxygen permeability, and the perovskite phase is fluorite phase. Compared with the chemical and mechanical stability is significantly low compared to the result that there is a problem that the durability of the oxygen separation membrane. In addition, when the gas separation membrane is manufactured as a module or a stack and used for gas separation, a pressure is applied while injecting gas, and this pressure condition must be overcome.

U.S. Patent No. 7726767 discloses a configuration in which a porous support layer is formed on an outer side of an ion conductive membrane, a flow path of slits is formed under the ion conductive membrane, and oxygen is collected through a long flow path crossing the slits under the ion conductive membrane. . However, the slit can be easily damaged due to the concentration of stress at the end of the flow path, and in order to overcome this problem, the thickness is increased, so that an efficient oxygen separation membrane cannot be manufactured.

Therefore, there is a need for an oxygen separation membrane structure for improving the mechanical stability of the separation membrane while maintaining an appropriate oxygen permeability.

[Preceding technical literature]

[Patent Documents]

(Patent Document 1) US 7279027

The present invention is to provide a thin ceramic oxygen separator with improved durability by using a dense support layer having a plurality of flow paths vertically formed.

In order to solve the above problems, the present invention provides a ceramic oxygen separator module, wherein the module includes an ion conductive membrane frame having an electrode active layer coated on both surfaces of an upper surface and a lower surface thereof, and having a space therein; A dense support layer having a plurality of holes at upper and lower parts positioned symmetrically with each other in contact with the electrode active layer coated on the inner surface of the ion conductive membrane frame at the top and the bottom of the inner space of the frame; A gas channel layer forming a gas flow space between the upper and lower dense support layers having a plurality of holes; And an oxygen trap penetrating up and down the upper and lower surfaces of the module and connected to the gas flow space of the gas channel layer.

The present invention also provides a ceramic oxygen separation membrane module, wherein the gas channel layer further includes a support column supporting between the dense support layer having a plurality of upper and lower holes located symmetrically with each other.

The present invention, the ion conductive membrane frame is made of a ceramic oxygen separator, ion-conductive material, ion-electron mixed conductive material, a mixture of an electron conductive material and an ion conductive material or a mixture of an ion-electron mixed conductive material and an ion conductive material, ceramic oxygen separator Provide a module.

The present invention, the ion conductive material is yttria-stabilized zirconia (YSZ), Scandia-stabilized zirconia (ScZ), gadolinia doped-ceria (GDC), Sama Smaria doped-Ceria (SDC), strontium and magnesium-injected lanthanum gallates (LSGM), and bismuth oxide (Bisuth oxide, Bi ₂ O ₃ ) and perovskite materials strontium and magnesium-injected lanthanum gallium Provided is a ceramic oxygen separator module, which is at least one selected from the group consisting of latent gallates (LSGM).

The present invention, the ion-electron mixed conductive material is strontium titanium ferrite (STF), lanthanum strontium ferrite (LSF), lanthanum strontium coblatite (LSC), strontium cobalt ferrite (Strontium cobalt ferrite (SFC), barium strontium cobalt ferrite (BSCF), lanthanum strontium cobalt ferrite (LSCF), and lanthanum nickelate (LNO) The above, the ceramic oxygen separation membrane module is provided.

The present invention also provides a conductive material is lanthanum strontium manganite (LSM), lanthanum strontium chromite (LSCr), manganese ferrite (MnFe ₂ O ₄ ), and nickel ferrite (NiFe ₂ O ₄ ). ₄ ) at least one selected from the group consisting of, provides a ceramic oxygen separator module.

The present invention also provides a ceramic oxygen separator module, wherein the dense support layer is made of Y ₂ O ₃ -doped Zirconia.

The present invention also provides a ceramic oxygen separator module, the gas channel layer is 0.1 mm to 1.0 mm thick.

The present invention also stacks a plurality of ceramic oxygen separator modules so that the oxygen collecting ports of each module are connected to each other, the upper oxygen collecting port of the uppermost module is sealed with a cap, and the lower oxygen collecting hole of the uppermost module is the The process of sealing connection with the upper oxygen collecting port is repeated, and the lower oxygen collecting hole of the lowermost module is sealingly connected to the manifold or the metal frame, and the sealing connection uses a glass sealing material, ceramic paste or brazing material, and the ceramic oxygen separator stack module To provide.

The present invention also provides a method for manufacturing a plurality of ion conductive ceramic green sheets using a tape casting process; Preparing an ion conductive membrane layer by coating a porous conductive active layer on both sides of the green sheet; Manufacturing a dense support layer having a plurality of holes by drilling a plurality of holes in the green sheet; Manufacturing a gas channel layer by punching a central portion of the green sheet; Preparing a laminate by laminating the ion conductive membrane layer, the dense support layer, the gas channel layer, the dense support layer, and the ion conductive membrane layer in order; Forming an oxygen collecting hole connected to the gas channel layer while vertically penetrating the green sheet of the stack so as not to be connected to the plurality of holes; And forming a heat treatment at 900 ° C to 1500 ° C after forming the oxygen trap.

The present invention also provides a method for manufacturing a ceramic oxygen separator module, wherein the porous conductive active layer is manufactured by a tape casting process or coated on the green sheet.

The present invention also provides a method of manufacturing a ceramic oxygen separator module, wherein the preparing of the gas channel layer further includes inserting a support column into a portion of the punched central portion.

The ceramic oxygen separator module of the present invention can effectively support an oxygen permeable membrane composed of a thin ion conductive membrane frame and a conductive active layer by using a dense support layer having a plurality of flow paths vertically formed therein, and oxygen flow using an oxygen trapping space therein. It is possible to capture the permeated oxygen effectively without disturbing. In addition, the durability of the module can be improved by inserting the support structure into the inner space of the gas channel layer.

1 is a schematic diagram showing a cross section of a ceramic oxygen separator module according to an embodiment of the present invention.

Figure 2 is a schematic diagram showing a cross section of the ceramic oxygen separator module with a support pillar further in accordance with an embodiment of the present invention.

FIG. 3 is a schematic diagram illustrating a cross section of a ceramic oxygen separator module using a dense support layer, a gas channel layer, and a support pillar ion conductive membrane frame material different from each other according to an embodiment of the present invention.

4 is a schematic diagram showing a cross section of a ceramic oxygen separator stack module in which a ceramic oxygen separator module is laminated according to an embodiment of the present invention.

Figure 5a is a schematic diagram showing a sheet of each layer for producing a ceramic oxygen separator module according to an embodiment of the present invention.

Figure 5b is a schematic diagram showing a gas channel layer having a support pillar according to an embodiment of the present invention.

FIG. 5C is a schematic diagram showing a sheet of each layer using a dense support layer, a gas channel layer, and a support pillar ion conductive membrane frame material according to one 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. Here, in the whole drawings for explaining embodiment of this invention, the thing which has the same function is attached | subjected with the same code | symbol, and detailed description is abbreviate | omitted.

In one aspect, the present invention provides a ceramic oxygen separation membrane module, the module comprising: an ion conductive membrane frame having an electrode active layer coated on both surfaces of an upper surface and a lower surface thereof, and having a space therein; A dense support layer having a plurality of holes at upper and lower parts positioned symmetrically with each other in contact with the electrode active layer coated on the inner surface of the ion conductive membrane frame at the top and the bottom of the inner space of the frame; A gas channel layer forming a gas flow space between the upper and lower dense support layers having a plurality of holes; And an oxygen collecting port penetrating up and down the upper and lower surfaces of the module and connected to the gas flow space of the gas channel layer.

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. 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 in the present invention is the partial pressure difference for the oxygen gas component applied across the membrane.

1 is a schematic diagram showing a cross section of a ceramic oxygen separation membrane module 1 according to one embodiment of the invention. The cross section is a cross section obtained by cutting the side surface including the oxygen collecting port 40. The module 1 has a dense support layer 20 inside the dense ion conductive membrane frame 101, in which the electrode active layers 11 are coated on both sides of the upper and lower surfaces, respectively, and spaces are formed therein. And a gas channel layer 30. The dense support layer 20 having the electrode active layer 11 of the uppermost surface of the inner space of the frame and the plurality of holes abuts, and symmetrically with the electrode active layer 11 of the lowermost surface of the inner space of the frame and the plurality of holes The dense support layer 20 is in contact with each other. A gas channel layer 30 is formed between the dense support layer 20 and oxygen moves through the gas channel layer 30. The gas channel layer 30 may have a space connected to the oxygen collecting port 40, and oxygen flowing through the oxygen collecting hole may collect oxygen by being connected to, for example, a manifold or a metal frame from the outside of the module. . The module has a dense support layer 20 having a plurality of holes around the gas channel layer 30-a dense separator layer coated on both sides of the conductive active layer and forms a symmetrical structure on both sides of the gas channel layer 30.

In the present invention, the ion conductive membrane frame is a dense ceramic densified through sintering, for example, and the preferred thickness of the frame of the ion conductive membrane on the top and bottom surfaces of the module is 10 μm to 100 μm. Although the thickness may be less than 10 μm, the thickness is preferably 10 μm or more in consideration of the ease of manufacturing process and the mechanical strength of the prepared oxygen separation membrane, and preferably not more than 100 μm in consideration of the oxygen permeability. In one embodiment, the ion conductive membrane frame consists of an ion conductive material, an ion-electron mixed conductive material, a mixture of an electron conductive material and an ion conductive material or a mixture of an ion-electron mixed conductive material and an ion conductive material. Preferably, the material of the ion conductive membrane frame exhibits excellent oxygen permeability when an electron conductive-ion conductive composite separator is used. The ion conductive material may be, for example, yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScZ), gadolinia doped-ceria (GDC), samarium Smaria doped-Ceria (SDC), strontium and magnesium injected lanthanum gallates (LSGM), and bismuth oxide (Bismuth oxide, Bi ₂ O ₃ ) and perovskite materials strontium, magnesium injected lanthanum gallate (Lanthanum gallates, LSGM) is one or more selected from the group consisting of, ion-electron mixed conductive material is, for example, strontium titanium ferrite (STF), lanthanum strontium ferrite (LSF), lanthanum Lanthanum strontium coblatite (LSC), Strontium cobalt ferrite (SFC), barium strontium cobalt One or more selected from the group consisting of barium strontium cobalt ferrite (BSCF), lanthanum strontium cobalt ferrite (LSCF), and lanthanum nickelate (LNO). For example, lanthanum strontium manganite (LSM), lanthanum strontium chromite (LSCr), manganese ferrite (MnFe ₂ O ₄ ), and nickel ferrite (NiFe ₂ O ₄ ) are selected. More than one.

The electrode active layer 11 is coated on both sides of the inner and outer surfaces of the top and bottom surfaces of the dense ion conductive membrane frame of the module, and the electrode active layer 11 having a thickness of 1 to 100 μm in a symmetrical or asymmetrical shape on both sides. By coating the oxygen can reduce the rate of reaction. If the thickness is less than 1 μm, the coating layer may be easily peeled off from the separator and if the thickness is more than 100 μm, the diffusion rate of gas molecules may not be sufficient in the coating layer. The thickness of this coating layer is preferably maintained at 13 to 134% with respect to the top and bottom dense ion conductive membrane frame. If the thickness of the coating layer is less than 13%, there may be a problem that the increase of oxygen permeability by coating on the surface of the separator is not sufficient, and when the coating layer exceeds 134%, the diffusion rate of gas molecules is not sufficient in the coating layer. May occur. The electrode active layer 11 serves as a catalyst for the ionization of oxygen and the gasification reaction of oxygen ions, in one embodiment the electrode active layer 11 is a porous electron conductive metal oxide, porous cermet, porous metal and The electron conductive metal oxide may be selected from a complex of an electron conductive metal oxide and an ion conductive electrolyte material, and the electron conductive metal oxide may include strontium titanium ferrite (STF), lanthanum strontium ferrite (LSF), and lanthanum strontium manganite (LSF). Lanthanum strontium Manganite (LSM), Lanthanum strontium Cobatite (LSC), Lanthanum strontium Chromite (LSCr), Lanthanum strontium cobalt ferrite (Lanthanum strontium LS) CobalM ferrite ₂ OFC ₄ ) and nickel ferrite (NiFe ₂ O ₄ ). 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 , At least one selected from La ₂ Zr ₂ O ₇ , and La ₂ Ce ₂ O ₇ . The porous metal is also nickel or inconel.

The composite of the electron conductive metal oxide and the ion conductive electrolyte material is composed of the electron conductive metal oxide and the ion conductive electrolyte material, the volume ratio of the ion conductive electrolyte material in the composite is 20 to 80%, 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 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 ion conductive electrolyte material-electroconductive metal oxide composite may adopt the same material as the oxygen separation membrane of the present invention to minimize the difference in coefficient of thermal expansion during simultaneous sintering.

In the present invention, the dense support layer 20 is provided to maximize the durability while minimizing the thickness of the module, and is a dense ceramic layer having a plurality of holes penetrating up and down, and is the top and bottom layers of the module. An ion conductive membrane frame coated with the electrode active layer 11 may be supported up and down, and the gas channel layer 30 between the dense support layer 20 may also be supported. The plurality of holes are passages through which oxygen can flow into the gas channel layer 30, and in one embodiment, the holes may have a diameter of 0.01 mm to 1 mm or less. The gas channel layer 30 is a passage through which oxygen is collected from the outside of the module by collecting oxygen into the module through the ion conductive membrane frame and the collected oxygen flows. The dense support layer 20 is in contact with the upper and lower portions of the gas channel layer 30 to support the gas channel layer 30. In one embodiment, the gas channel layer 30 is an empty space at the center of the module having a vertical thickness of 10.1 mm to 1.0 mm, and a space in which oxygen supplied through the dense support layer 20 flows. In order to withstand the pressure load of the gas supplied from the outside of the module according to the space thickness of the gas channel layer 30 may be further provided with a support pillar 31 as shown in FIG. If it is in the form of not limited to any one, the diameter of the pillar can be formed, for example 1mm to 1cm. Oxygen collected in the gas channel layer 30 is collected through an oxygen collecting port penetrating up and down the module of the present invention.

3 is a ceramic oxygen separation membrane module according to an embodiment of the present invention, wherein the dense support layer 20, the gas channel layer 30, and the support pillar 31 use different materials from those of the ion conductive membrane frame 101. A schematic is shown. In order to improve mechanical durability of the ceramic oxygen separation membrane, the dense support layer 20, the gas channel layer 30, and the support pillar 31 may be formed of different materials, for example, the dense support layer 20 and the gas. Y ₂ O ₃ -doped Zirconia (YSZ) may be used as the material of the channel layer 30 and the support pillar 31, and preferably 3 mol% to 8 mol% Y ₂ O ₃ -doped Zirconia may be used.

4 is a stack according to another embodiment of the present invention, in which a plurality of ceramic oxygen separator modules are stacked such that oxygen collecting holes of each module are connected to each other, the upper oxygen collecting holes of the uppermost module are sealed with a cap 100, and the uppermost module of the The lower oxygen collecting port repeats the sealing connection with the upper oxygen collecting hole of the module located below, and the lower oxygen collecting hole of the lowermost module is sealingly connected to the manifold or the metal frame, and the sealing connection is a glass sealing material, ceramic paste or brazing material. Using, a ceramic oxygen separator stack module. In the stack module of the present invention, when oxygen-containing gas is supplied from the outside under a constant pressure, only oxygen is permeated through the ion conductive membrane frame into each module and collected in the gas channel layer 30 of each module. Oxygen trapped by the gas channel layer 30 of each module may trap only pure oxygen gas through an oxygen collecting hole penetrating up and down the upper and lower surfaces of the module.

In another aspect, the present invention is a method of manufacturing a ceramic oxygen separator module. The manufacturing method may include the steps of manufacturing a plurality of ion conductive ceramic green sheets using a tape casting process with reference to FIGS. Preparing an ion conductive membrane layer 10 by coating a porous conductive active layer 11 on both sides of the green sheet; Manufacturing a dense support layer 20 having a plurality of holes by drilling a plurality of holes in the green sheet; Manufacturing a gas channel layer 30 by punching a central portion of the green sheet; Preparing a laminate by laminating the ion conductive membrane layer 10, the dense support layer 20, the gas channel layer 30, the dense support layer 20, and the ion conductive membrane layer 10 in order; Forming an oxygen collecting hole connected to the gas channel layer 30 while vertically penetrating the green sheet of the laminate not to be connected to a plurality of holes of the dense support layer; And heat treating at 900 ° C. to 1500 ° C. after forming the oxygen trap. Figure 5a shows the configuration of the ceramic oxygen separation membrane of the present invention can be produced by the tape casting method of each layer. A plurality of green sheets may be manufactured by a tape casting method using the ion conductive membrane layer material constituting the frame of the module of the present invention, and the modules may be manufactured by processing and laminating them into respective constituent layers of the present ceramic oxygen separator. In order to manufacture the module, for example, a slurry is prepared using a composite conductive material such as powder raw material LSCF-GDC, LSM-GDC, or a mixed conductive material of perovskite material, and ceramics using a tape casting method. Five green sheets are prepared, and on each of the two green sheets, a composite material such as powder raw material LSCF-GDC, LSM-GDC, or perovskite material, which will form the porous electrode active layer 11 on both sides, respectively. A slurry may be prepared by mixing a conductive material and a powder raw material (carbon black, graphite, etc.) powder, and may be laminated by, for example, manufacturing a green sheet having a thickness of 10 to 100 μm by a tape casting method. Alternatively, in order to implement a thinner membrane, two green sheets may be prepared by coating a raw material of constituting an electrode active layer on both sides of a thickness of 1 to 10 μm. Another two sheets of the dense support layer 20 are prepared by punching each of the two green sheets with a plurality of holes therethrough. In addition, a gas channel layer 30 penetrating the center of one green sheet is manufactured to be connected to the plurality of holes of the dense support layer 20. Ion-conductive membrane layer 10-density support layer 20-gas channel layer 30-density support layer 20-porous electrode active layer 11 coated porous electrode active layer 11 Oxygen collecting port connected to the gas channel layer while forming a stack by stacking layers 10 and penetrating the green sheet of the stack upward and downward so as not to be connected to a plurality of holes of the dense support layer 20. To form. The laminate in which the oxygen collecting port is formed is densified by heat treatment at 900 ° C. to 1500 ° C. to prepare a ceramic oxygen separator module. FIG. 5B illustrates a layer in which the support pillar is inserted into a portion of the punched center portion of the gas channel layer in one embodiment of the present invention, which may further improve durability of the ceramic oxygen separator module or stack of the present invention. Separation membrane can be implemented. 5C is a ceramic oxygen separation membrane module according to one embodiment, wherein the dense support layer 20, the gas channel layer 30, and the support pillar 31 are fabricated using materials different from those of the ion conductive membrane layer. Indicates. In order to further improve the mechanical durability of the ceramic oxygen separation membrane, the dense support layer 20, the gas channel layer 30, and the support pillar 31 may be formed of different materials, for example, the dense support layer 20 and Y ₂ O ₃ -doped Zirconia (YSZ) may be used as the material of the gas channel layer 30 and the support pillar 31, and the dense support layer may be preferably formed by using 3 mol% to 8 mol% Y ₂ O ₃ -doped Zirconia. 20 and the green sheet of the gas channel layer can be produced and used.

Although the exemplary embodiments of the present invention have been described in detail above, the scope of the present invention 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 the scope of the invention.

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]

1. Ceramic Oxygen Membrane Module

2. Ceramic Oxygen Membrane Stack Module

10. Ion conductive membrane layer

11. Electrode active layer

20. Dense support layer

30. Gas channel layer

31.support pillar

40. Oxygen Collector

100. Cap

101. Ion Conductive Membrane Frame

200. Sealants

Claims

Ceramic oxygen separator module,

The module includes an ion conductive membrane frame coated with an electrode active layer on both sides of the upper and lower surfaces, respectively, and having a space therein;

A dense support layer having a plurality of holes at upper and lower parts positioned symmetrically with each other in contact with the electrode active layer coated on the inner surface of the ion conductive membrane frame at the top and the bottom of the inner space of the frame;

A gas channel layer forming a gas flow space between the upper and lower dense support layers having a plurality of holes; And

An oxygen collecting port penetrates the upper and lower surfaces of the module up and down, and is connected to the gas flow space of the gas channel layer.

Ceramic oxygen separator module.
The method of claim 1,

The gas channel layer further includes a support column supporting between the dense support layer having a plurality of upper and lower holes located symmetrically with each other.

Ceramic oxygen separator module.
The method of claim 1,

The ion conductive membrane frame is composed of an ion conductive material, an ion-electron mixed conductive material, a mixture of an electron conductive material and an ion conductive material or a mixture of an ion-electron mixed conductive material and an ion conductive material,

Ceramic oxygen separator module.
The method of claim 3, wherein

The ion conductive material is yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (SCSZ), gadolinia doped-ceria (GDC), samaria injection ceria (Smaria). doped-Ceria (SDC), strontium and magnesium-injected lanthanum gallates (LSGM), bismuth oxide (Bismuth oxide, Bi 2 O 3 ) and perovskite materials strontium, magnesium-injected lanthanum gallates, LSGM), one or more selected from the group consisting of

Ceramic oxygen separator module.
The method of claim 3, wherein

The ion-electron mixed conductive material is strontium titanium ferrite (STF), lanthanum strontium ferrite (LSF), lanthanum strontium cobaltite (LSC), strontium cobalt ferrite (Strontium ferrite) SFC), barium strontium cobalt ferrite (BSCF), lanthanum strontium cobalt ferrite (LSCF), and lanthanum nickelate (LNO), one or more selected from the group consisting of

Ceramic oxygen separator module.
The method of claim 3, wherein

The electron conductive material is composed of lanthanum strontium manganite (LSM), lanthanum strontium chromite (LSCr), manganese ferrite (MnFe 2 O 4 ), and nickel ferrite (NiFe 2 O 4 ). One or more selected from

Ceramic oxygen separator module.
The method of claim 1,

The dense support layer is made of Y 2 O 3 -doped Zirconia,

Ceramic oxygen separator module.
The method of claim 1,

The gas channel layer is 0.1 mm to 1.0 mm thick,

Ceramic oxygen separator module.
A plurality of ceramic oxygen separation membrane modules of any one of claims 1 to 8 are laminated so that the oxygen collecting port of each module are connected to each other,

The upper oxygen trap of the uppermost module is sealed with a cap,

The lower oxygen collecting port of the uppermost module repeats the process of sealingly connecting with the upper oxygen collecting port of the module located below,

The lower oxygen trap of the lowermost module is hermetically connected to the manifold or the metal frame,

The sealing connection uses glass sealing material, ceramic paste or brazing material,

Ceramic Oxygen Membrane Stack Module.
Manufacturing a plurality of ion conductive ceramic green sheets using a tape casting process;

Preparing an ion conductive membrane layer by preparing a porous conductive active layer in contact with both sides of the green sheet;

Manufacturing a dense support layer having a plurality of holes by drilling a plurality of holes in the green sheet;

Manufacturing a gas channel layer by punching a central portion of the green sheet;

Preparing a laminate by laminating the ion conductive membrane layer, the dense support layer, the gas channel layer, the dense support layer, and the ion conductive membrane layer in order;

Forming an oxygen collecting hole connected to the gas channel layer while vertically penetrating the green sheet of the stack so as not to be connected to the plurality of holes; And

After the oxygen trap is formed, comprising the step of heat treatment at 900 ℃ to 1500 ℃,

Ceramic Oxygen Membrane Module Manufacturing Method.
The method of claim 10,

The porous conductive active layer is manufactured by a tape casting process or coated on the green sheet,

Ceramic Oxygen Membrane Module Manufacturing Method.
The method of claim 10,

Manufacturing the gas channel layer further comprises inserting a support column into a portion of the punched center portion;

Ceramic Oxygen Membrane Module Manufacturing Method.