WO2015152494A1 - Membrane de séparation d'oxygène - Google Patents

Membrane de séparation d'oxygène Download PDF

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Publication number
WO2015152494A1
WO2015152494A1 PCT/KR2014/012119 KR2014012119W WO2015152494A1 WO 2015152494 A1 WO2015152494 A1 WO 2015152494A1 KR 2014012119 W KR2014012119 W KR 2014012119W WO 2015152494 A1 WO2015152494 A1 WO 2015152494A1
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Prior art keywords
oxygen
thickness
oxide
membrane
coating layer
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PCT/KR2014/012119
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English (en)
Korean (ko)
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유지행
주종훈
유충열
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한국에너지기술연구원
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Publication of WO2015152494A1 publication Critical patent/WO2015152494A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B01D71/0271—Perovskites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0251—Physical processing only by making use of membranes
    • C01B13/0255—Physical processing only by making use of membranes characterised by the type of membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1213—Laminated layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/12—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/20—Specific permeability or cut-off range
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/26—Electrical properties

Definitions

  • the present invention relates to an oxygen separation membrane, and more particularly, to an oxygen separation membrane having a mixed structure to improve the stability and durability of the separation membrane while improving oxygen permeability.
  • Oxygen is used in large quantities in petrochemical processes such as hydrogen production through partial oxidation of methane and in combustion processes such as incinerators, combustion furnaces, heating furnaces, and small cogeneration. Recently, the demand for oxygen in air conditioning systems, refrigerators, air conditioners, and air purifiers has increased, and the market for small and medium-sized oxygen generators as well as large oxygen generators is expanding.
  • the adsorption method can produce oxygen having a purity of 94% and can be applied on a small and medium scale.
  • the adsorption method has a high manufacturing cost because it requires pretreatment of carbon dioxide or moisture contained in air.
  • the membrane separation method is divided into advantages and disadvantages according to the type of separation membrane such as hollow fiber membrane, ceramic membrane.
  • Oxygen separation using polysulfone and polyimide-based polymers has low oxygen production cost, but The disadvantage is that the concentration is as low as 30-40%.
  • the polymer membrane has a low heat resistance and thus cannot be applied to oxygen separation in a high temperature gas mixture, which makes it impossible to separate oxygen from high temperature gas in an industrial process such as a glass melting furnace or a heating furnace.
  • Oxygen separation process using ion permeation ceramic membrane of the membrane separation method has an advantage that can be applied to high temperature process.
  • Ion-permeable ceramic separators for gas permeation are classified into pure gas ion conductive separators and mixed ion-electronic conducting (MIEC) separators.
  • Pure gas ion conductive membranes require an external power source and electrodes to supply current, the gas ion permeation rate is precisely controlled by the current supply, and the gas is in any direction regardless of the partial pressure of the separation gas located in both directions of the membrane. I can move it.
  • the ion-electron mixed conductive membrane permeates gas ions and electrons by a pressure difference between gases without supplying external power.
  • FIG. 1 is a conceptual diagram illustrating an oxygen permeation process in an ion-electron mixed conductive separator.
  • Oxygen gas filled in the mixed gas supply space 23 in which the mixed gas containing oxygen is introduced through the injection port 21 and maintaining a high oxygen partial pressure is adsorbed on the surface of the oxygen supply separator 25.
  • the adsorbed oxygen receives electrons conducted inside the separator and is ionized through charge transfer to be separated into oxygen ions.
  • the separated oxygen ions move to the oxygen vacancies of the crystal lattice inside the membrane and move to the surface of the opposite oxygen producing membrane.
  • the electrons generated by the charge transfer from the surface of the oxygen production membrane to the surface of the oxygen supply separator through the inside of the separator, and the electrons that reach the surface of the oxygen supply separator supply electrons to the adsorbed oxygen again.
  • the combined oxygen molecules are desorbed from the surface of the oxygen production membrane and separated from the separator, and the separated oxygen is operated at the purge gas inlet 26 or the oxygen generating part 27 in the oxygen production space 24. Oxygen is captured by the pump.
  • the mixed gas supply space 23 in which the mixed gas containing oxygen exists and the oxygen production space 24 in which the separated oxygen gas exists are divided into separation membranes 25 through which no gas other than ionized oxygen can pass. Because of this, it is possible to separate pure oxygen.
  • the driving force of oxygen separation is the oxygen partial pressure difference between two gas spaces across the membrane, that is, the mixed gas supply space 23 and the oxygen production space 24.
  • a separator is manufactured using a perovskite-based material (US Pat. Nos. 5,702,959, 5,712,220 and 5,733,435).
  • the separation membrane that allows gas ions and electrons to pass through perovskite alone is called a single phase ion-electron mixed conductive membrane.
  • the perovskite-based separator has a problem in that the oxygen permeability is decreased during the oxygen separation process, and the safety of the separator and the durability of the separator are reduced after oxygen permeation.
  • the heterostructure ion-electron mixed conductive separator includes a mixture of an electron conducting oxide material or metal phase for electron transmission and a fluorite structure or a fluorite phase for ion transmission, and a perovskite series for electron transmission.
  • Heterogeneous membranes incorporating ion permeable fluorspar series have been proposed (US Pat. No. 6,514,314).
  • the separation membrane of the heterostructure has a disadvantage in that the formation of the membrane is not easy due to the oxide having a perovskite structure having relatively low mechanical and chemical stability.
  • the secondary structure is formed by an additional reaction of the oxide having a perovskite-type structure and the oxide having a fluorite structure has a disadvantage in that the oxygen permeability of the separator produced is rather reduced.
  • the present invention is to provide an oxygen separation membrane having excellent safety and durability, and at the same time significantly improved oxygen permeability, by containing an oxide and a fluorite-based oxide having a perovskite structure, a spinel structure, or a mixture thereof. There is this.
  • the present invention is to form a coating layer on a heterostructure containing a compound having a different crystal structure, and to optimize the mixing ratio of the compound having the hetero crystal structure and the thickness of the membrane and the coating layer of the hetero structure As a result, an oxygen separation membrane with an improved oxygen permeability is significantly improved.
  • the present invention provides a separator with improved stability and durability.
  • the present invention is a separator having a heterostructure containing an oxide having a perovskite structure, a spinel structure, or a mixture thereof, and an oxide having a fluorite structure; And an oxygen separator in which a coating layer containing an oxide having a perovskite-type structure, a spinel-type structure, or a mixture thereof is formed on at least one side of the separator, wherein the hetero-type separator has a perovskite-type structure, a spinel-type structure, or a mixture thereof.
  • the oxygen separator Silver provides an oxygen separation membrane, characterized in that the oxygen permeability is 1 ml / cm 2 ⁇ min or more under conditions of 850 °C, 1 atm and oxygen partial pressure difference of 0.21 atm to 10-4 atm.
  • the thickness of the coating layer may maintain 13 to 134% with respect to the total thickness of the oxygen separator.
  • the oxygen permeability may satisfy Equation 1 below.
  • J 1 is a membrane oxygen permeability of a heterostructure having a thickness of 1 mm
  • J is an oxygen permeability of an oxygen separator having a coating layer of thickness Lc formed on a membrane of a heterostructure having a thickness of Lm
  • Lm is a Membrane thickness
  • Lc is the thickness of the coating layer, 2.54 ⁇ a ⁇ 0.94, 0.02 ⁇ b ⁇ 0.08.
  • the oxygen separation membrane may have a porosity of 30 to 60%, an electrical conductivity of 1 to 2000 S / cm (dry air and 300 to 850 ° C., measured by a four-electrode direct current method), and a grain size of 10 to 1000 nm. .
  • the oxide having the perovskite type structure is lanthanum strontium cobaltite (LSC), lanthanum strontium ferrite (LSF), lanthanum strontium manganite (LSM), lanthanum strontium chromite (LSCr), lanthanum strontium cobalt ferrite (LSCF), barium strontium It may be one or more selected from the group consisting of cobalt ferrite (BSCF) and strontium titanium ferrite (STF).
  • LSC lanthanum strontium cobaltite
  • LSM lanthanum strontium manganite
  • LSCr lanthanum strontium chromite
  • LSCF lanthanum strontium cobalt ferrite
  • barium strontium It may be one or more selected from the group consisting of cobalt ferrite (BSCF) and strontium titanium ferrite (STF).
  • the oxide having the fluorite structure may be at least one selected from the group consisting of yttria stabilized zirconia (YSZ), scandia stabilized zirconia (ScSZ), samarium implanted ceria (SDC), gadolinium implanted ceria (GDC), and LaGaO 3 . have.
  • YSZ yttria stabilized zirconia
  • ScSZ scandia stabilized zirconia
  • SDC samarium implanted ceria
  • GDC gadolinium implanted ceria
  • LaGaO 3 LaGaO 3
  • the oxide having the spinel structure may be at least one selected from the group consisting of manganese ferrite (MnFe 2 O 4 ), nickel ferrite (NiFe 2 O 4 ), and cobalt ferrite (CoFe 2 O 4 ).
  • the heterostructure separator is at least one oxide selected from the group consisting of lanthanum strontium cobalt ferrite (LSCF), barium strontium cobalt ferrite (BSCF) and lanthanum strontium manganite (LSM) and gadolinium-infused ceria (GDC).
  • the coating layer may include at least one oxide selected from the group consisting of lanthanum strontium cobalt ferrite (LSC), barium strontium cobalt ferrite (BSCF), and lanthanum strontium cobalt ferrite (LSCF).
  • Oxygen separation membrane according to the present invention has the advantage of forming a coating layer on at least one side of the separation membrane of the heterostructure, and significantly improved oxygen permeability by controlling the thickness of the separation membrane and the coating layer of the heterostructure.
  • the oxygen separation membrane according to the present invention has the advantage that the durability is improved by the coating layer formed on the separation membrane of the heterostructure.
  • Example 2 is a SEM photograph of the oxygen separation membrane prepared in Example 1 according to the present invention.
  • Example 3 is a graph of oxygen permeability of the oxygen separation membranes of Example 4 and Comparative Example 17 according to the present invention, and the oxygen permeability was measured while controlling the membrane thickness ratio (Lm / Lc) of the heterostructure to the coating layer thickness, respectively.
  • the present invention relates to an oxygen separation membrane with significantly improved oxygen permeability.
  • Oxygen separator of the present invention is a separator having a heterostructure containing an oxide having a perovskite structure, a spinel structure or a mixture thereof, and an oxide having a fluorite structure; And a coating layer containing an oxide having a perovskite structure, a spinel structure, or a mixture thereof on at least one surface of the separator.
  • Oxygen separator according to the present invention is a membrane having a heterogeneous structure in which a specific amount of oxide having a perovskite structure, a spinel structure, or a mixture thereof, and an oxide having a fluorite structure that permeates ions, Use
  • the heterostructure separator contains 18 to 40% by volume oxide having a perovskite type structure, a spinel type structure or a mixture thereof, and 60 to 82% by volume oxide having a fluorite structure.
  • the content range of each crystal structure forming the oxygen separation membrane is calculated using General Effective Medium Theory (GEMT) of Equation 2 below.
  • GEMT General Effective Medium Theory
  • p eff is the percolation threshold
  • t is the penetration slope
  • ⁇ tot is the electrical conductivity of the composite
  • ⁇ 1 is the electrical conductivity of the oxide with fluorite structure
  • ⁇ 2 is the perovskite Electrical conductivity of the oxide having the structure having a structure, a spinel structure, or a mixture thereof
  • p is a volume fraction of the oxide having a perovskite structure, a spinel structure, or a mixture thereof.
  • Equation 2 it was confirmed that the percolation threshold of the conduction phenomenon of the heterostructured membrane was 17.7%, and the content of oxide having a perovskite-type structure, a spinel-type structure, or a mixture thereof was 18 vol. If it is more than% it can be confirmed that it can be used as an oxygen separation membrane.
  • the content of the oxide having a perovskite structure, a spinel structure, or a mixture thereof is less than 18% by volume, it may be difficult to play a role as an oxygen separation membrane because the electron conductivity is not sufficient, and exceeds 40% by volume. There may be a problem that the durability of the separator is degraded due to mechanical and chemical perovskite oxide.
  • the oxide having the perovskite-type structure has an ABO 3 structure, where A is an alkali, alkaline earth metal ion or rare earth cation, and B is a transition metal or rare earth cation.
  • the ideal perovskite-like structure is a cubic crystal structure sharing a corner, with 12 A cations and 6 B cations surrounded by oxygen. Since each oxygen ion is bound to four A cations and two B cations, and the A cation is large enough to be compared to the oxygen ion, the perovskite-like structure is geometrically occupied by O and A cations. Small B cations have structures that occupy octahedral lattice gaps.
  • the oxide having a perovskite type structure is not particularly limited, but specifically, lanthanum strontium cobaltite (LSC), lanthanum strontium ferrite (LSF), lanthanum strontium manganite (LSM), lanthanum strontium chromite (LSCr), and lanthanum
  • LSC lanthanum strontium cobaltite
  • LSM lanthanum strontium ferrite
  • LSM lanthanum strontium manganite
  • LSCr lanthanum strontium chromite
  • LSCF strontium cobalt ferrite
  • BSCF barium strontium cobalt ferrite
  • STF strontium titanium ferrite
  • the oxide having the spinel structure has an AB 2 O 4 structure
  • a and B are alkaline earth metals and transition metals and have a cubic crystal structure.
  • a metal is arranged at the tetrahedral 4 coordination position
  • B metal is arranged at the octahedral 6 coordination position.
  • an oxide having a spinel structure is not particularly limited, but specifically, one kind selected from the group consisting of manganese ferrite (MnFe 2 O 4 ), nickel ferrite (NiFe 2 O 4 ), and cobalt ferrite (CoFe 2 O 4 ). The above can be used.
  • the oxide having the fluorspar structure has an AO 2 structure, tetravalent cations occupy the face-centered cubic lattice sites, and oxygen ions are present at eight tetrahedral centers composed of four cations. Therefore, cations have 8 coordination and oxygen ions have 4 coordination.
  • bivalent and trivalent cations are substituted for tetravalent cations in the fluorspar structure oxides, oxygen vacancies are generated in the oxygen ion site to meet charge neutral conditions, and conduction of oxygen ions through the oxygen vacancies at high temperature occurs.
  • an oxide having a fluorite structure is not particularly limited, but specifically, yttria stabilized zirconia (YSZ), scandia stabilized zirconia (ScSZ), samarium implanted ceria (SDC), gadolinium implanted ceria (GDC) and LaGaO 3 .
  • YSZ yttria stabilized zirconia
  • ScSZ scandia stabilized zirconia
  • SDC samarium implanted ceria
  • GDC gadolinium implanted ceria
  • LaGaO 3 LaGaO 3
  • the present invention in order to improve the oxygen permeability degradation of the prepared separator by the difference between the mechanical and chemical stability of the oxide and the reaction between the oxide, the perovskite-type structure, spinel on the membrane of the heterostructure of the double structure A coating layer containing an oxide having a mold structure or a mixture thereof is formed.
  • the dissociation of oxygen molecules is activated on the surface of the oxygen separation membrane by the coating layer, and the electron is conductive oxide (perovskite structure, spinel type structure) by the heterogeneous separation membrane in which two oxides are mixed in a specific amount inside the oxygen separation membrane. Or an oxide having a mixed structure thereof, and ions are conducted through the fluorite structure oxide, thereby significantly improving oxygen permeability.
  • the electron is conductive oxide (perovskite structure, spinel type structure) by the heterogeneous separation membrane in which two oxides are mixed in a specific amount inside the oxygen separation membrane.
  • an oxide having a mixed structure thereof, and ions are conducted through the fluorite structure oxide, thereby significantly improving oxygen permeability.
  • the separation membrane of the hetero structure maintains the thickness of 30 to 100 ⁇ m.
  • the membrane of the heterostructure according to the present invention may have a thickness of 30 ⁇ m or less, but preferably 30 ⁇ m or more in consideration of ease of manufacturing process and mechanical strength of the prepared oxygen separator, and 300 ⁇ m in consideration of oxygen permeability. It is preferable not to exceed it.
  • the coating layer preferably maintains 13 to 134% of the total thickness of the oxygen separator. If the thickness of the coating layer is less than 1%, a problem may occur that it is difficult to deposit the coating layer on the surface of the separator.
  • the oxygen separation membrane of the present invention satisfies the following equation 1 in which the correlation between the coating layer and the separation membrane of the heterostructure, and the oxygen permeability is modified.
  • J 1 is a membrane oxygen permeability of a heterostructure having a thickness of 1 mm
  • J is an oxygen permeability of an oxygen separator having a coating layer of thickness Lc formed on a membrane of a heterostructure having a thickness of Lm
  • Lm is a Membrane thickness
  • Lc is the thickness of the coating layer, 0.95 ⁇ a ⁇ 2.2, 0.01 ⁇ b ⁇ 0.03).
  • Equation 1 is an example of using La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3- ⁇ as the oxide having a perovskite structure and Gd 0.1 Ce 0.9 O 2- ⁇ as the oxide having a fluorite structure.
  • the present invention can adjust the degree of improvement of oxygen permeability according to the combination of components of the oxide having a perovskite structure and the oxide having a fluorite structure.
  • Such a coating layer may be prepared by using a liquid film forming method of coating and drying a coating layer forming composition containing an oxide having a perovskite type structure, and the coating may be performed by a roll coating method, a bar coating method, a dip coating method, or a spin coating method.
  • Casting method, die coating method, blade coating method, bar coating method, gravure coating method, spray coating method, doctor coating method and the like can be used.
  • a direct pattern forming method using an inkjet printing method, a gravure printing method, a screen printing method, or the like can be used.
  • the oxygen separation membrane according to the present invention has an oxygen permeability of 1 ml / cm 2 ⁇ min or more at 850 ° C., 1 atmosphere, air / helium, argon, or carbon dioxide conditions, and the porosity of the coating layer is 30 to 60%.
  • the electrical conductivity is 1 to 2000 S / cm (dry air and 300 to 850 ° C., measured by four-electrode direct current method), and the grain size is 10 to 1000 nm.
  • the mixture was ball-milled with zirconia balls at 180 rpm for 5 days.
  • the mixture was transferred to a beaker to remove zirconia balls, and then a green sheet was manufactured using a tape casting equipment (STC-14C, Hansung Machinery Co., Korea).
  • the interval between the doctor blade and the tape carrier of the equipment was fixed to 300 ⁇ m, the speed of the tape carrier was set to about 1cm / s. If the drying rate of the green sheet is too fast, cracking may occur during drying, so the heater temperature of the tape carrier is set to 40 ° C.
  • a green sheet was laminated using a heating press and a sintering process was performed to prepare a separator having a heterogeneous structure.
  • the sintering was performed at 1300 to 1350 ° C. to prepare a separator (LSCF-GDC) having a heterogeneous structure.
  • La 0.6 Sr 0.4 Co 0 O 3- ⁇ and a commercial screen printing solvent (Heraeus, V-006) was mixed in a 1.5: 1 weight ratio to prepare a coating composition.
  • the surface was cleaned using a sonicator.
  • the thickness of this coating layer is 13-134% of the total thickness of the oxygen separator.
  • FIG. 2 The SEM photograph of the oxygen separator prepared above is shown in FIG. 2.
  • Example 2-12 and Comparative Example 1-2 Example of changing the thickness of the separator
  • Example 2 In the same manner as in Example 1, but the oxygen separation membrane having a coating layer of the same thickness was prepared by varying the thickness of the separation membrane of the heterostructure as shown in Table 1.
  • Example 2 The same procedure as in Example 1, except that the oxygen separation membrane was prepared by varying the composition of the separation membrane and the components of the coating layer as shown in Table 2.
  • Comparative Example 17 is a comparative example because the ratio of oxide having a perovskite structure, a spinel structure, or a mixture thereof and an oxide having a fluorite structure is 50:50)
  • Figure 3 below is to control the membrane thickness ratio (Lm / Lc) of the heterostructure to the coating layer thickness of the oxygen separation membrane according to Example 4 and Comparative Example 17, and shows the oxygen permeability accordingly.
  • Example 3 The same procedure as in Example 1 was performed, but the oxygen separation membrane was prepared by changing the composition of the separation membrane and the components of the coating layer as shown in Table 3 below.
  • the porosity and grain size were measured by analyzing the image of the microstructure of the membrane and the coating layer obtained using a scanning electron microscope (SEM4800, Hitachi).
  • the electrical conductivity was measured at 300 to 850 ° C. while flowing dry air at a flow rate of 30 ml / min.
  • ⁇ is the electrical conductivity
  • L is the thickness of the specimen
  • A is the cross-sectional area of the specimen.
  • the heterostructure membrane includes an oxide having a perovskite structure and a fluorite structure. That is, at least one oxide is selected from the group consisting of lanthanum strontium cobalt ferrite (LSCF), barium strontium cobalt ferrite (BSCF), and lanthanum strontium manganite (LSM) as a perovskite structure, and an oxide having a fluorite structure is injected with gadolinium. Select Ceria (GDC).
  • LSCF lanthanum strontium cobalt ferrite
  • BSCF barium strontium cobalt ferrite
  • LSM lanthanum strontium manganite
  • the coating layer is selected from the group consisting of lanthanum strontium cobalt ferrite (LSC), barium strontium cobalt ferrite (BSCF) and lanthanum strontium cobalt ferrite (LSCF) as an oxide having a perovskite structure.
  • LSC lanthanum strontium cobalt ferrite
  • BSCF barium strontium cobalt ferrite
  • LSCF lanthanum strontium cobalt ferrite

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  • Inorganic Chemistry (AREA)
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  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne une membrane de séparation d'oxygène et, plus spécifiquement, une membrane de séparation d'oxygène possédant : une membrane de séparation hétérostructurée contenant un oxyde possédant une structure de perovskite et un oxyde possédant une structure de fluorine ; et une couche de revêtement contenant un oxyde possédant une structure de perovskite et formé sur au moins une surface de la membrane de séparation, la membrane de séparation hétérostructurée contenant 18 à 40 % en volume d'un oxyde possédant une structure de perovskite et 60 à 82 % en volume d'un oxyde possédant une structure de fluorine, l'épaisseur de la membrane de séparation hétérostructurée allant de 30 à 300 μm et l'épaisseur de la couche de revêtement étant maintenue dans la fourchette de 1 à 100 μm, et ainsi la porosité, la conductivité électrique et la durabilité de la couche de revêtement étant excellentes et la perméabilité à l'oxygène pouvant être maintenue pour se situer à une valeur de 1 mL/cm2•min ou plus dans les conditions de 850 °C, 1 atm et une différence de pression partielle en oxygène de 0,21 à 10-4 atm.
PCT/KR2014/012119 2014-04-02 2014-12-10 Membrane de séparation d'oxygène WO2015152494A1 (fr)

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WO2017216420A1 (fr) * 2016-06-14 2017-12-21 Teknologian Tutkimuskeskus Vtt Oy Procédé et réacteur d'oxydation catalytique partielle d'hydrocarbures
CN109734438A (zh) * 2019-02-01 2019-05-10 中国科学院青岛生物能源与过程研究所 一种不含钴和铁的钛基钙钛矿型陶瓷透氧膜及其制备方法和应用

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KR101905500B1 (ko) * 2016-12-07 2018-10-15 한국에너지기술연구원 산소 분리막을 사용한 메탄 산화 이량화 방법

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