KR20180065137A - Method for Oxidative Coupling of Methane Using Oxygen ion Conductive Membrane - Google Patents

Abstract

The present invention relates to a methane oxidizing dimerization method using a fluidized bed catalyst and an oxygen separator having a catalyst layer. The methane oxidizing dimerization method of the present invention is a spontaneous methane oxidizing dimerization reaction using oxygen partial pressure difference and also uses the oxygen separator and the catalyst-containing fluidized bed. It is possible to obtain hydrocarbon with at least two carbon atoms at a high yield by additionally dimerizing unreacted methane.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for oxidizing methane,

More particularly, the present invention relates to a methane oxidation dimerization method using an oxygen separation membrane having a catalyst layer and a fluidized bed catalyst.

Ethylene (ehtylene), which is a basic compound, is the most abundant compound in industrial use and it is converted into polyethylene, ethylene oxide, olefin, vinyl chloride and so on by polymerizing or oxidizing it. Ethylene can be produced mainly by thermal cracking or steam cracking of ethane, naphtha LPG or the like, which produces not only ethylene but also impurities such as acetylene and diolefine. In addition, since the raw material is crude oil, the production cost of ethylene is increasing due to recent resource depletion and high cost. Therefore, attempts have been made to produce ethylene from resources (coal, natural gas, etc.) that can replace them.

Recently, researches on the development of methane as a liquid fuel and a basic compound such as ethane, ethylene, etc., which are contained in large amounts in shale gas, gas hydrate, and landfill gas in landfills, are actively being carried out. Methane to carbon-rich hydrocarbons can be divided into indirect and direct conversion. The methane indirect conversion method is a method in which a synthesis gas (H2, CO, CO2) is produced by a high-temperature catalytic reaction in methane, and then a hydrocarbon compound is produced by a Fischer-Tropsch reaction or by a catalytic reaction of Cu, Zn and alumina It is possible to synthesize methanol and obtain a synthetic fuel using a dehydration catalyst such as ZSM-5, but it has disadvantages that the total equipment cost is increased due to the synthesis gas production process being included in the methane conversion process. Direct methane coupling (DMC) method of methane is attracting attention, and methane is reacted with oxygen on catalyst to directly produce ethane or ethylene.

The methane direct conversion method is generally classified into the Oxidative Coupling of Methane (OCM) method and the Non-oxidative Coupling of Methane NCM method. Methane oxidative dimerization is a method that directly converts methane to oxygen by reacting methane with oxygen as shown in formula (1). Up to now, many studies have been made with direct methane conversion technology. However, in spite of high reaction rate and conversion rate, The loss due to the reaction and the coking phenomenon cause the catalytic activity to deteriorate and the commercial yield can not be overcome because the yield can not be overcome. As an alternative to overcome this problem, non-oxidative methane dimerization methods such as the formula (2) have been studied.

Methane direct conversion formula

2 K ₄ + O ₂ ↔ C ₂ H ₄ + 2H ₂ O, Δ Go (1000 K) = -152 kJ / mol (1)

2CH ₄ ↔ C ₂ H ₄ + 2H ₂ , Δ Go (1000 K) = 40 kJ / mol (2)

The non-oxidizing methane dimerization process produces a corresponding compound while dehydrogenating and dimerizing or cyclizing methane and releasing hydrogen. However, the non-oxidizing methane dimerization method requires involuntary endothermic reaction, which depends on external heat supply, and requires a large heat exchange area when the conversion of methane is low and the reaction is indirectly heated. This complicates the process, Is required. In addition, undesired side reactions, such as caulking, can occur on the heat exchange surface due to the relatively high temperature.

Korean Unexamined Patent Publication No. 2000-0004984 discloses a method for converting aliphatic hydrocarbons into aromatic hydrocarbons, and discloses a method for electrochemically removing hydrogen by using a hydrogen separation membrane in the non-oxidized methane dimerization method. do. However, this requires separate dehydrogenation catalysts and high temperature reaction conditions.

Therefore, there is a need for a high-efficiency methane direct conversion method capable of obtaining a stable reaction and yield while exhibiting a high reaction rate and conversion ratio.

Korea Patent Publication No. 2012-0004984

The present invention provides an apparatus and method for methane oxidation dimerization which exhibits a stable reaction even in a reducing atmosphere by using a methane oxidation dimerization apparatus using an oxygen separation membrane having a catalyst layer and a fluidized bed catalyst.

In order to solve the above problems, the present inventors have completed the present invention by discovering a methane oxidation dimerization method using an oxygen separation membrane and a fluidized bed catalyst.

The present invention is a methane oxidation dimerization method using a reactor in which a support layer, a stabilization layer and a catalyst layer are sequentially divided into a first space and a second space with an oxygen separation membrane as a boundary, Supplying an oxygen-containing gas so as to be in contact with the support layer surface; Forming a fluidized bed in the second space, the fluidized bed including a methane-containing gas and a flow catalyst so as to contact the surface of the catalyst layer of the oxygen separation membrane; And obtaining a hydrocarbon having 2 or more carbon atoms produced in the second space. The present invention also provides a method for diminishing methane oxidation using an oxygen separation membrane.

The present invention is also characterized in that the support layer is a perovskite structure material selected from the group consisting of lanthanum strontium cobaltite (LSC), lanthanum ferrite (LF), lanthanum strontium manganite (LSM) LSCr, Calcium Titanate Ferrite (CTF), CaTiFeO3, Barium Strontium Cobalt Ferrite (BSCF), and Strontium Titanate Ferrite (STF) Wherein the doped lanthanum ferrite is doped with Sr, Ca or Ba to A-site (La site) to the basic structure of LaFeO _{3 - x} , and B-site (Fe- site) is doped with Co, Cr, Ga, or Ti. The present invention provides a methane oxidation dimerization method using an oxygen separation membrane.

The present invention also relates to a method for producing a fluorite-structured oxide, wherein the stabilizing layer is a fluorosilicic oxide or a mixture of fluorosilicic oxide and perovskite structure material, wherein the fluorosilicic oxide is selected from the group consisting of Yttria-stabilized zirconia (YSZ), Scandia stabilized zirconia wherein the perovskite structure material is at least one selected from the group consisting of lanthanide-stabilized zirconia (ScSZ), samarium-doped ceria (SDC), and gadolinium-doped ceria Lanthanum strontium cobaltite (LSC), lanthanum ferrite (LF), lanthanum strontium manganite (LSM), lanthanum strontium chromite (LSCr), calcium titanate ferrite (Calcium Titanate Ferrite, CTF, CaTiFeO3), barium strontium cobalt ferrite It is preferable that the doped lanthanum ferrite is at least one selected from the group consisting of LaFeO _{3 - x} and LaFeO _{3 - x} , (Fe-site) is doped with Sr, Ca, or Ba, and B-site (Fe-site) is doped with Co, Cr, Ga, or Ti.

In the present invention, the catalyst layer is formed of La ₂ O ₃ / MgO, MnNa ₂ WO ₄ / SiO ₂ , La ₂ O ₃ (SrO) / CaO, Li ₂ O / MgO, LaMnO ₃ , La _0.9 K _0.1 MnO ₃ , La _{1 - x} Na _x MnO ₃ (0 < x < 1) _, Ba _{0 . 5} Sr _{0 . 5} TiO ₃ (BST), Na-BST, Mg-BST, Li-BST, SrTi _{1 - x} Li _x O ₃ (0 <x <1) _, SrTi _0.9 Li _0.1 O ₃ and Bi _{1 . 5} Y _{0 . 3} Sm _{0 . 2} O ₃ Wherein the at least one oxygen separation membrane comprises at least one selected from the group consisting of oxygen and oxygen.

In the present invention, the flow catalyst may be a particulate material having a size of 20 μm to 2000 μm, and may include La ₂ O ₃ / MgO, MnNa ₂ WO ₄ / SiO ₂ , La ₂ O ₃ (SrO) / CaO, Li ₂ O / MgO _{, LaMnO 3, La 0 .9 K} 0. 1 MnO 3, La 1 - x Na x MnO 3 (0 <x <1), Ba 0. ₅ Sr _{0 . 5} TiO ₃ (BST), Na-BST, Mg-BST, Li-BST, SrTi _{1 - x} Li _x O ₃ (0 <x <1) _, SrTi _{0 . 9} Li _{0 . 1} O ₃ And Bi _{1 . 5} Y _{0 . 3} Sm _{0 . 2} O ₃ Wherein the at least one oxygen separation membrane comprises at least one selected from the group consisting of oxygen and oxygen.

The present invention also provides a methane oxidation dimerization method using an oxygen separation membrane, wherein the support layer, the stabilization layer or the catalyst layer is porous.

The present invention also provides a methane oxidation dimerization method using an oxygen separation membrane, wherein the stabilization layer has a thickness of 1 to 100 mu m.

The present invention also provides a methane oxidation dimerization method using an oxygen separation membrane, wherein the fluidized bed comprises a carbon dioxide adsorbent.

The present invention also provides a methane oxidation dimerization method using an oxygen separation membrane, wherein the methane-containing gas comprises at least 3 vol% of methane.

The present invention also provides a methane oxidation dimerization method using the oxygen separation membrane, wherein the hydrocarbon having 2 or more carbon atoms is ethane (C ₂ H ₆ ) or ethylene (C ₂ H ₄ ).

The present invention also provides a methane oxidation dimerization method using an oxygen separation membrane, wherein the reactor is maintained at a temperature of 700 ° C to 1000 ° C.

The methane oxidation dimerization method using the oxygen separation membrane and the fluidized bed catalyst having the catalyst layer of the present invention is a spontaneous methane oxidation dimerization reaction using the oxygen partial pressure difference. As the fluidized bed containing the catalyst is used, unreacted methane is further dimerized It is possible to obtain hydrocarbons having 2 or more carbon atoms in the yield.

1 is a schematic diagram showing a methane oxidation dimerization reaction using an oxygen separation membrane according to an embodiment of the present invention.
2 is a schematic view showing the structure of an oxygen separation membrane according to one embodiment of the present invention.
3 is a schematic diagram showing a methane oxidation dimerization reactor using a fluidized bed including an oxygen separation membrane and a catalyst according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to the detailed description of the present invention, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms. Therefore, the embodiments described in this specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, It is to be understood that equivalents and modifications are possible.

In one embodiment, the present invention is a methane oxidation dimerization method using a reactor in which a support layer, a stabilization layer, and a catalyst layer are sequentially divided into a first space and a second space with an oxygen separation membrane as a boundary, Supplying an oxygen-containing gas so as to be in contact with the support layer surface of the oxygen separation membrane; Forming a fluidized bed in the second space, the fluidized bed including a methane-containing gas and a flow catalyst so as to contact the surface of the catalyst layer of the oxygen separation membrane; And a step of obtaining a hydrocarbon having 2 or more carbon atoms generated in the second space.

Gas separation using a mixed ionic electronic conductor membrane proceeds by selective gas permeation principle for the membrane. That is, when the gas mixture contacts the surface of the membrane, the gas component dissolves and diffuses into the membrane, where the solubility and permeability of each gas component is different for the membrane material. The propulsive force for gas separation is the partial pressure difference for the particular gas component applied across the membrane. Particularly, the membrane separation process using ion - electron mixed conductive film is widely used in various fields because of its low energy consumption. The ion separation membrane of the present invention is an oxygen separation membrane which selectively permeates oxygen ions. FIG. 1 shows the principle of the methane oxidation dimerization reaction (1) and the methane oxidation dimerization reaction using the oxygen separation membrane of the present invention, wherein the oxygen separation membrane 2 is divided into a first space 3 and a second space 4 ) Into the first space and the methane-containing gas into the second space, the oxygen in the first space is converted into oxygen ions by passing through the conductive film in contact with the surface of the oxygen separation membrane. Oxygen ions passing through the conductive film react with methane gas containing methane on the opposite side of the conductive membrane at the catalyst layer, which leads to oxidation-induced dehydrogenation coupling reaction to produce a compound having 2 or more carbon atoms in the second space. The methane dimerization reaction is carried out at a temperature of 700 ° C to 900 ° C.

The methane-containing gas may form the fluidized bed 5 in the second space together with the flow catalyst as shown in FIG. The fluidized bed is a layer in which a powder is formed and moves according to a constant flow rate of a fluid in a certain space. In the fluidized bed, the particles are uniformly mixed to allow good contact between particles and fluid, and temperature control is also easy. In the present invention, by forming the methane-containing gas and the flowing catalyst in the second space as a fluidized bed, the unreacted methane that has not reacted on the surface of the separation membrane is additionally oxidized, and a high dimerization reaction yield can be obtained. The flow rate of the fluidized bed is not limited to this, but it can be supplied at a flow rate of 0.02 to 2 m / s, for example. In the case of the velocity below 0.02 m / s, the fine flow catalyst molecules in the fluidized bed do not have a smooth flow and can not sufficiently perform the role of the catalyst. At a velocity of 2 m / s or higher, the contact between the oxygen separator and the methane- The efficiency of dimerization of the gas may be lowered. In one embodiment, the flow catalyst is selected from the group consisting of La ₂ O ₃ / MgO, MnNa ₂ WO ₄ / SiO ₂ , La ₂ O ₃ (SrO) / CaO, Li ₂ O / MgO, _{LaMnO 3, La 0 .9 K 0.} 1 MnO 3, La 1 - x Na x MnO 3 (0 <x <1), Ba 0. ₅ Sr _{0 . 5} TiO ₃ (BST), Na-BST, Mg-BST, Li-BST, SrTi _{1 - x} Li _x O ₃ (0 <x <1) _, SrTi _{0 . 9} Li _{0 . 1} O ₃ And Bi _{1 . 5} Y _{0 . 3} Sm _{0 . 2} O ₃ And at least one selected from the group consisting of The fluidized bed may also comprise a carbon dioxide adsorbent. When the carbon dioxide adsorbent is flowed using the fluidized bed of the second space, carbon dioxide generated by the combustion reaction as an additional reaction can be adsorbed, and the process efficiency of the methane oxidation dimerization reaction can be enhanced. The carbon dioxide adsorbent is preferably La ₂ O ₃ Or MgO. When the metal oxide is used, the carbon dioxide adsorbent can be simultaneously used as a catalyst for the methane dimerization reaction.

In one embodiment, the methane feed gas may be a methane / argon mixed gas, And 3% by volume or more of methane. If less than 3% by volume of methane is not sufficient, the oxygen supplied through the oxygen separation membrane can not sufficiently react with methane. The oxygen-containing gas and the methane-containing gas may be applied at different flow rates, for example, 100 ml / min to 500 ml / min to induce sufficient reaction at the surface of the oxygen separation membrane. , But is not limited thereto. When the flow rate is 100ml / min, the reaction rate is slowed due to the low reactant concentration at the surface of the oxygen separation membrane. When the flow rate is 500ml / min, the active sites of the oxygen separation membrane become saturated and the oxygen separation membrane may be damaged. The methane oxidation dimerization reaction of the present invention is a spontaneous methane oxidation reaction at a temperature of 700 ° C to 1000 ° C due to the difference in oxygen partial pressure. Through this reaction, methane is produced from a compound having two or more carbon atoms, preferably ethylene.

Since the support layer is an oxygen ion conductive layer, and the stabilization layer may be damaged when the support layer is exposed to the reducing gas, the oxygen separation membrane according to the present invention may have a layer , And the catalyst layer is a layer containing a catalyst material for promoting the dimerization reaction of methane. 2 shows an oxygen separation membrane according to one embodiment of the present invention. (a) shows a dense support layer 10 and a stabilized layer 11, and a stabilized layer is laminated on one surface of the support layer. (b) shows a porous support layer 100 for enhancing the ionization degree of the oxygen-containing gas by increasing the surface area of the support layer in the single-layer structure according to the present invention, and a stabilization layer 11 laminated on one surface of the support layer. (C) and (d) show the form of the methane oxidation diminution catalyst layer of the oxygen separation membrane, which indicates that the porous catalyst layer 12 for maximizing the reaction area is laminated on one surface of the stabilization layer. The catalyst layer C is formed by sequentially laminating a support layer 10, a stabilizing layer 11 and a catalyst layer 12. The catalyst layer is formed by mixing a catalyst with, for example, activated carbon to form a mixed layer, The reaction area can be widened by the pores to be formed. (d) is a support layer, a stabilizing layer, and a catalyst layer sequentially laminated, and the catalyst layer is obtained by mixing and sintering the powder materials of the stabilizing layer and the catalyst layer to make them porous. The methane oxide dimerization catalyst is thermally stable as a metal oxide and preferably an alkali metal or an alkaline earth metal is introduced into the Mg and La oxides to achieve a high activation catalyst. This catalytic material promotes ionic conductivity due to oxygen vacancy and is suitable for oxygen ion transport.

In one embodiment, the support layer is a perovskite structure material selected from the group consisting of lanthanum strontium cobaltite (LSC), lanthanum ferrite (LF), lanthanum strontium manganite (LSM), lanthanum (LSCr), calcium titanate ferrite (CTF), CaTiFeO3, barium strontium cobalt ferrite (BSCF), and strontium titanate ferrite (STF). And at least one selected from the group consisting of The lanthanum ferrite is doped with Sr, Ca, Ba or the like in the basic structure of LaFeO _{3 - x} , and A-site (La site) is doped with Co, Cr, Ga, Ti or the like. Can be used.

In one embodiment of the present invention, the stabilizing layer is a fluorosilicic oxide, or a mixture of fluorosilicic oxide and perovskite structure material, wherein the fluorosilicic oxide is selected from the group consisting of Yttria-stabilized zirconia (YSZ), Scandia stabilized zirconia At least one selected from the group consisting of Scandia-stabilized zirconia (ScSZ), samarium-doped ceria (SDC) and gadolinium-doped ceria (GDC) Is preferably selected from the group consisting of Lanthanum strontium cobaltite (LSC), Lanthanum ferrite (LF), Lanthanum strontium Manganite (LSM), Lanthanum strontium chromite (LSCr) Calcium Titanate Ferrite (CTF, CaTiFeO3), barium strontium cobalt ferrite (Barium Strontium A-site (La site on the primary structure of the _{x) -} Cobalt Ferrite, BSCF) and strontium titanate ferrite (Strontium Titanate Ferrite, STF) group 1 that contains the least, and the doped lanthanum ferrite LaFeO ₃ selected from the consisting of And B-site (Fe-site) is doped with Co, Cr, Ga, or Ti. It is preferably gadolinia doped-ceria (GDC). The catalyst layer of the present invention is _{La 2 O 3 / MgO, MnNa} 2 WO 4 / SiO 2, La 2 O 3 (SrO) / CaO, Li 2 O / MgO, LaMnO 3, La 0 .9 K 0. 1 MnO 3 , La _{1- x} Na _x MnO ₃ (0 &lt; x < 1) _, Ba _{0 . 5} Sr _{0 . 5} TiO ₃ (BST), Na-BST, Mg-BST, Li-BST, SrTi _{1 - x} Li _x O ₃ (0 <x <1) _, SrTi _{0 . 9} Li _{0 . 1} O ₃ And Bi _1.5 Y _0.3 Sm _0.2 O ₃ .

The support layer of the present invention may have a thickness of 20 to 300 占 퐉 and a thickness of less than 20 占 퐉, but it is preferably 20 占 퐉 or more in consideration of easiness in the production process and mechanical strength of the oxygen ion conductive film produced, It is preferable that it does not exceed 300 mu m. The stabilizing layer maintains a thickness of 1 to 100 mu m. If the thickness is less than 1 탆, the support layer may easily peel off. If the thickness exceeds 100 탆, the oxygen ion diffusion rate may not be sufficient in the stabilization layer. The catalyst layer maintains a thickness of 1 to 5,000 탆. If the thickness is less than 1 mu m, the stabilized layer is easily peeled off. If the thickness exceeds 5000 mu m, the gas diffusion rate may not be sufficient in the catalyst layer.

While the present invention has been described in connection with what is presently considered to be the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, .

All technical terms used in the present invention are used in the sense that they are generally understood by those of ordinary skill in the relevant field of the present invention unless otherwise defined. The contents of all publications referred to herein are incorporated herein by reference.

1. Methane oxidation dimerization reactor
2. Oxygen separator
3. First space
4. The second space
5. Fluidized bed
10. Support layer
11. Stabilization layer
12. Catalyst layer
100. Porous support layer

Claims (11)

A methane oxidation dimerization method using a reactor divided into a first space and a second space with an oxygen separation membrane in which a support layer, a stabilization layer and a catalyst layer are sequentially stacked,
The method includes the steps of: supplying an oxygen-containing gas to the first space so as to contact with the surface of the support layer of the oxygen separation membrane;
Forming a fluidized bed in the second space, the fluidized bed including a methane-containing gas and a flow catalyst so as to contact the surface of the catalyst layer of the oxygen separation membrane; And
Thereby obtaining a hydrocarbon having 2 or more carbon atoms generated in the second space.
Methane oxidation dimerization method using an oxygen separation membrane.
The method according to claim 1,
The support layer may be a perovskite structure material such as lanthanum strontium cobaltite (LSC), lanthanum ferrite (LF), lanthanum strontium manganite (LSM), lanthanum strontium chromite Selected from the group consisting of Lanthanum strontium chromite (LSCr), calcium titanate ferrite (CTF, CaTiFeO3), barium strontium cobalt ferrite (BSCF) and strontium titanate ferrite Comprising at least one species,
The doped lanthanum ferrite is doped with Sr, Ca or Ba to A-site (La site) to the basic structure of LaFeO _3-x , and B-site (Fe- However,
Methane oxidation dimerization method using an oxygen separation membrane.
The method according to claim 1,
The stabilizing layer is a fluorosilicic oxide, or a mixture of a fluorosilicic oxide and a perovskite structure material,
The fluorosilicic oxide may be selected from the group consisting of yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScSZ), samarium-doped ceria (SDC) and gadolinium- doped ceria, GDC), and more preferably,
The perovskite structure material may be selected from the group consisting of lanthanum strontium cobaltite (LSC), lanthanum ferrite (LF), lanthanum strontium manganite (LSM), lanthanum strontium chromite (LSCr), calcium titanate ferrite (CTF, CaTiFeO3), barium strontium cobalt ferrite (BSCF), and strontium titanate ferrite (STF) / RTI &gt;
The doped lanthanum ferrite is one in which Sr, Ca, or Ba is doped in the A-site (La site) to the basic structure of LaFeO _{3 - x} , and B, However,
Methane oxidation dimerization method using an oxygen separation membrane.
The method according to claim 1,
The catalyst layer is _{La 2 O 3 / MgO, MnNa} 2 WO 4 / SiO 2, La 2 O 3 (SrO) / CaO, Li 2 O / MgO, LaMnO 3, La 0 .9 K 0. 1 MnO 3, La 1 _-x Na _x MnO ₃ (0 &lt; x < 1) _, Ba _{0 . 5} Sr _{0 . 5} TiO ₃ (BST), Na-BST, Mg-BST, Li-BST, SrTi _{1 - x} Li _x O ₃ (0 <x <1) _, SrTi _{0 . 9} Li _{0 . 1} O ₃ And Bi _1.5 Y _0.3 Sm _0.2 O ₃ .
Methane oxidation dimerization method using an oxygen separation membrane.
The method according to claim 1,
The flow catalyst is a particulate material having a size of 20 μm to 2000 μm and includes La ₂ O ₃ / MgO, MnNa ₂ WO ₄ / SiO ₂ , La ₂ O ₃ (SrO) / CaO, Li ₂ O / MgO, LaMnO ₃ , La _{0 .9 K 0. 1 MnO 3,} La 1 - x Na x MnO 3 (0 <x <1), Ba 0. ₅ Sr _{0 . 5} TiO ₃ (BST), Na-BST, Mg-BST, Li-BST, SrTi _{1 - x} Li _x O ₃ (0 <x <1) _, SrTi _{0 . 9} Li _{0 . 1} O ₃ And Bi _{1 . 5} Y _{0 . 3} Sm _{0 . 2} O ₃ &Lt; RTI ID = 0.0 &gt; and / or < / RTI &gt;
Methane oxidation dimerization method using an oxygen separation membrane.
The method according to claim 1,
The support, stabilization or catalyst layer may be porous,
Methane oxidation dimerization method using an oxygen separation membrane.
The method according to claim 1,
Wherein the stabilizing layer has a thickness of 1 to 100 mu m,
Methane oxidation dimerization method using an oxygen separation membrane.
The method according to claim 1,
Wherein the fluidized bed comprises a carbon dioxide adsorbent.
Methane oxidation dimerization method using an oxygen separation membrane.
The method according to claim 1,
Wherein the methane-containing gas comprises at least 3 vol%
Methane oxidation dimerization method using an oxygen separation membrane.
The method according to claim 1,
Wherein the hydrocarbon having 2 or more carbon atoms is ethane (C ₂ H ₆ ) or ethylene (C ₂ H ₄ )
Methane oxidation dimerization method using an oxygen separation membrane.
The method according to claim 1,
Wherein the reactor is maintained at a temperature of &lt; RTI ID = 0.0 &gt; 700 C &lt;
Methane oxidation dimerization method using an oxygen separation membrane.

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