JP2006298664A - Solid electrolyte membrane-type reactor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a supporting membrane-type membrane-type reactor having a new structure which provides gas species having high utilization value, such as synthesis gases, by a high efficiency chemical conversion reaction by employing a structure for eliminating the influence of the gas diffusion in a porous support. <P>SOLUTION: The solid electrolyte membrane-type reactor has reaction structure of a three layer structure comprising a porous support 1, a dense layer 2 comprising an oxygen ion-electron mixed conductive solid electrolyte formed on the support 1, and a catalyst layer 3 formed on the dense layer 2, wherein a gas 4 to be treated containing a hydrocarbon as main component is supplied onto the surface of the catalyst layer 3 and a high purity oxygen gas 5 is supplied onto the surface of the porous support 1 side, respectively. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is a membrane type in which a gas to be treated mainly composed of hydrocarbon is partially oxidized or reformed by using a mixed solid electrolyte of oxygen ions and electrons, and converted into a gas type having high utility value such as synthesis gas. Reactor related.

  Syngas, a mixed gas of hydrogen and carbon monoxide, is a raw material for clean fuels such as methanol, Fischer-Tropsch synthetic oil, and dimethyl ether, and uses a catalytic steam reforming method from saturated hydrocarbon gases such as natural gas and LPG. Have been put to practical use. In recent years, development related to an ATR (Auto Thermal Reforming) reaction in which a reforming reaction, which is a large endothermic reaction, is thermally compensated by heat generated by combustion has been actively performed. Along with ATR development, the development of membrane reactors using mixed solid ion electrolytes with oxygen ions and electrons has been energetically promoted, and the membrane reactors can significantly reduce the production cost of synthesis gas. Trial calculations have also been reported (for example, Non-Patent Document 1).

  The characteristics of membrane reactors using solid electrolytes are the selective gas permeation and the provision of a reaction field (solid electrolyte-catalyst-gas phase three-phase interface with a catalyst arranged on the permeate side). it is conceivable that. In the case of a membrane reactor that uses a mixed conductive solid electrolyte of oxygen ions and electrons, the hydrocarbon gas is partially oxidized or reformed in the reaction field centering on the three-phase interface, and it is highly useful as a synthesis gas. Chemically converted to gas species. The rate of the conversion reaction at this time is determined in relation to the oxygen supply rate (permeation rate) and the catalytic reaction rate on the surface. However, since the catalytic reaction proceeds very rapidly, the oxygen permeation rate (oxygen supply side) It can be said that the ionization rate on the surface and the diffusion rate of ions moving in the solid electrolyte) are rate-limiting.

  Conventional membrane reactors can be broadly divided into a type in which the solid electrolyte itself separates hydrocarbon gas and oxygen-containing gas (self-supporting membrane type), and a type in which a solid electrolyte thin film is formed on a porous substrate (support membrane). Type). For example, as described in Patent Document 1, when both are compared, it can be said that the support membrane type is an ideal structure.

  In other words, the former has a sufficient mechanical strength, so it is highly reliable in isolating two kinds of gases, but because it is thicker, the permeation rate of oxygen is significantly reduced. Is damaged. On the other hand, the latter is disadvantageous in terms of reliability and, at the same time, has the disadvantage of having a three-layer structure of porous support / solid electrolyte dense layer / catalyst layer, but the mechanical strength of the porous support Therefore, the solid electrolyte itself can be made thin. This reduction in the thickness of the solid electrolyte directly contributes to an increase in the oxygen permeation rate, and thus produces a great merit that the chemical conversion reaction of the membrane reactor can be dramatically improved.

JP 2002-97083 A Paul N. Dyer et al., "Ion transport membrane technology for oxygen separation and syngas production", Solid State Ionics, 134 (2000) p.21-33

  From the above, it is considered that in the future the type of the membrane reactor must be a support membrane type, and the present inventors have so far developed a support membrane type membrane reactor. However, many improvements have been made in the process of developing a support membrane type membrane reactor, and the above-mentioned reliability and the disadvantages of the three-layer structure have been overcome. It has been found that the film thickness does not increase as much as expected. As a result of intensive studies, it was found that this cause was caused by gas diffusion in the porous support.

  That is, when an attempt is made to operate a support membrane type membrane reactor by a conventional method, only oxygen in an oxygen-containing gas (for example, air) that has entered the porous support passes through the thin film of the solid electrolyte. The oxygen concentration temporarily decreases in the atmosphere. Although the temporary decrease in the oxygen concentration is compensated by the diffusion of oxygen from the supplied oxygen-containing gas, when the oxygen transmission rate exceeds the diffusion rate, the oxygen concentration is permanently reduced. The support membrane type is characterized in that the thickness of the solid electrolyte is reduced to increase the oxygen permeation rate, and the porous support requires a certain thickness to provide strength. Then, the relationship between the oxygen transmission rate and the diffusion rate is always increased. Therefore, a decrease in the oxygen concentration in the porous support is inevitable, and this directly leads to a decrease in the permeation rate, so that it is difficult to obtain the merit of thinning the solid electrolyte.

  The above explanation is based on the assumption that the oxygen concentration in the porous support is flown in the conventional support membrane type membrane reactor on the premise that the oxygen-containing gas flows on the porous support side and the hydrocarbon gas flows on the catalyst layer side. Although the problem regarding the reduction was pointed out, a membrane reactor in which the gas supply method is reversed by changing the structure of the support membrane type is also conceivable. That is, a membrane reactor in which the support membrane structure is a porous support / catalyst layer / solid electrolyte dense layer, and a hydrocarbon gas is supplied to the porous support side and an oxygen-containing gas is supplied to the dense layer side. However, even in this configuration, unless the gas diffusion is sufficiently fast between the product gas reacted in the porous support due to the coexistence of the catalyst and the hydrocarbon gas of the raw material, the rate of the chemical conversion reaction is significantly hindered.

  In view of the above problems, the present invention has a structure that eliminates the influence of gas diffusion in the porous support, and thus it is possible to obtain a highly useful gas species such as synthesis gas by a highly efficient chemical conversion reaction. The purpose of the present invention is to provide a support membrane type membrane reactor having a new structure.

That is, in order to achieve the above object, it is fundamental to use high-purity oxygen instead of oxygen-containing gas as the supply gas to the solid electrolyte thin film so as not to affect the gas diffusion in the porous body. The conclusion was reached that the solution was reached and the present invention was made. The gist of the present invention is as follows.
(1) Three layers comprising a porous support, a dense layer made of oxygen ion / electron mixed conductive solid electrolyte formed on the porous support, and a catalyst layer formed on the dense layer A membrane reactor using a reaction structure having a structure in which a gas to be treated mainly containing hydrocarbons is supplied to the surface of the catalyst layer and a high-purity oxygen gas is supplied to the surface of the porous support. A solid electrolyte membrane reactor.
(2) The solid electrolyte membrane reactor according to (1), wherein the high-purity oxygen gas has an oxygen concentration of 93% or more.
(3) The solid electrolyte membrane type according to (1) or (2), wherein the high-purity oxygen gas is oxygen separated and generated from an oxygen-containing gas using an oxygen ion / electron mixed conductive solid electrolyte Reactor.
(4) Any one of (1) to (3), wherein a function of separating and generating oxygen from an oxygen-containing gas using an oxygen ion / electron mixed conductive solid electrolyte is provided in the membrane reactor. A solid electrolyte membrane reactor according to claim 1.
(5) A porous support, a first dense layer made of an oxygen ion / electron mixed conductive solid electrolyte formed on the porous support, and the first dense layer sandwiching the porous support. A four-layer reaction structure comprising a second dense layer made of an oxygen ion / electron mixed conductive solid electrolyte formed at a position facing the layer, and a catalyst layer formed on the first dense layer The solid electrolyte membrane is characterized in that a gas to be treated mainly containing hydrocarbons is supplied to the catalyst layer side of the four-layer structure and an oxygen-containing gas is supplied to the second dense layer side. Type reactor.

  According to the present invention, since it is possible to suppress a decrease in oxygen concentration that has occurred in a porous support, which has been a problem in the past, there is no decrease in the permeation rate of oxygen, and a gas to be treated such as hydrocarbons can be efficiently processed. By chemical conversion, it is possible to easily obtain gas species having high utility value such as synthesis gas.

The present invention will be specifically described below.
FIG. 1 is an example of the present invention. FIG. 1 (a) shows a porous support 1, a dense layer 2 made of an oxygen ion / electron mixed conductive solid electrolyte formed thereon, and a catalyst layer 3 formed on the dense layer 2. A membrane type reactor using a three-layered reaction structure made of the above, a gas 4 to be treated mainly containing hydrocarbons on the surface of the catalyst layer 3 and a high purity on the surface of the porous support 1 side. An example of a solid electrolyte membrane reactor that supplies oxygen gas 5 respectively, FIG. 1B shows a schematic cross-sectional view of the reaction structure (reaction tube 6) having the three-layer structure.

  The membrane reactor according to the present invention also has an advantage that it can have a simple reactor structure as compared with a conventional membrane reactor. That is, as shown in FIG. 2, the conventional membrane reactor has a nozzle for constantly supplying the oxygen-containing gas 105 to the inside of the reaction tube 106 while supplying the gas 104 to be treated to the outside of the reactor 106. It was necessary to provide each reaction tube. On the other hand, in the membrane reactor according to the present invention, it is not necessary to consider the influence of the gas flow, so that a nozzle for constantly supplying the oxygen-containing gas is not necessary.

  However, as the high-purity oxygen 5 supplied here cannot use ideal pure oxygen containing no impurity gas as a practical problem, in FIG. It comes with a mechanism to prevent it. That is, a mechanism for replenishing the amount of oxygen reduced by permeation is provided at the same time using the oxygen purifier 7 in the circulation system while constantly circulating high-purity oxygen gas. Alternatively, the operation is performed by replenishing the oxygen content reduced by permeation without circulating the high-purity oxygen gas, and replacing it with a high-purity oxygen atmosphere when the impurity gas concentration becomes high due to the long-term operation ( (Flushing) may be performed.

  As described above, in the membrane reactor shown in FIG. 1 (a), oxygen in the porous support 1 permeates the solid electrolyte and moves to the catalyst layer 3 side. Since the gas pressure drop generated in the process is supplied from the outside, the pressure is kept constant as a steady state.

  If the purity of the oxygen gas to be used is extremely deteriorated, the gas (for example, nitrogen) whose purity has been reduced immediately stays on the porous support 1 before the oxygen purifier 7 in the circulation system works effectively. As a result, the rate of oxygen permeation decreases. Or the frequency of flushing operation increases and it becomes difficult to receive the merit of this invention. For this reason, the higher the purity of the oxygen gas used, the more effective, but as a result of various studies, it has been found that 93% or more is more desirable.

  The high-purity oxygen used here does not depart from the scope of the present invention by any method. That is, oxygen obtained by an oxygen production method using an adsorbent called PSA (Pressure Swing Adsorption) or an oxygen production method by distillation of air at a cryogenic temperature called a cryogenic separation method can be used.

  However, when comparing the efficiency of chemical conversion from the gas to be treated (mainly composed of hydrocarbon gas) 4 to the reformed gas 8 having a high utility value such as synthesis gas, the total efficiency including oxygen production, oxygen ions -It is more preferable to use oxygen obtained by a method of separating and producing oxygen from an oxygen-containing gas using an electron mixed conductive solid electrolyte. In the oxygen separation method using a solid electrolyte, for example, when compressed air is supplied as a raw material at a high temperature of about 700 ° C. to 900 ° C., high purity oxygen gas is separated and generated using a difference in oxygen partial pressure as a driving force. This is because heat and pressure energy can be recovered from the high-temperature and high-pressure air of the raw material having a reduced oxygen concentration, so that oxygen can be produced with less energy.

  Furthermore, since the membrane reactor operates in the same high temperature region, the overall efficiency is further improved by integrating the oxygen separation using the mixed electrolyte of oxygen ions and electrons with the membrane reactor. A specific example for realizing this is shown in FIG. Since oxygen separation uses the difference in oxygen partial pressure as a driving force, the oxygen-containing gas 15 such as air is usually compressed so as to have a partial pressure higher than the oxygen pressure on the separation side. However, since the gas to be treated (mainly hydrocarbon gas) 4 on the reactor 6 side has a very low oxygen partial pressure, oxygen permeation occurs even when the pressure on the high purity oxygen side is reduced. Therefore, it is not always necessary to compress the oxygen-containing gas 15. Moreover, when compressing, the pressure balance in a container can be taken by compressing so that a hydrocarbon gas area | region may also become the same pressure. The oxygen separation tube 16 shown in FIG. 3 may be a self-supporting membrane type, but needs to have sufficient oxygen permeability so that the supply of oxygen is not rate-determined. Is desirable.

  FIG. 4 shows another example of a high-purity oxygen-utilizing membrane reactor in which oxygen separation using an oxygen ion / electron mixed conductive solid electrolyte is incorporated in the membrane reactor. Also in this case, as in the case of FIG. 3, the oxygen-containing gas 15 and the gas to be processed (mainly hydrocarbon gas) 4 may or may not be compressed. The oxygen separation tube 16 may be a self-supporting membrane type, but a support membrane type is more desirable.

  Another example of the present invention is shown in FIG. FIG. 5A shows a porous support 1, a first dense layer 9 made of an oxygen ion / electron mixed conductive solid electrolyte formed thereon, and a first support sandwiching the porous support 1. Four layers comprising a second dense layer 10 made of an oxygen ion / electron mixed conductive solid electrolyte formed at a position facing the dense layer 9 and a catalyst layer 3 formed on the first dense layer 9 1 is a cross-sectional view of a structure reaction tube. A gas to be treated 4 containing hydrocarbon as a main component is supplied to the catalyst layer 3 side of the four-layer structure reaction tube, and an oxygen-containing gas 15 is supplied to the second dense layer 10 side. FIG. 5B illustrates an example of a solid electrolyte membrane reactor using the reaction tube having the four-layer structure.

  Only the oxygen is separated from the oxygen-containing gas 15 by the second dense layer 10 made of the mixed conductive electrolyte of oxygen ions and electrons, and supplied to the porous support 1. The high-purity oxygen in the porous material permeates the first dense layer 9 made of a mixed electrolyte of oxygen ions and electrons and reforms the gas to be treated (mainly hydrocarbon gas) 4 in the catalyst layer 3. Then, it is chemically converted to a reformed gas 8 having high utility value such as synthesis gas.

  This structure is a further evolution of the above-described embodiment in which the porous support 1 side is made of high-purity oxygen, and it can be said that high-purity oxygen production and a membrane reactor are incorporated into one structure. The structure itself is more complicated than the above-described three-layer structure, but conversely, the entire system is compact, which has the effect of reducing equipment costs.

There are no particular restrictions on the materials used to form the support membrane structure disclosed in the present invention. Already known materials are preferably used. As an example, as the first or second dense layer (2, 9, 10) made of mixed oxygen ion / electron conductive solid electrolyte, (La, Sr) (Co, Fe) _Ox- based perovskite oxide, porous Examples of the quality support 1 include the same material as the dense layer and oxides such as MgO, and examples of the catalyst layer 3 include Ni-based and Fe-based catalysts.

  Further, the thickness of each layer is not particularly limited. However, it is desirable that the dense layers (2, 9, 10) be as thin as possible within a range in which no through-holes are generated so that a gas other than oxygen does not permeate. For example, it is selected in the range of 1 μm to 100 μm. The porous support 1 is preferably thin if it has sufficient strength, and is selected, for example, in the range of 1 mm to 10 mm. The catalyst layer 3 is selected, for example, in the range of 0.1 μm to 10 μm so that the diffusion of hydrocarbon gas is not suppressed.

  The support membrane structure can be produced by combining already known methods. For example, the porous support 1 can be produced by mixing a pore material that is gasified and removed at a high temperature with a ceramic powder and then heat-treating it. The dense layers (2, 9, 10) can be formed by using a slurry in which ceramic powder is dispersed and applying and baking the porous support 1 or a method such as vapor deposition. The catalyst layer 3 can also be formed by slurrying a commercially available catalyst, applying and drying the dense layer (2, 9), and baking it.

  The reaction structure has been exemplified as a cylindrical tube shape so far, but as long as it conforms to the concept of the present invention to exclude the influence of gas diffusion in the porous body, the shape is not limited, for example, Other shapes such as a flat plate type can also be applied.

  Hereinafter, the present invention will be described with reference to examples and comparative examples.

Example 1
La ₂ O ₃ , SrO, Co ₃ O ₄ , Fe ₂ O ₃ powder is made to have a composition of La _0.3 Sr _0.7 Co _0.5 Fe _0.5 O _x (x is a value determined to satisfy the charge neutrality condition). The mixture was pulverized and calcined at 900 ° C. in air for 4 hours. The obtained calcined powder is pulverized, adjusted for particle size, mixed with PVA (polyvinyl alcohol) powder as a pore material, uniaxial press-molded, fired at 1100 ° C., and disk-shaped porous with a diameter of 20 mm and a thickness of 2 mm A support was obtained.

  Separately, a slurry for forming a dense layer was prepared using the calcined pulverized powder. In the preparation method, 1900 g of calcined powder, 3500 ml of solvent (ethanol), and 290 g of binder (polyvinyl butyral resin) were mixed in a rolling mill.

  The slurry was applied to the surface on one side of the porous support and baked at 1250 ° C. for 5 hours to form a dense layer having a thickness of 50 μm.

  The catalyst layer was formed by dispersing a commercially available Ru-based catalyst (manufactured by Toyo Sea Cai Co., Ltd.) in an organic solvent, applying the slurry to a dense layer, drying it, and baking it at 850 ° C. The thickness of the catalyst layer was about 0.1 mm.

  The sample thus formed was subjected to methane gas partial oxidation reaction measurement using a simple evaluation apparatus shown in FIG. In the simple evaluation apparatus, two spaces are provided with a reactor including a porous support 21, a solid electrolyte dense layer 22 and a catalyst layer 23 interposed therebetween, and high purity oxygen or air 24 is provided on the porous support 21 side. Methane 25 was supplied to the catalyst layer 23 side. Further, the outer peripheral portion of the reactor was sealed with a sealing material 26. Furthermore, an electric furnace 27 was arranged on the side of the reactor. The gas recovered from the space on the catalyst layer 23 side is analyzed by gas chromatography (gas chromatography).

The measurement was conducted at a temperature of 850 ° C., supplying methane gas to the surface of the catalyst layer 23 side at a supply rate of 1 × 10 ⁻⁶ m ³ (STP) / sec, and high-purity oxygen (99.99995% purity, (Supplied from a commercially available cylinder) was supplied at a supply rate of 1 × 10 ⁻⁶ m ³ (STP) / sec. The pressure was normal on both sides. As a result of analyzing the gas recovered from the methane gas side with a gas chromatograph, a stoichiometric ratio of partial oxidation reaction of 90% conversion of methane and H ₂ / CO = 2 was obtained. Further, based on the conversion rate of methane, the oxygen permeation rate was estimated in consideration of the effective permeation area of oxygen (1.1 × 10 ⁻⁴ m ² ), and 4 × 10 ⁻³ m ³ (STP) · It was found to be a high value of sec ⁻¹ · m ⁻² .

(Comparative Example 1)
Using the same sample as in Example 1, the partial oxidation reaction measurement of methane gas was performed using the simple evaluation apparatus shown in FIG. Measurement is performed at a temperature of 850 ° C., methane gas is supplied to the surface of the catalyst layer 23 at a supply rate of 1 × 10 ⁻⁶ m ³ (STP) / sec, and air is supplied to the surface of the porous support 21 at a rate of 5 × 10 ⁻⁶ m. ³ (STP) / sec. The pressure was normal on both sides. As a result of analyzing the gas collected from the methane gas side with a gas chromatograph, the conversion rate of methane was 5%, which was 1/18 of the conversion rate of Example 1. This corresponds to an extremely low value of 2 × 10 ⁻⁴ m ³ · sec ⁻¹ · m ⁻² as the oxygen transmission rate.

(Example 2)
In the same procedure as in Example 1, a three-layered disk sample of porous support 21 / dense layer 22 / catalyst layer 23 and a two-layered disk sample of porous support 31 / dense layer 32 were prepared. The thickness of each layer was the same as in Example 1. The three-layer disc sample was set on the upper side of the simplified evaluation apparatus shown in FIG. 7 so that the catalyst layer 23 was on the upper side, and the two-layer disc sample was set on the lower side so that the dense layer 32 was on the lower side.

At a temperature of 850 ° C., methane gas is supplied from the top at a supply rate of 1 × 10 ⁻⁶ m ³ (STP) / sec, and air is supplied from the bottom at a supply rate of 5 × 10 ⁻⁶ m ³ (STP) / sec. The partial oxidation reaction of methane gas was measured. The pressure was normal on both sides. As a result of analyzing the gas recovered from the methane gas side with a gas chromatograph, a stoichiometric ratio of partial oxidation reaction of 70% conversion of methane and H ₂ / CO = 2 was obtained. In addition, based on the conversion rate of methane, the oxygen permeation rate was estimated in consideration of the effective permeation area of oxygen (1.1 × 10 ⁻⁴ m ² ) and found to be 3.2 × 10 ⁻³ m ³ (STP ) · Sec ⁻¹ · m ⁻² It was found to be a high value.

(Example 3)
A four-layered disk sample of dense layer / porous support / dense layer / catalyst layer was prepared in the same procedure as in Example 1. The thickness of each layer was the same as in Example 1. A simple evaluation apparatus shown in FIG. 6 was used to set a four-layer disk sample so that the catalyst layer was on top.

At a temperature of 850 ° C., methane gas is supplied from the top at a supply rate of 1 × 10 ⁻⁶ m ³ (STP) / sec, and air is supplied from the bottom at a supply rate of 5 × 10 ⁻⁶ m ³ (STP) / sec. Measurement of partial oxidation reaction of methane gas was performed. The pressure was normal on both sides. As a result of analyzing the gas recovered from the methane gas side with a gas chromatograph, a stoichiometric ratio of partial oxidation reaction of 78% conversion of methane and H ₂ / CO = 2 was obtained. Further, based on the conversion rate of methane, the oxygen permeation rate was estimated in consideration of the effective permeation area of oxygen (1.1 × 10 ⁻⁴ m ² ), and found to be 3.5 × 10 ⁻³ m ³ (STP ) · Sec ⁻¹ · m ⁻² It was found to be a high value.

Example 4
A partial oxidation reaction measurement of methane was performed using an experimental apparatus in which oxygen separation using a mixed solid electrolyte of oxygen ions and electrons shown in FIG. 8 was incorporated in a membrane reactor. The oxygen separation tube 16 was produced according to the following procedure. First, a mixture of the same calcined powder and PVA powder as in Example 1 is filled into a rubber mold so as to have a cylindrical tube shape, CIP (hydrostatic pressure press) molding, and then fired at 1100 ° C. to form a porous support. It was. This was dipped in a container filled with a slurry for forming a dense layer with the tamman part down, dried, and then fired at 1250 ° C. to form a dense layer only on the outer surface. Thus, an oxygen separation tube 16 having an outer diameter of about 20 mm, an inner diameter of about 15 mm, a length of about 300 mm, and a dense layer thickness of about 50 μm was obtained. A reaction tube for partial oxidation of methane was prepared in the same procedure, and then a slurry in which a commercially available Ru-based catalyst was dispersed was applied onto the dense layer and baked to form a catalyst layer having a thickness of about 50 μm.

At a temperature of 850 ° C., air 24 is supplied to the oxygen separation unit at a supply rate of 5 × 10 ⁻⁴ m ³ (STP) / sec, and methane gas is supplied to the partial oxidation unit at a supply rate of 1 × 10 ⁻⁴ m ³ (STP) / sec. Each was supplied to measure the partial oxidation reaction of methane gas. In both cases, the pressure was normal pressure. The gas recovered from the partial oxidation side was analyzed by gas chromatography. As a result, the stoichiometric ratio of partial oxidation reaction was obtained, with a methane conversion of 69% and H ₂ / CO = 2. In addition, based on the conversion rate of methane, the oxygen permeation rate was estimated in consideration of the effective oxygen permeation area (1.8 × 10 ⁻² m ² ), and 1.9 × 10 ⁻³ m ³ (STP) ) · Sec ⁻¹ · m ⁻² It was found to be a high value.

(A) is a figure which shows the example of the high purity oxygen utilization solid electrolyte membrane type | mold reactor which supplied the high purity oxygen gas to the porous support body side surface, (b) is a cross section of the three-layer structure reaction tube of (a) It is a schematic diagram which shows. It is a figure which shows the typical example of the conventional membrane-type reactor. It is a figure which shows the example of the high purity oxygen utilization solid electrolyte membrane type reactor which incorporated oxygen separation using the oxygen ion and electron mixed conductive solid electrolyte into the membrane type reactor. It is a figure which shows another example of the high purity oxygen utilization solid electrolyte membrane type reactor which incorporated oxygen separation using oxygen ion and electronic mixed conductive solid electrolyte in the membrane type reactor. (A) is a schematic diagram showing a cross section of a membrane reaction tube having a four-layer structure, and (b) is a diagram showing an example of a solid electrolyte membrane reactor using a membrane reaction tube having a four-layer structure. It is a figure which shows the simple evaluation apparatus used for the methane gas partial oxidation reaction measurement. It is a figure which shows another simple evaluation apparatus used for the methane gas partial oxidation reaction measurement. It is a figure which shows the experimental apparatus for methane gas partial oxidation reaction measurement which incorporated oxygen separation using oxygen ion and electronic mixed conductive solid electrolyte in the membrane reactor.

Explanation of symbols

1: porous support 2, 9, 10: dense layer 3: catalyst layer 4: gas to be treated 5: high purity oxygen 6, 17: reaction tube 7: oxygen purifier 8: reformed gas 15: oxygen-containing gas 16 : Oxygen separator tube 21, 31: Porous support 22, 32: Solid electrolyte dense layer 23: Catalyst layer 24: High purity oxygen or air 25: Methane 26: Sealing material 27: Electric furnace 28: Air

Claims (5)

A porous support;
A dense layer made of an oxygen ion / electron mixed conductive solid electrolyte formed on the porous support;
A catalyst layer formed on the dense layer;
A membrane reactor using a three-layer reaction structure comprising:
A solid electrolyte membrane reactor, wherein a gas to be treated mainly comprising hydrocarbon is supplied to the surface of the catalyst layer, and a high-purity oxygen gas is supplied to the surface of the porous support.   The solid electrolyte membrane reactor according to claim 1, wherein the high-purity oxygen gas has an oxygen concentration of 93% or more.   3. The solid electrolyte membrane reactor according to claim 1, wherein the high-purity oxygen gas is oxygen separated and generated from an oxygen-containing gas using an oxygen ion / electron mixed conductive solid electrolyte.   4. The function according to claim 1, wherein a function of separating and generating oxygen from an oxygen-containing gas using an oxygen ion / electron mixed conductive solid electrolyte is provided in the membrane reactor. 5. Solid electrolyte membrane reactor. A porous support;
A first dense layer made of an oxygen ion / electron mixed conductive solid electrolyte formed on the porous support;
A second dense layer composed of an oxygen ion / electron mixed conductive solid electrolyte formed at a position facing the first dense layer with the porous support interposed therebetween;
A catalyst layer formed on the first dense layer;
A four-layered reaction structure comprising:
A solid electrolyte membrane reactor characterized in that a gas to be treated mainly containing hydrocarbons is supplied to the catalyst layer side of the four-layer structure and an oxygen-containing gas is supplied to the second dense layer side.

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