JP4127685B2 - Carbon monoxide selective methanator, carbon monoxide shift reactor and fuel cell system - Google Patents

Description

  The present invention relates to a CO selective methanator that selectively removes CO using a carbon monoxide (CO) selective methanation catalyst, a fuel cell system including the CO selective methanator, and a reforming reactor. A carbon monoxide shift reactor that is provided in the subsequent stage to selectively remove carbon monoxide by reacting carbon monoxide with water vapor and producing hydrogen and carbon dioxide, and this carbon monoxide shift reactor The present invention relates to a provided fuel cell system.

  A reformer that reforms light hydrocarbons such as natural gas and naphtha, alcohols such as methanol, or dimethyl ether in the presence of a reforming catalyst to produce reformed gas containing hydrogen. A fuel cell system has been developed that combines a fuel electrode to which a quality gas is supplied and an electromotive part having an oxidant electrode to which air is supplied. Since such a fuel cell system has a higher output voltage and higher efficiency than a direct methanol fuel cell using a liquid fuel such as methanol, high performance is expected.

In the reformed gas obtained by reforming the above fuel, carbon dioxide (CO ₂ ) is generated as a by-product in addition to hydrogen, and in addition, carbon monoxide (CO) is about 1% to 2%. About% is included. This CO deteriorates the anode catalyst of the fuel cell and causes a decrease in power generation performance. Therefore, it is desirable to reduce the CO concentration in the reformed gas to several tens of ppm or less. Therefore, a fuel cell system having a CO converter (CO shifter) and a CO remover downstream of the reformer has been developed.

In the fuel cell system, the CO converter (CO shifter) uses a so-called CO water gas shift reaction represented by the reaction formula [CO + H ₂ O → CO ₂ + H ₂ ] to change the CO concentration in the reformed gas. Reduction is being done. The CO converter can only reduce the CO concentration to about 1%, but cannot completely remove it. Therefore, after removing CO using a selective oxidation reaction represented by the reaction formula [CO + 1 / 2O ₂ → CO ₂ ] in a CO remover disposed further downstream of the CO converter (CO shifter), Supplying a quality gas to a fuel cell is performed.

  However, when CO is selectively oxidized, a pump for supplying oxygen (air) necessary for the oxidation reaction is required, and there is a problem that the system becomes complicated and large.

Thus, methods for removing CO by a methanation reaction represented by a reaction formula [CO + 3H ₂ → CH ₄ + H ₂ O] have been studied, for example, as shown in Patent Documents 1 to 4.

These Patent Documents 1 to 4 disclose a method of removing CO by using a catalyst in which Ru (ruthenium) is supported on an inorganic oxide carrier such as alumina and contacting with hydrogen gas containing CO. . However, in the catalysts described in Patent Documents 1 to 4, when carbon dioxide is contained in hydrogen gas, a methanation reaction of carbon dioxide [CO ₂ + 4H ₂ → CH ₄ + 2H ₂ O], which is a side reaction, is also performed simultaneously. Occur. Methanation of carbon dioxide is not preferable because it consumes hydrogen in the reformed gas. Therefore, development of a catalyst that selectively methanates CO is desired.
Japanese Patent Laid-Open No. 3-93602 JP-A-11-86892 JP 2002-66321 A JP 2002-68707 A

  An object of the present invention is to provide a carbon monoxide selective methanator, a carbon monoxide shift reactor, and a fuel cell system, which have high selectivity for removing carbon monoxide from a hydrogen-containing gas.

A carbon monoxide selective methanator according to the present invention is a carbon monoxide selective methanator comprising a reactor and a carbon monoxide selective methanation catalyst charged in the reactor,
The carbon monoxide selective methanation catalyst includes a base material of a composite oxide containing a nonreducible metal oxide composed of magnesium oxide, a reducible metal oxide composed of nickel oxide, and an additive metal element, and the easy reductivity Active metal particles deposited on at least the surface of the base material by reduction of the conductive metal oxide ,
The additive metal element, Al, at least one kind of Sc, Cr, B, Ga, In, Lu, is selected the group or al consisting Nb and Si, the additive metal of the carbon monoxide selective methanation catalyst Element content is 0.01 mol% or more and 0.25 mol% or less by element amount.

The carbon monoxide shift reactor according to the present invention is a carbon monoxide shift reactor comprising a reactor and a carbon monoxide shift catalyst charged in the reactor,
The carbon monoxide shift catalyst includes a base material of a composite oxide containing a nonreducible metal oxide composed of magnesium oxide, a reducible metal oxide composed of cobalt oxide, and an additive metal element, and the reducible metal Comprising active metal particles deposited on at least the surface of the substrate by reduction of the oxide ,
The additive metal element, Al, Sc, Cr, B , Ga, In, at least one kind of Lu, is selected the group or al consisting Nb and Si, the additive metal element of the carbon monoxide shift catalyst Content is 0.01 mol% or more and 0.25 mol% or less by element amount, It is characterized by the above-mentioned.

A fuel cell system according to the present invention includes a reformer that reforms a fuel to obtain a reformed gas containing hydrogen;
A carbon monoxide shift reactor disposed downstream of the reformer;
A carbon monoxide selective methanator disposed downstream of the carbon monoxide shift reactor;
A fuel electrode that is disposed downstream of the carbon monoxide selective methanator and is supplied with a reformed gas from the carbon monoxide selective methanator, and an electromotive unit that includes an oxidant electrode;
The carbon monoxide selective methanation catalyst contained in the carbon monoxide selective methanator is a composite containing a hardly reducible metal oxide composed of magnesium oxide, a readily reducible metal oxide composed of nickel oxide, and an additive metal element. Comprising an oxide base material and active metal particles deposited on at least the surface of the base material by reduction of the easily reducible metal oxide ;
The additive metal element, Al, at least one kind of Sc, Cr, B, Ga, In, Lu, is selected the group or al consisting Nb and Si, the additive metal of the carbon monoxide selective methanation catalyst Element content is 0.01 mol% or more and 0.25 mol% or less by element amount.

A fuel cell system according to the present invention includes a reformer that reforms a fuel to obtain a reformed gas containing hydrogen;
A carbon monoxide shift reactor disposed downstream of the reformer;
A carbon monoxide remover disposed downstream of the carbon monoxide shift reactor;
A fuel electrode disposed downstream of the carbon monoxide remover, to which a reformed gas is supplied from the carbon monoxide remover, and an electromotive unit comprising an oxidant electrode;
The carbon monoxide shift catalyst included in the carbon monoxide shift reactor is a complex oxide containing a hardly reducible metal oxide composed of magnesium oxide, a reducible metal oxide composed of cobalt oxide, and an additive metal element. Comprising a base material and active metal particles deposited on at least the surface of the base material by reduction of the easily reducible metal oxide ,
The additive metal element, Al, Sc, Cr, B , Ga, In, at least one kind of Lu, is selected the group or al consisting Nb and Si, the additive metal element of the carbon monoxide shift catalyst Content is 0.01 mol% or more and 0.25 mol% or less by element amount, It is characterized by the above-mentioned.

  According to the present invention, it is possible to provide a carbon monoxide selective methanator, a carbon monoxide shift reactor, and a fuel cell system having high selectivity for carbon monoxide removal reaction in the presence of hydrogen gas.

  The inventors of the present application have heretofore made active metal particles precipitate on the surface and inside of a composite oxide substrate using a composite oxide of a hardly-reducible metal oxide and an easily-reducible metal oxide. Successful. It was also found that the specific surface area, particle size, and interparticle distance of the active metal particles can be controlled by containing a certain amount of a specific additive metal in the composite oxide. In general, when considering catalyst design, it is known that the specific surface area of active metal, particle size, interparticle distance, and the type of base material on which the active metal is supported greatly affect the catalytic reaction characteristics. There is a possibility that the metal particle-dispersed composite oxide can be used as a catalyst capable of selectively removing carbon monoxide by optimizing materials and synthesis conditions.

  The inventors of the present application initially examined the use of a metal particle-dispersed composite oxide in which easily reducible metal particles were deposited on the surface of the composite oxide as a methanol steam reforming catalyst for hydrogen production. For example, a metal particle-dispersed (supported) composite oxide formed into a honeycomb shape and subjected to reduction treatment to deposit nickel particles on the surface can be used as a reforming catalyst for hydrocarbon fuel. This metal particle-dispersed composite oxide is also very stable thermally because the metal particles are in close contact with the composite oxide substrate, and it is understood that it does not deteriorate even when used as a catalyst for a long time. It was. Furthermore, even when the metal particle dispersed composite oxide is used for the steam reforming reaction of ethanol or the carbon dioxide reforming reaction of methane, it has a high hydrogen generating ability and a wide range as in the case of the steam reforming reaction of methanol. It has been found that it is possible to cope with a catalytic reaction.

  The inventors of the present application actually produced such a metal particle-dispersed composite oxide and evaluated the characteristics as a methanol steam reforming catalyst. As a result, a metal particle-dispersed composite oxide containing a certain amount of a specific additive metal was obtained. I noticed that the amount of by-product methane was particularly high. In order to investigate this in more detail, as a result of examining the selectivity based on carbon, it became clear that the selectivity of methane is about 38% and the selectivity of carbon monoxide is as low as about 1%. It was. Usually, from the viewpoint of methanol reforming, it is preferable that the carbon monoxide concentration in the reformed gas is low, that is, the selectivity of carbon monoxide is low, but if the selectivity of methane is high, the reforming This is not preferable because it consumes the hydrogen obtained. In view of this, the inventors of the present application have tried to use such a metal particle-dispersed composite oxide as a CO removal catalyst in the reformed gas by methanation by utilizing this characteristic. As a result, surprisingly, even when a reformed gas containing about 20% of carbon dioxide is used as a reaction gas, carbon dioxide is not methanated, only carbon monoxide is selectively methanated, and CO The present inventors have found that it functions as a selective methanation catalyst, and have reached the present invention.

  Furthermore, the present inventors made a carbon monoxide water gas shift reaction using a reformed gas containing ten to several percent of carbon monoxide as a reaction gas for other types of metal particle-dispersed composite oxides. As a result, carbon monoxide methanation hardly occurred, and carbon monoxide was selectively carbonized to provide a knowledge of functioning as a carbon monoxide shift catalyst.

  The catalyst used in the carbon monoxide selective methanator and the carbon monoxide shift reactor will be described.

  The carbon monoxide (CO) selective methanation catalyst and the carbon monoxide (CO) shift catalyst are each a composite oxide substrate containing a hardly-reducible metal oxide, a readily-reducible metal oxide, and an additive metal element. (Carrier) and active metal particles deposited on at least the surface of the substrate. The active metal particles may be precipitated only on the surface of the base material, or may be precipitated not only on the surface but also in the internal crystal grain boundaries and crystal grains.

  An easily reducible oxide refers to a metal oxide that can be reduced to a metal in a hydrogen atmosphere at room temperature to 1500 ° C. or under plasma conditions, or in an inert atmosphere using a carbon jig. When used as a CO selective methanation catalyst, specifically, nickel oxide, cobalt oxide, and iron oxide are preferable, and nickel oxide is most preferable. On the other hand, when used as a CO shift catalyst, cobalt oxide is most preferred. Such easily reducible oxides may be used alone or in combination of two or more.

On the other hand, a non-reducible oxide refers to an oxide that is not reduced to a metal in a reducing atmosphere such as hydrogen at room temperature to 1500 ° C. Specific examples include oxides such as Al, Mg, Si, Zr, Ti, Hf, and Ce. The hardly reducible metal oxides may be used alone or in combination of two or more. When used as a CO selective methanation catalyst, among these difficult-to-reduced metal oxides, magnesium oxide (eg MgO), cerium oxide (eg CeO ₂ ) and silicon dioxide (SiO ₂ ) form a stable solid solution. Therefore, magnesium oxide is most preferable. On the other hand, when used as a CO shift catalyst, at least one metal oxide selected from magnesium oxide, cerium oxide, zirconium oxide and aluminum oxide is preferable. Among these hardly-reducible metal oxides, magnesium oxide is most preferable in that it forms a stable solid solution.

The composite oxide is preferably formed mainly from a solid solution of the above-described easily reducible metal oxide and hardly reducible metal oxide. As the solid solution, for example, a complete solid solution of oxides such as NiO—MgO, CoO—MgO, FeO—MgO, and NiO—CoO—MgO is preferable. Alternatively, a system in which the solid solubility limit of the easily reducible metal oxide with respect to the hardly reducible metal oxide is 1 atomic% or more at the hydrogen reduction temperature, such as ZrO ₂ —NiO, may be used. When used as a CO selective methanation catalyst, nickel oxide-magnesium oxide (NiO-MgO) is preferred. On the other hand, when used as a CO shift catalyst, cobalt oxide-magnesium oxide is most preferable because it forms a solid solution. However, cobalt oxide is not limited to CoO.

  The additive metal element is at least one selected from the group consisting of Al, Sc, Cr, B, Fe, Ga, In, Lu, Nb, and Si, and is different from the metal of the hardly-reducible metal oxide It is. For example, when the hardly-reducible metal oxide is aluminum oxide, at least one selected from the group consisting of Sc, Cr, B, Fe, Ga, In, Lu, Nb, and Si is used as the additive metal element. The As long as the additive metal is contained in the composite oxide, the form of the additive metal is not particularly limited. For example, the additive metal may be dissolved in the composite oxide or may exist at the crystal grain boundary of the composite oxide. . The content of the additive metal element in the catalyst is desirably 0.01 mol% or more and 0.25 mol% or less in terms of element amount. A more preferable range is 0.1 mol% or more and 0.2 mol% or less.

  By containing the above-mentioned additive metal in the above-mentioned amount, significant metal particle precipitation can be caused during the reduction. Such a metal is preferably added in the form of an oxide, but is not limited thereto, and may be added in any form such as a hydroxide or a carbonate compound. When the additive metal is used as a CO selective methanation catalyst, Cr and Sc are preferable. On the other hand, when used as a CO shift catalyst, at least one selected from the group consisting of Al, Sc and Cr is desirable. When aluminum oxide is used as the hardly-reducible metal oxide, Sc or Cr is used as the additive metal.

  The metal particle-dispersed (supported) composite oxide used in the present invention can be produced, for example, by preparing a mixed powder, sintering it, and subjecting it to a reduction treatment.

  In preparing the mixed powder, first, a non-reducing oxide, a compound containing an easily reducing oxide, and an additive metal are uniformly mixed by a ball mill or the like. At this time, it is desirable to use a material made of nylon or the like for the balls and pots so that no mixing occurs. Although it may mix by any method of a wet type and a dry type, wet mixing is preferable in order to perform more uniform mixing, and binders, such as PVA (polyvinyl alcohol), may be added.

  For example, it is preferable to mix magnesium oxide powder, which is a hardly-reducible oxide, and nickel oxide powder or cobalt-oxide powder, which is an easily-reducible oxide, at a molar ratio of 2: 1. By mixing the hardly-reducible oxide and the easily-reducible oxide at a ratio of 2: 1, the amount of deposited metal by hydrogen reduction can be suppressed to an appropriate amount, and coalescence and particle growth between metal particles can be suppressed. .

On the other hand, the aforementioned additive metal element is preferably added in the form of an oxide such as Sc ₂ O ₃ . The amount of added metal element component such as Sc is defined as 0.01 to 0.25 mol% with respect to the entire mixed powder. When the amount of added metal is less than 0.01 mol%, a sufficient amount of easily reducible metal particles cannot be deposited on the surface of the composite oxide. On the other hand, if it exceeds 0.25 mol%, the added compound itself remains at the grain boundary of the solid solution, impairing the sinterability of the composite oxide, and causing a decrease in strength. Further, precipitation due to reduction becomes excessive, and metal particles aggregate and coalesce, resulting in a decrease in catalyst performance.

  The optimum amount to be added varies depending on the metal particles to be precipitated, the reduction conditions, and the like, but if the reduction temperature is too high or the reduction time is too long, the precipitated particles grow large. In this case, since the catalytic activity is lowered, it is desirable to perform the reduction treatment at an appropriate temperature and time.

  The obtained mixed powder is molded into a predetermined shape to obtain a molded body. For example, it can be formed into a powder form, a granule form, a porous form such as a honeycomb form or a foam form, or a sheet form with a groove serving as a fluid flow path. It is possible to properly use the shape of the molded body depending on the application. That is, when a simple and efficient catalytic reaction is desired, a powdery or granular shape is used. On the other hand, when it is desired to reduce the pressure loss with respect to the flow of the reformed gas and cause the catalytic reaction to occur with high efficiency, it is preferable to use a porous body shape or a sheet shape with engraved flow paths.

  A compact having a predetermined shape is sintered in the range of 1000 ° C. to 1400 ° C. to produce a composite oxide sintered body. The obtained composite oxide sintered body is reduced in a reducing atmosphere such as hydrogen gas to deposit metal particles on the composite oxide surface and the grain boundary interface. For example, in the case of a nickel oxide-magnesium oxide system, a part of the composite oxide sintered body, nickel particles that are easily reduced, are reduced and deposited on the surface of the composite oxide. In the case of the cobalt oxide-magnesium oxide system, a part of the composite oxide sintered body, easily reducible cobalt particles are reduced and deposited on the surface of the composite oxide. These nickel particles and cobalt particles are excellent in dispersibility, and have high adhesion to the base material because they are formed by precipitation from the inside of the composite oxide as the base material. The metal particle-dispersed composite oxide in which nickel particles are deposited on the surface through reduction treatment can be suitably used as a CO selective methanation catalyst. On the other hand, a metal particle-dispersed composite oxide in which cobalt particles are deposited on the surface by performing a reduction treatment can be suitably used as a CO shift catalyst.

  The temperature and time of the reduction treatment can be appropriately selected according to the material used. For example, in the case of a nickel oxide-magnesium oxide system, it is preferable to perform a reduction treatment for about 10 minutes at a temperature of 500 to 1000 ° C. On the other hand, in the case of the cobalt oxide-magnesium oxide system, it is preferable to perform a reduction treatment for about 10 minutes at a temperature of 600 to 1000 ° C. If the reduction temperature is too high, the growth of metal particles may proceed more than necessary, causing aggregation and destruction at the grain boundary, or reducing the catalyst performance. On the other hand, if the reduction temperature is too low, the heat treatment takes a long time, which is not industrially preferable.

  Through the above steps, the CO selective methanation catalyst and CO shift catalyst used in the present invention are obtained.

Each of the CO selective methanation catalyst and the CO shift catalyst preferably has an active metal specific surface area of 0.5 m ² / g or more. Since such a catalyst has a large amount of active metal deposited on its surface, a high catalytic activity can be obtained with a small amount. Furthermore, when the reduction weight loss of the catalyst having such an active metal specific surface area is 1% or more, a large amount of active metal particles having a small particle diameter can be precipitated, so that the catalyst activity can be further increased. .

  The reactor filled with each of the CO selective methanation catalyst and the CO shift catalyst is preferably formed from a metal such as aluminum or stainless steel from the viewpoint of heat resistance.

  Next, an example of the configuration of a fuel cell system according to an embodiment of the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a schematic configuration diagram showing an embodiment of a fuel cell system according to the present invention. The fuel cell system 1 includes a fuel tank 2, a vaporizer 3, a reformer 4, a CO shift reactor 5, a CO selective methanator 6, and an electromotive unit (membrane electrode assembly) 7. The fuel tank 2 is composed of, for example, a cartridge type container. A vaporizer 3 is connected to the fuel tank 2 via a flow path 8. The liquid feed pump 9 is interposed in the flow path 8. The fuel in the fuel tank 2 is supplied to the vaporizer 3 through the flow path 8. The supplied fuel is heated by the vaporizer 3 to become vaporized fuel. A reformer 4 is connected to the vaporizer 3 via a flow path 10. The reformer 4 is supplied with vaporized fuel from the vaporizer 3 via the flow path 10. The reformer 4 reforms vaporized fuel (fuel gas) to generate a reformed gas containing hydrogen, and a reforming catalyst is carried inside the reformer 4.

A CO shift reactor 5 is connected to the reformer 4 via a flow path 11. The reformed gas generated in the reformer 4 is supplied to the CO shift reactor 5 via the flow path 11. A CO shift catalyst is supported inside the CO shift reactor 5. In the CO shift reactor 5, carbon monoxide contained in the reformed gas is removed by a carbon monoxide water gas shift reaction using a CO shift catalyst: [CO + H ₂ O → CO ₂ + H ₂ ]. The CO concentration is reduced.

A CO selective methanator 6 is connected to the CO shift reactor 5 via a flow path 12. A CO selective methanation catalyst is supported inside the CO selective methanator 6. A reformed gas with a reduced CO concentration is supplied to the CO selective methanator 6 from the CO shift reactor 5 via the flow path 12. In the CO selective methanator 6, CO remaining in the reformed gas is removed using CO methanation reaction [CO + 3H ₂ → CH ₄ + H ₂ O] using a selective methanation (methanation) catalyst.

The number of electromotive parts (membrane electrode assemblies; MEAs) 7 used in the fuel cell system can be one or more. In the case of FIG. 1, a stack in which a plurality of electromotive units 7 are stacked is used. Each electromotive unit 7 includes a fuel electrode 13, an oxidant electrode 14, and an electrolyte membrane 15 having proton conductivity disposed between the fuel electrode 13 and the oxidant electrode 14. A CO selective methanator 6 is connected to the fuel electrode 13 via a flow path 16. The reformed gas that has undergone the CO methanation treatment is supplied from the CO selective methanator 6 to the fuel electrode 13 via the flow path 16. Further, a compression pump 18 is connected to the oxidant electrode 14 via a flow path 17. The compressed air is supplied from the compression pump 18 to the oxidant electrode 14 via the flow path 17. Hydrogen in the reformed gas supplied to the fuel electrode 13 and oxygen in the air supplied to the oxidant electrode 14 react as [H ₂ → 2H ⁺ + 2e ⁻ ] at the fuel electrode 13 while oxidizing. Reaction occurs at the agent electrode 14 as [1 / 2O ₂ + 2H ⁺ + 2e ⁻ → H ₂ O] to generate water and to generate power.

Along with the progress of power generation, the surplus gas in the reaction [H ₂ → 2H ⁺ + 2e ⁻ ] at the fuel electrode 13 is discharged from the fuel electrode 13 as exhaust gas, and unreacted hydrogen is contained in this exhaust gas. It is included. Similarly, as the power generation proceeds, the surplus gas in the reaction [1 / 2O ₂ + 2H ⁺ + 2e ⁻ → H ₂ O] at the oxidant electrode 14 is discharged as an exhaust gas from the oxidant electrode 14. This exhaust gas contains unreacted oxygen.

  In addition, a heater 20 for the reformer 4 may be installed in the fuel electrode 13 through the flow path 19. Exhaust gas containing unreacted hydrogen discharged from the fuel electrode 13 is supplied to the heater 20 through the flow path 19 and air is supplied, thereby causing the exhaust gas to be fueled, and the reformer using the combustion heat. 4 can be heated.

  Hereinafter, each configuration will be described in detail.

1) Fuel tank 2
As the fuel stored in the fuel tank 2, for example, a mixture of methanol and water, a mixture of methanol, dimethyl ether and water, or the like is used. Alternatively, fuel such as methanol and water may be stored in separate tanks and mixed in the vaporizer 3.

The ratio of water to methanol, that is, the (steam / carbon) ratio in the mixture of methanol and water used as the fuel is preferably in the range of 1 or more and 4 or less. This is due to the following reason. The steam reforming reaction of methanol is represented by [CH ₃ OH + H ₂ O → 3H ₂ + CO ₂ ]. Here, the (steam / carbon) ratio required for the reaction is 1 stoichiometrically. However, generally, when this ratio is close to the stoichiometric number, the amount of CO produced increases. Further, the surplus water can be used for the subsequent CO shift reaction and humidification of the fuel electrode of the fuel cell. A more preferable range of the (steam / carbon) ratio is 2 or more and 4 or less.

2) Reformer 4
As the reforming catalyst, for example, a known catalyst such as CuO / ZnO / γ-Al ₂ O ₃ or Pd / ZnO can be used.

  Further, as a reforming catalyst, a metal oxide-supported composite oxidation comprising a base material of a composite oxide of a hardly-reducible metal oxide and a readily-reducible metal oxide, and active metal particles deposited on at least the surface of the base material Things can also be used.

  The metal oxide-supported composite oxide used as the reforming catalyst is obtained by, for example, reducing the surface of the oxide by hydrogen reduction of a mixture of a non-reducible metal oxide such as a NiO-MgO-CuO system and a readily reducible metal oxide. And Ni-Cu alloy particles formed thereon.

  The temperature and time of the reduction treatment can be set in the same range as described above.

  When the metal particle-supported composite oxide is used as a reforming catalyst, as described above, the unsintered mixed powder is provided with a porous body shape such as a honeycomb type or a foam type, or a groove serving as a fluid flow path. After forming into a sheet shape or the like, it is possible to use a sintered body and deposit metal particles on the surface of the sintered body by reduction treatment. By forming the reformed gas (reactive gas) flow path itself from the reforming catalyst in this way, the pressure loss with respect to the flow of fuel or reformed gas can be remarkably reduced, which is preferable.

3) CO shift reactor 5
As the CO shift reactor 5, it is desirable to use the above-described CO shift reactor according to the present invention.

  The form of the CO shift catalyst can be in the form of a powder, a granule, a porous body such as a honeycomb or foam, or a sheet with a groove serving as a fluid flow path. Among them, a porous body shape such as a honeycomb type or a foam type and a sheet shape provided with a groove serving as a fluid flow path are preferable because pressure loss with respect to the flow of the reformed gas can be significantly reduced. One embodiment of a CO shift reactor using a honeycomb type catalyst is shown in FIG.

  The CO shift reactor 5 includes a heat-resistant, bottomed rectangular tube 21 made of a metal such as aluminum or stainless steel. An inlet pipe 22 for gas distribution is provided on the side surface of the reactor 21 (right side surface as viewed from FIG. 2). An outlet pipe 23 is provided on the side surface opposite to the inlet pipe 22. The CO shift catalyst 24 formed into a honeycomb shape is accommodated in the reactor 21. For example, a cover plate 25 formed of a metal such as aluminum or stainless steel is welded to the opening of the reactor 21. In this reactor 21, not only a catalytic reaction such as a water gas shift reaction of carbon monoxide but also a reduction treatment of the catalyst can be performed. That is, after the unsintered mixed powder is formed into a honeycomb shape, it is sintered and accommodated in the reactor 21. When hydrogen gas is circulated from the gas inlet pipe 22 and the reactor 21 is heated to a predetermined temperature, the easily-reducible metal oxide on the flow path 26 through which the hydrogen gas flows is reduced by hydrogen, and metal particles are formed on the flow path 26. Can be deposited.

  The method of heating the CO shift reactor 5 may be either a method of heating with a heater or a method of using combustion heat of hydrogen or hydrocarbons.

  The operating temperature of the CO shift reactor 5 is preferably 300 ° C. or higher and 400 ° C. or lower. This is because if the operating temperature is lower than 300 ° C. or higher than 400 ° C., the carbon monoxide conversion rate and the carbon dioxide selectivity are lowered, and there is a possibility that the CO shift reaction cannot be efficiently performed. A more preferable range is 300 ° C. or higher and 350 ° C. or lower.

  The reformed gas supplied to the CO shift reactor 5 is mainly composed of hydrogen and preferably has a CO concentration of 5% or more and 20% or less. Here, that hydrogen is the main component means that hydrogen gas is the most among the gas components constituting the reformed gas.

As the CO shift catalyst, a noble metal CO shift catalyst containing at least Pt may be used instead of the above-described metal particle dispersed composite oxide. Specifically, for example, it is composed of Pt / Al ₂ O ₃ as a main component and supporting at least one element selected from K, Mg, Ca, La, Ce, and Re. Such a catalyst is preferable because of its excellent oxidation resistance.

4) CO selective methanator 6
As the CO selective methanator 6, it is desirable to use the aforementioned CO selective methanator according to the present invention.

  The form of the CO selective methanation catalyst can be in the form of a powder, a granule, a porous body such as a honeycomb or foam, or a sheet with a groove serving as a fluid flow path. Among them, a porous body shape such as a honeycomb type or a foam type and a sheet shape provided with a groove serving as a fluid flow path are preferable because pressure loss with respect to the flow of the reformed gas can be significantly reduced. In the reactor shown in FIG. 2 described above, when a CO selective methanation catalyst is used instead of the CO shift catalyst, it can be used as a CO selective methanator.

  The method for heating the CO selective methanator may be either a method of heating with a heater or a method of using the combustion heat of hydrogen or hydrocarbons.

The operating temperature of the CO selective methanator is preferably 275 ° C. or higher and 350 ° C. or lower. This is due to the reason explained below. If the operating temperature is less than 275 ° C., the reaction rate is low, so the CO conversion rate decreases, that is, the methanation to CO ₂ may not proceed sufficiently. On the other hand, when the operating temperature exceeds 350 ° C., the reaction rate increases, but a reverse shift reaction: [CO ₂ + H ₂ → CO + H ₂ O] is likely to occur due to chemical equilibrium, so the CO concentration increases on the contrary. There is a fear. In addition, since CO ₂ methanation easily occurs, CO methanation selectivity may be lowered. A more preferable range is 275 ° C. or higher and 300 ° C. or lower.

  The reformed gas supplied to the CO selective methanator is preferably composed mainly of hydrogen and has a CO concentration of 1% or less. Here, that hydrogen is the main component means that hydrogen gas is the most among the gas components constituting the reformed gas.

5) Electromotive part 7
The electrolyte membrane having proton conductivity is preferably made of a fluorocarbon polymer having a cation exchange group such as a sulfonic acid group or a carboxylic acid group. Specifically, brand name: Nafion (manufactured by Du Pont) or the like can be used. Each of the fuel electrode and the oxidant electrode includes a conductive porous body and a catalyst layer formed thereon. As the fuel electrode and the oxidizer electrode, for example, a porous sheet in which platinum-supported carbon black powder is held by a water-repellent resin binder such as polytetrafluoroethylene (PTFE) can be used. This porous sheet is allowed to contain sulfonic acid type perfluorocarbon polymer and fine particles coated with the polymer.

[Example]
Embodiments of the present invention will be described in more detail with specific examples below, but the present invention is not limited to these.

<CO conversion and CO methanation selectivity>
(Example 1)
NiO powder (average particle size of about 1 μm) as an easily reducible metal oxide and MgO powder (average particle size of about 1 μm) as a hardly reducible metal oxide are in a molar ratio of NiO: MgO = 1: 2. Weighed so that As an additive compound, high-purity Sc ₂ O ₃ was prepared and added so as to be 0.15 mol% in terms of Sc element. This was uniformly mixed with a nylon ball for 20 hours to obtain a mixed powder.

The mixed powder was pressure-molded with a die press at a pressure of 1 ton / cm ² , and then the compact was sintered in air at 1300 ° C. for 5 hours to prepare a composite oxide sintered body. Next, the temperature was raised at a rate of 15 ° C./min while flowing hydrogen gas with a purity of 99.9% at a rate of 500 cc / min, and a reduction treatment was performed at 1000 ° C. for 10 minutes to precipitate Ni particles. Thermogravimetric analysis was performed during this reduction treatment. The sample used for the weight loss measurement was prepared by pulverizing the sintered body with a mortar until the size became about several μm. Reduction weight loss was 10.1 wt%.

The obtained sintered body was pulverized with a mortar and classified to 20-40 mesh. As a result of observation with a scanning electron microscope (SEM), it was confirmed that Ni particles as metal particles were uniformly dispersed on the surface of the MgO—NiO-based composite oxide substrate. Moreover, it was 2.0 m < ² > / g when the active metal specific surface area by hydrogen adsorption was measured with the chemical adsorption measuring device.

(Comparative Example 1)
A metal particle composite oxide of Comparative Example 1 was produced in the same manner as in Example 1 except that Sc ₂ O ₃ was not added. The reduction in weight of this metal particle composite oxide was 0.8 wt%, and the active metal specific surface area was 0.2 m ² / g.

(Comparative Example 2)
Ru ruthenium chloride (RuCl ₃ ) was used as a Ru raw material, and potassium nitrate (KNO ₃ ) was used as a potassium raw material, and this was dissolved in water. Using alumina prepared by 20-40 mesh as a carrier (Sumitomo Chemical Co., Ltd .: AKP-GO15), impregnating with a rotary evaporator with stirring for 60 minutes under reduced pressure, and drying at 60 ° C, Baked at 120 ° C. overnight. This was charged into a reactor and subjected to hydrogen reduction at 400 ° C. for 2 hours. As a result, Ru—K / Al ₂ O ₃ composed of 1 wt.% Ru and 0.1 wt. Obtained as a catalyst.

(Comparative Example 3)
A commercially available Ni-based methanation catalyst (Ni / Al ₂ O ₃ / CaO) was prepared and used as Comparative Example 3.

2 g of each of the obtained CO selective methanation catalysts of Example 1 and Comparative Examples 1 to 3 was charged in a tubular reactor. At this time, glass wool was filled before and after the catalyst layer in order to prevent reaction gas from being blown out. As the reaction gas, H ₂ : 46.1%, CO ₂ : 17.1%, CH ₄ : 4.3%, CO: 0.9%, N ₂ : 17.1%, H ₂ O: 14. A composition having a composition of 3% was used and reacted at a predetermined temperature. Then, the CO concentration, methane concentration, CO ₂ concentration and N ₂ concentration at the outlet of the reactor were quantified with a gas chromatograph (column: molecular sieve 5A, carrier gas: helium), and the CO outlet using N ₂ gas as an internal standard substance The flow rate was determined, and the CO conversion rate (%) was calculated by the following equation (1).

CO conversion rate (%) = {(C ₁ −C ₂ ) / C ₁ } × 100 (1)
Here, C ₁ is the CO inlet flow rate (cc / min), and C ₂ is the CO outlet flow rate (cc / min).

  The selectivity (%) of CO methanation reaction at each temperature was calculated by the following equation (2).

CO methanation selectivity (%) = {(C ₁ -C ₂ ) / (M ₂ -M ₁ )} × 100 (2)
Here, C ₁ is the CO inlet flow rate (cc / min), C ₂ is the CO outlet flow rate (cc / min), M ₁ is the CH ₄ inlet flow rate (cc / min), and M ₂ is the CH ₄ outlet flow rate. (Cc / min).

  FIGS. 3 and 4 show the CO conversion and CO methanation selectivity at each temperature.

  As apparent from FIGS. 3 and 4, in Example 1, the CO conversion reached 99.6% at 275 ° C. and 100% at 300 ° C. At this time, CO methanation selectivity was as high as 90% or more.

  On the other hand, in Comparative Example 1, both the CO conversion rate and the CO methanation selectivity were inferior to those in Example 1. In Comparative Example 2, the CO conversion was as high as 99.5% at 250 ° C., but the CO methanation selectivity was as low as 38%. Further, Comparative Example 3 hardly reacted at a temperature of 300 ° C. or lower as shown in FIG. Moreover, at 350 ° C., the CO concentration rather increased due to the influence of the CO reverse shift reaction (thus, the CO conversion rate was a negative value in the calculation).

(Example 2, Example 3)
A metal particle-dispersed composite oxide was produced in the same manner as in Example 1 except that 0.01 and 0.25 mol% were added in terms of Sc element.

(Examples 4 to 8, 10, 11 and Reference Example 9 )
The additive compound was changed to Cr ₂ O ₃ , In ₂ O ₃ , Lu ₂ O ₃ , Ga ₂ O ₃ , B ₂ O ₃ , Fe ₂ O ₃ , Nb ₂ O ₃ , and SiO ₂ , each of which was a metal element Eight types of metal particle-dispersed composite oxides were obtained in the same manner as in Example 1 except that about 0.15 mol% was added.

( Reference Examples 12-14)
Three metal particle-dispersed composite oxides were obtained in the same manner as in Example 1 except that the composition of the composite oxide was changed as shown in Table 1 below.

(Comparative Example 4)
A metal particle composite oxide was produced in the same manner as in Example 1 except that it was added to 0.3 mol% in terms of Sc element.

The reaction tests were carried out under the same conditions as described above for the obtained CO selective methanation catalysts of Examples 2 to 8, 10, 11, Reference Examples 9, 12 to 14 and Comparative Example 4, and the CO conversion at 275 ° C. And CO methanation selectivity were measured and the results are shown in Table 1 below. Table 1 also shows the results of Example 1 described above.

  In Comparative Example 4 in which the metal addition amount exceeds 0.25 mol%, the CO conversion rate was significantly reduced. From the observation of the structure by SEM, it is considered that the cause is that the coarsening and aggregation of the precipitated particles become remarkable. In the case of using a compound containing another metal element, the same tendency was obtained when the metal addition amount exceeded 0.25 mol%.

<Fuel cell system>
(Example 15)
<Production of vaporizer>
Glass wool was accommodated in a stainless steel container (35 mm × 50 mm), and a lid was welded to constitute a reactor (vaporizer).

<Production of reformer>
MgO (average particle diameter of about 1 μm) as a hardly-reducible metal oxide, and NiO powder and CuO powder (average particle diameter of 1 μm) as easily-reducible metal oxide, the mixed composition is MgO: NiO: CuO = 2 : Weighed so as to be 1: 0.1 (mol ratio). This was uniformly mixed with a nylon ball mill for 20 hours to obtain a mixed powder. After mixing, polyvinyl alcohol (PVA) was added as a binder and kneaded, and the kneaded product was molded to produce a green sheet. Next, a carbon slurry containing carbon and an organic binder was applied to the surface of the green sheet in a flow path pattern to form a carbon slurry layer. In addition, a green sheet provided with holes for gas distribution was prepared by punching. And these were laminated | stacked, crimping | compression-bonding / integrated, the binder was removed, and also the carbon in a carbon slurry layer was burned, and the molded object in which the flow path pattern was formed was obtained. The obtained molded body was introduced into a degreasing furnace, heated to 500 ° C. over 8 hours, and degreased at 500 ° C. for 5 hours. After degreasing, it was sintered at 1300 ° C. for 5 hours. Thus, the molded object in which the flow path was formed was produced.

  And after reducing at 900 ° C. for 10 minutes in a hydrogen stream of 500 cc / min to precipitate Ni particles, this compact was placed inside a stainless steel container (35 mm × 50 mm) and the lid was welded. Thus, a reactor (reformer) was constructed.

<Production of CO shifter>
A commercially available Pt / Al ₂ O ₃ -based catalyst (φ4 mm) was prepared as the CO shift catalyst. This was accommodated in a stainless steel container (35 mm × 50 mm), and a lid was welded to constitute a reactor (CO shifter).

<Production of CO selective methanator>
NiO powder (average particle size of about 1 μm) as an easily reducible metal oxide and MgO powder (average particle size of about 1 μm) as a hardly reducible metal oxide are in a molar ratio of NiO: MgO = 1: 2. Weighed so that As the additive compound, high-purity Sc ₂ O ₃ was prepared and added so as to be 0.05 mol% in terms of Sc element. This was mixed uniformly for 20 hours in a wet manner using a nylon ball to obtain a mixed powder.

  After mixing, polyvinyl alcohol (PVA) was added as a binder and kneaded, and the kneaded product was formed into a honeycomb shape. Next, this compact was introduced into a degreasing furnace, heated to 500 ° C. over 8 hours, and degreased at 500 ° C. for 5 hours. After degreasing, it was sintered at 1300 ° C. for 5 hours. In this way, a honeycomb-shaped sintered body was produced.

  The sintered body was reduced in a hydrogen stream of 500 cc / min at 900 ° C. for 10 minutes to precipitate Ni particles, which were then housed in a stainless steel container (35 mm × 50 mm) and placed in the opening of the container. The lid was welded to constitute the reactor (CO selective methanator) having the structure shown in FIG.

  The reactor thus produced was connected using a pipe in the order of vaporizer-reformer-CO shifter-CO selective methanator to construct the fuel cell system shown in FIG. The operating temperature of each reactor was operated as a vaporizer: 150 ° C, a reformer: 350 ° C, a CO shifter: 275 ° C, and a CO selective methanator: 275 ° C.

<Methanol steam reforming test>
As the fuel, an aqueous methanol solution having a mixing ratio of CH ₃ OH and H ₂ O of 1: 4 (molar ratio) was used. This was supplied to the vaporizer by a liquid feed pump so that the methanol gas flow rate was 30 cc / min and the water vapor flow rate was 120 cc / min in terms of gas flow rate.

  Next, the vaporized fuel gas was introduced into a reformer to perform a steam reforming reaction of methanol. Subsequently, the obtained reformed gas was led to a CO shifter to perform a CO shift reaction. At this time, the CO concentration at the outlet of the CO shifter was about 2000 ppm. This reformed gas was introduced into a CO selective methanator, and CO was removed by methanation. As a result, the outlet CO concentration of the CO selective methanator was 12 ppm.

(Example 16)
The fuel cell system was the same as that described in Example 15 above, except that the composite oxide composition of the CO selective methanation catalyst, the type of additive compound or the additive metal content was changed as shown in Table 2 below. Was made. Table 2 below shows the outlet CO concentration of the CO selective methanator for the fuel cell system of each example.

( Examples 17-22, 24, 25 and Reference Examples 23, 26-28 )
The fuel cell system was the same as that described in Example 15 above, except that the composite oxide composition of the CO selective methanation catalyst, the type of additive compound or the additive metal content was changed as shown in Table 2 below. Was made. Then, the system was operated with the operating temperature of each reactor as a vaporizer: 150 ° C, a reformer: 350 ° C, a CO shifter: 300 ° C, and a CO selective methanator: 300 ° C. Table 2 below shows the outlet CO concentration of the CO selective methanator for the fuel cell system of each example.

(Comparative Example 5)
<Selective oxidation of CO>
A commercially available Ru / Al ₂ O ₃ (φ4 mm) was used as the CO selective oxidation catalyst. This was accommodated in a stainless steel container (35 mm × 50 mm), and a lid was welded to constitute a reactor (CO selective oxidizer).

  A fuel cell system comprising a vaporizer-reformer-CO shifter-CO selective oxidizer in the same manner as in Example 15 except that the above-mentioned CO selective oxidizer was used instead of the CO selective methanator. Built. The operating temperature of each reactor was operated as a vaporizer: 150 ° C, a reformer: 350 ° C, a CO shifter: 275 ° C, and a CO selective oxidizer: 130 ° C.

The reformed gas obtained in the same manner as in Example 15 was introduced into a CO shifter to perform a CO shift reaction. The CO concentration at the outlet of the CO shifter was about 2000 ppm. A small amount of air containing 21% oxygen was added to the reformed gas and introduced into a CO selective oxidizer. The amount of air added was supplied using a pump with a minute flow rate adjusting valve so that the flow rate ratio was O ₂ / CO = 2. As a result, the outlet CO concentration of the CO selective oxidizer was 60 ppm.

As described above, according to the fuel cell systems of Examples 15 to 22, 24 and 25 and Reference Examples 23 and 26 to 28, the CO concentration in the reformed gas can be removed to about 10 ppm with a simple system. It could be confirmed.

  In contrast, in Comparative Example 5 in which a CO selective oxidation catalyst was used instead of the CO selective methanation catalyst, the CO concentration in the reformed gas could be removed up to about 60 ppm, but it was necessary to selectively oxidize CO. Necessitating a pump and a minute flow rate adjusting valve for supplying oxygen (air), making the system complicated and large.

  As can be understood from the above description, the fuel cell system according to an embodiment of the present invention uses a catalyst excellent in selectivity of CO methanation reaction for the CO remover, and is modified with a simple system. It is possible to remove the CO concentration in the quality gas to about 10 ppm. As a result, there is little hydrogen loss in the reformed gas, and there is no need for a pump for supplying oxygen (air) necessary for selective oxidation of CO, as in the case of using a selective oxidation catalyst for the CO remover. Thus, the fuel cell system can be reduced in size. Therefore, it is extremely useful as a power source for electronic devices such as notebook personal computers and VTRs in addition to portable power sources.

<CO conversion rate and CO ₂ selectivity>
(Example 29)
The CoO powder as the easily reducible metal oxide and the MgO powder as the hardly reducible metal oxide were weighed so that the molar ratio was CoO: MgO = 1: 2. As the additive compound, a high-purity Sc ₂ O ₃ powder was prepared and added so that the element amount was 0.2 mol%. This was uniformly mixed with a nylon ball for 20 hours to obtain a mixed powder.

The mixed powder was pressure-molded with a die press at a pressure of 1 ton / cm ² , and then the compact was sintered in air at 1300 ° C. for 5 hours to prepare a composite oxide sintered body. Next, while flowing hydrogen gas with a purity of 99.9% at a flow rate of 500 cc / min, the temperature was raised at a rate of 15 ° C./min, and reduction treatment was performed at 1000 ° C. for 10 minutes to precipitate Co particles. Thermogravimetric analysis was performed during this reduction treatment. The sample used for the weight loss measurement was prepared by pulverizing the sintered body with a mortar until the size became about several μm. The reduction weight loss was 9.5 wt%.

The obtained sintered body was pulverized with a mortar and classified to 20-40 mesh. As a result of observation with a scanning electron microscope (SEM), it was confirmed that Co particles as metal particles were uniformly dispersed on the surface of the MgO—CoO-based composite oxide substrate. Moreover, it was 1.9 m < ² > / g when the active metal specific surface area by hydrogen adsorption was measured with the chemical adsorption measuring device.

(Comparative Example 6)
A Co metal particle composite oxide was produced in the same manner as in Example 29 except that Sc ₂ O ₃ was not added. The reduction in weight of this metal particle composite oxide was 0.6 wt%, and the active metal specific surface area was 0.2 m ² / g.

3 g of each of the obtained CO shift catalysts of Example 29 and Comparative Example 6 was charged into a tubular reactor. At this time, glass wool was filled before and after the catalyst layer in order to prevent reaction gas from being blown out. The temperature of the catalyst layer was changed from 300 ° C to 400 ° C. A reaction gas having a composition of H ₂ : 41.1%, CO ₂ : 9.7%, CO: 5.7%, CH ₄ : 0.6%, H ₂ O: 42.9% is used. As an internal standard gas, 19.2% N ₂ gas was mixed with respect to the reaction gas. The CO concentration, CO ₂ concentration, CH ₄ concentration and N ₂ concentration at the inlet and outlet of the reactor were quantified with a gas chromatograph (column: molecular sieve 5A, carrier gas: helium), and N ₂ gas contained in the reaction gas was determined. The CO outlet flow rate was obtained as an internal standard substance, and the CO conversion rate (%) was calculated by the above-described equation (1).

Moreover, the CO ₂ conversion selectivity (%) of CO at the outlet of the reactor at each temperature was calculated by the following equation (3).

CO ₂ conversion selectivity (%) = {X / (X + C ₂ + M ₂ )} × 100 (3)
Here, C ₂ is the CO outlet flow rate (cc / min), M ₂ is the CH ₄ outlet flow rate (cc / min), and X is the CO ₂ outlet flow rate (cc / min).

FIGS. 5 and 6 show the CO conversion ratio and CO ₂ conversion selectivity at each temperature. 5 and 6, in Example 29, when the temperature of the catalyst layer was 300 ° C., the CO conversion rate was 92.3% and the CO ₂ conversion selectivity was 90.8%, both being the maximum, 300 ° C. Even in a wide temperature range from 400 to 400 ° C., the CO conversion was maintained at a high value between 81.1% and 92.3% and the CO ₂ conversion selectivity was between 80.5% and 90.8%. This indicates that carbon monoxide was selectively carbonized in Example 29 without causing side reactions such as methanation in a wide temperature range. On the other hand, in Comparative Example 6, as the temperature is increased, both the CO conversion rate and the CO ₂ conversion selectivity increase, but at 400 ° C., the CO conversion rate is 36.0% and the CO ₂ conversion selectivity is 72.8%. And it remained at a low value compared with Example 29. From the above results, a sufficient amount of Co particles is precipitated on the surface of the composite oxide by mixing the additive of Sc ₂ O ₃ when preparing the metal particle-dispersed composite oxide, and a wide temperature range of 300 ° C. to 400 ° C. It was proved that the carbon monoxide shift reaction occurred efficiently and selectively in the range.

Further, with respect to metal particles dispersed oxide of Example 29 described above, in the case where the CO concentration in the inlet reaction gas was as high as 12.7% even at 300 ° C., CO conversion was 93.9%, CO ₂ reduction The selectivity was 88.7%, and it was found that the carbon monoxide shift reaction occurred efficiently and selectively. That is, it has been found that the selective carbon dioxide conversion of carbon monoxide occurs with high efficiency in a wide concentration range where the CO concentration contained in the reaction gas is 10 to several percent. Furthermore, the metal particle-dispersed oxide of Example 29 was thermally stable and could be used any number of times without causing significant aggregation of the catalyst particles due to heat generation.

(Example 30, Example 31)
The additive compound was changed to Al ₂ O ₃ (Example 30) and Cr ₂ O ₃ (Example 31), and each was added in the same manner as in Example 29 except that about 0.2 mol% of each element was added. Two types of metal particle-dispersed composite oxide were obtained.

(Examples 32-34)
Three metal particle-dispersed composite oxides were obtained in the same manner as in Example 29 except that the reduction treatment temperature with hydrogen was changed as shown in Table 3 below.

(Example 35)
A mixed powder of the same type as described in Example 29 was pressure-molded into a honeycomb type, and the molded body was sintered and reduced under the same conditions as in Example 29 to obtain a metal particle-dispersed composite oxide. Obtained.

(Examples 36 and 37 and Reference Examples 38 to 40)
Five types of metal particle-dispersed composite oxides were obtained in the same manner as in Example 29 except that the additive metal content or the composite oxide composition was changed as shown in Table 3 below.

(Comparative Examples 7-8)
Two types of metal particle-dispersed composite oxide were obtained in the same manner as in Example 29 described above except that the composite oxide composition and the content of added metal in the catalyst were changed as shown in Table 3 below.

With respect to these Examples 30 to 37, Reference Examples 38 to 40, and Comparative Examples 7 to 8, the same reaction test as described above (reaction gases were H ₂ : 41.1%, CO ₂ : 9.7%, CO: 5 0.7%, CH ₄ : 0.6%, H ₂ O: 42.9%), and CO conversion and CO ₂ CO ₂ conversion selectivity were determined. Table 3 below shows the CO conversion and CO ₂ conversion selectivity when the temperatures of Examples 30 to 37, Reference Examples 38 to 40, and Comparative Examples 7 to 8 were set to 300 ° C. Table 3 also shows the results of Example 29 and Comparative Example 6 described above. The temperature of Comparative Example 6 was set to 400 ° C. with the highest shift efficiency.

From the experimental results, it was found that in Examples 30 to 37 and Reference Examples 38 to 40, the same results as those of Example 29 described above were obtained. In Comparative Example 7, the content of the added metal is less than 0.01 mol%, and a sufficient amount of easily reducible metal particles cannot be deposited on the surface of the composite oxide, resulting in a decrease in catalyst performance. It was. On the other hand, in Comparative Example 8, the added metal content exceeded 0.25 mol%, precipitation due to reduction was excessive, and metal particles aggregated and coalesced, resulting in a decrease in catalyst performance. From the above, it is preferable that the metal content added to the composite oxide is in the range of 0.01 to 0.25 mol%.

(Example 41)
A fuel cell system similar to that of Example 15 described above was constructed and operated, except that the metal particle-dispersed oxide produced in Example 29 was used for the CO shifter. The operating temperature of the CO shift reactor was 300 ° C.

  As a result, it was confirmed that the CO concentration in the reformed gas was removed to about 30 ppm.

  As can be understood from the above description, the carbon monoxide shift reactor according to the present invention is a side reaction such as methanation in which the carbon monoxide concentration in the reaction gas having a carbon monoxide concentration of ten to several percent is several percent. This makes it possible to selectively remove carbon dioxide without causing any trouble. This method can efficiently and selectively cause a carbon monoxide shift reaction in a wide temperature range from 300 ° C. to 400 ° C., is thermally stable, and does not cause significant aggregation of catalyst particles due to heat generation. It can be used any number of times. In addition, the shape of the catalyst can be made into a porous body shape such as powder, granule, honeycomb type and foam type, and a sheet shape with a groove serving as a fluid flow path. By using a porous body shape such as a mold or a sheet shape in which a flow path is cut, the pressure loss with respect to the flow of fuel or reformed gas can be remarkably reduced, and a catalytic reaction can be caused with high efficiency.

  Based on the above results, a reformer, a carbon monoxide shifter, and a carbon monoxide remover that reforms a hydrocarbon-based fuel into hydrogen gas containing about several tens of ppm of carbon monoxide and supplies it to the fuel cell to generate electricity. It has become clear that the carbon monoxide shifter according to the present invention can be applied to a fuel cell system including an electromotive unit.

  Note that the present invention is not limited to the above-described embodiment as it is, and can be embodied by modifying the constituent elements without departing from the scope of the invention in the implementation stage. In addition, various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the embodiment. For example, some components may be deleted from all the components shown in the embodiment. Furthermore, constituent elements over different embodiments may be appropriately combined.

1 is a schematic configuration diagram showing an embodiment of a fuel cell system according to the present invention. FIG. 2 is a schematic exploded perspective view showing an embodiment of a CO shift reactor of the fuel cell system of FIG. 1. The characteristic view which shows the relationship between CO conversion rate and operating temperature in CO selective methanation reaction of Example 1 and Comparative Examples 1-3. The characteristic view which shows the relationship between CO methanation selectivity in CO selective methanation reaction of Example 1 and Comparative Examples 1-3, and operating temperature. The characteristic view which shows the relationship between CO conversion rate and operating temperature in CO shift reaction of Example 29 and Comparative Example 6. Characteristic diagram showing the relationship between the operating temperature CO ₂ reduction selectivity in the CO shift reaction of Example 29 and Comparative Example 6.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Fuel cell system, 2 ... Fuel tank, 3 ... Vaporizer, 4 ... Reformer, 5 ... CO shifter, 6 ... CO selective methanator, 7 ... Electromotive part (MEA), 9 ... Liquid feed pump , 13 ... Fuel electrode, 14 ... Oxidant electrode, 15 ... Electrolyte membrane, 18 ... Air supply pump, 21 ... Reactor, 22 ... Inlet piping, 23 ... Outlet piping, 24 ... CO shift catalyst, 25 ... Cover plate, 26 ... the flow path.

Claims (7)

A carbon monoxide selective methanator comprising a reactor and a carbon monoxide selective methanation catalyst charged in the reactor,
The carbon monoxide selective methanation catalyst includes a base material of a composite oxide containing a nonreducible metal oxide composed of magnesium oxide, a reducible metal oxide composed of nickel oxide, and an additive metal element, and the easy reductivity Active metal particles deposited on at least the surface of the base material by reduction of the conductive metal oxide ,
The additive metal element, Al, at least one kind of Sc, Cr, B, Ga, In, Lu, is selected the group or al consisting Nb and Si, the additive metal of the carbon monoxide selective methanation catalyst The carbon monoxide selective methanator, wherein the element content is 0.01 mol% or more and 0.25 mol% or less in terms of element amount. The carbon monoxide selective methanator according to claim 1, wherein the additive metal element is at least one of Sc and Cr . A carbon monoxide shift reactor comprising a reactor and a carbon monoxide shift catalyst charged in the reactor,
The carbon monoxide shift catalyst includes a base material of a composite oxide containing a nonreducible metal oxide composed of magnesium oxide, a reducible metal oxide composed of cobalt oxide, and an additive metal element, and the reducible metal Comprising active metal particles deposited on at least the surface of the substrate by reduction of the oxide ,
The additive metal element, Al, Sc, Cr, B , Ga, In, at least one kind of Lu, is selected the group or al consisting Nb and Si, the additive metal element of the carbon monoxide shift catalyst Content is 0.01 mol% or more and 0.25 mol% or less by element amount, The carbon monoxide shift reactor characterized by the above-mentioned. The carbon monoxide shift reactor according to claim 3, wherein the additive metal element is at least one of Sc and Cr . A reformer that reforms the fuel to obtain a reformed gas containing hydrogen;
A carbon monoxide shift reactor disposed downstream of the reformer;
The carbon monoxide selective methanator disposed downstream of the carbon monoxide shift reactor,
The fuel cell is disposed downstream of the carbon monoxide selective methanator and is provided with a fuel electrode to which a reformed gas is supplied from the carbon monoxide selective methanator, and an electromotive unit including an oxidizer electrode. A fuel cell system. A reformer that reforms the fuel to obtain a reformed gas containing hydrogen;
A carbon monoxide shift reactor disposed downstream of the reformer; and
A carbon monoxide remover disposed downstream of the carbon monoxide shift reactor;
A fuel cell comprising a fuel electrode disposed downstream of the carbon monoxide remover and supplied with a reformed gas from the carbon monoxide remover, and an electromotive unit having an oxidant electrode. system. 7. The fuel cell system according to claim 6, wherein the carbon monoxide selective methanator according to claim 1 is used as the carbon monoxide remover.

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