JP2008279427A - Catalyst for reforming oxygen-containing hydrocarbon, and hydrogen or synthetic gas production method and fuel cell system using the catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for reforming an oxygen-containing hydrocarbon, the reforming activity and durability of which are improved by improving the performance of a copper-containing metal oxide having a spinel structure as the catalyst for reforming the oxygen-containing hydrocarbon and to provide a hydrogen or synthetic gas production method and a fuel cell system both using the catalyst. <P>SOLUTION: The catalyst for reforming the oxygen-containing hydrocarbon is prepared by the step of firing a mixture of the copper-containing metal oxide (A) having the spinel structure with a solid acid (B) at 300-850°C in an atmosphere containing at least oxygen. The method for producing hydrogen or a synthetic gas comprises a step of subjecting the oxygen-containing hydrocarbon to any one of various reforming treatments using the catalyst. The fuel cell system comprises a reformer having the catalyst and a fuel cell utilizing hydrogen produced by the reformer as fuel. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an oxygen-containing hydrocarbon reforming catalyst, a method for producing hydrogen or synthesis gas using the same, and a fuel cell system. More specifically, the present invention relates to an oxygen-containing hydrocarbon prepared by subjecting a mixture of a metal oxide having a spinel structure containing copper and a solid acid to a firing process at a specific temperature in an oxygen-containing gas atmosphere. The present invention relates to a reforming catalyst, a method for efficiently producing hydrogen or synthesis gas by variously reforming an oxygen-containing hydrocarbon using the reforming catalyst, and a fuel cell system using the reforming catalyst. .

Syngas is composed of carbon monoxide and hydrogen, and is used as a raw material gas for methanol synthesis, oxo synthesis, Fischer-Tropsch synthesis, etc., and is widely used as a raw material for ammonia synthesis and various chemical products.
This synthesis gas has been conventionally produced by a method of gasification of coal, a steam reforming method or a partial oxidation reforming method of hydrocarbons using natural gas or the like as a raw material. However, the coal gasification method has problems such as a complicated and expensive coal gasification furnace and a large-scale plant. Moreover, in the steam reforming method of hydrocarbons, since the reaction involves a large endotherm, a high temperature of about 700 to 1200 ° C. is required for the progress of the reaction, and a special reforming furnace is required and used. There were problems such as high heat resistance required for the catalyst. Furthermore, even in the partial oxidation reforming of hydrocarbons, a special partial oxidation furnace is required because it requires a high temperature, and a large amount of soot is generated with the reaction, so that the treatment becomes a problem. In addition, there is a problem that the catalyst is easily deteriorated.

In order to solve such problems, attempts have been made in recent years to produce synthesis gas by using oxygen-containing hydrocarbons such as dimethyl ether (DME) as a raw material and subjecting them to various modifications. On the other hand, in recent years, new energy technology has attracted attention due to environmental problems, and fuel cells are attracting attention as one of the new energy technologies.
This fuel cell converts chemical energy into electrical energy by electrochemically reacting hydrogen and oxygen, and has a feature of high energy use efficiency. Alternatively, research into practical use is actively conducted for automobiles and the like. In addition, solid oxide fuel cells with high power generation efficiency and high attention recently can use carbon monoxide in addition to hydrogen. As a hydrogen source of this fuel cell (in the solid oxide fuel cell, hydrogen and carbon monoxide source), liquefied natural gas mainly composed of methanol and methane, city gas mainly composed of this natural gas, and natural gas Research has been conducted on synthetic liquid fuels made from methane, and petroleum hydrocarbons such as petroleum naphtha and kerosene.

When hydrogen is produced using these petroleum hydrocarbons, generally, the hydrocarbon is subjected to steam reforming treatment, autothermal reforming treatment, partial oxidation reforming treatment, etc. in the presence of a catalyst. In this case, however, the above-mentioned problem occurs. Therefore, in the production of hydrogen, various methods using an oxygen-containing hydrocarbon such as dimethyl ether as a raw material have been tried. Various catalysts have been disclosed so far, using oxygen-containing hydrocarbons such as dimethyl ether as raw materials, and various modifications to these to produce hydrogen and synthesis gas. As a technology for reforming oxygen-containing hydrocarbons using a Cu-based catalyst, a catalyst for producing synthesis gas from oxygen-containing hydrocarbons and carbon dioxide using, for example, a Cu-containing catalyst, and synthesis using the same Gas production method (Patent Document 1, etc.), catalyst containing hydrogen from oxygen-containing hydrocarbon and water vapor using Cu-containing catalyst, hydrogen production method using the same (Patent Document 2, etc.), solid acid with Cu Oxygen-containing hydrocarbon reforming catalyst (Patent Documents 3 and 4, etc.) comprising a metal-supported metal, a mixture of a Cu-containing material and a solid acidic material, oxygen-containing hydrocarbon and steam to water And a method for producing hydrogen using the same (Patent Document 5, etc.), a catalyst comprising a mixture of a Cu-containing substance and a solid acidic substance, and producing a synthesis gas from oxygen-containing hydrocarbon and steam A synthesis gas production method (Patent Document 6, etc.) has been disclosed.
However, all of the Cu-based catalysts used in the techniques of Patent Documents 1 to 6 have insufficient activity, and therefore the problem is that the catalyst is inevitable to deteriorate when the reaction temperature is raised to improve the reaction activity. was there.

In order to solve the above problem, a metal oxide containing spinel structure containing copper or an oxygen-containing hydrocarbon reforming catalyst further containing a solid acidic substance has been proposed (Patent Document 7, etc.) The activity is still not enough. In Patent Document 7, alumina, silica / alumina, zeolite and the like are listed as solid acidic substances, and it is described that alumina is preferable. Further, Patent Document 8 discloses a catalyst in which a Cu-Zn-Al type methanol decomposition catalyst and ZSM-5 are mixed. However, compared with the catalyst of Patent Document 7, coke which causes catalyst deterioration is disclosed. The problem is that it is easy to generate.
On the other hand, Patent Document 9 discloses that as an example of the reforming catalyst II, CuMn is supported on alumina and then calcined and calcined at a temperature of 500 to 1000 ° C. In this technique, spinel is disclosed. The spinel is supported by being supported on alumina before becoming, and then fired at a high temperature, and the technique of mixing and firing the spinel structure and alumina is essentially different.

JP-A-10-174869 Japanese Patent Application Laid-Open No. 10-174871 JP 2001-96159 A JP 2001-96160 A JP 2003-10684 A Japanese Patent Laid-Open No. 2003-33656 JP 2005-342543 A JP-A-9-118501 WO2004 / 103555 pamphlet (8, 9 pages)

  The present invention has been made under such circumstances, and further improves the performance as a catalyst for reforming oxygen-containing hydrocarbons of metal oxides containing copper and having a spinel structure, and oxygen-containing carbon such as dimethyl ether. A reforming catalyst having excellent hydrogen reforming activity and improved durability, and a method for efficiently producing hydrogen or syngas by subjecting oxygen-containing hydrocarbons to various reforming using the reforming catalyst In addition, an object of the present invention is to provide a fuel cell system using the reforming catalyst.

  In order to achieve the above object, the present inventors have conducted intensive research. As a result, a catalyst prepared by subjecting a mixture of a metal oxide having a spinel structure containing copper and a solid acid to a firing process at a specific temperature in an oxygen-containing gas atmosphere has improved the oxygen-containing hydrocarbon. It has been found that the catalyst can be adapted to its purpose as a quality catalyst. The present invention has been completed based on such findings.

That is, the present invention
(1) (A) It is prepared through a step of firing a mixture of a metal oxide containing copper and having a spinel structure and (B) a solid acid at 300 to 850 ° C. at least in an oxygen-containing gas atmosphere. A catalyst for reforming an oxygen-containing hydrocarbon,
(2) The oxygen-containing composition according to (1) above, wherein the metal oxide of component (A) is at least one selected from the group consisting of Cu—Fe type spinel, Cu—Mn type spinel and Cu—Mn—Fe type spinel. Hydrocarbon reforming catalyst,
(3) The oxygen-containing hydrocarbon reforming catalyst according to (2), wherein the metal oxide of component (A) is a Cu—Fe type spinel obtained by firing at a temperature of 500 to 1000 ° C. ,
(4) The above reforming catalyst containing at least a Cu—Fe type spinel and a solid acid, and having diffraction lines at least in the following three positions in the measurement of X-ray diffraction incident with CuKα rays: Or the oxygen-containing hydrocarbon reforming catalyst according to (3),
2θ = 24.1 °, 33.2 °, 49.6 °
(5) The ratio between the diffraction line intensity appearing at 2θ = 33.2 ° and the diffraction line intensity which is the strongest line of CuFe ₂ O ₄ spinel appearing at 2θ = 36.1 ° is 0.1 to 0.9. A catalyst for reforming an oxygen-containing hydrocarbon according to (4) above,
(6) The oxygen-containing hydrocarbon according to any one of (1) to (5) above, wherein the metal oxide of component (A) contains at least one element selected from nickel, cobalt, and platinum group elements. Reforming catalyst,
(7) The catalyst for reforming an oxygen-containing hydrocarbon according to any one of (1) to (6), wherein the solid acid of the component (B) is alumina,
(8) The oxygen-containing hydrocarbon reforming catalyst according to (7), wherein the solid acid of the component (B) is γ-alumina obtained by firing at a temperature of 300 to 750 ° C.
(9) The oxygen-containing hydrocarbon reforming catalyst according to any one of (1) to (8), wherein the oxygen-containing gas atmosphere in the calcination treatment step is an air atmosphere,
(10) An oxygen-containing hydrocarbon reforming catalyst obtained by reducing the reforming catalyst according to any one of (1) to (9) above,
(11) The oxygen-containing hydrocarbon reforming catalyst according to any one of (1) to (10), wherein the oxygen-containing hydrocarbon is dimethyl ether,
(12) A method for producing hydrogen or synthesis gas, characterized by steam reforming an oxygen-containing hydrocarbon using the reforming catalyst according to any one of (1) to (11) above,
(13) A method for producing hydrogen or synthesis gas, wherein the reforming catalyst according to any one of (1) to (11) is used, and an oxygen-containing hydrocarbon is subjected to autothermal reforming,
(14) A method for producing hydrogen or synthesis gas, characterized by partially oxidizing and reforming an oxygen-containing hydrocarbon using the reforming catalyst according to any one of (1) to (11) above,
(15) A method for producing hydrogen or synthesis gas, wherein the reforming catalyst according to any one of (1) to (11) above is used, and an oxygen-containing hydrocarbon is reformed with carbon dioxide,
And (16) a reformer including the reforming catalyst according to any one of (1) to (11), and a fuel cell using hydrogen produced by the reformer as a fuel. A fuel cell system,
I will provide a.

  According to the present invention, the performance of a metal oxide containing copper and having a spinel structure as an oxygen-containing hydrocarbon reforming catalyst is further improved, and the reforming activity of oxygen-containing hydrocarbons such as dimethyl ether is excellent, and A reforming catalyst with improved durability, a method for efficiently producing hydrogen or synthesis gas by using the reforming catalyst to perform various reforming on an oxygen-containing hydrocarbon, and using the reforming catalyst It is possible to provide a fuel cell system.

First, the oxygen-containing hydrocarbon reforming catalyst of the present invention will be described.
[Reforming catalyst for oxygen-containing hydrocarbons]
The reforming catalyst for oxygen-containing hydrocarbons of the present invention calcinates a mixture of (A) a metal oxide containing copper and having a spinel structure and (B) a solid acid in at least an oxygen-containing gas atmosphere. It is the catalyst prepared through the process.
(Spinel structure metal oxide containing copper)
In the present invention, the metal oxide having a spinel structure used as the component (A) is one of the typical crystal structure types found in AB ₂ O ₄ type metal double oxides and has a cubic system. . In the AB ₂ O ₄ , A is usually a divalent metal and B is a trivalent metal.
In the present invention, a metal oxide having a spinel structure containing copper is used, and as such a metal oxide, Cu—Mn type spinel, Cu—Fe type spinel, Cu, and the like from the viewpoint of catalytic activity and heat resistance. -Mn-Fe type spinel is preferred. Examples of the Cu—Mn type spinel include CuMn ₂ O ₄ , and examples of the Cu—Fe type spinel include CuFe ₂ O ₄ . The Cu-Mn-Fe type _{spinel, Cu (Mn, Fe) 2} O 4 Cu (Mn 1.5 Fe 0.5) spinel _{O 4, Cu (Mn 1.0 Fe} 1.0) O 4, Cu (Mn 2/3 Fe 4 _{/ 3} ) O ₄ , Cu (Mn _0.5 Fe _1.5 ) O ₄ spinel, and the like.
Further, CuCr-type spinels such as CuCr ₂ O _4, more and CuAl ₂ O ₄ spinel, Cu (FeCr) may _{2 O 4, Cu (FeAl)} 2 O 4 spinel, etc. be used.

The metal oxide of the component (A) can contain at least one element selected from nickel, cobalt, and platinum group elements. As described above, the nickel, cobalt, and platinum group elements may have a spinel structure together with Cu, or may be mixed with a Cu-containing spinel. The platinum group element includes Pt, Ru, Rh, Pd, and Ir.
The nickel and cobalt having a spinel structure together with Cu include Cu-Ni-Mn type spinel, Cu-Co-Mn type spinel, Cu-Ni-Mn-Fe, in which a part of the spinel is replaced by Ni and Co. Examples thereof include spinel, Cu—Ni—Fe spinel, Cu—Co—Fe spinel, and Cu—Co—Mn—Fe spinel.
In the reforming catalyst of the present invention, a compound containing copper having a non-spinel structure is desired as the metal oxide having a spinel structure containing copper as the component (A) as long as the object of the present invention is not impaired. It can also be used.

Next, an example of a method for preparing a metal oxide having a spinel structure containing copper will be described by taking a case of preparing a CuMn ₂ O ₄ spinel as an example.
First, a water-soluble copper salt such as copper nitrate is used as the copper source, and a water-soluble manganese salt such as manganese nitrate is used as the manganese source, and these are substantially stoichiometric, that is, the molar ratio of Cu and Mn. An aqueous solution containing 1: 2 is prepared. Next, a chelating agent such as citric acid is added to the aqueous solution, and then heated to evaporate the water to form a gel. Next, this gel is heat-treated, and oxide fine powder obtained by decomposing nitrate radicals and citric acid in the gel is temporarily treated in air at a temperature of about 300 to 500 ° C. for about 1 to 5 hours. After calcination, a catalyst made of CuMn ₂ O ₄ spinel is obtained by further calcination at a temperature of about 500 to 1,000 ° C. for about 5 to 15 hours. Moreover, when it is fired at a high temperature of 700 ° C. or higher, it is said that it becomes a mixture of Mn ₂ O ₃ and Cu _1.5 Mn _1.5 O ₄ spinel, but this case can also be used as the component (A).

In this method, a copper source can be used so that Cu is in excess of the stoichiometric ratio with respect to Mn. In this case, the obtained catalyst becomes a mixture of a copper oxide (Cu ₂ O or CuO or a mixture thereof) and a spinel oxide, and this can also be used as the component (A).
Also, when preparing a catalyst comprising CuFe ₂ O ₄ spinel, instead of the manganese source, it may be used iron source, such as a water-soluble iron salts such as iron nitrate. Furthermore, a catalyst made of Cu (FeMn) ₂ O ₄ spinel can be obtained by using a mixture of an iron source and a manganese source instead of the manganese source. Of course, this can also be used as the component (A).
These components (A) are usually used after being formed into pellets of an appropriate size.
In the present invention, as the metal oxide having a spinel structure containing copper as the component (A), the spinel may be used alone or in combination of two or more, but from the viewpoint of catalytic activity. In particular, a Cu—Fe type spinel obtained by firing at a temperature of 500 to 1000 ° C. is suitable.

(Solid acid)
In the reforming catalyst of the present invention, the solid acid used as component (B) is a solid that exhibits the characteristics of Bronsted acid or Lewis acid. Specifically, alumina, silica-alumina, silica- Examples thereof include titania, zeolite, and aluminum silicolinate (SAPO). These may be used singly or in combination of two or more, but alumina is preferred from the viewpoint of the activity of the catalyst obtained in these.
As the alumina used as the solid acid, commercially available α, β, γ, η, θ, κ, and χ ones can be used. Moreover, what baked alumina hydrates, such as boehmite, bayerite, and gibbsite, can also be used. In addition to this, an alkaline buffer solution having a pH of about 8 to 10 may be added to aluminum nitrate to form a hydroxide precipitate, which may be fired, or aluminum chloride may be fired. Also, a sol-gel method in which an alkoxide such as aluminum isopropoxide is dissolved in an alcohol such as 2-propanol, an inorganic acid such as hydrochloric acid is added as a catalyst for hydrolysis to prepare an alumina gel, and this is dried and fired. It is also possible to use those prepared by
In the present invention, as the component (B), the solid acid may be used singly or in combination of two or more. However, from the viewpoint of catalytic activity, particularly at a temperature of about 300 to 750 ° C. Γ-alumina obtained by firing is preferred.

(Baking process)
The reforming catalyst of the present invention comprises a step of firing the mixture of the above-described metal oxide having a spinel structure containing copper as the component (A) and the solid acid as the component (B) in an oxygen-containing gas atmosphere. To be prepared.
Although there is no restriction | limiting in particular about the mixing ratio of the said (A) component and (B) component, From a viewpoint of catalyst activity, it is 1-50 mass% normally as Cu in a mixture, Preferably it is 2-30 mass%. It is desirable to be included in the range.
Although there is no restriction | limiting in particular in the preparation method of the said mixture, Various physical mixing methods are employable.
The atmosphere during firing may be an oxygen-containing gas and is not particularly limited, but an air atmosphere is preferable from the viewpoint of economy and the like.
The calcination temperature is selected in the range of 300 to 850 ° C, preferably 350 to 800 ° C, more preferably 700 to 800 ° C, from the viewpoint of catalytic activity. If it is less than 300 ° C., the effect of improving the catalyst activity or durability is not sufficient, and if it exceeds 850 ° C., solid acid aggregation and phase change occur, and the performance as an acid cannot be exhibited. The firing time depends on the firing temperature and cannot be generally determined, but is usually about 10 minutes to 50 hours, preferably about 1 to 20 hours.

The reforming catalyst of the present invention has diffraction line intensities at least at three positions of 2θ = 24.1 °, 33.2 °, and 49.6 ° in the measurement of X-ray diffraction incident with CuKα rays. Those are preferred. When the diffraction line intensity is present at this position, the reforming ability of the oxygen-containing hydrocarbon is improved. Particularly preferably, the ratio between the diffraction line intensity appearing at 2θ = 33.2 ° and the diffraction line intensity which is the strongest line of CuFe ₂ O ₄ spinel appearing at 2θ = 36.1 ° is 0.1 to 0.3. The reforming catalyst is in the range of 9.
The present inventors estimated that CuFeAl spinel is produced by firing a mixture of CuFe spinel and alumina at a high temperature, which may be a factor of high activity. At that time, since Fe in the spinel substitutes for Al, the extruded Fe exists in the form of Fe ₂ O ₃ , and new peaks appear at 2θ = 24.1 °, 33.2 °, and 49.6 °. Presumed to have appeared.
That is, (i) a catalyst for reforming an oxygen-containing hydrocarbon having a CuFe-type spinel, and the catalyst has an X-ray diffraction line intensity at least at 2θ = 24.1 °, 33.2 °, 49.6 ° More preferably, the ratio between the diffraction line intensity appearing at 2θ = 33.2 ° and the diffraction line intensity which is the strongest line of CuFe ₂ O ₄ spinel appearing at 2θ = 36.1 ° is <ii>. The reforming catalyst in the range of 0.1 to 0.9 is excellent as a reforming catalyst for oxygen-containing hydrocarbons.

  As a method for producing an oxygen-containing hydrocarbon reforming catalyst having such an X-ray diffraction line intensity, for example, a mixture of the above-mentioned Cu-Fe type spinel (A) and (B) a solid acid is 700 to 800. The method of baking at a temperature can be mentioned.

(Reduction treatment)
In the present invention, the activity can be further improved by reducing the reforming catalyst obtained by the firing treatment as described above. The reduction treatment includes a gas phase reduction method in which treatment is performed in an air stream containing hydrogen and a wet reduction method in which treatment is performed with a reducing agent. The former reduction treatment is usually carried out at a temperature of about 150 to 500 ° C., preferably 200 to 400 ° C. for 30 minutes to 24 hours, preferably 1 to 10 hours under an air stream containing hydrogen. In addition to hydrogen gas, an inert gas such as nitrogen, helium, or argon may coexist.
As the latter wet reduction method, liquid ammonia / alcohol / Na, Birch reduction using liquid ammonia / alcohol / Li, Benkeser reduction using methylamine / Li, Zn / HCl, Al / NaOH / H ₂ O, NaH, There is a method of treating with a reducing agent such as LiAlH ₄ or a substituted product thereof, hydrosilanes, sodium borohydride or a substituted product thereof, diborane, formic acid, formalin and hydrazine. In this case, the reaction is usually performed at room temperature to 100 ° C. for about 10 minutes to 24 hours, preferably 30 minutes to 10 hours.
In addition, by flowing the reaction raw material, the catalyst is reduced during the reaction by the generated hydrogen and CO.
In the present invention, the catalyst is reduced by pre-reduction treatment or product gas, so that Cu or other elements are desorbed from the spinel structure, and the spinel structure is in a state where a part or all of the spinel structure is not retained. First, it is an important point of the present invention to use a Cu catalyst having a spinel structure.

Preferred examples of the oxygen-containing hydrocarbon to which the reforming catalyst of the present invention is applied include alcohols such as methanol and ethanol, and ethers such as dimethyl ether and methyl ethyl ether. Of these, dimethyl ether is particularly preferred.
In the method for producing hydrogen or synthesis gas of the present invention, oxygen-containing hydrocarbons such as dimethyl ether are converted into (1) steam reforming, (2) autothermal reforming, ( Hydrogen or synthesis gas is produced by 3) partial oxidation reforming or (4) carbon dioxide reforming.
Next, the case of using dimethyl ether will be described as an example for each reforming method.

[Steam reforming]
When the reforming catalyst of the present invention is used, the steam reforming of dimethyl ether is considered to proceed according to the following reaction formula.
CH ₃ OCH ₃ + H ₂ O → 2CH ₃ OH (1)
2CH ₃ OH + 2H ₂ O → 2CO ₂ + 6H ₂ (2)
2CO ₂ + 2H ₂ → 2CO + 2H ₂ O (3)
Therefore, when producing hydrogen, the reaction (3) is less likely to proceed.
That is, CH ₃ OCH ₃ + 3H ₂ O → 2CO ₂ + 6H ₂ (4)
The reaction conditions may be selected so that the following reaction occurs.
On the other hand, when producing synthesis gas, the reactions of (1), (2) and (3) occur, that is, CH ₃ OCH ₃ + H ₂ O → 2CO + 4H ₂ (5)
The reaction conditions may be selected so that the following reaction occurs.
When producing hydrogen, the water vapor / dimethyl ether molar ratio is theoretically 3 but is preferably about 3-6, while when producing synthesis gas, the water vapor / dimethyl ether molar ratio is theoretically 1 However, about 1-2 is preferable.
The reaction temperature is usually selected in the range of 200 to 500 ° C, preferably 250 to 450 ° C. If this temperature is 200 ° C. or higher, a decrease in the conversion rate of dimethyl ether can be suppressed, and if it is 500 ° C. or lower, thermal deterioration of the catalyst can be prevented. GHSV (gas hourly space velocity), 50～5,000H ^-1 with diethyl ether basis, more preferably in the range of 100~1600h ^-1. The GHSV is able to inhibit the production efficiency is reduced if the 50h ^-1 or more, it is possible conversion of dimethyl ether as long 5,000H ^-1 or less can be suppressed. The reaction pressure is usually about normal pressure to 1 MPa. By making this pressure into such a range, it can prevent that the conversion rate of a dimethyl ether falls.

[Self-thermal reforming]
In the autothermal reforming reaction, the oxidation reaction of dimethyl ether and the reaction of water vapor occur in the same reactor or in a continuous reactor. In this case, although the reaction conditions are slightly different between hydrogen production and synthesis gas production, in general, the oxygen / dimethyl ether molar ratio is preferably selected in the range of 0.1 to 1, and the water vapor / dimethyl ether molar ratio is Preferably it is selected in the range of 0.5-3. If the oxygen / dimethyl ether molar ratio is 0.1 or more, the reaction heat can be sufficiently supplied by exotherm, while if it is 1 or less, complete oxidation can be prevented from lowering the hydrogen concentration. . Further, when the water vapor / dimethyl ether molar ratio is 0.5 or more, a decrease in hydrogen concentration can be suppressed, and when it is 3 or less, supply of heat can be prevented from being insufficient.
The reaction temperature is usually selected in the range of 200 to 800 ° C, preferably 250 to 500 ° C. The GHSV and the reaction pressure are the same as in the case of the steam reforming.

[Partial oxidation reforming]
In the partial oxidation reforming reaction, a partial oxidation reaction of dimethyl ether occurs, and reaction conditions differ slightly between hydrogen production and synthesis gas production. In general, the oxygen / dimethyl ether molar ratio is preferably 0.3 to 1. 5 is selected. If the oxygen / dimethyl ether molar ratio is 0.3 or more, the conversion rate of dimethyl ether is sufficiently high. On the other hand, if the oxygen / dimethyl ether molar ratio is 1.5 or less, complete oxidation occurs and the hydrogen concentration can be prevented from decreasing. The reaction temperature is usually selected in the range of 200 to 900 ° C, preferably 250 to 600 ° C. The GHSV and the reaction pressure are the same as in the case of the steam reforming.

[CO2 reforming]
In the carbon dioxide reforming reaction, a reaction between dimethyl ether and carbon dioxide occurs, and in the hydrogen production and synthesis gas production, although reaction conditions are slightly different, in general, the CO ₂ / dimethyl ether molar ratio is preferably 0.8 to 2, more preferably in the range of 0.9 to 1.5. If the CO ₂ / dimethyl ether molar ratio is 0.8 or more, the conversion rate of dimethyl ether is sufficiently high, while if it is 2 or less, a large amount of CO ₂ remains in the product and the hydrogen partial pressure is reduced. Can be prevented. In this reaction, water vapor can be introduced, and the hydrogen concentration can be increased by this introduction. The reaction temperature, GHSV and reaction pressure are the same as in the case of the steam reforming.

[Fuel cell system]
A fuel cell system of the present invention is a fuel cell system comprising a reformer provided with the above-described reforming catalyst, and a fuel cell using hydrogen produced by the reformer as fuel, This will be described with reference to FIG. FIG. 1 is a flowchart of an example of the fuel cell system of the present invention.
The fuel (oxygen-containing hydrocarbon) in the fuel tank 21 is introduced into the desulfurizer 23 (not shown in FIG. 1, but is introduced via a pump when the oxygen-containing hydrocarbon is liquid). Usually, sulfur is not included when dimethyl ether or methanol suitable as an oxygen-containing hydrocarbon is used, but a desulfurizer is effective when a sulfur-containing compound is included as an odorant or the like. The desulfurizer 23 can be filled with, for example, activated carbon, zeolite, or a metal-based adsorbent. The fuel desulfurized by the desulfurizer 23 is mixed with water from the water tank via the water pump 24, introduced into the vaporizer 1, vaporized, and sent to the reformer 31. The reformer 31 is filled with the aforementioned reforming catalyst, and hydrogen is produced from the fuel mixture (oxygen-containing hydrocarbon and steam) fed into the reformer 31 by the aforementioned steam reforming reaction.

  The hydrogen produced in this way is reduced through the CO converter 32 and the CO selective oxidizer 33 to such an extent that the CO concentration does not affect the characteristics of the fuel cell. Examples of catalysts used in these reactors include iron-chromium-based, copper-zinc-based and noble metal-based catalysts in the CO converter 32, and ruthenium-based, platinum-based catalysts or Those mixed catalysts are used. When the CO concentration in the hydrogen produced by the reforming reaction is low, the CO converter 32 may not be attached.

The fuel cell 34 is an example of a polymer electrolyte fuel cell including a polymer electrolyte 34C between a negative electrode 34A and a positive electrode 34B. The hydrogen-rich gas obtained by the above method is introduced into the negative electrode side, and the air sent from the air blower 35 is introduced into the positive electrode side after performing appropriate humidification treatment if necessary (humidifier not shown). Is done.
At this time, a reaction in which hydrogen gas becomes protons and emits electrons proceeds on the negative electrode side, and a reaction in which oxygen gas obtains electrons and protons to become water proceeds on the positive electrode side, and a direct current is generated between both electrodes 34A and 34B. To do. In that case, platinum black or a Pt catalyst supported on activated carbon or a Pt—Ru alloy catalyst is used for the negative electrode, and platinum black or a Pt catalyst supported on activated carbon is used for the positive electrode.

  The surplus hydrogen can be used as fuel by connecting the burner 31A of the reformer 31 to the negative electrode 34A side. In addition, an air / water separator 36 is connected to the positive electrode 34B side, water and exhaust gas generated by the combination of oxygen and hydrogen in the air supplied to the positive electrode 34B side are separated, and water is used to generate water vapor. can do. Since heat is generated in the fuel cell 34 with power generation, an exhaust heat recovery device 37 can be attached to recover the heat for effective use. The exhaust heat recovery device 37 is attached to the fuel cell 34 to deprive the heat generated during the reaction, a heat exchanger 37A, a heat exchanger 37B for exchanging the heat deprived by the heat exchanger 37A with water, 37C and a heat pump 37D that circulates the refrigerant to the heat exchangers 37A and 37B and the cooler 37C, and the hot water obtained in the heat exchanger 37B can be effectively used in other facilities.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Preparation Example 1 CuFe ₂ O ₄ Spinel Oxide 24.184 g of Copper Nitrate (manufactured by Wako Pure Chemical Industries, Ltd., 99.9% Cu (NO ₃ ) ₂ .3H ₂ O) and iron nitrate (Wako Pure Chemical Industries, Ltd.) 80.881 g of 99.9% Fe (NO ₃ ) ₃ .9H ₂ O) manufactured by Co., Ltd. was added and dissolved in distilled water to make 300 ml. It was warmed to 60 ° C. and stirred for 2 hours.
Next, 92.926 g of citric acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., 99.5% C ₆ H ₈ O ₇ .3H ₂ O) was added to this solution, and the mixture was further stirred at 60 ° C. for 1 hour. The temperature was raised to 90 ° C. to evaporate the water.
The nitrate radical and citric acid of the gel thus produced were decomposed in air at 140 to 200 ° C. to obtain fine oxide powder, and then fired in air at 900 ° C. for 10 hours to obtain CuFe ₂ O _4. A spinel oxide was obtained.

Preparation Example 2 CuMn ₂ O ₄ Spinel Type Oxide 24.184 g of copper nitrate (manufactured by Wako Pure Chemical Industries, 99.9% Cu (NO ₃ ) ₂ .3H ₂ O) and manganese nitrate (manufactured by Aldrich, 58.588 g of 98% Mn (NO ₃ ) ₂ · 6H ₂ O) was added and dissolved in distilled water to make 300 ml. It was warmed to 60 ° C. and stirred for 2 hours.
Next, 92.926 g of citric acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., 99.5% C ₆ H ₈ O ₇ .3H ₂ O) was added to this solution, and the mixture was further stirred at 60 ° C. for 1 hour. The temperature was raised to 90 ° C. to evaporate the water.
The nitrate nitrate and citric acid of the gel thus produced were decomposed in air at 140 to 200 ° C. to obtain fine oxide powder, and then fired in air at 900 ° C. for 10 hours to obtain CuMn ₂ O _4. A spinel oxide was obtained.

Preparation Example 3 CuFe _1.5 Mn _0.5 O ₄ Spinel Type Oxide 24.184 g of Copper Nitrate (99.9% Cu (NO ₃ ) ₂ .3H ₂ O, Wako Pure Chemical Industries, Ltd.) and Iron Nitrate (Wako Pure) Yakugyo Co., Ltd., 99.9% Fe (NO ₃ ) ₃ · 9H ₂ O) 60.661 g and manganese nitrate (Aldrich, 98% Mn (NO ₃ ) ₂ · 6H ₂ O) 14.647 g Dissolve in distilled water to make 300 ml. It was warmed to 60 ° C. and stirred for 2 hours.
Next, 92.926 g of citric acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., 99.5% C ₆ H ₈ O ₇ .3H ₂ O) was added to this solution, and the mixture was further stirred at 60 ° C. for 1 hour. The temperature was raised to 90 ° C. to evaporate the water.
The nitrate nitrate and citric acid of the gel thus produced were decomposed in air at 140 to 200 ° C. to obtain fine oxide powder, and then calcined in air at 900 ° C. for 10 hours. CuFe _1.5 Mn _{A 0.5} O ₄ spinel type oxide was obtained.

Example 1
10 g of the CuFe ₂ O ₄ spinel oxide obtained in Preparation Example 1 and 5 g of γ-alumina (“AKP-G015” manufactured by Sumitomo Chemical Co., Ltd.) calcined at 700 ° C. for 30 minutes were mixed in a mortar. A reforming catalyst was prepared by reducing it at 600 ° C. for 3 hours in nitrogen gas containing 10% by volume of hydrogen, and then calcining it at 350 ° C. for 10 hours in an air atmosphere.
Example 2
In Example 1, a reforming catalyst was prepared in the same manner as in Example 1 except that the calcination conditions in the air atmosphere were changed to 500 ° C. and 10 hours.
Example 3
In Example 1, a reforming catalyst was prepared in the same manner as in Example 1 except that the firing conditions in the air atmosphere were changed to 700 ° C. and 10 hours.
Example 4
A reforming catalyst was prepared in the same manner as in Example 1 except that the calcination conditions in the air atmosphere were changed to 800 ° C. and 10 hours in Example 1.

Example 5
In Example 1, a reforming catalyst was prepared in the same manner as in Example 1 except that the reduction conditions in nitrogen gas containing 10% by volume of hydrogen were changed to 350 ° C. for 3 hours.
Example 6
In Example 2, a reforming catalyst was prepared in the same manner as in Example 2 except that the reduction conditions in nitrogen gas containing 10% by volume of hydrogen were changed to 350 ° C. for 3 hours.
Example 7
In Example 3, a reforming catalyst was prepared in the same manner as in Example 3 except that the reducing conditions in nitrogen gas containing 10% by volume of hydrogen were changed to 350 ° C. for 3 hours.

Example 8
After pressure-molding the catalyst obtained in Example 7 to 10 to 18.5 mesh, a predetermined amount is charged into a reactor and reduced at 350 ° C. for 3 hours in nitrogen gas containing 10% by volume of hydrogen. Thus, a reforming catalyst was prepared.
Example 9
In Example 4, a reforming catalyst was prepared in the same manner as in Example 4 except that the reducing conditions in nitrogen gas containing 10% by volume of hydrogen were changed to 350 ° C. for 3 hours.

Example 10
10 g of the CuFe ₂ O ₄ spinel oxide obtained in Preparation Example 1 and 5 g of γ-alumina (“AKP-G015” manufactured by Sumitomo Chemical Co., Ltd.) calcined at 700 ° C. for 30 minutes were mixed in a mortar. Thereafter, a reforming catalyst (SCFAc35, calcining temperature: 350 ° C.) was prepared by calcining at 350 ° C. for 10 hours in an air atmosphere. Using the obtained catalyst, X-ray diffraction was performed under the following measurement conditions. The chart is shown in FIG.
Apparatus: Rigaku-RINT-2200, radiation source: CuKα ray, 40 kV, 40 mA,
Step: 0.02 °, scan speed: 1 ° / min Note that in FIG. 2, SCAFc100 was used in the same manner as in Example 10 except that the firing condition was changed to 1000 ° C. in an air atmosphere. Although it is an X-ray diffraction pattern of the catalyst, as a result of X-ray diffraction, it was judged that the performance was worse than that of SCFAc90, and DME reforming reactivity was not evaluated.
Example 11
In Example 10, a reforming catalyst (SCFAc50, calcination temperature: 500 ° C.) was prepared in the same manner as in Example 10 except that the calcination conditions in the air atmosphere were changed to 500 ° C. and 10 hours. Using the obtained catalyst, X-ray diffraction was performed under the measurement conditions shown in Example 10. The chart is shown in FIG.
Example 12
In Example 10, a reforming catalyst (SCFAc 70, calcination temperature 700 ° C.) was prepared in the same manner as in Example 10 except that the calcination conditions in the air atmosphere were changed to 700 ° C. and 10 hours.
Using the obtained catalyst, X-ray diffraction was performed under the measurement conditions shown in Example 10. The chart is shown in FIG. As a result, the ratio between the diffraction line intensity appearing at 2θ = 33.2 ° and the diffraction line intensity which is the strongest line of CuFeO ₄ spinel appearing at 2θ = 36.1 ° was 0.23.
Example 13
After the catalyst obtained in Example 12 was pressure-molded to 10 to 18.5 mesh, a predetermined amount was charged into the reactor and reduced at 350 ° C. for 3 hours in nitrogen gas containing 10% by volume of hydrogen. Thus, a reforming catalyst was prepared.
Example 14
In Example 10, a reforming catalyst (SCFAc80, calcination temperature 800 ° C.) was prepared in the same manner as in Example 10 except that the calcination conditions in the air atmosphere were changed to 800 ° C. and 10 hours.
Using the obtained catalyst, X-ray diffraction was performed under the measurement conditions shown in Example 10. The chart is shown in FIG. As a result, the ratio of the diffraction line intensity appearing at 2θ = 33.2 ° to the diffraction line intensity which is the strongest line of CuFeO ₄ spinel appearing at 2θ = 36.1 ° was 0.68.

Example 15
In Example 10, a reforming catalyst was prepared in the same manner as in Example 10 except that the firing conditions in the air atmosphere were changed to 700 ° C. for 1 hour.
Example 16
In Example 10, a reforming catalyst was prepared in the same manner as in Example 10 except that the firing conditions in the air atmosphere were changed to 700 ° C. for 5 hours.
Example 17
In Example 10, a reforming catalyst was prepared in the same manner as in Example 10 except that the firing conditions in the air atmosphere were changed to 700 ° C. for 20 hours.

Comparative Example 1
10 g of the CuFe ₂ O ₄ spinel oxide obtained in Preparation Example 1 and 5 g of γ-alumina (“AKP-G015” manufactured by Sumitomo Chemical Co., Ltd.) calcined at 700 ° C. for 30 minutes were mixed in a mortar. A reforming catalyst was prepared by reducing it in nitrogen gas containing 10% by volume of hydrogen at 600 ° C. for 3 hours.
Comparative Example 2
In Example 1, a reforming catalyst was prepared in the same manner as in Example 1 except that the firing conditions in the air atmosphere were changed to 900 ° C. and 10 hours.
Comparative Example 3
In Comparative Example 1, a reforming catalyst was prepared in the same manner as in Comparative Example 1, except that the reduction conditions in nitrogen gas containing 10% by volume of hydrogen were changed to 350 ° C. for 3 hours.

Comparative Example 4
In Comparative Example 2, a reforming catalyst was prepared in the same manner as in Comparative Example 2, except that the reducing conditions in nitrogen gas containing 10% by volume of hydrogen were changed to 350 ° C. for 3 hours.
Comparative Example 5
By mixing 10 g of the CuFe ₂ O ₄ spinel oxide obtained in Preparation Example 1 and 5 g of γ-alumina (“AKP-G015” manufactured by Sumitomo Chemical Co., Ltd.), which was calcined at 700 ° C. for 30 minutes, in a mortar Catalyst (SCFA) was prepared. Using the obtained catalyst, X-ray diffraction was performed under the measurement conditions shown in Example 10. The chart is shown in FIG.
Comparative Example 6
In Example 10, a reforming catalyst (SCFAc90, calcination temperature 900 ° C.) was prepared in the same manner as in Example 10 except that the calcination conditions in the air atmosphere were changed to 900 ° C. and 10 hours. Using the obtained catalyst, X-ray diffraction was performed under the measurement conditions shown in Example 10. The chart is shown in FIG.

Example 18
10 g of the CuMn ₂ O ₄ spinel type oxide obtained in Preparation Example 2 and 5 g of γ-alumina (“AKP-G015” manufactured by Sumitomo Chemical Co., Ltd.) calcined at 700 ° C. for 30 minutes were mixed in a mortar. Thereafter, a reforming catalyst was prepared by calcining at 700 ° C. for 10 hours in an air atmosphere.

Comparative Example 7
By mixing 10 g of the CuMn ₂ O ₄ spinel oxide obtained in Preparation Example 2 and 5 g of γ-alumina (“AKP-G015” manufactured by Sumitomo Chemical Co., Ltd.), which was baked at 700 ° C. for 30 minutes, in a mortar A catalyst was prepared.

Example 19
10 g of CuFe _1.5 Mn _0.5 O ₄ spinel type oxide obtained in Preparation Example 3 and 5 g of γ-alumina (“AKP-G015” manufactured by Sumitomo Chemical Co., Ltd.) calcined at 700 ° C. for 30 minutes were mixed in a mortar. Thereafter, a reforming catalyst was prepared by calcining at 700 ° C. for 10 hours in an air atmosphere.

Comparative Example 8
By mixing 10 g of CuFe _1.5 Mn _0.5 O ₄ spinel type oxide obtained in Preparation Example 3 and 5 g of γ-alumina (“AKP-G015” manufactured by Sumitomo Chemical Co., Ltd.), which was baked at 700 ° C. for 30 minutes, in a mortar, A reforming catalyst was prepared.
Comparative Example 9
10 g of CuFe ₂ O ₄ spinel oxide obtained in Preparation Example 1 calcined at 700 ° C. for 10 hours in air atmosphere and γ-alumina calcined at 700 ° C. for 10 hours (“AKP-” manufactured by Sumitomo Chemical Co., Ltd.) A reforming catalyst was prepared by mixing 5 g of G015 ”) in a mortar.

Reference example 1
A reforming catalyst was prepared by mixing 10 g of CuZnAl (“MDC-3” manufactured by Sued Chemie) and 5 g of γ-alumina (“AKP-G015” manufactured by Sumitomo Chemical Co., Ltd.) calcined at 700 ° C. for 30 minutes in a mortar. .
Reference example 2
10 g of CuZnAl (“MDC-3” manufactured by Sued Chemie) and 5 g of γ-alumina (“AKP-G015” manufactured by Sumitomo Chemical Co., Ltd.) fired at 700 ° C. for 30 minutes were mixed in a mortar. Thereafter, a reforming catalyst was prepared by calcining at 700 ° C. for 10 hours in an air atmosphere.

Test Examples For the reforming catalysts obtained in Examples 1 to 19, Comparative Examples 1 to 9, and Reference Examples 1 and 2, performance evaluation tests as shown below were performed. The results are shown in Table 1.
<Pretreatment conditions>
-A catalyst molded to 10 to 18.5 mesh was charged into the reactor.
(As described in Examples 8 and 13, hydrogen reduction was performed in the reactor before the reaction)
<Reaction conditions: DME steam reforming reaction>
GHSV = 9100 h ⁻¹ (DME + H ₂ O standard) (1517 h ^{−1 based on} DME standard), steam / carbon molar ratio = 2.5, reaction temperature = 375 ° C., reaction time = 50 hours, DME conversion (%) = (A / B) × 100,
A: Outlet CO molar concentration + Outlet CO ₂ molar concentration + Outlet CH ₄ molar concentration B: Outlet CO molar concentration + Outlet CO ₂ molar concentration + Outlet CH ₄ molar concentration + Outlet DME molar concentration x 2
Deterioration rate (%) = [(C−D) / C] × 100
C: DME conversion rate 7 hours after the start of the reaction D: DME conversion rate 50 hours after the start of the reaction (however, Comparative Example 8 and Example 19 use the data after 35 hours as D)

From Table 1, it can be seen that:
-Comparison between Comparative Example 1 and Examples 1-4:
By including a firing step at 350 ° C. and 500 ° C. (Examples 1 and 2), the deterioration is greatly suppressed as compared with unfired (Comparative Example 1), and the activity after 50 hours is higher in the Example.
By including a firing step at 700 ° C. and 800 ° C. (Examples 3 and 4), the initial activity and durability were greatly improved as compared with those without firing (Comparative Example 1). In addition, the initial activity is remarkably low in firing at 900 ° C. (Comparative Example 2).
Comparison between Comparative Examples 3 and 4 and Examples 5-9:
By putting a baking step at 350 ° C. (Example 5), the initial performance is slightly reduced compared to that of unfired (Comparative Example 3), but the activity deterioration is suppressed, and the activity after 50 hours is higher in Example 5. ing. By including a firing step at 500 ° C., 700 ° C., and 800 ° C. (Examples 6, 7, 8, and 9), the initial activity and durability were greatly improved as compared with those without firing (Comparative Example 3). Further, the initial activity is remarkably low in the firing at 900 ° C. (Comparative Example 4).
Moreover, the influence of the presence or absence of reduction immediately before the reaction is small (comparison between Examples 7 and 8).

Comparison between Comparative Examples 5 and 6 and Examples 10-14:
By introducing a firing step at 350 ° C. and 500 ° C. (Examples 10 and 11), the deterioration in activity is suppressed even when the initial performance is almost the same as that in the unfired (Comparative Example 5), and the activity after 50 hours is high. . By including a firing step at 700 ° C. and 800 ° C. (Examples 12, 13, and 14), the initial activity and durability were greatly improved as compared with those without firing (Comparative Example 5). In addition, the initial activity is remarkably low in firing at 900 ° C. (Comparative Example 6).
Moreover, the influence of the presence or absence of the reduction just before reaction is not large (comparison of Examples 12 and 13).
Comparison between Comparative Example 5 and Examples 12, 15, 16, and 17 (comparison of baking time at 700 ° C.):
The baking time at 700 ° C. is effective even if it is 1 hour (Example 15), but it is more effective if it is 5 hours or longer (Examples 16, 12, and 17).
Comparison between Comparative Example 7 and Example 18:
Also in CuMn spinel, the initial activity improvement effect was recognized by baking at 700 ° C. after mixing with alumina.
Comparison between Comparative Example 8 and Example 19:
Also in the CuFeMn spinel, the effect of improving the initial activity and durability was confirmed by firing at 700 ° C. after mixing with alumina.
-Comparison between Comparative Example 9 and Example 12:
Even if CuFe spinel and alumina are each fired at 700 ° C. and then mixed (Comparative Example 9), the fired effect after mixing as in Example 12 does not appear. In addition, the initial activity is slightly lower than that in the case of mixing each without firing and not firing after mixing (Comparative Example 5).
-Comparison of Reference Examples 1 and 2 Even when CuZnAl (non-spinel) and alumina are mixed and fired at 700 ° C., there is an effect of improving initial activity, but the absolute value of activity is low.

  The oxygen-containing hydrocarbon reforming catalyst of the present invention can efficiently produce hydrogen or synthesis gas from an oxygen-containing hydrocarbon at a high conversion rate, and can be applied to a highly efficient fuel cell system.

It is a flowchart of an example of the fuel cell system of this invention. It is an X-ray diffraction pattern of the reforming catalyst obtained in Examples 10-12 and 14 and Comparative Examples 5 and 6. SCAFc100 is an X-ray diffraction pattern of the reforming catalyst obtained in the same manner as in Example 10 except that the firing condition is changed to 1000 ° C. in an air atmosphere.

Explanation of symbols

1: Vaporizer 11: Water supply pipe 12: Fuel introduction pipe 15: Connection pipe 21: Fuel tank 23: Desulfurizer 24: Water pump 31: Reformer 31A: Reformer burner 32: CO converter 33: CO Selective oxidizer 34: Fuel cell 34A: Fuel cell negative electrode 34B: Fuel cell positive electrode 34C: Fuel cell polymer electrolyte 35: Air blower 36: Air / water separator 37: Waste heat recovery device 37A: Heat exchanger 37B: Heat exchanger 37C: Cooler 37D: Refrigerant circulation pump

Claims (16)

  (A) An oxygen-containing composition prepared by baking a mixture of a metal oxide containing copper and a spinel structure and (B) a solid acid at 300 to 850 ° C. in an oxygen-containing gas atmosphere. Hydrocarbon reforming catalyst.   The oxygen-containing hydrocarbon modification according to claim 1, wherein the metal oxide of component (A) is at least one selected from the group consisting of Cu-Fe type spinel, Cu-Mn type spinel and Cu-Mn-Fe type spinel. Catalyst for quality.   The oxygen-containing hydrocarbon reforming catalyst according to claim 2, wherein the metal oxide of component (A) is a Cu-Fe type spinel obtained by firing at a temperature of 500 to 1000C. The reforming catalyst containing at least a Cu-Fe type spinel and a solid acid, which has diffraction lines at least at the following three positions in the measurement of X-ray diffraction incident with CuKα rays. Catalyst for reforming oxygen-containing hydrocarbons.
2θ = 24.1 °, 33.2 °, 49.6 ° The ratio between the diffraction line intensity appearing at 2θ = 33.2 ° and the diffraction line intensity which is the strongest line of CuFe ₂ O ₄ spinel appearing at 2θ = 36.1 ° is in the range of 0.1 to 0.9. The oxygen-containing hydrocarbon reforming catalyst according to claim 4.   The catalyst for reforming an oxygen-containing hydrocarbon according to any one of claims 1 to 5, wherein the metal oxide of the component (A) contains at least one element selected from nickel, cobalt, and a platinum group element.   (B) The solid acid of a component is an alumina, The reforming catalyst of the oxygen containing hydrocarbon in any one of Claims 1-6.   The oxygen-containing hydrocarbon reforming catalyst according to claim 7, wherein the solid acid of component (B) is γ-alumina obtained by firing at a temperature of 300 to 750 ° C.   The oxygen-containing hydrocarbon reforming catalyst according to any one of claims 1 to 8, wherein the oxygen-containing gas atmosphere in the firing treatment step is an air atmosphere.   An oxygen-containing hydrocarbon reforming catalyst obtained by reducing the reforming catalyst according to any one of claims 1 to 9.   The oxygen-containing hydrocarbon reforming catalyst according to any one of claims 1 to 10, wherein the oxygen-containing hydrocarbon is dimethyl ether.   A method for producing hydrogen or synthesis gas, wherein the reforming catalyst according to any one of claims 1 to 11 is used to steam reform an oxygen-containing hydrocarbon.   A method for producing hydrogen or synthesis gas, wherein the reforming catalyst according to any one of claims 1 to 11 is used to autothermally reform an oxygen-containing hydrocarbon.   A method for producing hydrogen or synthesis gas, wherein the reforming catalyst according to any one of claims 1 to 11 is used for partial oxidation reforming of an oxygen-containing hydrocarbon.   A method for producing hydrogen or synthesis gas, comprising reforming an oxygen-containing hydrocarbon with carbon dioxide using the reforming catalyst according to claim 1.   A fuel cell system comprising: a reformer comprising the reforming catalyst according to claim 1; and a fuel cell using hydrogen produced by the reformer as fuel.

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