Catalyst for reforming oxygen-containing hydrocarbon, and hydrogen or synthetic gas production method and fuel cell system using the catalyst
|Date of filing||平成20年4月8日(2008.4.8)|
|International application number||JP2008056952|
|International publication number||WO2008126844|
|Date of international filing||平成20年4月8日(2008.4.8)|
|Date of international publication||平成20年10月23日(2008.10.23)|
|Title||Catalyst for reforming oxygen-containing hydrocarbon, and hydrogen or synthetic gas production method and fuel cell system using the catalyst|
The object is to improve the catalytic activity of reforming an oxygen-containing hydrocarbon of a cupper-containing metal oxide having a spinel structure, and thus to provide a reforming catalyst having an improved reforming activity and improved durability and a hydrogen or synthetic gas production method and a fuel cell system both using the catalyst. Specifically disclosed are: a catalyst for reforming an oxygen-containing hydrocarbon, which is prepared by the step of firing a mixture of (A) a copper-containing metal oxide having a spinel structure with (B) a solid acid at 300 to 850.deg.C in an atmosphere containing at least oxygen; a method for producing hydrogen or a synthetic gas, which comprises subjecting an oxygen-containing hydrocarbon to any one of various reforming treatments using the catalyst; and a fuel cell system which comprises a reformer having the catalyst and a fuel cell utilizing hydrogen produced by the reformer as a fuel.
COPYRIGHT KIPO & WIPO 2010
|Outline of related art and contending technology||
The synthesis gas and carbon monoxide and hydrogen, methanol synthesis, oxo synthesis, fischer-Tropsch synthesis may be used as a raw material gas or the like as well as, or as a raw material of various chemicals to the ammonia synthesis is widely used in the present invention.
The synthesis gas from gasification of coal by conventional methods, such as natural gas or hydrocarbons as a raw material of the water vapor produced by partial oxidation or modifications such as modifications that have been present. However, in the method of gasification of coal, complex and expensive coal gasification of (furnace) is required as well, such as the scale of the plant has been a serious problem. In addition, it is preferable that the water vapor reforming of the hydrocarbons, since a large endothermic reaction, the progress of the reaction at a temperature of about 1200°C to about 700 and requires a high temperature, special reforming furnace is required as well as, the catalyst used or the like which require high heat resistance have been problems. In addition, the partial oxidation reforming of hydrocarbons because it requires a high temperature, and required a special partial oxidation furnace, a large amount of soot is produced also by reacting a thus, the processing leads to a problem that the catalyst tends to deteriorate as well as the problem of the like.
Thus, in order to solve these problems, recently such as dimethyl ether (DME) used as a raw material containing hydrocarbon and oxygen, and various modifications to this embodiment is the production of synthesis gas have been attempted. On the other hand, in recent years environmental concern has drawn much attention and been enthusiastically from technique, is described as one of the fuel cell is attracting attention enthusiastically nerve and.
A fuel cell by electrochemically reacting hydrogen with oxygen to thereby convert chemical energy into electrical energy and, efficiency of energy use is high and has a feature that, civil, industrial or automotive applications and the like are actively performed in practical use as a research and others. In addition, a power generation efficiency is high and, in the form of a solid oxide fuel cell having a high degree of attention in recent years in which carbon monoxide and hydrogen can be used in the present invention. The fuel cell hydrogen won (solid oxide fuel cell in the, hydrogen and carbon monoxide won) such as, methanol, liquefied natural gas mainly consists of methane, natural gas composed mainly of a city gas, natural gas as a raw material for liquid fuel synthesis, petroleum naphtha and kerosene also hydrocarbon and many studies are being made on the presence of hydrogen.
These petroleum hydrocarbon used for the production of hydrogen, generally in the presence of a catalyst for hydrocarbon steam reforming or autothermal reforming, partial oxidation reforming treatment and the like but it is, in this case causing a problem as described above. Thus, even in the production of hydrogen, oxygen containing hydrocarbons such as dimethyl ether as raw materials for a variety of methods have been attempted. Dimethyl ether and other oxygen containing hydrocarbon as a starting material, and various modifications to this embodiment, the production of synthesis gas or hydrogen to be used for the catalyst, various ones have hitherto been disclosed, inter alia Cu catalyst under an oxygen containing hydrocarbon as a technique for modifying the, for example by using a catalyst containing the oxygen containing hydrocarbon Cu carbon dioxide and hydrogen and a catalyst for production of synthesis gas from synthesis gas using the same (patent document 1 etc.) the method of manufacturing, by using a catalyst containing the oxygen containing hydrocarbon Cu hydrogen and water vapor which produces hydrogen from the catalyst and using the same (patent document 2 etc.) the method for producing hydrogen, comprising a solid acid supported metal Cu consisting in oxygen containing hydrocarbons (such as disclosed in patent document 3 and 4) reforming catalyst, containing material with a solid acidic substance Cu consisting of a mixture, containing water vapor and oxygen for producing hydrogen from hydrocarbons and using the same catalyst (patent document 5 etc.) the method for producing hydrogen, a mixture with a solid acidic substance Cu containing substance from the group consisting of, oxygen containing hydrocarbons and water vapor between the catalyst and the production of synthesis gas from synthesis gas using the same (patent document 6 etc.) the method of manufacturing and the like are disclosed.
However, patent documents 1 to 6 are available in the art of catalyst activity that all Cu was insufficient, therefore the reaction activity of increasing the reaction temperature in order to improve the deterioration of the catalyst faces the problem that it cannot.
In order to solve the above problems, comprises copper and a metal oxide having a spinel structure, or a solid acidic substance containing a larger amount of oxygen containing hydrocarbon reforming catalyst which has been proposed (patent document 7 etc.) however, there is still a sufficient activity cannot be. Patent document 7 in which, a solid acidic substance such as alumina, silica alumina, zeolite and the like are listed, it is preferable that alumina is also described. In addition, in Patent document 8, a methanol decomposition catalyst Cu field Zn field Al mixed with catalyst ZSM field 5 but, compared to the catalyst of Patent document 7 which is a cause of deterioration of the catalyst by coke generation since it is easier for the plaque of the problem.
On the other hand, in Patent document 9, as an example of a reforming catalyst II, supported on alumina was then CuMn, 500 to 1000°C across (cave) plasticizer at a temperature in the calcine has been disclosed, in the technology, supported on alumina spinel and before, after firing at high temperature to produce a spinel and thus, and a spinel structure by mixing of alumina calcining essentially different from the technology of the present invention.
[Patent document 1] Japanese Unexamined Patent Publication (hei) No. 10-174869
[Patent document 2] Japanese Unexamined Patent Publication (hei) No. 10-174871
[Patent document 3] Japanese Unexamined Patent Application Publication No. 2001-96159
[Patent document 4] Japanese Unexamined Patent Application Publication No. 2001-96160
[Patent document 5] Japanese Unexamined Patent Application Publication No. 2003-10684
[Patent document 6] Japanese Unexamined Patent Application Publication No. 2003-33656
[Patent document 7] Japanese Unexamined Patent Application Publication No. 2005-342543
[Patent document 8] Japanese Unexamined Patent Publication (hei) No. 9-118501
[Patent document 9] publication (page 8, 9) No. WO2004/103555
|Scope of claims||
1. (A) Comprises copper and a metal oxide having a spinel structure and a mixture of a solid acid (B), at least 700 to 800°C in an atmosphere of oxygen containing gas is produced through the calcination in the oxygen containing hydrocarbon reforming catalyst consisting of.
2. Method according to claim 1, metal oxides (A) component of the spinel type Cu - Fe, spinel and Cu - Mn spinel type selected from among Cu - Mn - Fe type 1 which is at least one of an oxygen containing hydrocarbon reforming catalyst.
3. Method according to claim 2, a metal oxide component of from 500 (A) at a temperature of 1000°C obtained by firing a spinel type oxygen Cu field Fe hydrocarbon containing a reforming catalyst.
4. Method according to claim 2, at least one solid acid type Cu - Fe spinel as a reforming catalyst, an incident X CuK α line in the diffraction measurement, of less than or equal to 3 X the position of the at least two of the oxygen containing hydrocarbons with a reforming catalyst.
2 θ=24.1 °, 33.2 °, 49.6 °
5. Method according to claim 4, as shown in the intensity of the 2 θ=33.2 °, 2 θ=36.1 ° to CuFe appearing2O4 choi, gang-sun diffraction intensity of the spinel is 0.1 to 0 ratio with the. 9 An oxygen containing hydrocarbon is in the range of the reforming catalyst.
6. Method according to claim 1, metal oxides (A) component of nickel, cobalt and platinum group elements of the at least one element 1 selected from the group comprising a hydrocarbon reforming catalyst of the oxygen.
7. Method according to claim 1, alumina (B) component of the solid acid is an oxygen containing hydrocarbon reforming catalyst.
8. Method according to claim 7, the solid acid component is from 300 (B) 750°C of γ - alumina obtained by baking at a temperature of the hydrocarbon reforming catalyst contains oxygen.
9. Method according to claim 1, fired in an air atmosphere in an oxygen containing gas atmosphere in the processing of a hydrocarbon containing a reforming catalyst is oxygen.
10. 1 Apparatus as described in the first reforming catalyst to a reduction treatment of an oxygen containing hydrocarbon reforming catalyst.
11. Method according to claim 1, oxygen containing hydrocarbons and oxygen containing hydrocarbon is dimethyl ether reforming catalyst.
12. A method according to any one of claims 1 to 11 described by using a catalyst for reforming, steam reforming of a hydrocarbon containing oxygen is a method of producing hydrogen or synthesis gas.
13. 11 Apparatus according to any one of the first 1 based on the reforming catalyst to be used, oxygen containing hydrocarbons to heat the magnetic modifying method for the production of hydrogen or synthesis gas.
14. Agent according to any one of claims 1 to 11 described by using a catalyst for reforming, partial oxidation reforming of the oxygen containing hydrocarbons to the production method of hydrogen or synthesis gas.
15. 1 Method according to any one of the first base material 11 is using a reforming catalyst, the reforming of the hydrocarbon to carbon dioxide and oxygen in the production method of hydrogen or synthesis gas.
16. 1 Method according to any one of the first base material 11 is provided with a reformer reforming catalyst, the hydrogen produced by the reformer fuel to a fuel cell having fuel cell system.
|IPC(International Patent Classification)|
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