JP2000169107A - Production of hydrogen-containing gas reduced in carbon monoxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a gas reduced in carbon monoxide by bringing a reaction gas consisting essentially of hydrogen into contact at a specific temp. with a catalyst prepared by carrying ruthenium and an alkali metal and/or an alkaline earth metal on a fire resisting inorganic oxide carrier. SOLUTION: The fire resisting inorganic oxide carrier is desirably composed of titania and alumina in the weight ratio (titania)/(alumina) of (0.1-99.9) to (90-10). Ruthenium of 0.3-3 wt.% and the alkali metal and/or the alkaline earth metal of 0.03-3 wt.% expressed in terms of metal are carried on the carrier by an impregnation method. The selective oxidation reaction of CO is performed by bringing the reaction gas, which is formed by adding oxygen to a gas consisting essentially of hydrogen and contains CO, into contact at 60-150 deg.C with the catalyst reduced by hydrogen under hydrogen stream at 300-530 deg.C for 1-2 hr. The adding quantity of gaseous oxygen is preferably controlled to be the molar ratio oxygen/CO of 1-4 and the pressure of the reaction is preferably the normal pressure to 10 kg/cm2. The hydrogen-containing gas suitable for a H2 combustion type fuel cell is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a hydrogen gas-containing gas for use in a fuel cell or the like.
The present invention relates to a method for producing a hydrogen-containing gas with reduced carbon monoxide, which selectively oxidizes and removes carbon monoxide from a gas containing hydrogen as a main component.

[0002]

2. Description of the Related Art In recent years, power generation by a fuel cell has attracted particular attention in recent years because it has various advantages such as low pollution, low energy loss, and advantages in terms of installation location selection, expansion, operability, and the like. I have. Various types of fuel cells are known depending on the type of fuel or electrolyte, operating temperature, and the like. Among them, hydrogen is used as a reducing agent (active material) and oxygen (air or the like) is used as an oxidizing agent. The development of a hydrogen-oxygen fuel cell (low-temperature operation type fuel cell) is the most advanced, and it is expected that the hydrogen-oxygen fuel cell will spread more and more in the future.

There are various types of such hydrogen-oxygen fuel cells depending on the type of electrolyte, the type of electrodes, and the like. Representative examples thereof include a phosphoric acid type fuel cell, a KOH type fuel cell, There is a polymer electrolyte fuel cell and the like. In the case of such a fuel cell, particularly a low-temperature operation type fuel cell such as a polymer electrolyte fuel cell, platinum (a platinum catalyst) is used for an electrode. However, since the platinum used for the electrode is easily poisoned by CO, if CO is contained in the fuel at a certain level or more, the power generation performance is reduced,
There is a serious problem that power cannot be generated at all depending on the concentration.

Accordingly, pure hydrogen is preferable as a fuel for a fuel cell using such a platinum-based electrode catalyst.
From a practical point of view, various fuels which are inexpensive and have excellent storage properties or are already equipped with a public supply system [for example, methane or natural gas (LNG), propane,
Hydrogen obtained by steam reforming of petroleum gas (LPG) such as butane, various hydrocarbon-based fuels such as naphtha, kerosene and light oil, alcohol-based fuels such as methanol, city gas, and other hydrogen-producing fuels] It is common to use a contained gas, and fuel cell power generation systems incorporating such reforming equipment have been widely used. However, in such reformed gas, generally,
Because it contains CO in addition to significant concentrations of hydrogen, the CO was converted to innocuous CO ₂ and the like to the platinum-based electrode catalyst, strong development of technologies for reducing the CO concentration in the fuel of the fuel cell Nozomu It is rare. At that time, the concentration of CO is usually set to 100 p.
It is desirable to reduce the concentration to a low concentration of pm or less, preferably 10 ppm or less.

In order to solve the above-mentioned problem, as one of means for reducing the concentration of CO in the fuel gas (hydrogen-containing gas in the reformed gas) of the fuel cell, the following formula (1) is used. A technique utilizing a shift reaction (water gas shift reaction) has been proposed. CO + H ₂ O = CO ₂ + H ₂ (1) However, in the reaction using only this shift reaction, there is a limit in reducing the CO concentration due to restrictions on chemical equilibrium. In general, the CO concentration is reduced to 1% or less. It is difficult.

Therefore, as a means for reducing the CO concentration to a lower concentration, a method has been proposed in which oxygen or an oxygen-containing gas (such as air) is introduced into a fuel gas to convert CO into CO ₂ . However, in this case, since a large amount of hydrogen is present in the fuel gas, when oxidizing CO, the hydrogen is also oxidized, and the CO concentration may not be sufficiently reduced.

[0007] As a method for solving this problem,
CO or C is introduced by introducing oxygen or oxygen-containing gas into the fuel gas.
When oxidizing to O ₂ , a method using a catalyst that selectively oxidizes only CO can be considered. Conventionally, CO oxidation catalysts include Pt / alumina, Pt / SnO ₂ , Pt /
Catalyst systems such as C, Co / TiO ₂ , popcalite, and Pd / alumina are known, but these catalysts do not have sufficient resistance to humidity, and have a low and narrow reaction temperature range.
Due to low selectivity for oxidation of O, in order to reduce a small amount of CO in a large amount of hydrogen such as fuel gas of a fuel cell to a low concentration of 10 ppm or less, a large amount of hydrogen is simultaneously oxidized. Must be sacrificed.

Japanese Patent Application Laid-Open No. Hei 5-201702 discloses a method for producing a CO-free hydrogen-containing gas for selectively removing CO from the hydrogen-enriched CO-containing gas and supplying the CO to an automotive fuel cell system. I have. A catalyst in which Rh or Ru is supported on an alumina carrier is used as a catalyst, but has a problem that it can be applied only to a low CO concentration.

Japanese Patent Application Laid-Open No. Hei 5-258766 discloses that a gas reformed by a methanol reformer (in addition to hydrogen, CO ₂ : 20% by volume, CO: 7 to 10% by volume) is used.
Using an e-Cr catalyst to reduce the CO concentration to 1% by volume,
Further, it is disclosed that CO is reduced by methanation using a catalyst containing a metal selected from Rh, Ni, and Pd as a catalyst component. The CO that could not be reduced by the catalyst is oxidized and removed by plasma. Although this method can provide a reformed gas that does not poison the platinum catalyst used as the electrode of the polymer electrolyte fuel cell, it has a problem that the size of the reaction apparatus is increased due to the use of the plasma generator. Further, since the methanation reaction is performed at a reaction temperature of 150 to 500 ° C., not only CO but also CO ₂ is methanated, a large amount of hydrogen used as a fuel is consumed, and CO is removed from hydrogen gas for a fuel cell. There is also a problem that it is unsuitable as a device.

[0010] Further, Japanese Patent Application Laid-Open No. 9-131531 discloses a catalyst for removing CO in a hydrogen-containing gas comprising ruthenium and an alkali metal compound and / or an alkaline earth metal compound supported on a titania carrier. I have. However, there is no specific disclosure of a catalyst using a carrier in which both titania and alumina are combined. Further, there is no disclosure which suggests that a catalyst using a carrier combining both titania and alumina is particularly superior to a titania carrier catalyst or an alumina carrier catalyst. Furthermore, no mention is made of the effect of the methanation reaction.

Further, a ruthenium / alumina catalyst is used for
A method for removing CO in a hydrogen-containing gas while suppressing the methanation reaction in a temperature range of up to 160 ° C. (Preprints of the 2nd Fuel Cell Symposium B2-7 p235 (199)
5)) and the same ruthenium / alumina catalyst for 140-18
A method of reducing CO in a hydrogen-containing gas to 10 ppm or less while suppressing a methanation reaction in a temperature range of 0 ° C. (Int
ersoc. Energy Conversions
Eng. Conf. Vol. 32 No. Vol. 2
p847 (1997)). But C
There is a problem that the reaction temperature range for removing O is narrow, and the activity is particularly poor at low temperatures.

[0012]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above viewpoints, and a catalyst for efficiently and selectively oxidizing and removing CO in a hydrogen-containing gas even in a wide reaction temperature range, particularly at a relatively high temperature. It is an object of the present invention to provide a method for producing a hydrogen-containing gas, particularly a hydrogen-containing gas, which can be suitably used for a fuel cell.

[0013]

Means for Solving the Problems As a result of intensive studies, the present inventors have oxidized carbon monoxide in a gas containing hydrogen as a main component with oxygen to produce a hydrogen-containing gas with reduced carbon monoxide. As a method, it has been found that it is effective to contact a reaction gas with a catalyst in which ruthenium and an alkali metal and / or an alkaline earth metal are supported on a refractory inorganic oxide carrier in a temperature range of 60 to 150 ° C. Is completed.

That is, the gist of the present invention is as follows. (1) A method for producing a hydrogen-containing gas in which carbon monoxide is reduced by oxidizing carbon monoxide in a gas containing hydrogen as a main component with oxygen, wherein the reaction gas is added to a refractory inorganic oxide carrier by ruthenium and alkali. A method for producing a hydrogen-containing gas with reduced carbon monoxide, comprising contacting a metal and / or an alkaline earth metal-supported catalyst at a temperature in the range of 60 to 150 ° C.

(2) The method for producing a hydrogen-containing gas with reduced carbon monoxide as described in (1), wherein the refractory inorganic oxide carrier comprises at least one selected from alumina, titania, silica and zirconia. (3) The method for producing a hydrogen-containing gas with reduced carbon monoxide according to (1) or (2), wherein the refractory inorganic oxide carrier comprises titania and another refractory inorganic oxide.

(4) The method for producing a hydrogen-containing gas with reduced carbon monoxide according to any one of (1) to (3), wherein the refractory inorganic oxide carrier comprises at least titania and alumina. (5) The weight ratio of titania to alumina is 0.1 / 99.
(4) The method for producing a hydrogen-containing gas in which carbon monoxide is reduced, which is 9 to 90/10.

(6) The production of a hydrogen-containing gas with reduced carbon monoxide according to any one of (1) to (5), wherein the alkali metal is at least one selected from potassium, cesium, rubidium, sodium and lithium. Method. (7) The method for producing a hydrogen-containing gas with reduced carbon monoxide according to any one of (1) to (6), wherein the alkaline earth metal is at least one selected from barium, calcium, magnesium, and strontium.

(8) The reduction of carbon monoxide according to any one of (1) to (7), wherein the gas containing hydrogen as a main component is a gas obtained by reforming or partially oxidizing a raw material for hydrogen production. Method for producing a hydrogen-containing gas. (9) The method for producing a hydrogen-containing gas with reduced carbon monoxide according to any one of (1) to (8), wherein the hydrogen-containing gas with reduced carbon monoxide is a fuel gas for a fuel cell.

[0019]

Embodiments of the present invention will be described below. First, C in the hydrogen-based gas of the present invention is used.
The O oxidation catalyst will be described. The support used for the catalyst of the present invention is made of a refractory inorganic oxide. JP 9
A catalyst in which ruthenium and an alkali metal and / or an alkaline earth metal are supported on a support made of a refractory inorganic oxide, such as a support made of titania and alumina, as disclosed in JP-A-131531, is used in a wide reaction temperature range. Demonstrates an excellent effect of removing CO by oxidation. In particular,
Compared to a catalyst in which only ruthenium is supported on an alumina support,
It has excellent reactivity for oxidative removal of CO at low temperatures.

The refractory inorganic oxide carrier may be any refractory inorganic oxide, but it is preferable to use at least one selected from alumina, titania, silica and zirconia. These are widely used as catalyst carrier components, and raw materials can be easily obtained, and a method for producing and handling a carrier is easy. Among these, a carrier containing titania and other refractory inorganic oxides, particularly alumina, is preferably used. Titania exhibits a suitable activity as a carrier component, but may have a problem in moldability. When used together with a carrier component having good moldability such as alumina, an overall suitable catalyst can be obtained.

As a method for producing a carrier comprising titania and alumina, for example, a method of mixing titania and alumina, and a method of adhering titania to an alumina compact (including alumina particles and powder) are preferably used. As a method for mixing titania and alumina, there is a method in which titania powder and alumina powder or pseudo-boehmite alumina are mixed with water, followed by molding, drying, and firing. Extrusion may be usually used for molding, and at that time, an organic binder can be added to improve moldability. Suitable carriers can also be obtained by mixing titania with an alumina binder. In addition, titanium alkoxide and aluminum alkoxide are hydrolyzed by adding water to a mixed solution obtained by dissolving the same in a solvent such as alcohol, and the coprecipitated precipitate is formed, dried, and calcined in the same manner as described above. Good. In this case, the weight ratio of the obtained titania / alumina is preferably 10/90 to 90/10.

On the other hand, the method of adhering titania to the alumina compact may be as follows. In an organic solvent, titania powder (titania powder may be a titania powder supporting a metal to be described later), and an organic binder and pseudo-boehmite alumina powder are added as necessary. The alumina compact is sufficiently immersed in the mixed solution, and titania powder or the like is adhered to the alumina compact. The alumina compact may be taken out, dried and fired. As another method, titanium alkoxide or titanium tetrachloride and an aluminum molded body are added to alcohol, water is added to this solution to hydrolyze the titanium alkoxide or titanium tetrachloride, and the aluminum molded body is placed on the aluminum molded body. The precipitate of titanium hydroxide may be dried and fired. As can be seen from these attaching methods, titania may be adhered in a manner of supporting titania on the alumina molded body. In the case of a method in which titania is adhered to an alumina molded body, the weight ratio of the obtained titania / alumina is 0.1 / 99.9-5.
0/50, preferably 0.5 / 99.5 to 50/50,
More preferably, the ratio is 1/99 to 50/50. Including both methods, the weight ratio of titania / alumina is between 0.1 / 99.9 and 90/10, preferably 0.1.
5 / 99.5 to 90/10, more preferably 1/99
It is desirably about 90/10.

The raw material of alumina used in the production of the carrier only needs to contain an aluminum atom. Examples of commonly used materials include aluminum nitrate, aluminum hydroxide, aluminum alkoxide, pseudoboehmite alumina, α-alumina, and γ-alumina. Pseudo-boehmite alumina, α-alumina, γ-alumina and the like can be made from aluminum nitrate, aluminum hydroxide, aluminum alkoxide and the like. What is necessary is just to select these raw materials which are easy to use according to a manufacturing method etc.

Representative forms of titania usable as a carrier include amorphous, anatase and rutile types. As the titania raw material, any material containing a titanium atom may be used, but usually, titanium alkoxide, titanium tetrachloride, amorphous titania powder,
Anatase type titania powder, rutile type titania powder and the like can be mentioned. Amorphous titania powder, anatase-type titania powder, rutile-type titania powder and the like can be made of titanium alkoxide, titanium tetrachloride or the like. What is necessary is just to select these raw materials which are easy to use according to a manufacturing method etc.

The carrier is preferably made of titania and alumina, but a carrier containing another refractory inorganic oxide, for example, a carrier made of zirconia, titania and alumina, a carrier made of silica, titania and alumina and the like are also suitable. It is a carrier. Further, other refractory inorganic oxides or a mixture thereof may be used. For example, a carrier made of alumina and zirconia and / or silica may be used.

The zirconia source may be any source containing a zirconium atom, but zirconium hydroxide, zirconium oxychloride, zirconium oxynitrate, zirconium tetrachloride, zirconia powder and the like can be used. The zirconia powder can be made from zirconium hydroxide, zirconium oxychloride, zirconium oxynitrate, zirconium tetrachloride. A catalyst containing zirconia as a carrier can also be prepared by placing the above-described zirconium compound in an aqueous solution together with a supported metal compound such as ruthenium or potassium and impregnating the carrier component such as alumina.

The silica source contains a silicon atom.
Silicon tetrachloride, sodium silicate, ethyl silicate
, Silica gel, silica sol and the like can be used. silica
Gels include silicon tetrachloride, sodium silicate, ethyl silicate,
Cazol and the like can be mentioned. Next, ruthenium
The support on the carrier will be described. Ruthenium supported on carrier
For example, RuCl_Three・ NH_TwoO, Ru_Two(O
H)_TwoCl_Four・ 7NH_Three・ 3H_TwoO, K_Two(RuCl_Five
(H_TwoO)), (NH_Four)_Two(RuCl_Five(H
_TwoO)), K_Two(RuCl_Five(NO)), RuBr_Three・
nH_TwoO, Na_TwoRuO_Four, Ru (NO) (N
O_Three)_Three, (Ru_ThreeO (OAc)₆(H_TwoO)_Three) OA
c ・ nH_TwoO, K_Four(Ru (CN)₆) · NH_TwoO, K
_Two(Ru (NO_Two)_Four(OH) (NO)), (Ru (N
H_Three)₆) Cl_Three, (Ru (NH_Three)₆) Br_Three, (R
u (NH_Three)₆) Cl_Two, (Ru (NH_Three)₆) B
r _Two, (Ru_ThreeO_Two(NH_Three)₁₄) Cl₆・ H_TwoO,
(Ru (NO) (NH_Three)_Five) Cl_Three, (Ru (OH)
(NO) (NH_Three)_Four) (NO_Three)_Two, RuCl_Two(P
Ph_Three)_Three, RuCl_Two(PPh_Three)_Four, (RuClH
(PPh_Three)_Three) ・ C ₇H₈, RuH_Two(PP
h_Three)_Four, RuClH (CO) (PPh_Three)_Three, RuH
_Two(CO) (PPh_Three)_Three, (RuCl_Two(Cod))
_n, Ru (CO)₁₂, Ru (acac)_Three, (Ru (H
COO) (CO)_Two)_n, Ru_TwoI_Four(P-cymen
e)_TwoRuthenium salt is dissolved in water, ethanol, etc.
The resulting catalyst preparation is used. Preferably, the
RuCl in terms of handling_Three・ NH_TwoO, Ru _Two(OH)_Two
Cl_Four・ 7NH_Three・ 3H_TwoO is used.

The loading of ruthenium on a carrier may be carried out by using the catalyst preparation solution by a usual impregnation method, coprecipitation method or competitive adsorption method. The treatment conditions may be appropriately selected according to various methods, but usually, the carrier may be brought into contact with the catalyst preparation solution at room temperature to 90 ° C. for 1 minute to 10 hours. The amount of ruthenium supported is not particularly limited, but is usually preferably 0.05 to 10% by weight as ruthenium relative to the carrier, particularly preferably 0.3 to 10% by weight.
The range of 3% by weight is optimal. When the content of ruthenium is less than the lower limit, the conversion activity of CO becomes insufficient,
On the other hand, if the loading ratio is too high, the amount of ruthenium used becomes excessively large and the catalyst cost increases. After supporting ruthenium on the carrier, drying is performed. As a drying method,
For example, natural drying, evaporation to dryness, drying using a rotary evaporator or a blow dryer is performed. After drying,
Usually 350-550 ° C, preferably 380-500 ° C
For 2 to 6 hours, preferably 2 to 4 hours.

Next, an alkali metal and / or alkaline earth
The loading of a class of metal on a carrier will be described. First, the alkali
The loading of the metal on the carrier will be described. As an alkali metal
Potassium, cesium, rubidium, sodium
And lithium are preferably used. Carry alkali metal
To do, K_TwoB_TenO₁₆, KBr, KBrO_Three, KC
N, K _TwoCO_Three, KCl, KCLO_Three, KCLO_Four, K
F, KHCO_Three, KHF_Two, KH_TwoPO_Four, KH_Five(P
O_Four)_Two, KHSO_Four, KI, KIO_Three, KIO_Four, K
_FourI_TwoO₉, KN_Three, KNO_Two, KNO_Three, KOH, K
PF₆, K_ThreePO_Four, KSCN, K_TwoSO_Three, K_TwoSO
_Four, K_TwoS_TwoO_Three, K_TwoS_TwoO_Five, K_TwoS_TwoO₆, K_Two
S_TwoO₈, K (CH_ThreeCO salts such as COO); CsCl, C
sCLO_Three, CsCLO_Four, CsHCO_Three, CsI, C
sNO_Three, Cs_TwoSO_Four, Cs (CH_ThreeCOO), Cs
_TwoCO_Three, CsF and the like; Rb_TwoB_TenO₁₆, RbB
r, RbBrO_Three, RbCl, RbClO_Three, PbCl
O_Four, RbI, RbNO_Three, Rb_TwoSO_Four, Rb (CH
_ThreeCOO)_Two, Rb_TwoCO_ThreeRb salt; Na_TwoB_FourO
₇, NaB_TenO₁₆, NaBr, NaBrO_Three, NaC
N, Na_TwoCO_Three, NaCl, NaClO, NaClO
_Three, NaClO_Four, NaF, NaHCO_Three, NaHPO
_Three, Na_TwoHPO_Three, Na_TwoHPO_Four, NaH_TwoP
O_Four, Na_ThreeHP_Two0₆, Na_TwoH_TwoP_TwoO₇, Na
I, NaIO_Three, NaIO_Four, NaN_Three, NaNO_Two,
NaNO_Three, NaOH, Na_TwoPO_Three, Na_ThreePO_Four,
Na_FourP_TwoO₇, Na_TwoS, NaSCN, Na_TwoS
O_Three, Na_TwoSO_Four, Na_TwoS_TwoO_Five, Na_TwoS
_TwoO ₆, Na (CH_ThreeNa salt such as COO); LiB
O_Two, Li_TwoB_FourO₇, LiBr, LiBrO_Three, Li
_TwoCO_Three, LiCl, LiClO_Three, LiClO_Four, L
iHCO_Three, Li_TwoHPO_Three, LiI, LiN_Three, Li
NH_FourSO_Four, LiNO_Two, LiNO_Three, LiOH, L
iSCN, Li_TwoSO_Four, Li_ThreeVO_FourLi salt such as
Use a catalyst preparation solution obtained by dissolving in water, ethanol, etc.
Can be.

The theory of supporting alkaline earth metals on carriers
I will tell. Barium and calcium are the alkaline metal earths.
, Magnesium and strontium are preferably used
Can be To support the alkaline earth metal, BaB
r_Two, Ba (BrO_Three)_Two, BaCl _Two, Ba (ClO
_Two)_Two, Ba (ClO_Three)_Two, Ba (ClO_Four)_Two, B
aI_Two, Ba (N_Three)_Two, Ba (NO_Two)_Two, Ba (N
O_Three)_Two, Ba (OH)_Two, BaS, BaS_TwoO₆, B
aS_FourO₆, Ba (SO_ThreeNH_Two)_TwoBa salt such as Ca;
Br_Two, CaI_Two, CaCl_Two, Ca (ClO_Three)_Two,
Ca (IO_Three)_Two, Ca (NO_Two)_Two, Ca (NO_Three)
_Two, CaSO_Four, CaS_TwoO_Three, CaS_TwoO₆, Ca
(SO_ThreeNH_Two)_Two, Ca (CH_ThreeCOO)_Two, Ca
(H_TwoPO_Four)_TwoCa salt, etc .; MgBr_Two, MgC
O_Three, MgCl_Two, Mg (ClO_Three)_Two, MgI_Two, M
g (IO_Three)_Two, Mg (NO_Two)_Two, Mg (N
O_Three)_Two, MgSO_Three, MgSO_Four, MgS_TwoO₆, M
g (CH_ThreeCOO)_Two, Mg (OH)_Two, Mg (ClO
_Four)_TwoMg salt such as SrBr_Two, SrCl_Two, Sr
I_Two, Sr (NO_Three)_Two, SrO, SrS_TwoO_Three, Sr
S_TwoO₆, SrS_FourO₆, Sr (CH_ThreeCOO)_Two, S
r (OH)_TwoIs dissolved in water, ethanol, etc.
Can be used.

The loading of the alkali metal or alkaline earth metal on the carrier may be carried out using the catalyst preparation solution by a usual impregnation method, coprecipitation method or competitive adsorption method. The treatment conditions may be appropriately selected according to various methods, but are usually from room temperature to 90 ° C.
The carrier may be brought into contact with the catalyst preparation solution for 1 minute to 10 hours. The loading of ruthenium, alkali metal and alkaline earth metal may be carried out in any order, and if they can be carried out simultaneously, they may be carried out simultaneously. Further, not only the method of supporting these supported metals on the resulting carrier, but also a part of the carrier component, for example, in the case of titania / alumina carrier, the supported titania is supported and the supported titania is removed as described above. The catalyst can also be used by a method of attaching it to alumina. As a result, any catalyst may be used as long as a supported metal such as ruthenium is supported on a titania / alumina carrier.

The amount of the alkali metal or alkaline earth metal to be carried is not particularly limited, but is usually preferably 0.01 to 10% by weight, more preferably 0.03 to 3% by weight of the metal relative to the carrier. It is. When the content of these metals is less than the lower limit, the selective oxidation activity of CO becomes insufficient,
On the other hand, if the loading ratio is too high, the selective oxidation activity of CO becomes insufficient, and at the same time, the amount of metal used becomes unnecessarily excessive and the catalyst cost increases.

After carrying the above-mentioned alkali metal and alkaline earth metal, drying is performed. As a drying method, for example, natural drying, evaporation to dryness, drying using a rotary evaporator or a blow dryer may be performed. After drying, usually 3
50-550 ° C, preferably 380-500 ° C,
Bake for 6 hours, preferably 2 to 4 hours. The shape and size of the catalyst thus prepared are not particularly limited, and examples thereof include powder, sphere, granule, honeycomb, foam, fiber, cloth, plate, and ring. Various commonly used shapes and structures are available. The production method is not limited. For example, the catalyst itself may be formed by extrusion or the like, or a method of attaching the catalyst to a honeycomb or ring-shaped substrate may be used.

Next, a method for producing a hydrogen-containing gas with reduced carbon monoxide by oxidizing carbon monoxide in a gas containing hydrogen as a main component with oxygen using the above catalyst will be described. Since the catalyst prepared as described above is usually calcined, the supported metal exists in an oxide state. Before use, the catalyst is reduced by hydrogen reduction. Hydrogen reduction is usually
250 to 550 ° C, preferably 300 to 5 under a hydrogen stream
The reaction is performed at a temperature of 30 ° C. for 1 to 5 hours, preferably 1 to 2 hours.

The selective oxidation reaction of CO with oxygen is performed by bringing the reaction gas into contact with the catalyst obtained as described above in a temperature range of 60 to 150 ° C. The reaction gas of the present invention is obtained by adding oxygen or an oxygen-containing gas to a hydrogen-containing gas containing hydrogen as a main component and containing at least CO, and is used as a raw material (including oxygen in this case) for the above-mentioned catalytic reaction. A thing. The method for oxidizing CO of the present invention provides hydrogen obtained by reforming or partially oxidizing a raw material for hydrogen production that can be converted into a hydrogen-containing gas by a reforming reaction and a partial oxidation reaction (hereinafter, referred to as a reforming reaction or the like). It is suitably used for selectively removing CO in a gas containing as a main component (hereinafter, referred to as a reformed gas, etc.)
It is used for producing a hydrogen-containing gas for a fuel cell, but is not limited thereto.

A method for producing a hydrogen-containing gas for a fuel cell or the like by oxidizing and removing CO in a gas containing hydrogen as a main component will be described below. 1. Reforming or Partial Oxidation Step of Hydrogen Production Raw Material In the present invention, CO contained in a reformed gas or the like obtained by reforming various hydrogen production raw materials is selectively oxidized and removed by oxygen using a catalyst. , To produce the desired hydrogen-containing gas with sufficiently reduced CO concentration. The step for obtaining the reformed gas or the like can be performed by any method such as a method implemented or proposed in a conventional hydrogen production step, particularly a hydrogen production step in a fuel cell system, as described below. Therefore, in a fuel cell system provided with a reformer or the like in advance, a reformed gas or the like may be prepared by using the reformer as it is.

First, the reforming or partial oxidation of the raw material for hydrogen production will be described. Hydrogen production raw materials are hydrocarbons that can produce gas rich in hydrogen by steam reforming or partial oxidation, that is, hydrocarbons such as methane, ethane, propane, and butane, or natural gas (LNG), naphtha, gasoline, Hydrocarbon materials such as kerosene, light oil, heavy oil and asphalt; alcohols such as methanol, ethanol, propanol and butanol; oxygenated compounds such as methyl formate, methyl tertiary butyl ether and dimethyl ether; various city gases; LPG , Synthesis gas, coal and the like. Among these, what kind of raw material for hydrogen production is used may be determined in consideration of various conditions such as the scale of the fuel cell system and the circumstances of supply of the raw material, but usually, methanol, methane or LNG, propane, etc. Alternatively, LPG, naphtha or lower saturated carbon, city gas or the like is suitably used.

Techniques belonging to reforming or partial oxidation (hereinafter referred to as "reforming")
It is called a reforming reaction. Examples of (2) include steam reforming, partial oxidation, a combination of steam reforming and partial oxidation, autothermal reforming, and other reforming reactions. Usually, steam reforming (steam reforming) is the most common reforming reaction, but depending on the raw material, partial oxidation or other reforming reactions (for example, thermal reforming reaction such as thermal decomposition, contact reforming) Various catalytic reforming reactions such as decomposition and shift reaction) can also be appropriately applied.

At this time, different types of reforming reactions may be used in appropriate combination. For example, since the steam reforming reaction is generally an endothermic reaction, a steam reforming reaction and a partial oxidation may be combined (autothermal reforming) to compensate for the endothermic component, or C by-produced by the steam reforming reaction or the like.
Various combinations are possible, such as by reacting O with H ₂ O using a shift reaction to convert a part of the O to CO ₂ and H ₂ in advance to reduce it. The raw material for hydrogen production may be partially oxidized without a catalyst or in a catalytic manner, followed by steam reforming in a subsequent stage. In this case, the heat generated by the partial oxidation can be used as it is in the subsequent steam reforming.

Hereinafter, the steam reforming will be mainly described as a typical reforming reaction. In such a reforming reaction, catalysts and reaction conditions are generally selected so that the yield of hydrogen is as large as possible. However, it is difficult to completely suppress CO by-products. Even if it is used, there is a limit to the reduction of the CO concentration in the reformed gas. In fact, for the steam reforming reaction of hydrocarbons such as methane, the hydrogen yield and C
For O-product inhibition, the following formula (2) or the formula _{(3): CH 4 + 2H} 2 O → 4H 2 + CO 2 (2) C n H m + 2nH 2 O → (2n + m / 2 It is preferable to select various conditions so that the reaction represented by H ₂ + nCO ₂ (3) takes place with as high selectivity as possible.

Similarly, for the steam reforming reaction of methanol, the reaction represented by the following formula (4): CH ₃ OH + H ₂ O → 3H ₂ + CO ₂ (4) is as selective as possible. It is preferable to select the conditions to occur. Further, CO is added to the above (1)
The metamorphic reforming may be performed by utilizing the shift reaction represented by the formula. However, since this shift reaction is an equilibrium reaction, a considerable concentration of CO remains. Thus, the reformed gas or the like by such reaction (of the present invention is a starting material gas containing mainly hydrogen, hereinafter the same) during normal, the CO ₂ and unreacted another large amount of hydrogen water vapor or the like and slightly CO will be included.

As the catalyst effective for the reforming reaction, a wide variety of catalysts are known according to the kind of the raw material, the kind of the reaction or the reaction conditions. Specific examples of some of them include catalysts effective for steam reforming of hydrocarbons and methanol, for example, Cu-ZnO-based catalysts, Cu
-Cr ₂ O ₃ catalyst, supported Ni-based catalyst, Cu-Ni-Z
nO-based catalyst, Cu-Ni-MgO-based catalyst, Pd-ZnO
And the like.Examples of catalysts effective for catalytic reforming reaction and partial oxidation of hydrocarbons include, for example,
Supported Pt-based catalysts, supported Ni-based catalysts, and the like can be given.

There is no particular limitation on the reforming apparatus, and any type such as those commonly used in conventional fuel cell systems and the like can be applied. However, many reforming apparatuses such as a steam reforming reaction and a decomposition reaction can be used. Since the reaction is an endothermic reaction, generally, a reactor or a reactor having a good heat supply property (a heat exchanger type reactor or the like) is suitably used. Examples of such a reactor include a multitubular reactor, a plate-fin reactor, and the like. Examples of the heat supply method include heating using a burner, a method using a heat medium, and a catalyst using partial oxidation. Examples include, but are not limited to, heating by combustion.

The reaction conditions for the reforming reaction vary depending on the raw materials used, the reforming reaction, the catalyst, the type of the reaction apparatus, and other conditions such as the reaction system, and may be appropriately determined. In any case, it is desirable to select various conditions so that the conversion of the raw material is sufficiently increased (preferably to 100% or nearly 100%) and the yield of hydrogen is as large as possible. If necessary, a method of separating and recycling unreacted hydrocarbons and alcohols may be adopted.
Also, if necessary, the produced or unreacted CO ₂
And moisture or the like may be removed as appropriate.

2. Selective Oxidation (Conversion) Removal Step of CO As described above, a desired reformed gas or the like having a large hydrogen content and sufficiently reduced raw material components other than hydrogen such as hydrocarbons and alcohols is obtained. In the present invention, CO is selectively oxidized (converted) by adding oxygen to a raw material gas (reformed gas or the like) containing hydrogen as a main component and a small amount of CO to convert CO ₂ into CO _2.
It is necessary to suppress oxidation of hydrogen as much as possible. In addition, it is necessary to suppress the conversion reaction of CO ₂ generated or present in the raw material gas into CO (normally, hydrogen is present in the raw material gas, so that a reverse shift reaction may occur). is there. Since the catalyst of the present invention is generally used in a reduced state, it is preferable to perform a reduction operation with hydrogen when the catalyst is not in a reduced state. The use of the catalyst of the present invention, of course, shows good results in the selective oxidative removal of CO with respect to the raw material gas having a low CO ₂ content.
Good results can be obtained even under conditions with a high CO ₂ content. Generally, in a fuel cell system, a source gas having a general CO ₂ concentration, that is, a source gas containing ₅ to 33% by volume, preferably 10 to 25% by volume, and more preferably 15 to 20% by volume of CO ₂ is used. Used.

On the other hand, steam is usually present in the source gas obtained by steam reforming or the like, but the lower the steam concentration in the source gas, the better. Usually, it is contained in an amount of about 5 to 30%. When the catalyst of the present invention is used, the CO concentration is low (0.6% by volume).
Hereinafter, the CO concentration in the source gas can also be effectively reduced, and the CO concentration in the source gas having a relatively high CO concentration (0.6 to 2.0% by volume) can be suitably reduced.

In the method of the present invention, the selective conversion and removal of CO can be efficiently performed by using the above-mentioned catalyst of the present invention even under conditions where CO ₂ is present in the raw material gas in a volume of 15% or more. . In addition, the CO conversion removal reaction is an exothermic reaction, as is the simultaneous oxidation of hydrogen, which is a side reaction, and recovering the generated heat and utilizing it in the fuel cell is effective in improving the power generation efficiency. is there.

Here, the selective oxidation and removal reaction of CO while suppressing the oxidation reaction of hydrogen can be carried out in a relatively wide reaction temperature range of 60 to 300 ° C. However, if the reaction temperature exceeds 150 ° C., undesired side reactions for oxidative removal of CO, ie, CO or CO
_The methanation reaction (hydrogenation) by hydrogen of ₂ occurs. When methanation occurs, hydrogen in the source gas is consumed, which is not preferable for producing a hydrogen-containing gas.
To suppress the methanation and selectively remove CO by oxidation, the reaction temperature is 150 ° C. or lower, preferably 120 ° C. or lower,
More preferably, the temperature must be 115 ° C. or lower. By doing so, the amount of methane generated can be suppressed to 50 ppm or less. In order to advance the CO oxidation reaction at an industrially useful rate, the reaction temperature must be 60 ° C. or higher, preferably 80 ° C. or higher.

In order to add oxygen gas to the raw material gas for reaction, usually, pure oxygen (O ₂ ), air or oxygen-enriched air is suitably used. The amount of the oxygen gas added is oxygen /
The CO (molar ratio) is suitably adjusted to be preferably 0.5 to 5, more preferably 1 to 4. If this ratio is small, the removal rate of CO is low, and if it is large, the consumption of hydrogen is too large, which is not preferable.

The reaction pressure is not particularly limited, but in the case of a fuel cell, the reaction is usually carried out at a normal pressure to 10 kg / cm ² G, preferably at a normal pressure to 5 kg / cm ² G. If the reaction pressure is set too high, the power for pressurization must be increased accordingly, which is economically disadvantageous.
If it exceeds 0 kg / cm ² G, it is not preferable because it is subject to the regulations of the High Pressure Gas Control Law and the explosion limit is widened, causing a problem that safety is reduced.

The above reaction can be suitably carried out at a low temperature of 60 ° C. to 150 ° C. in a wide temperature range while stably maintaining the selectivity to the CO conversion reaction. Although the reaction takes place even at a reaction temperature of less than 60 ° C., the reaction rate is reduced, and the oxidation removal rate (conversion rate) of CO is insufficient in a practical range of GHSV (gas volume space velocity), which is not efficient.

In addition, the above-mentioned reaction is usually carried out at a GHSV of 50
It is preferable to select from the range of 00 to 50000 hr ^-1 . Here, when the GHSV is reduced, a large amount of catalyst is required.
Removal rate decreases. Preferably, 6000-3000
Select within the range of ⁰ hr ^-1 . Since the CO conversion reaction in the CO conversion removal step is an exothermic reaction, the reaction raises the temperature of the catalyst layer. If the temperature of the catalyst layer is too high, the selectivity of the catalyst for CO conversion removal usually deteriorates. For this reason, it is not preferable to react too much CO on a small amount of catalyst in a short time. G from the meaning
In some cases, the HSV should not be too small.

There are no particular restrictions on the reactor used for the conversion and removal of CO, and various types of reactors can be used as long as the above reaction conditions can be satisfied. However, this conversion reaction is an exothermic reaction. Therefore, in order to facilitate temperature control, it is desirable to use a reaction apparatus or a reactor having good removability of reaction heat. Specifically, for example, a heat exchange type reactor such as a multitube type or a plate fin type is suitably used. Depending on the case, a method of circulating the cooling medium in the catalyst layer or circulating the cooling medium outside the catalyst layer can be adopted.

Since the hydrogen-containing gas produced by the method of the present invention has a sufficiently reduced CO concentration as described above, the poisoning and deterioration of the platinum electrode catalyst of the fuel cell can be sufficiently reduced. , Its life, power generation efficiency and power generation performance can be greatly improved. Also, this CO
It is also possible to recover the heat generated by the conversion reaction. Further, the CO concentration in the hydrogen-containing gas containing a relatively high concentration of CO can be sufficiently reduced. It is desirable that the CO concentration in the hydrogen-containing gas for a fuel cell be 100 ppm or less, preferably 50 ppm or less, more preferably 10 ppm or less. According to the method of the present invention, it is possible to achieve this under a wide range of reaction conditions. It is possible enough.

The hydrogen-containing gas obtained according to the present invention can be suitably used as a fuel for various H ₂ -combustion fuel cells. In particular, platinum (platinum catalyst) is used at least for the fuel electrode (negative electrode). type various H ₂ combustion type fuel cell using (phosphoric acid fuel cell, KOH-type fuel cell, such as low temperature operation type fuel cell including a polymer electrolyte fuel cell)
Can be advantageously used as a fuel to be supplied to the fuel cell.

The method of the present invention is provided between a fuel cell and a reformer of a conventional fuel cell system (if a reformer is provided after the reformer, the reformer is also regarded as a part of the reformer). The reaction conditions are adjusted as described above by incorporating an oxygen introducing device and a reaction device according to the above or using the catalyst as a CO conversion removing catalyst in the case of already having an oxygen introducing device and a conversion reaction device. This makes it possible to configure a fuel cell system that is superior to conventional fuel cell systems.

[0057]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. [Example 1] An ethanol solution (0.0356 M) of ruthenium trichloride (hydrate) was prepared, and 50 cc of water was added to this solution.
Was added to obtain an impregnated liquid. As a carrier to the impregnation solution, titania (TiO _2, manufactured by Ishihara Sangyo Kaisha, Ltd., CR-EL, surface area: 7m ² / g) were added, and then impregnated with ruthenium trichloride titania carrier. Ruthenium was impregnated so as to be 1% by weight (in terms of metal) with respect to the obtained catalyst.

The drying of the catalyst was performed using a rotary evaporator. After drying, in a muffle furnace,
For 4 hours at 500 ° C for ruthenium carrier 1
I got Next, the above-mentioned ruthenium carrier 1 was treated with water 100c.
c, and KNO ₃ was added therein so that the content of the resulting catalyst was 0.1% by weight of K metal. The drying of the catalyst was performed using a rotary evaporator. After drying, use a muffle furnace at 120 ° C for 2 hours and 500 ° C for 4 hours.
Calcination was performed for a period of time to obtain Catalyst 1. Table 1 shows the composition of Catalyst 1.

Example 2 Rutile type titania (Ti
O_Two, Manufactured by Ishihara Sangyo Co., Ltd., CR-EL, surface area: 7 m ^Two
/ G) 160g and pseudo boehmite alumina powder (catalyst formation
Industrial Co., Ltd., Cataloid-AP) 59.7 g
Mixed with ion-exchanged water in a kneader under heating
The mixture was kneaded, and the water content was adjusted to an extent suitable for extrusion molding. this
Is a cylinder of 2mm in diameter and 0.5-1cm in length with an extruder
It was dried in a dryer at 120 ° C. for 24 hours. Continued
And calcined in a calcining furnace at 500 ° C. for 4 hours to obtain a carrier 2
Was. The weight ratio of titania / alumina of the carrier 2 is 80/20.
Met.

Take 10 g of the carrier 2 and prepare ethanol in 5.25 cc of a ruthenium chloride ethanol solution prepared in advance (0.952 g of Ru in 50 cc).
The impregnation liquid to which 75 cc was added was impregnated. After removing the ethanol by evaporation at 60 ° C., the mixture was heated at 120 ° C. in a muffle furnace.
It was calcined for 2 hours at 500 ° C. for 4 hours to obtain a ruthenium carrier 2. Next, an aqueous solution 10 containing 0.0259 g of potassium nitrate prepared in advance was added to the ruthenium carrier 2.
cc. After evaporating and removing the water at 60 ° C., the mixture was calcined in a muffle furnace at 120 ° C. for 2 hours and at 500 ° C. for 4 hours to obtain Catalyst 2. Table 1 shows the composition of Catalyst 2.

Example 3 Activated alumina having a particle size of 16 to 32 mesh (KHD2 manufactured by Sumitomo Chemical Co., Ltd.)
4) 10 g was impregnated with an impregnation liquid prepared by adding 4.75 cc of ethanol to 5.25 cc of a previously prepared ethanol solution of ruthenium chloride (containing 0.952 g of Ru in 50 cc). After ethanol was removed by evaporation at 60 ° C., the mixture was heated in a muffle furnace at 120 ° C. for 2 hours and at 500 ° C. for 4 hours.
After calcination for a period of time, a ruthenium carrier 3 was obtained. The obtained ruthenium carrier 3 was impregnated with an impregnation liquid prepared by dissolving 0.0259 g of potassium nitrate prepared in advance in 10 cc of ion-exchanged water. After evaporating and removing the water at 60 ° C., the mixture was calcined in a muffle furnace at 120 ° C. for 2 hours and at 500 ° C. for 4 hours to obtain Catalyst 3. Table 1 shows the composition of Catalyst 3.

Example 4 Titanium tetraisopropoxide (TTIP, manufactured by Wako Pure Chemical Industries, Ltd., Reagent 1)
Grade) (14.2 g) was dissolved in isopropyl alcohol (97 ml), diethanolamine (5.25 g) was added, and the mixture was stirred for 2 hours. Thereafter, a solution in which 1.8 g of water was dissolved in 3.6 ml of isopropyl alcohol was gradually added, followed by stirring for 2 hours. 25 ml of this solution was fractionated, and the particle size was 16
10 g of activated alumina (KHD24, manufactured by Sumitomo Chemical Co., Ltd.) having a mesh size of up to 32 mesh was added, and the mixture was allowed to stand for 1 hour. Then, the particles were filtered off, sufficiently washed with isopropyl alcohol, and dried. The particles were placed in a muffle furnace at 120 ° C. for 2 hours,
It was calcined at 00 ° C. for 4 hours to obtain a carrier 4. The carrier 4 is a carrier in which titania is adhered on an alumina molded body (alumina particles). The weight ratio of titania / alumina of the carrier 4 is 1/99.
Met.

10 g of the carrier 4 is taken, and ethanol is added to 5.25 cc of a ruthenium chloride ethanol solution prepared beforehand (0.952 g of Ru is contained in 50 cc).
The impregnation liquid to which 75 cc was added was impregnated. After removing the ethanol by evaporation at 60 ° C., the mixture was heated at 120 ° C. in a muffle furnace.
It was calcined for 2 hours at 500 ° C. for 4 hours to obtain a ruthenium carrier 4. Next, an aqueous solution 10 containing 0.0259 g of potassium nitrate prepared in advance was added to the ruthenium carrier 4.
cc. After evaporating and removing water at 60 ° C., the mixture was calcined in a muffle furnace at 120 ° C. for 2 hours and at 500 ° C. for 4 hours to obtain Catalyst 4. Table 1 shows the composition of Catalyst 4.

Example 5 Rutile type titania (Ti
O_Two, Manufactured by Ishihara Sangyo Co., Ltd., CR-EL, surface area: 7 m ^Two
/ G), and dioxyoxychloride prepared in advance.
Ruconium aqueous solution (35.2% by weight aqueous solution as Zr,
Specific gravity 1.62) 1.297 cc and ruthenium chloride
Aqueous solution (contains 0.947 g of Ru in 50 cc)
5.81 cc were impregnated. Evaporate water at 60 ° C
After removal, 500 ° C in a muffle furnace at 120 ° C for 2 hours
By calcining for 4 hours, a ruthenium carrier 5 was obtained. Then,
To the ruthenium carrier 5 of FIG.
4.5 cc of an aqueous solution containing 0.0259 g of
Was. After evaporating and removing the water at 60 ° C.,
It was calcined in a furnace at 500 ° C. for 4 hours to obtain Catalyst 5. Set of catalyst 5
The results are shown in Table 1.

Example 6 In Example 1, ruthenium carrier 1 was charged into 100 cc of water, and KNO ₃ was added thereto.
Instead of adding 0.1% by weight of K metal to the resulting catalyst, the ruthenium carrier 1 was
Catalyst 6 was obtained in the same manner as in Example 1, except that the mixture was charged to 0 cc, CsNO ₃ was added therein, and the resulting catalyst was adjusted to 0.1% by weight of Cs metal. Catalyst 6
Is shown in Table 1.

Example 7, Comparative Example 1 Prior to the selective oxidation reaction of CO gas, the particle size of the catalyst was set to 16 to 32 mesh. The catalyst 1, the catalyst 5 and the catalyst 6 are formed by a tableting machine and then crushed to 16 to 32 mesh, the catalyst 2 is crushed to 16 to 32 mesh, and the catalyst 3 and the catalyst 4
Since it was 6-32 mesh, it was used as it was.
Each of the sized catalysts is filled into a fixed-bed flow reactor,
The reduction treatment was performed at 500 ° C. for 1 hour while flowing hydrogen gas.

Thereafter, the selective oxidation reaction of CO gas was carried out in each fixed bed flow reactor under the conditions shown in Table 2.
In addition, the reaction temperature was changed in the range of 60 to 160 ° C. Table 3 shows the results.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

As shown in Table 3, the amount of CO remaining and the amount of methane produced differ depending on the reaction temperature even with the catalyst of the same supported metal.
If the reaction temperature was 60 ° C. or higher, the CO concentration in the product gas could be reduced to 10 ppm or less even at a GHSV of 10,000 h ⁻¹ . At a reaction temperature of 160 ° C., the amount of methane produced in the product gas was 70 ppm, but at 130 ° C., 50 ppm.
Thereafter, at 115 ° C., it decreased to 0 ppm.

[0072]

According to the present invention, it is possible to efficiently and selectively oxidize and remove CO by suppressing the oxidation of hydrogen and the generation of methane over a wide temperature range for a gas containing hydrogen as a main component. . This generated gas can prevent the platinum of the hydrogen electrode of the hydrogen-oxygen type fuel cell from being poisoned by CO, prolong the life of the battery and improve the stability of the output.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroyuki Endo 1280 Kamiizumi, Kamiizumi, Sodegaura-shi, Chiba F-term (reference) BC08A BC70A BC70B CA07 CA14 CC21 DA06 FA03 FB06 FB17 FB19 FC08 5H027 AA03 AA04 AA06 BA01 BA16

Claims (9)

[Claims] 1. A method for producing a hydrogen-containing gas having reduced carbon monoxide by oxidizing carbon monoxide in a gas containing hydrogen as a main component with oxygen, wherein the reaction gas is converted to ruthenium on a refractory inorganic oxide carrier. And a catalyst supporting an alkali metal and / or an alkaline earth metal, and 60 to 150 ° C.
A method for producing a hydrogen-containing gas with reduced carbon monoxide, wherein the gas is contacted in a temperature range of: 2. The method for producing a hydrogen-containing gas with reduced carbon monoxide as claimed in claim 1, wherein the refractory inorganic oxide carrier comprises at least one selected from alumina, titania, silica and zirconia. 3. The method for producing a hydrogen-containing gas with reduced carbon monoxide according to claim 1, wherein the refractory inorganic oxide carrier comprises titania and another refractory inorganic oxide. 4. The method for producing a hydrogen-containing gas with reduced carbon monoxide according to claim 1, wherein the refractory inorganic oxide carrier comprises at least titania and alumina. 5. The method according to claim 1, wherein the weight ratio of titania to alumina is 0.1 /.
The method for producing a hydrogen-containing gas in which carbon monoxide is reduced is in the range of 99.9 to 90/10. 6. The method for producing a hydrogen-containing gas with reduced carbon monoxide according to claim 1, wherein the alkali metal is at least one selected from potassium, cesium, rubidium, sodium and lithium. 7. The method for producing a hydrogen-containing gas with reduced carbon monoxide according to claim 1, wherein the alkaline earth metal is at least one selected from barium, calcium, magnesium and strontium. 8. Hydrogen with reduced carbon monoxide according to claim 1, wherein the gas containing hydrogen as a main component is a gas obtained by reforming or partially oxidizing a raw material for producing hydrogen. Method for producing contained gas. 9. The method for producing a hydrogen-containing gas with reduced carbon monoxide according to claim 1, wherein the hydrogen-containing gas with reduced carbon monoxide is a fuel gas for a fuel cell.