JP2003147372A - Hydrocarbon desulfurization method and fuel cell system - Google Patents

Abstract

(57) [Problem] A catalyst in various processes up to the production of fuel hydrogen for a fuel cell, and a catalyst used for a cathode of a fuel cell,
Since noble metals or copper are often used in a reduced state, it is necessary to sufficiently remove the sulfur content in the fuel.In addition, in order to incorporate the desulfurization device into the fuel cell system, under low pressure conditions, Effective desulfurization is required. The present invention provides a desulfurization method that solves such a problem and a fuel cell system using the method. SOLUTION: A carrier containing a sulfur-containing hydrocarbon and (1) a zeolite or a clay compound in an amount of 30% by mass or more is provided.
Contacting catalyst A carrying at least one metal selected from Pt, Pd and Re in an amount of 0.01 to 10% by mass, and then (2) containing at least 20% by mass of zinc oxide and / or nickel oxide. By contacting with catalyst B, the sulfur-containing hydrocarbon can be desulfurized to a sulfur concentration of 0.1 mass ppm or less.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for desulfurizing a hydrocarbon using a specific catalyst. The present invention also relates to a fuel cell system including a desulfurization device filled with this specific catalyst.

[0002]

2. Description of the Related Art A fuel cell is characterized in that it can obtain a high efficiency because a free energy change due to a combustion reaction of a fuel can be directly taken out as an electric energy. Furthermore, in combination with the fact that harmful substances are not emitted, it is being developed for various uses. In particular, polymer electrolyte fuel cells are characterized by high power density, compact size, and low temperature operation.

Generally, a gas containing hydrogen as a main component is used as a fuel gas for a fuel cell, and its raw materials are natural gas, hydrocarbons such as LPG, naphtha and kerosene, and alcohols such as methanol and ethanol. Ethers such as dimethyl ether are used. These raw materials containing carbon and hydrogen are treated with steam at high temperature on a catalyst for reforming, or partially oxidized with oxygen-containing gas, or in a system where steam and oxygen-containing gas coexist, a self-heat recovery type reforming reaction. The hydrogen obtained by performing the above is basically used as the fuel hydrogen for the fuel cell.

However, since elements other than hydrogen are also present in these raw materials, it is inevitable that impurities derived from carbon are mixed in the fuel gas to the fuel cell. Above all, carbon monoxide poisons the platinum-based noble metal used as the electrode catalyst of the fuel cell, so that if carbon monoxide is present in the fuel gas, sufficient power generation characteristics cannot be obtained. In particular, a fuel cell operated at a low temperature has a stronger carbon monoxide adsorption and is more likely to be poisoned. For this reason, it is essential that the concentration of carbon monoxide in the fuel gas be reduced in a system using a polymer electrolyte fuel cell.

Therefore, a method of reacting carbon monoxide in a reformed gas obtained by reforming a raw material with steam to convert it into hydrogen and carbon dioxide, and further removing a small amount of carbon monoxide remaining by selective oxidation Is taken. Finally, the fuel hydrogen, which has been removed to a sufficiently low concentration of carbon monoxide, is introduced into the cathode of the fuel cell, where it is converted into protons and electrons on the electrocatalyst. The produced protons move to the anode side in the electrolyte, and react with oxygen together with the electrons that have passed through the external circuit to produce water. Electrons generate electricity by passing through an external circuit.

[0006] In each step of reforming raw materials and removing carbon monoxide until the production of hydrogen for fuel cells, the catalyst used for the cathode electrode is often a noble metal or copper in a reduced state. In such a state, if sulfur coexists, it becomes a catalyst poison, which lowers the catalytic activity of the hydrogen production process or the battery itself, and lowers the efficiency. Therefore, it is considered that sufficient removal of the sulfur content contained in the fuel is indispensable in order to use the catalyst used in the hydrogen production process and further the electrode catalyst with the original performance. The so-called desulfurization process, which basically removes sulfur, is performed at the very beginning of the hydrogen production process. Immediately thereafter, it is necessary to reduce the sulfur concentration to a level at which the catalyst used in the reforming step functions sufficiently, but it is usually 0.1 mass ppm or less.

Heretofore, as a method of removing the sulfur content of the fuel cell raw material, a desulfurization catalyst is used to hydrodesulfurize the hardly desulfurizable organic sulfur compound, and once converted into hydrogen sulfide which is easily adsorbed and removed, and then appropriately adsorbed. The method of treating with the agent was considered suitable. However, in general hydrodesulfurization catalysts, hydrogen pressure is used at high pressure, but when used in fuel cell systems, technological development is proceeding at atmospheric pressure or at most 1 MPa, so normal desulfurization catalysts are being developed. The current situation is that systems cannot handle it.

Therefore, an invention relating to an adsorbent capable of sufficiently exhibiting a desulfurizing function even in a low pressure system has been proposed, and various catalyst systems have been introduced so far. For example, Japanese Patent Laid-Open No. 1-184040
No. 4, JP-A-1-188405, a method for producing hydrogen by steam reforming kerosene desulfurized with a nickel-based desulfurizing agent is reported. However, in this case, the temperature range in which desulfurization is possible under good conditions is 150 to 300 ° C., which is a process limitation. The inlet temperature of the steam reforming device in the latter stage of desulfurization is 400 to 500 ° C, and the desulfurization temperature is preferably close to this temperature in the process. Also, Japanese Patent Laid-Open No. 2-30
2302 and JP-A-2-302303 disclose a copper-zinc-based desulfurizing agent. However, even if this catalyst is used at a relatively high temperature, carbon deposition is small, but its desulfurization activity is lower than that of nickel, so it can desulfurize light hydrocarbons such as natural gas, LPG, and naphtha. Is insufficient. Further, JP-A-1-143155 discloses a method of using activated carbon or a chemical solution for performing a desulfurization action. However, although this catalyst has been shown to be effective for desulfurization at room temperature at startup, the raw material is limited to gas at room temperature and has no effect on naphtha and kerosene.

[0009]

As described above, the steps of raw material reforming and carbon monoxide removal for producing fuel hydrogen for fuel cells, and the catalyst used for the cathode electrode are reduction of noble metal or copper. It is often used in the state, and when sulfur coexists in such a state, it becomes a catalyst poison and reduces the catalytic activity of the hydrogen production process or the battery itself,
Efficiency is reduced. Therefore, it is indispensable to sufficiently remove the sulfur content contained in the fuel in order to use the catalyst used in the hydrogen production process and the electrode catalyst with the original performance. Moreover, it is necessary to effectively desulfurize the hardly desulfurizable substance under low pressure conditions. The present invention provides a catalyst that clears such difficult conditions and a fuel cell system based on the catalyst.

[0010]

Means for Solving the Problems The present inventor has conducted earnest research and found a catalyst for efficiently desulfurizing a sulfur compound contained in a hydrocarbon raw material and hydrocracking a hydrocarbon, thereby completing the present invention. It came to. That is, according to the present invention, (1) a carrier containing a sulfur-containing hydrocarbon (1) zeolite or a clay compound in an amount of 30% by mass or more, Pt, Pd
And at least one metal selected from Re and 0.0
The sulfur concentration of the hydrocarbon is increased by bringing the catalyst A into contact with the catalyst A supported by 1 to 10% by mass and then (2) contacting the catalyst B containing 20% by mass or more of zinc oxide and / or nickel oxide. The present invention relates to a hydrocarbon desulfurization method characterized by desulfurization to 0.1 mass ppm or less.

Further, in the desulfurization method of the present invention, it is preferable that the carrier contains 50% by mass or more of Y-type zeolite or Y-type zeolite after dealumination treatment.
In the desulfurization method of the present invention, the carrier is Si and M.
It is preferable that the clay compound containing g as a main component is contained in an amount of 50% by mass or more.

Further, the present invention is a desulfurization apparatus having a first reaction section filled with the catalyst A and a second reaction section filled with the catalyst B, and a hydrocarbon desulfurized by the desulfurization apparatus containing hydrogen as a main component. The present invention relates to a fuel cell system including a reforming device for reforming into a fuel gas.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The present invention provides a carrier containing sulfur-containing hydrocarbon (1) to a carrier containing 30% by mass or more of a zeolite or a clay compound,
at least one metal selected from t, Pd and Re is brought into contact with a catalyst A supporting 0.01 to 10% by mass, and then (2) containing 20% by mass or more of zinc oxide and / or nickel oxide. The method for desulfurizing hydrocarbons is characterized in that the sulfur concentration of the hydrocarbons is desulfurized to 0.1 mass ppm or less by contact with the catalyst B. The sulfur concentration is measured by the ultraviolet fluorescence method.

The type of zeolite is not particularly limited, but Y type zeolite, X type zeolite, L type zeolite, β type zeolite, ZSM-5, mordenite and the like can be used. The clay compound is not particularly limited, but stevensite, hectorite, montmorillonite, bentonite, sepiolite, flypontite and the like can be used.

The content of zeolite or clay compound in the carrier must be 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more. If it is less than 30% by mass, the catalyst performance cannot be sufficiently exhibited. The upper limit is 100% by mass.

In the present invention, the zeolite is Y
Type zeolite or Y-type zeolite after dealumination treatment is preferable, and a carrier containing 50% by mass or more of Y-type zeolite or Y-type zeolite after dealumination treatment is particularly preferable. The Y-type zeolite has a Cavan ratio of 4 to 6 and the dealuminated Y-type zeolite has a Cavan ratio of 6 to 10.
Those of 0 are particularly preferable. The surface area is not particularly limited, but is usually preferably 150 to 800 m ² / g. Here, the surface area means the BET surface area measured by the nitrogen adsorption method.

Further, in the present invention, the clay compound is preferably a clay compound containing Si and Mg as main components,
A carrier containing at least 50% by mass or more of a clay compound containing Si and Mg as main components is particularly preferable. The clay compound containing Si and Mg as main components is not particularly limited, but examples thereof include stevensite, hectorite, saponite, sepiolite, and vermiculite. The surface area is not particularly limited, but is usually 100-
It is preferably 800 m ² / g.

The shape, size and molding method of the carrier are not particularly limited. Further, during molding, an appropriate binder may be added to improve moldability. The binder is not particularly limited, but alumina, silica, titania, zirconia, or a composite oxide thereof can be used. Alumina is preferably used, and the type of alumina is not particularly limited, but α-alumina, γ-alumina, δ-alumina, η-
Alumina, θ-alumina, χ-alumina and the like can be used. The blending ratio of the binder in the carrier is preferably 70% by mass or less, more preferably 50% by mass or less, and further preferably 30% by mass or less. The lower limit is not particularly limited as long as the function as a binder is exhibited, and is usually 1% by mass or more, preferably 5% by mass or more.

The method for supporting the metal selected from Pt, Pd and Re on the carrier is not particularly limited, and a known method such as an ordinary impregnation method or an ion exchange method can be used. For example, in the impregnation method, a metal salt or metal complex of Pt, Pd or Re is dissolved in a solvent such as water, ethanol or acetone, particularly preferably water, and the carrier is impregnated. When supporting multiple metals,
It may be carried simultaneously or sequentially, but preferably simultaneously. After that, a catalyst (catalyst A) carrying such a metal can be obtained by performing treatments such as drying and calcination.

The metal salt or metal complex of Pt, Pd or Re is not particularly limited as long as it can be dissolved in a solvent, and various chlorides, organic acid salts, complexes and the like can be mentioned. Is tetraaminedichloroplatinum, platinum chloride, platinum acetylacetonate, potassium hexachloroplatinate, etc., Pd is tetraaminedichloropalladium, palladium acetate, palladium acetylacetonate, palladium chloride, potassium hexachloropalladate, etc. Rhenium, potassium hexachlororhenate, potassium perrhenate, ammonium perrhenate, etc. can be used.

The drying method is not particularly limited,
For example, drying in air, deaeration drying under reduced pressure, or the like can be used. The drying temperature is usually room temperature to 15
It can be carried out at 0 ° C, preferably 50 to 140 ° C, particularly preferably 80 to 120 ° C. The firing method is also not particularly limited, and it is usually desirable to carry out in an air atmosphere at a temperature of 200 to 500 ° C, preferably 250 to 450 ° C, and a firing time of 0.1 to 10 ° C.
Time is preferable, and 0.5 to 5 hours is more preferable.

The total amount of one or more metals selected from Pt, Pd and Re supported is preferably 0.01 to 10.
%, More preferably 0.05 to 5% by mass, further preferably 0.1 to 2% by mass. The total amount carried is 0.
If it is less than 01% by mass, the catalytic performance is not exhibited, and if the total supported amount exceeds 10% by mass, not only is the dispersibility reduced, but it is also not economically preferable.

When the catalyst prepared by the above-mentioned method is used, it can be directly used for the reaction, but a reduction treatment with hydrogen or the like may be carried out as a pretreatment. The condition is a temperature of 150 to 500 ° C., preferably 200 to 400.
C is desirable, the time is 0.1 to 10 hours, preferably 0.5 to 5 hours.

The shape of the catalyst A is not particularly limited. For example, a catalyst which is tableted and crushed and then sized to an appropriate range, an extruded catalyst, an extruded catalyst to which an appropriate binder is added, and a powder are used. It is possible to use a catalyst in the form of particles. Alternatively, the above-mentioned metal may be applied to a carrier which is tableted and crushed and then sized in an appropriate range, an extruded carrier, a powder, or a carrier shaped into a suitable shape such as a sphere, a ring, a tablet, a cylinder or a flake. A supported catalyst or the like can be used.

The raw hydrocarbon containing sulfur is brought into contact with the catalyst A and then with a catalyst (catalyst B) containing 20% by mass or more of zinc oxide and / or nickel oxide to obtain a sulfur concentration of 0. It is desulfurized to 1 mass ppm or less. The main function of the catalyst B is to adsorb hydrogen sulfide produced by the catalyst A.

The content of zinc oxide and / or nickel oxide in catalyst B is preferably 20% by mass or more, more preferably 50% by mass or more. Two
If it is less than 0% by mass, the volume becomes too large to exhibit sufficient adsorption performance, which is not preferable. The upper limit is 10
It is 0 mass%. The catalyst B may contain silica and the like in addition to zinc oxide and / or nickel oxide.

The shape of the catalyst B is not particularly limited, and may be, for example, a tablet-molded catalyst, crushed and then sized to an appropriate range, an extruded catalyst, an extruded catalyst with a suitable binder, and a powder. It is possible to use a catalyst in the form of particles.

The sulfur-containing hydrocarbon used in the present invention is not particularly limited, but methane,
Examples include ethane, propane, butane, natural gas, LPG, naphtha, gasoline, kerosene, and mixtures thereof. These hydrocarbons used in the present invention usually contain sulfur of 100 mass ppm or less.

In the case of a fuel cell system, the pressure in the desulfurization reaction is preferably a low pressure in the range of atmospheric pressure to 1 MPa, particularly preferably atmospheric pressure to 0.9 MPa, in consideration of economical efficiency and safety of the fuel cell system. . When used in a hydrogen station or hydrogen production device, there is no pressure limit,
Considering economical efficiency and the like, the range of normal pressure to 20 MPa is preferable, and the range of normal pressure to 10 MPa is more preferable. The reaction temperature is not particularly limited as long as it is a temperature that reduces the sulfur concentration, but it is preferably room temperature to 450 ° C. The temperature is more preferably 120 to 400 ° C, and particularly preferably 140 to 380 ° C. If the SV is too high, the desulfurization reaction will not readily proceed, while if it is too low, the equipment will be large, and thus there is a suitable range. When using a liquid raw material, the range of 0.01 to 15 h ⁻¹ is preferable, and the range of 0.
The range of 05-5h ^-1 is more preferable, and 0.1-3h ^-1
Is particularly preferred. 10 when using gas fuel
The range of 0 to 10000 h ⁻¹ is preferable, and the range of 200 to 500
The range of 0h ^-1 is more preferable, and 300 to 2000h ^-1
Is particularly preferred. Regarding the flow rate of hydrogen, 1 g of raw material
Therefore, it is preferable to introduce 0.05 to 1.0 NL of hydrogen.

The form of the desulfurization apparatus using the desulfurization method of the present invention is not particularly limited, but for example, a flow type fixed bed system can be used. The desulfurization device may have any known shape such as a cylindrical shape or a flat plate shape depending on the purpose of each process.

By using the desulfurization method of the present invention, the sulfur concentration of the above-mentioned sulfur-containing hydrocarbon raw material is set to 0.1.
It can be reduced to mass ppm or less. Sulfur concentration 0.
The hydrocarbon raw material desulfurized to 1 mass ppm or less then undergoes a reforming step, a shift step, a carbon monoxide selective oxidation step, etc., so that the produced hydrogen-rich gas can be used as a fuel for a fuel cell.

The modification step is not particularly limited.
However, it is modified by treating the raw material with steam at high temperature on the catalyst.
Quality steam reforming, partial oxidation with oxygen-containing gas,
Autothermal recovery in a system in which water vapor and oxygen-containing gas coexist
Auto thermal reforming, etc. that perform mold reforming reaction
Can be used. The reaction conditions for reforming are limited.
The reaction temperature is preferably 200 to 1000 ° C.
More preferably, 500-850 degreeC is especially preferable. The reaction pressure is
Normal pressure to 1 MPa is preferable, and normal pressure to 0.2 MPa is particularly preferable.
preferable. LHSV is 0.01-40h ^-1Is preferred,
Especially 0.1-10h^-1Is preferred.

The mixed gas containing carbon monoxide and hydrogen obtained at this time can be directly used as a fuel for a fuel cell in the case of a solid oxide fuel cell. Also, for fuel cells that require removal of carbon monoxide, such as phosphoric acid fuel cells and polymer electrolyte fuel cells,
It can be suitably used as a raw material of hydrogen for the fuel cell.

The production of hydrogen for a fuel cell can be carried out by a known method, for example, by carrying out a shift step and a carbon monoxide selective oxidation step. The shift step is a step of reacting carbon monoxide and water to convert into hydrogen and carbon dioxide, for example, a mixed oxide of Fe—Cr,
Using a catalyst containing a mixed oxide of Zn-Cu, platinum, ruthenium, iridium, etc., a carbon monoxide content of 2 v
ol% or less, preferably 1 vol% or less, and more preferably 0.5 vol% or less. The reaction conditions for the shift reaction are not necessarily limited depending on the composition of the reformed gas as a raw material, but the reaction temperature is 120 to 500.
C. is preferable, and 150 to 450 ° C. is particularly preferable. The pressure is preferably atmospheric pressure to 1 MPa, particularly atmospheric pressure to 0.2 MPa.
Is preferred. GHSV is preferably 100~50000h ^-1, especially 300～10000H ^-1 are preferred. Normal,
In a phosphoric acid fuel cell, the mixed gas in this state can be used as a fuel.

On the other hand, in the polymer electrolyte fuel cell, since it is necessary to further reduce the carbon monoxide concentration, it is desirable to provide a step of removing carbon monoxide. This step is not particularly limited, and the adsorption separation method,
Although various methods such as a hydrogen separation membrane method and a carbon monoxide selective oxidation step can be used, it is particularly preferable to use the carbon monoxide selective oxidation step from the viewpoint of compactness of the apparatus and economy. In this step, a catalyst containing iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, etc. is used, and the amount of remaining carbon monoxide is 0.5 to 10 times. The carbon monoxide concentration is reduced by adding moles, preferably 0.7 to 5 times, and more preferably 1 to 3 times the molar amount of oxygen to selectively convert carbon monoxide into carbon dioxide. The reaction conditions of this method are not limited, but the reaction temperature is preferably 80 to 350 ° C, particularly preferably 100 to 300 ° C. The pressure is preferably atmospheric pressure to 1 MPa, particularly preferably atmospheric pressure to 0.2 MPa. GHSV is 1000-50
000 h ^-1 is preferable, and particularly 3000 to 30000 h ^-1
Is preferred. In this case, it is possible to reduce the carbon monoxide concentration by reacting with the coexisting hydrogen and producing methane simultaneously with the oxidation of carbon monoxide.

The first aspect of the present invention is that the carrier containing at least 30% by mass of zeolite or clay compound is filled with the catalyst A carrying 0.01 to 10% by mass of at least one metal selected from Pt, Pd and Re. Desulfurization apparatus having a reaction section and a second reaction section filled with a catalyst B containing at least 20% by mass of at least one of zinc oxide and nickel oxide, and a fuel containing hydrogen as a main component of the hydrocarbon desulfurized by the desulfurization apparatus. The present invention relates to a fuel cell system equipped with a reformer for reforming gas.

An example of this fuel cell system is shown below in FIG.
Explain. The raw fuel in the fuel tank 3 flows into the desulfurizer 5 via the fuel pump 4. At this time, if necessary, the hydrogen-containing gas from the selective oxidation reactor 11 can be added.
The desulfurizer 5 comprises a first reaction part filled with the catalyst A and a second reaction part filled with the catalyst B. The desulfurizer 5 may be composed of two reactors, a first reaction section and a second reaction section. The fuel desulfurized by the desulfurizer 5 is mixed with water from the water tank 1 through the water pump 2, and then introduced into the vaporizer 6 and fed into the reformer 7.

The reformer 7 is heated by a heating burner 18. The anode off gas of the fuel cell 17 is mainly used as the fuel for the heating burner 18, but the fuel pump 4 may be used as necessary.
It is also possible to supplement the fuel discharged from the. Reformer 7
As a catalyst to be filled in, a nickel-based, ruthenium-based, rhodium-based catalyst or the like can be used. The thus-produced gas containing hydrogen and carbon monoxide is sequentially passed through the high temperature shift reactor 9, the low temperature shift reactor 10 and the selective oxidation reactor 11 so that the concentration of carbon monoxide can be adjusted to the characteristics of the fuel cell. It is reduced to the extent that it has no effect. Examples of catalysts used in these reactors include high temperature shift reactor 9
Is an iron-chromium based catalyst, and the low temperature shift reactor 10 is copper-
Examples of the zinc-based catalyst and the selective oxidation reactor 11 include ruthenium-based catalysts.

The polymer electrolyte fuel cell 17 has an anode 1
2, a cathode 13, and a solid polymer electrolyte 14, a fuel gas containing the high-purity hydrogen obtained by the above method is required on the anode side, and air sent from an air blower 8 is required on the cathode side. If so, it is introduced after a suitable humidification treatment (a humidifier is not shown). At this time, a reaction in which hydrogen gas becomes a proton and releases an electron proceeds in the anode, and a reaction in which oxygen gas obtains an electron and a proton to become water proceeds at the cathode. In order to accelerate these reactions, platinum black, and
Activated carbon-supported Pt catalyst or Pt-Ru alloy catalyst is used, and cathode is platinum black, activated carbon-supported Pt catalyst or the like. Normally, both the anode and cathode catalysts are molded into a porous catalyst layer together with polytetrafluoroethylene, a low molecular weight polymer electrolyte membrane material, activated carbon, etc., if necessary.

Next, Nafion (made by DuPont), G
oRe (made by Gore), Flemion (made by Asahi Glass),
MEA in which the porous catalyst layers are laminated on both sides of a polymer electrolyte membrane known under the trade name such as Aciplex (manufactured by Asahi Kasei)
(Membrane Electrode Assemble
bly) is formed. Further, the fuel cell is assembled by sandwiching the MEA with a separator made of a metal material, graphite, carbon composite or the like, which has a gas supply function, a current collecting function, and particularly an important drainage function in the cathode. The electric load 15 is electrically connected to the anode and the cathode. Anode burner 1 for heating off gas
8 consumed. Exhaust port 16 for cathode off gas
Emitted from.

[0041]

INDUSTRIAL APPLICABILITY The catalyst of the present invention can desulfurize sulfur-containing hydrocarbons and reduce the sulfur concentration to 0.1 mass ppm or less. The fuel gas obtained is particularly a polymer electrolyte fuel cell. It can be suitably used for a fuel cell system using the.

[0042]

The present invention will be described below with reference to examples, but the present invention is not limited thereto.

(Example 1) ² g per 18 g of in-house manufactured Y-type zeolite (Cayvan ratio 5, surface area 390 m ² / g)
Was added and kneaded to obtain an extruded body. After drying this molded body at 120 ° C. overnight, an air atmosphere,
Firing was performed at 400 ° C. to obtain a carrier. Tetraaminedichloropalladium (Pd: 41% by mass) 0.20 g and rhenium trichloride (Re: 63.5% by mass) 0.09 g were dissolved in 12 g of water and impregnated and carried on this carrier. Then 1
After drying overnight at 20 ° C., it was calcined for 3 hours under the conditions of an air atmosphere and 300 ° C. to obtain a catalyst (1). The supported Pd amount and Re amount are 0.4% by mass and 0.3% by mass, respectively.
Met.

Example 2 With respect to 20 g of Ionite T (Stevensite, surface area 440 m ² / g) manufactured by Mizusawa Chemical Co., Ltd., 0.11 g of tetraaminedichloroplatinum (Pt:
55% by mass) and 0.24 g of tetraaminedichloropalladium (Pd: 41% by mass) were dissolved in 14 g of water and impregnated and supported. Then, after drying at 120 ° C. overnight,
It was calcined in an air atmosphere at 300 ° C. for 3 hours to obtain a catalyst (2). The amounts of Pt and Pd supported were 0.3% by mass and 0.5% by mass, respectively.

Example 3 Mizusuka Chemical Co., Ltd. Mizuka Life (silica magnesia clay compound, surface area 570 m ² /
g) With respect to 20 g, 0.11 g of tetraaminedichloroplatinum (Pt: 55% by mass) and 0.24 g of tetraaminedichloropalladium (Pd: 41% by mass) were dissolved in 14 g of water and impregnated and supported. Then, it was dried overnight at 120 ° C., and then calcined for 3 hours under an air atmosphere at 300 ° C. to obtain a catalyst (3). The amounts of Pt and Pd supported were 0.3% by mass and 0.5% by mass, respectively.

Example 4 With respect to 20 g of Ionite H (hectorite, surface area 350 m ² / g) manufactured by Mizusawa Chemical Co., Ltd., 0.11 g of tetraaminedichloroplatinum (Pt: 5) was used.
5% by mass) and 0.24 g of tetraaminedichloropalladium (Pd: 41% by mass) were dissolved in 14 g of water and impregnated and supported. Then, after drying overnight at 120 ° C., it was calcined for 3 hours under the condition of air atmosphere and 300 ° C. to obtain a catalyst (4). The amounts of Pt and Pd supported were 0.3% by mass and 0.5% by mass, respectively.

Example 5 0.11 g of tetraaminedichloroplatinum (Pt: 5) per 20 g of Smecton SA (saponite, surface area 230 m ² / g) manufactured by Kunimine Co., Ltd.
5% by mass) and 0.24 g of tetraaminedichloropalladium (Pd: 41% by mass) were dissolved in 14 g of water and impregnated and supported. Then, it was dried overnight at 120 ° C. and then calcined for 3 hours under an air atmosphere at 300 ° C. to obtain a catalyst (5). The amounts of Pt and Pd supported were 0.3% by mass and 0.5% by mass, respectively.

(Comparative Example 1) ² g per 18 g of in-house produced Y-type zeolite (Cayvan ratio 5, surface area 250 m ² / g)
Was added and kneaded to obtain an extruded body. After drying this molded body at 120 ° C. overnight, an air atmosphere,
Firing was performed at 400 ° C. to obtain a carrier. 0.7 g of nickel nitrate and 2.8 g of phosphomolybdic acid were dissolved in 12 g of water and impregnated and supported on this carrier. The zeolite molded body supporting nickel nitrate and phosphomolybdic acid was dried overnight at 120 ° C., and then calcined for 3 hours in an air atmosphere at 300 ° C. to obtain a catalyst (6). Supported MoO ₃ amount, N
The amounts of iO were 12% by mass and 3% by mass, respectively.

Comparative Example 2 With respect to 20 g of Ionite H (hectorite, surface area 350 m ² / g) manufactured by Mizusawa Chemical Co., Ltd., 0.7 g of nickel nitrate and 2.8 g of phosphomolybdic acid were dissolved in 12 g of water. And impregnated and supported. After drying the supported clay compound at 120 ° C. overnight, the air atmosphere, 35
It was calcined at 0 ° C. for 3 hours to obtain a catalyst (7). The supported amount of MoO ₃ and NiO are 12% by mass and 3 respectively.
It was mass%.

Comparative Example 3 With respect to 20 g of γ-alumina produced in-house (surface area 220 m ² / g), 0.11 g of tetraaminedichloroplatinum (Pt: 55% by mass) and 0.24 g of tetraaminedichloropalladium (Pd). : 41 mass%)
Was dissolved in 14 g of water and impregnated and supported. After drying the supported γ-alumina at 120 ° C. overnight, the air atmosphere, 300
It was calcined for 3 hours under the condition of ° C to obtain a catalyst (8). The amounts of Pt and Pd supported were 0.3% by mass and 0.5% by mass, respectively.

Next, 10 cm ³ of the catalyst (1) was filled in the first reaction part, and a commercially available zinc oxide catalyst (Zudchemy catalyst Co., Ltd.) was used.
The second reaction part was filled with 5 cm ³ of SC72 manufactured by the company. Similarly for catalysts (2) to (8), 10 cm each
³ was charged in the first reaction part, and 5 cm ³ of a commercially available zinc oxide catalyst (SC72 manufactured by Sudchemy Catalyst Co., Ltd.) was charged in the second reaction part. In this example, the first reaction section and the second reaction section are continuously filled in one reaction tube in the order of first and second.

After the catalyst was charged, the catalysts (1) to (5) were reduced in a hydrogen stream at 300 ° C. for 5 hours, and then 1
The desulfurization reaction of No. kerosene (sulfur concentration: 15 mass ppm) was evaluated. Regarding catalysts (6) and (7), after pre-sulfiding in a 5% by volume hydrogen sulfide / hydrogen stream at 300 ° C. for 5 hours,
The desulfurization reaction of No. 1 kerosene (sulfur concentration: 15 mass ppm) was evaluated. The reaction evaluation is 250 NL for 1 L of kerosene.
Was circulated and the conditions were as follows. 500
The sulfur concentration in the produced kerosene after the lapse of time is shown in the reaction conditions shown in Table 1: 320 ° C., hydrogen pressure 0.8 MPa, LHSV
0.5 h ⁻¹ reaction condition 2: 280 ° C., hydrogen pressure 5 MPa, LHSV 1.
0h ^-1

[0053]

[Table 1]

Example 6 In the fuel cell system of FIG. 1, the desulfurizer 5 was charged with the catalyst (1) obtained in Example 1 in the first reaction section and zinc oxide in the second reaction section, A power generation test was performed using No. 1 kerosene (sulfur concentration: 15 mass ppm) as a fuel. During the 200 hours of operation, the desulfurizer worked normally,
No decrease in the activity of the catalyst was observed. The desulfurization conditions are a temperature of 280 ° C., a hydrogen pressure of 0.8 MPa, and a hydrogen flow rate of 250 NL /
Kerosene 1L, LHSV = 0.5h- ¹ . As the hydrogen, an off gas after selective oxidation (hydrogen concentration of about 75% by volume) was used. At this time, Ru-based catalyst was used for steam reforming, and S / C
= 3, temperature 700 ° C., LHSV = 5 h ⁻¹ , the shift step (reactor 10) uses a Cu—Zn-based catalyst, and 2
Under the conditions of 00 ° C. and GHSV = 2000 h ⁻¹ , a Ru-based catalyst was used in the carbon monoxide selective oxidation step (reactor 11), and O
₂ / CO = 3, temperature 150 ° C, GHSV = 5000h ^-1
It was operated under the conditions. The fuel cell also operated normally, and the electric load 15 also operated smoothly.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing an example of a fuel cell system of the present invention.

[Explanation of symbols]

1 water tank 2 water pump 3 fuel tank 4 fuel pump 5 desulfurizer 6 vaporizer 7 reformer 8 air blowers 9 High temperature shift reactor 10 Low temperature shift reactor 11 Selective oxidation reactor 12 Anode 13 cathode 14 Solid polymer electrolyte 15 Electric load 16 exhaust port 17 Polymer electrolyte fuel cell 18 Heating burner

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C10G 45/10 C10G 45/10 Z 45/12 45/12 Z C10L 3/10 H01M 8/06 G H01M 8 / 06 8/10 8/10 C01B 3/38 // C01B 3/38 C10L 3/00 BF term (reference) 4G040 EA03 EA06 EA07 EB01 4G069 AA03 AA08 BA01B BA07A BA07B BA10A BA10B BB04A BB04B BC10A BC35A BC35B BC64A BC72B BC72B BC75A BC75B BD05A CC02 CC32 DA05 EC03Y EC04Y FA01 FA02 FB14 FB30 FC08 ZA03A ZA04A ZA04B ZA05A ZA06A ZA08A ZA11A ZA19A ZC04 ZC07 4H029 CA00 DA00 DA09 5H026 AA06 HH06 BA0 AH

Claims (4)

[Claims] 1. A carrier containing (1) zeolite or a clay compound in an amount of 30% by mass or more of a hydrocarbon containing sulfur,
It is brought into contact with a catalyst A supporting at least one metal selected from Pt, Pd and Re in an amount of 0.01 to 10% by mass, and then (2) containing 20% by mass or more of zinc oxide and / or nickel oxide. A method for desulfurizing a hydrocarbon, characterized in that the sulfur concentration of the hydrocarbon is desulfurized to 0.1 mass ppm or less by contact with the catalyst B. 2. The desulfurization method according to claim 1, wherein the carrier contains 50% by mass or more of Y-type zeolite or Y-type zeolite after dealumination treatment. 3. The desulfurization method according to claim 1, wherein the carrier contains 50% by mass or more of a clay compound containing Si and Mg as main components. 4. A desulfurizer having a first reaction part filled with the catalyst A and a second reaction part filled with the catalyst B,
A fuel cell system provided with a reformer for reforming hydrocarbon desulfurized by the desulfurizer into a fuel gas containing hydrogen as a main component.