JP2003103176A - Desulfurization catalyst for hydrocarbon, desulfurization method and fuel cell system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst which desulfurizes hydrocarbon raw material including sulfur, reduces the concentration of sulfur to 0.1 wt.ppm or less and allows the obtained fuel gas to be suitably used for a fuel cell system using a solid polymer type fuel cell in particular. SOLUTION: The hydrocarbon raw material containing sulfur can be desulfurized to sulfur concentration of 0.1 ppm or less by using the desulfurization catalyst for hydrocarbon made by depositing 0.1-50 mass% of rare earth element such as lanthanum and yttrium or rare earth element compound as element on Y-type zeolite.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a desulfurization catalyst for hydrocarbons. Further, the present invention relates to a desulfurization method using this catalyst, and further to a fuel cell system equipped with a desulfurization device filled with this 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 and carbon monoxide obtained by performing the above are basically used as fuel hydrogen for fuel cells.

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 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 treatment with the agent seems to be 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 a sorbent that exhibits a sufficient 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 raw material, and completed the present invention. That is, the present invention relates to a desulfurization catalyst for hydrocarbons, which comprises 0.1 to 50 mass% of a rare earth element or a rare earth compound as an element supported on Y-type zeolite. The Y-type zeolite preferably has a Cavan ratio of 4 or more and 11 or less. The rare earth element is preferably La or Y.

The present invention also uses the above-mentioned catalyst,
The present invention relates to a method for desulfurizing a hydrocarbon raw material containing sulfur to a sulfur concentration of 0.1 ppm or less. Further, the present invention is a desulfurization apparatus for desulfurizing a hydrocarbon raw material containing sulfur, which is filled with a desulfurization catalyst for hydrocarbons in which Y-type zeolite carries 0.1 to 50% by mass of a rare earth element or a rare earth compound as an element. And a fuel cell system having at least a reformer for reforming the hydrocarbon raw material desulfurized by the desulfurizer into a fuel gas containing hydrogen as a main component.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
TECHNICAL FIELD The present invention relates to a desulfurization catalyst for hydrocarbons, which is obtained by supporting a rare earth element or a rare earth compound as an element on Y-type zeolite in an amount of 0.1 to 50% by mass. The Cayvan ratio (SiO ₂ / Al ₂ O ₃ ratio) of the Y-type zeolite as the carrier is
It is preferably 4 or more and 11 or less. It is particularly preferably 5 or more and 6 or less. C-ban ratio of Y-type zeolite is 4
If it is less than 11, the carrier performance is not exhibited, and if it is more than 11, the acid points are reduced, and stable loading becomes difficult. Surface area of the Y-type zeolite is not particularly limited, the upper limit is preferably 1000 m ² / g, particularly preferably 800 m ² / g, the lower limit is preferably 50 m ² /
g, particularly preferably 200 m ² / g. The shape, size, and molding method of the carrier are not particularly limited. At the time of molding, an appropriate binder may be added to improve moldability. The binder is not particularly limited, but alumina, silica, titania, zirconia, a composite oxide thereof, or the like can be used. The upper limit of the addition amount of the binder is 50% by mass, preferably 30% by mass, and the lower limit is not particularly limited as long as it can exhibit the function as a binder, but is, for example, 1% by mass, preferably 5% by mass. Is.

La, Y, Ce, S are used as rare earth elements.
c, Yb, Gd, Sm, etc. can be used, but L
Especially preferred is a or Y. L as a rare earth compound
It is possible to use chlorides, nitrates, sulfates, organic acid salts and the like of rare earth elements such as a, Y, Ce, Sc, Yb, Gd and Sm. A compound of La or Y is particularly preferable.

The method for supporting the rare earth element 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, the rare earth compound is dissolved in water, a solvent such as ethanol or acetone, particularly preferably water, and the carrier is impregnated.
After that, a supported catalyst is obtained by performing drying, firing and the like. The rare earth compound is not particularly limited as long as it is soluble in a solvent, various chlorides, nitrates, sulfates,
Examples of the organic acid salt include lanthanum nitrate, lanthanum chloride, yttrium nitrate, and yttrium chloride.

The amount of the rare earth element or rare earth compound supported as an element is 0.1 to 50% by mass, preferably 5 to 45% by mass, and particularly preferably 10 to 40% by mass. When the supported amount is less than 0.1% by mass, the catalytic performance is not exhibited, and when the supported amount exceeds 50% by mass, not only the dispersibility of the rare earth element decreases but also from the economical aspect. Not preferable.

The drying method is not particularly limited, but, for example, natural drying in air, degassing drying under reduced pressure and the like can be used. The firing method is not particularly limited, but usually in an air atmosphere and at a temperature of 250 to 650.
C., preferably 400 to 550.degree. C., and the time is 0.1 to 10 hours, preferably 0.5.
It is desirable to carry out for about 5 hours. When the catalyst prepared by the above method is used, it can be directly used for the reaction, but a reduction treatment with hydrogen or the like may be performed as a pretreatment. As the conditions, the temperature is 150 to 500 ° C, preferably 250 to 400 ° C, and the time is 0.1 to 10 ° C.
Time is desirable, preferably 0.5 to 5 hours.

The shape of the catalyst is not particularly limited. For example, a catalyst which has been tableted and crushed and then sized to an appropriate range, an extruded catalyst, an extruded catalyst with an appropriate binder, and a powdered form. A catalyst or the like can be used. The binder is not particularly limited, but alumina, silica, titania, zirconia,
Alternatively, a composite oxide thereof or the like can be used. Alternatively, the metal is carried on a carrier which has been tableted and crushed and then sized in an appropriate range, an extrusion-molded carrier, a powder or a carrier shaped into a suitable shape such as a spherical shape, a ring shape, a tablet shape, a cylindrical shape, or a flake shape. A catalyst or the like can be used.

The present invention also uses the above-mentioned catalyst,
The present invention relates to a method for desulfurizing a hydrocarbon raw material containing sulfur to a sulfur concentration of 0.1 ppm or less. The sulfur-containing hydrocarbon raw material used in the present invention is not particularly limited, but includes methane, ethane, propane, butane, natural gas, LPG, naphtha, gasoline, kerosene, and mixtures thereof. . The raw material may contain hydrogen. These hydrocarbon raw materials used in the present invention usually contain 0.1 to 100 mass ppm of sulfur.

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 0.2 MPa, in consideration of economical efficiency and safety of the fuel cell system. The reaction temperature is not particularly limited as long as it is a temperature that lowers the sulfur concentration, but also when starting the equipment,
It is necessary to work effectively from room temperature, and it is preferably room temperature to 450 ° C in consideration of the steady state. More preferably, the temperature is from room temperature to 350 ° C, and particularly preferably from room temperature to 300 ° 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, 0.01 to
Is preferably in the range of 15h ^-1, more preferably in the range of 0.05~5h ^-1, range 0.1～3H ^-1 are particularly preferred. When using gas fuel, 100 to 10,000 h ^-1
Preferably in the range of, more preferably in the range of 200～5000H ^-1, range 300～2000H ^-1 are particularly preferred.

The form of the desulfurization apparatus filled with the desulfurization catalyst of the present invention is not particularly limited, but for example, a flow type fixed bed system can be used. The shape of the desulfurizer is
It 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 catalyst of the present invention, a sulfur concentration of 0.1% can be obtained from the above-mentioned sulfur-containing hydrocarbon raw material.
It can be ppm or less. Sulfur concentration 0.1ppm
The hydrocarbon raw material desulfurized below is then subjected to the reforming step,
By passing through the shift process, the carbon monoxide selective oxidation process, and the like, the generated hydrogen-rich gas can be used as the fuel for the fuel cell. The reforming step is not particularly limited, but steam reforming in which the raw material is subjected to high temperature treatment with steam on the catalyst for reforming, partial oxidation with an oxygen-containing gas,
In addition, autothermal reforming or the like in which a self-heat recovery type reforming reaction is performed in a system in which water vapor and an oxygen-containing gas coexist can be used.

The reaction conditions for reforming are not limited.
However, the reaction temperature is preferably 200 to 1000 ° C.
It is preferably 500 to 850 ° C. Reaction pressure is normal pressure to 1M
Pa is preferable, and normal pressure to 0.2 MPa is particularly preferable.
LHSV is 0.01-40h ^-1Is preferred, especially 0.1
-10h^-1Is preferred. Carbon monoxide obtained at this time
Mixed gas containing hydrogen can be used in solid oxide fuel cells such as
In some cases, use it as it is as fuel for fuel cells.
You can In addition, phosphoric acid fuel cells and solid polymer fuel
When it is necessary to remove carbon monoxide as in a battery,
It can be suitably used as a raw material of hydrogen for fuel cells
It

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, and is a mixed oxide of Fe—Cr and Zu—C.
Using a catalyst containing a mixed oxide of u, platinum, ruthenium, iridium, etc., the carbon monoxide content is 2 vol% or less, preferably 1 vol% or less, more preferably 0.
Drop to 5 vol% or less. The reaction conditions for the shift reaction are not necessarily limited depending on the composition of the reformed gas used as a raw material, but the reaction temperature is preferably 120 to 500 ° C, and particularly preferably 150 to 450 ° C. Pressure is normal pressure ~
1 MPa is preferable, and normal pressure to 0.2 MPa is particularly preferable. GHSV is preferably 100~50000h ^-1, especially 300～10000H ^-1 are preferred. Usually, in a phosphoric acid fuel cell, a 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, but an adsorption separation method, a hydrogen separation membrane method, a carbon monoxide selective oxidation step or the like can be used. The carbon monoxide selective oxidation step is preferable from the viewpoints of compactness of the apparatus and economy. In this process, iron, cobalt, nickel, ruthenium, rhodium,
Palladium, osmium, iridium, platinum, copper, silver,
Using a catalyst containing gold or the like, adding oxygen in an amount of 0.5 to 10 times, preferably 0.7 to 5 times, and more preferably 1 to 3 times the molar amount of the remaining carbon monoxide. The carbon monoxide concentration is reduced by selectively converting carbon monoxide into carbon dioxide. The reaction conditions of this method are not limited, but the reaction temperature is 80 to 35.
0 ° C. is preferable, 100 to 300 ° C. is particularly preferable, and pressure is normal pressure to 1 MPa, particularly preferably normal pressure to
0.2 MPa, GHSV is preferably 1000~50000h ^-1, particularly preferably selected respectively in the range of 3000~30000h ^-1. 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.

In the present invention, the Y-type zeolite contains a rare earth element or a rare earth compound as an element in an amount of 0.1 to 50% by mass.
A desulfurization apparatus for desulfurizing a hydrocarbon raw material containing sulfur, which is filled with a desulfurization catalyst for supporting hydrocarbons, and a hydrocarbon raw material desulfurized by the desulfurization apparatus are converted into a fuel gas containing hydrogen as a main component. TECHNICAL FIELD The present invention relates to a fuel cell system including at least a reforming device that improves quality.

An example of this fuel cell system is shown 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 is filled with a desulfurization catalyst in which Y-type zeolite has 0.1 to 50 mass% of a rare earth element as an element. 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 (manufactured by Gore), Flemion (manufactured by Asahi Glass Co., Ltd.),
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.

[0030]

INDUSTRIAL APPLICABILITY The catalyst of the present invention is capable of desulfurizing a hydrocarbon raw material containing sulfur to reduce the sulfur concentration to 0.1 mass ppm or less. It can be suitably used for a fuel cell system using a fuel cell.

[0031]

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

(Example 1) 20 g of Y-type zeolite having a Cayvan ratio of 5 was immersed in 150 ml of a 50% by mass lanthanum nitrate solution, allowed to stand for 3 hours, then air-dried, and then air atmosphere, 500 ° C. After being calcined for 3 hours, 20% by mass of alumina was added, and the mixture was kneaded and extruded to obtain a catalyst (1) having a diameter of 1.6 mm. The amount of lanthanum carried was 30% by mass.

Example 2 20 g of Y-type zeolite having a Cavan ratio of 5 was added to 150 ml of a 50 mass% yttrium nitrate solution.
Soak it in water and let it sit for 3 hours, then let it air dry in the air,
Then, after calcining for 3 hours in an air atmosphere at 500 ° C., 20% by mass of alumina was added, and kneading and extrusion molding were performed to obtain a catalyst (2) having a diameter of 1.6 mm. The amount of supported yttrium was 30 mass%.

Comparative Example 1 20 g of Y-type zeolite having a Cavan ratio of 5 was immersed in 350 ml of a 50% by mass lanthanum nitrate solution, allowed to stand for 3 hours, then air-dried, and then in an air atmosphere at 500 ° C. After being calcined for 3 hours, 20% by mass of alumina was added, and the mixture was kneaded and extruded to obtain a catalyst (3) having a diameter of 1.6 mm. The amount of lanthanum supported was 55% by mass.

(Comparative Example 2) 20 g of Y-type zeolite having a Cavan ratio of 5 was added to 350 ml of a 50 mass% yttrium nitrate solution.
Soak it in water and let it sit for 3 hours, then let it air dry in the air,
Then, after calcining for 3 hours in an air atmosphere at 500 ° C., 20% by mass of alumina was added, and the catalyst (4) having a diameter of 1.6 mm was obtained by kneading and extrusion molding. The amount of supported yttrium was 55 mass%.

One of each of these catalysts (1) to (4) was used.
After filling a 0 ml reaction tube and reducing it in a hydrogen stream at 300 ° C. for 2 hours, the desulfurization reaction of kerosene was evaluated. The reaction evaluation is 300 ° C., normal pressure, LHSV 1.0 h ⁻¹ , catalyst amount 10
cm ³ and the concentration of sulfur in the starting kerosene was 35 mass ppm, and the sulfur concentration in the produced kerosene after 300 hours is shown in Table 1.

[0037]

[Table 1]

Further, 10 ml of each of these catalysts (1) to (4) was filled in a reaction tube and reduced in a hydrogen stream at 300 ° C. for 2 hours, and then the desulfurization reaction of kerosene was evaluated. The reaction was evaluated at room temperature, normal pressure, LHSV 0.5h ^-1 , and catalyst amount 10
cm ² and the concentration of sulfur in the raw kerosene was 35 mass ppm, and the sulfur concentration in the produced kerosene after 200 hours is shown in Table 2.

[0039]

[Table 2]

Example 3 In the fuel cell system of FIG. 1, the catalyst (1) obtained in Example 1 was filled in the desulfurizer 5, and kerosene was used as a fuel to perform a power generation test. During the operation for 200 hours, the desulfurizer worked normally and no decrease in the activity of the catalyst was observed. At this time, Ru-based catalyst was used for steam reforming, Cu / Zn-based catalyst was used for CO shift under conditions of S / C = 3, 700 ° C. and LHSV = 5, and 200
C, GHSV = 2000, CO selective oxidation process uses Ru-based catalyst, O ₂ / CO = 3, 150 ° C., GH
The operation was performed under the condition of SV = 5000. 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

Continued front page    F-term (reference) 4G040 EA02 EA03 EA04 EA06 EB01                 4G069 AA03 AA08 BA01B BA07A                       BA07B BC38A BC40A BC40B                       BC42A BC42B CC02 DA05                       EA02Y FA01 FA02 FB14                       FB67 FC08 ZA04A ZA04B                       ZC04                 4H029 CA00 DA00                 5H027 AA06 BA01 BA16 BA17 KK31

Claims (5)

[Claims] 1. A desulfurization catalyst for hydrocarbons, which comprises a Y-type zeolite supporting a rare earth element or a rare earth compound as an element in an amount of 0.1 to 50% by mass. 2. A C-ban ratio of Y-type zeolite is 4 or more and 1
It is 1 or less, The desulfurization catalyst of Claim 1 characterized by the above-mentioned. 3. The desulfurization catalyst according to claim 1 or 2, wherein the rare earth element is La or Y. 4. A method for desulfurizing a sulfur-containing hydrocarbon raw material to a sulfur concentration of 0.1 ppm or less, using the catalyst according to any one of claims 1 to 3. 5. A desulfurization apparatus for desulfurizing a hydrocarbon raw material containing sulfur, which is filled with a desulfurization catalyst for hydrocarbons in which Y-type zeolite carries 0.1 to 50% by mass of a rare earth element or a rare earth compound as an element. And a reformer for reforming the hydrocarbon raw material desulfurized by the desulfurizer into a fuel gas containing hydrogen as a main component.