JP2003064386A - Desulfurizing agent for removing sulfur compound in fuel gas, and fuel cell power generation system utilizing the agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a desulfurizing agent for enabling a sulfur compound used as odorant to be removed for a long time at -20 to 300 deg.C from a fuel gas such as town gas or LPG (liquefied petroleum gas), and to provide a fuel cell power generation system utilizing the desulfurizing agent. SOLUTION: This desulfurizing agent for adsorbing and removing a sulfur compound from a fuel gas containing the sulfur compound comprises a zeolite- based carrier and a catalytically active metal borne on the carrier. The other objective fuel cell power generation system includes a reformer 2 for producing hydrogen by reaction between the desulfurizing agent, the fuel gas desulfurized by the agent and water and a solid polymer fuel cell 5 set downstream of the reformer 5 and designed to generate electric power from the hydrogen produced as above.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a desulfurizing agent for removing sulfur compounds in fuel gas. Further, in detail, city gas, LPG (Liquifie)
d Petroleum Gas: liquefied petroleum gas) as a hydrogen raw material
(Polymer Electrolyte Fuel
Cell: PEFC) relating to a desulfurizing agent used in the preceding stage.

[0002]

2. Description of the Related Art In recent years, with the strong demand for prevention of global warming, various attempts have been made to solve energy problems in consideration of environmental problems. Above all, a cogeneration system, which is a system that efficiently uses energy by converting primary energy such as city gas and LPG into electricity and power and a plurality of secondary energy such as hot water and steam, has attracted attention. Since the cogeneration system is manufactured at the place where energy is needed, there is no loss due to energy transportation such as power transmission, and it is also possible to recover and effectively use the waste heat that was discarded by the conventional power generation method. .

Further, among the cogeneration systems, what is said to be an ideal system is a fuel cell power generation system which functions as a distributed power source. It is said that the fuel cell power generation system has very clean exhaust gas, has environmentally friendly characteristics, has high power generation efficiency even with a small capacity, and further improves overall energy efficiency by effectively using exhaust heat. It is positioned as one of the energy sources, and it is highly desired to promote it. Currently, there are examples of fuel cell power generation systems used in factories, housing complexes, hospitals, and the like.

In a fuel cell power generation system using a fuel gas such as city gas or LPG as a hydrogen raw material, the chemical energy of the fuel is directly converted into electric energy by an electrochemical reaction, so that the loss caused by the energy conversion is small. , High power generation efficiency can be obtained. However, city gas and LPG contain a sulfur compound called an odorant, which causes a problem that it functions as a poisoning substance that damages various catalysts used in the fuel cell power generation system. is there. Here, the various catalysts are a reforming catalyst that produces hydrogen from fuel gas and a catalyst that obtains electric power from hydrogen and oxygen. In order for various catalysts in the fuel cell power generation system to function efficiently, it is necessary to remove the sulfur compound of the odorant until it reaches the ppb order.

However, since the odorant is originally added for safety so that a person may notice when the fuel gas leaks, it is a safety problem to remove it at the stage of supplying the fuel gas to the user. It's difficult. Generally, as the odorant, a sulfur compound such as tertiary butyl mercaptan having a malodor, dimethyl sulfide, or tetrahydrothiophene, which has a peculiar odor even in a small amount, is used.

[0006]

As described above, in the fuel cell power generation system, the sulfur compound added as the odorant at the supply stage to the fuel gas such as city gas and LPG gas is added to the fuel gas by ppb. Must be desulfurized to order. In addition, considering economic efficiency,
00 hours or more), it is necessary to be able to desulfurize the sulfur compound at -20 ° C to 300 ° C. In view of these needs, the present invention provides a sulfur compound used as an odorant from a fuel gas such as city gas or LPG for a long time at -20 ° C to 300 ° C.
The purpose is to provide a desulfurizing agent that can be removed by. Further, the present invention utilizes a desulfurizing agent capable of removing a sulfur compound used as an odorant from a fuel gas such as city gas or LPG at -20 ° C to 300 ° C for a long time (1600 hours or more). An object is to provide a fuel cell power generation system.

[0007]

In order to achieve the above object, the desulfurizing agent of the present invention is a desulfurizing agent for adsorbing and removing a sulfur compound from a fuel gas containing a sulfur compound. And a catalytically active metal supported on a zeolite-based carrier.

The fuel gas is a kind selected from a hydrocarbon-based gas composed of C1 (compound containing one carbon, such as CH ₄ ) to C12 (compound containing 12 carbons, such as C ₁₂ H ₂₆ ). Including the above compounds. For example, the fuel gas is CH ₄ (methane) and C ₂ H ₆ (ethane)
, C ₃ H ₈ (propane), C ₄ H ₁₀ (butane), C ₅
H ₁₂ (pentane), C ₆ H ₁₄ (hexane), C ₇ H ₁₆
(Heptane), C ₈ H ₁₈ (octane), C ₉ H ₂₀ (nonane), C ₁₀ H ₂₂ (decane), C ₁₁ H _24, C ₁₂ H ₂₆ selected from hydrocarbon gases One or more compounds that are The fuel gas in the present invention includes a wide range of general city gas, LPG (liquefied petroleum gas), LNG (liquefied natural gas), methane gas, kerosene, and so-called fossil fuels such as gasoline. The city gas in the present invention refers to a gaseous fuel supplied to an unspecified number of consumers through a conduit, and broadly includes a gas produced by modifying or mixing natural gas, crude oil, naphtha, coal or the like. Although not intended to be limiting, city gas may include, as standard components, for example, methane at about 70 wt% or more and about 80 wt% or less, ethane at about 10 wt% or less, and propane at about 10 wt%.
In many cases, the content is not less than about 20% by weight and not more than about 10% by weight butane. Further, LPG (liquefied petroleum gas) in the present invention is a mixture of hydrocarbons such as propane and butane. LPG (liquefied natural gas) in the present invention
Refers to pressurized natural gas containing methane as a main component and cooled.

The zeolite-based carrier used in the desulfurizing agent of the present invention is a crystalline silicate, and the crystalline silicate is (1 ± 0.8) R ₂ O. [aM ₂ O ₃ .bL
O.cAl ₂ O ₃ ] .ySiO ₂ in which R is at least one element selected from the group consisting of alkali metals and H, M is a Group 8 element, a rare earth element, Ti, V, Cr, Nb, Sb and G
at least one element selected from the group consisting of a, L is at least one element selected from the group consisting of Mg, Ca, Sr and Ba, and the molar ratios a, b, c and y are 0 ≦ a, 0 ≦ b ≦ 20, a +
b = 1 and 11 ≦ y ≦ 3000, and the lattice plane spacing is 3.65 ± 0.1Å in powder X-ray diffraction using CuKα ray.
3.75 ± 0.1Å, 3.85 ± 0.1Å, 10.0 ±
It is preferable that peaks from the strongest peak to the fifth place appear at 0.3Å and 11.2 ± 0.3Å.

It is preferable that the catalytically active metal is at least one selected from the elements of Groups 4 to 12.
The elements of Groups 4 to 12 are, for example, T as Group 4
elements of i, Zr, and Hf, elements of V, Nb, and Ta as a group 5, elements of Cr, Mo, and W as a group 6, elements of Mn, Tc, and Re as a group 7, Fe as a group 8, Ru,
An element of Os, and elements of Co, Rh, and Ir as Group 9
Ni, Pd, and Pt elements as the 10th group, Cu, Ag, and Au elements as the 11th group, and Zn and C as the 12th group element
It contains the elements d and Hg. As the catalytically active metal, 4 to
It is desirable to use two or more kinds of catalytically active metals selected from Group 12 elements. Specifically, it is preferable to use zinc (Zn) and iron (Fe) at the same time.

The desulfurizing agent of the present invention is characterized in that it is usually used at -20 ° C to 300 ° C, preferably -20 ° C to 50 ° C when removing sulfur compounds in fuel gas. The sulfur compound contains one or more compounds selected from the group consisting of dimethyl sulfide, tertiary butyl mercaptan, and tetrahydrothiophene.

The fuel cell system of the present invention comprises the above desulfurizing agent for adsorbing and removing the sulfur compound from the fuel gas containing the sulfur compound, and the fuel gas desulfurized by the desulfurizing agent.
A reformer that produces a hydrogen-containing gas by reacting with water, and a solid-state reactor that is in the latter stage of the reformer and that obtains electric power by introducing the hydrogen-containing gas and the oxygen-containing gas from their respective gas introduction parts. And a molecular fuel cell. Air is preferably used as the oxygen-containing gas, and oxygen in the air is preferably used. The fuel gas is methane, ethane,
It contains one or more compounds selected from the group consisting of propane and butane.

As described above, by providing the desulfurizing agent according to the present invention, from the fuel gas containing the sulfur compound of the odorant to the sulfur compound up to the ppb order for a long time (1
It becomes possible to remove by adsorption at -20 ° C to 300 ° C for 600 hours or more). Further, the fuel cell power generation system according to the present invention can remove the sulfur compound of the odorant contained in the fuel gas, efficiently at a normal temperature of 400 ° C. for a long time.
As described above, it becomes possible to reform the fuel gas, take out hydrogen, and efficiently generate power from this hydrogen.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of a desulfurizing agent and a fuel cell power generation system according to the present invention will be described below with reference to the drawings.

[Preparation of Desulfurizing Agent] The desulfurizing agent according to the present embodiment comprises a step of preparing a crystalline silicate, a step of supporting a catalytically active metal on the crystalline silicate, a drying and baking after supporting, and a pressure molding. It is prepared through the steps of

[Preparation of Crystalline Silicate] Next, a method for preparing crystalline silicate which is a zeolite-based carrier will be described. Water glass No. 1 (containing SiO ₂ ) 560 parts by weight of water 5
It is dissolved in 30 to 550 parts by weight, and this solution is referred to as solution A. On the other hand, aluminum sulfate 70 to 7 is added to 400 parts by weight of water.
5 parts by weight, 10 to 12 parts by weight of ferric chloride, 4 to 6 parts by weight of calcium acetate, 24 to 28 parts by weight of sodium chloride, and 190 to 210 parts by weight of concentrated hydrochloric acid are dissolved, and this solution is used as solution B.
And Solution A and solution B are supplied at a constant ratio to form a precipitate, which is sufficiently stirred to obtain a PH8 slurry. This slurry was charged into an autoclave, 48 to 52 parts by weight of tetrapropylammonium bromide was further added, and hydrothermal synthesis was performed at 100 ° C. to 200 ° C. for 1 hour to 100 hours. After synthesis, washing with water and drying were performed, and further 300 ℃ ~
The crystalline silicate is obtained in a dehydrated state by baking at 600 ° C. for 1 to 12 hours.

The chemical formula of this crystalline silicate is that the crystalline silicate is (1 ± 0.8) R ₂ O. [aM ₂ O ₃ .b
LO.cAl ₂ O ₃ ] .ySiO ₂ where R is at least one element selected from the group consisting of alkali metals and H, M is a Group 8 element, a rare earth element, Ti, V, Cr, Nb, Sb and at least one element selected from the group consisting of Ga, L is at least one element selected from the group consisting of Mg, Ca, Sr and Ba,
The molar ratios a, b, c and y are 0 ≦ a, 0 ≦ b ≦ 20, a
+ B = 1 and 11 ≦ y ≦ 3000, and the lattice spacing is 3.65 ± 0.1 in powder X-ray diffraction using CuKα rays.
Å, 3.75 ± 0.1 Å, 3.85 ± 0.1 Å, 10.
It is characterized in that peaks from the strongest peak to the fifth place appear at 0 ± 0.3Å and 11.2 ± 0.3Å.

This crystalline silicate was prepared at 30 to 50 ° C.
It is immersed in a 2 to 6N aqueous NH ₄ Cl solution and stirred for 2 to 4 hours to perform NH ₄ ion exchange. After ion exchange, washing and drying at 80 ° C to 120 ° C for 22 to 26 hours, 38
H-type crystalline silicate is obtained by firing at 0 to 420 ° C. for 2 to 4 hours. The H type means that the active species of the ion exchange site in the crystalline silicate is H ⁺ (proton). The crystalline silicate has a cylindrical shape,
Spherical, ring-shaped, honeycomb-shaped (solid type, coated type)
Is good. However, the crystalline silicate of the present invention is
It is not limited to these shapes.

[Support of catalytically active metal on crystalline silicate] The catalytically active metal supported on the obtained H-type crystalline silicate is preferably a metal of Groups 4 to 12. The elements of Groups 4 to 12 are, for example, Ti of Group 4 and
Zr and Hf elements, V, Nb and Ta elements as group 5, Cr, Mo and W elements as group 6 and M as group 7
Elements of n, Tc, Re, and Fe, Ru, Os as Group 8
Element, Co, Rh, Ir element as group 9 and 10
Ni, Pd, and Pt elements as group and C as group 11
u, Ag, Au elements, Zn and C as Group 12 elements
It contains the elements d and Hg.

As an example of the solution of the metal salt containing the catalytically active metal, it is preferable to use nitrates such as iron nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, manganese nitrate, and chromium nitrate.

In the present embodiment, a solution of a metal salt containing a catalytically active metal is used to support the catalytically active metal on the crystalline silicate by an impregnation method. As a method of supporting the active metal on the crystalline silicate, other than the impregnation method, there is a method of immersing the crystalline silicate previously molded into a spherical shape or a cylindrical shape in an active metal solution to impregnate it with water.

[Drying and firing after loading and pressure molding] Next, the catalyst powder obtained by drying and firing the H-type crystalline silicate carrying the catalytically active metal is pressure-molded into a solid type. Obtain a desulfurizing agent. The solid type includes, but is not limited to, a cylindrical shape, a spherical shape, a ring shape, and a honeycomb shape (solid type, coat type).

[Fuel Cell Power Generation System] Next, the fuel cell power generation system according to the present invention when the desulfurizing agent of the present embodiment is installed in the front stage part of a polymer electrolyte fuel cell (also referred to as PEFC device) An embodiment will be described. Figure 1
FIG. 1 is a block diagram illustrating an outline of an embodiment of a fuel cell power generation system to which a low temperature oxidation catalyst is preferably applied. As shown in FIG. 1, the configuration of the fuel cell power generation system according to the present embodiment is connected to a supply conduit (not shown) for fuel gas such as city gas, and the desulfurizing agent according to the present embodiment described above is used. Ryukyu 1, reformer 2 connected to desulfurizer 1, and HTS (high
temperature shift) device 3 and / or
Or LTS (low temperature sh
ift) device 3 and HTS device 3 and / or LTS
PROx device 4 connected to device 3 and PROx device 4
And a PEFC device 5 connected to the.

Next, the operation of the fuel cell power generation system of this embodiment will be described. Fuel gas such as city gas is supplied to the desulfurizer 1 from a supply conduit (not shown). The desulfurizing agent of the present embodiment provided in the desulfurizer 1 adsorbs and removes sulfur compounds such as tertiary butyl mercaptan, dimethyl sulfide, and tetrahydrothiophene, which are odorants in the fuel gas.

Next, the desulfurized fuel gas is supplied to the reformer 2
Is a device for reforming fuel gas with a fuel gas reforming catalyst. For example, in the reformer 2, hydrogen is obtained from methane in the fuel gas by the following reaction. Similar to methane, other hydrocarbons such as ethane, propane, butane in the fuel gas also act as hydrogen feedstocks as in the following chemical reactions (1) to (6). Since this reforming temperature is preferably 700 ° C. to 800 ° C., the reformer 2 is raised to fall within this temperature range. CH ₄ + 2H ₂ O → CO ₂ + 4H ₂ (1) CH ₄ + O ₂ → CO + H ₂ + H ₂ O (2) CH ₄ + H ₂ O → CO + 3H ₂ (3) Reaction (1) is a reaction for reforming methane to obtain hydrogen. This reaction (1) is an endothermic reaction. Therefore,
The heat (2), which is an exothermic reaction, is used to maintain the reforming reaction. However, in this reaction (2), C
Produces O. CO hinders the function of the catalyst for power generation of the PEFC device 5. The reaction of the formula (3) is a side reaction of the steam reforming reaction, and the generated CO adversely affects the fuel cell on the downstream side. Therefore, as described below,
CO is removed between the reformer 2 and the PEFC device 5 as in the reactions (4) and (5) in the HTS device and / or LTS device 3 and the PROx device 4.

Therefore, the fuel gas is the HTS device 3 and / or
Alternatively, it is sent to the LTS device 3, and CO is removed by the HTS device 3 and / or the LTS device 3 as in the reaction (4). CO + H ₂ O → CO ₂ + H ₂ (4) Here, the reaction temperature of the HTS device 3 is about 500 ° C., LT
The temperature of the S device 3 is about 200 ° C.

HTS device 3 and / or LTS device 3
The fuel gas from is added to air and is sent to the PROx device 4. The PROx device 4 is a device for selectively removing CO with a carbon monoxide selective oxidation catalyst, and removes CO by the following reaction. CO + 1 / 2O ₂ → CO ₂ (5) By the reaction (4), the HTS device 3 and / or L
CO generated in the TS device 3 is removed. However, HT
In the S device 3 and / or the LTS device 3, 0.3-
It is removed up to 0.4%. This HTS device 3 and /
Alternatively, the LTS device 3 further removes CO to 10 ppm or less.

The gas containing hydrogen from the PROx device 4 is
It is sent to the PEFC device 5. The PEFC device 5 causes the following reactions in the anode electrode by the anode electrode catalyst. H ₂ → 2H ⁺ + 2e ⁻ (6) H ⁺ generated by this reaction (6) diffuses. on the other hand,
At the cathode electrode, the following reaction is caused by the cathode electrode catalyst. 2H ⁺ + 2e ⁻ + 1 / 2O ₂ → H ₂ O (7) These reactions (6) and (7) are combined to form a battery reaction, and an electromotive force can be obtained.

[0029]

EXAMPLES Next, examples of the desulfurizing agent according to the present invention will be described. [Example 1: Preparation of crystalline silicate, preparation of catalyst by impregnation method] Next, the results of preparing a catalyst by the impregnation method using crystalline silicate as a raw material will be described. Water glass No. 1 (SiO ₂ : 30 wt% content) 5616 g was added to water 5429
g, and this solution was designated as solution A. On the other hand, water 417
Aluminum sulfate 718.9g, ferric chloride 11 to 5g
0 g, calcium acetate 47.2 g, sodium chloride 26
2 g and 2020 g of concentrated hydrochloric acid were dissolved, and this solution was designated as solution B. Solution A and solution B were supplied at a constant ratio to form a precipitate, which was sufficiently stirred to obtain a slurry having a pH of 8. This slurry was charged into a 20-liter autoclave, 500 g of tetrapropylammonium bromide was further added, hydrothermally synthesized at 160 ° C. for 72 hours, washed with water after synthesis, dried and then calcined at 500 ° C. for 3 hours for dehydration. H ₂ O [0.25Fe ₂ O ₃
A crystalline silicate having a composition of 0.8Al ₂ O ₃ .0.2CaO] 27SiO ₂ was obtained.

Regarding the obtained crystalline silicate, Cu
Powder X-ray diffraction measurement using Kα ray was performed, and the lattice plane spacing (d value) of peaks from the strongest line to the 15th position and the relative intensity are shown in Table 1 below.

[Table 1]

As is clear from Table 1, crystalline silicate 1 has a lattice spacing of 3.65 ± 0.1Å, 3.75 ± 0.1Å, in powder X-ray diffraction measurement using CuKα rays.
3.85 ± 0.1Å, 10.0 ± 0.3Å and 11.
The peak from the strongest peak to the 5th place is shown at 2 ± 0.3Å, and the lattice spacing is 3.0 ± 0.1Å, 3.3 ± 0.1Å
4.25 ± 0.1Å, 5.6 ± 0.2Å, 6.0 ± 0.
Peaks from 6th to 11th at 2Å and 6.4 ± 0.2Å and 3.05 ± 0.1Å, 4.6 ±
The peaks from the 12th place to the 15th place were shown at 0.1Å, 5.7 ± 0.2Å and 6.7 ± 0.2Å.

The above crystalline silicate was immersed in a 4N NH ₄ Cl aqueous solution at 40 ° C. and stirred for 3 hours to carry out NH ₄ ion exchange. After ion exchange, wash at 100 ℃, 2
After being dried for 4 hours, H-type crystalline silicate was obtained by baking at 400 ° C. for 3 hours. The H-type crystalline silicate was loaded with 3% of iron oxide by an impregnation method using an aqueous solution of iron (II) nitrate, dried and calcined to obtain a catalyst powder, which was press-molded to obtain a solid desulfurizing agent. Obtained.

[Example 2: Preparation by impregnation method] Example 1
In the impregnation method, instead of the iron nitrate aqueous solution, cobalt nitrate,
Example 1 described above, except that nickel nitrate, copper nitrate, zinc nitrate, manganese nitrate and chromium nitrate were used.
Solid type desulfurizing agents 2 to 7 were obtained in the same manner as in. (See Table 2)

[Table 2]

[Example 3: Preparation by impregnation method] Example 1
Example 1 described above, except that cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate, manganese nitrate or chromium nitrate was added simultaneously with the iron nitrate aqueous solution by the impregnation method of 1.
Solid type desulfurizing agents 8 to 13 were obtained in the same manner as in. (See Table 2)

Example 4 Using the crystalline silicate obtained in Example 1, it was immersed in an iron chloride aqueous solution containing 10 mmol of Fe at 75 ° C. and stirred for 12 hours to carry out Fe ion exchange. After ion exchange, filtration, washing with water, 110 ° C
After drying overnight in, the catalyst powder was pressure-molded to obtain a solid desulfurization agent 14. (See Table 2)

[Embodiment 5] Cobalt chloride, nickel chloride, as raw materials for the ion-exchange catalytically active metal of Embodiment 4,
Solid type desulfurizing agents 15 to 20 were obtained in the same manner as in Example 1 except that copper chloride, zinc chloride, manganese chloride or chromium chloride was used. (See Table 2)

[Comparative Example 1] Example 1 except that Al ₂ O ₃ was used in place of the H-type crystalline silicate of Example 1.
Comparative solid catalyst 1 was obtained in the same manner as in. (See Table 2)

[Example 6] With respect to the solid desulfurizing agents 1 to 20, a test for removing sulfur contained in city gas was carried out. The test conditions are listed in Table 3. As shown in Table 3, the amount of desulfurizing agent is 10 CC and the pressure is normal pressure (about 1 atm: 101
3.25 hPa (hectopascals), reaction tube inlet temperature is room temperature (15 ° C to 35 ° C), GHSV (Gas H)
ourrySpace Velocity: Processing gas volume per unit volume of catalyst per hour (m ³ / m ³ ·
h)) was 7000 h-1, and the gas used was city gas.
At this time, the composition of the city gas is as follows: CH ₄ is about 88%, C ₂ H
₆ was about 6%, C ₃ H ₈ was about 4%, i-C ₄ H ₉ was about 2%, dimethyl sulfide was about 1 ppm, and tert-butyl mercaptan was about 1 ppm.

[Table 3] During the test, after periodically sampling the S concentration of the gas discharged from the reaction tube outlet, measure the S concentration with a gas chromatograph of the FPD method, and let the gas flow continuously until the S concentration at the inlet and outlet of the reaction tube becomes equal. It was Doorway S
The desulfurization performance of the catalyst (h:
Time).

As shown in Table 2 together with the results of the desulfurization performance evaluation, together with the catalyst preparation list, the desulfurizing agent using the crystalline silicate was used for 15 hours at 15 ° C. for a long time until the ppb order of the S content in city gas was higher than that of the comparative catalyst. It can be seen that it can be removed at 35 ° C. In particular, No. It was found that 11 of the desulfurization agents carrying both active metals of Fe and Zn had the desulfurization performance of 1620 hours and were the best. In addition, No. 10 Fe and C
It was found that the desulfurization agent supporting both active metals of u has a desulfurization performance of 1400 hours and is excellent. However, in the example using Al ₂ O ₃ as the carrier of Comparative Example 1, the desulfurization performance was only 120 hours, and the desulfurization performance was lower than that of the desulfurization agent using the crystalline silicate of the present invention as the carrier.

[0040]

As is apparent from the above description, according to the desulfurizing agent according to the present invention, from the fuel gas containing the sulfur compound of the odorant to the sulfur compound in the ppb order, for a long time (1600 hours or more). , −20 ° C. to 300 ° C. can be removed by adsorption. In addition, the fuel cell power generation system according to the present invention can remove the sulfur compound of the odorant contained in the fuel gas, and efficiently removes the sulfur compound from the odorant for a long time, usually 4
At 00 ° C. or higher, the fuel gas is reformed, hydrogen is taken out, and it becomes possible to efficiently generate electricity from this hydrogen.

[Brief description of drawings]

FIG. 1 is a block diagram illustrating an embodiment of a fuel cell power generation system using a desulfurizing agent according to the present invention.

[Explanation of symbols]

1 desulfurizer 2 reformer 3 HTS device and / or LTS device 4 PROx device 5 PEFC equipment

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01M 8/06 H01M 8/06 Z 8/10 8/10 C10L 3/00 B (72) Inventor Satoshi Abutake 4-6-22 Kannon Shinmachi, Nishi-ku, Hiroshima City, Hiroshima Prefecture Mitsubishi Heavy Industries, Ltd. Hiroshima Research Laboratory F-term (reference) 4G040 EA03 EA06 EB01 4G066 AA61B BA31 BA36 CA25 DA04 FA37 4G069 AA03 AA08 BA07A BC01A BC09A BC09B BC12A BC13A BC17A BC26A BC26A BC26A BC26A BC26A BC26A BC35B BC38A BC49A BC50A BC53A BC54A BC55A BC57A BC58A BC58B BC61A BC62B BC65A BC66B BC67B BC68B BC69A CC02 DA06 EA02Y EC25 FA01 FA02 FB14 FB61 FC08 ZA33A ZA33B 5H026 AA06 5H016 AA06 BA01

Claims (9)

[Claims] 1. A desulfurizing agent for adsorbing and removing a sulfur compound from a fuel gas containing a sulfur compound, the desulfurizing agent comprising a zeolite-based carrier and a catalytically active metal supported on the zeolite-based carrier. 2. The desulfurizing agent according to claim 1, wherein the fuel gas contains one or more compounds selected from hydrocarbon-based gases composed of C1 to C12. 3. The zeolite-based carrier is a crystalline silicate, and the crystalline silicate is (1 ± 0.8) R ₂
O · represented by the chemical formula _{[aM 2 O 3 · bLO ·} cAl 2 O 3] · ySiO 2, in chemical formula, at least one element R is selected from the group consisting of alkali metal and H, M Is a Group 8 element, rare earth element, Ti, V, C
At least one element selected from the group consisting of r, Nb, Sb and Ga, and L is Mg, Ca, S
It is at least one element selected from the group consisting of r and Ba, and the molar ratios a, b, c and y are 0 ≦.
a, 0 ≦ b ≦ 20, a + b = 1 and 11 ≦ y ≦ 300
0, and the lattice plane spacing was 3.65 ± 0.1Å, 3.75 ± 0.1Å, 3.85 in powder X-ray diffraction using CuKα rays.
± 0.1Å, 10.0 ± 0.3Å and 11.2 ± 0.
The desulfurizing agent according to claim 1 or 2, wherein peaks from the strongest peak to the fifth position appear at 3Å. 4. The desulfurizing agent according to claim 1, wherein the catalytically active metal is at least one selected from elements of Groups 4 to 12. 5. The desulfurizing agent according to claim 1, wherein two or more kinds of catalytically active metals selected from elements of Groups 4 to 12 are simultaneously used as the catalytically active metals. 6. The desulfurizing agent according to claim 1, which is used at −20 ° C. to 300 ° C. when removing the sulfur compounds in the fuel gas. 7. The desulfurizing agent according to claim 1, wherein the sulfur compound contains one or more compounds selected from the group consisting of dimethyl sulfide, tertiary butyl mercaptan, and tetrahydrothiophene. 8. The desulfurizing agent according to claim 1, wherein the sulfur compound is adsorbed and removed from the fuel gas containing the sulfur compound, and the fuel gas desulfurized by the desulfurizing agent is reacted with water. As a result, a reformer that generates a hydrogen-containing gas, and a solid polymer fuel cell that is located after the reformer and that introduces the hydrogen-containing gas and the oxygen-containing gas from their respective gas introduction parts to obtain electric power A fuel cell power generation system comprising: 9. The fuel gas comprises methane, ethane,
The fuel cell power generation system according to claim 8, comprising one or more compounds selected from the group consisting of propane and butane.