JP2006036616A - Method for producing zeolite and adsorbent for removing sulfur compound containing the zeolite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a metal ion exchange zeolite which can be suitably used as an adsorbent for removing sulfur compounds which can efficiently remove a sulfur compound in a hydrocarbon fuel or dimethyl ether fuel to a low concentration even at room temperature, and the metal ion exchange. An adsorbent for removing sulfur compounds containing zeolite, a method of effectively producing hydrogen usable for fuel cells from a hydrocarbon fuel or dimethyl ether fuel desulfurized using the adsorbent, and a fuel cell using the hydrogen Provide a system.
A metal ion-exchanged zeolite in which a Y-type zeolite having a sodium content of 0.5 to 5% by mass is preferably subjected to metal ion exchange using a solution containing a metal ammine complex ion to carry the metal on the zeolite. Production method, sulfur compound-removing adsorbent containing said metal ion-exchanged zeolite, and further a method for producing hydrogen usable for fuel cell from hydrocarbon fuel or dimethyl ether fuel desulfurized using the adsorbent and its This is a fuel cell system using hydrogen.
[Selection figure] None

Description

  The present invention relates to a method for producing a metal ion-exchanged Y-type zeolite having a high desulfurization performance and good retention by performing metal ion exchange using a Y-type zeolite having a specific sodium content, and the metal ion An adsorbent for removing sulfur compounds containing exchanged Y-type zeolite, a method for effectively producing hydrogen usable in a fuel cell from a hydrocarbon fuel or dimethyl ether fuel desulfurized using the adsorbent, and hydrogen The present invention relates to a fuel cell system to be used.

In recent years, new energy technology has attracted attention due to environmental problems, and fuel cells are attracting attention as one of the new energy technologies. This fuel cell converts chemical energy into electrical energy by electrochemically reacting hydrogen and oxygen, and has a feature of high energy use efficiency. Or, practical research has been actively conducted for automobiles.
For this fuel cell, types such as a phosphoric acid type, a molten carbonate type, a solid oxide type, and a solid polymer type are known depending on the type of electrolyte used.
On the other hand, as a hydrogen source, liquefied natural gas mainly composed of methanol and methane, city gas mainly composed of this natural gas, synthetic liquid fuel using natural gas as a raw material, and petroleum-based systems such as LPG, naphtha and kerosene The use of hydrocarbons has been studied.

When producing hydrogen using these gaseous or liquid hydrocarbons, generally, there is a method of treating the hydrocarbons by partial oxidation reforming, autothermal reforming or steam reforming in the presence of a reforming catalyst. It is used.
When reforming hydrocarbon fuels such as LPG, city gas, and kerosene to produce hydrogen for fuel, the sulfur content in the fuel is reduced to 0.1 ppm or less in order to suppress poisoning of the reforming catalyst. Is required.
Further, when propylene, butene, etc. are used as a raw material for petrochemical products, the sulfur content is required to be reduced to 0.1 ppm or less in order to prevent poisoning of the catalyst.
In the LPG, dimethyl sulfide (DMS), 2-methyl-2-propanethiol (MPT), methyl added as a odorant in addition to methanethiol, carbonyl sulfide (COS) or the like as a sulfur compound. Ethyl sulfide and the like are included.
Recently, a plan to use dimethyl ether as a fuel is underway.
Although this dimethyl ether itself does not contain a sulfur compound, the addition of the above odorant has been studied intentionally in order to prevent leakage.

Various adsorbents that adsorb and remove sulfur compounds in hydrocarbon fuels such as LPG and city gas are known, but conventional adsorbents do not have sufficient adsorption capacity and need to be replaced frequently for long-term use. is there.
For example, as a sulfur compound removing adsorbent, a zeolite-based desulfurization agent in which polyvalent metal ions other than alkaline earth metals (Mn, Fe, Co, Ni, Cu, Sn, and Zn) are exchanged (see, for example, Patent Document 1) , A desulfurization agent in which Ag, Cu, Zn, Fe, Co, Ni, etc. are supported on a hydrophobic zeolite by ion exchange (for example, see Patent Document 2), Y-type zeolite, β-type zeolite or X-type zeolite with Ag or A desulfurization agent supporting Cu (for example, see Patent Document 3) is disclosed.
All of these desulfurizing agents are described as performing ion exchange using nitrate, acetate, and chloride.
However, when ion exchange is performed by such a method, it is actually difficult to sufficiently increase the loading amount by one ion exchange.
Therefore, in order to increase the loading amount, it is necessary to repeatedly perform ion exchange, and even if a metal-exchanged zeolite having a large loading amount is prepared in this manner, the adsorption performance of the sulfur compound is not sufficient.
Moreover, although the desulfurization agent (for example, refer patent document 4) containing the metal ion exchange zeolite manufactured using the solution containing a metal ammine complex ion is disclosed, performance may not be enough.

JP-A-6-306377 JP 2001-286753 A JP 2001-305123 A JP 2004-168648 A

  The present invention has been made under such circumstances, and is a metal that can be suitably used as an adsorbent for removing sulfur compounds that can efficiently remove sulfur compounds in hydrocarbon fuels or dimethyl ether fuels to a low concentration even at room temperature. A method for producing ion-exchanged Y-type zeolite, an adsorbent for removing sulfur compounds containing the metal ion-exchanged Y-type zeolite, and a hydrocarbon fuel or dimethyl ether fuel desulfurized using the adsorbent can be used for fuel cells. An object of the present invention is to provide a method for effectively producing hydrogen and a fuel cell system using the hydrogen.

As a result of intensive studies to achieve the above object, the present inventors have used a Y-type zeolite having a sodium content of 0.5 to 5% by mass, preferably using a solution containing a metal ammine complex ion. Y-zeolite having a sodium content of 0.5 to 4% by mass subjected to metal ion exchange can increase the amount of supported metal in one operation, and there is little aggregation of the supported metal, and is the sodium content too much? Compared to metal ion-supported zeolitic desulfurization agent using too much Y-type zeolite, it has excellent adsorption performance for sulfur compounds and good retention, and carbonized by desulfurization treatment using this adsorbent It has been found that hydrogen that can be used for fuel cells can be effectively obtained by reforming hydrogen fuel or dimethyl ether fuel.
The present invention has been completed based on such findings.

That is, the present invention
1. A process for producing a metal ion-exchanged Y-type zeolite, characterized in that a metal ion-exchanged Y-type zeolite having a sodium content of 0.5 to 5% by mass is supported on the zeolite,
2. The method for producing a metal-exchanged Y-type zeolite according to the above 1, wherein the sodium content of the Y-type zeolite is 2 to 5% by mass,
3. The method for producing a metal-exchanged Y-type zeolite according to 1 or 2 above, wherein the Y-type zeolite is obtained by substituting a part of sodium ions of NaY-type zeolite with ammonium ions,
4). The method for producing a metal exchange Y-type zeolite according to any one of the above 1 to 3, wherein a metal ion exchange is performed using a solution containing at least one metal ammine complex ion selected from silver and copper,
5. The method for producing a metal-exchanged Y-type zeolite according to any one of the above 1 to 4, wherein the Y-type zeolite is a molded Y-type zeolite,
6). The method for producing a metal ion-exchanged zeolite according to any one of 1 to 5 above, wherein the sodium content of the metal-exchanged Y-type zeolite is 0.5 to 4% by mass,
7). An adsorbent for removing sulfur compounds in hydrocarbon fuel or dimethyl ether fuel, comprising the metal ion-exchanged zeolite obtained by the method according to any one of 1 to 6 above,
8). 8. The sulfur compound according to 7 above, wherein the hydrocarbon fuel is at least one hydrocarbon compound selected from LPG, city gas, natural gas, naphtha, kerosene, light oil or ethane, ethylene, propane, propylene, butane and butene. Removal adsorbent,
9. After the sulfur compound in the hydrocarbon fuel or dimethyl ether fuel is desulfurized using the sulfur compound removing adsorbent described in 7 or 8 above, the desulfurized fuel is used as a partial oxidation reforming catalyst, autothermal reforming catalyst or A method for producing hydrogen, characterized by contacting with a steam reforming catalyst;
10. 10. The method for producing hydrogen according to 9 above, wherein the partial oxidation reforming catalyst, the autothermal reforming catalyst, or the steam reforming catalyst is a ruthenium-based or nickel-based catalyst,
11. The present invention provides a fuel cell system using hydrogen produced by the method described in 9 or 10 above.

  According to the present invention, the sodium content that can be suitably used for an adsorbent for removing sulfur compounds that can efficiently remove sulfur compounds in hydrocarbon fuel or dimethyl ether fuel to a low concentration even at room temperature is 0.5 to 5 masses. % Y-type zeolite for metal ion exchange, a method for producing metal ion-exchanged Y-type zeolite having high desulfurization performance and good retention, and an adsorbent for removing sulfur compounds containing the metal ion-exchanged Y-type zeolite Furthermore, it is possible to provide a method for effectively producing hydrogen usable for a fuel cell from a hydrocarbon fuel or dimethyl ether fuel desulfurized using the adsorbent, and a fuel cell system using the hydrogen.

The method for producing a metal ion-exchanged Y-type zeolite according to the present invention comprises subjecting a Y-type zeolite having a sodium content of 0.5 to 5% by mass, preferably 2 to 5% by mass, to metal ion exchange to convert the metal into a Y-type zeolite. It is a method of carrying.
The adsorbent containing metal ion-exchanged Y-type zeolite that has been subjected to metal ion exchange after the sodium content in the Y-type zeolite before the metal ion exchange is within the above range can maintain its performance for a long period of time.
In the present invention, first, NaY-type zeolite is used with an ammonium salt solution such as ammonium nitrate, ammonium chloride, or ammonium carbonate, or an acid solution such as nitric acid, sulfuric acid, or hydrochloric acid. A Y-type zeolite having a content of 0.5 to 5% by mass is used.
A commercially available HY-type zeolite or ammonium Y-type zeolite can be used, and a zeolite having a sodium content within the above-mentioned range can be used. The one treated with an ammonium salt solution is optimal.

In the present invention, subsequently, it is preferable that the Y-type zeolite is subjected to metal ion exchange using a solution containing a metal ammine complex ion.
As the solution containing the metal ammine complex ion, a solution in which a water-soluble metal ammine complex ion is dissolved in water, or a water-soluble metal compound such as a metal nitrate, carbonate, acetate, sulfate, or chloride is added to water. A solution prepared by adding an excess of aqueous ammonia or ammonium nitrate to form a metal amine complex ion can be used.
Here, the metal species of the solution containing the metal ammine complex ion is preferably at least one selected from Ag and Cu, and Ag is particularly preferable from the viewpoint of the adsorption performance of the sulfur compound.

In order to prepare the metal ion-exchanged zeolite in the present invention, first, a Y-type zeolite having a predetermined sodium content is added to a solution containing the above metal ammine complex ions, and usually 0 to 90 ° C, preferably 20 to 70 ° C. At a temperature in the range, the ion exchange treatment is performed for about 1 to several hours, preferably with stirring.
The solid is then separated by means such as filtration. Here, you may wash | clean with water etc.
Next, a drying process is performed at a temperature of 500 ° C. or less (preferably about 50 to 200 ° C.).
By repeatedly performing this ion exchange treatment, the amount of metal supported can be increased, but conversely, the sodium content gradually decreases, so that the ion exchange treatment is performed so that the sodium content does not become less than 0.5% by mass. Do.
Next, the target metal ion-exchanged zeolite is obtained by firing for several hours at a temperature of 500 ° C. or less (preferably about 200 to 500 ° C.).
The amount of metal supported in the metal ion-exchanged zeolite thus obtained is preferably in the range of 1 to 30% by mass as the metal, more preferably 3 to 30% by mass, and still more preferably 5 to 20% by mass, Sodium content is 0.5-4 mass%.
The Y-type zeolite subjected to metal exchange in this way can be used after being molded by an ordinary method such as extrusion molding, tableting molding, rolling granulation, spray drying and the like using an appropriate binder.
Alternatively, pre-shaped Y-type zeolite can be used after the metal ion exchange of this method.
Zeolite is preferably molded zeolite rather than powder, and the smaller the particle size, the more preferable.

  The metal ion exchange Y-type zeolite produced by the above method is not only an adsorbent for removing sulfur compounds, but also production of ethylene oxide by oxidation of ethylene, production of formaldehyde by dehydrogenation of methanol, and production of nitrogen oxides from exhaust gas. It is suitably used for adsorbents such as catalysts for removal, adsorption of various hydrocarbons, adsorption of hydrocarbons in automobile exhaust gas, adsorption of sulfur compounds, selective adsorption of nitrogen in the air, and the like.

The adsorbent for removing sulfur compounds containing the metal ion-exchanged Y-type zeolite obtained as described above is applied to hydrocarbon fuel or dimethyl ether fuel.
Here, examples of the hydrocarbon fuel include LPG, city gas, natural gas, naphtha, kerosene, light oil, or at least one hydrocarbon compound selected from ethane, ethylene, propane, propylene, butane, and butene. be able to.
The concentration of the sulfur compound in the hydrocarbon-containing gas to which the adsorbent of the present invention is applied is preferably 0.001 to 10,000 ppm by volume, and particularly preferably 0.1 to 100 ppm by volume.
As desulfurization conditions, the normal temperature is selected in the range of −50 to 150 ° C., and the GHSV is selected in the range of 100 to 1,000,000 h ⁻¹ .
When the desulfurization temperature exceeds 150 ° C., adsorption of sulfur compounds is difficult to occur.
A preferred temperature is in the range of −50 to 120 ° C., more preferably −20 to 100 ° C.
Also preferred GHSV is 100～100,000H ^-1, more preferably from 100~50,000h ^-1.
Moreover, when using liquid fuel, the density | concentration of a sulfur compound has preferable 0.001-10,000 mass ppm, and 0.1-100 mass ppm is especially preferable.
As the desulfurization conditions, the normal temperature is selected in the range of −50 to 150 ° C., and the WHSV is selected in the range of 0.1 to 1,000 h ⁻¹ .

The metal ion-exchanged Y-type zeolite of the present invention is a metal ion-exchanged zeolite using a solution containing a Y-type zeolite having a sodium content of 0.5 to 5% by mass, and preferably a metal ammine complex ion. Can be manufactured.
The metal ion exchanged Y-type zeolite thus obtained has a sodium content of usually about 0.5 to 4% by mass, preferably 1.0 to 3.5% by mass.
This metal ion-exchanged Y-type zeolite has excellent desulfurization performance and retainability by using a Y-type zeolite having a sodium content of 0.5 to 5% by mass as the Y-type zeolite before the metal ion exchange. Is also good.
Next, in the method for producing hydrogen for a fuel cell according to the present invention, after the sulfur compound in the hydrocarbon fuel or dimethyl ether fuel is desulfurized using the adsorbent of the present invention, the desulfurized fuel is reformed. By doing so, hydrogen is produced.

At this time, methods such as partial oxidation reforming, autothermal reforming, and steam reforming can be used as reforming methods.
In this reforming method, the concentration of the sulfur compound in the desulfurized hydrocarbon fuel or dimethyl ether fuel is preferably 0.1 ppm by volume or less, particularly preferably 0.005 ppm by volume or less, from the viewpoint of the life of each reforming catalyst. preferable.
The partial oxidation reforming is a method for producing hydrogen by a partial oxidation reaction of hydrocarbons, and in the presence of a partial oxidation reforming catalyst, usually a reaction pressure of normal pressure to 5 MPa, a reaction temperature of 400 to 1,100 ° C. The reforming reaction is carried out under the conditions of GHSV 1,000 to 100,000 h ⁻¹ and oxygen (O ₂ ) / carbon ratio 0.2 to 0.8.
Autothermal reforming is a method in which partial oxidation reforming and steam reforming are combined. In the presence of an autothermal reforming catalyst, the reaction pressure is usually from normal pressure to 5 MPa, and the reaction temperature is from 400 to 1,100. The reforming reaction is carried out under the conditions of ° C., oxygen (O ₂ ) / carbon ratio of 0.1 to 1, steam / carbon ratio of 0.1 to 10, and GHSV of 1,000 to 100,000 h ⁻¹ .
Furthermore, steam reforming is a method for producing hydrogen by bringing steam into contact with a hydrocarbon, usually in the presence of a steam reforming catalyst, at a reaction pressure of normal pressure to 3 MPa, a reaction temperature of 200 to 900 ° C., steam. The reforming reaction is performed under the conditions of / carbon ratio of 1.5 to 10 and GHSV of 1,000 to 100,000 h ⁻¹ .

In the present invention, the partial oxidation reforming catalyst, autothermal reforming catalyst, and steam reforming catalyst can be appropriately selected from conventionally known catalysts, but are particularly ruthenium-based and nickel-based. A catalyst is preferred.
Moreover, as a support | carrier of these catalysts, the support | carrier containing at least 1 type chosen from manganese oxide, a cerium oxide, and a zirconia can be mentioned preferably.
The carrier may be a carrier composed of only these metal oxides, or may be a carrier obtained by adding the above metal oxide to another refractory porous inorganic oxide such as alumina.

The present invention also provides a fuel cell system using hydrogen obtained by the production method.
The fuel cell system of the present invention will be described below with reference to FIG.
FIG. 1 is a schematic flowchart showing an example of the fuel cell system of the present invention.
According to FIG. 1, the fuel in the fuel tank 21 flows into the desulfurizer 23 via the fuel pump 22.
The desulfurizer can be filled with the adsorbent of the present invention.
The fuel desulfurized in the desulfurizer 23 is mixed with water from the water tank through the water pump 24, then introduced into the vaporizer 1, vaporized, and then mixed with the air sent out from the air blower 35 to the reformer 31. It is sent.
The reformer 31 is filled with the above-described reforming catalyst, and from the fuel mixture (mixed gas containing water vapor, oxygen and hydrocarbon fuel or oxygen-containing hydrocarbon fuel) fed into the reformer 31, Hydrogen or synthesis gas is produced by any of the reforming reactions described above.

The hydrogen or synthesis gas thus produced is reduced through the CO converter 32 and the CO selective oxidizer 33 to such an extent that the CO concentration does not affect the characteristics of the fuel cell.
Examples of the catalyst used in these reactors include an iron-chromium catalyst, a copper-zinc catalyst or a noble metal catalyst in the CO converter 32, and a ruthenium catalyst, a platinum catalyst or a noble metal catalyst in the CO selective oxidation furnace 33. The mixture etc. can be mentioned.
The fuel cell 34 is a solid polymer fuel cell having a polymer electrolyte 34C between a negative electrode 34A and a positive electrode 34B.
The hydrogen-rich gas obtained by the above method is introduced into the negative electrode side, and the air sent from the air blower 35 is introduced into the positive electrode side after performing appropriate humidification treatment as necessary (humidifier not shown). Is done.
At this time, a reaction in which hydrogen gas becomes protons and emits electrons proceeds on the negative electrode side, and a reaction in which oxygen gas obtains electrons and protons to become water proceeds on the positive electrode side, and a direct current is generated between both electrodes 34A and 34B. .
Platinum black, activated carbon-supported Pt catalyst or Pt-Ru alloy catalyst is used for the negative electrode, and platinum black, Pt catalyst supported on activated carbon is used for the positive electrode.

The surplus hydrogen can be used as fuel by connecting the burner 31A of the reformer 31 to the negative electrode 34A side.
Further, in the steam separator 36 connected to the positive electrode 34B side, water and exhaust gas generated by the combination of oxygen and hydrogen in the air supplied to the positive electrode 34B side are separated, and the water is used to generate water vapor. Can be used.
In the fuel cell 34, since heat is generated with power generation, an exhaust heat recovery device 37 can be attached to recover the heat for effective use.
The exhaust heat recovery device 37 includes a heat exchanger 37A that takes away the heat generated during the reaction, a heat exchanger 37B that exchanges heat taken by the heat exchanger 37A with water, a cooler 37C, and these heat exchanges. The hot water obtained in the heat exchanger 37B can be effectively used in other facilities. The pumps 37A and 37B and the pump 37D circulate the refrigerant to the cooler 37C.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Example 1
A commercially available NaY-type zeolite molding [manufactured by ZEOLYST, CBV100CY (1.6)] was crushed to a particle size of 0.5 to 1 mm.
The sodium content of this zeolite was 7.9% by mass.
A 10 L cylindrical container (with a lower screen) was filled with 3 L of a 1 mol / L ammonium nitrate solution, and 1 kg of the NaY molded body (pulverized product) was added thereto.
The ammonium nitrate solution was circulated with a roller pump for 3 hours and then washed with pure water.
When a part of the washed zeolite was analyzed, the sodium content was 3.6% by mass.
Next, 394 g of silver nitrate was dissolved in 1 L of water, and 325 g of 30% by mass of aqueous ammonia was added to obtain a silver ammine complex ion solution.
This silver ammine complex ion solution was put into the cylindrical container, and the solution was circulated for 8 hours to perform silver ion exchange treatment.
Thereafter, the solid matter was collected by filtration, washed with water, dried at 120 ° C., and further subjected to calcination treatment at 400 ° C. for 3 hours to obtain a silver ion exchange Y-type zeolite.
The silver content was 12.0% by mass, and the sodium content was 2.8% by mass.

Example 2
In Example 1, a washed zeolite was obtained in the same manner as in Example 1 except that it was treated with 3 L of 1 mol / L ammonium chloride solution for 12 hours instead of 1 mol / L ammonium nitrate solution. Ion exchange treatment was performed to obtain a silver ion exchange Y-type zeolite.
The sodium content of the washed zeolite was 3.7% by mass.
The silver ion-exchanged Y-type zeolite had a silver content of 11.8% by mass and a sodium content of 2.9% by mass.

Example 3
After obtaining a washed zeolite in the same manner as in Example 1 except that 3 L of 0.5 mol / L ammonium sulfate solution was used instead of 1 mol / L ammonium nitrate solution in Example 1, silver ions were obtained. Exchange treatment was performed to obtain a silver ion exchange Y-type zeolite.
The sodium content of the washed zeolite was 4.6% by mass.
The silver ion-exchanged Y-type zeolite had a silver content of 12.1% by mass and a sodium content of 2.8% by mass.

Comparative Example 1
The NaY zeolite molding (0.5 to 1 mm particle size) used in Example 1 was put into a cylindrical container containing 1.5 L of water, and a solution of 394 g of silver nitrate dissolved in 1 L of water was added. The silver ion exchange process was performed by circulating over time.
Thereafter, the solid matter was collected by filtration, washed with water, dried at 120 ° C., and further subjected to calcination treatment at 400 ° C. for 3 hours to obtain a silver ion-exchanged Y-type zeolite.
The silver content was 16.5% by mass, and the sodium content was 2.9% by mass.

Comparative Example 2
The NaY zeolite molding (0.5 to 1 mm particle size) used in Example 1 was treated with 3 L of an ammonium nitrate solution having a concentration of 1 mol / L in the same manner as in Example 1.
After washing with water, this treatment was repeated with 3 L of a 1 mol / L ammonium nitrate solution for a total of 10 treatments.
The sodium content of the washed zeolite was 0.1% by mass.
Next, in the same manner as in Example 1, silver ion exchange treatment was performed using a silver ammine complex ion solution to obtain a silver ion exchange Y-type zeolite.
The silver ion exchange Y-type zeolite had a silver content of 11.5% by mass and a sodium content of less than 0.1% by mass.

Test example 1
Each metal exchange zeolite of Examples 1 to 3 and Comparative Examples 1 to 2 was molded to 0.5 to 1 mm, and 1 cm ³ of an adsorbent was filled into a desulfurization tube having an inner diameter of 9 mm.
The adsorbent temperature is 20 ° C. at normal pressure, and propane gas containing 20 ppm by volume (total 40 ppm by volume) of dimethyl sulfide (DMS) and 2-methyl-2-propanethiol (MPT) is used at normal pressure, GHSV (gas It was made to circulate on the condition of space-time velocity 20,000h < ^-1 >.
The concentration of each sulfur compound in the desulfurization pipe outlet gas was measured every hour by SCD (Sulfur Chemiluminescence Detector) gas chromatography.
Table 1 shows the time for each sulfur compound concentration to exceed 0.1 ppm by volume.

  As can be seen by comparing Examples 1 to 3 and Comparative Examples 1 and 2, the adsorbent containing metal ion-exchanged zeolite using Y-type zeolite having a sodium content of 0.5 to 5% by mass has a sodium content. However, it is superior in desulfurization performance as compared with metal ion exchange zeolite using Y-type zeolite outside the present invention.

It is a schematic flowchart which shows an example of the fuel cell system of this invention.

Explanation of symbols

1: Vaporizer 2: Fuel cell system 20: Hydrogen production system 21: Fuel tank 23: Desulfurizer 31: Reformer 31A: Boiler 32: CO converter 33: CO selective oxidizer 34: Fuel cell 34A: Negative electrode 34B: Cathode 34C: Polymer electrolyte 36: Steam separator 37: Waste heat recovery device 37A: Heat exchanger 37B: Heat exchanger 37C: Cooler

Claims (11)

  A method for producing a metal ion-exchanged Y-type zeolite, characterized in that a metal ion-exchanged Y-type zeolite having a sodium content of 0.5 to 5% by mass is supported on the zeolite.   The method for producing a metal-exchanged Y-type zeolite according to claim 1, wherein the sodium content of the Y-type zeolite is 2 to 5% by mass.   The method for producing a metal-exchanged Y-type zeolite according to claim 1 or 2, wherein the Y-type zeolite is obtained by substituting a part of sodium ions of NaY-type zeolite with ammonium ions.   The method for producing a metal-exchanged Y-type zeolite according to any one of claims 1 to 3, wherein metal ion exchange is performed using a solution containing at least one metal ammine complex ion selected from silver and copper.   The method for producing a metal-exchanged Y-type zeolite according to any one of claims 1 to 4, wherein the Y-type zeolite is a molded Y-type zeolite.   The method for producing a metal ion-exchanged zeolite according to any one of claims 1 to 5, wherein the sodium content of the metal-exchanged Y-type zeolite is 0.5 to 4% by mass.   An adsorbent for removing sulfur compounds in hydrocarbon fuel or dimethyl ether fuel, comprising the metal ion exchanged zeolite obtained by the method according to any one of claims 1 to 6.   The sulfur according to claim 7, wherein the hydrocarbon fuel is at least one hydrocarbon compound selected from LPG, city gas, natural gas, naphtha, kerosene, light oil or ethane, ethylene, propane, propylene, butane and butene. Adsorbent for compound removal.   The sulfur compound removal adsorbent according to claim 7 or 8 is used to desulfurize a sulfur compound in a hydrocarbon fuel or a dimethyl ether fuel, and the desulfurized fuel is used as a partial oxidation reforming catalyst or an autothermal reforming catalyst. Or the manufacturing method of hydrogen characterized by making it contact with a steam reforming catalyst.   The method for producing hydrogen according to claim 9, wherein the partial oxidation reforming catalyst, autothermal reforming catalyst, or steam reforming catalyst is a ruthenium-based or nickel-based catalyst. A fuel cell system using hydrogen produced by the method according to claim 9 or 10.

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