JP2001279257A - Desulfurizing agent, desulfurizing method, and method for producing hydrogen for fuel cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a desulfurizing agent capable of effectively removing sulfur from petroleum hydrocarbons and having a long life, and desulfurization for efficiently removing sulfur from hydrocarbons to a low concentration. A method and a method for producing hydrogen for a fuel cell. SOLUTION: A desulfurizing agent for petroleum hydrocarbons in which iron is supported on a carrier, a desulfurization method for desulfurizing petroleum hydrocarbons using the desulfurizing agent and, optionally, contacting with a second desulfurizing agent, And a method for producing hydrogen for a fuel cell by contacting a petroleum hydrocarbon contacted with the second desulfurizing agent with a steam reforming catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a desulfurizing agent, a desulfurizing method, and a method for producing hydrogen for a fuel cell. More specifically, the present invention is a desulfurizing agent capable of effectively removing the sulfur content of petroleum hydrocarbons and having a long service life. Desulfurization method that efficiently removes the petroleum hydrocarbon treated by this desulfurization method, and a desulfurization method that can maintain the performance of the reforming catalyst in the steam reforming section that is a downstream facility for a long time, The present invention relates to a method for producing hydrogen for a fuel cell.

[0002]

2. Description of the Related Art In recent years, new energy technologies have been spotlighted due to environmental problems, and fuel cells have attracted attention as one of the new energy technologies. This fuel cell converts chemical energy into electric energy by electrochemically reacting hydrogen and oxygen, and has the feature of high energy use efficiency.
Practical research is being actively conducted for industrial or automotive use. As the fuel cell, types such as a phosphoric acid type, a molten carbonate type, a solid oxide type, and a solid polymer type are known according to 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 natural gas, synthetic liquid fuel composed of natural gas as raw material, and petroleum LP
The use of hydrocarbons such as G, naphtha, kerosene is being studied. When using fuel cells for consumer or automotive applications,
The petroleum hydrocarbon is advantageous as a hydrogen source because it is easy to store and handle, and has a supply system such as a gas station and a store.

[0003] However, petroleum hydrocarbons have a problem that they have a higher sulfur content than methanol and natural gas fuels. When hydrogen is produced using this petroleum hydrocarbon, a method is generally used in which the hydrocarbon is subjected to steam reforming or partial oxidation reforming treatment in the presence of a reforming catalyst. In such a reforming treatment, since the reforming catalyst is poisoned by the sulfur content in the hydrocarbon, the hydrocarbon is desulfurized to reduce the sulfur content from the viewpoint of the catalyst life. It is important that the content be 0.2 ppm by weight or less. Many studies have been made on the desulfurization method of petroleum hydrocarbons. For example, a hydrodesulfurization catalyst such as Co-Mo / alumina or Ni-Mo / alumina and a hydrogen sulfide adsorbent such as ZnO have been used. Under a pressure of ~ 5MPa,
A method for hydrodesulfurization at a temperature of 200 to 400 ° C is known. This method is a method of performing hydrodesulfurization under severe conditions to remove the sulfur content into hydrogen sulfide, and it is difficult to reduce the sulfur content to 0.2 ppm by weight or less. Hard to apply to hydrogen.

On the other hand, as a desulfurization method of petroleum fraction, a method of removing a part of sulfur compounds by physical adsorption is known (US Pat. No. 4,188,285;
No. 28989, JP-A-6-154615, US Pat. No. 5,482,617, US Pat. No. 5,807.
475, International Patent Publication No. 98151762, and US Pat. No. 5,935,422), and activated carbon and zeolite are known as substances used for removal.
Furthermore, a method is known in which a petroleum fraction from which a part of a sulfur compound has been removed by physical adsorption is further brought into contact with a desulfurizing agent (U.S. Pat. No. 5,114,689;
No. 4214). However, activated carbon and zeolites have low adsorption performance for sulfur compounds, and the physical adsorbent used in the above method has not reached a practical level in terms of life as a desulfurizing agent for fuel cells. .

[0005]

In such a situation,
A first object of the present invention is to provide a desulfurizing agent that can effectively remove sulfur from petroleum hydrocarbons and has a long life. Further, a second object of the present invention is to use this desulfurizing agent to efficiently remove the sulfur content of petroleum hydrocarbons to a low concentration and improve the performance of the reforming catalyst in the steam reforming section, which is downstream equipment. It is to provide a desulfurization method that can be maintained for a long time. Further, a third object of the present invention is that
An object of the present invention is to provide a method for efficiently producing hydrogen for fuel cells using petroleum hydrocarbons processed by the above desulfurization method.

[0006]

Means for Solving the Problems In order to achieve the above object, the present inventors first analyzed in detail the properties of sulfur compounds in petroleum hydrocarbons. As a result, sulfur compounds contained in petroleum hydrocarbons include mercaptan, sulfide, disulfide, thiophene, benzothiophene,
Dibenzothiophenes, etc., and their distillation properties and distribution of molecular sizes such as alkyl groups were found to be complex and diverse. Also, mercaptans, sulfides, disulfides, and thiophenes are relatively easily desulfurized,
We also found that benzothiophenes and dibenzothiophenes are difficult to desulfurize. Furthermore, through experiments such as adsorption of a desulfurizing agent on a sulfur compound, it was clarified that a sulfur compound having a relatively high boiling point inhibited adsorption of a sulfur compound having a lower boiling point onto the desulfurizing agent. Therefore, it has been noted that sulfur compounds in petroleum hydrocarbons can be effectively removed by selectively removing sulfur compounds having a relatively high boiling point.

Based on this attention, the present inventors set alkyldibenzothiophenes having the highest boiling point as sulfur compounds in petroleum hydrocarbons to be selectively removed, and selectively adsorb these sulfur compounds. As a result of intensive studies to develop a desulfurizing agent for removal, carriers, especially those with iron supported on porous carriers, can selectively adsorb and remove alkyldibenzothiophenes, It has been found that as a desulfurizing agent for hydrogen, it can meet the first object. In addition, it has been found that the second object can be achieved by desulfurizing petroleum hydrocarbons using the above desulfurizing agent and, if necessary, bringing the hydrocarbon into contact with a second desulfurizing agent. Furthermore, in the above desulfurization method, it has been found that the third object can be achieved by contacting the petroleum hydrocarbon after contacting with the second desulfurizing agent with the steam reforming catalyst. The present invention has been completed based on such findings. That is, the present invention provides (1) a desulfurizing agent for petroleum hydrocarbons in which iron is supported on a carrier, (2) a method for desulfurizing petroleum hydrocarbons using the desulfurizing agent, (3) A desulfurization method for petroleum hydrocarbons, which comprises desulfurizing petroleum hydrocarbons by the method (2) and then contacting the same with a second desulfurizing agent; and (4) petroleum-based hydrocarbons by the method (3). It is intended to provide a method for producing hydrogen for fuel cells, which comprises contacting a hydrocarbon with a steam reforming catalyst after desulfurization treatment.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the desulfurizing agent of the present invention will be described. The desulfurizing agent of the present invention is obtained by supporting iron as a metal component on a carrier, and the carrier is preferably porous. Examples of such a porous carrier include porous inorganic oxides such as silica, alumina, silica-alumina, zeolite, titania, zirconia, magnesia,
Preferable examples include zinc oxide, clay, clay, and diatomaceous earth. Activated carbon can also be used. These porous carriers may be used alone or in combination of two or more. Among them, zeolite or activated carbon is particularly preferable. The amount of iron supported on these carriers was 0.5% as iron oxide based on the total amount of the desulfurizing agent.
The range is preferably from 30 to 30% by weight. If the amount is less than 0.5% by weight, the desulfurization performance may not be sufficiently exhibited. On the other hand, if the amount exceeds 30% by weight, the particle diameter of the supported iron increases, and it is difficult to obtain sufficient desulfurization performance, which is not preferable. .
From the viewpoint of desulfurization performance, the more preferable amount of iron is in the range of 1 to 20% by weight as iron oxide.

In the present invention, if necessary, at least one metal selected from copper, cobalt, nickel, manganese and chromium is optionally added to the carrier together with the above-mentioned iron as long as the effects of the present invention are not impaired. It can be carried. The method for supporting the metal component on the carrier is not particularly limited, and any known methods such as an impregnation method, a coprecipitation method, a kneading method with a carrier gel, and an ion exchange method can be used. Among the methods, the ion exchange method is preferred. Specifically, for example, an aqueous solution of iron nitrate, iron sulfate, iron chloride or the like, which is an iron source, and a carrier described below are mixed,
The mixture was stirred at a temperature of 0 ° C. for 6 to 36 hours, reacted, washed, dried at a temperature of 50 to 150 ° C., and further dried at a temperature of 300 to 5 hours.
It can be prepared by firing at a temperature of 50 ° C.

The shape of the desulfurizing agent is not particularly limited, and may be, for example, a crushed shape, a pellet shape, a tablet shape, a honeycomb shape,
Alternatively, a state in which the desulfurizing agent powder is coated on another honeycomb-shaped substrate can be exemplified. Petroleum hydrocarbons to which the desulfurizing agent of the present invention is applied include, for example, LP
G, gasoline, naphtha, kerosene, light oil, etc., among which petroleum hydrocarbons having a boiling point range equal to or lower than kerosene are preferred. Kerosene has a sulfur content of 80
It is preferably applied to JIS No. 1 kerosene having a weight ppm or less. Next, the desulfurization method of the present invention will be described. The desulfurization method of the present invention includes (1) a method of desulfurizing a petroleum hydrocarbon using the desulfurizing agent of the present invention described above (hereinafter, referred to as a desulfurizing method I of the present invention), and (2) the above. There are two modes of a method of desulfurizing a petroleum hydrocarbon by desulfurization method I and then contacting it with a second desulfurizing agent (hereinafter referred to as desulfurization method II of the present invention).

In the desulfurization method I of the present invention, as a desulfurization mode, a method of flowing a petroleum hydrocarbon through a desulfurization agent, putting a petroleum hydrocarbon in a container such as a tank in which the desulfurization agent is fixed, and allowing it to stand still or Preferable examples include a stirring method. In this case, the temperature at which the desulfurizing agent is brought into contact with the petroleum hydrocarbon is preferably in the range of -40 to 100C. When the temperature is -40 ° C or lower, the fluidity of the hydrocarbon is lowered, and thus it is not preferable. In addition,
At this time, the pressure is usually from normal pressure to 1 MPa. In the desulfurization method II of the present invention, the desulfurizing agent of the present invention is used as a preliminary desulfurizing agent, and the petroleum hydrocarbon is desulfurized as described above, and then contacted with a second desulfurizing agent. Adsorption desulfurization of hydrocarbons can be performed efficiently.

The second desulfurizing agent is not particularly limited, and another adsorptive desulfurizing agent may be used, or a hydrodesulfurization catalyst such as Co-Mo / alumina or Ni-Mo / alumina may be used. . Examples of the other adsorptive desulfurizing agents include Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, and I.
It is preferable that at least one selected from r and Pt is supported on a porous carrier. In particular, those in which nickel is supported on a porous carrier are preferred. The amount of these metal components carried is preferably 50 to 70% by weight based on the total amount of the desulfurizing agent from the viewpoint of desulfurization performance and the like. These adsorptive desulfurization agents can improve desulfurization performance by hydrogen reduction in advance. When the latter hydrodesulfurization catalyst is used as the second desulfurization agent, a small amount of hydrogen may be added when the petroleum hydrocarbon is brought into contact with the hydrodesulfurization catalyst.

As the desulfurization method using the second desulfurizing agent, it is preferable to directly contact the petroleum hydrocarbon desulfurized by the desulfurizing agent of the present invention with the second desulfurizing agent. Alternatively, the petroleum hydrocarbon may be desulfurized in advance at another place with the desulfurizing agent of the present invention, and may be brought into contact with the second desulfurizing agent during the reaction. The reaction conditions for contacting the petroleum hydrocarbon with the second desulfurizing agent can be appropriately selected according to the type of the second desulfurizing agent used. For example, when a nickel-based adsorption desulfurizing agent is used as the second desulfurizing agent and kerosene is used as the petroleum hydrocarbon, the contact temperature is usually 130 to 2
30 ° C., and the pressure is usually from normal pressure to 1 MPa.
・ Approximately G. In such desulfurization method II of the present invention, by appropriately selecting the desulfurization conditions, the sulfur content in petroleum hydrocarbons can be reduced to 0.2 ppm by weight or less.

Next, a method for producing hydrogen for a fuel cell according to the present invention will be described. In this method, the petroleum hydrocarbon desulfurized in the desulfurization method II of the present invention is
By contacting with a steam reforming catalyst, hydrogen for a fuel cell is produced. There is no particular limitation on the steam reforming catalyst used in the method of the present invention, and among known catalysts conventionally known as hydrocarbon steam reforming catalysts,
Any one can be appropriately selected and used. As such a steam reforming catalyst, for example, a catalyst in which a noble metal such as nickel, zirconium, ruthenium, rhodium, and platinum is supported on a suitable carrier can be exemplified. One of the above-mentioned supported metals may be supported, or two or more may be supported in combination. Among these catalysts, those supporting ruthenium (hereinafter referred to as ruthenium-based catalyst) are preferable, and have a large effect of suppressing carbon deposition during the steam reforming reaction. In the case of this ruthenium-based catalyst, the supported amount of ruthenium is 0.05 to 20 on the basis of the carrier.
% By weight, more preferably from 0.05 to 1% by weight.
It is in the range of 5% by weight, particularly preferably 0.1 to 2% by weight.

When ruthenium is supported, it can be supported in combination with another metal, if desired. Examples of the other metal include zirconium, cobalt, and magnesium. On the other hand, as the carrier, an inorganic oxide is preferable, and specific examples include alumina, silica, zirconia, magnesia, and a mixture thereof. Of these, alumina and zirconia are particularly preferred. The reaction conditions in the steam reforming process include:
Ratio S / C of steam and carbon derived from petroleum hydrocarbon
(Molar ratio) is selected in the range of usually 2 to 5, preferably 2 to 4, more preferably 2 to 3. S / C molar ratio is 2
If it is less than 5%, the amount of hydrogen generated may decrease.
Exceeding the above requires excessive steam, large heat loss,
It is not preferable because the efficiency of hydrogen production decreases.

Further, the inlet temperature of the steam reforming catalyst layer is set to 63
It is preferable to carry out steam reforming at a temperature of 0 ° C. or lower, more preferably 600 ° C. or lower. If the inlet temperature exceeds 630 ° C., thermal decomposition of hydrocarbons is promoted, and carbon is deposited on the catalyst or the reaction tube wall, which may make the operation difficult. The outlet temperature of the catalyst layer is not particularly limited, but is preferably in the range of 650 to 800 ° C. If the outlet temperature of the catalyst layer is lower than 650 ° C., the amount of generated hydrogen may not be sufficient. If the temperature exceeds 800 ° C., the reactor may require a heat-resistant material, which is not economically preferable. The reaction pressure is usually from normal pressure to 3 MPa,
It is preferably in the range of normal pressure to 1 MPa.
V is usually 0.1 to 100 h ^-1 , preferably 0.2 to 5 h
0h ^-1 . In this way, hydrogen for a fuel cell can be efficiently produced.

[0017]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The kerosene used in the desulfurization test was
It is JIS No. 1 kerosene having a sulfur content of 65 ppm by weight. Example 1 (1) Preparation of desulfurizing agent 1 liter of 0.1 mol / liter iron nitrate aqueous solution and 100 g of NaY type zeolite (Si / Al molar ratio: 34)
And stirred at 75 ° C. for 12 hours, followed by washing.
After drying at 0 ° C., and further sintering at 400 ° C.,
A desulfurizing agent composed of zeolite was prepared. The amount of Fe supported in this desulfurizing agent was 5.1% by weight as iron oxide. (2) Desulfurization test 50 g of the desulfurizing agent obtained in (1) above and JIS No. 1 kerosene 200
Milliliter was placed in a 500 ml glass container and stirred at room temperature for 24 hours, after which kerosene was separated and collected. The sulfur concentration in the recovered kerosene is 17 weight pp
m.

Example 2 (1) Preparation of desulfurizing agent Example 1 (1) was the same as Example 1 (1) except that beta zeolite (Si / Al molar ratio: 50) was used instead of NaY zeolite. In the same manner as described above, a desulfurizing agent comprising a Fe-supported beta zeolite was prepared. The amount of Fe supported in this desulfurizing agent was 3.0% by weight as iron oxide. (2) Desulfurization test A desulfurization test was performed using the desulfurizing agent obtained in the above (1) in the same manner as in Example 1 (2). As a result, the sulfur content in the recovered kerosene was 6 ppm by weight. . Example 3 (1) Preparation of desulfurizing agent 0.1 mol / mol was added to 100 g of commercially available activated carbon (specific surface area: 1000 m ² / g, pore volume: 0.98 ml / g).
100 ml of an aqueous solution of iron nitrate having a concentration of 1 liter was impregnated and dried at 120 ° C. to prepare a desulfurizing agent composed of activated carbon carrying Fe. The amount of Fe supported in this desulfurizing agent was 6.5% by weight as metallic iron. (2) Desulfurization test A desulfurization test was carried out using the desulfurizing agent obtained in the above (1) in the same manner as in Example 1 (2), and the sulfur content in the recovered kerosene was 10 ppm by weight. .

Comparative Example 1 (1) Preparation of desulfurizing agent Ni-Ni was prepared in the same manner as in Example 1 (1) except that nickel nitrate was used in place of iron nitrate.
A desulfurizing agent comprising a supported Y-type zeolite was prepared. The amount of Ni carried in this desulfurizing agent was 5.4 as nickel oxide.
% By weight. (2) Desulfurization test Using the desulfurizing agent obtained in the above (1), a desulfurization test was carried out in the same manner as in Example 1 (2). The sulfur content in the recovered kerosene was 53 ppm by weight. . Comparative Example 2 (1) Preparation of desulfurizing agent A desulfurizing agent comprising a non-supported Y-type zeolite was prepared in the same manner as in Example 1 (1) except that an aqueous solution of iron nitrate was not used in Example 1 (1). Prepared. (2) Desulfurization test Using the desulfurizing agent obtained in the above (1), a desulfurization test was carried out in the same manner as in Example 1 (2). The sulfur content in the recovered kerosene was 53 ppm by weight. .

Comparative Example 3 (1) Preparation of Desulfurizing Agent An unsupported beta zeolite was prepared in the same manner as in Example 2 (1) except that an aqueous solution of iron nitrate was not used in Example 2 (1). A desulfurizing agent was prepared. (2) Desulfurization test A desulfurization test was carried out using the desulfurizing agent obtained in the above (1) in the same manner as in Example 1 (2). The sulfur content in the recovered kerosene was 46 ppm by weight. . Comparative Example 4 (1) Preparation of desulfurizing agent A desulfurizing agent composed of unsupported activated carbon was prepared in the same manner as in Example 3 (1) except that an aqueous solution of iron nitrate was not used in Example 3 (1). . (2) Desulfurization test A desulfurization test was carried out using the desulfurizing agent obtained in the above (1) in the same manner as in Example 1 (2). As a result, the sulfur concentration in the recovered kerosene was 50 ppm by weight. .

Example 4 (1) Pre-desulfurization treatment 500 g of the desulfurizing agent prepared in Example 1 and JIS No. 1 kerosene 2
Liters in a 5 liter container
After stirring for 4 hours and performing a preliminary desulfurization treatment, a kerosene component was separated and collected. The sulfur content in the pre-desulfurized kerosene was 17 ppm by weight. (2) Desulfurization treatment with nickel-supported diatomaceous earth desulfurizing agent As a second desulfurizing agent, 15 ml of nickel-supported diatomaceous earth (amount of Ni supported: 54.3% by weight as metallic nickel) was calcined at 400 ° C., and then stainless steel having an inner diameter of 17 mm was used. Into a reaction tube. Next, the temperature was raised to 120 ° C. in a hydrogen stream at normal pressure, and the temperature was maintained for 1 hour. After that, the temperature was further raised and the temperature was maintained at 380 ° C. for 1 hour to activate the nickel-supporting diatomite desulfurizing agent. Thereafter, the temperature was kept at 150 ° C. Next, the pre-desulfurized kerosene is subjected to a liquid hourly space velocity (L
(HSV) at 5 h ⁻¹ , and the sulfur content in the treated kerosene after 5 hours was analyzed. As a result, the sulfur concentration was 0.2 ppm by weight.

Example 5 In Example 4, the liquid hourly space velocity (LHSV) was set to 2 h ^-1.
In the same manner except that the ruthenium-based reforming catalyst (Ru supported amount:
(0.5% by weight) steam reforming treatment was performed by a reformer filled with 15 cc. The reforming conditions are pressure: normal pressure, steam /
The carbon (S / C) molar ratio was 2.5, the LHSV was 2 h ⁻¹ , the inlet temperature was 500 ° C., and the outlet temperature was 750 ° C. As a result,
After 600 hours, the conversion at the outlet of the reformer was 100%. The sulfur content of the desulfurized kerosene during this period was 0.2 ppm by weight or less. Comparative Example 5 Example 4 was carried out in the same manner as in Example 4 (2) except that (1) was not performed and (2) was replaced with a new JIS No. 1 kerosene in place of the pre-desulfurized kerosene. As a result, the sulfur concentration in the treated kerosene was 2.3 wt p
pm.

Comparative Example 6 In Example 4, without performing (1), in (2), JIS No. 1 kerosene was diluted with sulfur-free decane in place of the pre-desulfurized kerosene to reduce the sulfur content to 17% by weight. The procedure was performed in the same manner as in Example 4 (2), except that ppm was used. As a result, the sulfur concentration in the treatment liquid was 0.6 ppm by weight. As described above, from Example 4 and Comparative Examples 5 and 6, as a result of the desulfurizing agent of the present invention adsorbing and removing some of the alkyldibenzothiophenes in kerosene, the inhibition of adsorption of the second desulfurizing agent by adsorption and desulfurization was reduced. Thus, it can be seen that the desulfurization performance of the second desulfurizing agent was improved even when compared at the same sulfur concentration. Comparative Example 7 A sulfur content of 17 wt. P prepared in the same manner as in Comparative Example 6.
A steam reforming treatment was performed in the same manner as in Example 5, except that kerosene of pm was used. As a result, the conversion was less than 100% after 400 hours. At that time, the sulfur content of the desulfurized kerosene was 8 ppm.

[0024]

The desulfurizing agent of the present invention is obtained by supporting iron on a carrier, and can effectively remove petroleum hydrocarbons, particularly sulfur in kerosene, and has a long life. Further, according to the desulfurization method of the present invention, the sulfur content in petroleum hydrocarbons can be efficiently removed to a low concentration, and the performance of the reforming catalyst in the steam reforming section, which is downstream equipment, can be maintained for a long time. Can be. Further, by subjecting petroleum hydrocarbons treated by this desulfurization method to steam reforming treatment, hydrogen for fuel cells can be efficiently produced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C01B 3/40 C01B 3/40 5H027 C10G 25/05 C10G 25/05 53/08 53/08 H01M 8/06 H01M 8/06 G F term (reference) 4D017 AA04 BA04 CA05 CA06 CB01 DA07 EB07 4G040 EA03 EA06 EB01 EC03 4G066 AA05C AA15B AA16C AA18B AA18C AA20 BC AA22C AA26B AA27A AA27A 4H029 DA06 5H027 AA02 BA01 BA16 KK01 KK42

Claims (11)

[Claims] 1. A desulfurizing agent for petroleum hydrocarbons comprising iron supported on a carrier. 2. The desulfurizing agent for petroleum hydrocarbons according to claim 1, wherein the petroleum hydrocarbon is kerosene. 3. The desulfurizing agent for petroleum hydrocarbons according to claim 1, wherein the carrier is porous. 4. The carrier according to claim 1, wherein the carrier is at least one selected from silica, alumina, silica-alumina, zeolite, titania, zirconia, magnesia, zinc oxide, clay, clay, diatomaceous earth and activated carbon.
3. The desulfurizing agent for petroleum hydrocarbon according to any one of 3. 5. The desulfurizing agent for petroleum hydrocarbons according to claim 1, wherein 0.5 to 30% by weight of iron is supported on the carrier as iron oxide based on the total amount of the desulfurizing agent. . 6. A method for desulfurizing petroleum hydrocarbons, comprising using the desulfurizing agent according to claim 1. Description: 7. The method for desulfurizing petroleum hydrocarbon according to claim 6, wherein the petroleum hydrocarbon is brought into contact with a desulfurizing agent at a temperature of -40 to 100 ° C. 8. A method for desulfurizing petroleum hydrocarbons, comprising subjecting a petroleum hydrocarbon to desulfurization treatment according to the method of claim 6 and then bringing the petroleum hydrocarbon into contact with a second desulfurization agent. 9. The method according to claim 9, wherein the second desulfurizing agent is Cr, Mn, Fe, C
9. A material containing at least one metal selected from the group consisting of o, Ni, Cu, Zn, Pd, Ir and Pt.
The method for desulfurizing petroleum hydrocarbons according to the above. 10. A method for producing hydrogen for a fuel cell, comprising subjecting a petroleum hydrocarbon to desulfurization treatment by the method according to claim 8 and then contacting the desulfurization treatment with a steam reforming catalyst. 11. The method for producing hydrogen for a fuel cell according to claim 10, wherein the steam reforming catalyst is a ruthenium-based catalyst.