JP2003292974A - Method for desulfurizing hydrocarbon containing organic sulfur compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for desulfurizing fuel for fuel cells by using oxidation reaction, promoting oxidation of sulfur compounds in the fuel and effectively desulfurizing. <P>SOLUTION: The method for desulfurizing a hydrocarbon containing organic sulfur compounds comprises treating the hydrocarbon with an oxidizing agent in a static mixer and removing the organic sulfur compounds by contacting to an adsorbent or by distillation or extraction. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for oxidative desulfurization of a hydrocarbon containing an organic sulfur compound and a method for producing hydrogen for a fuel cell using the desulfurization method.

[0002]

2. Description of the Related Art In recent years, new energy technologies have been in the spotlight due to environmental problems, and fuel cells have been attracting attention as one of these new energy technologies. This fuel cell is one for converting chemical energy into electric energy by electrochemically reacting hydrogen and oxygen, and is characterized by high energy utilization efficiency.
Practical studies are being actively conducted for industrial use or automobile use. In the reforming treatment of hydrocarbons for the purpose of producing hydrogen for fuel cells, in order to suppress poisoning of the reforming catalyst by the organic sulfur compounds in the hydrocarbons, the sulfur content in the hydrocarbons should be 0 over a long period of time. It is necessary to maintain the content of 0.2 mass ppm or less.

As a method for desulfurizing a hydrocarbon containing an organic sulfur compound, for example, a petroleum fraction, a method is known in which a sulfur compound is oxidized by an oxidant to increase the melting point and boiling point to separate and remove it from the hydrocarbon ( JP-A-4-72387). Further, a method of introducing an oxidation catalyst in order to promote the reaction between the sulfur compound and the oxidizing agent is also known (Japanese Patent Laid-Open No. 11-140462). Thiophenes, which are organic sulfur compounds in hydrocarbons containing organic sulfur compounds,
It is known to be oxidized to sulfoxide or sulfone by various oxidizing agents.

However, even if these methods are applied to desulfurization of hydrocarbons containing organic sulfur compounds, sufficient oxidation efficiency cannot be obtained because the sulfur concentration in hydrocarbons containing organic sulfur compounds is very small, and hydrogen for fuel cells is not obtained. It has not reached a practical level as a method for desulfurizing hydrocarbons used in the production of Further, in the method described in JP-A No. 11-140462, a petroleum fraction and an oxidizing agent are mixed and stirred using a homogenizer or the like during the oxidation reaction of a sulfur compound. Due to the low contact efficiency between the compound and the oxidizing agent, the oxidation reaction could not be sufficiently advanced.

[0005]

DISCLOSURE OF THE INVENTION The present invention can desulfurize a sulfur compound to a low concentration by efficiently oxidizing a sulfur compound in the hydrocarbon in a desulfurization treatment using an oxidation reaction of a hydrocarbon for a fuel cell. It is an object of the present invention to provide a method and a method for producing hydrogen for a fuel cell using the desulfurization method.

[0006]

In order to achieve the above object, the present inventors efficiently oxidize organic sulfur compounds (thiophenes) in hydrocarbons and convert them into highly polar compounds such as sulfoxide or sulfone. Then, the method for efficient removal by adsorption, distillation or solvent extraction was earnestly studied. As a result, static mixers, such as static mixers,
It is possible to efficiently oxidize an organic sulfur compound by carrying out an oxidation reaction of a hydrocarbon by using, and further, the oxidized organic sulfur compound is adsorbed by an adsorbent, distilled or solvent-extracted to extract an organic sulfur compound from the hydrocarbon. The inventors have found that the compounds can be efficiently removed and have reached the present invention. Furthermore, after removing the organic sulfur compound by contact with an adsorbent, distillation or solvent extraction, the sulfur content remaining in the hydrocarbon is adsorbed and removed by using a second desulfurization agent, so that the sulfur content is reduced to a lower concentration. It was also found that can be removed.

[0007] That is, the present invention, in a static mixer,
A method for desulfurizing a hydrocarbon containing an organic sulfur compound, which comprises treating a hydrocarbon containing an organic sulfur compound with an oxidant, and then further removing the organic sulfur compound by adsorption with an adsorbent, distillation or solvent extraction. And a method for desulfurizing a hydrocarbon containing an organic sulfur compound. Furthermore, the present invention provides a method for producing hydrogen for a fuel cell, which comprises subjecting a hydrocarbon to desulfurization using the above desulfurization method and then subjecting it to a reforming treatment.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The desulfurization method of an organic sulfur compound-containing hydrocarbon of the present invention (hereinafter, sometimes referred to as the desulfurization method of the present invention) is a method of removing a hydrocarbon containing an organic sulfur compound in a static mixer. It is characterized by being treated with an oxidizing agent. Here, as the hydrocarbon containing the organic sulfur compound, LP is
G, city gas, naphtha, gasoline, kerosene, light oil, heavy oil,
Those selected from the group consisting of asphaltene, oil sand oil, coal liquefied oil, petroleum heavy oil, shale oil, GTL, waste plastic oil and biofuel can be preferably used. In the desulfurization method of the present invention, the static mixer, for example, a static mixer, promotes the oxidation reaction of the organic sulfur compound-containing hydrocarbon, that is, efficiently mixes / stirs the organic sulfur compound-containing hydrocarbon and the oxidizing agent. Used to do. In the present invention,
The static reactor is a stirrer that uses the kinetic energy of the fluid flowing into the reaction tube to mix the fluid, unlike a normal stirring method that uses a stirring blade and stirring power. Torsion blades, spacers that change the flow of fluid inside the reaction tube,
Some have introduced obstacle walls, some have fine through holes, and include the recently developed micromixers and microstatic mixers.

Since the reaction rate of the oxidation reaction of the organic sulfur compound in the hydrocarbon is slow, the contact efficiency between the organic sulfur compound and the oxidizing agent is low in the conventionally used stirring mixer such as a homogenizer and the oxidation reaction is It was insufficient. On the other hand, according to the static mixer used in the desulfurization method of the present invention, the organic sulfur compound and the oxidizing agent can be sufficiently brought into contact with each other, and the oxidation reaction proceeds efficiently. In the desulfurization method of the present invention, an oxidizing agent is added to the organic sulfur compound-containing hydrocarbon,
The sulfur compounds contained in the hydrocarbon are oxidized to sulfoxides or sulfones.

The oxidizing agent used in the desulfurization method of the present invention is not particularly limited as long as it can oxidize a sulfur compound to a sulfoxide or sulfone. Specific examples of the oxidizer include, for example, oxygen, air, nitrogen tetraoxide, ozone,
Chlorine, bromine, sodium metaperiodate, potassium dichromate, potassium permanganate, chromic anhydride, hypochlorous acid, hydrogen peroxide, peracetic acid, hydrogen peroxide + acetic acid, performic acid, hydrogen peroxide + formic acid , Metachloroperbenzoic acid, hydrogen peroxide + metachlorobenzoic acid, perchloroacetic acid, hydrogen peroxide + chloroacetic acid, perdichloroacetic acid, hydrogen peroxide + dichloroacetic acid, pertrichloroacetic acid, hydrogen peroxide + trichloroacetic acid, pertrifluoro Examples thereof include acetic acid, hydrogen peroxide + trifluoroacetic acid, permetasulphonic acid, hydrogen peroxide + metasulphonic acid, hydrogen peroxide + salicylic acid, persulfuric acid, hydrogen peroxide + sulfuric acid. Only one of these may be used, or two or more may be used in combination. The oxidant may be in the form of gas, liquid or solid, but is preferably a solution prepared by dissolving the above compound in ion-exchanged water, and an aqueous solution of hydrogen peroxide + formic acid is particularly preferred.

The present invention is characterized in that a hydrocarbon containing an organic sulfur compound is treated with an oxidizing agent in a static mixer, and then the organic sulfur compound is removed by contact with an adsorbent, distillation or solvent extraction. The present invention provides a method for desulfurizing a hydrocarbon containing an organic sulfur compound. That is, contact with an adsorbent, distillation, or solvent extraction can be used as a method for separating the sulfur oxide compound generated by the treatment with the oxidizing agent.

The adsorbent used in the desulfurization method of the present invention is preferably a porous inorganic oxide adsorbent that strongly adsorbs sulfoxide or sulfone. Specific examples of the porous inorganic oxide include silica, alumina, silica-alumina, zeolite, titania, zirconia, magnesia, silica-magnesia, clay, clay, diatomaceous earth, activated carbon or insoluble synthetic resin. The adsorbent may be only one of the above compounds or a combination of two or more thereof. Further, the adsorbent may contain a metal in addition to the porous inorganic oxide. Examples of such metal include, for example,
Examples thereof include Ag, Pt, Ru, Rh, Ni and Cu. The adsorbent is preferably in the form of powder, pellets, tablets or beads.

The adsorbent is preferably used in the temperature range of -40 to 100 ° C. If the temperature is -40 ° C or lower, the fluidity of the hydrocarbon containing an organic sulfur compound decreases, and if the temperature exceeds 100 ° C, the adsorbing ability of the adsorbent decreases, which is not preferable. The method of contacting the organic sulfur compound-containing hydrocarbon with the adsorbent is not particularly limited. For example, after the oxidation treatment, a method of adding and stirring the adsorbent in the hydrocarbon from which the oxidizing agent has been separated / removed, a method of circulating the hydrocarbon in a reaction tube filled with the adsorbent, and the like can be mentioned. According to the desulfurization method of the present invention, the sulfur content in the hydrocarbon is 1 mass ppm over a long period of time.
You can remove up to: In addition, by using a static mixer, the time required to oxidize sulfur compounds is
It can be shortened as compared with the conventional one, and the life of the adsorbent can be extended.

As the solvent used in the solvent extraction in the desulfurization method of the present invention, acetonitrile, propionitrile,
Butyronitrile, nitromethane, nitroethane, nitropropane, nitrobenzene, dimethyl sulfoxide,
N, N'-dimethylformamide, N, N'-dimethylacetamide, N-methylpyrrolidine, trimethyl phosphate ester, triethyl phosphate ester, hexamethyl phosphate amide, phosphorane, methanol, ethanol,
Examples thereof include one or two or more selected from the group consisting of propanol, butanol and acetone, or those containing water.

Further, in the desulfurization method of the present invention, after removing the organic sulfur compound by contact with an adsorbent, distillation or solvent extraction, the organic sulfur compound remaining in the hydrocarbon is further adsorbed by the second desulfurizing agent. It is preferable to remove. By using the second desulfurizing agent, the sulfur compound can be further reduced. The second desulfurizing agent is not particularly limited as long as it can adsorb and remove the sulfur compound, and an adsorbing desulfurizing agent or a hydrodesulfurization catalyst other than the above adsorbing agent can be used. Another adsorptive desulfurization agent is N
i, Ag, Cr, Mn, Fe, Co, Cu, Zn, P
A catalyst in which one or more selected from the group consisting of d, Ir, Pt, Ru, Rh and Au is supported on a porous carrier is preferable, and a catalyst supporting Ni or Ag is particularly preferable. . By desulfurizing these catalysts with hydrogen in advance, the desulfurization performance can be improved. Also,
The hydrodesulfurization catalyst is not particularly limited, and those usually used for desulfurization of hydrocarbons can be used. When the hydrodesulfurization catalyst is used as the second desulfurizing agent, a small amount of hydrogen may be added.

The second desulfurizing agent is preferably used in the temperature range of -40 to 220 ° C. At -40 ° C or lower, the fluidity of the petroleum-based hydrocarbon is lowered, and the contact efficiency between the hydrocarbon and the second desulfurizing agent is lowered, so that a good fluidized state cannot be maintained. Both are not preferable because the adsorbing ability of the desulfurizing agent decreases. In the desulfurization method of the present invention, by using the second desulfurizing agent, the concentration of the organic sulfur compound in the hydrocarbon can be reduced to 0.2 mass ppm or less over a long period of time. Hydrocarbons desulfurized by the desulfurization method of the present invention have a very low concentration of sulfur compounds as described above, and therefore, when used in the production of hydrogen for fuel cells, the poisoning by the sulfur of the reforming catalyst can be reduced and the efficiency is extremely high. It is possible to manufacture a fuel cell having a good life and a long life.

Next, a method for producing hydrogen for a fuel cell of the present invention (hereinafter sometimes referred to as the hydrogen production method of the present invention) will be described. The hydrogen production method of the present invention is characterized in that after the hydrocarbon is desulfurized by using the desulfurization method of the present invention, a reforming treatment is performed. Hydrocarbons desulfurized by the desulfurization method of the present invention, the sulfur compound is reduced to an extremely low concentration, it is possible to suppress the poisoning of the reforming catalyst for hydrogen production for fuel cells, deterioration of the reforming catalyst It can be prevented. Therefore, hydrogen for a fuel cell can be efficiently produced, and the life of the fuel cell can be extended. The reforming treatment used in the method for producing hydrogen of the present invention is preferably partial oxidation reforming treatment, autothermal reforming treatment or steam reforming.

The reforming catalyst (partial oxidation reforming catalyst, autothermal reforming catalyst and steam reforming catalyst) used in the hydrogen production method of the present invention is not particularly limited, and is conventionally known as a hydrocarbon reforming catalyst. Any known one can be appropriately selected and used.
As such a reforming catalyst, for example, nickel or zirconium, ruthenium, rhodium,
Examples thereof include those carrying a noble metal such as platinum. The above-mentioned supported metals may be one kind or a combination of two or more kinds. Among these catalysts, nickel-supported catalysts (hereinafter referred to as nickel-based catalysts) and ruthenium-supported catalysts (hereinafter referred to as ruthenium-based catalysts) are preferable. These are partial oxidation reforming treatment and autothermal treatment. The effect of suppressing carbon precipitation during the reforming treatment or steam reforming treatment is great. The carrier for supporting the reforming catalyst preferably contains one or more selected from the group consisting of manganese oxide, cerium oxide and zirconia.

In the case of a nickel-based catalyst, the amount of nickel supported is preferably in the range of 3 to 60 mass% based on the carrier. If the supported amount is less than 3% by mass, the activity of the partial oxidation reforming catalyst, autothermal reforming catalyst or steam reforming catalyst may not be sufficiently exhibited, while if it exceeds 60% by mass,
The effect of improving the catalytic activity commensurate with the supported amount is not recognized so much, which is rather economically disadvantageous. Considering the catalyst activity and economic efficiency, the more preferable loading amount of nickel is 5 to 50% by mass, and the range of 10 to 30% by mass is particularly preferable. Further, in the case of a ruthenium-based catalyst, the amount of ruthenium supported is preferably in the range of 0.05 to 20 mass% based on the carrier. If the supported amount of ruthenium is less than 0.05% by mass, the activity of the partial oxidation reforming catalyst, autothermal reforming catalyst or steam reforming catalyst may not be sufficiently exhibited, while if it exceeds 20% by mass, The effect of improving the catalyst activity corresponding to the supported amount is not recognized so much, which is rather economically disadvantageous. Considering the catalytic activity and economical efficiency, the more preferable amount of ruthenium supported is 0.05 to 15.
It is mass%, and the range of 0.1 to 2 mass% is particularly preferable. As the reaction conditions in the partial oxidation reforming treatment, the pressure is usually atmospheric pressure to 5 MPa, and the temperature is 400 to 1100.
C., oxygen (O ₂ ) / carbon (molar ratio) is 0.2-0.
8. Liquid hourly space velocity (LHSV) is 0.1 to 100 hr ^-1
Conditions are adopted.

The reaction conditions in the autothermal reforming treatment are usually pressure of atmospheric pressure to 5 MPa, temperature of 400 to 1100 ° C., steam / carbon (molar ratio) of 0.1 to 10 and oxygen (O ₂ ) / Carbon (molar ratio) is 0.1 to 1, and liquid hourly space velocity (LHSV) is 0.1 to 2 h.
r ^-1 , gas hourly space velocity (GHSV) is 1000 to 100
The condition of 000 hr ^-1 is adopted. Furthermore, the reaction conditions in the steam reforming treatment are steam / carbon (molar ratio), which is the ratio of steam and carbon derived from fuel oil.
Is usually selected in the range of 1.5 to 10, preferably 1.5 to 5, and more preferably 2 to 4. If the steam / carbon (molar ratio) is less than 1.5, the amount of hydrogen produced may decrease. If it exceeds 10, excessive steam is required, heat loss is large, and the efficiency of hydrogen production decreases. It is not preferable.

The inlet temperature of the steam reforming catalyst layer is set to 63
It is preferable to carry out steam reforming while maintaining the temperature at 0 ° C or lower, more preferably 600 ° C or lower. If the inlet temperature exceeds 630 ° C., the thermal decomposition of fuel oil is promoted, and carbon may be deposited on the catalyst or reaction tube wall via the generated radicals, which may make operation difficult. The catalyst layer outlet temperature is not particularly limited, but is preferably in the range of 650 to 800 ° C. If the temperature is lower than 650 ° C, the amount of hydrogen produced may not be sufficient.
If the temperature is higher than 0 ° C, the reactor may need to be made of a heat-resistant material, which is not economically preferable. The reaction pressure is
It is usually in the range of normal pressure to 3 MPa, preferably normal pressure to 1 MPa, and LHSV is usually 0.1 to 100 h.
r ⁻¹ , preferably in the range of 0.2 to 50 hr ⁻¹ .

In the method for producing hydrogen according to the present invention, CO obtained by the partial oxidation reforming, autothermal reforming or steam reforming has a bad influence on hydrogen generation. Therefore, CO is converted into CO ₂ by a reaction and removed. It is preferable. Thus, according to the hydrogen production method of the present invention, hydrogen for fuel cells can be efficiently produced.

[0023]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples. <Example 1: Desulfurization performance test> Kerosene was desulfurized with each of the following configurations and their desulfurization performances were compared. In the following desulfurization experiment, kerosene had an initial distillation temperature of 153 ° C and a 10% distillation temperature of 176.
℃, 30% distillation temperature 194 ℃, 50% distillation temperature 209
℃, 70% distillation temperature 224 ℃, 90% distillation temperature 249
℃, end point 267 ℃ distillation properties, sulfur content 48 mass p
JIS-1 kerosene containing pm was used. The oxidizing agent is 500 mL of ion-exchanged water at room temperature, 1 mL of hydrogen peroxide solution (6% hydrogen peroxide) and 0.5 m of formic acid (90%).
The one prepared by adding L (hydrogen peroxide + formic acid) was used. A static mixer (C-33, manufactured by Noritake Co., Ltd.) was used as the static mixer. D used as a comparative example
C motor agitation involves rotating a propeller impeller agitation rod with a DC motor (manufactured by Three One Motor Co., 600
G) was used.

Desulfurization Experiment 1 -Oxidation treatment (using static mixer) + porous adsorbent (using silica gel) 1) JIS-1 kerosene 500 mL and oxidizing agent 500 mL
Was introduced into the static mixer simultaneously at a rate of 5 ml / min to obtain oxidized kerosene. The processing time of kerosene at this time was 1 hour and 40 minutes. 2) After separating the obtained oxidized kerosene and the oxidizing agent,
Store 500 mL of oxidized kerosene in a L container and add silica gel 5
0 g was added, and the mixture was stirred at room temperature for 24 hours. Then, the kerosene content was separated and collected, and the sulfur concentration was analyzed to obtain the value of the desulfurization performance.

Desulfurization Experiment 2 -Oxidation treatment (using static mixer) + porous adsorbent (using silica gel) + second desulfurizing agent (using Ni-supported diatomaceous earth catalyst) 1) Firing 15 mL of Ni-supported diatomaceous earth catalyst as the second desulfurization agent Then, a stainless steel reaction tube having an inner diameter of 17 mm was filled. 2) Under normal pressure, the temperature was raised to 120 ° C. in a hydrogen gas stream, kept for 1 hour, further raised, and kept at 380 ° C. for 1 hour, to obtain Ni.
The supported diatomaceous earth catalyst was activated. Then, the temperature of the reaction tube was lowered to 150 ° C. and maintained. 3) The kerosene component separated and recovered in 2) of the desulfurization experiment 1 was circulated under normal pressure at a liquid hourly space velocity of 10 hr ^-1 into a reaction tube filled with a Ni-supported diatomaceous earth catalyst. 4) The sulfur concentration after 5 hours was analyzed and used as the value of desulfurization performance.

Desulfurization Experiment 3 -Oxidation treatment (using static mixer) + porous adsorbent (using silica gel) + second desulfurizing agent (using Ag-supported SiAl catalyst) 1) 500 mL of JIS-1 kerosene and 500 mL of oxidizing agent
Were simultaneously introduced into the static mixer at a rate of 5 mL / min to obtain oxidized kerosene. The processing time of kerosene at this time was 1 hour and 40 minutes. 2) After separating the obtained oxidized kerosene and the oxidizing agent,
400 mL of the above oxidized kerosene was stored in a L container, 50 g of silica gel was added, and the mixture was stirred at room temperature for 24 hours. And kerosene was separated and collected. 3) 15 mL of Ag / SiAl as the second desulfurizing agent was filled in a stainless steel reaction tube having an inner diameter of 17 mm. 4) The reaction tube was heated to 170 ° C. in a nitrogen stream under normal pressure, kept at 170 ° C. for 3 hours, and then cooled to room temperature. 5) The kerosene recovered in the above 2) was circulated at room temperature under normal pressure at a liquid hourly space velocity of 10 hr ^-1 into a reaction tube filled with an Ag / SiAl catalyst. 6) After 5 hours, the sulfur concentration was analyzed and used as the value of desulfurization performance.

Desulfurization Experiment 4 -Oxidation treatment (DC motor agitation) + Porous adsorbent (silica gel) 1) Mix 500 mL of JIS No. 1 kerosene and 500 mL of an oxidant, and use a propeller impeller stirring rod to rotate at 200 rpm Then, the mixture was stirred for 1 hour and 40 minutes. 2) 2 L of the above oxidized kerosene was placed in a 5 L capacity container, 200 g of silica gel was added, and the mixture was stirred at room temperature for 24 hours. Then, the kerosene content was separated and collected, and the sulfur concentration was analyzed to obtain the value of the desulfurization performance.

Desulfurization experiment 5 -oxidation treatment (DC motor stirring) + porous adsorbent (silica gel) + second desulfurization agent (Ni
Use of supported diatomaceous earth catalyst) 1) As a second desulfurizing agent, 15 mL of Ni-supported diatomaceous earth catalyst was baked and filled in a stainless steel reaction tube having an inner diameter of 17 mm. 2) Under normal pressure, the temperature was raised to 120 ° C. in a hydrogen gas stream, kept for 1 hour, further raised, and kept at 380 ° C. for 1 hour, to obtain Ni.
The supported diatomaceous earth catalyst was activated. Then, the temperature of the reaction tube was lowered to 150 ° C. and maintained. 3) The kerosene collected in 2) of the desulfurization experiment 4 is
The liquid was passed through a reaction tube filled with a Ni-supported diatomaceous earth catalyst at a liquid hourly space velocity of 10 hr ⁻¹ . 4) The sulfur concentration after 5 hours was analyzed and used as the value of desulfurization performance. The desulfurization performance obtained in the desulfurization experiments 1 to 5 is shown in Table 1 below.

[0029]

[Table 1]

From the results shown in Table 1, in the desulfurization experiments 1 to 3 using the static mixer, the oxidation reaction was performed much more efficiently than in the desulfurization experiments 4 and 5 using the DC motor stirring, and therefore the desulfurization was performed efficiently. I understand that Further, it can be seen that the desulfurization efficiency is further improved by performing desulfurization using the second desulfurizing agent after desulfurization by the oxidation reaction.

<Example 2: Hydrogen production test for fuel cell by steam reforming treatment> A ruthenium-based reforming catalyst (ruthenium loading amount: 0.5% by mass, downstream of the desulfurizer (desulfurization system) of the desulfurization experiment 2 was used. A reformer filled with 20 mL of carrier (standard) was placed, and kerosene desulfurized to 0.10 mass ppm by the desulfurizer was steam-reformed. The reforming conditions are: pressure: atmospheric pressure, steam / carbon (molar ratio) 2.5, L
HSV: 1.0 hr ^-1 , inlet temperature: 500 ° C, outlet temperature: 750 ° C. As a result, the conversion rate to hydrogen at the reforming outlet after 200 hours was 100%. The sulfur content of the desulfurized kerosene during this reaction period is 0.1 mass pp.
It is m, and it can be seen that hydrogen for fuel cells can be efficiently produced by using kerosene desulfurized by the desulfurization method of the present invention.

[0032]

According to the desulfurization method of the present invention, since the oxidation reaction of the organic sulfur compound in the hydrocarbon is carried out by using the static mixer, the oxidation reaction proceeds extremely efficiently and the sulfur compound concentration is 1 mass. It can be efficiently reduced to ppm or less. Furthermore, by combining the second desulfurizing agent, the sulfur compound concentration can be reduced to 0.2 mass ppm or less. The method for producing hydrogen for a fuel cell of the present invention can efficiently produce hydrogen for a fuel cell by reforming the desulfurized hydrocarbon using the desulfurization method of the present invention. The life of the quality catalyst can be extended.

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Claims (15)

[Claims] 1. A method for desulfurizing a hydrocarbon containing an organic sulfur compound, which comprises treating a hydrocarbon containing an organic sulfur compound with an oxidant in a static mixer. 2. A method of treating a hydrocarbon containing an organic sulfur compound with an oxidizing agent in a static mixer, and then removing the organic sulfur compound by contact with an adsorbent, distillation or solvent extraction. A method for desulfurizing a hydrocarbon containing an organic sulfur compound. 3. The organic sulfur compound is removed by contact with an adsorbent, distillation or solvent extraction, and then the organic sulfur compound remaining in the hydrocarbon is further adsorbed and removed by a second desulfurizing agent. Item 2. The desulfurization method according to Item 2. 4. The hydrocarbon containing the organic sulfur compound is LPG, city gas, naphtha, gasoline, kerosene, light oil, heavy oil, asphaltene, oil sand oil, coal liquefied oil, petroleum heavy oil, shale oil, 4. The desulfurization method according to claim 1, wherein the desulfurization method is selected from the group consisting of GTL, waste plastic oil and biofuel. 5. As the oxidant, oxygen, air, nitrogen tetraoxide, ozone, chlorine, bromine, sodium metaperiodate, potassium dichromate, potassium permanganate, chromic anhydride, hypochlorous acid, peroxidic acid, Hydrogen oxide, peracetic acid, hydrogen peroxide + acetic acid, performic acid, hydrogen peroxide + formic acid, metachloroperbenzoic acid, hydrogen peroxide + metachlorobenzoic acid, perchloroacetic acid, hydrogen peroxide + chloroacetic acid, perdichloroacetic acid, perfluoroacetic acid Hydrogen oxide + dichloroacetic acid, pertrichloroacetic acid, hydrogen peroxide +
Selected from the group consisting of trichloroacetic acid, pertrifluoroacetic acid, hydrogen peroxide + trifluoroacetic acid, permetasulphonic acid, hydrogen peroxide + metasulphonic acid, hydrogen peroxide + salicylic acid, persulfuric acid and hydrogen peroxide + sulfuric acid 1 or 2
The desulfurization method according to any one of claims 1 to 4, wherein at least one kind is used. 6. The desulfurization method according to claim 2, wherein the adsorbent is made of a porous inorganic oxide. 7. Silica as the porous inorganic oxide,
Alumina, silica-alumina, zeolite, titania,
Zirconia, magnesia, silica-magnesia, white clay,
The desulfurization method according to claim 6, wherein one kind or two or more kinds selected from the group consisting of clay, diatomaceous earth, activated carbon and insoluble synthetic resin is used. 8. The solvent in the solvent extraction is acetonitrile, propionitrile, butyronitrile, nitromethane, nitroethane, nitropropane, nitrobenzene, dimethylsulfoxide, N, N′-dimethylformamide, N, N′-dimethylacetamide, N- One or more selected from the group consisting of methylpyrrolidine, trimethyl phosphate, triethyl phosphate, hexamethyl phosphate amide, phosphorane, methanol, ethanol, propanol, butanol and acetone, or containing water. Claim 2 characterized by
7. The desulfurization method according to any one of 7. 9. The second desulfurizing agent is Ni, Ag, Cr,
Mn, Fe, Co, Zn, Pb, Ir, Pt, Ru, R
The desulfurization method according to any one of claims 3 to 8, which is a catalyst in which one or more selected from the group consisting of h and Au is supported on a porous carrier. 10. The desulfurization method according to claim 2, wherein the adsorbent is used in a temperature range of −40 to 100 ° C. 11. The desulfurization method according to claim 3, wherein the second desulfurizing agent is used in a temperature range of −40 to 220 ° C. 12. A method for producing hydrogen for a fuel cell, which comprises subjecting a hydrocarbon to desulfurization using the desulfurization method according to any one of claims 1 to 11 and then carrying out a reforming treatment. 13. The reforming treatment is a partial oxidation reforming treatment,
The method for producing hydrogen for a fuel cell according to claim 12, which is an autothermal reforming treatment or a steam reforming treatment. 14. The method for producing hydrogen for a fuel cell according to claim 13, wherein the partial oxidation reforming catalyst, autothermal reforming catalyst or steam reforming catalyst is a ruthenium-based catalyst or a nickel-based catalyst. . 15. The fuel cell according to claim 14, wherein the carrier component of the reforming catalyst contains one or more selected from the group consisting of manganese oxide, cerium oxide and zirconia. For producing hydrogen for industrial use.