WO2007020800A1

WO2007020800A1 - Desulfurizing agent for hydrocarbon oil and method of desulfurization

Info

Publication number: WO2007020800A1
Application number: PCT/JP2006/315280
Authority: WO
Inventors: Yasuhiro Toida; Satoshi Teshigawara; Nobuto Kobayashi
Original assignee: Japan Energy Corporation; Sued-Chemie Catalysts Japan, Inc.
Priority date: 2005-08-12
Filing date: 2006-08-02
Publication date: 2007-02-22
Also published as: JP5032992B2; JPWO2007020800A1

Abstract

A desulfurizing agent and desulfurization method for hydrocarbon oils, especially kerosine for use as a raw fuel for fuel cells, and a desulfurizing agent and desulfurization method for hydrocarbons for use in oil refineries. The desulfurizing agents and desulfurization methods necessitate neither a reduction treatment nor hydrogen and can effectively remove benzothiophene compounds or thiophene compounds at a temperature of from room temperature to about 150°C. When the agent and method are applied to a fuel cell, starting and maintenance are relatively easy and the fuel cell system can be simplified. The desulfurizing agent for hydrocarbon oils is characterized by comprising a copper ingredient and a silver ingredient. The fuel cell system is characterized by employing this desulfurizing agent.

Description

Specification

Hydrocarbon oil desulfurization agent and desulfurization method

Technical field

[0001] The present invention relates to a hydrocarbon oil desulfurization agent and a desulfurization method, in particular, a desulfurization agent and a desulfurization method for kerosene which is a raw fuel for generating hydrogen used in a fuel cell, and a refinery, a petrochemical factory, and a chemical factory. The present invention relates to a desulfurization agent and desulfurization method for hydrocarbon oils used in Japan.

Background art

[0002] For desulfurization of kerosene used in stationary fuel cells for home use, etc., a chemisorption desulfurization method using a nickel-based desulfurization agent at around 200 ° C has been studied! There were problems such as consuming energy, taking time to start up, and complicating the system because it was necessary to perform under pressurized conditions to prevent vaporization of kerosene. The nickel-based desulfurization agent added with copper has a certain level of activity even at a lower temperature of about 150 ° C., but has not yet been able to solve the above problems. In addition, nickel-based desulfurization agents must be subjected to a reduction treatment in advance, and a sudden exothermic reaction occurs when they come into contact with oxygen, resulting in a decrease in activity. Therefore, there are also problems in storage and stopping methods. Furthermore, since nickel compounds are toxic, there is also a problem that strict management methods are required when they are spread to ordinary households. (Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4)

[0003] In addition, copper oxide desulfurization agents used in refineries are used for desulfurization of naphtha fractions containing sulfur compounds such as mercaptans at a relatively low temperature of around 120 ° C. However, there was no copper oxide-based desulfurization agent that had sufficient performance for desulfurization of kerosene containing mainly benzothiophenes and aromatics containing thiophenes. (Patent Document 5)

[0004] On the other hand, a physical adsorption desulfurization method using zeolite, activated carbon, etc. near room temperature is also being studied, but it contains aromatic compounds that compete with sulfur compounds, such as kerosene, and especially benzothiophenes. For removal, there was no physical adsorbent with high performance, and a very large volume was required, which was impractical. (Patent Document 6, Patent Document 7)

[0005] The types of sulfur compounds contained in kerosene are benzothiophenes and dibenzothiops. The ratio of benzothiophenes to the total sulfur compounds, where the ratio of benzothiophenes is large, is particularly 70% or more in many cases. Therefore, desulfurization agents that can efficiently remove benzothiophenes and thiophenes at temperatures from room temperature to around 150 ° C that do not require reduction treatment, hydrogen, or pressurization. There was a need for a desulfurization method.

Patent Document 1: Japanese Patent Publication No. 6-65602

Patent Document 2: Japanese Patent Publication No. 7-115842

Patent Document 3: Japanese Patent No. 3410147

Patent Document 4: Japanese Patent No. 3261192

Patent Document 5: Japanese Patent No. 3324746

Patent Document 6: Japanese Unexamined Patent Publication No. 2003-49172

Patent Document 7: Japanese Unexamined Patent Publication No. 2005-2317

Disclosure of the invention

Problems to be solved by the invention

[0006] The present invention relates to a desulfurization agent and desulfurization method for hydrocarbon oils, particularly kerosene, which is a raw fuel of fuel cells, and a desulfurization agent and desulfurization method for hydrocarbon oils used in refineries, petrochemical plants, and chemical factories. Therefore, it is an object of the present invention to provide a desulfurization agent and a desulfurization method capable of efficiently removing benzothiophenes and thiophenes at a temperature from room temperature to about 150 ° C without requiring reduction treatment or hydrogen. To do. When applied to a fuel cell, startup and maintenance are relatively easy, and the fuel cell system can be simplified.

Means for solving the problem

[0007] As a result of intensive studies to solve the above problems, the present inventor has found that a desulfurization agent containing copper and silver, or a desulfurization agent containing copper, silver and manganese is subjected to reduction treatment or hydrogen. The present inventors have found that sulfur compounds such as benzothiophenes contained in kerosene can be efficiently removed under relatively mild conditions even at 150 ° C. or lower without needing the present invention.

[0008] That is, the present invention is as follows. (1) A hydrocarbon oil desulfurization agent comprising a copper component and a silver component.

(2) The desulfurizing agent according to (1), wherein the ratio of the copper component and the silver component is 99: 1 to 80:20 in terms of the mass ratio of the metal.

(3) The desulfurization agent according to (1) or (2), further comprising a manganese component.

(4) The desulfurization agent according to (3) above, wherein the ratio of the copper component to the manganese component is 85:15 to 50:50 as the mass ratio of the metal.

[0009] (5) A hydrocarbon oil desulfurization method using the desulfurization agent according to any one of (1) to (4).

(6) A method for desulfurizing a hydrocarbon oil, characterized by using the desulfurizing agent according to any one of (1) to (4) in a refinery, a petrochemical factory, or a chemical factory.

(7) The desulfurization method according to (5) or (6), wherein the desulfurization is performed at a temperature of 150 ° C. or lower.

(8) The desulfurization method according to (5) or (6) above, wherein the hydrocarbon oil is kerosene

(9) A fuel cell system using the desulfurization agent described in any one of (1) to (4) above.

The invention's effect

[0010] According to the desulfurizing agent and the desulfurizing method of the present invention, a hydrocarbon oil, preferably a hydrocarbon oil containing benzothiophenes as a main component of a sulfur compound, more preferably kerosene, is contacted with a specific desulfurizing agent. By doing so, desulfurization can be efficiently performed at a temperature from room temperature to about 150 ° C without performing reduction treatment or hydrogenation. Therefore, when applied to the desulfurization of kerosene, which is the raw fuel of the fuel cell, startup and maintenance are relatively easy, and the fuel cell system can be simplified. It can also be suitably applied to desulfurization of hydrocarbon oils used in refineries, petrochemical plants, and chemical plants.

Brief Description of Drawings

FIG. 1 is a conceptual diagram showing an example of a fuel cell system.

FIG. 2 is a graph showing the results of the desulfurization experiment of Example 2. FIG. 3 is a graph showing the results of a desulfurization experiment of Example 4.

FIG. 4 is a graph showing the results of the desulfurization experiment of Example 5.

FIG. 5 is a graph showing the results of the desulfurization experiment of Example 5.

FIG. 6 is a graph showing the results of the desulfurization experiment of Example 6.

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] In the desulfurizing agent and desulfurization method of the present invention, as the hydrocarbon oil to be desulfurized, a hydrocarbon oil containing benzothiophenes as a main component of the sulfur compound, preferably kerosene, can be suitably used. Desulfurization performance similar to that of benzothiophenes can be obtained for thiophenes. It may also contain other types of sulfur compounds such as mercabtans (thiols), sulfides, disulfides, and disulfur carbon, but the main components are benzothiophenes and Z. Alternatively, the effect of the present invention can be remarkably obtained for hydrocarbon oils containing thiophenes. The ratio of benzothiophenes or thiophenes to the total sulfur compound is not less than 70%, preferably not less than 80%, particularly preferably not less than 90% as a sulfur content.

The hydrocarbon oil that can be suitably applied is specifically a hydrocarbon oil having 5 to 20 carbon atoms such as naphtha, gasoline, kerosene, light oil, benzene, toluene, xylene, naphthalene, and the like.

[0013] The sulfur content of the hydrocarbon oil to which the desulfurization method of the present invention is applied is not technically limited. However, if the sulfur content is too high, a large amount of desulfurization agent is required, and other desulfurization methods such as hydrodesulfurization are more efficient. Therefore, the desulfurization method of the present invention is preferably applied. The sulfur content in the hydrocarbon oil is 20 ppm by mass or less, more preferably 10 ppm by mass or less.

The kerosene to be desulfurized in the present invention is mainly composed of hydrocarbons having about 12 to 16 carbon atoms, has a density (15 ° C.) of 0.790 to 0.850 gZcm ³ , and a boiling point range of 150 to 320. . It ’s about oil. Although it contains a lot of raffin-based hydrocarbons, it contains about 0-30% by volume of aromatic hydrocarbons and about 0-5% by volume of polycyclic aromatic hydrocarbons. In general, it is No. 1 kerosene defined in Japanese Industrial Standard JIS K2203 as a fuel for lamps and heating. As for quality, flash point 40 ° C or higher, 95% distillation temperature 270 ° C or lower, sulfur content 0.008 mass% or lower, smoke point 23 mm or higher (21 mm or higher for cold weather), copper plate corrosion (50 ° C, 3 hours) 1 or less, color (s Bolts) + 25 or more provisions. Usually, the sulfur content includes several ppm power of 80 ppm or less, and the nitrogen content includes several ppm to 10 ppm.

[0015] The main sulfur compounds contained in kerosene are benzothiophenes and dibenzothiophenes, but may contain thiophenes, mercaptans (thiols), sulfides, disulfides, disulfur carbon, etc. is there. For qualitative and quantitative analysis of sulfur compounds in kerosene, gas chromatograph (Gas Chromatograph: GC) Flame Photometric Detector (FPD), GC atomic emission detector (AED), GC —Sulfur Chemiluminescence Detector (SCD), GC Inductively Coupled Plasma Mass Spectrometer (ICP—MS) can be used. GC-ICP- The use of MS is most preferred.

[0016] Benzthiophenes are heterocyclic compounds containing one or more sulfur atoms as heteroatoms, and the heterocyclic ring is a penta- or hexa-atom ring and has aromaticity (a double bond is attached to the heterocyclic ring). 2 or more) and a sulfur compound in which the heterocycle is condensed with one benzene ring and its derivatives. Benzothiophene, also called thionnaphthene or thiocoumarone, is a sulfur compound with a molecular weight of 134 that can be represented by the molecular formula C H S. Other typical benzo

8 6

Thiophones include methylbenzothiophene, dimethylbenzothiophene, trimethylbenzothiophene, tetramethylbenzothiophene, pentamethylbenzothiophene, hexamethylbenzothiophene, methylethylbenzothiophene, dimethylether. Tylbenzothiophene, trimethylethylbenzothiophene, tetramethylethylbenzothiophene, pentamethylethylbenzothiophene, methyljetylbenzothiophene, dimethyl jetylbenzothiophene, trimethyljetylbenzothione Ohmone, tetramethylethylbenzothiophene, methylpropylbenzothiophene, dimethylpropylbenzothiophene, trimethylpropylbenzothiophene, tetramethylpropylbenzothiophene, pentamethylpropylbenzothiophene, Alkylbenzothiophenes such as acetylethylpropyl benzothiophene, dimethylethylpropyl benzothiophene, trimethylethylpropyl benzothiophene, tetramethylethylpropyl benzothiophene, thiachromene (benzothia _monopyran , molecular formula CHS, Molecular weight 148), dithiaphthalene ( Molecular formula CHS, molecular weight 166) and their derivatives.

8 6 2

[0017] Dibenzothiophenes are heterocycles containing one or more sulfur atoms as heteroatoms, and the heterocycle is a penta- or hexa-atom ring and has aromaticity (heterocycle In addition, sulfur compounds and derivatives thereof in which the heterocycle is condensed with two benzene rings. Dibenzothiophene, also known as diphenylsulfide, biphenylsulfide, sulfur disulfide, is a sulfur with a molecular weight of 184, represented by the molecular formula C H S

12 8

A compound.

[0018] 4-Methyldibenzothiophene and 4,6-dimethyldibenzothiophene are well known as difficult desulfurization compounds in hydrorefining. Other representative dibenzothiophenes include trimethyldibenzothiophene, tetramethyldibenzothiophene, pentamethyldibenzothiophene, hexamethyldibenzothiophene, heptamethyldibenzothiophene, otamethyldibenzothiophene, methyl Ethyl dibenzothiophene, dimethyl ethyl dibenzothiophene, trimethylethyl dibenzothiophene, tetramethylethyl dibenzothiophene, pentamethylethyl dibenzothiophene, hexamethylethyl dibenzothiophene, heptamethylethyl dibenzothiophene Ohmone, methyljetyldibenzothiophene, dimethyljetyldibenzothiophene, trimethyljetyldibenzothiophene, tetramethyljetyldibenzothiophene, pentamethyljetyldibenzothiophene Hexamethyljetyldibenzothiophene, heptamethyljetyldibenzothiophene, methylpropyldibenzothiophene, dimethylpropyldibenzothiophene, trimethylpropyldibenzothiophene, tetramethylpropyldibenzothiophene, pentamethylpropyldibenzo Thiophene, hexamethylpropyldibenzothiophene, heptamethylpropyldibenzothiophene, methylethylpropyldibenzothiophene, dimethylethylpropyldibenzothiophene, trimethylethylpropyldibenzothiophene, tetramethylethylpropyl Alkyl dibenzothiophenes such as dibenzothiophene, pentamethylethyl propyl dibenzothiophene, and hexamethylethylpropyl dibenzothiophene, and thianthrene Ido, molecular formula C H

12 8

S, molecular weight 216), thixanthene (dibenzothiopyran, diphenylmethanesulfide,

2

Molecular formula CHS, molecular weight 198) and their derivatives. [0019] Thiophenes are heterocycles containing at least one sulfur atom as a heteroatom, and the heterocycle is a penta- or hexa-atom ring and has aromaticity (two heterocycles). A sulfur compound in which the heterocyclic ring is not condensed with a benzene ring and derivatives thereof. Also included are compounds in which heterocycles are fused together. Thiophene, also called thiofuran, is a sulfur compound with a molecular weight of 84.1 that can be represented by the molecular formula CHS. Other representative

4 4

Methylthiophene (thiotolene, molecular formula C H S, molecular weight 98 · 2)

5 6

, Thiapyran (pentthiophene, molecular formula C H S, molecular weight 98.2), thiophene (molecular formula C

5 6 6

H 2 S, molecular weight 140), tetraphenylthiophene (Tionesal, molecular formula C H S, molecule

4 2 20 20 388), dichenenomethane (molecular formula C H S, molecular weight 180) and their derivatives.

9 8 2

I can get lost.

[0020] Thiophenes and benzothiophenes have similar chemical properties. In both cases, in the presence of a solid acid desulfurization agent in which a heterocycle containing a sulfur atom as a hetero atom is highly reactive, the cleavage of the heterocycle, the reaction between the heterocycle and the aromatic ring, or the decomposition easily occurs. Dibenzothiophenes are less reactive than thiophenes and benzothiophenes because benzene rings are bonded on both sides of the thiophene ring. Dibenzothiophenes having many alkyl groups such as trimethyldibenzothiophene, tetramethyldibenzothiophene, and pentamethyldibenzothiophene are particularly difficult to remove with a solid acid desulfurization agent.

[0021] Mercaptans are sulfur compounds RSH (R is a hydrocarbon group such as an alkyl group or a aryl group) having a mercapto group (-SH), and are also called thiols or thioalcohols. Mercapto groups are highly reactive, especially with metals. Typical mercaptans include methyl mercaptan, ethyl mercaptan, propyl mercaptan (including isomers), butyl mercaptan (including isomers such as tertiary butyl mercaptan), pentyl mercaptan, hexyl mercaptan, heptyl mercaptan. Octyl mercaptan, normercaptan, decyl mercaptan and thiophenols Ar—SH (Ar is an aryl group).

[0022] Sulfides, also called thioethers, are generic names for sulfur alkyl and sulfur reels, and are represented by the general formula R—S—R ′ (where R and R ′ are hydrocarbon groups such as alkyl groups and aryl groups). ) Is a sulfur compound. Replace two hydrogen atoms of hydrogen sulfide with an alkyl group. Compound of the form. Sulfides are classified into chain sulfides and cyclic sulfides. The chain sulfides are sulfur compounds having no heterocyclic ring containing a sulfur atom as a heteroatom among the sulfides. Typical chain sulfides include dimethylsulfide, methylethylsulfide, methylpropylsulfide, jetylsulfide, methylbutenosulfenolide, ethylpropylsulfide, methylpentylsulfide, ethinolev. Tinolesulfide, dipropylsulfide, methylhexylsulfide, ethylpentylsulfide, propylbutylsulfide, methylheptylsulfide, ethylhexylsulfide, propylpentylsulfide, dibutylsulfide and the like. Cyclic sulfides have a heterocyclic ring containing at least one sulfur atom as a heteroatom among sulfides, and have no aromaticity (a penta- or hexa-atom ring and two double bonds). It is a sulfur compound without a heterocyclic ring. Typical cyclic sulfides include tetrahydrothiophene (sulfur tetramethylene, molecular formula CHS, molecular weight 88.1), methyltetrathiophene, etc.

4 8

I can get lost.

[0023] Disulfides are disulfuric substances. It is a generic name for alkyl disulfide and aryl disulfide, and is a sulfur compound represented by the general formula R—S—S—R ′ (R and R ′ are hydrocarbon groups such as alkyl groups). The sum of the number of carbon atoms of the hydrocarbon group constituting R and R ′ is preferably 2-8. Specifically, dimethyldisulfide, methylethyldisulfide, methylpropyldisulfide, jetyldis Rufide, methyl butyl disulfide, ethyl propyl disulfide, methyl pentyl disulfide, ethyl butyl disulfide, dipropyl disulfide, methyl hexyl disulfide, ethyl pentyl disulfide, propyl butyl disulfide, methyl heptyl Examples thereof include chain disulfides such as disulfide, ethylhexyl disulfide, propylpentyl disulfide, and dibutyl disulfide.

[0024] When kerosene is used as the raw fuel of a fuel cell, sulfur contained in kerosene must be strictly removed because it is a catalyst poison of the reforming catalyst during the hydrogen production process. The sulfur content after desulfurization needs to be 50 mass ppb or less, preferably 20 mass ppb or less, more preferably 5 mass ppb or less.

[0025] The desulfurization agent and the desulfurization method of the present invention are based on benzothiophenes contained in kerosene. A particularly remarkable effect is obtained. By combining other desulfurization methods before and after applying the desulfurization method of the present invention, it is possible to desulfurize sulfur contained in kerosene to a very low value. Specifically, if the dibenzothiophenes are previously removed by distillation separation or adsorption separation using activated carbon or the like, the effects of the present invention can be obtained remarkably.

[0026] The desulfurizing agent of the present invention contains copper and silver, or further manganese. Both copper and silver belong to the IB group in the elementary periodic table, and their physical and chemical properties are relatively similar, but the present inventors have shown that the removal performance of benzothiophenes by adding silver Has been found to improve significantly. The ratio of copper to silver is 99: 1 to 80:20, preferably 98: 2 to 90:10, particularly preferably 97: 3 to 95: 5 as the weight of the metal. If the silver ratio is less than 99: 1, the effect of adding silver is small. If it is more than 80:20, the effect of adding more is not obtained, so it is not economical. The ratio of copper to manganese is 100: 0 to 40:60, preferably 85:15 to 50:50, particularly preferably 80:20 to 60:40 as the weight of the metal. It may contain transition metals other than copper, silver and manganese, and Z or transition metal oxides, but the effect of addition is small. I prefer to be there. Examples of the transition metal include silver, mercury, copper, cadmium, lead, molybdenum, zinc, cobalt, nickel, platinum, platinum, radium, and iron.

[0027] The copper contained in the desulfurizing agent of the present invention is copper oxide (CuO) or cuprous oxide (Cu 2 O).

2 is preferred. Copper oxide has a sufficiently high activity near room temperature. Also, when it is subjected to reduction treatment, heat is generated when it comes into contact with air. Silver may be metallic silver, silver oxide such as AgO and AgO, or silver salt such as silver carbonate, silver nitrate, and silver acetate.

2

preferable. As will be described later, in the preparation of the desulfurizing agent, when baking is performed, after the baking, a part of the silver on the surface of the desulfurizing agent is acid silver, and it is not necessary to perform a reduction treatment. Manganese includes manganese oxides such as MnO, MnO, MnO, MnO, and MnO.

2 2 3 2 4 2 7

In particular, MnO easily reacts with sulfur to produce MnS and the like. Manganese is copper and silver.

2

It is considered that a complex oxide is formed and oxygen atoms in the oxide easily move, and as a result, the adsorption ability of the sulfur compound is remarkably improved. Therefore, the form of the oxide can include both a single oxide and a complex oxide, but is preferably a complex oxide. [0028] The desulfurizing agent of the present invention preferably contains silica and Z or activated carbon as a metal carrier. Silica and activated carbon do not have acid sites, and therefore, undesirable side reactions such as polymerization reactions do not occur. In particular, activated carbon has an adsorptive force due to π electrons in the partially present graphite structure and the benzene ring, and is particularly preferable when removing benzothiophenes and dibenzothiophenes. The amount of silica contained in the desulfurizing agent is 5 to 40% by mass, preferably 7 to 30% by mass, particularly preferably 8 to 20% by mass, based on the total weight of the metal and soot or metal compound and silica. is there. If the amount of silica is less than 5% by mass, the dispersibility of the metal and soot or the metal compound is lowered and sufficient desulfurization performance cannot be obtained. More than 40% by mass and the content of metal and soot or metal compound is less than 60% by mass, the desulfurization performance per unit weight of the desulfurizing agent is lowered, and the life is shortened. The amount of the activated carbon contained in the desulfurizing agent is 50 to 99% by mass, preferably 60 to 98% by mass, particularly preferably 70 to 97% by mass, based on the weight of the desulfurizing agent. The balance is mainly metal and metal or a metal compound, and when used with a silica support, the silica support is also included in the balance. The activated carbon support contributes to the improvement of adsorption removal performance of dibenzothiophenes, not only by the role of supporting metals and soot or metal compounds in a highly dispersed state. If the amount of the activated carbon is less than 50% by mass, not only the dispersibility of the metal and soot or the metal compound is lowered, but also the adsorption removal performance of dibenzothiophenes is reduced, and sufficient desulfurization performance cannot be obtained. If it exceeds 99% by mass, the content of metal and soot or metal compound is reduced and the desulfurization performance is lowered.

[0029] The method for preparing the desulfurizing agent of the present invention is not particularly limited. For example, a physical mixing method, an impregnation method and a coprecipitation method using a raw material and a carrier containing a copper compound and a silver compound are used. Can be mentioned. A method of physically mixing each component in which a copper component, a silver component or a manganese component is supported on a carrier is also preferable. At this time, the manganese component itself can be used as a carrier for the manganese component. In particular, after preparing a copper support in which a copper component is highly dispersed on a support such as silica, it is also preferable to further support a silver component and a manganese component on the copper support.

[0030] When the support is activated carbon, the copper support is prepared by the graphite structure of the activated carbon, the adsorption force due to the π electrons of the benzene ring of the sulfur compound, and the sulfur atom on the supported metal. In order to obtain a synergistic effect with the adsorptive force due to coordinate adsorption, the graphite structure and its vicinity (range in which the adsorbing power of both the graphite structure and the metal affects one sulfur compound molecule Particularly preferred is an impregnation method in which a metal is preferably supported on (3).

When the support is silica, the copper support is preferably prepared by coprecipitation with a copper component rather than adding the structure-stabilized product as a powder to the precipitation mother liquor. For example, alkali hydroxide, alkali carbonate or alkali bicarbonate is used as a precipitating agent, and alkali silicate is added and dissolved therein, followed by neutralization reaction with a metal salt, so that a copper component and a silicon component are added. When co-precipitated, the resulting precipitate consists of a mixture of these component compounds, or a mixture in which a part of these component compounds forms a complex, and the copper component is highly dispersed and has a high surface area. preferable.

[0031] In the present invention, a copper hydroxide produced by a neutralization reaction between an aqueous copper salt solution and an aqueous solution of an alkali hydroxide, an alkali carbonate or an alkali bicarbonate containing an alkali silicate, A mixture in which basic copper carbonate is mixed with a silicon compound, or a mixture in which the copper hydroxide or a part of the basic copper carbonate forms a complex with a silicon compound, and the CuZSi atom of the mixture The ratio is preferably 1-10.

[0032] The copper salts used in the present invention may be any salts as long as they are water-soluble salts such as nitrates, sulfates, chlorides, and organic acid salts. In the present invention, an aqueous solution of the copper salt (referred to as solution A) is used as the precipitation mother liquor. Compounds used as precipitating agents are alkali hydroxides, alkali carbonates or alkali bicarbonates, sodium or potassium is used as alkali, and Na 2 O 3 SiO · ηΗ 0 (η =

2 2 2

2-4) Sodium silicate represented by chemical formula, Κ O 'nSiO · ηΗ 0 (η = 3-4)

2 2 2

A mixed aqueous solution in which alkali silicate is added to an aqueous solution of alkali hydroxide, alkali carbonate or alkali bicarbonate, which is preferred by potassium silicate, and dissolved therein is used as a precipitant.

[0033] The content of Cu and Si is preferably in the range of 1 to 10 in terms of Cu / Si atomic ratio. When the atomic ratio of CuZSi is less than 1, it is confirmed by X-ray diffraction structure analysis that most copper compounds form a complex with silicon compounds. Since the content is reduced, the adsorption capacity is not preferable. one On the other hand, if the CuZSi atomic ratio is greater than 10, a high surface area desulfurization agent composed of a refined copper compound cannot be obtained, and it is preferred as a desulfurization agent.

[0034] For the precipitation operation, forward neutralization by adding solution B to solution A, reverse neutralization by adding solution A to solution B, or water is added to the prepared precipitation tank, and both solutions A and B are added simultaneously. Neutralization under a certain pH. Ability to generate good precipitates by any operation It is important to make the pH value at the end of this operation neutral to weakly alkaline, and if the pH value falls outside this range, it is preferable. You can't get a treatment with a compound power!

The precipitate obtained by the neutralization reaction is aged, washed with water and dried. It may be fired before the silver component or manganese component is supported, or may be fired after the silver component or manganese component is supported. It is preferable to fire after the silver component or manganese component is supported in order to shorten the process. . Here, washing with water is performed to remove alkaline compounds mixed in the precipitate, and to prevent the physical properties of the resulting treatment agent from being altered in the subsequent process, and remain in the finally obtained treatment agent. It is preferable to wash with water until the amount of alkali to be reduced is 0.1% or less. Subsequent drying does not cause thermal alteration of the treating agent compound, and is preferably performed at a temperature range of 80 to 200 ° C. that is reasonable for shortening the production time.

[0035] The obtained dried copper-silica product is composed of fine crystals having a BET surface area of 80 m ² Zg or more determined by nitrogen adsorption and a crystallite diameter of the copper compound by X-ray diffraction of 50 nm or less. When the surface area is less than 80 m ² / g, no desulfurizing agent exhibiting high performance is obtained, and even when the crystallite diameter of the copper compound is larger than 50 nm, desulfurization exhibiting high performance due to insufficient dispersibility of copper. No agent can be obtained.

[0036] In order to support the silver component on the carrier, a silver-containing solution is used. As the silver-containing solution, an aqueous silver nitrate solution, an aqueous silver chloride solution, or the like can be used. However, since the silver content can be increased and there is no inhibition of adsorption of sulfur compounds by the chlorine, use of an aqueous silver nitrate solution is preferable. . The impregnation method includes an equilibrium adsorption method in which a carrier is immersed in a silver-containing solution and adsorbs silver until equilibrium, an evaporation to dryness method in which the carrier is immersed in a silver-containing solution to evaporate the solvent, and a silver-containing solution while drying the carrier. It is possible to use a commonly used method such as a spray method of spraying and impregnating.

[0037] In order to support the manganese component on the support, a manganese-containing solution is used. manganese As the containing solution, it is possible to use salty manganese (II), manganese borate, manganese sulfate (II), potassium permanganate, etc. The manganese content can be increased, and the adsorption of sulfur compounds by chlorine is also inhibited. Therefore, the use of an aqueous manganese sulfate solution is preferred. The impregnation method includes an equilibrium adsorption method in which a carrier is immersed in a manganese-containing solution to adsorb manganese to equilibrium, an evaporation to dryness method in which the carrier is immersed in a manganese-containing solution to evaporate the solvent, and manganese is dried while the carrier is dried. Commonly used methods such as a spray method in which the contained solution is sprayed and impregnated can be used.

The silver-containing solution and the manganese-containing solution are not particularly limited, such as a method in which the silver-containing solution and the manganese-containing solution are mixed in advance and then supported and dried, and a method in which the silver-containing solution and the manganese-containing solution are separately supported and dried. Is preferred.

[0038] Firing is preferably performed at 300 to 400 ° C, particularly 330 to 380 ° C for 1 to 12 hours. Part of hydroxy copper, basic copper carbonate, silver nitrate, manganese sulfate, etc. decomposes, and black oxide such as black, silver oxide, and acid manganese are produced in the drying stage in a steam atmosphere. If it is less than 300 ° C, hydroxyl group, carbonate radical, nitrate radical, sulfate radical, etc. will remain and the desulfurization performance will deteriorate. At temperatures higher than 400 ° C, the desulfurization performance decreases due to a decrease in specific surface area. It is particularly preferred to bake at 330 to 380 ° C until no hydroxyl groups, carbonate radicals, nitrate radicals, sulfate radicals, etc. remain.

[0039] When an alkali carbonate or alkali bicarbonate aqueous solution is used in the neutralization reaction with an aqueous copper salt solution, the content of carbon dioxide (CO 2) as a carbonate radical is 5% of the total weight.

2

It is preferable that it is 1 mass% or less, especially 1 mass% or less. If the carbon dioxide content is higher than 5% by mass, the desulfurization performance will be lowered due to the inhibition of adsorption of sulfur compounds by carbonic acid radicals.

[0040] The desulfurizing agent of the present invention can be obtained by directly using a powder of silica and Z or activated carbon containing a copper component and a silver component. A compact containing 50% by mass or more, particularly 80% by mass or more of the above powder is preferably used. Examples of other components include binders and other desulfurizing agent components. As the shape, in order to increase the concentration gradient of sulfur compounds, in the case of flow-through type, the shape is small, especially spherical, as long as the differential pressure before and after the container filled with desulfurizing agent does not increase. Is preferred. In the case of a spherical shape, the diameter is preferably 0.5 to 5 mm, particularly 1 to 3 mm. In the case of a cylindrical shape, the diameter is preferably 0.1 to 4 mm, particularly 0.12 to 2 mm, and the length is preferably 0.5 to 5 times, particularly 1 to 2 times the diameter. It is preferable that the fracture strength of the molded product is 0.5 kgZ pellets or more, especially 1. OkgZ pellets or more, since the adsorbent will not crack. Usually, the breaking strength is measured by a compressive strength measuring instrument such as a Kiya-type tablet breaking strength measuring instrument (Toyama Sangyo Co., Ltd.).

[0041] Examples of the binder used for molding include clays such as alumina and smectite, and inorganic binders such as water glass. These binders are not particularly limited as long as they are used to such an extent that they can be molded, but usually 0.05 to 30% by mass with respect to the raw material is used. It is difficult to desulfurize copper and silver by mixing inorganic fine particles such as silica, alumina, other zeolites, and organic materials such as activated charcoal. 脱 Improve the desulfurization performance of sulfur compounds, and the abundance of mesopores and macropores The diffusion rate of the sulfur compound may be improved by increasing the amount of sulfur.

[0042] The specific surface area of the desulfurizing agent of the present invention greatly affects the desulfurization performance, and is preferably 80 m ² / g or more, more preferably 100 m ² / g or more, and particularly preferably 150 m ² / g or more. The pore volume of pores having a pore diameter of 10 A or less is preferably at least 0.10 ml Zg, particularly preferably at least 0.20 ml Zg, in order to increase the adsorption capacity of the sulfur compound. In addition, the pore volume of pores having a pore diameter larger than 10 A and 0.1 μm or smaller is 0.05 mlZg or more, in particular, 0. It is preferable to set it as lOmlZg or more. The pore volume of pores having a pore diameter greater than 0 .: L m is preferably 0.3 mlZg or less, particularly preferably 0.25 mlZg or less, in order to increase the mechanical strength of the molded product. Usually, the specific surface area and the total pore volume are measured by a nitrogen adsorption method, and the macropore volume is measured by a mercury intrusion method. The nitrogen adsorption method is simple and commonly used and is described in various literature. For example, Kazuhiro Hagio: Shimazu Review, 48 (1), 35-49 (1991), ASTM (American Society for Testing and Materials) ¾tandard Test Method D43o5-95.

[0043] The method of contacting the desulfurizing agent and hydrocarbon oil of the present invention may be a batch type (batch type) or a flow type, but a flow type in which a molded product is filled in a container and the hydrocarbon oil is circulated is more preferable. Like Yes.

[0044] In the case of the flow type, as the contact condition, the pressure is normal pressure to 50 kgZcm ² G, preferably normal pressure to 10 kgZcm ² G, and particularly preferably 0.1 to 3 kgZcm ² G. The flow rate is 0 at LHSV.

Especially 0.05-20hr- ¹ force. The temperature for the desulfurization treatment is preferably 10 to 150 ° C, particularly 30 to 100 ° C.

[0045] It is preferable that the desulfurizing agent removes a small amount of adsorbed moisture in advance as a pretreatment. If moisture is adsorbed, not only the adsorption of sulfur compounds will be inhibited, but also the moisture that has been desorbed immediately after the introduction of hydrocarbon oil will be mixed into the hydrocarbon oil. It is preferable to dry at about 130 to 350 ° C, preferably about 150 to 200 ° C.

[0046] When the present desulfurizing agent is used in a fuel cell system, the present desulfurizing agent and another desulfurizing agent may be used in combination. Since this desulfurization agent is particularly excellent in removal performance of benzothiophenes, other desulfurization agents excellent in removal performance of other types of sulfur compounds such as dibenzothiophenes, mercaptans, or sulfides. When combined with, it is more effective. The present desulfurizing agent and other desulfurizing agents may be connected in series as separate packed layers, or the present desulfurizing agent and other desulfurizing agents may be physically mixed to form a single packed bed. Further, the present desulfurizing agent and another desulfurizing agent may be physically mixed and then molded, and the present desulfurizing agent and other desulfurizing agent may be contained in one grain.

[0047] Since the present desulfurizing agent is preferably heated, it is preferable to use exhaust heat from a fuel cell and a reformer that generates a hydrogen-containing gas. In the case of a polymer electrolyte fuel cell, exhaust heat of about 80 ° C. can be obtained. Therefore, it is preferable to use the exhaust heat for heating the desulfurization agent. Further, not only the polymer electrolyte fuel cell but also a fuel cell having a hot water storage tank, it is preferable to use hot water for heating the present desulfurization agent. An example of a conceptual diagram of a fuel cell system is shown in Fig. 1. Fill the desulfurizer with this desulfurizing agent. Since this desulfurization agent is relatively low at around 80 ° C and its desulfurization performance is high even at a temperature, the fuel cell can utilize exhaust heat even if it is a polymer electrolyte fuel cell.

[0048] When using this desulfurizing agent in refineries, petrochemical plants, chemical factories, etc., it is preferable to install two or more desulfurization tanks. First, the hydrocarbon oil to be desulfurized is circulated in one desulfurization tank, and it is separated when the desulfurization performance of the desulfurizing agent is reduced and sufficient desulfurization performance cannot be obtained. A method of switching to a desulfurization tank is preferable. Furthermore, two or more desulfurization tanks are connected in series, and when the desulfurization performance of the desulfurization tank on the most upstream side is completely lost or significantly deteriorated, the use of the desulfurization tank is stopped and the newest desulfurization tank is most downstream. A method of connecting a desulfurization tank filled with a desulfurizing agent is particularly preferable.

[0049] The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.

Example 1

[0050] Kerosene, manufactured by Japan Energy, has a boiling range of 158.5 to 270.0 ° C, a 5% distillation point.

Five. C, 10% distilling point 175.0. C, Distillation point 20% 181.5. C, 30% distilling point 188.0. C, 40% Distillation point 194.5. C, Distillation point 50% 202.5. C, Distillation point 60% 211.0. C, 70% distilling point 22 1.0. C, 80% distilling point 2332. C, 90% distilling point 245.5. C, 95% distillate point 255.5. C, 97% Distillation point 263.5 5 ° C, Density (15 ° C) 0. 7982g / mU Aromatic content 17.5% by volume, Saturation 82.5% by volume, Sulfur content 13.6 mass ppm { Sulfur content 16 mass ppb derived from light sulfur compounds (lighter sulfur compounds than benzothiophene), benzothiophenes (sulfur compounds that are heavier than benzothiophene and benzothiophene and lighter than dibenzothiophene) Sulfur content derived from 9.6 mass ppm, sulfur content derived from dibenzothiophenes (a heavier sulfur compound than dibenzothiophene and dibenzothiophene) 4.0 mass ppm}, nitrogen content 1 mass ppm The following were used. The sulfur content is measured using a combustion oxidation ultraviolet fluorescence sulfur analyzer, and the sulfur compound is a gas chromatograph, inductively coupled plasma mass spectrometer (GC-ICP—MS). ) Was used!

[0051] Copper sulfate 1. Weigh 7 kg in a 20 L beaker, add 10 L of pure water, stir, dissolve, and precipitate mother liquor.

(Liquid A) was prepared. Separately, 1.5kg of No. 3 sodium silicate 1.5kg and 0.7kg of sodium carbonate were weighed into a 20L beaker, charged with 10L of pure water, dissolved and dissolved in a precipitant solution (Liquid B). Was prepared. Solution A was gradually added dropwise to solution B, which was vigorously stirred, to form a precipitate. The resulting precipitate was aged, sufficiently washed with water, then filtered, dried in air at 110 ° C, and then calcined at 350 ° C to obtain a copper-based desulfurization agent. In addition, a silver nitrate solution was impregnated and supported on silica so that the amount of Ag supported was 10% by mass and dried at 110 ° C for 12 hours. Calcination was performed at 00 ° C for 3 hours to obtain a silver-based desulfurization agent. A desulfurization agent containing copper and silver was prepared by a physical mixing method of a copper desulfurization agent and a silver desulfurization agent. Desulfurizing agent containing 55% by mass of copper and 1% by mass of silver (Example), Desulfurizing agent containing 58% by mass of copper and not containing silver (Comparative Example 1), y Amount of Ag supported by 5% by mass of silver nitrate solution on alumina The copper-containing desulfurization agent (AgZ o -A1 O, Comparative Example 2) was obtained by impregnating and supporting so as to be, dried at 110 ° C for 12 hours, and calcined at 400 ° C for 3 hours. ) And a silver nitrate solution on a manganese oxide support with an Ag loading of 5% by mass.

twenty three

The copper-free desulfurization agent (AgZMnO, Comparative Example 3) loaded with silver obtained by impregnation and drying at 110 ° C for 12 hours and then calcined at 400 ° C for 3 hours to kerosene Soaking

2

An experimental adsorption desulfurization experiment was conducted. Soaked 5 g of desulfurizing agent in 20 g of kerosene, and allowed to stand at 10 ° C for 4 days, and then analyzed the types of sulfur and sulfur compounds.

[0052] Table 1 shows the kerosene sulfur content after desulfurization. It can be seen that the desulfurization agent containing copper and silver has high desulfurization performance. The residual amount of benzothiophenes was less than 0.05 mass ppm when both copper and silver were contained, which was 0.6 mass ppm or more when only one of copper and silver was not contained.

[0053] [Table 1]

Example 2

[0054] Six types of desulfurizing agents prepared in the same manner as in Example 1 and different desulfurizing agents not containing silver (comparative examples) with different ratios of copper and silver were immersed in the same kerosene as in Example 1. A desulfurization experiment was conducted. After 5g of desulfurization agent was immersed in 20g of kerosene and allowed to stand at 10 ° C for 4 days, the type of sulfur and sulfur compounds were analyzed.

[0055] Fig. 2 shows the relationship between the mass ratio of silver Z copper and the sulfur content of kerosene after desulfurization. Without silver 3.

It can be desulfurized only up to 2 mass ppm, but it can be desulfurized up to 1 mass ppm if the AgZ (Ag + Cu) mass ratio is 0.03 or more. In addition, the remaining amount of benzothiophenes was 1.77 mass ppm when silver was not included. Met. It can be seen that the effect is effective when the mass ratio of AgZ (Ag + Cu) is 0.01 or more, and further effective when the mass ratio is 0.03 or more.

Example 3

[0056] A desulfurizing agent containing copper and silver (Example 3-1 to Example 3-4) prepared in the same manner as in Example 2, and manganese prepared by using a part of copper sulfate as manganese sulfate. 15 mass ^_0/0 containing desulfurizing agent (example 3 5), were evaluated by a model oil was prepared by using a reagent. Prepare model oil by diluting benzothiophene to 10% by mass with decane solvent or toluene solvent, then leave each model oil 4. Og with each desulfurization agent 1. Leave Og at room temperature (10 ° C) for 4 days, then immerse. The adsorbed amount was measured by analyzing the benzothiophene content before and after with a gas chromatograph- Flamelonization Detector (FID). Table 2 shows the composition of the desulfurization agent and the measurement results of the adsorption amount. The amount of adsorption is different between decane solvent and toluene solvent, and the inhibition of adsorption by aromatics is noticeable. In this experimental condition using model oil with a high concentration of benzothiophene, it can be seen that the adsorption amount is larger as the Ag content is higher. Moreover, the manganese addition effect is also understood.

[0057] [Table 2] Composition [mass%]

Sample name Adsorption amount [g- -S / kg]

Ag Cu Mn Decane solvent Toluene solvent Example 3-1 1. 1 50-2.4 4 0. 0

Example 3-• 2 5. 6 50-7. 0 0. 6

Example 3-■ 3 3.5 5 52-3. 2 0. 0

Example 3-∎ 4 10 48-40 20

Example 3-5 1. 6 40 15 25 0.0 Example 4

A desulfurizing agent was prepared using activated carbon (specific surface area 1,992 m ² / g, pore volume 0.760 mlZg) as a carrier.

In a 30 L tank, 2.4 kg of copper sulfate and 12 L of pure water were added and dissolved by stirring to prepare solution A. Separately, sodium silicate No. 3 containing 1.3 kg of sodium carbonate and 30% of SiO in a 50 L tank

2

0.8 l kg and 12 L of pure water were added and dissolved by stirring to prepare solution B. While stirring at room temperature, solution A was gradually added dropwise to solution B to form a precipitate. The resulting precipitate is aged, washed thoroughly with water, and filtered with suction. I had. Then dry in air at 110 ° C, then fire at 350 ° C and CuO / SiO system

2 powders were obtained. A solution in which 6.3 g of this CuOZSiO-based powder and lg of silver nitrate are dissolved in pure water,

2

Then, after thoroughly mixing 63 g of activated carbon and drying at 110 ° C., a copper-silver activated carbon desulfurization agent was obtained (Example 41). Similarly, preparation of CuO / SiO powder, silver nitrate and activated carbon

2

The desulfurizing agents having different metal contents were prepared by changing the amount (Examples 4 to 4-6). Table 3 shows the Ag, Cu, C and Si contents and specific surface area of each desulfurizing agent. The content is the value measured using ICP-AES (inductively coupled plasma emission spectrometer) after melting the sample with an alkaline flux and dissolving the melt with dilute nitric acid solution (moisture is not corrected). )showed that.

[0059] The same immersion desulfurization experiment in kerosene as in Example 1 was carried out on Examples 4 1 to 4 6 and the activated carbon (comparative example) used for the carrier.

A desulfurization agent of 0.5 g (liquid Z solid ratio: 30) was immersed in 15 g of kerosene and allowed to stand at 10 ° C. for 9 days, and then the type of sulfur and sulfur compounds were analyzed. For Examples 4-1 to 4-3 and activated carbon (comparative example), an experiment was also conducted in which 4 g of desulfurizing agent (liquid Z solid ratio: 4) was immersed in 16 g of kerosene.

Figure 3 shows the relationship between the metal (silver and copper) content and the sulfur content of kerosene after desulfurization. In the case of the activated carbon carrier, it can be seen that the metal content is higher up to a metal content of 20% by mass, and the desulfurization rate is higher. It can also be seen that when the metal content is 20% by mass or more and the liquid Z solid ratio is 4, desulfurization can be performed to 0.5 mass ppm or less.

[0060] [Table 3]

Example 5

Silver nitrate 0.55 g and copper nitrate 11. lg were dissolved in 21 g of pure water. After fully mixing 36 g of the same activated carbon as in Example 4 with this solution, it was calcined at 400 ° C for 2 hours in a nitrogen atmosphere, and then copper-silver-based Activated carbon was obtained (Example 5). In Example 5, the copper content was 7.07% by mass, the silver content was 0.81% by mass, and the specific surface area was 1,905 m ² Zg.

For Example 5, Example 4-1, and activated carbon (comparative example), the amount of sulfur per unit weight of the desulfurizing agent was changed by changing the liquid Z solid ratio to 8 to 240, and the desulfurizing agent was added to kerosene. Immersion-type adsorptive desulfurization experiments were carried out, which were immersed and left at 10 ° C for 6 days. For Example 5, the liquid Z solid ratio was set at 8, 30, and 240. For Example 4-1 and the comparative example, the liquid Z solid ratio was set at 30, 60, and 240. went. Figure 4 shows the relationship between the sulfur content of kerosene after desulfurization and the sulfur adsorption amount (adsorption isotherm). When the liquid Z solid ratio is large (the sulfur content per unit weight of the desulfurizing agent is large), the decrease in the sulfur content of kerosene after desulfurization is small, but the sulfur adsorption amount per unit weight of the desulfurizing agent is large. The result is shown in the right part of the figure. Example ⁵ and Example ⁴ - 1, then since dibenzo Chio Fen acids also Benzochiofen acids can also be adsorbed and removed, when the liquid Z solid ratio is small (less sulfur per weight desulfurizing agent units) As a result, the amount of sulfur remaining in kerosene after desulfurization decreases, and the amount of sulfur adsorbed per unit weight of desulfurizing agent decreases, resulting in the results on the left side of the figure. When the sulfur content of kerosene after desulfurization on the horizontal axis is less than about 9 ppm by mass, the amount of dibenzothiophenes remaining is small and the amount of adsorption decreases accordingly, so there is an inflection point in the adsorption isotherm. In the case of activated charcoal, which is a comparative example, only dibenzothiophenes are mainly removed, so even if the liquid Z solid ratio is reduced, the decrease in the sulfur content of kerosene after desulfurization on the horizontal axis is slight. From this result, it can be seen that Example 5 and Example 41 have significantly improved sulfur adsorption compared to activated carbon not supporting metal.

Figure 5 shows the relationship (adsorption isotherm) between the content of dibenzothiophenes in kerosene after desulfurization and the amount of dibenzothiophenes adsorbed in the desulfurizing agent. The adsorption isotherm when focusing on dibenzothiophenes is a straight line that almost passes through the origin, and is similar to the adsorption isotherm when the adsorbate is a single component and has a low concentration. From this result, it can be seen that the amount of dibenzothiophenes adsorbed is larger than that of activated carbon not supporting metal. It can also be seen that the adsorption amount of dibenzothiophenes is larger in Example 5, which is an impregnation method, than in Example 41, which is a mixing method of activated carbon and a physical mixing method.

Example 6 [0063] In a 2 L beaker, 67 g of copper sulfate, 32 g of manganese sulfate, and 71 OmL of pure water were added and dissolved by stirring to prepare solution A. Separately, in a 2L beaker, 53g of sodium carbonate and SiO 3

2

Solution B was prepared by adding 18.2 g of sodium silicate No. 3 containing 0% and 710 mL of pure water with stirring and dissolution. While stirring at room temperature, solution A was gradually added dropwise to solution B to form a precipitate. The resulting precipitate was aged, washed thoroughly with water and filtered with suction. Thereafter, it was dried in air at 110 ° C. A solution of 0.6 g of silver nitrate dissolved in 26 g of pure water was thoroughly mixed with 47 g of the obtained dried product and calcined at 350 ° C to obtain a copper-silver-manganese desulfurization agent (Example 6-2) . Similarly, desulfurization agents having different metal contents were prepared by changing the amounts of copper sulfate and manganese sulfate (Examples 6-1 and 6-3). Table 4 shows the Ag, Cu and Mn contents of each desulfurizing agent, the mass ratio of Cu and Mn, and the specific surface area.

For Examples 6-1 to 6-3, the same immersion adsorption desulfurization experiment in kerosene as in Example 1 was performed.

[0064] For Examples 6-1 to 6-3, the immersion adsorptive desulfurization experiment similar to Example 5 was carried out at liquid Z solid ratios of 8, 30, and 240. Figure 6 shows the relationship between the sulfur content of kerosene after desulfurization and the amount of sulfur adsorption (adsorption isotherm). When the support was silica, most of the benzothiophenes were adsorbed and removed from the result of sulfur type analysis. Since the adsorption removal performance of dibenzothiophenes is low, the adsorption amount per unit weight is significantly reduced under conditions where the liquid Z solid ratio is further reduced to lower the sulfur content to about 2 mass ppm or less. From this result, it is understood that the desulfurization performance is improved by setting the ratio of the copper component and the manganese component to 85:15 to 50:50 as the mass ratio of the metal.

[0065] [Table 4] Content (® *) Cu: Mn Specific surface area

Ag Cu Mn (mass ratio) (mVg) Example 6— 1 0. 94 51. 3 7. 51 87: 13 84 Example 6— 2 0. 94 38. 2 19. 0 67: 33 153 Example 6— 3 0. 94 26. 5 30. 0 47: 53 113

Claims

The scope of the claims

[1] A hydrocarbon oil desulfurization agent comprising a copper component and a silver component.

[2] The desulfurization agent according to item 1 of the claim, wherein the ratio of the copper component to the silver component is 99: 1 to 80:20 in terms of the mass ratio of the metal.

[3] The desulfurization agent according to any one of claims 1 and 2, further comprising a manganese component.

[4] The desulfurizing agent according to claim 3, wherein the ratio of the copper component to the manganese component is 85:15 to 50:50 as a mass ratio of the metal.

[5] A method for desulfurizing a hydrocarbon oil, comprising using the desulfurizing agent according to any one of claims 1 to 4.

[6] A method for desulfurizing a hydrocarbon oil, characterized by using the desulfurizing agent according to any one of claims 1 to 4 in a refinery, a petrochemical factory, or a chemical factory.

[7] The desulfurization method according to claim 5 or 6, wherein desulfurization is performed at a temperature of 150 ° C or lower.

[8] The desulfurization method according to claim 5 or 6, wherein the hydrocarbon oil is kerosene.

[9] A fuel cell system using the desulfurizing agent according to any one of claims 1 to 4.