JP2007224212A - Desulfurizing agent for hydrocarbon - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a desulfurizing agent for hydrocarbons with long service life by prolonging time to breakthrough which can efficiently remove the sulfur content in hydrocarbons to a ppb level. <P>SOLUTION: This desulfurizing agent for hydrocarbons comprises 50-95% by mass of nickel in terms of an oxide (NiO), 0.1-12% by mass in terms of an oxide (RuO<SB>2</SB>) and an inorganic oxide. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a hydrocarbon desulfurization agent used as a reforming raw material for producing hydrogen in hydrocarbons, particularly in fuel cells.

  In recent years, new energy technology has attracted attention due to environmental problems, and fuel cells are attracting attention as one of the new energy technologies. This fuel cell converts chemical energy into electrical energy by electrochemically reacting hydrogen and oxygen, and has a feature of high energy use efficiency. Alternatively, research into practical use is actively conducted for automobiles and the like. As the hydrogen source of this fuel cell, liquefied natural gas mainly composed of methanol and methane, city gas mainly composed of this natural gas, synthetic liquid fuel using natural gas as a raw material, and further LPG, naphtha, kerosene, etc. The use of various hydrocarbons, such as petroleum-based fuels, has been studied.

  When hydrogen is produced using these hydrocarbons, generally, a method is used in which the hydrocarbon is subjected to steam reforming or partial oxidation reforming treatment in the presence of a reforming catalyst. However, these hydrocarbons contain sulfur, and the reforming catalyst is poisoned by the sulfur in the hydrocarbons. This is because an active metal such as nickel or ruthenium generally used for the reforming catalyst has low resistance to sulfur. Therefore, when the raw material hydrocarbon contains a sulfur content, from the viewpoint of the life of the reforming catalyst, it is required that the hydrocarbon be subjected to a desulfurization treatment in advance to make the sulfur content normally 100 mass ppb or less.

As a general desulfurization method, there are many so-called hydrodesulfurization methods in which sulfur compounds are removed in the form of hydrogen sulfide with a cobalt-molybdenum or nickel-molybdenum-based catalyst in a hydrogen atmosphere of 200 to 400 ° C. and 2 to 15 MPa. Used (see, for example, Patent Document 1). Such hydrogen desulfurization methods using hydrocarbons (kerosene, etc.) have been actively researched for a long time, but high-temperature and high-pressure conditions are necessary when reducing the sulfur content of raw material hydrocarbons by hydrodesulfurization methods. It is economically disadvantageous because there are certain things and hydrogen is required separately. In addition, this hydrodesulfurization method has not yet achieved desulfurization to a level sufficient to protect the reforming catalyst from poisoning.
Therefore, in the stationary fuel cell power generation system, various techniques for desulfurizing commercially available hydrocarbons by adsorption on-site have been proposed, and hydrocarbons, especially heavy hydrocarbons such as kerosene, are reacted under reaction conditions around 200 ° C. A method of desulfurization using a Ni-Cu desulfurizing agent or a Ni-Zn desulfurizing agent has been proposed. (For example, refer to Patent Documents 2 and 3).
JP-A-6-91173 JP 2004230317 A JP 2003-290660 A

However, some conventional Ni-based desulfurization agents may break through in a relatively short time (the sulfur concentration of the product oil exceeds the standard value), and the life of the desulfurization agent is not sufficient. Extending the time to reach breakthrough (breakthrough time) is desired from the viewpoint of reducing the frequency of replacement of the desulfurizing agent and reducing the size and efficiency of the apparatus.
Therefore, the present invention can efficiently remove sulfur in hydrocarbons to a low concentration of ppb level without supplying hydrogen together with hydrocarbons, and has a long lifetime for hydrocarbons with a long breakthrough time. The object is to provide a desulfurization agent.

The present inventors diligently studied about desulfurization by adsorption of hydrocarbons in order to achieve the above object, and found that by using a desulfurizing agent having a specific composition, the breakthrough time in the desulfurization reaction can be improved. The present invention has been achieved based on this finding. That is, the present invention relates to the following hydrocarbon desulfurization agent.
1. A desulfurizing agent for hydrocarbons containing nickel in an amount of 50 to 95% by mass in terms of oxide (NiO), ruthenium in an amount of 0.1 to 12% by mass in terms of oxide (RuO ₂ ), and an inorganic oxide. .
2. _2. The hydrocarbon desulfurization agent according to 1 above, wherein the inorganic oxide is any one or a combination of two or more of SiO ₂ , Al ₂ O ₃ , and SiO ₂ —Al ₂ O ₃ .
3. Using the desulfurizing agent according to 1 or 2 above, the sulfur content in the hydrocarbon is 50 masses under the conditions of a reaction temperature of 0 to 400 ° C., a reaction pressure of 0.1 MPa or more, and a liquid space velocity of 0.01 to 100 hr ^−1. A hydrocarbon desulfurization method of ppb or less.

  Since the desulfurization agent of the present invention has a specific composition, sulfur content in hydrocarbons such as kerosene, jet fuel, naphtha, gasoline, LPG, and natural gas can be removed very efficiently, and the 50 mass ppb breakthrough time is remarkably increased. It is a long-life hydrocarbon desulfurization agent that can be made to be used.

<Desulfurization agent composition>
The desulfurizing agent in the present invention contains nickel and ruthenium, and adsorbs and removes sulfur-containing compounds present in the raw material hydrocarbon to reduce (desulfurize) the sulfur concentration in the raw material hydrocarbon.
The content of nickel in the desulfurizing agent is 50 to 95% by mass, preferably 60 to 90% by mass in terms of oxide (NiO). If the amount of nickel oxide is 50% by mass or more, the desired desulfurization performance is exhibited, and if it is 95% by mass or less, the desulfurization effect is not saturated, and the desulfurization performance is not easily lowered due to the aggregation of Ni. Therefore, it is preferable.

The ruthenium content in the desulfurizing agent is 0.1 to 12% by mass, preferably 0.1 to 10% by mass in terms of oxide (RuO ₂ ). If the amount of ruthenium oxide is 0.1% by mass or more, the desired desulfurization performance is exhibited, and if it is 12% by mass or less, the effect of desulfurization is not saturated and it is economically desirable.

The desulfurizing agent further contains an inorganic oxide in addition to the nickel and ruthenium. When an inorganic oxide is used, the adsorptive active metal is dispersed and attached to the oxide, thereby improving the dispersibility, improving the desulfurization performance, and extending the breakthrough time. Also, since the moldability and strength of the desulfurizing agent are improved, it is desirable to use an inorganic oxide in order to obtain a highly active and highly durable desulfurizing agent.
The kind of the inorganic oxide is not particularly limited, but an oxide of any one element selected from the group consisting of Si, Al, B, Mg, Ce, Zr, P, Ti, W, Mn, or a mixture thereof, Alternatively, a composite oxide of two or more elements is preferable, and these may have an amorphous structure or a crystalline structure. For _{example, SiO 2, Al 2 O 3} , TiO 2, B 2 O 3, MgO, SiO 2 -Al 2 O 3, Al 2 O 3 -B 2 O 3, MgO-SiO 2, etc. zeolites. Among various inorganic oxides, SiO ₂ , Al ₂ O ₃ , and SiO ₂ —Al ₂ O ₃ are particularly preferable because they have a high surface area, high moldability, and high resistance to fracture and wear. The content of the inorganic oxide component is not particularly limited and may be appropriately selected under various conditions. Usually, it is preferably 0.5 to 50% by mass, more preferably 0.5 to 40% with respect to the entire desulfurizing agent. It may be in the range of mass%. If the content is 0.5% by mass or more, the effect as an inorganic oxide component is sufficiently exhibited, and if it is 50% by mass or less, a decrease in desulfurization performance due to a decrease in the adsorption active component can be prevented. ,preferable.

  Furthermore, in the desulfurizing agent of the present invention, it is preferable that the above-mentioned contained metal is reduced to a metal state suitable for the desulfurization reaction before the desulfurization reaction. Thereby, the contained metal is activated and the sulfur adsorbing ability of the desulfurizing agent can be improved. In order to bring the metal contained in the desulfurizing agent into a metallic state, reduction treatment with hydrogen or the like may be performed before use. The state of the metal can be confirmed by measuring the peak of each metal by X-ray diffraction (XRD). For example, the presence of metallic nickel can be confirmed by detecting a diffraction peak having a peak top in the vicinity of 2θ = 51.6 ° by X-ray diffraction measurement (ray source Cu—Kα ray).

The specific surface area of the desulfurization agent of the present invention, 150~600m ² / g, more preferably 180~500m ² / g are preferred in the state before reduction treatment. If the specific surface area is 150 m ² / g or more, the number of adsorption points for adsorbing sulfur increases, and a sufficient adsorption capacity is obtained, which is preferable. Moreover, if a specific surface area is 600 m < ² > / g or less, an average pore diameter becomes comparatively large and sufficient adsorption capacity is obtained and it is preferable.

  The shape of the desulfurizing agent is not particularly specified, and it may be in any state such as a molded body (extruded cylinder, tablet cylinder, sphere, etc.), a granular body screened with a mesh, or powder, but considering the ease of handling Granules sieved with a molded body or mesh are preferred. In order to make the shape of the desulfurizing agent into a granulated body or a granular body sieved with a mesh, it is desirable to use an inorganic oxide. Further, the size of the desulfurizing agent is not particularly limited regardless of a molded body or a granular body sieved with a mesh, but usually the diameter or length is 0.1 to 10 mm, more preferably 0.1 to 5 mm. It is preferable that

<Preparation of desulfurizing agent>
The method for preparing the desulfurizing agent is not particularly defined and can be appropriately prepared by any method, but preferably using an inorganic oxide, impregnation method, kneading method, coprecipitation method, sol-gel method, equilibrium adsorption method, etc. The impregnation method and the coprecipitation method are preferable in order for nickel and ruthenium to function effectively. Furthermore, in the case of nickel, the coprecipitation method is more preferable because the impregnation method has a small amount of support in one operation. In the case of ruthenium, the impregnation method is more preferable because high activity is obtained.

Although the manufacturing method of the desulfurization agent of this invention is demonstrated concretely below, the manufacturing method of the desulfurization agent of this invention is not limited to this.
As a suitable method for preparing the desulfurizing agent, first, an acidic aqueous solution containing a nickel raw material and an aluminum raw material and a basic aqueous solution containing a Si raw material and an inorganic base are separately prepared.
Although it does not specifically limit as said nickel raw material, Water-soluble nickel metal salts, such as nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, and its hydrate can be used conveniently. These nickel raw materials may be used alone or in combination of two or more.
Further, the aluminum raw material is not particularly limited, but boehmite, pseudoboehmite, γ alumina, β alumina and the like are preferable. These can be used in the form of powder or sol, and may be used alone or in combination of two or more.
The aqueous solution containing the nickel raw material and the aluminum raw material is preferably adjusted with an acid such as hydrochloric acid, sulfuric acid or nitric acid.

Furthermore, the Si raw material is not particularly limited, but silica, water glass, sodium metasilicate, diatomaceous earth, mesoporous silica (MCM41) and the like are preferable.
The inorganic base is preferably an alkali metal carbonate or hydroxide, and examples thereof include sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide. These may be used alone or in combination of two or more, but sodium carbonate is particularly preferred. The amount of the inorganic base used is advantageously selected in the next step so that the mixed solution obtained when the acidic aqueous solution and the basic aqueous solution are mixed is substantially neutral to base.
In addition, the said aluminum raw material and Si raw material are used in order to add an inorganic oxide component to a desulfurization agent.

  Next, each aqueous solution prepared in this way is each heated to 25-90 degreeC, and both are mixed as quickly as possible. And it stirs for about 0.5 to 3 hours at 25-90 degreeC, and completes reaction. The precipitate is filtered and washed with water, and then the solid is dried at a temperature of about 50 to 150 ° C. by a known method. The dried product thus obtained is preferably fired at a temperature in the range of 200 to 450 ° C. for 1 to 5 hours.

Then, the fired body obtained as described above is impregnated and supported with an aqueous solution in which a ruthenium raw material is dissolved in ion-exchanged water. After drying, the ruthenium component is insoluble and fixed with an alkaline aqueous solution, followed by filtration, washing with water and drying.
Although it does not specifically limit as a ruthenium raw material, Water-soluble ruthenium metal salts, such as ruthenium chloride and ruthenium nitrate, and its hydrate can be used conveniently.

Moreover, the alkaline aqueous solution used for immobilizing the ruthenium component is not particularly limited, but aqueous solutions of ammonia water, ammonium carbonate, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate and the like can be used.
Next, the temperature at which the ruthenium component is impregnated and the immobilized product is dried is preferably 120 ° C. or lower. If it is 120 degrees C or less, the production | generation of ruthenium oxide can be suppressed and a subsequent reduction | restoration process can be made efficient. Further, the drying method is not particularly limited, and any of drying under normal pressure, drying under reduced pressure, drying in air, and drying under an inert gas atmosphere can be arbitrarily selected.

<Desulfurization method>
The desulfurizing agent prepared as described above is preferably subjected to a reduction treatment before being subjected to a desulfurization reaction. As a result, the metal contained in the desulfurizing agent is activated and the sulfur component is easily adsorbed. As the reduction method, a known method such as gas phase reduction using hydrogen, CO, etc., liquid phase reduction using formaldehyde, ethanol, or the like can be used, but hydrogen reduction by gas phase is preferable, and in this case, hydrogen reduction It is preferable to carry out at a temperature of 200 to 500 ° C., more preferably 300 to 450 ° C. in an atmosphere.
The hydroreduction treatment may be carried out in the actual desulfurizer (on-site) or in advance in the hydroreduction treatment device (off-site), but off-site reduction is preferable in consideration of the heat resistance of the desulfurizer used. . Further, in the off-site hydroreduction treatment, it is more preferable to perform a stabilization treatment with oxygen, carbon dioxide or the like in order to improve the stability of the desulfurizing agent after the reduction treatment.

  In order to desulfurize hydrocarbons using the desulfurizing agent of the present invention, desulfurization is usually performed by filling the adsorption tank with a desulfurizing agent and bringing the raw material hydrocarbon into contact with the desulfurizing agent in the adsorption tank. As a method for bringing hydrocarbons into contact with the desulfurizing agent, generally, a fixed bed type desulfurizing agent bed is formed in the adsorption tank, the raw material is introduced into the lower part of the adsorption tank, and passed from below the fixed bed to above. The produced oil is preferably allowed to flow out from the upper part of the adsorption tank.

The conditions for the desulfurization reaction are not particularly specified, but the pressure is preferably normal pressure (0.1 MPa) or more, more preferably 0.1 to 1.1 MPa. In order to reduce the pressure to 0.1 MPa or less, special equipment such as a decompression device is required, which is not economically preferable. On the other hand, if the pressure is set to 1.1 MPa or more, the pressure resistance of the desulfurizer and the supply pump is required, which is not economically preferable.
Moreover, 0-400 degreeC is preferable, More preferably, it is 100-300 degreeC, More preferably, it is 140-300 degreeC. If the temperature is too low, the adsorptive desulfurization rate decreases. On the other hand, if the temperature is too high, the nickel component in the desulfurizing agent aggregates and the number of desulfurization sites decreases, which may reduce the desulfurization performance.
Also, liquid hourly space velocity (LHSV) 0.01～100Hr ^-1, more preferably 0.1 to 20 ^-1.

Kerosene, jet fuel, naphtha, gasoline, LPG and natural gas are preferred as the hydrocarbon used as a raw material, and kerosene is particularly preferred from the viewpoint of market distribution and ease of handling. As kerosene, if the sulfur content is about 80 mass ppm, the desired effect of the desulfurizing agent of the present application can be obtained.
By appropriately selecting the desulfurization conditions within the above range, a hydrocarbon having a sulfur content reduced to the ppb level can be obtained for a long time.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The physical properties of the desulfurizing agent and the instrumental analysis method for the sulfur content in the hydrocarbon (produced oil) in Examples and Comparative Examples are shown below.

<Measurement of specific surface area of desulfurization agent>
A BET surface area measuring device (Belsorb Mini) was used for measurement of BET (Braunauer-Emmett-Tailor specific surface area) specific surface area. About 200 to 300 mg of the sample is precisely weighed, filled in a quartz sample tube, heated from room temperature to 400 ° C. over 1 hour while reducing the pressure to 10 ⁻¹ to 10 ⁻³ mmHg level, The deaeration treatment was performed by maintaining at the same temperature for 3 hours. Thereafter, the temperature was lowered to room temperature while reducing the pressure, the gas was replaced with high purity helium gas, and the weight of the sample after deaeration was precisely weighed. Thereafter, nitrogen adsorption was performed at the liquefied nitrogen temperature, and the specific surface area was measured.
<Sulfur analysis in hydrocarbons>
For analysis of sulfur in hydrocarbons, Thermo Onix XVI manufactured by HOUSTON ATLAS was used.

Example 1; Ni coprecipitated + Ru-impregnated boehmite AP-3 (Shokubai Kasei Kogyo) 1.24 g, after warming 1N HNO ₃ solution 40ml to 80 ° C. In addition to ion-exchanged water _{1L, Ni (NO 3) 2} · 6H the ₂ O to give a 159g added preparation a. Colloidal silica Snowtex XS (manufactured by Nissan Chemical Co., Ltd.) 33.9 g and sodium carbonate 99.4 g were added to 1 L of ion-exchanged water separately prepared, and heated to 80 ° C. to obtain Preparation B. While maintaining the prepared solutions A and B at 80 ° C., the solution B was instantaneously added to the solution A and stirred for 1 hour. Then, using 5 L of ion-exchanged water, washed and filtered, dried in air at 120 ° C. for 12 hours, and fired at 400 ° C. for 1 hour. The resulting fired product was crushed, and 1.0 mm and 1.4 mm meshes were obtained. It sieved with the sieve which has. Next, 30 g of the above-mentioned mesh-crushed 30 g of RuCl ₃ · nH ₂ O (manufactured by Kojima Chemical Co., Ltd., Ru content 41 mass%, n = 1 to 3) dissolved in 11.4 g of ion exchange water 1 Soaked for a period of time, impregnated and supported with the aqueous solution on the mesh crushed, dried, soaked in 150 g of 7 N (mol / L) NH ₃ water for 1 hour, filtered, filtered and washed with 2 L of ion-exchanged water, 120 ° C. And desulfurizing agent 1 was obtained.

Example 2 Ni coprecipitation + Ru impregnation 40 ml of 1NHNO ₃ aqueous solution was added to 1 L of ion-exchanged water and heated to 80 ° C., and 160 g of Ni (NO ₃ ) ₂ .6H ₂ O was added to obtain Preparation Liquid A. 36.4 g of colloidal silica Snowtex XS (Nissan Chemical) and 99.4 g of sodium carbonate were added to 1 L of ion-exchanged water separately prepared, and heated to 80 ° C. to obtain Preparation B. While maintaining the prepared solutions A and B at 80 ° C., the solution B was instantaneously added to the solution A and stirred for 1 hour. Then, using 5 L of ion-exchanged water, washed and filtered, dried in air at 120 ° C. for 12 hours, and fired at 400 ° C. for 1 hour. The resulting fired product was crushed, and 1.0 mm and 1.4 mm meshes were obtained. It sieved with the sieve which has. Subsequently, 30 g of 30 g of mesh-crushed 30 g of RuCl ₃ · nH ₂ O (manufactured by Kojima Chemical Co., Ltd., Ru content 41 mass%, n = 1 to 3) dissolved in 11.4 g of ion-exchanged water was dissolved in 11.4 g of ion-exchanged water. The aqueous solution is impregnated and supported on the crushed mesh, dried, soaked in 150 g of 7N NH ₃ water for 1 hour, filtered, filtered and washed with 2 L of ion-exchanged water, dried at 120 ° C., and desulfurizing agent 2 Got.

Example 3; Ni coprecipitated + Ru-impregnated boehmite AP-3 (manufactured by Catalysts & Chemicals Industries) 1.9 g, after warming the 1NHNO ₃ solution 40ml to 80 ° C. In addition to ion-exchanged water _{1L, Ni (NO 3) 2} · 6H 2 Preparation solution A was obtained by adding 140 g of O. Colloidal silica Snowtex XS (manufactured by Nissan Chemical Co., Ltd.) 53.3 g and sodium carbonate 99.4 g were added to 1 L of ion-exchanged water separately prepared, and heated to 80 ° C. to obtain Preparation B. While maintaining the prepared solutions A and B at 80 ° C., the solution B was instantaneously added to the solution A and stirred for 1 hour. Then, using 5 L of ion-exchanged water, washed and filtered, dried in air at 120 ° C. for 12 hours, and fired at 400 ° C. for 1 hour. The resulting fired product was crushed, and 1.0 mm and 1.4 mm meshes were obtained. It sieved with the sieve which has. Next, 30 g of the above-mentioned mesh-crushed 30 g of RuCl ₃ · nH ₂ O (manufactured by Kojima Chemical Co., Ltd., Ru content 41 mass%, n = 1 to 3) in an aqueous solution prepared by dissolving 5.4 g in ion-exchanged water 11.4 g Soaked in time, impregnated with the aqueous solution, and dried, soaked in 150 g of 7N NH ₃ water for 1 hour, filtered, filtered and washed with 2 L of ion-exchanged water, dried at 120 ° C., desulfurizing agent 3 was obtained.

Example 4; NiRu coprecipitated boehmite AP-3 (Shokubai Kasei Kogyo) 1.24 g, after warming 1NHNO ₃ solution 40ml to 80 ° C. In addition to ion-exchanged water 1L, Ni a _{(NO 3) 2 · 6H 2} O 164 g, RuCl ₃ · nH 2 O (manufactured by Kojima Chemical Co., Ru content 41 mass%, n = 1 to 3) 3.6 g was added to obtain Preparation Liquid A. 26.7 g of colloidal silica Snowtex XS (manufactured by Nissan Chemical Industries) and 99.4 g of sodium carbonate were added to 1 L of separately prepared ion-exchanged water, and heated to 80 ° C. to obtain Preparation B. While maintaining the prepared solutions A and B at 80 ° C., the solution B was instantaneously added to the solution A and stirred for 1 hour. Then, using 5 L of ion-exchanged water, washed and filtered, dried in air at 120 ° C. for 12 hours, and fired at 400 ° C. for 1 hour. The resulting fired product was crushed, and 1.0 mm and 1.4 mm meshes were obtained. The resultant was sieved with a sieve having the above to obtain a desulfurizing agent 4.

Comparative Example 1; Ni coprecipitated boehmite AP-3 (Shokubai Kasei Kogyo) 1.24 g, after warming 1N HNO ₃ solution 40ml to 80 ° C. In addition to ion-exchanged water _{1L, Ni (NO 3) 2} · 6H 2 O 159g was added and the preparation liquid A was obtained. Colloidal silica Snowtex XS (manufactured by Nissan Chemical Co., Ltd.) 33.9 g and sodium carbonate 99.4 g were added to 1 L of ion-exchanged water separately prepared, and heated to 80 ° C. to obtain Preparation Solution B. While maintaining the prepared solutions A and B at 80 ° C., the solution B was instantaneously added to the solution A and stirred for 1 hour. Then, using 5 L of ion-exchanged water, washed and filtered, dried in air at 120 ° C. for 12 hours, and fired at 400 ° C. for 1 hour. The resulting fired product was crushed, and 1.0 mm and 1.4 mm meshes were obtained. Sieving was carried out with a sieve having the above to obtain a desulfurizing agent 5.

Comparative Example 2; NiCu coprecipitated boehmite AP-3 (Shokubai Kasei Kogyo) 1.24 g, after pressurizing the 1N HNO ₃ solution 40ml to 80 ° C. In addition to ion-exchanged water 1L _{temperature, Ni (NO 3) 2 ·} 6H 2 O 149 g and Cu (NO ₃ ) ₂ .4H ₂ O 7.9 g were added to obtain Preparation A. Colloidal silica Snowtex XS (manufactured by Nissan Chemical Co., Ltd.) 33.9 g and sodium carbonate 99.4 g were added to 1 L of ion-exchanged water separately prepared, and heated to 80 ° C. to obtain Preparation Solution B. While maintaining the prepared solutions A and B at 80 ° C., the solution B was instantaneously added to the solution A and stirred for 1 hour. Then, using 5 L of ion-exchanged water, washed and filtered, dried in air at 120 ° C. for 12 hours, and fired at 400 ° C. for 1 hour. The resulting fired product was crushed, and 1.0 mm and 1.4 mm meshes were obtained. The resultant was sieved with a sieve having the above to obtain a desulfurizing agent 6.

Comparative Example 3; NiZn coprecipitated boehmite AP-3 (manufactured by Catalysts & Chemicals Industries) 1.24 g, after warming 1N HNO ₃ solution 40ml to 80 ° C. In addition to ion-exchanged water _{1L, Ni (NO 3) 2} · 6H 2 O 149 g and Zn (NO ₃ ) ₂ · 6H ₂ O 8.9 g were added to obtain Preparation A. Colloidal silica Snowtex XS (manufactured by Nissan Chemical Co., Ltd.) 33.9 g and sodium carbonate 99.4 g were added to 1 L of ion-exchanged water separately prepared, and heated to 80 ° C. to obtain Preparation Solution B. While maintaining the prepared solutions A and B at 80 ° C., the solution B was instantaneously added to the solution A and stirred for 1 hour. Then, using 5 L of ion-exchanged water, washed and filtered, dried in air at 120 ° C. for 12 hours, and fired at 400 ° C. for 1 hour. The resulting fired product was crushed, and 1.0 mm and 1.4 mm meshes were obtained. The resulting product was sieved with a sieve having a desulfurizing agent 7.

<The kerosene desulfurization test of the desulfurization agent of Examples 1-4 and Comparative Examples 1-3>
A desulfurization test of kerosene was performed using desulfurizing agents 1 to 7, and desulfurization performance was compared. In this desulfurization test, initial distillation temperature 148 ° C., 10% distillation temperature 172 ° C., 30% distillation temperature 185 ° C., 50% distillation temperature 202 ° C., 70% distillation temperature 225 ° C., 90% distillation temperature 251 ° C. JIS No. 1 kerosene having a distillation property at an end point of 281 ° C. and containing a sulfur content of 6 mass ppm was used. Table 1 shows the properties of the kerosene used.
First, prior to the desulfurization reaction, the desulfurizing agent was reduced and activated. For desulfurizing agents 1 to 3 and 5 to 7, 11.6 ml of a desulfurizing agent was filled in a SUS reaction tube having an inner diameter of 16 mm. Then, the temperature of the reaction tube was raised to 400 ° C., and the desulfurization agent was reduced and activated by maintaining it in a hydrogen stream under normal pressure for 3 hours.
On the other hand, for the desulfurizing agent 4, 20 ml of the desulfurizing agent was filled in a SUS reaction tube having an inner diameter of 16 mm. The temperature was raised to 400 ° C. under a hydrogen gas flow, held at 400 ° C. for 3 hours, cooled to room temperature, and then oxidized and stabilized at 100 ° C. or lower in a diluted oxygen atmosphere. Subsequently, the oxidation-stabilized desulfurizing agent was extracted, and 11.6 ml thereof was filled into another SUS reaction tube having an inner diameter of 16 mm. Then, the temperature of the reaction tube was raised to 220 ° C., and the desulfurization agent was reduced and activated by maintaining it in a hydrogen stream under normal pressure for 3 hours.
Thereafter, the JIS No. 1 kerosene was passed through each reaction tube containing the activated desulfurizing agent at a pressure of 0.4 MPa, a temperature of 220 ° C., and a liquid space velocity of 10 hr ⁻¹ , and the product oil was formed downstream of the reaction tube. Was collected every hour. The desulfurization experiment was continued until the sulfur content in the collected product oil exceeded 50 mass ppb, and the time taken to break through 50 mass ppb was defined as the 50 mass ppb breakthrough time. The results are shown in Table 2.

  From the above results, it can be seen that the desulfurization agent of the present invention containing specific amounts of nickel and ruthenium significantly extends the breakthrough time of 50 mass ppb and is a long-life desulfurization agent.

Claims (3)

A desulfurizing agent for hydrocarbons containing nickel in an amount of 50 to 95% by mass in terms of oxide (NiO), ruthenium in an amount of 0.1 to 12% by mass in terms of oxide (RuO ₂ ), and an inorganic oxide. . _2. The hydrocarbon desulfurization agent according to claim 1, wherein the inorganic oxide is any one of SiO ₂ , Al ₂ O ₃ , and SiO ₂ —Al ₂ O ₃ , or a combination of two or more. Using the desulfurizing agent according to claim 1 or 2, the sulfur content in the hydrocarbon is reduced to 50 under the conditions of a reaction temperature of 0 to 400 ° C., a reaction pressure of 0.1 MPa or more, and a liquid space velocity of 0.01 to 100 hr ^−1. A hydrocarbon desulfurization method with a mass of ppb or less.