JP2012030211A - Method for producing hydrocarbon desulfurization agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a desulfurizing agent for hydrocarbon capable of further efficiently removing a sulfur content in hydrocarbon to low concentration at a ppb level, extended in a breakthrough time, and long in service life.SOLUTION: This method is used for manufacturing a desulfurizing agent for hydrocarbon containing nickel and molybdenum by producing a sediment by mixing and reacting an acidic solution containing nickel with a basic solution containing molybdenum. In the method of manufacturing a desulfurizing agent, pH of the solution after mixing the acidic solution containing nickel with the basic solution containing molybdenum is 6-8, and the temperature thereof is 50-90°C. In the method of manufacturing a desulfurizing agent, the acidic solution containing nickel is prepared to set the pH at 3-4 by using nickel sulfate as a material of nickel.

Description

  The present invention relates to a method for producing a desulfurization agent used for desulfurization of raw fuel used for reforming for hydrocarbon production, particularly for hydrogen production used in fuel cells and the like.

  A fuel cell is a device that converts chemical energy into electric energy by electrochemically reacting hydrogen and oxygen, and has a feature of high energy use efficiency. Research into practical use has been actively conducted for automobiles. 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.

  By the way, in such hydrogen production from hydrocarbons, a reforming reaction that generates hydrogen from hydrocarbons and steam or oxygen (air) is used. In this reforming reaction, nickel or ruthenium is used as an active metal. A catalyst is used. Since these active metals such as nickel and ruthenium have low resistance to sulfur, when the raw material hydrocarbon contains a sulfur content, it is necessary to perform a desulfurization treatment in advance and use it for the reforming reaction.

  Therefore, in the stationary fuel cell power generation system, various methods for desulfurizing commercially available hydrocarbons by adsorption on-site have been proposed. The reaction conditions of hydrocarbons, particularly heavy hydrocarbons such as kerosene, are about 200 ° C. A method of desulfurization using a nickel-copper desulfurization agent or a nickel-zinc desulfurization agent has been proposed. (For example, refer to Patent Documents 1 and 2).

  However, some of the nickel-based desulfurization agents that have been proposed in the past have been broken through in a relatively short time (the sulfur concentration of the product oil exceeds the standard value), and the life is not sufficient. Extending the time to reach breakthrough (breakthrough time) and sufficiently extending the life of the desulfurizing agent is desired from the viewpoint of reducing the desulfurizing agent replacement frequency and reducing the size and efficiency of the apparatus.

In view of the above-described conventional situation, the present inventors examined the development of a desulfurization agent that extends breakthrough time and improves the performance by combining molybdenum with nickel, and first, nickel is oxidized ( Ni-Mo based hydrocarbon desulfurization agent containing 50 to 95% by mass in terms of NiO), 0.5 to 25% by mass in terms of molybdenum (MoO ₃ ) and inorganic oxides (patent) Reference 3).

  The present inventors have further studied and include nickel under predetermined conditions that can further extend the breakthrough time and improve the performance of the proposed Ni-Mo hydrocarbon desulfurization agent. A method for producing a Ni-Mo-based hydrocarbon desulfurization agent in which an acidic solution and a basic solution containing molybdenum are mixed to produce a coprecipitate was developed, and this production method was also proposed previously (see Patent Document 4). ).

  The Ni-Mo-based desulfurization agent previously proposed by the present inventors and the desulfurization agent obtained by the production method of the Ni-Mo-based desulfurization agent were each correspondingly extended in breakthrough time and extended in service life. Although each of them has excellent performance, desulfurization for hydrocarbons with longer lifespan and longer lifespan from the viewpoint of further reducing the frequency of desulfurization agent replacement and downsizing and increasing the efficiency of equipment. It is desired to provide an agent and a method for producing the same.

JP 2004230317 A JP 2003-290660 A JP 2007-254275 A JP 2009-45536 A

  SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a hydrocarbon desulfurization agent that can further efficiently remove sulfur content in hydrocarbons to a low concentration of ppb level and has a long life span and has an extended breakthrough time. It is what.

  The present inventors diligently studied to achieve the above object, and as a result, the acidic solution containing nickel and the basic solution containing molybdenum were mixed and coprecipitated under the predetermined conditions previously proposed by the inventors. In the method for producing a desulfurization agent for Ni-Mo based hydrocarbons, a nickel-containing acidic solution is prepared by using a certain nickel raw material so as to have a certain pH, thereby achieving the above object. The present inventors have found that a desired desulfurization agent having excellent desulfurization activity and extended breakthrough time can be produced, and the present invention has been completed based on this finding.

That is, the present invention provides the following method for producing a hydrocarbon desulfurization agent.
(1) A method for producing a hydrocarbon desulfurization agent containing nickel and molybdenum by mixing an acidic solution containing nickel and a basic solution containing molybdenum and reacting to produce a precipitate, A method for producing a hydrocarbon desulfurization agent having a pH of 6 to 8 and a temperature of 50 to 90 ° C. after mixing an acidic solution containing nickel and a basic solution containing molybdenum, the nickel A method for producing a hydrocarbon desulfurization agent, wherein the acidic solution is prepared using nickel sulfate as a nickel raw material so as to have a pH of 3 to 4.
(2) the hydrocarbon desulfurizing agent, desulfurization agent basis, nickel oxide (NiO) 50 to 95 wt% in terms of molybdenum oxide 0.5 to 25% by weight (MoO ₃₎ in terms of, and The method for producing a hydrocarbon desulfurization agent according to (1) above, which contains an inorganic oxide.

  According to the present invention, when an Ni-Mo-based desulfurization agent is produced by mixing an acidic solution containing nickel and a basic solution containing molybdenum to produce a coprecipitate, By using nickel sulfate as a raw material and using an acidic solution containing nickel prepared to have a pH of 3-4, a desulfurization agent having even better desulfurization activity, longer breakthrough time, and longer life is produced. be able to. The desulfurizing agent produced by the method of the present invention is most suitable for desulfurization of hydrocarbons, especially for desulfurization of fuel used for reforming for hydrogen production used in fuel cells and the like.

[Method for producing desulfurizing agent]
The method for producing a desulfurizing agent of the present invention is a method for producing a desulfurizing agent containing nickel and molybdenum by a coprecipitation method. And manufacture of the desulfurization agent by this coprecipitation method is performed by mixing the acidic solution containing a nickel raw material, and the basic solution containing a molybdenum raw material, making it react and producing | generating a deposit.

  In the method of the present invention, the acidic solution containing the nickel raw material has a pH of 3 to 4, preferably 3.2 to 4. When the pH of this acidic solution deviates from the range of 3 to 4, the breakthrough time of the obtained desulfurizing agent tends to decrease. Moreover, 8-12 are preferable and, as for pH of the basic solution containing a molybdenum raw material, 9-11 are especially preferable.

  Moreover, nickel sulfate and its hydrate are used as a nickel raw material of the acidic solution containing a nickel raw material. When a nickel compound other than nickel sulfate, such as nickel nitrate, nickel chloride, or nickel acetate, is used as the nickel raw material, the breakthrough time of the resulting desulfurizing agent tends to decrease. Further, the molybdenum raw material of the basic solution containing the molybdenum raw material is not particularly limited. For example, water-soluble molybdenum metal salts such as ammonium molybdate and molybdophosphoric acid and hydrates thereof can be preferably used.

  The acidic solution containing the nickel raw material and the basic solution containing the molybdenum raw material will be described later in detail again.

  In the method of this invention, the pH of the solution after mixing the acidic solution containing a nickel raw material and the basic solution containing a molybdenum raw material is 6-8, and 6.5-7.5 are preferable. Setting the pH in the specific range is important for obtaining a desulfurization agent having a desired desulfurization performance. When the pH of the mixed solution is less than 6, nickel precipitation becomes insufficient, and conversely, when the pH exceeds 8, precipitation of molybdenum becomes insufficient. Therefore, when the pH of the mixed solution deviates from the above range, the amount of nickel or molybdenum contained in the desulfurizing agent is insufficient, or the amount of nickel ions or molybdenum ions in the filtrate serving as drainage increases. become. The pH of this mixed solution can be adjusted according to the amount and type of an inorganic base contained in the basic solution, and can be adjusted according to the amount and type of the acidic solution containing an inorganic acid. You can also.

  In the present invention, it is also important to obtain a desulfurization agent having a desired desulfurization performance by setting the temperature of the solution after mixing the acidic solution and the basic solution to 50 to 90 ° C. and making this temperature within this specific range. It is. And it is more effective that the temperature of this liquid mixture shall be 60-80 degreeC preferably. By setting the solution temperature to 50 ° C. or higher, the coprecipitation reaction between nickel and molybdenum when the acidic solution and the basic solution are mixed is further promoted. On the other hand, the solution temperature may be 90 ° C. or higher. However, when the solution temperature exceeds 90 ° C., water as a solvent is likely to evaporate, and it may be difficult to control nickel and molybdenum in the solution.

After mixing the acidic solution and the basic solution, the mixture is generally stirred for about 0.5 to 3 hours under the above conditions to complete the reaction. Then, the produced precipitate is filtered, washed with water, then molded, and dried at a temperature of about 50 to 150 ° C. The dried product thus obtained is preferably fired at a temperature in the range of 200 to 450 ° C. for 1 to 5 hours.
In the present invention, the desulfurizing agent is produced as described above.

Hereinafter, each raw material used for the manufacturing method of the desulfurization agent of this invention and its solution are demonstrated.
First, as a nickel raw material, nickel sulfate and its hydrate are used as described above. These nickel raw materials may be used alone or in combination of two or more.

  For the acidic solution containing the nickel raw material, water may be used as a solvent, and the pH may be appropriately adjusted to 3 to 4 with an inorganic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and nitric acid. These may be used alone or in combination of two or more.

  Further, the molybdenum raw material is not particularly limited as described above. For example, water-soluble molybdenum metal salts such as ammonium molybdate and molybdophosphoric acid and hydrates thereof can be preferably used. These molybdenum raw materials may be used alone or in combination of two or more.

  Water is used as a solvent for the basic solution containing the molybdenum raw material, and the pH of the basic solution containing the molybdenum raw material is generally adjusted appropriately with an inorganic base. As the inorganic base, for example, alkali metal carbonates and hydroxides are preferable, and examples thereof include sodium carbonate, sodium hydrogen carbonate, 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.

  Further, as will be described later, the desulfurization agent produced by the production method of the present invention can contain an inorganic oxide in addition to nickel and molybdenum, and in that case, molybdenum for the coprecipitation reaction. It is preferable that an inorganic oxide raw material is contained in a basic solution containing the raw material or an acidic solution containing the nickel raw material and precipitated together with nickel and molybdenum.

  The kind of the inorganic oxide to be contained in the desulfurizing agent is not particularly limited as will be described later, and particularly preferable examples include silica, alumina, and silica-alumina. For example, when alumina or silica-alumina is contained, examples of the aluminum raw material include boehmite, pseudoboehmite, γ-alumina, and β-alumina. There may be. For example, when silica or silica-alumina is contained, examples of the silica raw material include silica, water glass, sodium metasilicate, diatomaceous earth, and mesoporous silica (MCM41).

[Desulfurizing agent produced]
The desulfurizing agent produced by the production method of the present invention essentially contains nickel and molybdenum, and contains an inorganic oxide and other active components as necessary.

  The desulfurizing agent preferably contains 50 to 95% by mass of nickel in terms of oxide (NiO), more preferably 60 to 90% by mass, and particularly preferably 60 to 85% by mass. If the amount of nickel is 50% by mass or less, the desired desulfurization performance is not exhibited, which is not preferable. Conversely, if it exceeds 95% by mass, not only the effect is saturated, but also the desulfurization performance decreases due to aggregation of nickel. In addition, a decrease in moldability is expected.

The desulfurizing agent preferably contains 0.5 to 20% by mass, more preferably 2 to 10% by mass, in terms of oxide (MoO ₃ ) in terms of molybdenum. If the molybdenum oxide is 0.5% by mass or less, the desired desulfurization performance is not exhibited, which is not preferable. Conversely, if it exceeds 20% by mass, not only the effect is saturated, but also the desulfurization performance is reduced, A decrease in moldability is expected.

  Further, the desulfurizing agent may contain an inorganic oxide in order to increase the surface area, improve the moldability, and enhance the resistance to breakage and wear. Examples of such inorganic oxides include silica, alumina, titania, boria, magnesia, silica-alumina, alumina-boria, magnesia-silica, and zeolite. Of these, silica, alumina, and silica-alumina are preferable from the viewpoint of the above effects.

  The content of the inorganic oxide in the desulfurizing agent is not particularly limited and may be appropriately selected under various conditions. Usually, it is preferably in the range of 0.5 to 50% by mass with respect to the total desulfurizing agent. Furthermore, it is more preferable to set it as 0.5-40 mass%, especially 0.5-30 mass%. An effect is easily acquired by making content of an inorganic oxide into 0.5 mass% or more. On the other hand, when the amount exceeds 50% by mass, the desulfurization performance is expected to decrease due to the decrease in the active ingredient, which is not preferable.

Furthermore, the desulfurizing agent may contain other active ingredients. For example, in order to achieve higher activity, ruthenium may be contained in an amount of about 0.1 to 12% by mass in terms of a desulfurizing agent standard and oxide (RuO ₂ ).

  The shape of the desulfurizing agent is not particularly specified, and any shape such as a molded body (extruded cylinder, tablet cylinder, sphere, etc.), mesh, and powder may be used, but considering the ease of handling, the molded body and mesh are preferable. .

[Desulfurization reaction using the obtained desulfurization agent]
The desulfurizing agent produced as described above is preferably subjected to a reduction treatment before being subjected to the 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, It is preferable to carry out at a temperature of 200 to 500 ° C. in a hydrogen atmosphere, and more preferably 300 to 450 ° C.

  The hydrogen reduction treatment may be performed in the actual desulfurizer (on-site) or in advance with a hydrogen reduction treatment apparatus (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, in order to improve the stability of the desulfurization agent after the reduction treatment, a stabilization treatment is performed in which the surface of the desulfurization agent after the reduction treatment is lightly oxidized with oxygen or carbon dioxide. More preferably.

  In order to desulfurize hydrocarbons using the desulfurizing agent obtained in 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, Most 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, the liquid hourly space velocity (LHSV) is preferably in the 0.01～100Hr ^-1, and more preferably to 0.1 to 20 ^-1.

  As the hydrocarbon used as a raw material, kerosene, jet fuel, naphtha, gasoline, LPG and natural gas are preferable, and kerosene is particularly preferable from the viewpoint of market distribution and ease of handling. As kerosene, if the sulfur content is up to about 80 ppm by mass, the desired effect of the desulfurizing agent obtained in 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 still 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
1.24 g of boehmite AP-3 (manufactured by Catalyst Kasei Kogyo) was added to 1 L of ion-exchanged water and heated to 80 ° C., and then 126.5 g of NiSO ₄ .6H ₂ O was added to obtain Preparation Liquid A. The pH of the preparation liquid A was 3.7. Colloidal silica Snowtex XS (Nissan Chemical, 20% as SiO ₂ (hereinafter the same)) 33.9 g, sodium carbonate 59.4 g, (NH ₄ ) ₆ Mo ₇ O ₂₄ 9g was added and it heated at 80 degreeC and the preparation liquid B was obtained. 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. When pH was measured after 1 hour of stirring, it was 6.83. Thereafter, the precipitate is filtered off, washed with 5 L of ion-exchanged water, filtered, dried in air at 120 ° C. for 12 hours, calcined at 400 ° C. for 1 hour, and the resulting calcined product is crushed. The desulfurization agent 1 was obtained by sieving with a sieve having a mesh of 0 mm and 1.4 mm. Table 1 shows the composition of the obtained desulfurizing agent, the BET specific surface area, the Ni raw material used, and the pH of the acidic solution.

Example 2
Boehmite AP-3 (manufactured by Catalyst Kasei Kogyo Co., Ltd.) 1.24 g of 1N H ₂ SO ₄ aqueous solution 10 mL was added to 1 L of ion-exchanged water, heated to 80 ° C., and 126.5 g of NiSO ₄ · 6H ₂ O was added to prepare Preparation A. Obtained. The pH of the preparation liquid A was 3.2. Colloidal silica Snowtex XS (Nissan Chemical) 33.9 g, sodium carbonate 59.4 g, (NH ₄ ) ₆ Mo ₇ O ₂₄ 3.9 g was added to 1 L of ion-exchanged water separately prepared, and heated to 80 ° C., Preparation liquid B was obtained. 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. When pH was measured after 1 hour of stirring, it was 6.91. Thereafter, the precipitate is filtered off, washed with 5 L of ion-exchanged water, filtered, dried in air at 120 ° C. for 12 hours, calcined at 400 ° C. for 1 hour, and the resulting calcined product is crushed. The desulfurization agent 2 was obtained by sieving with a sieve having a mesh of 0 mm and 1.4 mm. Table 1 shows the composition of the obtained desulfurizing agent, the BET specific surface area, the Ni raw material used, and the pH of the acidic solution.

Comparative Example 1
Boehmite AP-3 (Catalyst Kasei Kogyo Co., Ltd.) 1.24 g, 40 mL of 1N H ₂ SO ₄ aqueous solution was added to 1 L of ion-exchanged water, heated to 80 ° C., and 126.5 g of NiSO ₄ · 6H ₂ O was added. Obtained. The pH of the preparation liquid A was 2.5. Colloidal silica Snowtex XS (Nissan Chemical) 33.9 g, sodium carbonate 59.4 g, (NH ₄ ) ₆ Mo ₇ O ₂₄ 3.9 g was added to 1 L of ion-exchanged water separately prepared, and heated to 80 ° C., Preparation liquid B was obtained. 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. When the pH was measured after 1 hour of stirring, it was 6.95. Thereafter, the precipitate is filtered off, washed with 5 L of ion-exchanged water, filtered, dried in air at 120 ° C. for 12 hours, calcined at 400 ° C. for 1 hour, and the resulting calcined product is crushed. The desulfurization agent 3 was obtained by sieving with a sieve having a mesh of 0 mm and 1.4 mm. Table 1 shows the composition of the obtained desulfurizing agent, the BET specific surface area, the Ni raw material used, and the pH of the acidic solution.

Comparative Example 2
Boehmite AP-3 (manufactured by Catalysts & Chemicals Industries) 1.24 g, after warming to _1N H 2 SO ₄ aqueous solution 40mL to 80 ° C. In addition to ion-exchanged water 1L, added 139.9g of _{Ni (NO 3) 2 · 6H} 2 O Preparation liquid A was obtained. The pH of the preparation liquid A was 1.3. Colloidal silica Snowtex XS (Nissan Chemical) 33.9 g, sodium carbonate 59.4 g, (NH ₄ ) ₆ Mo ₇ O ₂₄ 3.9 g was added to 1 L of ion-exchanged water separately prepared, and heated to 80 ° C., Preparation liquid B was obtained. 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. When pH was measured after 1 hour of stirring, it was 7.39. Thereafter, the precipitate is filtered off, washed with 5 L of ion-exchanged water, filtered, dried in air at 120 ° C. for 12 hours, calcined at 400 ° C. for 1 hour, and the resulting calcined product is crushed. The desulfurization agent 4 was obtained by sieving with a sieve having a mesh of 0 mm and 1.4 mm. Table 1 shows the composition of the obtained desulfurizing agent, the BET specific surface area, the Ni raw material used, and the pH of the acidic solution.

Comparative Example 3
6.2 g of boehmite AP-3 (manufactured by Catalyst Kasei Kogyo) was added to 1 L of ion-exchanged water and heated to 80 ° C., and then 126.5 g of NiSO ₄ .6H ₂ O was added to obtain Preparation Liquid A. The pH of the preparation liquid A was 4.1. Colloidal silica Snowtex XS (Nissan Chemical) 33.9 g, sodium carbonate 59.4 g, (NH ₄ ) ₆ Mo ₇ O ₂₄ 3.9 g was added to 1 L of ion-exchanged water separately prepared, and heated to 80 ° C., Preparation liquid B was obtained. 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. When pH was measured after 1 hour of stirring, it was 7.14. Thereafter, the precipitate is filtered off, washed with 5 L of ion-exchanged water, filtered, dried in air at 120 ° C. for 12 hours, calcined at 400 ° C. for 1 hour, and the resulting calcined product is crushed. The desulfurization agent 5 was obtained by sieving with a sieve having a mesh of 0 mm and 1.4 mm. Table 1 shows the composition of the obtained desulfurizing agent, the BET specific surface area, the Ni raw material used, and the pH of the acidic solution.

<The kerosene desulfurization test of the desulfurization agent of Examples 1-2 and Comparative Examples 1-3>
A desulfurization test of kerosene was performed using desulfurizing agents 1 to 3, and desulfurization performance was compared. In this desulfurization test, initial distillation temperature 154 ° C., 10% distillation temperature 171 ° C., 30% distillation temperature 186 ° C., 50% distillation temperature 201 ° C., 70% distillation temperature 224 ° C., 90% distillation temperature 253 ° C. JIS No. 1 kerosene having a distillation property of 277 ° C. at the end point and containing 8.8 ppm by mass of sulfur was used. Table 2 shows the properties of the kerosene used.

  First, prior to the desulfurization reaction, the desulfurizing agent was reduced and activated. That is, 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.

Thereafter, the JIS No. 1 kerosene was circulated through each reaction tube containing the activated desulfurizing agent at a pressure of 0.7 MPa, a temperature of 200 ° C., and a liquid space velocity of 2.4 hr ⁻¹ , and generated downstream of the reaction tube. Oil 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 1.

  From the results shown in Table 1 above, nickel sulfate was used as the nickel raw material of Example 1, and an acidic solution containing nickel and a basic solution containing molybdenum prepared so as to have a pH of 3 to 4 were mixed and reacted. The Ni—Mo-based desulfurizing agent produced by producing precipitates is a long-life desulfurizing agent with an extended breakthrough time of 50 ppb compared to the Ni—Mo-based desulfurizing agents of Comparative Examples 1 to 3. I understood it. In addition, although the comparative example 1 used nickel sulfate as a nickel raw material, the pH of the acidic solution containing nickel is as low as 2.5, and the comparative example 2 uses nickel nitrate as a nickel raw material, and nickel. The pH of the acidic solution containing nickel is as low as 1.3, and Comparative Example 3 uses nickel sulfate as the nickel raw material, but the pH of the acidic solution containing nickel is as high as 4.1.

Claims (2)

  A method for producing a hydrocarbon desulfurization agent containing nickel and molybdenum by mixing an acidic solution containing nickel and a basic solution containing molybdenum and reacting to produce a precipitate, the nickel containing molybdenum A method for producing a hydrocarbon desulfurization agent having a pH of 6 to 8 and a temperature of 50 to 90 ° C after mixing an acidic solution and the basic solution containing molybdenum, the acidic solution containing nickel However, the manufacturing method of the desulfurization agent for hydrocarbons characterized by using nickel sulfate as a raw material of nickel, and adjusting so that pH may be set to 3-4. The desulfurizing agent for hydrocarbon is based on a desulfurizing agent, nickel is 50 to 95% by mass in terms of oxide (NiO), molybdenum is 0.5 to 25% by mass in terms of oxide (MoO ₃ ), and inorganic oxide The method for producing a hydrocarbon desulfurization agent according to claim 1, comprising: