JP2008291146A - Porous desulfurization agent and hydrocarbon oil desulfurization method using the same - Google Patents

Abstract

The present invention provides a desulfurization agent capable of desulfurizing a hydrocarbon oil stably and economically over a long period of time under specific conditions.
SOLUTION: It contains not more than 33% by weight of nickel, not less than 30% by weight of zinc, 0.1 to 9.0% by weight of alkaline earth metal, and has a specific surface area of not less than 30 m ² / g. It is a porous desulfurization agent. The porous desulfurization agent has an alkaline earth metal content of 0.1 to 9.0% by mass in the case of calcium, 0.1 to 9.0% by mass in the case of strontium, and 0 in the case of barium. It is preferable to contain 0.1-1.5 mass%, and it is preferable to manufacture by a coprecipitation method.
[Selection figure] None

Description

  The present invention relates to a porous desulfurization agent for removing sulfur contained in hydrocarbon oil, and a hydrocarbon oil desulfurization method using the porous desulfurization agent.

In the 21st century automobiles and their fuels, dealing with environmental issues is a major issue. From the viewpoint of reducing CO ₂ emissions, which are global warming gases, and so-called automobile exhaust emissions such as NOx, the sulfur content of the fuel Reduction is increasingly required. Specifically, the sulfur content of gasoline and light oil is regulated to sulfur-free (sulfur content of 10 ppm by mass or less), and further low sulfur content, that is, zero sulfur (sulfur content of 1 ppm by mass or less) fuel oil is also sought. It has been.

  Gasoline, light oil, etc. by applying hydrodesulfurization methods (eg, desulfurization in high-temperature and high-pressure hydrogen atmospheres using alumina catalysts supporting cobalt, nickel and molybdenum), which is a desulfurization technique that has been mainly used in the past In order to remove the sulfur compounds remaining in the fuel oil and reduce the sulfur content to 10 ppm by mass or less, and further to 1 ppm by mass or less, the hydrodesulfurization reaction, which is a high temperature / high pressure reaction, has a higher temperature / pressure higher than before. Therefore, energy consumption is increased and hydrogen consumption is enormous. Further, in the above hydrodesulfurization, if an attempt is made to react under mild conditions by reducing the space velocity, a huge amount of catalyst is required. Therefore, when the hydrodesulfurization reaction method is applied, any increase in cost is inevitable in any case. Furthermore, when the above hydrodesulfurization is applied, the gasoline base material is hydrogenated to the olefin content, resulting in a large octane loss.

  In response to this problem, a desulfurization agent in which nickel is supported on a mixture of zinc oxide, alumina and nacre has been proposed as a desulfurization agent for desulfurizing catalytic cracked gasoline while suppressing loss of octane number (Patent Document 1). ). However, since this desulfurizing agent has a small specific surface area, a sufficient desulfurization level cannot be obtained, and a high reaction temperature of 300 ° C. or higher is required.

  On the other hand, by repeating the step of adsorbing the sulfur compound by contacting the hydrocarbon oil with the adsorbent under specific conditions and the step of desorbing the sulfur compound from the adsorbent by passing hydrogen through the adsorbent, There has been proposed a method for continuously reducing the sulfur content contained in hydrocarbon oil that is a base material of gasoline while suppressing unnecessary reactions such as olefin hydrogenation (Patent Document 2). However, the method using such an adsorbent also needs to be frequently regenerated by being in the absence of hydrogen or by desulfurization at room temperature, and is always a satisfactory method from the viewpoint of economical desulfurization. is not.

  On the other hand, the present inventors have found that catalytic cracked gasoline can be highly desulfurized by desulfurization under specific conditions using a desulfurization agent containing nickel and zinc (Patent Documents 3 and 4). ). However, this method requires a relatively high reaction temperature of 300 ° C., which is not sufficient from the viewpoint of economical desulfurization.

JP 2005-522536 Gazette JP 2003-277768 A International Publication No. 2005/044959 Pamphlet JP 2006-31663 A

  As described above, a method for stably and economically desulfurizing the sulfur content of hydrocarbon oil under relatively mild conditions up to 10 ppm by mass and even 1 ppm by mass has not been established yet. Then, this invention makes it a subject to provide the desulfurization agent which can desulfurize hydrocarbon oil stably and economically over a long period of time on specific conditions.

  As a result of earnest research to solve the above problems, the present inventors have found that the sulfur content can be stably reduced for a long period of time by treating hydrocarbon oil with a specific porous desulfurization agent under specific conditions. The headline and the present invention were reached.

That is, the present invention
(1) Porous characterized in that it contains 33% by mass or less of nickel, 30% by mass or more of zinc, 0.1 to 9.0% by mass of alkaline earth metal, and has a specific surface area of 30 m ² / g or more. It is a quality desulfurization agent.
(2) The porous desulfurization agent according to (1), wherein the alkaline earth metal is at least one selected from the group consisting of calcium, strontium, and barium.
(3) The content of the alkaline earth metal is 0.1 to 9.0% by mass for calcium, 0.1 to 9.0% by mass for strontium, and 0.1 to 1 for barium. The porous desulfurization agent according to (1) or (2), which is contained in an amount of 0.5% by mass.
(4) The porous desulfurization agent according to any one of (1) to (3), which is produced by a coprecipitation method.
(5) Hydrocarbon oil containing 2 mass ppm or more of sulfur content in the presence of hydrogen and the porous desulfurization agent according to any one of (1) to (4), temperature 50 to 300 ° C., pressure 0.2 It is a desulfurization method for hydrocarbon oils that are brought into contact under conditions of ˜5.0 MPa and a liquid space velocity exceeding 2.0 h ⁻¹ .

  By applying the porous desulfurization agent of the present invention under specific conditions, desulfurization of hydrocarbon oil can be carried out stably and economically over a long period of time.

[Porous desulfurization agent]
The porous desulfurization agent of the present invention contains nickel, zinc, and alkaline earth metal, and is obtained by, for example, precipitating a metal component by coprecipitation method, filtering, washing, molding, and firing. be able to.

  The nickel content with respect to the total mass of the desulfurizing agent is 33% by mass or less, preferably 1 to 20% by mass, more preferably 5 to 20% by mass. Moreover, zinc content with respect to the desulfurization agent total mass is 30 mass% or more, Preferably it is 50-80 mass%, Most preferably, it is 60-80 mass%. Furthermore, the alkaline earth metal content with respect to the total mass of the desulfurizing agent is 0.1 to 9.0% by mass.

  In the porous desulfurizing agent of the present invention, the alkaline earth metal is preferably at least one selected from the group consisting of calcium, strontium and barium. When the alkaline earth metal is calcium, the content of calcium with respect to the total mass of the desulfurizing agent is 0.1 to 9.0% by mass, preferably 0.1 to 5.0% by mass. In the case of strontium, the content of strontium with respect to the total mass of the desulfurizing agent is 0.1 to 9.0% by mass, preferably 0.1 to 5.0% by mass. When the alkaline earth metal is barium, the total amount of the desulfurizing agent is The content of barium with respect to the mass is 0.1 to 1.5 mass%, preferably 0.1 to 1.0 mass%.

  When nickel content exceeds 33 mass% or zinc content is less than 30 mass%, since the lifetime of a porous desulfurization agent becomes short, it is unpreferable. On the other hand, when the nickel content is 20% by mass or less and the zinc content is 50% by mass or more, the lifetime of the porous desulfurization agent is long, the nickel content is 10% by mass or less, and the zinc content is 60% by mass or more. In this case, the lifetime of the porous desulfurizing agent is particularly long. In addition, the total content of nickel and zinc is preferably 20 to 85% by mass, particularly 50 to 80% by mass with respect to the total mass of the desulfurizing agent.

  Furthermore, if the alkaline earth metal content relative to the total mass of the desulfurizing agent is less than 0.1% by mass, the effect of adding alkaline earth metal cannot be obtained, which is not preferable. On the other hand, if the alkaline earth metal content with respect to the total mass of the desulfurization agent exceeds 9.0% by mass, the effect of the alkaline earth metal deposited on the surface hindering the sorption reaction with nickel or zinc is increased and the desulfurization activity is low. In addition, the contents of nickel and zinc in the entire desulfurization agent are reduced accordingly, the contact efficiency with the hydrocarbon oil is lowered, and the life is shortened, which is not preferable. When the alkaline earth metal is calcium, the calcium content with respect to the total mass of the desulfurizing agent is 9.0% by mass or less. When the alkaline earth metal is strontium, the strontium content with respect to the total mass of the desulfurizing agent is reduced. Desulfurization activity of the desulfurization agent by adjusting the content to 9.0% by mass or less, and when the alkaline earth metal is barium, the content of barium with respect to the total mass of the desulfurization agent is 1.5% by mass or less. In addition, the contact efficiency between the active metal and the hydrocarbon oil can be improved, and the life of the desulfurizing agent can be extended.

  Further, the mass ratio of nickel content to zinc content (Ni / Zn) is preferably 1.0 or less, more preferably 0.5 or less, and particularly preferably in the range of 0.05 to 0.35. When the mass ratio of the nickel content to the zinc content exceeds 1.0, the life of the porous desulfurization agent is remarkably shortened, which is not preferable.

  In the porous desulfurization agent of the present invention, the volume of the pores having a pore diameter of 2 to 30 nm is preferably 0.08 to 0.50 mL / g, more preferably 0.08 to 0.20 mL / g. . If the volume of the pores having a pore diameter of 2 to 30 nm is less than 0.08 mL / g, it is not preferable because the space where the desulfurization reaction occurs mainly decreases. In addition, when the volume of the pores having a pore diameter of 2 to 30 nm exceeds 0.50 mL / g, the bulk density of the desulfurizing agent is reduced, and the mass that can be charged in the reactor of a constant volume is reduced, and the life is shortened. Absent. On the other hand, if the volume of the pores having a pore diameter of 2 to 30 nm is 0.50 mL / g or less, a sufficient bulk density can be obtained.

The specific surface area of the porous desulfurization agent of the present invention is preferably 30 m ² / g or more, more preferably 45~600m ² / g. If the specific surface area of the porous desulfurizing agent is less than 30 m ² / g, the contact efficiency between nickel and zinc and hydrocarbon oil is lowered, and the life is shortened, which is not preferable. The specific surface area can be measured by a BET method using a nitrogen adsorption / desorption method.

  The porous desulfurization agent of the present invention is preferably used after being treated at 200 to 350 ° C. in a hydrogen atmosphere. A treatment temperature under a hydrogen atmosphere of less than 200 ° C. is not preferable because nickel is difficult to be reduced. On the other hand, when the treatment temperature exceeds 350 ° C., nickel is sintered and the activity is lowered, which is not preferable.

  The porous desulfurization agent of the present invention is preferably prepared by a coprecipitation method. The coprecipitation method uses a porous carrier such as alumina impregnated with metal components such as zinc, nickel, and alkaline earth metals, and supports nickel and zinc, which is more effective for desulfurization than the production method in which it is fired. Since it can be contained in a large amount in the agent, it is possible to extend the life of the desulfurizing agent. On the other hand, the method of impregnating the zinc oxide support with nickel and an alkaline earth metal is not preferable because the specific surface area and the pore volume are reduced due to the blockage of the pores of the zinc oxide support and the desulfurization activity is lowered. Furthermore, a method in which a support containing zinc and nickel is impregnated with an alkaline earth metal is not preferable because the specific surface area and the pore volume are reduced due to the blockage of the pores of the support and the desulfurization activity is lowered.

  In the present invention, a desulfurization agent containing nickel, zinc and alkaline earth metal can be prepared by mixing an acidic solution containing nickel, zinc and alkaline earth metal with an alkaline solution. The acidic solution containing nickel, zinc, and alkaline earth metal can be obtained by dissolving zinc, nickel, alkaline earth metal nitrate, acetate, etc. with water. Moreover, although sodium carbonate, ammonium carbonate, etc. can be used as said alkaline solution, it is preferable to use sodium carbonate especially.

  Although the precipitate produced | generated at said process needs to be dried after filtration, 100-200 degreeC is preferable for drying temperature. Subsequent firing is not necessarily required, but the temperature for firing is preferably 400 ° C. or lower, more preferably 350 ° C. or lower. When the firing temperature exceeds 400 ° C., the crystallization of nickel, zinc and alkaline earth metal oxides formed by decomposition of the salt proceeds, the crystallite diameter of nickel, zinc and alkaline earth metal increases, and the specific surface area increases. Since it falls, it is not preferable.

  In the present invention, the porous desulfurization agent refers to a porous desulfurization agent having a sulfur sorption function. The porous desulfurization agent having a sulfur sorption function mentioned here is to fix sulfur atoms in the organic sulfur compound to the desulfurization agent and to remove organic sulfur from hydrocarbon residues other than the sulfur atoms in the organic sulfur compound. A porous desulfurization agent having a function of desorbing from a desulfurization agent by cleavage of a carbon-sulfur bond in a compound. When the hydrocarbon residue in the organic sulfur compound is eliminated, hydrogen present in the system is added to the carbon whose bond with sulfur is cleaved. Therefore, a hydrocarbon compound obtained by removing a sulfur atom from an organic sulfur compound and adding hydrogen thereto is obtained as a product. However, the hydrocarbon compound from which the sulfur atom is removed may give a product that has undergone a reaction such as hydrogenation, isomerization, or decomposition. On the other hand, since sulfur is fixed to the desulfurizing agent, unlike a hydrorefining treatment, sulfur compounds such as hydrogen sulfide are not generated as a product. Therefore, when recycling and using hydrogen, the installation which removes hydrogen sulfide becomes unnecessary, and it is economically advantageous.

[Hydrocarbon oil]
The hydrocarbon oil as a raw material to be subjected to the desulfurization method according to the present invention is not particularly limited as long as it is a hydrocarbon oil containing a sulfur content, but preferably contains 2 ppm by mass or more of sulfur content, more preferably 2 to 1, 000 mass ppm, more preferably 2 to 100 mass ppm, particularly preferably 2 to 40 mass ppm. When the sulfur content exceeds 1,000 ppm by mass, the life of the desulfurizing agent is shortened, which is not preferable.

Specific examples of the hydrocarbon oil as a raw material include base materials corresponding to LPG fraction, gasoline fraction, naphtha fraction, kerosene fraction, light oil fraction, etc. that are generally produced in refineries and the like. . The LPG fraction is a fuel gas mainly composed of propane, propylene, butane, butylene, and industrial raw material gas. The LPG fraction is usually stored in a liquid phase in a spherical tank under pressure as called LPG (liquefied petroleum gas) or at a low temperature near atmospheric pressure. Stored in state. The gasoline fraction is generally composed mainly of hydrocarbons having 4 to 11 carbon atoms, and has a density (15 ° C.) of 0.783 g / cm ³ or less, a 10% distillation temperature of 24 ° C. or more, and a 90% distillation temperature of 180%. It is below ℃. The naphtha fraction is composed of gasoline fraction components (hole naphtha, light naphtha, heavy naphtha, or hydrodesulfurized naphtha thereof) or a raw material for catalytic reforming (desulfurized heavy naphtha) for producing a gasoline base. The boiling point range is almost the same as that of the gasoline fraction or it is included in the boiling range of the gasoline fraction. Therefore, it is often used in the same meaning as the gasoline fraction. The kerosene fraction is generally a hydrocarbon mixture with a boiling range of 150-280 ° C. The gas oil fraction is generally a hydrocarbon mixture having a boiling range of 190 to 350 ° C.

  The hydrocarbon oil as a raw material is not limited to those produced at refineries and the like, but contains 2 to 1,000 ppm by mass of sulfur, petroleum (hydrocarbon) gas produced from petrochemicals, A fraction having a similar boiling range may be used. Examples of hydrocarbon oils that can be preferably used include those obtained by further fractionating hydrocarbons obtained by pyrolysis or catalytic cracking of heavy oils.

  Particularly preferred as raw material hydrocarbon oils to be subjected to the desulfurization method according to the present invention are catalytic cracked gasoline and light oil fractions. Since catalytically cracked gasoline contains a large amount of olefins, hydrorefining with a hydrodesulfurization catalyst that is generally performed hydrogenates the olefin content and greatly reduces the octane number. However, in the desulfurization method of the present invention, almost no olefin content is present. Not hydrogenated. In addition, since the gas oil fraction contains a large amount of aromatics, the amount of hydrogen consumed is large because the aromatics are hydrogenated in the hydrorefining using a hydrodesulfurization catalyst that is generally performed. In the desulfurization method, the aromatic content is hardly hydrogenated. However, in the case of light oil fractions, it usually contains about 10,000 mass ppm of sulfur, so the sulfur content is reduced to some extent by hydrorefining with a hydrodesulfurization catalyst, specifically to 2 to 40 mass ppm. It is preferable to apply the desulfurization method of the present invention. When there is much sulfur content, the lifetime of a desulfurization agent will fall large.

[Desulfurization reaction conditions]
As conditions for bringing the hydrocarbon oil into contact with the porous desulfurizing agent, the reaction temperature is preferably 50 to 300 ° C, more preferably 100 to 300 ° C. When the reaction temperature is less than 50 ° C., the desulfurization rate decreases, and it is not preferable because desulfurization cannot be efficiently performed. On the other hand, when the reaction temperature exceeds 300 ° C., the desulfurizing agent is sintered, and both the desulfurization rate and the desulfurization capacity are lowered, which is not preferable. If the reaction temperature is 100 ° C. or higher, the desulfurization rate is sufficiently high and desulfurization can be performed efficiently.

  The reaction pressure is preferably 0.2 to 5.0 MPa in gauge pressure, more preferably 0.2 to 3.0 MPa, particularly 0.2 to 2.0 MPa. When the reaction pressure is less than 0.2 MPa, the desulfurization rate decreases, and it is not preferable because desulfurization cannot be efficiently performed. On the other hand, when the reaction pressure exceeds 5.0 MPa, side reactions such as hydrogenation of olefins and aromatics contained in the hydrocarbon oil proceed, which is not preferable. If the reaction pressure is 3.0 MPa or less, side reactions such as hydrogenation of olefins and aromatics can be sufficiently suppressed, and if it is 2.0 MPa or less, these side reactions can be reliably prevented.

Furthermore, the liquid hourly space velocity (LHSV) is preferably more than 2.0 h ⁻¹ , more preferably 2.1 h ⁻¹ or more. The LHSV is preferably 50.0 h ⁻¹ or less, more preferably 20.0 h ⁻¹ or less, and even more preferably 10.0 h ⁻¹ or less. If the LHSV is 2.0 h ⁻¹ or less, the amount of oil passing is limited or the desulfurization reactor becomes too large, so it is not preferable because it cannot economically desulfurize. On the other hand, if LHSV exceeds 50.0 h ⁻¹ , a contact time sufficient for desulfurization cannot be obtained, and the desulfurization rate decreases, which is not preferable. In addition, if LHSV is 2.1 h ⁻¹ or more, desulfurization can be performed sufficiently economically, and if LHSV is 20.0 h ⁻¹ or less, the contact time is sufficiently long so that the desulfurization rate is improved. If it is 10.0 h ⁻¹ or less, the desulfurization rate is particularly high.

  The hydrogen / oil ratio is not particularly limited, but is preferably 0.01 to 200 NL / L, more preferably 0.01 to 100 NL / L, and more preferably 0.1 to 100 NL in the case of a fraction containing a large amount of olefins such as catalytically cracked gasoline. / L is particularly preferred. If the hydrogen / oil ratio is less than 0.01 NL / L, desulfurization does not proceed sufficiently, which is not preferable. On the other hand, when the hydrogen / oil ratio exceeds 200 NL / L, the ratio of side reactions such as hydrogenation of olefins increases, which is not preferable.

  In the case of a fraction containing polycyclic aromatics such as a light oil fraction, the hydrogen / oil ratio is preferably 1 to 1,000 NL / L, more preferably 10 to 500 NL / L, and particularly preferably 50 to 400 NL / L. preferable. When the hydrogen / oil ratio is less than 1 NL / L, desulfurization does not proceed sufficiently, which is not preferable. On the other hand, if the hydrogen / oil ratio is 1,000 NL / L, the hydrogen flow rate becomes too high, and the hydrogen compressor becomes undesirably large.

  The hydrogen used may contain impurities such as methane, but the hydrogen purity is preferably 50% by volume or more, more preferably 80% by volume or more, and particularly preferably 95% or more so that the hydrogen compressor does not become too large. If the sulfur compound such as hydrogen sulfide is contained in hydrogen, the life of the desulfurizing agent is shortened. Therefore, the sulfur content in hydrogen is preferably 1,000 ppm by volume or less, more preferably 100 ppm by volume or less, particularly 10 volumes. ppm or less is preferable.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

Example 1
A solution prepared by dissolving 104 g of sodium carbonate in 250 mL of water is heated to 60 ° C., and 210 g of zinc nitrate hexahydrate, 23 g of nickel nitrate hexahydrate, and 3.8 g of calcium nitrate tetrahydrate are dissolved in 300 mL of water. The solution was added dropwise. The resulting precipitate was filtered and washed with water. Then, after drying at 120 degreeC for 16 hours, it baked at 300 degreeC for 3 hours, and obtained the desulfurization agent A. The metal content was measured by the alkali melting ICP method, the pore volume was measured by the BJH method by nitrogen adsorption / desorption method, and the specific surface area was measured by the BET method by nitrogen adsorption / desorption method.

The reactor was filled with desulfurizing agent A, subjected to reduction treatment at 300 ° C. for 16 hours in a hydrogen stream, and then an oil passage test for hydrocarbon oil was performed. As the hydrocarbon oil, catalytic cracked heavy gasoline having a sulfur content of 12.5 ppm by mass was used. Under the conditions of a reaction temperature of 120 ° C., a reaction pressure of 0.3 MPa, a hydrogen / oil ratio of 100 NL / L, and an LHSV of 10.0 h ⁻¹ , hydrocarbon oil flow was started from the reactor inlet. The sulfur content of the reactor exit product oil 6 hours after the start of oil passing was 0.1 mass ppm or less. Moreover, the sulfur content of the reactor outlet production oil 24 hours after the start of oil passing was 0.3 mass ppm. The sulfur content was measured according to ASTM D5453 (ultraviolet fluorescence method). The results are shown in Table 1.

(Example 2)
A desulfurizing agent B was obtained in the same manner as in Example 1 except that 193 g of zinc nitrate hexahydrate, 21 g of nickel nitrate hexahydrate, and 19 g of calcium nitrate tetrahydrate were used. Further, an oil passage test of hydrocarbon oil was performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
Desulfurizing agent C was obtained in the same manner as in Example 1 except that 169 g of zinc nitrate hexahydrate, 18 g of nickel nitrate hexahydrate, and 40 g of calcium nitrate tetrahydrate were used. Further, an oil passage test of hydrocarbon oil was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 4
In the same manner as in Example 1, except that 212 g of zinc nitrate hexahydrate and 23 g of nickel nitrate hexahydrate were added, and 1.6 g of strontium nitrate was added instead of calcium nitrate tetrahydrate. Obtained. Further, an oil passage test of hydrocarbon oil was performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 5)
Desulfurizing agent E was obtained in the same manner as in Example 4 except that 204 g of zinc nitrate hexahydrate, 22 g of nickel nitrate hexahydrate, and 8.1 g of strontium nitrate were used. Further, an oil passage test of hydrocarbon oil was performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 6)
Desulfurizing agent F was obtained in the same manner as in Example 4, except that 197 g of zinc nitrate hexahydrate, 21 g of nickel nitrate hexahydrate, and 13 g of strontium nitrate were used. Further, an oil passage test of hydrocarbon oil was performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 7)
The desulfurizing agent G was added in the same manner as in Example 1 except that 210 g of zinc nitrate hexahydrate and 23 g of nickel nitrate hexahydrate were added, and 3.8 g of barium nitrate was added instead of calcium nitrate tetrahydrate. Obtained. Further, an oil passage test of hydrocarbon oil was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
Desulfurizing agent H was obtained in the same manner as in Example 1 except that 214 g of zinc nitrate hexahydrate and 23 g of nickel nitrate hexahydrate were used and calcium nitrate tetrahydrate was not used. Further, an oil passage test of hydrocarbon oil was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
A desulfurizing agent I was obtained in the same manner as in Example 1 except that 114 g of zinc nitrate hexahydrate, 15 g of nickel nitrate hexahydrate, and 62 g of calcium nitrate tetrahydrate were used. Further, an oil passage test of hydrocarbon oil was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 3)
Desulfurizing agent J was obtained in the same manner as in Example 4, except that 193 g of zinc nitrate hexahydrate, 21 g of nickel nitrate hexahydrate, and 17 g of strontium nitrate were used. Further, an oil passage test of hydrocarbon oil was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 4)
A desulfurizing agent K was obtained in the same manner as in Example 7, except that 208 g of zinc nitrate hexahydrate, 23 g of nickel nitrate hexahydrate, and 6.3 g of barium nitrate were used. Further, an oil passage test of hydrocarbon oil was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 5)
26 g of the desulfurizing agent A obtained in Example 1 was impregnated with 7.7 mL of a solution in which 2.0 g of calcium nitrate tetrahydrate was dissolved in water to make 10 mL, dried at 120 ° C. for 16 hours, The desulfurizing agent L was obtained by firing for a period of time. Further, an oil passage test of hydrocarbon oil was performed in the same manner as in Example 1. The results are shown in Table 1.

  As shown above, it can be seen that the desulfurization agents of the examples according to the present invention can exhibit sufficient desulfurization performance even at a reaction temperature of 200 ° C. or lower.

Claims (5)

A porous desulfurization agent characterized by containing not more than 33% by weight of nickel, not less than 30% by weight of zinc and 0.1 to 9.0% by weight of an alkaline earth metal and having a specific surface area of not less than 30 m ² / g. .   The porous desulfurization agent according to claim 1, wherein the alkaline earth metal is at least one selected from the group consisting of calcium, strontium, and barium.   The content of the alkaline earth metal is 0.1 to 9.0% by mass in the case of calcium, 0.1 to 9.0% by mass in the case of strontium, and 0.1 to 1.5% by mass in the case of barium. The porous desulfurization agent according to claim 1 or 2, wherein the content is%.   The porous desulfurization agent according to any one of claims 1 to 3, wherein the porous desulfurization agent is produced by a coprecipitation method. A hydrocarbon oil containing 2 mass ppm or more of a sulfur content in the presence of hydrogen and the porous desulfurization agent according to any one of claims 1 to 4, a temperature of 50 to 300 ° C, a pressure of 0.2 to 5.0 MPa, a liquid A method for desulfurizing a hydrocarbon oil in which contact is made under a condition where the space velocity exceeds 2.0 h- ¹ .