JP5372338B2 - Porous desulfurization agent and hydrocarbon oil desulfurization method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a desulfurization agent which can be suitably used for stably and economically desulfurizing a hydrocarbon oil over a long period of time under specific conditions. <P>SOLUTION: The desulfurization agent is a porous desulfurization agent which contains nickel in an amount of not more than 33 mass% and zinc in an amount of not less than 30 mass% wherein a pore volume of pores each having a pore diameter of 2-30 nm is 0.08-0.50 mL/g and a ratio of the pore volume of pores each having a pore diameter of 2-30 nm to the total pore volume is 0.15-1.00. Preferably, the porous desulfurization agent has a crystallite size of a nickel oxide being not more than 7 nm, a crystallite size of a zinc oxide being not more than 20 nm, and a ratio of the crystallite size of the zinc oxide to the crystallite size of the nickel oxide being not less than 2.5. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a porous desulfurizing agent used when desulfurizing a sulfur compound in a hydrocarbon oil and a method for desulfurizing a hydrocarbon oil using the porous desulfurizing 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.

  Conventionally, hydrodesulfurization, which is a desulfurization technique that has been mainly used (for example, desulfurization in a high-temperature, high-pressure hydrogen atmosphere using an alumina catalyst supporting cobalt, nickel, and molybdenum) is applied to gasoline and light oil. 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 Since operation at high pressure is required, energy consumption increases and hydrogen consumption also becomes 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 FCC 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 serving as a gasoline base material while suppressing unnecessary reactions such as olefin hydrogenation (see 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.

  In contrast, the present applicant has found that FCC 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 diligent research to solve the above problems, the present applicants 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) The volume (V2) of pores containing not more than 33% by mass of nickel and not less than 30% by mass of zinc and having a pore diameter of 2 to 30 nm is 0.08 to 0.50 mL / g, The porous desulfurization agent is characterized in that the ratio (V2 / V1) of the pore volume (V2) having a pore diameter of 2 to 30 nm to the volume (V1) is 0.15 to 1.00.
(2) The crystallite diameter (X) of the nickel oxide is 7 nm or less, the crystallite diameter (Y) of the zinc oxide is 20 nm or less, the crystallite diameter (Y) of the zinc oxide and the crystallite of the nickel oxide The porous desulfurization agent according to (1), wherein the ratio (Y / X) of the diameter (X) is 2.5 or more.
(3) Hydrocarbon oil containing 2 mass ppm or more of sulfur content in the presence of the porous desulfurization agent and hydrogen described in (1) or (2) above, temperature 50 to 300 ° C., pressure 0.2 to 5.0 MPa This is a hydrocarbon oil desulfurization method in which the liquid space velocity is contacted under a condition 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 and zinc. For example, the porous desulfurization agent is obtained by precipitating metal components such as zinc and nickel by a 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 1 to 10% 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%. 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.

  The mass ratio of nickel content to zinc content (Ni / Zn) is preferably 0.5 or less, more preferably 0.35 or less, even more preferably in the range of 0.05 to 0.35, and 0.05. A range of ˜0.15 is particularly preferred. When the mass ratio of the nickel content to the zinc content exceeds 0.5, the life of the porous desulfurization agent is remarkably shortened, which is not preferable.

  In the porous desulfurization agent of the present invention, the crystallite diameter (X) of nickel oxide is preferably 7 nm or less, more preferably 5 nm or less, and the crystallite diameter (Y) of zinc oxide is It is preferably 20 nm or less, and more preferably 17 nm or less. When the crystallite diameter of the nickel oxide exceeds 7 nm, the contact efficiency between nickel and hydrocarbon oil decreases and the ability to take in sulfur decreases, which is not preferable. On the other hand, the crystallite diameter of the zinc oxide exceeds 20 nm. And, zinc oxide is not preferable because the efficiency of fixing sulfur is lowered. Moreover, if the crystallite diameter of nickel oxide is 5 nm or less, the contact efficiency between nickel and hydrocarbon oil is high, so the ability to take in sulfur is high, while the crystallite diameter of zinc oxide is 17 nm or less. Zinc oxide is highly efficient in immobilizing sulfur.

  The ratio (Y / X) of the crystallite diameter (Y) of the zinc oxide to the crystallite diameter (X) of the nickel oxide is preferably 2.5 or more, more preferably 3.0 or more. It is preferably 3.5 or more. If the ratio of the crystallite diameter of zinc oxide to the crystallite diameter of nickel oxide is less than 2.5, the contact efficiency between nickel and hydrocarbon oil decreases, and sulfur compounds in hydrocarbon oil are contained in the desulfurizing agent. At the same time, the ability of zinc to be incorporated is decreased, and at the same time, the efficiency of fixing zinc to sulfur is decreased. If the ratio (Y / X) is 3.0 or more, the contact efficiency between nickel and hydrocarbon oil is high, so the ability to take in sulfur from the porous desulfurizing agent is high, and zinc oxide fixes sulfur. In addition, when the ratio is 3.5 or more, the ability of the porous desulfurization agent to take in sulfur and the efficiency of fixing sulfur are particularly high.

  The porous desulfurization agent of the present invention has a pore volume (V2) having a pore diameter of 2 to 30 nm of 0.08 to 0.50 mL / g, 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 0.20 mL / g or less, a sufficient bulk density can be obtained.

  In the porous desulfurization agent of the present invention, the ratio (V2 / V1) of the pore volume (V2) having a pore diameter of 2 to 30 nm with respect to the total pore volume (V1) is preferably 0.15 to 1.00. Is between 0.15 and 0.40. When the ratio (V2 / V1) is less than 0.15, the contact efficiency between the hydrocarbon oil and nickel in the pores deteriorates, or sufficient strength is obtained when the desulfurizing agent is used industrially. Since it disappears, it is not preferable. When the ratio (V2 / V1) is 0.40 or less, a favorable contact efficiency can be obtained by an appropriate combination of pores having a large diameter and small pores.

The specific surface area of the porous desulfurization agent of the present invention is preferably at least 30 m ² / g, more preferably in the range of 50 to 600 m ² / g.

  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 not 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 preparation method by coprecipitation method contains more nickel and zinc effective for desulfurization in the desulfurization agent than the production method in which a porous carrier such as alumina is impregnated with metal components such as zinc and nickel, and is fired. Therefore, the life of the desulfurizing agent can be extended. In addition, the method of impregnating the zinc oxide support with nickel 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.

  In the present invention, an acid solution containing nickel and zinc can be mixed with an alkaline solution to prepare a desulfurization agent containing nickel and zinc. The acidic solution containing nickel and zinc is obtained by dissolving zinc, nickel nitrate, acetate, etc. with water, and the pH is preferably 4.5 or less, more preferably 4.0 or less, particularly preferably. Is 0.5 to 3.0. When the pH of the acidic solution exceeds 4.5, it is not preferable because the nucleation rate in the solution becomes slow and the crystal grows easily, and the degree of dispersion of nickel and zinc becomes low. On the other hand, if the pH of the acidic solution is too low, particularly less than 0.5, the amount of the coprecipitation solution is small, the viscosity is high, the stirring is difficult, and uniform physical properties are difficult to obtain.

  Moreover, although sodium carbonate, ammonium carbonate, etc. can be used for the said alkaline solution, it is preferable to use sodium carbonate especially. The pH of the alkaline solution is preferably 11-13.

  The pH for coprecipitation is preferably 7.0 to 8.0. If the pH during coprecipitation is less than 7.0, a part of nickel does not precipitate, which is not preferable. On the other hand, if the pH at the time of coprecipitation exceeds 8.0, an alkali component tends to remain in the precipitation, which is not preferable. In addition, it is desirable to continuously stir for 1 hour or more after mixing the two solutions. Furthermore, the liquid temperature at the time of coprecipitation is preferably in the range of 50 to 70 ° C. from the viewpoint of the solubility of the alkali component.

  Although the precipitate produced | generated at said process needs to be dried after filtration, 100-200 degreeC is preferable for drying temperature. Moreover, 300-400 degreeC is preferable and the temperature in subsequent baking is 300-350 degreeC more preferable. A calcination temperature of less than 300 ° C. is not preferable because the salt is not completely decomposed when the nickel and zinc components are precipitated. On the other hand, if the firing temperature exceeds 400 ° C., crystallization of nickel and zinc oxide formed by decomposition of the salt proceeds, and the degree of dispersion of nickel with respect to zinc is lowered, which 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 sulfur atoms from the organic sulfur compound 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, the hydrorefining with a hydrodesulfurization catalyst 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 a light oil fraction, since the sulfur content is usually about 10,000 mass ppm, the sulfur content is reduced to some extent by hydrorefining with a hydrodesulfurization catalyst, specifically about 5 to 50 mass ppm. Thereafter, 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 50 to 300 ° C, 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 0.2 to 5.0 MPa, preferably 0.2 to 3.0 MPa, particularly preferably 0.2 to 2.0 MPa in terms of gauge pressure. 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) exceeds 2.0 h ⁻¹ , 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. 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 olefin such as catalytic 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 1000 NL / L, more preferably 10 to 500 NL / L, and particularly preferably 50 to 400 NL / L. 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 1000 NL / L, the hydrogen flow rate becomes too high, and the hydrogen compressor becomes undesirably large.

  The hydrogen to be 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 the hydrogen, the life of the desulfurizing agent is shortened. Therefore, the sulfur content in the hydrogen is preferably 1,000 ppm by volume or less, more preferably 100 ppm by volume or less, especially 10 ppm. A capacity of ppm or less is preferred.

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

Example 1
300 mL of a pH 2.8 solution in which 214 g of zinc nitrate hexahydrate and 23 g of nickel nitrate hexahydrate were dissolved in water was prepared. Further, 250 mL of a pH 12.1 solution in which 106 g of sodium carbonate was dissolved in water was heated to 60 ° C., and the whole amount of the prepared pH 2.8 solution was added dropwise thereto, followed by continuous stirring for 1 hour. The pH after dropping all was 7.5. 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 desulfurizing agent A has a nickel content of 6.9% by mass, a zinc content of 71.0% by mass, a sodium content of 0.01% by mass, and the ratio (mass) of the nickel content to the zinc content is It was 0.097. The ratio of the crystallite diameter of zinc oxide to that of nickel oxide was 3.50. The metal content was measured by the alkali melting ICP method, the crystallite diameter of the oxide was measured by XRD, and the pore volume was measured by the BJH method by nitrogen adsorption / desorption method.

The reactor was filled with desulfurizing agent A, subjected to reduction treatment at 350 ° C. for 16 hours in a hydrogen stream, and then an oil passage test for hydrocarbon oil was performed. As the hydrocarbon oil, cracked gasoline having a sulfur content of 12.5 mass ppm 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. Further, the sulfur content of the reactor outlet produced oil after 24 hours was 0.2 mass ppm. In addition, the sulfur content was measured based on ASTM D 5453 (ultraviolet fluorescence method).

(Example 2)
Using 50 mL of a pH 0.5 solution in which 214 g of zinc nitrate hexahydrate and 23 g of nickel nitrate hexahydrate were dissolved in water, and 250 mL of a pH 12.1 solution in which 106 g of sodium carbonate was dissolved in water, the firing temperature was 350 ° C. A desulfurizing agent B was obtained in the same manner as in Example 1 except that. 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)
Example 2 except that 150 mL of a pH 2.1 solution in which 214 g of zinc nitrate hexahydrate and 23 g of nickel nitrate hexahydrate were dissolved in water and 250 mL of a pH 12.1 solution in which 106 g of sodium carbonate were dissolved in water were used. A desulfurizing agent C was obtained in the same manner as described above. 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
Except for using 1,800 mL of a pH 4.0 solution in which 214 g of zinc nitrate hexahydrate and 23 g of nickel nitrate hexahydrate were dissolved in water, and 250 mL of a pH 12.1 solution in which 106 g of sodium carbonate was dissolved in water. A desulfurizing agent D was obtained in the same manner as in Example 2. 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)
A desulfurizing agent E was obtained in the same manner as in Example 1 except that the firing temperature was 500 ° C. 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)
Except for using 3,000 mL of pH 5.0 solution of 214 g of zinc nitrate hexahydrate and 23 g of nickel nitrate hexahydrate in water and 250 mL of pH 12.1 solution of 106 g of sodium carbonate in water. A desulfurizing agent F was obtained in the same manner as in Example 2. 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 in Table 1, it can be seen that the desulfurization agents of the examples according to the present invention can exhibit a sufficient desulfurization effect even at a reaction temperature of 120 ° C. On the other hand, the desulfurization agent of Comparative Example 1 has too high a calcination temperature in the preparation of the desulfurization agent, so that the crystallite diameters of nickel oxide and zinc oxide are too large. As a result, the pore diameter is 2 to 30 nm. Since the volume of the was too small, the desulfurization effect was very low. In addition, the desulfurization agent of Comparative Example 2 is too high in the pH of the acidic solution used for the preparation of the desulfurization agent, and as a result, the volume of pores having a pore diameter of 2 to 30 nm is insufficient. Desulfurization effect was low compared to the agent.

Claims (3)

  The volume of the pores containing nickel of 33% by mass or less and zinc of 30% by mass or more and having a pore diameter of 2 to 30 nm is 0.08 to 0.50 mL / g, and the pore diameter with respect to the total pore volume is 2 A porous desulfurization agent characterized in that the ratio of the volume of pores of ˜30 nm is 0.15 to 1.00.   The crystallite diameter of nickel oxide is 7 nm or less, the crystallite diameter of zinc oxide is 20 nm or less, and the ratio of the crystallite diameter of zinc oxide to the crystallite diameter of nickel oxide is 2.5 or more. 2. The porous desulfurization agent according to 1. A hydrocarbon oil containing 2 mass ppm or more of sulfur content in the presence of the porous desulfurizing agent and hydrogen according to claim 1 or 2 at a temperature of 50 to 300 ° C, a pressure of 0.2 to 5.0 MPa, and a liquid space velocity of 2 Hydrocarbon oil desulfurization method in which contact is made under conditions exceeding 0.0 h ⁻¹ .