JP2011157470A - Desulfurizing agent, manufacturing method therefor, and desulfurization method for hydrocarbon oil using this - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a desulfurizing agent capable of stably and economically desulfurizing a hydrocarbon oil under a specific condition for a long period of time. <P>SOLUTION: The desulfurizing agent contains 1-30 mass% of nickel, 30-80 mass% of zinc and 0.1-20 mass% of one kind or more of elements selected from Group 3A and has a specific surface area of 70 m<SP>2</SP>/g or higher. The desulfurizing agent can be manufactured by simultaneously dropwise adding an acidic solution and an alkaline solution containing nickel, zinc and one kind or more of elements selected from Group 3A to water and producing precipitation. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  Gasoline, light oil, etc. by applying the hydrodesulfurization method (for example, desulfurization under high-temperature and high-pressure hydrogen atmosphere using an alumina catalyst 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 containing nickel and zinc oxide has been proposed as a desulfurization agent for desulfurizing catalytic cracked gasoline while suppressing the loss of octane number (Patent Document 1). However, this desulfurization agent has a problem that a sufficient desulfurization level cannot be obtained because of its small specific surface area.

  In response to this problem, a technique has been developed in which a high surface area carrier component such as alumina or silica is added and nickel and zinc oxide are spread on the carrier to increase the surface area. For example, Patent Document 2 below discloses a technique for increasing the surface area by co-precipitation of a nickel component and a zinc component using alumina or pseudoboehmite as a core, and Patent Document 3 below precipitates silica sol. A method of increasing the surface area by mixing in a solution and coprecipitating a silica precursor with a nickel component and a zinc component is disclosed. However, in both cases, since nickel and zinc oxide are spread on a high surface area carrier, the mutual contact area is reduced, and zinc oxide cannot be fully utilized. Further, since the carrier component itself cannot take in sulfur, the life is further shortened when it contains a large amount of carrier component. Furthermore, there is a problem that the nickel component is hardly reduced due to the effect of the carrier.

  On the other hand, the present inventors have found that catalytic cracking gasoline can be highly desulfurized by adding an alkaline earth metal to a desulfurizing agent containing nickel and zinc (Patent Document 4). However, even with this method, it could not be said that sufficient desulfurization levels were obtained.

Japanese Patent Laid-Open No. 6-80972 JP 2004230317 A JP 2008-115309 A JP 2008-291146 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-mentioned problems, the present inventors have been able to stably treat sulfur oil for a long period of time by treating hydrocarbon oil with a specific desulfurizing agent containing one or more elements selected from Group 3A. Has been found to be able to be reduced, leading to the present invention.

That is, the present invention
(1) 1 to 30% by mass of nickel, 30 to 80% by mass of zinc, 0.1 to 20% by mass of one or more elements selected from Group 3A, and a specific surface area of 70 m ² / g or more A desulfurizing agent, characterized by
(2) The above-mentioned (1), wherein an acidic solution containing at least one element selected from nickel, zinc and 3A group and an alkaline solution are simultaneously dropped into water to form a precipitate. A method for producing a desulfurization agent,
(3) Hydrocarbon oil containing 2 mass ppm or more of sulfur content in the presence of the desulfurizing agent and hydrogen described in (1) above, temperature 50 to 300 ° C., pressure 0.2 to 5.0 MPa, liquid space velocity 1. This is a method for desulfurizing a hydrocarbon oil to be contacted under a condition of ⁰ h ⁻¹ or more.

  By applying the desulfurizing 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 without almost hydrogenating the olefin component.

[Desulfurizing agent]
The desulfurizing agent of the present invention contains one or more elements selected from nickel, zinc, and group 3A. For example, a metal component is precipitated by coprecipitation and filtered, washed, molded, fired, and the like. It can be obtained by going through.

  The nickel content with respect to the total mass of the desulfurizing agent is 1 to 30% by mass, preferably 10 to 20% by mass, and more preferably 13 to 16% by mass. Moreover, zinc content with respect to the desulfurization agent total mass is 30-80 mass%, Preferably it is 40-60 mass%, More preferably, it is 45-55 mass%.

  When the nickel content is 30% by mass or less and the zinc content is 30% by mass or more, the life of the desulfurization agent is long, and when the nickel content is 20% by mass or less and the zinc content is 45% by mass or more, desulfurization is performed. The life of the agent is particularly long. In addition, the total total content of nickel and zinc is 35 to 80% by mass, particularly 50 to 75% by mass with respect to the total mass of the desulfurizing agent.

  In the desulfurizing agent of the present invention, the content of one or more elements selected from Group 3A is 0.1 to 20% by mass, preferably 5 to 20% by mass, more preferably, based on the total mass of the desulfurizing agent. 7 to 16% by mass.

  When the content of the group 3A element with respect to the total mass of the desulfurizing agent is 0.1% by mass or more, it is possible to increase the pore volume with a pore diameter of 2 to 30 nm and the specific surface area by making nickel fine particles. The reaction with the compound can be promoted. Further, since the zinc oxide particles are also made fine, the contact area between nickel and zinc oxide can be increased and the movement of sulfur can be promoted. In addition, it is inadequate to acquire said effect as 3A group element content is less than 0.1 mass%. On the other hand, if the content of the group 3A element with respect to the total mass of the desulfurizing agent exceeds 20% by mass, a large amount of the group 3A element oxide exists on the surface of the desulfurizing agent particles, and the reaction between nickel and the sulfur compound or This not only increases the effect of hindering the movement of sulfur and lowers the desulfurization activity, but also reduces the nickel and zinc contents in the entire desulfurization agent, lowering the contact efficiency with hydrocarbon oil and shortening the life . Examples of the group 3A include scandium, yttrium, lanthanum, cerium, praseodymium, neodymium and the like, and cerium is particularly preferable.

  Further, the 3A group element content (molar ratio, 3A group element / Ni) with respect to the nickel content in the desulfurizing agent is preferably 0.01 to 0.6, more preferably 0.1 to 0.55, particularly 0. .15 to 0.50 is preferred. When the 3A group element content (molar ratio) with respect to the nickel content exceeds 0.6, the life of the desulfurizing agent is remarkably shortened, which is not preferable.

  In the desulfurizing agent of the present invention, the crystallite diameter of nickel oxide (NiO) is preferably 5.0 nm or less, more preferably 4.0 nm or less, and the crystallite diameter of zinc oxide (ZnO) is preferably 12 nm or less. More preferably, it is 10 nm or less. When the crystallite diameter of NiO exceeds 5 nm, it is not preferable because the effect of increasing the pore volume and specific surface area with the pore diameter of 2 to 30 nm cannot be obtained. Further, if the crystallite diameter of ZnO exceeds 12 nm, the effect of increasing the contact area between nickel and zinc oxide described above cannot be obtained, which is not preferable.

  The desulfurization agent of the present invention preferably has a pore volume having a pore diameter of 2 to 30 nm of 0.25 to 0.50 mL / g, more preferably 0.25 to 0.35 mL / g. If the volume of the pores having a pore diameter of 2 to 30 nm is less than 0.25 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 desulfurization agent of the present invention is 70m ² / g or more, preferably 90~600m ² / g. When the specific surface area of the porous desulfurization agent is less than 70 m ² / g, the contact efficiency between nickel or zinc oxide and hydrocarbon oil is lowered and the life is shortened. The specific surface area can be measured by a BET method using a nitrogen adsorption / desorption method.

  The desulfurizing 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 desulfurizing agent of the present invention is preferably prepared by a coprecipitation method. The coprecipitation method uses a desulfurization agent that is more effective for desulfurization than a production method in which a porous carrier such as alumina is impregnated with metal components such as zinc, nickel, and a group 3A element, and is fired. Since it can be contained in a large amount, the life of the desulfurizing agent can be extended. On the other hand, the method of impregnating the zinc oxide support with nickel and a group 3A element is not preferable because the specific surface area and the pore volume are reduced due to the clogging of the pores of the zinc oxide support and the desulfurization activity is lowered. Furthermore, a method of impregnating a group 3A element with a desulfurizing agent containing zinc and nickel is not preferable because the specific surface area and the pore volume are reduced due to the clogging of the pores of the carrier and the desulfurization activity is lowered.

  In the present invention, a desulfurization agent containing nickel, zinc and a group 3A element can be prepared by mixing an acidic solution containing nickel, zinc and a group 3A element with an alkaline solution. An acidic solution containing nickel, zinc, and a group 3A element is obtained by dissolving zinc, nickel, a group 3A element nitrate, sulfate, or the like with water. Moreover, although sodium carbonate, ammonium carbonate, etc. can be used as said alkaline solution, it is preferable to use sodium carbonate especially.

  The desulfurization agent of the present invention is a precipitate containing nickel, zinc, and a group 3A element by simultaneously dropping an acidic solution and an alkali solution containing one or more elements selected from nickel, zinc, and a group 3A into water. It is particularly preferred to be prepared by producing In the present invention, the simultaneous dropping of the acidic solution and the alkaline solution means that the acidic solution is dropped while the acidic solution is dropped for a period of 80% by volume or more, preferably 90% by volume or more. It means that the acidic solution is being dropped while the alkaline solution is being dropped while the solution is being dropped and the amount of 80% by volume or more, preferably 90% by volume or more of the alkaline solution is being dropped. In addition, it is not necessary that the start and end of the dropping of the acidic solution and the alkaline solution completely coincide with each other.

  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., crystallization of nickel, zinc, and group 3A element oxide formed by decomposition of the salt proceeds, and the crystallite size of nickel, zinc, and group 3A element oxide increases, and the specific surface area increases. Since it falls, it is not preferable.

  In the present invention, the desulfurizing agent refers to a desulfurizing agent having a sulfur sorption function. The desulfurization agent having a sulfur sorption function here is to fix the sulfur atom in the organic sulfur compound to the desulfurization agent, and for hydrocarbon residues other than the sulfur atom in the organic sulfur compound in the organic sulfur compound. The desulfurization agent has a function of desorbing from the desulfurization agent by cleaving the carbon-sulfur bond. 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 desulfurization agent, unlike a hydrorefining treatment, generation of sulfur compounds such as hydrogen sulfide is not involved as a reaction product. Therefore, when hydrogen in the reaction system is recycled and used, an equipment for removing hydrogen sulfide is unnecessary, which 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 about 10 to 50% by volume of olefin content, hydrorefining using a hydrodesulfurization catalyst generally performed hydrogenates the olefin content and greatly reduces the octane number. In the process, the olefin content is hardly hydrogenated. Therefore, it can be suitably used for hydrocarbon oils containing 10 to 50% by volume, preferably 10 to 30% by volume of olefin.

  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 ppm by mass of sulfur. Therefore, after the sulfur content has been reduced to some extent by hydrorefining with a hydrodesulfurization catalyst, specifically to 2 to 40 ppm by mass. 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. Although there is no restriction | limiting in the aromatic content of the hydrocarbon oil made into the object of this invention, It is suitable also for the hydrocarbon oil which contains an aromatic content 0.1 to 50 volume%, Preferably 0.1 to 45 volume%. Can be used.

[Desulfurization reaction conditions]
As conditions for bringing the hydrocarbon oil into contact with the desulfurizing agent, the reaction temperature is preferably 50 to 300 ° C, more preferably 100 to 300 ° C, and particularly preferably 100 to 200 ° 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 2.0 MPa, and particularly preferably 0.2 to 1.0 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 5.0 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.

Additionally, liquid hourly space velocity of the weight (WHSV) is preferably at 1.0 h ^-1 or more, more preferably 2.0 h ^-1 or more, and still more preferably 3.0 h ^-1 or more. Moreover, WHSV 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 WHSV is less than 1.0 h ⁻¹ , 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, when WHSV 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 WHSV is 2.0 h ⁻¹ or more, desulfurization can be performed sufficiently economically, and if WHSV 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. In addition, WHSV is the weight of the hydrocarbon oil which flowed per hour with respect to the weight of the desulfurizing agent.

  The hydrogen / oil ratio is not particularly limited, but is preferably 0.01 NL / L or more, more preferably 0.1 NL / L or more, and 200 NL / L for a fraction containing a large amount of olefins such as catalytic cracking gasoline. The following is preferable, and 100 NL / L is more preferable. If the hydrogen / oil ratio is less than 0.01 NL / L, desulfurization does not proceed sufficiently, which is not preferable. If the hydrogen / oil ratio exceeds 200 NL / L, side reactions such as hydrogenation of olefins are not preferable.

  In the case of a fraction containing polycyclic aromatics such as a light oil fraction, the hydrogen / oil ratio is preferably 0.1 to 1,000 NL / L, more preferably 1 to 500 NL / L, and more preferably 10 to 400 NL / L. Is particularly preferred. When the hydrogen / oil ratio is less than 0.1 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.

(Desulfurizing agent 1)
An acidic solution A was prepared by dissolving 170.5 g of zinc nitrate hexahydrate, 55.5 g of nickel nitrate hexahydrate, and 15.6 g of cerium nitrate hexahydrate in 300 mL of water. Further, an alkaline solution B in which 103.9 g of sodium carbonate was dissolved in 300 mL of water was prepared. The prepared acidic solution A and alkaline solution B were added dropwise while stirring 600 mL of distilled water at a temperature of 60 ° C. The acidic solution A and the alkaline solution B started dripping almost simultaneously, and the dripping was completed in 60 minutes. Thereafter, stirring was continued for 1 hour. The resulting precipitate was filtered and washed with water. Then, after drying at 120 degreeC for 16 hours, it baked at 350 degreeC for 3 hours, and obtained the desulfurization agent 1. With respect to the obtained desulfurizing agent 1, the metal content was determined by the alkali melting ICP method, and the crystallite diameter of the oxide was determined from the XRD measurement results. NiO was calculated from the (200) plane peak and ZnO was calculated from the (100) plane peak according to Scherrer's formula. The pore volume was measured by the BJH method using a nitrogen adsorption / desorption method, and the specific surface area was measured by the BET method using a nitrogen adsorption / desorption method. The results are shown in Table 1.

(Desulfurizing agent 2)
Same as desulfurizing agent 1 except that 160.7 g of zinc nitrate hexahydrate, 52.3 g of nickel nitrate hexahydrate, and 34.7 g of cerium nitrate hexahydrate were dissolved in 300 mL of water. The desulfurizing agent 2 was obtained by the method described above. Further, the metal content, oxide crystallite diameter, pore volume, and specific surface area of the obtained desulfurizing agent 2 were measured. The results are shown in Table 1.

(Desulfurizing agent 3)
A desulfurizing agent 3 was obtained in the same manner as the desulfurizing agent 1 except that an acidic solution A was prepared by dissolving 178.5 g of zinc nitrate hexahydrate and 58.2 g of nickel nitrate hexahydrate in 300 mL of water. Further, the metal content, oxide crystallite diameter, pore volume, and specific surface area of the obtained desulfurizing agent 3 were measured. The results are shown in Table 1.

Example 1
The reactor was filled with the desulfurizing agent 1 and subjected to reduction treatment at 300 ° C. for 16 hours in a hydrogen stream, and then a hydrocarbon oil permeation test was performed. As hydrocarbon oil, catalytic cracked heavy gasoline (density (15 ° C.): 0.7922 g / cm ³ , 10% distillation temperature: 120.5 ° C., 90% distillation temperature: 190.5 ° C., sulfur content 13 Mass ppm, aromatic content: 42.5% by volume, olefin content: 17.6% by volume, octane number (RON): 86.6) were used. Under the conditions of a reaction temperature of 140 ° C., a reaction pressure of 0.3 MPa, a hydrogen / oil ratio of 100 NL / L, and WHSV = 3.4 h ⁻¹ , hydrocarbon oil was introduced from the inlet of the reactor. As a result, the properties of the desulfurized oil when the desulfurization rate was 50% were as follows: sulfur content 6.5 mass ppm, aromatic content: 43.6 vol%, olefin content: 16.9 vol, octane number (RON) loss: It was 0.1. Moreover, the time (L50) until the desulfurization rate fell below 50% was 1,391 hours.

  The density was measured according to JIS K2249 “Crude oil and petroleum products—density test method”, the distillation property was measured according to JIS K2254 “petroleum product—distillation test method”, and the sulfur content was measured according to ASTM D5453 (ultraviolet fluorescence method). The aromatic content, olefin content, and RON were measured using a Hewlett Packard PIONA device in accordance with JIS K2536-2 (how to obtain all components by gas chromatography). The results are shown in Table 2.

(Example 2)
Using the desulfurizing agent 2, the oil passage test of hydrocarbon oil was carried out in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 1)
Using the desulfurizing agent 3, an oil passage test for hydrocarbon oil was conducted in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 2)
The reactor was filled with a hydrorefining catalyst (manufactured by Advanced Refining Technologies LLC, model number AT-505 (containing Ni and Mo)), and subjected to sulfurization treatment before the reaction was started. The sulfurization treatment was carried out for 8 hours at 320 ° C., 2.0 MPa, WHSV = 3.4 h ⁻¹ using oil obtained by adding 1000 ppm of dimethyl disulfide to catalytic cracked heavy gasoline.
Thereafter, the reaction pressure was set to 2.0 MPa, the reaction temperature was set to 50% (sulfur content 6.5 mass ppm), the hydrogen / oil ratio = 100 NL / L, and WHSV = 3.4 h ⁻¹ . Under the conditions, the same catalytic cracking heavy gasoline as in Example 1 was tested. As a result, the desulfurization rate was 50% when the reaction temperature was raised to 275 ° C. At that time, the aromatic content was 39.7% by volume, the olefin content was 12.2% by volume, and the octane number (RON) loss was 3.0.

  As described above, in the desulfurization using a conventional hydrorefining catalyst, the aromatic content and olefin content are reduced by hydrogenation, whereas the desulfurization agent of the embodiment according to the present invention is a hydrocarbon oil under relatively mild conditions. It can be seen that can be desulfurized stably and economically over a long period of time.

Claims (3)

1 to 30% by mass of nickel, 30 to 80% by mass of zinc, 0.1 to 20% by mass of one or more elements selected from Group 3A, and a specific surface area of 70 m ² / g or more Desulfurizing agent.   2. The desulfurization agent according to claim 1, wherein an acid solution containing at least one element selected from nickel, zinc, and a group 3A and an alkali solution are simultaneously dropped into water to form a precipitate. Production method. A hydrocarbon oil containing 2 mass ppm or more of sulfur content in the presence of the desulfurizing agent and hydrogen according to claim 1, a temperature of 50 to 300 ° C., a pressure of 0.2 to 5.0 MPa, a weight space velocity (WHSV) of 1. A hydrocarbon oil desulfurization method in which contact is made under a condition of ⁰ h ^-1 or more.