JP2005193209A - Hydrogenating desulfurization catalyst of petroleum hydrocarbon and hydrogenating desulfurizing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogenating desulfurization catalyst that is capable of an extremely high degree of desulfurization that sulfur content is 10 ppm or less and has a high denitrification activity also on a nitrogen compound that is an inhibitor to the desulfurization reaction. <P>SOLUTION: The hydrogenating desulfurization catalyst of the petroleum type hydrocarbon, wherein at least one kind of metal selected from group 8 metal in the periodic law as an active metal and at least one kind of metal selected from group 6A in the periodic law as an active metal are contained in the scope of 0.105 to 0.265 in the mole ratio of [group 8 metal oxide]/[group 6A metal oxide] in an inorganic porus carrier containing an alumina, and the content of group 6A metal is 20 to 30 mass% to the weight of the catalyst in oxide conversion. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a hydrodesulfurization catalyst and hydrodesulfurization method for petroleum hydrocarbon oil. Specifically, the present invention relates to a method for desulfurizing petroleum hydrocarbons using a specific catalyst and under specific reaction conditions when desulfurizing petroleum hydrocarbons containing sulfur.

  In recent years, awareness of environmental problems and air pollution is increasing, and the sulfur content in transportation fuel oil has attracted particular attention. For example, gasoline engines are strongly required to improve fuel efficiency not only from resource protection and economic aspects but also from the viewpoint of suppressing carbon dioxide emissions. For this reason, development and popularization of new combustion systems such as lean burn engines and direct injection engines are underway. However, in such an engine, the component composition of the exhaust gas does not necessarily apply to the composition that functions of the conventional ternary exhaust gas purification catalyst, and further improvement is required. It has been pointed out that the sulfur content in gasoline affects such a new exhaust gas cleaning device / catalyst.

On the other hand, exhaust gas discharged from diesel vehicles using light oil as fuel contains fine particles called particulates in addition to chemical substances such as SOx and NOx, and there is concern about damage to health. For this reason, it has been proposed to install a particulate removal filter such as DPF or a device having a particulate combustion removal function at the rear stage of the engine as a measure for removing particulates, and its application to diesel engine vehicles is being studied. Further, for NOx, a reduction removal catalyst or the like is being developed. However, these apparatuses and catalysts cause poisoning and deterioration due to SOx generated by changing the sulfur content in the fuel oil. In diesel vehicles such as transport trucks, which have a longer mileage than gasoline vehicles, the deterioration of these exhaust gas cleaning devices and catalysts is a more serious problem. In order to solve such problems, it is strongly desired to reduce the sulfur content in light oil as much as possible.
Furthermore, there is a need to reduce the aromatic compounds in fuel oil, which is said to be a causative agent of particulates.

  Since the light oil fraction obtained by distillation of crude oil or heavy oil cracking reaction contains about 1 to 3% by mass of sulfur, it is usually used as a light oil base material after hydrodesulfurization treatment. The sulfur compounds present in petroleum-based hydrocarbons are mostly in the form of aromatic compounds such as thiophene, benzothiophene, dibenzothiophene and their derivatives. In particular, sulfur compounds having a high boiling point include those having a developed heterocyclic structure or a structure having a large number of alkyl groups in the aromatic ring. Such compounds are particularly poor in reactivity, such as a sulfur content of 10 mass ppm, This is an obstacle when desulfurization is advanced to an extremely low sulfur concentration region. It is fully conceivable that the catalytic activity function required for the removal of such sulfur compounds differs from that in the conventional region.

  In the hydrodesulfurization reaction of petroleum hydrocarbons, it is known that there is a reaction mechanism that directly extracts sulfur atoms from sulfur compounds and a reaction mechanism that involves a reaction in which an aromatic ring adjacent to the sulfur atom is hydrogenated. . In particular, when desulfurizing a compound having poor desulfurization reactivity, a route via the latter aromatic ring hydrogenation is considered necessary. Furthermore, not only a hydrogenation reaction but also a decomposition reaction that can efficiently cleave a sulfur-carbon bond is strongly required.

Conventionally, as a hydrodesulfurization catalyst in petroleum refining, the active metal species and the amount and ratio of the metal have been optimized within the range conceivable in the past. Under such circumstances, the catalyst containing active metals such as cobalt-molybdenum and nickel-molybdenum is vigorously optimized. In hydrodesulfurization catalysts using these metals as active metals, cobalt / molybdenum or nickel / molybdenum are used. It has been said that there is an optimum point with the highest desulfurization activity in the molar ratio of molybdenum in the range of 0.3 to 1 (see, for example, Non-Patent Document 1 and Non-Patent Document 2). However, as a result of various studies by the inventors, in order to reach a very high desulfurization depth of 10 ppm by mass or less, such a conventional hydrotreating catalyst having a metal ratio has sufficient desulfurization activity. It became clear that it was not possible to demonstrate. This strongly suggests that a function different from the catalytic activity function required at the conventional desulfurization level as described above is necessary.
Henrik Topsoe et al., “Industrial & Engineering Chemistry Fundamentals” (USA), American Chemical Society, 1986, Vol. 25, p. 25-36 Emmanuel Lecrenay, Shinya Sakanishi, Isao Mochida, “Catalysis Today” (Netherlands), Elsevier, 1997, Vol. 39, p. 13-20

  As a method of achieving a high desulfurization activity, a method of increasing the number of active sites by increasing the amount of active metal supported can be considered. However, even when a porous support mainly composed of alumina and having a high surface area is used, active metal is supported. There is a limit to the amount, and if it is excessively supported, the active metal aggregates and the activity is reduced. Furthermore, there is a technical limit that the active metal is excessively supported and the pores of the catalyst are blocked, so that sufficient activity cannot be exhibited, or the decrease in activity becomes significant.

  An object of the present invention is to provide a catalyst and a hydrodesulfurization method which have a very high desulfurization activity and can achieve a very high desulfurization depth of 10 ppm by mass or less. Furthermore, the present invention also provides a catalyst having a high denitrification activity for a nitrogen compound which is a representative desulfurization reaction inhibitor.

  As a result of intensive studies on such problems, the inventors have completed the present invention. That is, the present invention relates to an inorganic porous carrier containing alumina, at least one metal selected from Group 8A metals and at least one metal selected from Group 8A metals in the periodic table as an active metal. Is contained in the range of 0.105 to 0.265 in a [Group 8 metal oxide] / [Group 6A metal oxide] molar ratio, and the content of the Group 6A metal is converted to oxide The hydrodesulfurization catalyst for petroleum hydrocarbon oils is characterized by being in the range of 20 to 30% by mass with respect to the catalyst weight.

  The present invention also relates to a hydrodesulfurization method for petroleum hydrocarbon oil, characterized in that petroleum hydrocarbon oil is hydrodesulfurized using the hydrodesulfurization catalyst.

  The present invention is described in detail below.

  The catalyst in the present invention uses an inorganic porous material containing alumina as a carrier. The content of alumina is preferably 80% by mass or more based on the carrier, more preferably 85% by mass or more, and still more preferably 90% by mass or more. Alumina is a porous carrier particularly suitable for providing a pore volume suitable for diffusing hydrocarbon molecules having a boiling point of 230 to 380 ° C., and is sufficient when the content of alumina is less than 80% by mass. It is difficult to obtain a large support pore volume.

  The support preferably contains at least one selected from Si, Ti, Zr, Mg, Ca and B as a component other than alumina in the range of 1 to 10% by mass in terms of oxide. As for content, 1.2-9 mass% is more preferable, and 1.5-8 mass% is still more preferable. As these elements, Si, Ti, and Zr are preferable, and Si and Ti are particularly preferable. These elements may be contained in combination, and it is particularly preferable to combine Si and Ti. Although the mechanism of the effect expression by these elements has not been elucidated, it forms a complex oxide state with alumina, and synergizes with the active metal supported at the molar ratio to promote the cleavage of the carbon-sulfur bond. It seems that the desulfurization activity is improved. When the content is less than 1% by mass, the desulfurization activity decreases, and when the content exceeds 10% by mass, the acidity of the carrier becomes strong, and there is a concern that undesirable side reactions such as decomposition may occur. is there.

  The method for preparing alumina as the main component of the carrier is not particularly limited. For example, it can be obtained via an alumina intermediate obtained from a method of neutralizing or hydrolyzing aluminum salt and aluminate, or a method of hydrolyzing aluminum amalgam or aluminum alcoholate. Moreover, you may use a commercially available alumina intermediate body and boehmite powder.

  On the other hand, there is no particular limitation on the carrier preparation method for any carrier constituent component other than alumina, such as an oxide of an element selected from Si, Ti, Zr, Mg, Ca and B. For example, there is a method of adding oxides, hydroxides, nitrates, sulfates or other salt compounds of these elements in a solid or solution state at any stage of preparing alumina. Alternatively, only alumina may be once fired and then impregnated and supported in a solution state. Preferably, it is added at any stage before firing the alumina.

  In the present invention, as the active metal, at least one metal selected from Group 8 metal of the periodic table and at least one metal selected from Group 6A metal of the periodic table are used. The Group 8 metal includes Co and Ni, and the Group 6A metal includes Mo and W. Co-Mo, Ni-Mo, Co-W, Ni-W, Co-Ni-Mo, and Co-Ni-W are preferable as a combination, and a combination of Co-Mo or Ni-Mo is more preferable, and Co-Mo is most preferable. preferable. The content of the Group 6A metal is preferably in the range of 20 to 30% by mass of the catalyst weight in terms of oxide, more preferably in the range of 21 to 26% by mass, and even more preferably 22 to 25% by mass. Range. When it is less than 20% by mass, there are few active sites and sufficient desulfurization activity cannot be exhibited. When the amount is more than 30% by mass, metal agglomeration occurs, and the desulfurization activity may be lowered.

  The supporting ratio of the Group 8 metal to the Group 6A metal needs to be in the range of 0.105 to 0.265 in terms of a [Group 8 metal oxide] / [Group 6A metal oxide] molar ratio. is there. Preferably it is 0.110-0.260, More preferably, it is 0.115-0.250, More preferably, it is 0.120-0.220. When the molar ratio is less than 0.105, the cocatalyst effect of the Group 8 metal cannot be sufficiently exerted and the desulfurization activity is lowered. On the other hand, when the molar ratio is larger than 0.265, it is considered that sufficient hydrogenation activity and carbon-sulfur cleavage activity cannot be exhibited, and the desulfurization activity is lowered.

  The total content of the Group 8 metal and the Group 6A metal is preferably 22% by mass or more, more preferably 23% by mass or more, and further preferably 25% by mass or more based on the catalyst weight in terms of oxide. When the amount is less than 22% by mass, there is a concern that sufficient desulfurization activity cannot be exhibited because there are few active metals.

  Moreover, it is preferable that phosphorus is supported. The amount of phosphorus supported on the carrier is in the range of 0.105 to 0.255, preferably 0.120 to 0.240, in a molar ratio of [phosphorus pentoxide] / [Group 6A metal oxide]. More preferably, it is 0.130-0.205. When the molar ratio is less than 0.105, the effect of phosphorus cannot be sufficiently exhibited. When the molar ratio is more than 0.255, the acid property of the catalyst becomes strong and a decomposition reaction may occur.

  The method for supporting the group 8 metal and the group 6A metal, which are active metal components, on the carrier is not particularly limited, and a known method applied when producing an ordinary hydrodesulfurization catalyst can be used. For example, a method of impregnating a support with a solution containing a salt of an active metal is preferably employed. Further, an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed. For example, the pore-filling method is a method in which the pore volume of the support is measured in advance and impregnated with the same volume of the metal salt solution, but the impregnation method is not particularly limited, and the amount of metal supported Further, it can be impregnated by an appropriate method depending on the physical properties of the carrier.

  The method for supporting phosphorus on the carrier is not particularly limited, and it may be supported in the aqueous solution containing the Group 8 metal and Group 6A metal described above, or sequentially before or after the metal is supported. You may carry. Further, the method described above such as the equilibrium adsorption method is preferably employed as the method for supporting.

  In the hydrodesulfurization catalyst of the present invention, the average pore radius of the catalyst determined by the BET method using nitrogen is preferably in the range of 30 to 45 mm, more preferably in the range of 32 to 40 mm. If it is less than 30 mm, the reaction molecules do not diffuse sufficiently in the pores and the activity becomes low, which is not preferable. On the other hand, if it is larger than 45 mm, the surface area of the catalyst becomes small and sufficient desulfurization activity cannot be exhibited, which is not preferable. The pore volume occupied by the pore radius of 30 mm or less of the catalyst is preferably in the range of 13 to 33% of the total pore volume, more preferably in the range of 15 to 30%, still more preferably 25 to 25%. The range is 30%. The ease of diffusion of reaction molecules in pores having a pore radius of 30 mm or less is inferior to pores larger than this, but the contribution to the desulfurization reaction cannot be ignored. If it is less than 13%, the effective catalyst surface area decreases. There is a concern that the activity will decrease. On the other hand, if it is larger than 33%, there is a concern that the activity may decrease due to the influence of diffusion. The pore volume occupied by the pore radius of 45 mm or more of the catalyst is preferably in the range of 5 to 20%, more preferably in the range of 8 to 15%, and still more preferably in the range of 12 to 15%. is there. The pores in this region are considered to be important pores that influence the degree of arrival of the reactive molecules at the reaction active point, and if it is less than 5%, there is a concern that the diffusion of the reactive molecules is not sufficient and the activity is lowered. is there. However, when the amount is more than 20%, the surface area of the catalyst itself is decreased, and there is a concern that the activity is lowered.

  The catalyst of the present invention is suitable for desulfurization from sulfur molecules having a structure such as thiophenes, benzothiophenes, dibenzothiophenes, and the fraction containing these compounds is a fraction having a boiling point of 230 to 380 ° C. Petroleum hydrocarbon oil containing 80% by volume or more can be suitably used as a raw material oil. In addition, the value of the distillation property shown here is a value measured according to the method described in JIS K 2254 “Petroleum products—evaporation test method”.

  The properties of petroleum hydrocarbon oils of such fractions are generally 20-30% by volume of total aromatics, 0.8-2% by weight of sulfur, and 100-500 ppm by weight of nitrogen. include. In the present invention, such a petroleum hydrocarbon oil can be hydrodesulfurized using the specific catalyst of the present invention to reduce the sulfur concentration to 10 ppm by mass or less, preferably 7 ppm by mass or less. it can.

  Further, by performing hydrodesulfurization treatment using the catalyst of the present invention, the nitrogen concentration can be reduced to 3 mass ppm or less, preferably 1 mass ppm or less.

  In hydrodesulfurization, nitrogen is known to be a catalyst poison. For this reason, if the nitrogen content can be efficiently removed in the hydrodesulfurization step, the operating conditions of the hydrodesulfurization reaction can be made mild, and the operation cost can be reduced. In the present invention, it can be said that a highly effective desulfurization reaction proceeds because the nitrogen concentration of the produced oil can be 3 ppm by mass or less. In other words, when the amount is more than 3 ppm by mass, the reaction inhibition by the nitrogen component is greatly hindered in the reaction tower in which the hydrodesulfurization reaction is proceeding, and the efficient reaction progress is hindered. Long contact time between pressure and catalyst and oil is required.

  In the present invention, the sulfur content (sulfur content) is based on the total amount of petroleum hydrocarbons measured according to the method described in JIS K2541 “Sulfur Content Test Method” or ASTM-D5453. It means the mass content of sulfur. The nitrogen content is the mass content of nitrogen based on the total amount of petroleum hydrocarbons measured in accordance with JIS K2609 “Method for testing nitrogen content” or ASTM-D4629, D-5762. Means.

  In addition, when the petroleum-based hydrocarbon oil serving as the raw material oil contains 80% by volume or more of a fraction having a boiling point of 230 to 380 ° C., it is included in the product oil by hydrodesulfurization treatment using the catalyst of the present invention. The total aromatic content can be reduced to 18% by volume or less, preferably 16% by volume or less. The aromatic content is said to be one of the causes of particulates contained in the exhaust gas of diesel engines. When the total aromatic content exceeds 18% by volume, the generation of particulates tends to increase.

  The total aromatic content in the present invention is a method described in JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” published by the Japan Petroleum Institute. Means the sum of the volume percentage (volume%) of each aromatic content measured according to the above.

  Furthermore, in the case where the petroleum-based hydrocarbon oil as the raw material oil contains a fraction having a boiling point of 230 to 380 ° C. of 80% by volume or more, by performing hydrodesulfurization treatment using the catalyst of the present invention, the hue of the product oil Can be made 1.0 or less in ASTM color. When it exceeds 1.0, the hue as a light oil becomes a hue close to yellow or brown, and the commercial value is lowered. It has been pointed out that the coloration in the hydrodesulfurization treatment is related to the desulfurization reaction temperature, but according to the present invention, such a high reaction temperature and other severe operating conditions are not employed. Diesel oil that is stable and colorless and has high commercial value can be produced.

  In the present invention, the ASTM color means a hue measured in accordance with the method described in JIS K2580 “Color Test Method”.

  In addition, as petroleum-based hydrocarbon oil that is a raw material oil, in addition to a so-called direct distillation system in which crude oil is fractionated to an appropriate boiling range by an atmospheric distillation unit, hydrocracking unit, fluid catalytic cracking unit, coker, etc. What mixed the fraction obtained from a thermal cracking apparatus or another hydrodesulfurization apparatus can also be processed.

In the present invention, hydrodesulfurization treatment of petroleum hydrocarbon oil is performed using the above-described catalyst.
As hydrodesulfurization reaction conditions in the present invention, LHSV is preferably 0.3~2.0h ^-1, more preferably at 0.35~1.7h ^-1, more preferably 0.4～1.2H ^-1 is there. When LHSV is lower than 0.3 h ⁻¹ , the volume of the reaction tower for obtaining a certain oil flow rate becomes extremely large, and therefore a huge capital investment such as installation of a reaction tower may be required. On the other hand, when LHSV is larger than 2.0 h ⁻¹ , the contact time between the catalyst and the oil is shortened, so that the desulfurization reaction does not proceed sufficiently, and the effects of desulfurization and dearomatization may not be exhibited.

  The hydrogen partial pressure is preferably 3 to 8 MPa, more preferably 3.5 to 7 MPa, and still more preferably 4 to 6.5 MPa. If the hydrogen partial pressure is lower than 3 MPa, there is a concern that the effects of desulfurization and dearomatization cannot be exhibited. If the hydrogen partial pressure is higher than 8 MPa, there is a possibility that a large capital investment such as a review of the compressor and equipment strength may be required. Is not preferable.

  The reaction temperature is preferably 300 to 380 ° C. When the reaction temperature is lower than 300 ° C., a sufficient desulfurization reaction rate or aromatic hydrogenation reaction rate may not be obtained, which is not preferable. Moreover, when higher than 380 degreeC, since there exists a possibility of causing the fall of the target fraction yield by the deterioration of the hue of a product oil, or decomposition | disassembly, it is unpreferable.

  The hydrogen / oil ratio is preferably 100 to 500 NL / L. The hydrogen / oil ratio indicates the ratio of the hydrogen gas flow rate to the feed oil flow rate. The higher the hydrogen / oil ratio is, the more hydrogen supply into the system becomes, and the faster the substances that poison the catalytic active sites such as hydrogen sulfide. Since it can be removed out of the system, the reactivity tends to be improved. However, when it exceeds 500 NL / L, the reactivity is improved, but the effect is gradually reduced. Moreover, there is a risk that a large capital investment such as a compressor may be required. On the other hand, when it is less than 100 NL / L, the reactivity is lowered, and there is a possibility that the progress of the desulfurization / dearomatic reaction is not sufficient.

  The catalyst of the present invention has a very high desulfurization activity and can achieve a very high desulfurization depth of 10 ppm by mass or less. In addition, nitrogen compounds that are desulfurization reaction inhibitors also have high denitrification activity.

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

(Example 1)
Water glass No. 3 was added to 1 kg of a sodium aluminate aqueous solution having a concentration of 5% by mass, and the mixture was placed in a container kept at 70 ° C. A solution obtained by adding a titanium (IV) sulfate aqueous solution (24 mass% as TiO ₂ content) to 1 kg of an aqueous aluminum sulfate solution having a concentration of 2.5 mass% was prepared in another container kept at 70 ° C. The solution was dropped into an aqueous solution containing sodium in 15 minutes. The amounts of the water glass and the titanium sulfate aqueous solution were adjusted to the predetermined silica and titania contents. The time when the pH of the mixed solution reached 6.9 to 7.5 was set as the end point, and the resulting slurry product was filtered through a filter to obtain a cake-like slurry. The cake-like slurry was transferred to a container equipped with a reflux condenser, 300 ml of distilled water and 3 g of 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 70 ° C. for 24 hours. The slurry was put into a kneading apparatus, heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product. The obtained kneaded material was extruded into a shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier. An impregnation solution prepared by taking 300 g of the obtained molded carrier, adding molybdenum trioxide, cobalt nitrate (II) hexahydrate, phosphoric acid (concentration 85%) to 150 ml of distilled water and adding malic acid until dissolved. Impregnation while spraying. The amounts of molybdenum trioxide, cobalt nitrate (II) hexahydrate and phosphoric acid used were adjusted to a predetermined loading amount. The impregnated sample was dried at 110 ° C. for 1 hour and then calcined at 550 ° C. to obtain Catalyst A. The physical properties of the prepared catalyst are summarized in Table 1.

(Example 2)
In Example 1, the amounts of cobalt nitrate (II) hexahydrate and molybdenum trioxide were adjusted to predetermined values, and Catalyst B was obtained in the same manner as in Example 1. The physical properties of the prepared catalyst are summarized in Table 1.

(Example 3)
Water glass No. 3 was added to 1 kg of a sodium aluminate aqueous solution having a concentration of 5% by mass, and the mixture was placed in a container kept at 70 ° C. 1 kg of an aluminum sulfate aqueous solution having a concentration of 2.5% by mass was placed in another container kept at 70 ° C. and dropped into the aqueous solution containing sodium aluminate described above over 15 minutes. The amount of water glass was adjusted to a predetermined silica content. The time when the pH of the mixed solution reached 6.9 to 7.5 was set as the end point, and the resulting slurry product was filtered through a filter to obtain a cake-like slurry. The cake-like slurry was transferred to a container equipped with a reflux condenser, 300 ml of distilled water and 3 g of 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 70 ° C. for 24 hours. The slurry was put into a kneading apparatus, heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product. The obtained kneaded material was extruded into a shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier. An impregnation solution prepared by taking 300 g of the obtained molded carrier, adding molybdenum trioxide, cobalt nitrate (II) hexahydrate, phosphoric acid (concentration 85%) to 150 ml of distilled water and adding malic acid until dissolved. Impregnation while spraying. The amounts of molybdenum trioxide, cobalt nitrate (II) hexahydrate and phosphoric acid used were adjusted to a predetermined loading amount. The impregnated sample was dried at 110 ° C. for 1 hour and then calcined at 550 ° C. to obtain Catalyst C. The physical properties of the prepared catalyst are summarized in Table 1.

Example 4
Catalyst D was obtained in the same manner as in Example 3, except that nickel nitrate hexahydrate was used instead of cobalt nitrate (II) hexahydrate used in Example 3. The amount of nickel nitrate hexahydrate used was adjusted to a predetermined loading amount.

(Example 5)
Using a straight-run gas oil (sulfur content 3% by mass) filled with 100 ml of any of catalysts A to D in a reaction tube having an inner diameter of 25 mm and added with dimethyl disulfide so that the sulfur concentration is 3% by mass. The catalyst was presulfided for 4 hours under the conditions of an average catalyst layer temperature of 300 ° C., a hydrogen partial pressure of 6 MPa, LHSV ¹ h ⁻¹ , and a hydrogen / oil ratio of 200 NL / L. After preliminary sulfidation, a Middle East straight oil (10% distillation point 240 ° C., 90% distillation point 340 ° C., sulfur content 1.28 mass%, nitrogen content 210 mass ppm) was reacted at 350 ° C., pressure 5 MPa, Hydrodesulfurization was performed by passing oil under conditions of LHSV1h ⁻¹ and a hydrogen / oil ratio of 200 NL / L. The reaction test results of each catalyst are summarized in Table 2.

(Comparative Example 1)
300 g of the molded carrier obtained in Example 3 was taken, and 150 ml of distilled water was added with molybdenum trioxide, cobalt (II) nitrate hexahydrate, phosphoric acid (concentration 85%), and malic acid was added until dissolved. The impregnation solution was impregnated while spraying. The amounts of molybdenum trioxide, cobalt nitrate (II) hexahydrate and phosphoric acid used were adjusted to a predetermined loading amount. The impregnated sample was dried at 110 ° C. for 1 hour and then calcined at 550 ° C. to obtain Catalyst E. The physical properties of the prepared catalyst are summarized in Table 1.

(Comparative Example 2)
100 ml of catalyst E was filled in a reaction tube having an inner diameter of 25 mm, presulfided under the conditions shown in Example 5, and then hydrodesulfurized under the same conditions as in Example 5. The reaction test results of each catalyst are summarized in Table 2.

Claims (11)

  The inorganic porous carrier containing alumina has at least one metal selected from Group 8 metal of the periodic table as an active metal and at least one metal selected from Group 6A metal of the periodic table [Group 8 metal. Oxide] / [Group 6A metal oxide] in a molar ratio of 0.105 to 0.265, and the content of Group 6A metal in terms of oxide is based on the catalyst weight. A hydrodesulfurization catalyst for petroleum hydrocarbon oil, characterized by being in the range of 20 to 30% by mass.   2. The hydrogen according to claim 1, wherein the inorganic porous carrier contains at least one selected from Si, Ti, Zr, Mg, Ca and B in the range of 1 to 10% by mass in terms of oxide. Hydrodesulfurization catalyst.   The phosphorus is supported on the inorganic porous carrier in a range of 0.105 to 0.255 in a molar ratio of [phosphorus pentoxide] / [Group 6A metal oxide]. The hydrodesulfurization catalyst described in 1.   The Group 8 metal of the periodic table is cobalt and / or nickel, the Group 6A metal is molybdenum and / or tungsten, and the total content of these metals is 22% by mass with respect to the catalyst weight in terms of oxide. It is the above, The hydrodesulfurization catalyst in any one of Claims 1-3 characterized by the above-mentioned.   The average pore radius of the catalyst determined by the BET method using nitrogen is in the range of 30 to 45 mm, the pore volume occupied by the pore radius of 30 mm or less is 13 to 33% of the total pore volume, and the pore radius is 45 mm. The hydrodesulfurization catalyst according to any one of claims 1 to 4, wherein the pore volume occupied is 5 to 20%.   A hydrodesulfurization method for petroleum hydrocarbon oil, comprising hydrodesulfurizing a petroleum hydrocarbon oil using the hydrodesulfurization catalyst according to any one of claims 1 to 5.   The hydrodesulfurization catalytic process according to claim 6, wherein the petroleum hydrocarbon oil is a petroleum hydrocarbon oil containing 80% by volume or more of a fraction having a boiling point of 230 to 380 ° C.   The hydrodesulfurization catalytic method according to claim 6 or 7, wherein the sulfur content of the product oil obtained by the hydrodesulfurization treatment is 10 mass ppm or less and the nitrogen content is 3 mass ppm or less.   The hydrodesulfurization catalytic method according to any one of claims 6 to 8, wherein the total aromatic content of the product oil obtained by the hydrodesulfurization treatment is 18% by volume or less.   The hydrodesulfurization catalytic method according to any one of claims 6 to 9, wherein the hue of the product oil obtained by the hydrodesulfurization treatment is 1.0 or less in terms of ASTM color. Hydrodesulfurization of petroleum hydrocarbon oils under conditions of LHSV 0.3 to 2.0 hr ⁻¹ , hydrogen pressure 3 to 8 MPa, reaction temperature 300 to 380 ° C., hydrogen / oil ratio 100 to 500 NL / L The hydrodesulfurization catalytic method according to any one of claims 6 to 10, wherein the hydrodesulfurization catalytic method is performed.