JPH09157661A - Hydrodesulfurization catalyst for light oil and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrodesulfurization catalyst for light oil and a process capable of effectively removing sulfur compounds which are hardly removed in the region of deep desulfurization. SOLUTION: This is a catalyst wherein 1-10 (mass)%, based on total catalyst as oxides, of at least one of Co and Ni, 1-5% of P, 10-25% of Mo and W that satisfies W/Mo=0.01-0.2 are supported on an inorganic oxide carrier and the average hole size of the catalyst is 60-90Å. This catalyst is prepared by supporting (1) at first step P, Mo and W at second step and at least one or both of Co and Ni at third step or (2) four ingredients comprising at least one or both of Co and Ni, and Mo, W and P in one step.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas oil hydrodesulfurization catalyst capable of effectively removing a sulfur compound which is considered to be difficult to desulfurize in a deep desulfurization region, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Hydrocarbon oils generally contain sulfur compounds, and when these oils are used as fuel, the sulfur present in the sulfur compounds is converted to sulfur oxides and discharged into the atmosphere. Therefore, considering the pollution of the air when it burns,
It is desirable that the sulfur content in the hydrocarbon oil be as low as possible. Reduction of sulfur content can be achieved by catalytic hydrodesulfurization of hydrocarbon oils.

Further, due to environmental problems, regulations on sulfur content in commercial gas oil are becoming more stringent (0.2 w of conventional products).
t% to 0.05 wt%), further deep desulfurization is required, and 4-MDBT (4 methyldibenzothiophene) and 4,6- It is necessary to treat a hardly desulfurizable substance centered on DMDBT (4,6 dimethyldibenzothiophene).

Catalysts used for hydrodesulfurization intended for such deep desulfurization include metals of Group VI (hereinafter referred to as "Group 6") of the periodic table and Group VIII of the periodic table (hereinafter referred to as "Group 6"). Group 8 ”) is a catalyst having a metal as an active metal and supported on an oxide carrier such as alumina, magnesia, or silica.
In general, Mo is used as the Group 6 metal, and Co or Ni is used as the Group 8 metal.

Further, in order to improve the activity of hydrodesulfurization and hydrocracking of heavy oil using this catalyst, that is, CoMo-based catalyst or NiMo-based catalyst, addition of phosphorus, boron, etc. has been reported (JP-A-52-52). 13503).

[0006] Further, a technique of incorporating tungsten into a combined system catalyst of Groups 6 and 8 for hydrodesulfurization of hydrocarbon oil has been reported (Applied Catalog).
lysis A: General 109 (1994)
195-210). However, this technique is mainly intended for deasphaltening heavy oil, and is not intended for deep desulfurization of light oil and desulfurization of difficult-to-desulfurize substances.

[0007] In addition, the present inventors have filed Japanese Patent Application No. 7-168.
In 296, it is reported that a certain level of desulfurization can be achieved in the desulfurization of light oil by using a CoMoW-based or NiMoW-based catalyst. Based on this technique, it is desired to provide a catalyst having even higher desulfurization activity from the viewpoints of reducing the amount of catalyst in an actual device and relaxing reaction conditions.

[0008]

OBJECT OF THE INVENTION The present invention has an even more excellent desulfurization activity in the deep desulfurization region in order to meet the above-mentioned requirements.
An object is to provide a hydrodesulfurization catalyst for light oil and a method for producing the same.

[0009]

SUMMARY OF THE INVENTION As a result of repeated studies to achieve the above object, the present inventors have found that tungsten and phosphorus (hereinafter,
(W may be described as “W” or “P”) is carried in the same catalyst, and the effect of hydrodesulfurization of the hardly desulfurizable sulfur compound is exerted. First, Mo and W are supported in a fixed ratio on the supported carrier,
After that, either or both of Co and Ni are supported, or (2) P is simultaneously impregnated and supported on Mo and / or Co and / or Ni at a fixed ratio, and (3) It was found that those having a specific average pore diameter can effectively remove even the hardly desulfurizable sulfur compound in the deep desulfurization region.

The present invention is based on the above findings,
[1] Cobalt and / or nickel on an inorganic oxide carrier on a catalyst basis in an amount of 1 to 1 in terms of oxide.
10 mass%, phosphorus is 1 to 5 mass% in terms of oxide, molybdenum is 10 to 25 mass% in terms of oxide, and the mass ratio of tungsten to molybdenum is 0.01 to in terms of oxide.
A hydrodesulfurization catalyst for light oil, which comprises supporting tungsten so as to have an amount of 0.2 and having an average pore diameter of the catalyst of 60 to 90Å. Is carried out, molybdenum and tungsten are carried at the second stage, and cobalt and / or nickel is carried at the third stage, a method for producing a hydrodesulfurization catalyst for light oil, [3] Inorganic The gist is a method for producing a hydrodesulfurization catalyst for light oil, which comprises simultaneously supporting one or both of cobalt and nickel, molybdenum, tungsten, and phosphorus on an oxide carrier in one step.

In the present invention, the catalyst carrier is a crystalline inorganic oxide. As this inorganic oxide, various ones can be used, and examples thereof include silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-
Beryllia, silica-titania, silica-boria, alumina-zirconia, alumina-titania, alumina-boria, alumina-chromia, titania-zirconia, silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, silica- Magnesia-zirconia, etc., which are used alone or
More than one species can be used in combination.

Among these inorganic oxides, preferred are alumina, silica-alumina, alumina-titania, alumina-boria, and alumina-zirconia, and γ-alumina is particularly preferred.

The above carrier (or the catalyst of the present invention comprising the above carrier) includes montmorillonite, kaolin,
One or more clay minerals such as halosite, bentonite, adabargite, bauxite, kaolinite, nacrite and anoxite may be contained.

The specific surface area of the carrier composed of these inorganic oxides is not particularly limited, but is 250 m ² / g.
The above is preferred. The pore volume of the carrier is not particularly limited, but is preferably 0.4 to 1.2 cc / g. The average pore size of the carrier is also not particularly limited, but in order to set the average pore size of the catalyst of the present invention to 60 to 90Å,
It is preferable to use the one having 0 to 130Å.

The catalyst of the present invention is one in which cobalt and / or nickel, molybdenum, tungsten, and phosphorus are supported in specific amounts on the above carrier.

The amount of cobalt and / or nickel supported on the catalyst is 1 to 1 in terms of oxide.
It is 10% by mass, preferably 3 to 7% by mass. 1% by mass of cobalt and / or nickel
If it is less than 10% by weight, hydrodesulfurization activity is not expressed
Even if it is more, the corresponding improvement in the activity cannot be obtained,
It is economically disadvantageous.

The supported amount of phosphorus is 1 to 5% by mass, preferably 1.5 to 3% by mass, calculated as oxide, based on the catalyst.
When the amount of phosphorus is too small, tungsten cannot be effectively made highly dispersed, while when it is too large, the pore volume of the catalyst after preparation tends to be too small and the catalyst activity tends to be lowered.

The supported amount of molybdenum is 10 to 25% by mass, preferably 15 to 20% by mass. If the amount of molybdenum is less than 10% by mass, the absolute amount of molybdenum that acts as an active point will be too small, and hydrodesulfurization activity will not be expressed. And the hydrodesulfurization activity is reduced.

The amount of tungsten supported is such that the mass ratio of tungsten to molybdenum is WO ₃ : MoO ₃ =
0.01: 1 to 0.20: 1, preferably 0.02: 1
~ 0.1: 1, more preferably 0.04: 1 to 0.0
The amount should be 7: 1. If the mass ratio of WO ₃ and MoO ₃ (hereinafter, simply referred to as “ratio”) is less than 0.01, the nuclear hydrogenation activity of the above-mentioned difficult-to-desulfurize substances will not be expressed,
When it is more than 0.2, the amount of tungsten to be carried is too large, and even if phosphorus is carried near the upper limit of the above-mentioned carrying amount range, agglomeration of metallic tungsten occurs, which is different from the case of molybdenum. Similarly, the number of active sites is reduced, and the efficiency of removing hardly desulfurizable substances in hydrodesulfurization is reduced.

In the catalyst of the present invention, the specific surface area and the pore volume are not particularly limited as long as it can function as a catalyst, but in order to effectively remove the hardly desulfurizable substance, the specific surface area is It is preferably 200 m ² / g or more and the pore volume is 0.4 to 1.2 cc / g.

The average pore diameter is 60 to 90Å, preferably 70 to 80Å. When the average pore size is less than 60Å, the reactants are less likely to diffuse into the pores, and therefore the nuclear hydrogenation reaction of the hardly desulfurizable substance does not occur effectively, and the physical properties required to function as a catalyst ( (Specific surface area, pore volume)
In order to obtain the above, problems such as insufficient mechanical strength will occur in manufacturing.

When it is larger than 90Å, although the diffusivity of the reaction substance into the pores is good, the effective surface area of the catalyst becomes small, so that it is also difficult to remove the hardly desulfurizable substance. More specifically, when performing a deep desulfurization reaction, it is important to reduce the sulfur content to below a predetermined level without deteriorating the hue of the produced gas oil. Many. In this case, since the contact time becomes long, it is not necessary to use a catalyst having an average pore size larger than 90Å to improve the diffusivity of the reactants, and conversely, to use a catalyst having an average pore size larger than 90Å. When it is used, the contact effect between the reaction substance diffused in the pores and the reaction surface is reduced, and the improvement in activity cannot be observed.

The pore size distribution of the catalyst (that is, the proportion of pores having an average pore size of ± 15Å) is 70
% Or more, preferably 80% or more is suitable. If the value of the pore size distribution is small and the distribution curve is broad, the number of effective pores for the reaction will be relatively small even if the average pore size is ideal, and a highly active catalyst will be obtained. Can not be expected.

The above-mentioned catalyst of the present invention can be produced by an appropriate method. However, it is particularly preferable that the catalyst of the present invention be produced by the production method of the present invention which will be described in detail below. It is preferable for obtaining high activity.

In the production method of the present invention, each component is loaded on the above carrier in the following order: (1) Phosphorus is loaded in the first stage, and molybdenum and tungsten are loaded in the second stage, Cobalt and / or nickel is carried in the third step (hereinafter, referred to as "method (1)").
Or (2) to support at once (hereinafter,
"(2) method").

An impregnation method is generally employed as a method for supporting the above-mentioned components. In the method (1), drying and firing are carried out each time each solution in which the compound of each component is dissolved is impregnated. . Specifically, after impregnating with a solution of phosphorus in the first step, drying and firing, impregnating with a solution of molybdenum and tungsten in the second step, and after drying and firing, both cobalt and nickel in the third step. Alternatively, one of the solutions is impregnated, followed by drying and firing. In the method (2), a solution in which the above components are dissolved is impregnated, followed by drying and firing.

In the impregnation sequence of the above method (1), when the impregnation of phosphorus is the second or third stage, phosphorus is selectively present at the catalytically active sites on the already supported molybdenum, tungsten, cobalt or nickel. Adsorbed on
Not only is it not possible to obtain high dispersion of tungsten with phosphorus, but it is rather a catalyst with low activity. Therefore,
It is important that phosphorus is impregnated in the first stage or simultaneously with these components so that tungsten is highly dispersed by phosphorus and a highly active catalytic action is exhibited.

In the compounds of the above respective components, various salts can be used as the cobalt or nickel compound, and examples thereof include carbonates, acetates, nitrates, lead sulfates and phosphates. Alone or 2
More than one species can be used in combination.

Examples of the phosphorus compound include orthophosphoric acid, metaphosphoric acid, triphosphoric acid, tetraphosphoric acid and polyphosphoric acid. These phosphoric acids can be used alone or in combination of two or more kinds. It is preferable to use orthophosphoric acid.

As the compound of molybdenum, various compounds can be used, for example, (NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H.
Ammonium molybdate represented by ₂ O, H ₃ (PM
o ₁₂ O ₄₀ ) .30H ₂ O, molybdophosphoric acid, MoO ₃ , molybdenum oxide, and the like.
These may be used alone or in combination of two or more.

Various compounds can be used as the tungsten compound, for example, 5 (NH ₄ ) ₂ O.12WO ₃
· 11H ammonium paratungstate represented by _{2 O, (NH 4) 2} W 4 O ammonium metatungstate represented by 13 · 8H _{2 O,} tungstic acid represented by _{H 2 WO 4, H 3 (} PW Examples thereof include tungstophosphoric acid represented by ₁₂ O ₄₀ ) .30H ₂ O, and these can be used alone or in combination of two or more kinds.

The amount of each of these components dissolved in each impregnating solution of molybdenum, tungsten, cobalt, nickel, or phosphorus (that is, the concentration of each component in each solution) is not particularly limited, but impregnation operation and dry firing are performed. Considering the easiness of the operation, it is suitable that the amount of the solvent in each of these impregnation operations is 50 to 150 g, preferably 70 to 90 g with respect to 100 g of the carrier.
Considering this amount of solvent, the ratio of each component to the catalyst after calcination may be the above-mentioned amount in terms of oxide.

The impregnation conditions for impregnating each of the above-mentioned solutions are not particularly limited, but usually, in any of the steps of the method (1) and the method (2), the temperature is 10 to 10.
Suitably, the temperature is 100 ° C., preferably 10 to 50 ° C., more preferably 15 to 30 ° C., and the time is 15 minutes to 3 hours, preferably 20 minutes to 2 hours, more preferably 30 minutes to 1 hour. Is suitable. At this time, it is preferable to carry out stirring.

In both the method (1) and the method (2), the drying and firing are performed as follows. Drying can be performed by various drying methods such as air drying, hot air drying, heat drying, and freeze drying. The temperature during firing is 400 to 500 ° C., preferably 450 to
500 ° C. is suitable, and the time is 2 to 10 hours, preferably 3 to 5 hours.

The shape of the catalyst of the present invention described above is not particularly limited, and various shapes used for ordinary catalyst shapes can be used. For example, a four-lobed shape or a cylindrical shape can be used. it can. The size of the catalyst of the present invention is usually
1/10 to 1/22 inch is suitable.

The catalyst of the present invention may be used as a mixture with a known catalyst or a known inorganic oxide carrier.

The feed oil which can be hydrodesulfurized using the catalyst of the present invention includes straight-run gas oil obtained by atmospheric distillation of crude oil,
Alternatively, cracked gas oil produced from a catalytic cracker, vacuum gas oil obtained by vacuum distillation, and the like can be mentioned. In general, the boiling point is 150 to 600 ° C, preferably 200 to 400 ° C.
A sulfur content of 3% by mass or less, preferably 2.5% by mass or less, and a density (15 ° C.) of 0.94 g / cm ³ or less are suitable.

When the catalyst of the present invention is used in a catalytic hydrotreating desulfurization unit on a commercial scale, it is used as a fixed bed, a moving bed or a fluidized bed, to which gas oil to be desulfurized is introduced, and high temperature is applied. , Under high pressure (equivalent hydrogen partial pressure),
Perform the desired desulfurization. Most commonly, the catalyst is maintained as a fixed bed with light oil passing downward through the fixed bed. The catalyst can be used in a single reactor or even in several reactors in series. In particular, when the feedstock oil is a relatively heavy gas oil, it is preferable to use a multistage reactor.

As a preferred example of the reaction, light oil is used at a temperature of about 200 to 500 ° C., more preferably about 250 to 40 ° C.
At 0 ° C., the liquid hourly space velocity is about 0.05 to 5.0 hr ⁻¹ , more preferably about 0.1 to 4.0 hr ⁻¹ , and the hydrogen partial pressure is about 1 to 20 MPa, more preferably about 3 to 10 MPa.
Then, contact with the catalyst.

[0040]

[Examples] The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 In an Erlenmeyer flask, 3.9 g of phosphoric acid was dissolved in 75 g of water and stirred to prepare an aqueous solution of phosphoric acid.

In another Erlenmeyer flask, 32.7 g of ammonium molybdate and 1.5 g of tungstic acid were added to water so that the WO ₃ / MoO ₃ ratio in the catalyst which was the final product of this example was 0.05. It was dissolved in 75 g, and ammonia water was further added and stirred until ammonium molybdate and tungstic acid were completely dissolved to prepare a mixed aqueous solution of ammonium molybdate and tungstic acid.

In another Erlenmeyer flask, cobalt nitrate 27
g was dissolved in 75 g of water and stirred to prepare an aqueous solution of cobalt nitrate.

The above aqueous phosphoric acid solution was placed in a round-bottomed flask to have a specific surface area of 336 m ² / g and a pore volume of 0.71 cc /
g, and 100 g of a γ-alumina carrier having an average pore diameter of 85Å. The impregnation temperature was room temperature and the impregnation time was 1 hour. After this, dry (air dry) and 500 ° C in a muffle furnace.
Calcination was carried out for 4 hours to complete the first stage impregnation and loading (impregnation and loading of phosphoric acid aqueous solution).

The catalyst after the completion of the impregnation in the first step was impregnated with a mixed aqueous solution of ammonium molybdate and tungstic acid in an eggplant-shaped flask under the same conditions as in the impregnation operation in the first step. Dry firing under the same conditions as dry firing,
The second stage impregnation and loading (impregnation and loading of a mixed aqueous solution of molybdenum and tungsten) was completed.

The catalyst after the completion of the second stage impregnation was impregnated with an aqueous cobalt nitrate solution in an eggplant type flask under the same conditions as in the first stage impregnation operation, and under the same conditions as in the first stage dry firing. Dry calcination was performed to complete the third stage impregnation and loading (impregnation and loading of an aqueous cobalt solution), and catalyst A was manufactured.

Example 2 Example 1 was changed except that 32.7 g of ammonium molybdate was replaced with 16.4 g and tungstic acid 1.5 g was replaced with 0.2 g so that the WO ₃ / MoO ₃ ratio became 0.01.
A catalyst B was produced in the same manner as in.

EXAMPLE 3 32.7 g of ammonium molybdate was replaced with 40.9 g, 1.5 g of tungstic acid was replaced with 7.5 g, and cobalt nitrate 2 was added so that the WO ₃ / MoO ₃ ratio was 0.20.
A catalyst C was produced in the same manner as in Example 1 except that 27 g of nickel nitrate was used instead of 7 g of nickel nitrate.

Example 4 A catalyst D was produced in the same manner as in Example 1 except that 1.5 g of tungstic acid was changed to 0.6 g so that the WO ₃ / MoO ₃ ratio became 0.02.

Example 5 A catalyst E was produced in the same manner as in Example 1 except that 1.5 g of tungstic acid was changed to 3.0 g so that the WO ₃ / MoO ₃ ratio became 0.10.

Example 6 In an Erlenmeyer flask, 2.0 g of phosphoric acid, 38.0 g of molybdophosphoric acid, 1.7 g of tungstophosphoric acid, and cobalt acetate 24.1 so that the WO ₃ / MoO ₃ ratio was 0.05.
g was dissolved in 75 g of water and stirred to prepare a four-component mixed aqueous solution.

In an eggplant-shaped flask, 100 g of a γ-alumina carrier having a specific surface area of 336 m ² / g, a pore volume of 0.71 cc / g and an average pore diameter of 85Å was impregnated with the above aqueous solution. The impregnation temperature was room temperature and the impregnation time was 1 hour.
Then, it was dried (air-dried) and calcined in a muffle furnace at 500 ° C. for 4 hours to produce a catalyst F.

Example 7 A catalyst G was produced in the same manner as in Example 6 except that 2.0 g of phosphoric acid was replaced with 10.0 g.

Example 8 A catalyst H was produced in the same manner as in Example 6 except that 2.0 g of phosphoric acid was replaced with 3.2 g.

Example 9 A catalyst I was produced in the same manner as in Example 6 except that 2.0 g of phosphoric acid was replaced with 6.0 g.

Example 10 A catalyst was prepared in the same manner as in Example 1 except that 1.5 g of tungstic acid was changed to 1.2 g and 27 g of cobalt nitrate was changed to 16 g so that the WO ₃ / MoO ₃ ratio became 0.04. J was manufactured.

Example 11 A catalyst was prepared in the same manner as in Example 1 except that 1.5 g of tungstic acid was replaced with 2.1 g and 27 g of cobalt nitrate was replaced with 38 g so that the WO ₃ / MoO ₃ ratio became 0.07. K was produced.

Example 12 Tungstic acid (1.5 g) was replaced with 2.1 g, cobalt nitrate (27 g) was replaced with cobalt nitrate (13 g) and nickel nitrate (14 g) so that the WO ₃ / MoO ₃ ratio was 0.07. Is 241 m ² / g, pore volume is 0.75 cc
/ G, a catalyst L was produced in the same manner as in Example 1 except that a γ-alumina carrier having an average pore diameter of 92A was used.

Comparative Example 1 A catalyst M was produced in the same manner as in Example 1 except that phosphorus impregnation was not performed.

Comparative Example 2 A catalyst N was produced in the same manner as in Example 1 except that impregnation with tungstic acid was not carried out.

Comparative Example 3 1.5 g of tungstic acid was added to 3.0 g, and 3.9 g of phosphoric acid was added.
In the same manner as in Example 1 except that 20 g of catalyst O
Was manufactured.

Comparative Example 4 A catalyst P was produced in the same manner as in Example 1 except that 1.5 g of tungstic acid was replaced with 0.15 g so that the WO ₃ / MoO ₃ ratio became 0.005.

Comparative Example 5 A catalyst Q was produced in the same manner as in Example 1 except that 1.5 g of tungstic acid was changed to 7.5 g so that the WO ₃ / MoO ₃ ratio was 0.25.

Comparative Example 6 A catalyst R was produced in the same manner as in Example 1 except that 32.7 g of ammonium molybdate was replaced with 13.1 g so that the WO ₃ / MoO ₃ ratio was 0.13.

Comparative Example 7 A catalyst S was produced in the same manner as in Example 1 except that 32.7 g of ammonium molybdate was replaced with 49.1 g so that the WO ₃ / MoO ₃ ratio was 0.03.

Comparative Example 8 The same procedure as in Example 1 was carried out except that the aqueous solution of cobalt was used for the first step, the mixed solution of molybdenum and tungsten was used for the second step, and the aqueous solution of phosphorus was used for the third step. Catalyst T
Was manufactured.

Comparative Example 9 Specific surface area of 190 m ² / g, pore volume of 0.71 cc /
A catalyst U was produced in the same manner as in Example 1 except that a γ-alumina carrier having an average pore size of 101Å g was used.

The compositions of the catalysts A to U produced in Examples 1 to 12 and Comparative Examples 1 to 9 are shown in Table 1, and their properties are shown in Table 2.

[0069]

[Table 1]

[0070]

[Table 2]

Catalyst A produced in the above Examples and Comparative Examples
~ U was used to carry out the hydrodesulfurization reaction of light oil under the reaction conditions shown in Table 3.

[0072]

[Table 3]

The performance of the catalyst was evaluated by operating under the above reaction conditions, measuring the sulfur content after passing oil for 100 hours, determining the reaction rate constant based on the following equation, and setting the value of catalyst M to 10
The relative evaluation was set to 0. The results are shown in Table 4.

[0074]

(Equation 1)

[0075]

[Table 4]

[0076]

According to the present invention, due to the synergistic effect of molybdenum, tungsten, and tungsten and phosphorus which are active metal species in the same catalyst, the desulfurization specific activity obtained from the rate constant under the reaction conditions can be applied to the conventional catalyst. It can be significantly higher in comparison. As a result, according to the present invention, it is possible to inexpensively produce a fuel oil having a low sulfur content, such as reducing the size of an actual reactor and reducing the amount of catalyst, which is extremely effective in practice.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Etsuo Suzuki 1134-2 Gongendo, Satte City, Saitama Prefecture Cosmo Research Institute Co., Ltd. R & D Center (72) Inventor Osamu Chiyoda Gongendo, Satte City, Saitama Prefecture 1134-2 Cosmo Research Institute Co., Ltd. R & D Center (72) Inventor Hitomi Inoue Saitama Prefecture Satte City Gongendo 1134-2 Cosmo Research Institute R & D Center

Claims (3)

[Claims] 1. An inorganic oxide carrier, wherein 1 to 10% by mass of cobalt and / or nickel is converted to oxide, 1 to 5% by mass of oxide is converted, and molybdenum is oxidized to the inorganic oxide carrier. 10 to 25 mass% in terms of material, and tungsten so that the mass ratio of tungsten and molybdenum is 0.01 to 0.20 in terms of oxide, and the average pore diameter of the catalyst is 60 to 90Å. A gas oil hydrodesulfurization catalyst characterized by: 2. The inorganic oxide carrier is characterized in that phosphorus is loaded in the first step, molybdenum and tungsten are loaded in the second step, and cobalt and / or nickel is loaded in the third step. A method for producing a hydrodesulfurization catalyst for diesel oil. 3. A method for producing a hydrodesulfurization catalyst for light oil, which comprises simultaneously supporting one or both of cobalt and nickel, and molybdenum, tungsten and phosphorus on an inorganic oxide carrier in one step.