JP2000093804A - Hydrogen treating catalyst for hydrocarbon oil and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a hydrogen treating catalyst so excellent in desulfurization activity as to make the sulfur content of a hydrocarbon oil as low as possible. SOLUTION: At least one selected from the group VIA metallic elements of the Periodic Table at least one selected from the group VIII metallic elements of the Periodic Table, phosphorus and boron are carried on a carrier comprising alumina or an alumina-base inorg. oxide by 10-30 mass%, 1-10 mass%, 1-7 mass% and 0.5-7 mass% (expressed in terms of oxides), respectively, based on the total amt. of the resultant catalyst to obtain the objective hydrogen treating catalyst. The carrier may contain 1-15 mass% zeolite based on the total amt. of the catalyst. The catalyst is produced by impregnating a fluid contg. the components into the carrier.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrotreating catalyst for hydrocarbon oils and a method for producing the same. It relates to a manufacturing method.

[0002]

BACKGROUND ART Each oil fraction obtained by distillation or cracking of crude oil generally contains sulfur compounds, and when these are used as fuel, the sulfur present in the sulfur compounds is converted into sulfur compounds such as oxides. Converted and released into the atmosphere. Therefore, from the viewpoint of preventing air pollution, it is desirable that the hydrocarbon oil used as the fuel oil has as small a sulfur content as possible. In particular, under the recent circumstances where environmental destruction due to acid rain and nitrogen oxides is progressing on a global scale, in order to solve this environmental destruction problem, the sulfur content in hydrocarbon oils must be further reduced. Technology development is desired.

[0003] Conventionally, the reduction of the sulfur content in hydrocarbon oil has been carried out by catalytic hydrodesulfurization of hydrocarbon oil, and the operating conditions of this catalytic hydrodesulfurization, for example, LH
This has been achieved to some extent by making the SV, temperature, pressure, etc. severe. However, under such severe operating conditions, there is a disadvantage that carbonaceous material precipitates on the catalyst and the activity of the catalyst is rapidly reduced. Further, when the hydrocarbon oil is light, there is an adverse effect on properties such as hue stability and storage stability. Thus, there is a limit to the technology for reducing the sulfur content under severe operating conditions. Therefore, the best way is to develop a catalyst with significantly better desulfurization activity.

[0004] Conventional catalysts used for hydrodesulfurization as described above are usually those of Group VIA metals of the periodic table (hereinafter referred to as "metals").
Simply referred to as “Group 6A metal”) and Group VIII metal of the periodic table (hereinafter simply referred to as “Group 8 metal”) as active metals;
A catalyst supported on an oxide carrier such as alumina, magnesia, and silica has a desulfurization activity higher than that of a conventional catalyst. In addition, the periodic table in the present specification refers to the one described on the back of the third printing cover of the popular edition of Chemical Dictionary published by Morikita Publishing Co., Ltd.

[0005] Meanwhile, in a hydrotreating catalyst for hydrocarbon oils, a technique has been proposed in which a component such as boron is added to a carrier and the activity is improved by increasing the number of acid sites. For example, Japanese Patent Publication No. 62-25418,
JP-A Nos. 8645 and 6-319994 disclose a technique in which boria (B ₂ O ₃ ) is contained in a carrier and hydrogenation is performed by the effect of acidity. It is intended for chemical cracking and does not cover light fractions such as atmospheric distillate. Japanese Patent Application Laid-Open No. 1-224049 discloses a technique of impregnating a carrier with a boron component together with an active metal component. However, it is intended for heavy oils such as residual oils, and the average pore diameter becomes as large as 100 ° or more. I have.

[0006]

An object of the present invention is to provide a catalyst in which a hydrodesulfurization active metal component is supported in a more dispersed state than conventional catalysts, and a hydrocarbon oil capable of exhibiting a higher desulfurization activity than conventional catalysts. It is an object of the present invention to provide a hydrotreating catalyst for use and a method for producing the same.

[0007]

Means for Achieving the Object As a result of repeated studies to achieve the above object, the present inventors have found that when alumina, which is usually used for this type of catalyst carrier, is impregnated and supported with a catalytically active component. As the impregnating liquid to be used, first, an impregnating liquid that is easily dispersed in a highly dispersed state (that is, an impregnating liquid containing a phosphorus component and a boron component together with the active components of groups 6A and 8) was found, and then this impregnating liquid was used. As a result of performing the impregnation-supporting operation by using the catalyst, it was found that the catalyst active component could be highly dispersed, and the present invention was proposed.

That is, the present invention relates to [1] a carrier comprising alumina or an inorganic oxide containing alumina as a main component, wherein at least one member selected from the group 6A metal elements is added to the total amount of the catalyst in terms of oxide. 10-30 mass%, at least one selected from Group 8 metal elements is 1-10 mass
s%, 1-7 mass% of phosphorus, and 0.5-7 mass% of boron.
The present invention provides a hydrotreating catalyst for hydrocarbon oil in which a mass% is supported, and in this case, the carrier may contain 1 to 15 mass% of zeolite with respect to the total amount of the catalyst. Also,
In the present invention, [2] a carrier is impregnated with an impregnating liquid containing a phosphorus compound and a boron compound together with at least one compound selected from Group 6A metal elements and at least one compound selected from Group 8 metal elements. The gist of the present invention is also a method for producing the above hydrotreating catalyst for hydrocarbon oils.

The carrier in the present invention comprises alumina or an inorganic oxide containing alumina as a main component. The inorganic oxide containing alumina as a main component refers to an inorganic oxide containing 80% or more, more preferably 90% or more of alumina, assuming that the entire inorganic oxide (including alumina) is 100%. Examples of the inorganic oxide other than alumina include amorphous oxides such as silica, boria, titania, zirconia, magnesia, hafnia, ceria, yttria, niobia, chromia, and thoria. Most preferably, the carrier in the present invention is 100% alumina.
Included, that is, a support made of alumina. These aluminas are more preferably γ-alumina. In addition,
Although zeolite generally falls into the category of inorganic oxides, zeolite is not included in the alumina or the inorganic oxide containing alumina as a main component in the present invention. Therefore,
In the present invention, when zeolite is used as one component of the carrier, it is referred to as a second component, and the content of zeolite is considered separately from alumina. Alumina reduces the entire inorganic oxide to 1
When the content is 80% or more when the content is set to 00%, a sufficient number of basic hydroxyl groups are present on the carrier, and the group 6A element which is an active metal is supported in a highly dispersed state. The dispersibility of the elements is extremely poor, and the group 6A elements are agglomerated, resulting in poor desulfurization activity.

The specific surface area, pore volume, and average pore diameter of the carrier in the present invention are not particularly limited, but the specific surface area is 200 m ² / m in order to obtain a catalyst that can remove even a non-desulfurized substance. g or more, preferably 250 m ² / g
The above is more preferable. The pore volume is 0.3-1.2cm
³ / g are preferred, 0.5 to 1.0 cm ³ / g is more preferable. The average pore size is preferably 50 to 130 °, and 5
0-100 ° is more preferred.

When the carrier contains zeolite as the second component, 1 to 15 mass of the total amount of the catalyst is used.
%, Preferably 2 to 10%. 15ma
If it exceeds ss%, the dispersibility of the active metal is deteriorated, and 1 m
If the content is less than ass%, the effect of increasing the activity of the desulfurization by dispersing the active metal in a high degree cannot be sufficiently obtained.

The group 6A metal component supported on the carrier is preferably tungsten or molybdenum, particularly preferably molybdenum. These metals are supported in the form of oxides. As a raw material for supporting these oxides is not particularly limited, for example, ammonium molybdate _{[(NH 4) 6 Mo 7 O} 24 · 4H 2 O ], ammonium tungstate _{[(NH 4)} 10 _{W 12} O ₄₁・
5H ₂ O], molybdenum oxide [MoO ₃ ], molybdophosphoric acid [H ₃ (PMo ₁₂ O ₄₀ ) · 30 H ₂ O], tungstophosphoric acid [H ₃ (PW ₁₂ O ₄₀ ) · 30 H ₂ O], and the like. These can be used alone or in combination of two or more.

The Group 8 metal components include iron, cobalt, nickel, rhodium, palladium, osmium, iridium,
Platinum and the like are preferable, and cobalt and nickel are particularly preferable. These metals are also carried in the form of oxides. Raw materials for supporting these oxides are also not particularly limited, but nitrates, carbonates, acetates, and phosphates are preferable.
These can also be used alone or in combination of two or more.

[0014] The phosphorus component and the boron component are also supported in the form of an oxide. The phosphorus component is, for example, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, polyphosphoric acid, etc., and preferably orthophosphoric acid. Boron component, for example, boric acid, sodium borate, ammonium borate,
Sodium perborate, orthoboric acid, tetraboric acid, boron pentasulfide, boron trichloride, ammonium biborate, calcium borate, diborane, magnesium borate, methyl borate, butyl borate, tricyclohexyl borate, anhydrous borate Boric acid containing boron such as an acid, boron oxide, or boron itself may be used, and boric acid is preferable.

In the present invention, the phosphorus component and the boron component are combined with 6
It is supported together with Group A and Group 8 metal components. Thereby, the dispersibility of these active ingredients in the carrier can be improved. The effect of improving the dispersibility can be seen with the phosphorus component or the boron component alone, but the effect is very small. A great effect can be obtained by carrying both these components simultaneously. Although the reason for this is not clear in detail, the active metal species of Group 6A and Group 8, the phosphorus component and the boron component are dissolved in the same impregnating solution, and these components are heteropolyoxidized to form a uniform impregnating solution. Can be prepared.

The content ratio of each of the above components is 10 to 10 in terms of oxide, based on the weight of the catalyst.
30 mass%, preferably 15 to 23 mass%, 8
Group metal component is 1 to 10 mass%, preferably 3 to 7 m
ass%, phosphorus component is 1 to 7 mass%, preferably 2 to
5 mass%, the boron component is 0.5 to 7 mass%, preferably 1 to 5 mass%. When a material containing phosphorus is used as a raw material for the Group 6A or Group 8 metal component, the amount of the phosphorus is also calculated as the amount of the phosphorus component. 6
If the group A metal component is less than 10 mass%, the sulfur content in the hydrocarbon oil cannot be efficiently removed, and the
If it exceeds s%, not only the dispersibility of the active metal is deteriorated, but also the effect of the Group 6A metal component is saturated, which is uneconomical.
If the Group 8 metal component is less than 1 mass%, the technical significance of including the Group 8 metal component will not be exhibited, and therefore, the sulfur content in the hydrocarbon oil cannot be efficiently removed, and
If it exceeds s%, the effect of the Group 8 metal component will be saturated and uneconomical. If the phosphorus component is less than 1 mass%, the effect of improving the dispersibility of the active metal is not exhibited even when used in combination with the boron component. 0.5 mass of boron component
%, The effect of improving the dispersibility of the active metal is not exhibited even when used in combination with the phosphorus component.
If it exceeds, the dispersibility of the active metal becomes rather poor, and inconveniences such as a decrease in surface area occur, and the technical meaning of containing a boron component is lost.

The specific method of supporting each of these components on the carrier is not particularly limited, but may be in accordance with the production method of the present invention.
It is desirable to carry out by a one-stage impregnation method using an impregnation liquid in which the raw materials of the components of the 6A group metal, the 8th group metal, phosphorus and boron are dissolved in the same liquid. The one-stage impregnation method refers to a method in which the active ingredient is supported on a carrier in one step. Hereinafter, preparation examples of the catalyst of the present invention along the production method of the present invention will be described. However, the catalyst of the present invention is not limited thereto, and can be prepared by various other known methods.

An impregnating solution obtained by dissolving a group 6A, group 8 metal compound, a phosphorus compound and a boron compound in water is impregnated into alumina or a carrier containing alumina as a main component by a one-stage impregnation treatment. When preparing these impregnating liquids, if these compounds are hardly soluble, various acids such as nitric acid, sulfuric acid and acetic acid can be added. After impregnation, drying and firing are performed. Drying is performed at 120 ° C. for 12 to 24 hours, and baking is performed at 400 to 550 ° C. for 12 to 24 hours.

The specific surface area, pore volume and average pore diameter of the catalyst of the present invention prepared by the above-mentioned method are not particularly limited. In order to also efficiently remove
00m ² / g or more, pore volume of 0.3 to 1.0 cm ³ /
g, the average pore diameter is preferably 60 to 120 °.

The shape of the catalyst is also not particularly limited, and various shapes generally used for this type of catalyst,
For example, a columnar shape, a four-leaf type, or the like can be adopted.
Usually, the size is preferably 1/10 to 1/22 inch in diameter and 3.2 to 3.6 inches in length.

When the catalyst of the present invention is used in a hydrocarbon oil hydrotreating process, it may be used alone or in combination with a known catalyst or a known inorganic oxide carrier. Further, in the multi-stage treatment process, it can be used in an appropriate combination with another catalyst.

In the hydrotreating of hydrocarbon oils with the catalyst of the present invention, the feedstock oil is not particularly limited, but it may be catalytically cracked gas oil, pyrolyzed gas oil, straight run gas oil, coker gas oil, hydrotreated gas oil, desulfurized gas oil, A vacuum gas oil or the like is desirable.
These can be used alone or in combination of two or more to form a feedstock. In addition, the desulfurized gas oil refers to a product oil that has already been desulfurized in the first stage in the multi-stage processing process. These feedstocks have a boiling range of 150 to 400.
° C, preferably 200-380 ° C, more preferably 22 ° C.
0 to 340 ° C, the sulfur content is 3 mass% or less, preferably 2.5 mass% or less, more preferably 2.0 mass%
Those having s% or less are preferred.

Hydrotreating of the above feedstock with the catalyst of the present invention
The processing (desulfurization) conditions are as follows: pressure (hydrogen partial pressure) 30 to 80 kg
/ Cm², Preferably 35-60 kg / cm²,temperature
320-360 ° C, preferably 330-360 ° C, liquid empty
Speed between 1.0-5.0hr ^-1, Preferably 1.0 to
2.0hr^-1, Hydrogen / oil ratio is 100-400L /
L, preferably 200 to 300 L / L. Pressure (water
30kg / cm²If the value is less than
80 kg / cm²Beyond
However, not only does the efficiency of removing non-desulfurizable substances saturate,
High cost equipment that can withstand such high pressure is required,
It will be done. If the temperature is lower than 320 ° C, it may cause
Can not be removed.
The efficiency of removing sulphate is saturated, which is uneconomical. Liquid space velocity
The degree is 5.0hr^-1Above, contact between catalyst and feedstock
The time is too short to remove even difficult-to-desulfurize substances.
1.0 hr^-1Less than this contact
Not only does the effect saturate, but processing efficiency decreases.

When the hydrodesulfurization of the above feedstock under the above conditions is carried out on a commercial scale, the catalyst of the present invention is used as a fixed bed, moving bed or fluidized bed in a suitable reactor. The feedstock may be introduced into the reactor and treated under the above conditions. Most commonly, the catalyst is maintained as a fixed bed such that feedstock passes down through the fixed bed. This reactor may be used alone,
Several reactors can be used in series.

[0025]

EXAMPLES Example 1 (Preparation of carrier) 900 g of aluminum hydroxide was 27 liters (hereinafter, liter is "L" and milliliter is "m").
L)), add nitric acid and add pH
It was set to 1. Further, aqueous ammonia was added until the pH reached 7. The obtained alumina gel is washed with ion-exchanged water,
After filtration, the mixture was heated and kneaded at 70 ° C. in a kneader to adjust the amount of moisture (humidity control) to such an extent that the kneaded product could be extruded, and then formed using an extruder. The obtained molded product is 12
And overnight drying at 0 ° C., followed by firing at 550 ° C. 12 hours, a specific surface area of 334m ² / g, pore volume 0.70 cc /
g of a carrier having an average pore diameter of 69 ° was obtained.

(Preparation of catalyst) In an Erlenmeyer flask at room temperature, 11.2 g of cobalt carbonate, 3.9 g of orthophosphoric acid, 38.6 g of molybdophosphoric acid and 2.5 g of boric acid were dissolved in 77 g of ion-exchanged water and stirred. Thus, an aqueous (impregnated) liquid was prepared. The impregnating solution was impregnated with 100 g of the above carrier in an eggplant-shaped flask at room temperature for 1 hour, air-dried, and calcined in a muffle furnace at 500 ° C. for 4 hours to obtain a catalyst. Table 1 shows the composition of this catalyst, and Table 2 shows its properties.

Example 2 At the time of kneading for preparing the carrier in Example 1, the alumina gel was mixed with HY-type zeolite (SiO ₂ / Al ₂ O ₃ molar ratio: 6, Na ₂ O content: 0.3 mass% or less, Surface area of 900 to 1100 (Langmuir, m ² / g)
And a specific surface area of 358 m ² / g, and a pore size of 600 to 700 (BET, m ² / g) and a crystal size of 0.7 to 1.0 μm. A carrier having a volume of 0.60 cc / g and an average pore diameter of 58 °
g was obtained. Using this carrier, a catalyst was prepared in the same manner as in Example 1. Table 1 shows the composition of this catalyst, and Table 2 shows its properties.

Example 3 A catalyst was prepared in the same manner as in Example 1 except that 11.5 g of cobalt carbonate, 39.7 g of molybdophosphoric acid, 4.1 g of phosphoric acid, and 7.7 g of boric acid were dissolved in 77 g of ion-exchanged water. did. Table 1 shows the composition of this catalyst, and Table 2 shows its properties.

Example 4 A catalyst was prepared in the same manner as in Example 1 except that 11.9 g of cobalt carbonate, 40.9 g of molybdophosphoric acid, 4.2 g of phosphoric acid, and 13.3 g of boric acid were dissolved in 77 g of ion-exchanged water. did. Table 1 shows the composition of this catalyst, and Table 2 shows its properties.

Comparative Example 1 In an Erlenmeyer flask at room temperature, 32.7 g of ammonium molybdate tetrahydrate and 10.7 g of 28-30 mass% ammonia water (Kanto Chemical Co., Ltd., special grade reagent) were ion-exchanged with water. The resultant was dissolved in 66 g and stirred to prepare an aqueous (impregnated) liquid. This impregnating liquid was applied to the same carrier 100 as in Example 1.
g in a eggplant-shaped flask at room temperature for 1 hour,
It was air-dried and calcined in a muffle furnace at 500 ° C. for 4 hours to obtain a molybdenum-supported alumina support. Subsequently, in an Erlenmeyer flask at room temperature, 25.9 g of cobalt nitrate hexahydrate was dissolved in 77 g of ion-exchanged water and stirred to prepare an aqueous (impregnated) liquid. The impregnating solution was impregnated with the above-mentioned molybdenum-supported alumina carrier (100 g) in a eggplant-shaped flask at room temperature for 1 hour, air-dried, and calcined in a muffle furnace at 500 ° C. for 4 hours to obtain a catalyst. Table 1 shows the composition of this catalyst, and Table 2 shows its properties.

Comparative Example 2 A catalyst was prepared in the same manner as in Example 1 except that 2.5 g of boric acid was not added. Table 1 shows the composition of this catalyst, and Table 2 shows its properties.

Comparative Example 3 Comparative Example 3 was repeated except that 32.7 g of ammonium molybdate tetrahydrate and 2.4 g of boric acid were used instead of 32.7 g of ammonium molybdate tetrahydrate when preparing molybdenum-supported alumina. A catalyst was prepared as in Example 1. Table 1 shows the composition of this catalyst, and Table 2 shows its properties.

Comparative Example 4 Example 1 was repeated except that 6.0 g of zeolite was added to the alumina gel during kneading for preparing the carrier in Example 1.
In the same manner as described above, the specific surface area is 324 m ² / g, and the pore volume is 0.1.
723 g of a carrier having 69 cc / g and an average pore diameter of 67 ° were obtained. Using this carrier, a catalyst was prepared in the same manner as in Comparative Example 2. Table 1 shows the composition of this catalyst, and Table 2 shows its properties.

Comparative Example 5 A catalyst was prepared in the same manner as in Example 1 except that 12.8 g of cobalt carbonate, 44.2 g of molybdophosphoric acid, 4.5 g of phosphoric acid, and 28.6 g of boric acid were dissolved in 77 g of ion-exchanged water. . Table 1 shows the composition of this catalyst, and Table 2 shows its properties.

[0035]

[Table 1]

[0036]

[Table 2]

Using the catalysts prepared in Examples 1 to 4 and Comparative Examples 1 to 5, a hydrogenation (desulfurization reaction) test was conducted under the following conditions. The results are shown in Table 3. Feed oil: straight run gas oil: specific gravity (15/4 ° C); 0.8567 sulfur content; 1.364 mass% nitrogen content; 150 ppm boiling point (50% point); 315 ° C viscosity (粘度 30 ° C); 6.608 cSt hydrogenation Treatment conditions: temperature; 320, 340, 350 ° C. Pressure (hydrogen partial pressure); 50 kg / cm ² liquid space velocity; 1.5 hr ⁻¹ device; high-pressure flow reactor with fixed bed system Pretreatment condition of catalyst: pressure ( 50 kg / cm ² atmosphere; hydrogen sulfide / hydrogen mixed gas flow temperature; step temperature rise 100 ° C. for 2 hours 250 ° C. for 2 hours 350 ° C. for 2 hours

[0038]

[Table 3] Note) The relative evaluation was made with the activity of Comparative Example 1 taken as 100.

Further, the influence (dependency) of the boron component content on the desulfurization activity in the catalyst of the present invention was examined. Table 4 shows the results.

[0040]

[Table 4] Note) The catalysts were arranged from the top in ascending order of the amount of B ₂ O ₃ supported. The activity of Comparative Example 2 was shown as a relative evaluation with the activity being 100.

Table 3 shows CoMo / Al ₂ O _{3 of} Comparative Example 1.
The results of comparison are shown with the desulfurization activity of the catalyst as a reference, which is set to 100. As is clear from Table 3, 33
At 0 ° C., Comparative Example 2 supporting 3% of P ₂ O ₅
04%, and 105% in Comparative Example 3 in which 1% of B ₂ O ₃ is supported.
Of P ₂ O ₅ and B ₂ O
_In Example 1 in which ₃ % was simultaneously supported by 1%, the activity was greatly improved, and a relative activity of 114% was exhibited. This tendency is 33
It becomes remarkable as the temperature rises from 0 ° C. to 340 ° C., and further to 350 ° C., indicating that the relative activity value is greatly increased. This means that the content of sulfur in the product oil is 0.05%
B ₂ O in the ultra-deep desulfurization region where the mass
₃ effectively acts, and particularly suggests that the effect becomes remarkable when coexisting with P ₂ O ₅ .

Table 4 confirms the B ₂ O ₃ content dependency of the catalyst of the present invention, based on the desulfurization activity of the CoMoP / Al ₂ O ₃ catalyst of Comparative Example 2 containing no B ₂ O _3. , The relative activity when this is set to 100. As is apparent from Table 4, at 330 ° C., P ₂ O ₅ was 3%
In Example 1 where 1% and B ₂ O ₃ were simultaneously supported, 111%
Shows the relative _activity, Example 3 was increased B 2 _{O 3} 3%
Shows 117% relative activity and B ₂ O ₃
Example 4 showed a relative activity of 108%.
On the other hand, in Comparative Example 5 in which the amount of B ₂ O ₃ carried was 10%, B
Less active than the reference catalyst of Comparative Example 2 containing no ₂ O ₃ ,
It showed a relative activity of 98%. Also, P ₂ O ₅ and B ₂ O ₃
The synergistic effect of the coexistence of
As the temperature increased to 50 ° C., it was remarkably observed. From the above, it can be seen that the activity is improved when P ₂ O ₅ and B ₂ O ₃ coexist, but it becomes worse when the B ₂ O ₃ content is too large, and there is an optimum range for the compounding amount.

[0043]

As described in detail above, according to the present invention,
A catalyst exhibiting high activity for hydrodesulfurization of hydrocarbon oils can be realized, thereby providing a fuel oil having a low sulfur content.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10G 45/12 C10G 45/12 A (72) Inventor Takashi Fujikawa 1134-2 Gongendo, Satte City, Saitama 4G069 AA04 AA08 BA01A BA01B BA07A BA07B BB02A BB02B BC57A BC59B BC65A BC67B BC69A BD03A BD03B BD07A BD07B CC02 DA06 FB14 FC08 4H029 CA00 DA00

Claims (4)

[Claims] 1. A support made of alumina or an inorganic oxide containing alumina as a main component, wherein at least one element selected from Group VIA metal elements of the periodic table is used in an amount of 10 to 30 mass in terms of oxide, based on the total amount of the catalyst. %, Periodic Table VIII
At least one member selected from the group consisting of group 1 to 10 m
ass%, 1-7 mass% of phosphorus, and 0.5% of boron.
A hydrotreating catalyst for hydrocarbon oils supported by about 7 mass%. 2. The hydrotreating catalyst for hydrocarbon oil according to claim 1, wherein the support contains 1 to 15 mass% of zeolite based on the total amount of the catalyst. 3. A carrier comprising at least one compound selected from Group VIA metal elements of the periodic table and V
The method for producing a hydrotreating catalyst for a hydrocarbon oil according to claim 1, wherein an impregnating liquid containing a phosphorus compound and a boron compound is impregnated with at least one compound selected from Group III metal elements. 4. The method for producing a hydrotreating catalyst for hydrocarbon oil according to claim 3, wherein the support contains 1 to 15 mass% of zeolite based on the total amount of the catalyst.