JPH04243546A - Manufacture of hydrogenation catalyst for hydrocarbon oil - Google Patents

Abstract

PURPOSE:To provide a method for producing a hydrogenation catalyst for hydrocarbon oil processing having an outstandingly higher catalytic activity than any catalyst which has hitherto been proposed and permitting reduction of the hydrocarbon operating cost. CONSTITUTION:As a base medium is used a catalyst supported on its carrier as an activated metal the group VI metal (Mo or W) and the group VIII metal (Co or Ni) in the periodic table or the catalyst containing phosphorus in addition thereto. To this catalyst are added at least one kind of glycolic acid, tartaric acid and the other specific carboxylic acids in an amt. of 0.3-3.5 times the total mols of the activated metals and mercaptoacetic acid, mercaptosuccinic acid or other specific org. sulfur compound in an amt. of at least 0.1 time the amt. required to change the activated metal into the sulfide form. The catalyst is thereafter dried at a temp. not higher than 200 deg.C to produce a hydrogenation catalyst. This permits an extremely easy production of the hydrogenation catalyst which can perform a high degree of the hydrogenation capable of desulfurization and denitrification of hydrocarbon oil under a milder operating condition than in the conventional operation.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a highly active catalyst for hydrotreating hydrocarbon oil that can meet the demand for lower sulfur in gas oil.

0002

[Prior Art] As a catalyst used in hydroprocessing for hydrogenation, desulfurization, denitrification, decomposition, etc. of hydrocarbon oil, porous catalyst supports such as alumina, silica, titania, and activated carbon are Group 6 metals molybdenum and tungsten,
Also, a catalyst is used in which Group 8 metals such as cobalt and nickel are supported as active metals. These active metals are supported in an oxide form on the catalyst carrier and do not exhibit any activity. For this purpose, it is used after being converted into a sulfurized substance by an appropriate pre-sulfurization treatment.

[0003] In the hydrotreating catalyst, active sites of the catalyst are formed on the surface of the active metal sulfide. Therefore, it is known that as the exposed surface area of the active metal sulfide increases, the number of active sites increases, resulting in a highly active catalyst. In order to increase the exposed surface area of the active metal sulfide, attempts have been made to make the active metal sulfide fine and highly dispersed, and various methods have been proposed. That is, for example, EP0181
No. 035 (A2) discloses that after impregnating a carrier such as alumina or silica with a mixed solution of a nitrogen-containing organic compound such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, or diethylenetriamine and an active metal, finally, A method of drying at a temperature of 200° C. or less is disclosed. This method is
By forming a complex ion between the active metal and the nitrogen-containing organic compound and supporting it, it is possible to prevent the aggregation of the active metal.
The purpose is to achieve high dispersion, and the activity of the catalyst produced by this method is higher than that of conventional products. However, recently, in line with exhaust gas regulations, a request for lower sulfur in diesel oil (recommendation to reduce the sulfur content in diesel oil to 0.05% by weight or less) has been submitted, but this goal can only be achieved through this method. Even the catalyst produced by

Recently, the applicant has reported that a mixed aqueous solution of a hydroxycarboxylic acid such as glycolic acid, tartaric acid, citric acid, gluconic acid, etc. and an active metal is supported on a catalyst carrier by an impregnation method or a kneading method, and then heated at 200°C. We proposed a method for producing a hydrotreating catalyst that is dried at the following temperatures. This method uses a hydroxycarboxylic acid as a complexing agent, and finally the catalyst is heated to 200°C without calcination.
Because only the drying process is performed at the following temperature, the hydroxycarboxylic acid is not decomposed and is stably retained on the catalyst carrier.
Furthermore, by complexing the active metal ion with the hydroxycarboxylic acid, the thermal aggregation that occurs during the pre-sulfurization treatment of the hydrotreating catalyst is significantly suppressed, and as a result, the active metal sulfide is supported in a highly dispersed manner. It has the characteristic of producing a hydrotreating catalyst having higher activity than a hydrotreating catalyst to which a nitrogen-containing compound is added.

[0005]

[Problems to be Solved by the Invention] If a conventional hydrotreating catalyst is used to achieve a high degree of desulfurization of hydrocarbon oil, so-called deep desulfurization operation, the hydrotreating operation will require extremely harsher operating conditions than conventional operating conditions. required to operate under these conditions. Therefore, the catalyst tends to deteriorate, and the life of the catalyst is shortened, which naturally increases operating costs. On the other hand, in the case of a catalyst obtained using the above-mentioned hydroxycarboxylic acid, deep desulfurization of hydrocarbon oil can be performed satisfactorily under conventional hydrotreating operating conditions, and the current operating cost level can be maintained. obtain. However, in case the price of crude oil rises, it is desired to conduct hydroprocessing operations at lower costs, and if more highly active hydroprocessing catalysts are developed, it would be possible to conduct hydroprocessing operations at lower costs than at present. Deep desulfurization operation of hydrocarbon oil becomes possible under certain conditions. Therefore, there is an urgent need to develop such extremely highly active catalysts.

The present invention has a catalytic activity significantly exceeding that of the hydroxycarboxylic acid addition hydrogenation catalyst,
The object of the present invention is to provide a method for producing a catalyst for hydrotreating hydrocarbon oil, which can reduce operating costs for hydrotreating.

[0007]

[Means for Solving the Problems] As a result of extensive research in order to solve the above problems and achieve the above objects, the present inventors have discovered that metals in groups 6 and 8 of the periodic table can be used as active metals. It was discovered that the objective could be achieved by adding specific amounts of a specific carboxylic acid and a specific sulfur compound to a catalyst containing phosphorus, and then drying the mixture at a temperature below 200°C. As a result, the present invention was completed. That is, in the first embodiment of the present invention, glycolic acid, lactic acid, tartaric acid, malic acid, and glyceric acid are added to a catalyst in which metals from groups 6 and 8 of the periodic table are supported as active metals on a catalyst carrier. , at least one type of carboxylic acid selected from the group consisting of citric acid, gluconic acid, methoxyacetic acid, ethoxyacetic acid, malonic acid, succinic acid, and glyoxylic acid, and the total number of moles of metals from Groups 6 and 8 of the periodic table. 0.
Add 3 to 3.5 times the amount, and further add mercaptoacetic acid, 1
-Mercaptopropionic acid, 2-mercaptopropionic acid, 2,3-dimercaptosuccinic acid, mercaptosuccinic acid, thioacetic acid, thiodiglycolic acid, dithiodiglycolic acid, thiosalicylic acid, mercaptoethanol, β-thiodiglycol, thio After adding at least one organic sulfur compound selected from the group consisting of urea at least 0.1 times the amount required to convert metals from Groups 6 and 8 of the periodic table into sulfide form, the mixture is heated at 200°C. This is a method for producing a catalyst for hydrotreating hydrocarbon oil, which is dried at the following temperature, and the second embodiment is a method for producing a catalyst for hydrotreating hydrocarbon oil, in which metals from groups 6 and 8 of the periodic table are supported as active metals on a catalyst carrier. Furthermore, glycolic acid,
At least one carboxylic acid selected from the group consisting of lactic acid, tartaric acid, malic acid, glyceric acid, citric acid, gluconic acid, methoxyacetic acid, ethoxyacetic acid, malonic acid, succinic acid, and glyoxylic acid from Group 6 of the periodic table. and 0.3 to 3.5 times the total number of moles of Group 8 metals, and further mercaptoacetic acid, 1-mercaptopropionic acid, 2-mercaptopropionic acid, 2,3-dimercaptosuccinic acid,
Mercaptosuccinic acid, thioacetic acid, thiodiglycolic acid,
At least one organic sulfur compound selected from the group consisting of dithiodiglycolic acid, thiosalicylic acid, mercaptoethanol, β-thiodiglycol, and thiourea, and metals from Groups 6 and 8 of the periodic table in the form of sulfide. This is a method for producing a catalyst for hydrotreating hydrocarbon oil, in which the catalyst is added in an amount 0.1 times or more of the amount required for hydrocarbon oil, and then dried at a temperature of 200° C. or less.

[0008]

[Operation] The catalyst carrier material used in the present invention is at least one selected from porous materials such as alumina, silica, titania, zirconia, and activated carbon.

At least one of molybdenum and tungsten is used as the Group 6 metal of the periodic table, and at least one of cobalt and nickel is used as the Group 8 metal. However, the amount of these active metals supported is
The amount generally employed as a catalyst for hydrotreating may be used, and the amount of Group 6 metal is 5 to 30% by weight as MoO3 and WO3, respectively, and the amount of Group 8 metal is 1 to 8% by weight as CoO and NiO, respectively. It is preferable that This is because if the supported amount of these active metals is less than the above range, high activity cannot be obtained, and even if the supported amount is greater than the above range, no further increase in activity can be obtained and economic efficiency will be lost. .

[0010] For phosphorus, any of metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid, etc. may be used, and soluble salts such as nickel phosphate may be used.
% by weight. By containing phosphorus within the above range, it acts as a stabilizer when impregnating active metals, and the activity is further improved.

As the carboxylic acid, at least one compound selected from glycolic acid, lactic acid, tartaric acid, malic acid, citric acid, glyceric acid, gluconic acid, methoxyacetic acid, ethoxyacetic acid, malonic acid, succinic acid, and glyoxylic acid is used. It is added to catalysts that support metals from groups 6 and 8 of the periodic table, or to catalysts that further contain phosphorus, and the amount of addition is determined according to the periodic table. 0.3 to 3.5 of the total number of moles of Group 6 and Group 8 metals
Add in twice the amount. This is because if the amount added is less than 0.3 times the amount, sufficient activity cannot be obtained, and if the amount added exceeds 3.5 times the amount, carbonaceous matter will remain in the catalyst and precipitate during pre-sulfurization. This is because the sulfidation of active metals is inhibited, and the catalytic activity is reduced.

[0012] Examples of organic sulfur compounds include mercaptoacetic acid, 1-mercaptopropionic acid, 2-mercaptopropionic acid, 2,3-dimercaptosuccinic acid, mercaptosuccinic acid, thioacetic acid, thiodiglycolic acid, and dithiodiglycolic acid. A catalyst in which at least one compound selected from acid, thiosalicylic acid, mercaptoethanol, β-thiodiglycol, and thiourea is supported together with a carboxylic acid and a metal of Groups 6 and 8 of the periodic table, or ,
Phosphorus is added to this catalyst, and the amount added is 0.1 of the amount necessary to convert the metals of Groups 6 and 8 of the periodic table into sulfides. 0.1 to 0.5 times is sufficient. Adding more than this will not further improve the catalytic activity, and in view of production costs, it is better to add a smaller amount of the organic sulfur compound.

[0013] The drying temperature is set at 200°C or lower, because if the temperature is 200°C or higher, the added carboxylic acid and organic sulfur compound may decompose.

[0014] The catalyst of the present invention produced in a manner that satisfies the conditions as described above contains molybdenum, tungsten,
Active metal ions such as cobalt and nickel form coordination compounds with carboxylic acids and are stabilized and supported on the catalyst carrier, and the addition of a small amount of organic sulfur compound significantly improves the catalytic activity. The reason for this is not clear, but in the case of a catalyst with only carboxylic acid added, it is assumed that the carboxylic acid is stored in the pores of the catalyst carrier and blocks the pores, and the active metal inside the pores becomes sulfurized during the pre-sulfidation treatment. This is thought to have an effect on the hydrotreating activity of the catalyst, but adding a small amount of an organic sulfur compound promoted the sulfidation of the active metal, resulting in high activity. considered to be a thing.

[0015]

[Example] Next, an example of the present invention will be described. Example 1 500 g of a γ-alumina carrier with a specific surface area of 280 m2/g and a pore volume of 0.75 ml/g was coated with 96.0 g of molybdenum trioxide.
2 g of cobalt carbonate, 41 g of cobalt carbonate, and 600 ml of an active metal aqueous solution prepared from water, and dried at 110° C. for 5 hours. Next, the dried product was impregnated with 540 ml of an aqueous solution containing 198 g of glycolic acid and 20 g of mercaptoethanol, and dried at 110° C. for 10 hours to obtain catalyst A.

The metal content of catalyst A is such that molybdenum is Mo
15% by weight as O3, 4% by weight as cobalt as CoO, the amount of glycolic acid added is 2.5 times the total number of moles of metals in Groups 6 and 8 of the periodic table, and mercapto The amount of ethanol added is 0.00000, which is the amount necessary for molybdenum and cobalt to form MoO2 and CoS, respectively.
It was 15 times the amount. Furthermore, as an activity test for the obtained catalyst A, a hydrodesulfurization reaction of Kuwait atmospheric gas oil having the following properties was carried out.

Specific gravity (15/4°C)
0.844 Sulfur
Yellow (wt%)
1.55 Distillation properties (initial boiling point ℃
) 231
(50vol%℃)
313 (end point
℃) 390 The reaction was carried out using a flow reactor under the following reaction conditions.

[0018] Catalyst amount (ml)
15 Raw material oil liquid space velocity (hr-1)
2 reaction hydrogen pressure (Kg/c
m2G) 30 reaction temperature
Degree (℃) 330
Hydrogen/oil flow ratio (Nl/l)
300 letters Oil time (hr)
88 results, the rate constant is calculated assuming that the desulfurization reaction rate is proportional to the 1.75th power of the sulfur concentration of the feedstock atmospheric gas oil, and the relative rate constant is determined by setting the rate constant of catalyst K of Comparative Example 1 to 100, which will be described later. The hydrodesulfurization activity was determined and the results are shown in Table 1. Example 2 96% of molybdenum trioxide was added to 500g of the above γ-alumina.
2g, cobalt carbonate 41g, 85% phosphoric acid 30.8g,
Then, it was impregnated with 600 ml of an active metal aqueous solution prepared from water and dried at 110°C. Next, the dried product was impregnated with 540 ml of an aqueous solution containing 190 g of tartaric acid and 55 g of mercaptoacetic acid, and dried at 110° C. for 10 hours to obtain catalyst B. The metal content of catalyst B was 15% by weight of molybdenum as MoO3, 4% by weight of cobalt as CoO, and 3% by weight of phosphorus as P2O5. The amount of tartaric acid added is
The amount is 1.25 times the total number of moles of metals in Groups 6 and 8 of the periodic table, and the amount of mercaptoacetic acid added is 0 times the amount required for molybdenum and cobalt to form MoS2 and CoS, respectively. .3 times the amount. Furthermore, the results of the activity test conducted in the same manner as in Example 1 are shown in Table 1. Example 3 Catalyst C was obtained in the same manner as in Example 2, except that 70 g of citric acid was used as the carboxylic acid and 65 g of β-thiodiglycol was used as the organic sulfur compound. The metal content of catalyst C is 15% by weight of molybdenum as MoO3, 4% by weight of cobalt as CoO, and 3% by weight of phosphorus as P2O5.
Met. The amount of citric acid added is 0.33 times the total number of moles of metals in Groups 6 and 8 of the periodic table, and the amount of β-thiodiglycol added is 0.33 times the total number of moles of metals in Groups 6 and 8 of the periodic table. 0.3 of the amount required to form CoS
It was double the amount. Furthermore, the results of the activity test conducted in the same manner as in Example 1 are shown in Table 1. Example 4 Catalyst D was obtained in the same manner as in Example 2, except that 142.2 g of citric acid was used as the carboxylic acid and 65 g of β-thiodiglycol was used as the organic sulfur compound. The metal content of catalyst D is as follows: molybdenum is 15% by weight as MoO3, cobalt is 4% by weight as CoO, and phosphorus is 3% by weight as P2O5.
% by weight. Further, the amount of citric acid added is 0.67 times the total number of moles of metals in Groups 6 and 8 of the periodic table,
The amount of β-thiodiglycol added was 0.3 times the amount of molybdenum and cobalt required to form MoS2 and CoS, respectively. Furthermore, the results of the activity test conducted in the same manner as in Example 1 are shown in Table 1. Example 5 Silica-alumina carrier (contains 10% by weight as SiO2, specific surface area 325 m2/g, pore volume 0.75 ml/g
) was impregnated with 600 ml of an active metal aqueous solution prepared from 96.2 g of molybdenum trioxide, 41 g of nickel carbonate, 30.8 g of 85% phosphoric acid, and water, and dried at 110° C. for 10 hours. Next, 227 g of methoxyacetic acid, β-
540 ml of an aqueous solution containing 108 g of thiodiglycol
was impregnated into the dried product and dried at 110° C. for 10 hours to obtain catalyst E. The metal content of catalyst E is as follows: molybdenum is MoO
15% by weight as 3, 4% by weight of nickel as NiO
, phosphorus was 3% by weight as P2O5. In addition, the amount of methoxyacetic acid added is 2.5 times the total number of moles of metals in Groups 6 and 8 of the periodic table, and the amount of β-thiodiglycol added is as follows: molybdenum and nickel are MoS2, MoS2 and nickel, respectively. N
The amount was 0.5 times the amount required to form iS. Furthermore, Table 1 shows the results of the activity test conducted in the same manner as in Example 1.
Shown below. Example 6 Catalyst F was obtained in the same manner as in Example 2, except that 171 g of malic acid was used as the carboxylic acid and 55 g of 1-mercaptopropionic acid was used as the organic sulfur compound. The metal content of catalyst F was 15% by weight of molybdenum as MoO3, 4% by weight of cobalt as CoO, and 3% by weight of phosphorus as P2O5. Further, the amount of malic acid added is 1.25 times the total number of moles of metals in Groups 6 and 8 of the periodic table, and the amount of 1-mercaptopropionic acid added is 1.25 times the total number of moles of metals in Groups 6 and 8 of the periodic table. The amount was 0.3 times the amount required to form CoS. Furthermore, the results of the activity test conducted in the same manner as in Example 1 are shown in Table 1. Example 7 Catalyst G was obtained in the same manner as in Example 2, except that 136 g of malonic acid was used as the carboxylic acid and 78 g of thiodiglycolic acid was used as the organic sulfur compound. The metal content of catalyst G is 15% by weight of molybdenum as MoO3, 4% by weight of cobalt as CoO, and 3% by weight of phosphorus as P2O5.
Met. In addition, the amount of malonic acid added is 12.5 times the total number of moles of metals in Groups 6 and 8 of the periodic table, and the amount of thiodiglycolic acid added is 12.5 times the total number of moles of metals in Groups 6 and 8 of the periodic table. The amount was 0.3 times the amount required to form . Furthermore, the results of the activity test conducted in the same manner as in Example 1 are shown in Table 1. Example 8 Titania support (specific surface area 186 m2/g, pore volume 0.
Catalyst H I got it. The metal content of catalyst H is molybdenum as MoO3.
wt%, cobalt is 4 wt% as CoO, phosphorus is P2
It was 3% by weight as O5. In addition, the amount of glyoxylic acid added is 2 of the total number of moles of metals in Groups 6 and 8 of the periodic table.
．． The amount of 2,3-dimercaptosuccinic acid added is 5 times that of molybdenum and cobalt, respectively.
The amount was 0.3 times the amount required to form S. Furthermore, the results of the activity test conducted in the same manner as in Example 1 are shown in Table 1. Example 9 Silica-alumina carrier (contains 10% by weight as SiO2, specific surface area 325 m2/g, pore volume 0.75 ml/g
), and gluconic acid (500 g) was used as the carboxylic acid.
Catalyst I was obtained in the same manner as in Example 2, except that 277 g of 0% by weight aqueous solution) and 38.3 g of thioacetic acid were used as the organic sulfur compound. The metal content of catalyst I is 15% by weight of molybdenum as MoO3 and 4% of cobalt as CoO.
% by weight, phosphorus was 3% by weight as P2O5. In addition, the amount of gluconic acid added is 0.7 times the total number of moles of metals in Groups 6 and 8 of the periodic table, and the amount of thioacetic acid added is 0.7 times the total number of moles of metals in Groups 6 and 8 of the periodic table.
The amount was 0.3 times the amount required to form . moreover,
Table 1 shows the results of the activity test conducted in the same manner as in Example 1. Example 10 Glyceric acid (65% by weight aqueous solution) 2 as carboxylic acid
06g, mercaptosuccinic acid 78 as an organic sulfur compound
Catalyst J was obtained in the same manner as in Example 9 except that g was used. The metal content of Catalyst J was 15% by weight of molybdenum as MoO3, 4% by weight of cobalt as CoO, and 3% by weight of phosphorus as P2O5. The amount of glyceric acid added is 1.25 times the total number of moles of metals in Groups 6 and 8 of the periodic table, and the amount of mercaptosuccinic acid added is 1.25 times the total number of moles of metals in Groups 6 and 8 of the periodic table. The amount was 0.3 times the amount required for formation. Furthermore, the results of the activity test conducted in the same manner as in Example 1 are shown in Table 1. Comparative Example 1 Catalyst K was obtained in the same manner as in Example 2, except that only 149 g of citric acid was added and no organic sulfur compound was added. The metal content of catalyst K was 15% by weight of molybdenum as MoO3, 4% by weight of cobalt as CoO, and 3% by weight of phosphorus as P2O5. In addition, the amount of citric acid added is 0.000000000000000000000000 of the total number of moles of metals in Groups 6 and 8 of the periodic table.
It was 7 times the amount. Table 1 shows the results of the activity test conducted in the same manner as in Example 1. Comparative Example 2 Catalyst L was obtained in the same manner as Comparative Example 1, except that 190 g of tartaric acid was used instead of citric acid. The metal content of catalyst L was 15% by weight of molybdenum as MoO3, 4% by weight of cobalt as CoO, and 3% by weight of phosphorus as P2O5. The amount of tartaric acid added was 1.25 times the total number of moles of metals in Groups 6 and 8 of the periodic table. Furthermore, Table 1 shows the results of the activity test conducted in the same manner as in Example 1.
Shown below.

[0019]

[Table 1] Catalyst
relative reaction rate constant
A
130
B
157
C
145
D
138E
143
F
152
G
143
H
135
I
138
J
155K
100
L
108

002
0]

Effects of the Invention The present invention provides a catalyst in which a metal of group 6 or group 8 of the periodic table is supported as an active metal, or a catalyst in which phosphorus is further supported, with a specific carboxylic acid and a specific organic sulfur compound. are added in specific amounts and dried at 200°C or below, making it possible to carry out advanced hydrotreating that can achieve extremely high levels of desulfurization and denitrification of hydrocarbon oils under milder operating conditions than before. The resulting catalyst can be obtained very easily and has a remarkable effect.

Claims (3)

[Claims] Claim 1: Catalyst carrier containing materials from groups 6 and 8 of the periodic table.
From the group consisting of glycolic acid, lactic acid, tartaric acid, malic acid, glyceric acid, citric acid, gluconic acid, methoxyacetic acid, ethoxyacetic acid, malonic acid, succinic acid, glyoxylic acid, on a catalyst supporting a metal of the group as an active metal. At least one selected carboxylic acid is added in an amount of 0.3 to 3.5 times the total number of moles of metals of Groups 6 and 8 of the periodic table, and further mercaptoacetic acid, 1-mercaptopropionic acid,
From the group consisting of 2-mercaptopropionic acid, 2,3-dimercaptosuccinic acid, mercaptosuccinic acid, thioacetic acid, thiodiglycolic acid, dithiodiglycolic acid, thiosalicylic acid, mercaptoethanol, β-thiodiglycol, thiourea At least one selected organic sulfur compound is added at least 0.1 times the amount required to convert metals from Groups 6 and 8 of the periodic table into sulfide form, and then dried at a temperature of 200°C or less. A method for producing a catalyst for hydrotreating hydrocarbon oil, characterized by: [Claim 2] The catalyst carrier contains groups 6 and 8 of the periodic table.
Group metals are supported as active metals, and phosphorus is further supported as P2O5.
The catalyst contains glycolic acid, lactic acid, tartaric acid, malic acid, glyceric acid, citric acid, gluconic acid, methoxyacetic acid, ethoxyacetic acid, malonic acid, succinic acid, glyoxylic acid. At least one type of carboxylic acid selected from the group consisting of 0.3 to 3.5 times the total number of moles of metals of Groups 6 and 8 of the periodic table is added, and mercaptoacetic acid, 1-mercaptoacetic acid, propionic acid,
From the group consisting of 2-mercaptopropionic acid, 2,3-dimercaptosuccinic acid, mercaptosuccinic acid, thioacetic acid, thiodiglycolic acid, dithiodiglycolic acid, thiosalicylic acid, mercaptoethanol, β-thiodiglycol, thiourea At least one selected organic sulfur compound is added at least 0.1 times the amount required to convert metals from Groups 6 and 8 of the periodic table into sulfide form, and then dried at a temperature of 200°C or less. A method for producing a catalyst for hydrotreating hydrocarbon oil, characterized by: [Claim 3] The metal of Group 6 of the periodic table is molybdenum,
At least one of tungsten, and its content is 5 to 3 in terms of MoO3 and WO3, respectively.
0% by weight, and the Group 8 metal is at least one of cobalt and nickel, and the content thereof is 1 to 8% by weight in terms of CoO and NiO, respectively. A method for producing a catalyst for hydrotreating hydrocarbon oil according to Items 1 and 2.