JPH07194979A - Hydrocarbon oil hydrotreating catalyst - Google Patents

Abstract

(57) [Summary] [Object] To provide a hydrotreating catalyst having a large pore volume and a large specific surface area, and a large pore volume. Composition: Alumina carrier containing 1 to 15% by weight of zinc oxide, based on the catalyst, 5 to 30% by weight of a metal component of Group VIB of the periodic table as an oxide, and VIII of the periodic table.
Carrying a group metal component as an oxide in an amount of 1 to 10% by weight, an average pore diameter of 50 to 200Å, and a total pore volume of 0.45 cm ^3.
/ G or more. The carrier is alumina gel, zinc nitrate,
A mixture of at least one powder selected from zinc sulfate, zinc carbonate, zinc chloride, and zinc acetate, which is then molded and fired, or alumina gel, and zinc nitrate, zinc sulfate, zinc carbonate, zinc chloride, acetic acid. Those prepared by a coprecipitation method using one or more kinds of metal salts selected from zinc are preferable.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a catalyst suitable for hydrotreating a hydrocarbon oil.

[0002]

2. Description of the Related Art Gas oil, atmospheric residue, vacuum gas oil, vacuum residue obtained by subjecting crude oil to atmospheric distillation or vacuum distillation contains many sulfur compounds. The content varies depending on the type of crude oil. When these hydrocarbon oils are used for combustion, they generate harmful substances such as sulfur oxides, corrode the combustion furnace and pollute the atmosphere.

[0003] Further, in the high-level treatment for lightening or improving the quality of these hydrocarbon oils, the sulfur compounds and nitrogen compounds contained in the oils, as well as metals, inactivate the catalyst. Is a major cause of hindering the higher-order treatment operation for effectively utilizing the oil.

For this reason, hydrocarbon oils containing a large amount of sulfur compounds and metals have heretofore been used as Mo and Cr of Group VIB metal (hereinafter simply referred to as "Group VIB metal") of the periodic table.
Alternatively, W, a catalyst in which Fe, Ni, Co, or Pt of Group VIII metal (hereinafter, simply referred to as “Group VIII metal”) of the periodic table is supported on alumina or an alumina-containing carrier, and under hydrogen pressure In order to remove sulfur and metals, the operation is performed. However, with this catalyst, even if the sulfur compound is sufficiently removed, the metal may not be sufficiently removed.

Further, in the hydrotreatment of atmospheric residual oil, vacuum residual oil, and vacuum distillate oil, it is necessary to use a plurality of catalysts having different pore distributions, as disclosed in Japanese Patent Publication No. 49-18763. It is said to be effective. In this method, in a fixed bed reactor, a catalyst having a large pore size and a large metal allowance is arranged on the inlet side of the oil to be treated, and then a catalyst having a medium pore size and a medium desulfurization activity is arranged. , A catalyst with a small pore size and high desulfurization performance is placed on the outlet side, the metal contained in the oil to be treated is removed on the inlet side, and a small pore size that easily causes pore clogging by the metal on the outlet side has high desulfurization activity The protection of the catalyst is fundamental.

However, even with this method, satisfactory results have not yet been obtained. In other words, the catalyst with a large pore size and a large metal allowance, which is arranged on the inlet side, cannot completely capture the metal contained in the treated oil, and as a result, the medium fine particles arranged next are used. Metal is deposited on a catalyst having a medium size desulfurization activity with a pore size and a catalyst having a small pore size and high desulfurization performance, which shortens the life of the catalyst.

Therefore, in order to prolong the catalyst life as a whole, it is conceivable to increase the amount of the catalyst having a large pore size and having a large metal allowance. However, since the large pore size catalyst has a small surface area, sufficient desulfurization is performed. It exhibits no activity and thus reduces the desulfurization efficiency. Further, it is difficult to increase the permissible metal amount because the catalyst having a medium pore diameter and the catalyst having a small pore diameter and high desulfurization performance have a small pore volume.

The present invention has been made in order to solve such a problem, and has the same pore diameter and specific surface area and a larger metal allowable amount. In other words, the pore diameter and specific surface area are equal and finer. It is an object to provide a hydrotreating catalyst having a large pore volume.

[0009]

The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, (1) a group VIB metal and a group VIII metal are added to an alumina carrier containing zinc oxide.
A catalyst supporting a group metal can have the same pore size and can increase the pore volume without reducing the specific surface area,
(2) As a precursor of zinc oxide contained in alumina,
What is obtained by using zinc nitrate, zinc sulfate, zinc carbonate, zinc chloride, zinc acetate, and further by incorporating into alumina by the kneading method or coprecipitation method, the increase in pore volume is remarkable,
The present invention has been completed and the present invention has been completed.

That is, according to the present invention, an alumina carrier containing 1 to 15% by weight of zinc oxide is added to a Group VIB metal 5 to 3
0% by weight and 1 to 10% by weight of Group VIII metal, having an average pore diameter of 50 to 200Å and a total pore volume of 0.45 cm ³ / g or more. The gist is the hydrotreating catalyst of.

The above carrier is obtained by kneading alumina gel with at least one powder selected from zinc nitrate, zinc sulfate, zinc carbonate, zinc chloride and zinc acetate, followed by molding and firing, or alumina. A gel prepared by a coprecipitation method using a gel and one or more kinds of metal salts selected from zinc nitrate, zinc sulfate, zinc carbonate, zinc chloride and zinc acetate is preferable.

The catalyst of the present invention will be described in detail below. The carrier of the catalyst of the present invention is alumina containing zinc oxide. As this alumina, γ-alumina, χ
Any one of alumina and η-alumina, or a mixture thereof can be preferably used.

The content of zinc oxide contained in alumina is 1 to 15% by weight based on the weight of the catalyst.
If it is less than 1% by weight, the effect of improving the metal allowable amount does not appear, and if it exceeds 15% by weight, the specific surface area is remarkably reduced.
This defeats the purpose of increasing the pore volume while maintaining the pore diameter and the specific surface area at the same level.

1 to 15% by weight of zinc oxide based on this catalyst
The contained alumina carrier can be obtained by a usual method, but in the present invention, a water-soluble compound of aluminum as an alumina source, specifically, aluminum sulfate, chloride, alkali metal aluminate, aluminum. One or more selected from alkoxides and other inorganic acid salts and organic acid salts, and various zinc salts as precursors of zinc oxide, preferably zinc nitrate, zinc sulfate, zinc carbonate, zinc chloride and zinc acetate. Using one or more selected from
It is preferably obtained by a kneading method or a coprecipitation method.

Specifically, in the case of the kneading method, an acidic aluminum aqueous solution (concentration: 0.3 to 2 mol / liter)
(Hereinafter, liter is referred to as "L", and milliliter is referred to as "m".
L ", the normal liter is referred to as" NL ") and an alkali aluminate solution are added with an alkali hydroxide solution to obtain a pH of 6.0 to 11.0, preferably 8.0 to 1
In the range of 0.5, hydrogel or hydrosol is produced, or ammonia water, nitric acid, acetic acid or the like is appropriately added, and the suspension is adjusted to 5
Heat to 0-90 ° C and hold for at least 2 hours. The precipitate is then filtered off and washed with ammonium carbonate and water to remove impurity ions. After this,
A zinc oxide precursor may be added and kneaded.

In the case of the coprecipitation method, the aqueous solution of the zinc oxide precursor may be mixed with the aqueous solution of the alumina raw material before the pH adjustment.

The average pore size of the catalyst of the present invention is 50 to 50.
In order to make the total pore volume of 200 Å and 0.45 cm ³ / g or more, the average pore diameter and the total pore volume of the alumina carrier or the zinc oxide-containing alumina carrier are the same as those of the above-mentioned alumina or zinc oxide precursor-containing alumina. It is preferable to make appropriate adjustments by adjusting the temperature, time, etc. when precipitating the hydrate or aging the precipitate.

The alumina gel containing the zinc oxide precursor obtained as described above is then molded into a desired shape by an extruder. This molding is performed while adjusting the molding pressure so that the average pore diameter and the total pore volume of the catalyst of the present invention are as described above. The molded product is dried at 100 to 140 ° C. for several hours, and further calcined at 200 to 700 ° C. for several hours to complete the carrier.

The above-mentioned shape may be various, but a columnar shape, a dumbbell shape in which two small circles are cross-sectioned, a small circle stacked in a three-leaf shape or a four-leaf shape, etc. However, these small circles do not have to be perfect circles, but may be oval, or close to a rectangle, a square, or a rhombus. Further, it may have a hollow columnar shape or a character-shaped columnar shape such as T, I, C, E, or a mouth shape. Furthermore, the cross section is triangular, square, 5
It may be in the shape of a square, hexagonal or octagonal honeycomb or column.

The Group VIB metal supported on the above carrier is preferably one or more of Cr, Mo and W, and particularly preferably Mo. Group VIII metals include Fe, Co, Ni, Pd, Pt, Os, Ir, R
One or more of u and Rh, and preferably one or both of Ni and Co.

The above Group VIB metal and Group VIII metal are preferably supported as oxides or sulfides. The amount of such a metal component supported is 5 to 30% by weight of Group VIB metal as an oxide, based on the catalyst.
Preferably 7 to 25% by weight, more preferably 10 to 20
% By weight, and the Group VIII metal component is 1 to 10% by weight, preferably 2 to 8% by weight.

When the Group VIB metal component is less than 5% by weight,
When the preferable activity cannot be obtained and the amount exceeds 30% by weight, the dispersibility is reduced and, at the same time, the cocatalyst effect of the Group VIII metal component is difficult to be exhibited. If the group VIII metal component is less than 1% by weight, a sufficient effect cannot be obtained, and if it exceeds 10% by weight, the amount of free group VIII metal component that does not bind to the carrier increases.

If desired, it is also possible to support a third metal component in addition to the above Group VIB metal component and Group VIII metal component. The third metal component includes boron and phosphorus.

The loading of these metal components on the carrier is carried out by a usual impregnation method or a dipping method.
The order of loading may be either the Group VIB metal or the Group VIII metal first, or may be the same, but when the Group VIII metal is loaded first, the Group VIII metal and alumina form a composite oxide. However, since the amount of the Group VIII metal that does not act as the active site of the hydrotreating catalyst increases, it is preferable to use the Group VIB metal first. When carrying a third metal component, a Group VIB metal and a Group VIII
It may be carried after carrying the group metal.

In these impregnation methods and dipping methods,
The Group IB metal component is used as a compound that can be an aqueous solution of the above Cr, Mo, and W, and particularly ammonium dichromate ((NH ₄ ) ₂ Cr ₂ O ₇ ) and ammonium paramolybdate tetrahydrate ((NH _{4) 6 Mo 7 O 24 ·} 4H
₂ O) and tungstic acid (H ₂ WO ₄ ), of which ammonium paramolybdate tetrahydrate is preferable from the viewpoints of low cost and high safety of gas generated during firing.

Further, the Group VIII metal component is the above-mentioned F
e, Co, Ni, Pd, Pt, Os, Ir, Ru, Rh
Used as a compound that can be an aqueous solution of, especially cobalt nitrate, nickel nitrate, cobalt sulfate, nickel sulfate,
Cobalt carbonate, nickel carbonate, cobalt chloride, nickel chloride and the like are preferable, and cobalt nitrate and nickel nitrate are particularly preferable because they have high hydrogenation activity.

Further, the third metal component is used as a compound that can be an aqueous solution of the above boron and phosphorus, and is preferably boric acid (H ₃ BO ₃ ), phosphoric acid (H ₃ PO ₄ ).
And boric acid is particularly preferable.

The carrier carrying the metal component in this manner is separated from the impregnation or immersion solution, washed with water, dried and fired. The drying and firing conditions may be the same as those for the above-mentioned carrier.

It is important that the catalyst of the present invention obtained as described above has an average pore diameter of 50 to 200 Å. If it is less than 50Å, when hydrocarbon oil is treated,
Due to the metal contained in the treated oil, the pores of the catalyst are likely to be blocked, and if it exceeds 200 Å, the specific surface area decreases,
This is because it is difficult to obtain a sufficient specific surface area for preparing the catalyst.

This average pore diameter is determined as follows. First, the surface area is determined by the BET method from the nitrogen adsorption isotherm. On the other hand, for the pore distribution, a nitrogen adsorption / desorption isotherm (−196 ° C.) up to a relative pressure of 0.967 is measured, and from this, the distribution for pores having a radius of 200 Å or less is obtained by the BJH method or the DH method. Then, the average pore diameter is calculated from these results. At this time, as a representative value of the average pore diameter, a pore diameter that divides the pore volume into a portion having a diameter larger than that and a portion having a diameter smaller than that, that is, pores having a pore volume The median value of the distribution with respect to diameter is shown.

The total pore volume of the catalyst of the present invention is 0.
It is necessary to be 45 cm ³ / g or more. When the total pore volume is less than 0.45 cm ³ / g, the amount of metal that can be captured (metal allowable amount) becomes small within a range in which a certain amount of catalyst does not cause a decrease in activity, and as a result, the long-term ( This is because continuous operation becomes impossible for one year, for example.

The upper limit of the total pore volume is not particularly limited, but if the total pore volume is too large, the mechanical strength (side fracture strength) of the catalyst becomes small, which is a practical problem. It is preferable to set it to about 9.9 cm ³ / g.

Further, the catalyst of the present invention has a specific surface area of 20.
0-400 m ² / g, bulk density 0.5-1.0 g / m
Those having L and a side surface breaking strength of 0.8 to 3.5 Lbs / mm are good as a catalyst for hydrotreating heavy hydrocarbon oil.

The above catalyst of the present invention is preferably subjected to pre-sulfurization before being used for hydrotreating a hydrocarbon oil. Presulfiding can be carried out in-situ in the reaction tower where the hydrotreating of the hydrocarbon oil is carried out. That is, the catalyst of the present invention can be used as a sulfur-containing hydrocarbon oil (for example, sulfur-containing distillate oil).
And temperature 150-400 ° C, pressure (total pressure) 15-150
Kg / cm ² G, liquid hourly space velocity 0.3 to 8.0 hr
^-1 , contacted in the presence of a hydrogen-containing gas of 50-1500 L / L gas / oil ratio, and after the completion of this treatment, the above-mentioned sulfur-containing distillate oil was switched to the oil to be hydrotreated, Set the operating conditions suitable for desulfurization and start the operation.

In addition to such a method, hydrogen sulfide or other sulfur compound is directly contacted with the catalyst of the present invention, or
Alternatively, the catalyst of the present invention can be pre-sulfurized by a method of bringing the sulfur compound added to an appropriate distillate into contact with the catalyst of the present invention.

The above-mentioned oils to be hydrotreated are light oil obtained by atmospheric distillation or vacuum distillation of crude oil, atmospheric distillation residual oil, vacuum distillation residual oil and vacuum distillate oil.
It also includes coker light oil, solvent deasphalted oil, tar sand oil, shale oil, and coal liquefied oil.

Further, the hydrotreating conditions when using the catalyst of the present invention can be appropriately selected depending on the type of oil to be treated, the desulfurization rate, etc., but generally, the temperature is 300 to 5
00 ° C., hydrogen partial pressure 50 to 200 kg / cm ² G, hydrogen-containing gas / oil ratio 50 to 10000 L / L, liquid space velocity 0.
It is preferably ¹ to 10 hr ^-1 . The hydrogen concentration in this hydrogen-containing gas is preferably in the range of 60 to 100%.

Incidentally, the hydrotreating in the present invention is a general term for the treatment by contacting hydrocarbon oil and hydrogen as described above, and the hydrorefining and the severity of the reaction are comparatively low. It includes hydrorefining, hydroisomerization, hydrodealkylation, and other reactions of hydrocarbon oils in the presence of hydrogen, with a relatively high degree of cracking reaction. Specifically, hydrodesulfurization, hydrodenitrogenation, hydrodemetalization of distillate or residual oil of atmospheric distillation or vacuum distillation,
It also includes hydrocracking and also includes hydrorefining of kerosene fractions, gas oil fractions, waxes, and lubricating oil fractions.

In the hydrotreating catalyst of the present invention, the supported Group VIII metal component such as Ni effectively functions as a cocatalyst, but Ni removed together with V during hydrotreating of hydrocarbon oils. Is the supported Ni
Unlike, it has no cocatalyst effect. This is because the Ni removed from the hydrocarbon oil exists in the catalyst in a state different from that of the supported Ni, and not only does it exhibit a cocatalyst effect but also blocks the pores in the catalyst. This hinders the progress of hydrocarbon oil into the catalyst, which is one of the causes of lowering the catalytic activity.

[0040]

【Example】

[Catalyst Preparation Example] Example 1 29.8 kg of sodium aluminate solution (containing 23% by weight as Al ₂ O ₃ ) in 50 L of ion-exchanged water.
And 38.0 kg of aluminum sulfate solution (Al ₂ O ₃
7.9% by weight) was slowly added dropwise. After dropping, add the remaining sodium aluminate solution,
Finally, the pH of the solution was set to 11. The alumina slurry produced by the above operation was filtered, and the filtered precipitate (alumina gel) was first adjusted to pH 9 by adding ammonia.
Repeatedly wash with water adjusted to 2, then add nitric acid to p
It was repeatedly washed again with water whose H was adjusted to 6 to obtain an alumina cake.

Ion-exchanged water was added again to the alumina powder obtained by spray-drying this alumina cake to adjust the humidity. To this, 1.9 kg of zinc nitrate hexahydrate was added, and the mixture was kneaded with a kneader until it became sufficiently uniform. With an extruder,
It was extruded to fit the required catalyst diameter. The extrudate was dried overnight at 120 ° C and then at 730 ° C for 4 hours.
Burned for hours. 1 kg of the carrier prepared in this way
Samples were collected and the group VIB metal component and the group VI
A Group II metal component was supported.

230 g of ammonium paramolybdate tetrahydrate was completely dissolved in purified water, and the total amount was 1050 cc.
I chose This aqueous solution was then carefully added dropwise to the above carrier. After dropping all the aqueous solution, it was left still for 1 hour and dried with dry air. Then, it was baked at 480 ° C. for 4 hours to support molybdenum.

On the other hand, 121.6 g of nickel nitrate hexahydrate and 121.4 g of cobalt nitrate were dissolved in purified water to a total amount of 1050 cc. This aqueous solution was carefully added dropwise to the above molybdenum-supported catalyst. After dropping all the aqueous solution, it was left still for 1 hour and dried with dry air. Then, it was baked at 480 ° C. for 4 hours to support nickel. The properties of the catalyst obtained as described above are shown in Tables 1 and 2.

Example 2 A catalyst was prepared in the same manner as in Example 1 except that 1.8 kg of zinc sulfate heptahydrate was used instead of 1.9 kg of zinc nitrate hexahydrate. The properties of the obtained catalyst are also shown in Tables 1 and 2.

Example 3 A catalyst was prepared in the same manner as in Example 1 except that 0.9 kg of zinc carbonate was used instead of 1.9 kg of zinc nitrate hexahydrate. The properties of the obtained catalyst are also shown in Tables 1 and 2.

Example 4 A catalyst was prepared in the same manner as in Example 1 except that 0.8 kg of zinc chloride was used instead of 1.9 kg of zinc nitrate hexahydrate. The properties of the obtained catalyst are also shown in Tables 1 and 2.

Example 5 A catalyst was prepared in the same manner as in Example 1 except that 1.4 kg of zinc acetate dihydrate was used instead of 1.9 kg of zinc nitrate hexahydrate. The properties of the obtained catalyst are also shown in Tables 1 and 2.

Example 6 A catalyst was prepared in the same manner as in Example 1 except that the firing temperature of the extruded product was 680 ° C. The properties of the obtained catalyst are also shown in Tables 1 and 2.

Example 7 A catalyst was prepared in the same manner as in Example 1 except that the firing temperature of the extruded product was 780 ° C. The properties of the obtained catalyst are also shown in Tables 1 and 2.

Example 8 Example 1 except that zinc nitrate hexahydrate was 0.7 kg.
A catalyst was prepared in the same manner as in. The properties of the obtained catalyst are also shown in Tables 1 and 2.

Example 9 Example 1 was repeated except that 3.1 kg of zinc nitrate hexahydrate was used.
A catalyst was prepared in the same manner as in. The properties of the obtained catalyst are also shown in Tables 1 and 2.

Example 10 Example 1 was repeated except that the amount of zinc nitrate hexahydrate was 4.9 kg.
A catalyst was prepared in the same manner as in. The properties of the obtained catalyst are also shown in Tables 1 and 2.

Example 11 29.8 kg of sodium aluminate solution (containing 23% by weight as Al ₂ O ₃ ) in 50 L of ion-exchanged water
And 38.0 kg of aluminum sulfate solution (Al ₂ O ₃
7.9% by weight) and zinc nitrate hexahydrate 1.9
A catalyst was prepared in the same manner as in Example 1 except that a zinc nitrate solution containing kg was slowly added dropwise. The properties of the obtained catalyst are also shown in Tables 1 and 2.

Comparative Example 1 230 g of ammonium paramolybdate tetrahydrate was completely dissolved in purified water to a total amount of 1000 cc, and 121.6 g of nickel nitrate hexahydrate and 121.4
g of cobalt nitrate and dissolved in purified water to a total amount of 1000c
A catalyst was prepared in the same manner as in Example 1 except that the catalyst c was used and the procedure of kneading the humidity-controlled alumina powder with a kneader was omitted. The properties of the obtained catalyst are shown in Table 1.
And also shown in Table 2.

Comparative Example 2 A catalyst was prepared in the same manner as in Comparative Example 1 except that the firing temperature of the extruded product was 680 ° C. The properties of the obtained catalyst are also shown in Tables 1 and 2.

Comparative Example 3 A catalyst was prepared in the same manner as in Comparative Example 1 except that the firing temperature of the extruded product was 780 ° C. The properties of the obtained catalyst are also shown in Tables 1 and 2.

[0057]

[Table 1]

[0058]

[Table 2]

[Catalyst Performance Evaluation Example 1] The performances of the catalysts obtained in the above Examples and Comparative Examples were evaluated by a hydrodesulfurization relative activity evaluation test under the conditions shown in Table 3. The results are shown in Table 4.
Shown in.

[0060]

[Table 3]

The evaluation method of the relative activity evaluation test for hydrodesulfurization was as follows. The hydrodesulfurization reaction was carried out under the conditions shown in Table 3, and the residual sulfur content (% by weight) of the reaction product on the 90th day and vanadium (pp
m) and nickel (ppm), and the reaction rate constant was calculated by the formula shown in Formula 1.

[0062]

[Equation 1]

The above-mentioned relative desulfurization activity is (Ks) _A
/ (Ks) _B. Here, A indicates a target catalyst, and B indicates a reference catalyst for comparison.

[0064]

[Table 4]

[Catalyst Performance Evaluation Example 2] The performances of the catalysts obtained in the above Examples and Comparative Examples were evaluated by a relative metal tolerance evaluation test under the conditions shown in Table 5. The results are shown in Table 6.

[0066]

[Table 5]

The evaluation method of the relative metal allowance test is as follows: the hydrogenation treatment is carried out under the conditions shown in Table 5, and the catalyst reference metal deposition amount when the desulfurization rate is 20% (residual sulfur concentration 3.57%) is the metal allowance. It was decided to evaluate as. The results are shown in Table 6.

[0068]

[Table 6]

[0069]

As described in detail above, according to the catalyst of the present invention containing zinc oxide in the carrier, the pore volume is increased even though the pore diameter and the specific surface area are equal, As a result, there is an advantage that the metal allowance can be increased by about 10%. Therefore, when the catalyst of the present invention is used to perform hydrotreating on atmospheric residual oil, vacuum residual oil, vacuum distillate, etc., without increasing the desulfurization activity, the catalyst life is improved, in other words, Continuous operation for a longer period becomes possible.

Continuation of the front page (72) Inventor Kaiji Usui 1134-2 Gongendo, Satte City, Saitama Cosmo Research Institute Co., Ltd.

Claims (3)

[Claims] 1. An alumina carrier containing 1 to 15% by weight of zinc oxide based on the catalyst, 5 to 30% by weight of a metal component of Group VIB of the periodic table as an oxide, and VI of the periodic table.
1 to 10% by weight of a Group II metal component supported as an oxide, an average pore diameter of 50 to 200Å, and a total pore volume of 0.45c
A catalyst for hydrotreating a hydrocarbon oil, characterized by having m ³ / g or more. 2. The carrier is formed by kneading alumina gel with at least one powder selected from zinc nitrate, zinc sulfate, zinc carbonate, zinc chloride and zinc acetate, and molding and firing. A catalyst for hydrotreating a hydrocarbon oil according to claim 1. 3. The carrier is prepared by a coprecipitation method using alumina gel and one or more kinds of metal salts selected from zinc nitrate, zinc sulfate, zinc carbonate, zinc chloride and zinc acetate. The catalyst for hydrotreating a hydrocarbon oil according to claim 1, which is characterized in that: