JPH06269670A - Production of catalyst composition for hydrogenation treatment of hydrocarbon oil - Google Patents

Abstract

PURPOSE:To produce a catalyst compsn. for hydrogenation treatment of hydrocarbon oil having high desulfurization activity by carrying hydrogenating active components of one kind of a metal belonging to the group VIA of the Periodic Table and one kind of metal belonging to the group VIII of the Periodic Table on a carrier containing alumina (A) and at least one kind of metal oxide (B) among Mo-oxide and W-oxide. CONSTITUTION:Hydrogenating active components of at least one kind of a metal (e.g. Mo) selected from group VIA metals and at least one kind of a metal (e.g. Co) selected from group VIII metals are carried by a carrier containing alumina (A) and metal oxide (B) among Mo-oxide and W-oxide. As a result, a large quantity of hydrodesulfurizing active metals can be carried in a highly dispersed state and desulfurization activity can be enhanced.

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 hydrotreating catalyst composition for a hydrocarbon oil, and more specifically, to a sulfur component contained in the hydrocarbon oil when hydrotreating the hydrocarbon oil. The present invention relates to a method for producing a hydrotreating catalyst composition for a hydrocarbon oil, which has an excellent activity capable of remarkably reducing the amount.

[0002]

BACKGROUND OF THE INVENTION Since hydrocarbon oils generally contain sulfur compounds, when these oils are used as fuel,
Sulfur existing in the sulfur compound is converted into a sulfur compound and discharged into the atmosphere, polluting the atmosphere. Therefore, in order to prevent air pollution, it is desirable that the hydrocarbon oil used as a fuel has a sulfur content as low as possible. Especially recently
Under the situation where environmental degradation due to acid rain and nitrogen oxides is progressing on a global scale, in order to solve this environmental degradation problem, the development of technology to further reduce the sulfur content in hydrocarbon oils has been developed. Is desired. Conventionally, reduction of the sulfur content in hydrocarbon oils has been carried out by catalytic hydrodesulfurization of hydrocarbon oils, and the operating conditions of this catalytic hydrodesulfurization, such as LHSV, temperature, pressure, etc., are severely affected. This has been achieved to some extent by doing.

However, such a harsh operating method has a drawback that carbonaceous matter is deposited on the catalyst and the activity of the catalyst is rapidly lowered. Furthermore, when the hydrocarbon oil is a light fraction, there are adverse effects on properties such as hue stability and storage stability. Thus, there is a limit to desulfurization under severe operating conditions. Therefore, the best strategy is to develop catalysts with significantly better desulfurization activity.

By the way, conventionally, as a general method for preparing a hydrodesulfurization catalyst, an aqueous solution of a metal salt of Group 8 of the periodic table and a metal salt of Group 6A of the periodic table is impregnated into a carrier, followed by drying and firing. The so-called "impregnation method", in which an aqueous solution of Group 6A metal salt of the periodic table and an aqueous solution of Group 8 metal salt of the periodic table are added to an aqueous solution in which alumina or alumina gel is dispersed,
The "coprecipitation method" of precipitating a metal compound, and further heating and moisture removal while kneading a mixed paste of alumina or alumina gel, an aqueous solution of a metal salt of Group 6A of the Periodic Table and an aqueous solution of a metal salt of Group 8 of the Periodic Table. There is a "kneading method" (catalyst preparation chemistry), edited by Ban Ozaki, Kodansha Scientific, pp. 205-252. Here, alumina is most often used as the alumina carrier.
As a method for producing the alumina, a method of mixing each aqueous solution of aluminum sulfate and sodium aluminate, adjusting the pH, and aging to produce a precipitate of aluminum hydroxide (JA Lewis. J. Appl. Che
m. , 8.223 (1958)), a method for obtaining a basic aluminum chloride hydrogel by dissolving aluminum metal in an aqueous solution of aluminum chloride (Universa).
Oil Products. Japanese Patent Publication 29-1977
No.), a method for obtaining a colloidal solution of basic aluminum sulfate by neutralizing the aluminum sulfate solution in calcium carbonate (Mizusawa Kagaku Kogy).
o, USP 3,183,194 (1965)) and the like. Although not so common as alumina, alumina-silica, alumina-titania, alumina-boria, etc. in which silica, titania, boria, etc. are combined with alumina may also be used as the carrier. As a method for producing this alumina-silica carrier, a method (Japanese Patent Publication No. 55-44795) obtained by mixing silica hydrogel obtained from a sodium silicate solution and alumina gel obtained from an aluminum nitrate solution has been reported. Alumina-titania and alumina-boria carriers can also be manufactured by the same method.

However, with the above-mentioned conventional catalyst manufacturing technology, it is not possible to reduce the sulfur content to a level that can prevent environmental deterioration such as air pollution. By the way, in order to enhance the desulfurization activity of the catalyst for hydrodesulfurization of hydrocarbon oil, it is necessary to use a carrier having a high specific surface area and highly disperse the active metal therein. For this,
The nature of the carrier portion supporting the active metal is extremely important, and it is necessary to manufacture a carrier capable of further increasing the dispersibility of the active metal as compared with the carrier obtained by the above-mentioned conventional technique.

[0006]

The present invention has been made in view of the above-mentioned situation of the prior art, and it is possible to support a large amount of hydrodesulfurization active metal components in a high dispersion, and as a result, desulfurization activity is achieved. It is an object of the present invention to provide a method for producing a hydrotreating catalyst composition for a hydrocarbon oil, which is capable of increasing the oil content.

[0007]

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention first found that the second component of the carrier was alumina, which is commonly used for this type of catalyst carrier. As a result, by mixing at least one selected from molybdenum oxide and tungsten oxide, and then carrying a step of supporting a catalytically active component thereon, it is possible to highly disperse the catalytically active component. The present invention has been completed and the present invention has been completed.

That is, the present invention provides a carrier containing (A) alumina and (B) at least one metal oxide of molybdenum and tungsten, and at least one metal selected from Group 6A metals of the periodic table. Provided is a method for producing a hydrotreating catalyst composition for a hydrocarbon oil, which comprises supporting at least one hydrogenation active component selected from Group 8 metals of the periodic table. Hereinafter, the present invention will be described in detail.

In the method for producing a hydrotreating catalyst composition for hydrocarbon oil of the present invention, a carrier containing (A) alumina and (B) at least one metal oxide of molybdenum and tungsten is used as a carrier. . As the first component of the carrier, various alumina such as α-alumina, β-alumina, γ-alumina, δ-alumina can be used, but γ-alumina is preferable. On the other hand, as the metal oxide of molybdenum or tungsten, which is the second component of the carrier, various oxides of molybdenum and tungsten can be used, but WO ₃ , M
oO ₃ is preferable, and MoO ₃ is particularly preferable. The mixing ratio of these two components is such that at least one metal oxide of molybdenum and tungsten is 1 to 2 with respect to the carrier.
It is in the range of 0% by weight, preferably 2 to 15% by weight. At least one of molybdenum and tungsten
If the content of the seed metal oxide is less than 1% by weight, the activity is unlikely to increase, while if it exceeds 20% by weight, the surface area of the carrier decreases and the activity tends to decrease. The molybdenum and tungsten oxides in the carrier are preferably well dispersed in the carrier.

The carrier used in the method of the present invention is preferably synthesized by the following two methods. Method (a): Alumina gel, which is a precursor substance of alumina which is the first component of the carrier, is obtained by neutralizing an aluminum salt such as aluminum sulfate with a base such as ammonium or an alumina salt such as sodium aluminate. The acid salt can be obtained by neutralizing the acid salt with an acid aluminum salt or an acid and thoroughly washing the resulting gel with aqueous ammonia. On the other hand, the precursor substances of the oxides of molybdenum and tungsten, which are the second component of the carrier, are ammonium paramolybdate, molybdic acid, ammonium molybdate, ammonium phosphomolybdate, phosphomolybdic acid, ammonium paratungstate, tungstic acid, An aqueous solution of ammonium tungstate, ammonium phosphotungstate, phosphotungstic acid, or the like is used. In this method, with the alumina gel obtained as described above,
At least one aqueous solution or hydroxide selected from molybdenum and tungsten compounds is put in a kneader and sufficiently kneaded. After kneading, it is molded with an extruder so as to have a required catalyst diameter, dried, and usually about 350 to 600.
C, preferably in the range of about 400-500 ° C,
Usually, the carrier is obtained by firing for 1 hour or more, preferably 2 to 24 hours.

Method (b): A raw material of alumina which is the first component of the carrier, for example, an aqueous solution of sodium aluminate, aluminum nitrate, aluminum sulfate and the like, and a raw material of oxides of molybdenum and tungsten which are the second component of the carrier. For example, an aqueous solution of ammonium paramolybdate, molybdic acid, ammonium molybdate, ammonium phosphomolybdate, phosphomolybdic acid, ammonium paratungstate, tungstic acid, ammonium tungstate, ammonium phosphotungstate, phosphotungstic acid, etc. Prepare by precipitation method. The slurry obtained by the coprecipitation method is filtered, kneaded, and extruded.
After kneading, it is molded into a required catalyst diameter with an extruder and is usually about 350 to 600 ° C., preferably about 400.
The carrier is obtained by baking at ˜500 ° C. for usually 1 hour or longer, preferably 2 to 24 hours.

The carrier of the method (a) or (b) is a method generally known in the catalyst manufacturing industry, for example, after extruding a precursor of a desired carrier through a die having an opening having a desired size and shape, Depending on the method such as cutting to the desired length,
It is used as shaped particles. The carrier of the present invention may contain other carrier components as long as the object of the present invention is not impaired. Other carrier components include, for example, silica, boria, chromia, magnesia, zirconia, 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 and the like or a mixture of one or more of these. Further, the carrier or catalyst of the present invention may contain one or more clay minerals such as montmorillonite, kaolin, halosite, bentonite, adabargite, bauxite, kaolinite, nacrite and anoxite. The shape of the carrier of the present invention is not particularly limited, and those having an ordinary catalyst carrier shape can be used, and the size is usually 1/10 to 1
The shape is preferably / 22 inches, and the shape thereof is preferably a four-lobed type if the hydrocarbon oil is a heavy oil and a cylindrical type if the hydrocarbon oil is a light oil.

In the method of the present invention, the hydrogenation active component loaded on the carrier is at least one selected from the metals of Group 6A of the Periodic Table and at least the metal of Group 8 of the Periodic Table. It is one hydrogenation active ingredient. Examples of the Group 6A metal of the periodic table include chromium, molybdenum, and tungsten. Molybdenum and tungsten are preferable, and molybdenum is particularly preferable. Examples of the Group 8 metal of the periodic table include iron, cobalt, nickel, ruthenium, rhodium, palladium, platinum and the like, with cobalt and nickel being preferred. The method of loading the Group 6A and Group 8 metal components on the carrier can be carried out by an ordinary loading method. Examples of the loading method include, for example, immersing the carrier in a solution containing these hydrogenation-active components, dropping this solution on the carrier, or precipitating the hydrogenation-active component in a state where the carrier is immersed in the solution. By contacting the carrier with the hydrogenation-active ingredient, such as adding an agent to deposit the hydrogenation-active ingredient on the carrier,
A method of supporting a hydrogenation active component on a carrier can be adopted. Further, the order of loading the 6A metal active component of the periodic table and the 8th metal active component of the periodic table may be either first or simultaneously.

Groups 6A and 8 of the Periodic Table which can be used to prepare solutions containing hydrogenating active ingredients.
Various compounds can be used as the group metal compound, and examples of the molybdenum compound include ammonium paramolybdate, molybdic acid, ammonium molybdate, ammonium phosphomolybdate, and phosphomolybdic acid. Examples thereof include nickel nitrate, sulfate, fluoride, chloride, bromide, acetate, carbonate and phosphate. In addition to these compounds, metal compounds of Groups 6A and 8 of the periodic table known to those skilled in the art as those that can be used in this kind of field can be used.

The solvent that can be used to prepare the solution containing the hydrogenation active component is not particularly limited, and various solvents can be used, for example, water, alcohols, ethers. , Ketones, aromatics, preferably water, acetone, methanol,
Ethanol, n-propanol, isopropanol, n
-Butanol, isobutanol, hexanol, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane and the like can be mentioned, and water is particularly preferable. The concentration of the hydrogenation active component in the solution containing the hydrogenation active component is not particularly limited and may be appropriately selected.
It is in the range of 60% by weight, preferably in the range of 5 to 40% by weight. The temperature at which the solution is brought into contact with the carrier is usually in the range of 0 to 60 ° C, preferably 10 to 3
It is in the range of 0 ° C.

After carrying out the treatment for supporting the hydrogenation active component on the carrier as described above, it is preferable to carry out drying and baking by a usual method. Drying is usually from room temperature to about 15
It is carried out by holding at 0 ° C, preferably 100 to 120 ° C for usually 10 minutes or longer, preferably 1 to 24 hours, and firing is usually about 350 to 600 ° C, preferably about 40.
0 to 550 ° C., usually 1 hour or more, preferably 2 to 24
It is performed by holding for a time.

The catalyst obtained by the process of the invention is usually about 7 to 35% by weight, preferably about 10 to 30% by weight, of Group 6A metal, calculated as oxide, based on the catalyst, and usually about 3%.
-15 wt%, preferably about 3-10 wt% Group 8 metal. It is considered that most of these hydrogenation active components become oxides and some become simple substance elements in the catalyst after the above-mentioned calcination. If the catalyst obtained by the process according to the invention is used in the form of sulphides, it is presulphurised. As a method of pre-sulfurization, a method of passing a hydrocarbon oil containing about 1% by weight or more of sulfur or a gas phase sulfide on a catalyst under high temperature and high pressure is adopted.

The hydrocarbon oil to which the catalyst obtained by the method of the present invention can be applied includes crude oil distillate and residual oil under atmospheric pressure, distillate oil and residual oil under reduced pressure, visbreaking oil, tar sands. Examples include oil and shale oil. In particular, the catalyst obtained by the method of the present invention is a medium distillate such as a kerosene fraction and a gas oil fraction, a heavy distillate of vacuum distillation,
It is suitable for carrying out the hydrotreatment of residual oil containing asphalt, or a mixed oil of these.

As the hydrotreating conditions of the hydrocarbon oil with the catalyst obtained by the method of the present invention, usual hydrotreating conditions can be adopted, but the temperature is about 200 to 450 ° C., the pressure is about 10 to 200 kg /. cm ² , LHSV (liquid hourly space velocity) is preferably about 0.1 to 5 hr ^-1 . In addition,
The hydrotreating in the present invention refers to a treatment by contacting a hydrocarbon oil with hydrogen, which is a hydrorefining with relatively low severity of reaction conditions and a hydrorefining with some cracking reaction with relatively high severity. , Hydrosulfurization, hydrodealkylation, and other reactions of hydrocarbon oils in the presence of hydrogen. For example, it includes hydrodesulfurization, hydrodenitrogenation and hydrocracking of distillate and residual oil of atmospheric distillation or vacuum distillation, and also hydrogenation of kerosene fraction, gas oil fraction, wax and lubricating oil fraction. Including purification etc.

[0020]

In the method of the present invention, unlike the conventional method of impregnating and supporting the hydrogenation active component on the alumina carrier, a part of the hydrogenation active component such as molybdenum and tungsten is used as the second component of the carrier in advance. Alumina, which is a component, is contained in a uniform state, and the carrier is loaded with an active component for hydrotreating, which comprises a metal of Groups 6A and 8 of the periodic table. Then, the above carrier is added to the 6A group and 8th group of the periodic table.
The group metal component is supported with a high degree of dispersibility. The reason for this is not clear, but the above two components and the 6A
It is presumed that this is due to the affinity with the group metals and the group 8 metals. As described above, since the catalyst obtained by the method of the present invention carries the hydrogenation active component in a highly dispersed state, it realizes extremely high efficiency hydrotreating as compared with hydrotreating of hydrocarbon oil. , It is possible to provide a highly desulfurized fuel product that can meet the demand for air pollution control on a global scale.

[0021]

EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples. The present invention is not limited to these examples. Example 1 113 g of gibbsite (34% LOI) was added to 87% of 27% sulfuric acid.
After putting into 7 g and slowly dissolving at a temperature of 100 ° C., the temperature was lowered to 60 ° C. to prepare 990 g of aluminum sulfate. After 282 g of gibbsite (34% LOI) was slowly dissolved in 482 g of 36% sodium hydroxide at 115 ° C, the temperature was lowered to 60 ° C to prepare 764 g of sodium aluminate. The above 2 aqueous solution was gradually added dropwise to a container containing 1400 g of water at 60 ° C. so that the pH became 7. The dropping time required 45 minutes. Excessive sodium aluminate aqueous solution 135 in the precipitation generation step
g was added dropwise to the slurry to raise the pH to 10. The total amount of the aqueous solution used above is 66 aqueous solution of aluminum sulfate.
It was 7 g and 549 g of an aqueous solution of sodium aluminate.

After aging the slurry for 1 hour, it was vacuum filtered and dissolved in 50 ml of deionized water. 20 g of ammonium molybdate was dissolved in 100 ml of ion-exchanged water.
530 g (76% LOI) of alumina hydrogel was reacted with the above aqueous solution at pH 6 for 2 hours. The pH was adjusted with nitric acid. The slurry was filtered and removed under reduced pressure with 200 ml of water. After kneading at 50 ° C until LOI becomes about 60%, extrusion molding is performed and firing is performed at 470 ° C for 5 hours.
A carrier (1/16 inch cylindrical molded product) composed of oO ₃ (11% by weight) and Al ₂ O ₃ (89% by weight) was obtained. In a eggplant-shaped flask, 20.0 g of ammonium molybdate was dissolved in 100 ml of ion-exchanged water, and 144 g of the above carrier was immersed in this solution at room temperature. It was air-dried for 1 hour and fired in a muffle furnace at 470 ° C. for 5 hours. Further, 25 g of cobalt nitrate was immersed in an aqueous solution in which 100 ml of ion-exchanged water was dissolved to carry cobalt. After air-drying, it was calcined at 470 ° C. for 5 hours, and was made of CoO (4 wt%), MoO ₃ (17 wt%) and Al ₂ O ₃ (79 wt%) (Catalyst A).
Got

Example 2 2.98 kg of sodium aluminate solution (containing about 2.3 wt% as Al ₂ O ₃ ) in 5 l of ion-exchanged water
And 3.80 kg of an aluminum sulfate solution (containing about 7.9% by weight of Al ₂ O ₃ ) were slowly added dropwise. At this time, the pH of the solution was maintained between 8 and 9. Finally, the remaining sodium aluminate solution was added to finally set the pH of the solution to 11. The alumina slurry produced by the above operation was filtered, and the precipitate (alumina gel) separated by filtration was first washed repeatedly with water prepared by adding ammonia to pH 9 and then adding nitric acid to prepare PH 6 Repeatedly washed with to obtain an alumina gel.

On the other hand, in 350 ml of deionized water,
62.6 g of ammonium molybdate was dissolved into an aqueous solution. The above-mentioned alumina gel and ammonium molybdate aqueous solution were placed in a kneader and kneaded for 3 hours. After that, the temperature in the kneader was set to 50 ° C. and the LOI was about 6
After kneading to 0%, extrusion molding is performed at 470 ℃
After firing for 5 hours, MoO ₃ (10 wt%) and Al ₂ O
_A carrier (1/16 inch cylindrical molded product) composed of ₃ (90% by weight) was obtained. The subsequent steps are the same as in Example 1. As a result, a catalyst (catalyst B) composed of CoO (4% by weight), MoO ₃ (17% by weight) and Al ₂ O ₃ (79% by weight) was obtained.

Example 3 253 g of ammonium molybdate was added to 8.33 l of water (pH 5.9) and stirred at room temperature for 20 minutes. The final PH was 5.1. 1.37 l of water (pH 5.9)
1020 g of sodium aluminate was added to the mixture and stirred at 60 ° C. for 20 minutes. The final pH was 14.07.
Aluminum sulphate 14 in 1.27 l of water (pH 5.9)
09 g was added and the mixture was stirred at room temperature for 20 minutes. The final pH is
It became 0.47.

In the above ammonium molybdate aqueous solution,
The sodium aluminate aqueous solution and the sodium sulfate aqueous solution were gradually added dropwise so as to have a pH of 6.5 to 7.3. The dropping time took 40 minutes. The final pH was 7.17. After completion of dropping, aging was carried out for 2 hours. The slurry was filtered and removed under reduced pressure with 200 ml of water. After kneading at 50 ° C. until the LOI becomes about 60%, extrusion molding is performed and baking is performed at 470 ° C. for 5 hours to obtain a carrier (MoO ₃ (20 wt%) and Al ₂ O ₃ (80 wt%) ( 1/16
Inch cylindrical molded product) was obtained. 13.0 g of ammonium molybdate in an eggplant-shaped flask is deionized water 70
100 g of the above carrier was immersed in this solution at room temperature. Air-dry for 1 hour, then in a muffle furnace at 470 ° C for 5
Burned for hours. Further, 40 g of cobalt nitrate was immersed in an aqueous solution in which 70 ml of ion-exchanged water was dissolved to carry cobalt. After air-drying, calcination is performed at 470 ° C. for 5 hours to obtain CoO.
(8% by weight), MoO ₃ (25% by weight) and Al ₂ O ₃ (6
A catalyst (Catalyst C) consisting of 7% by weight) was obtained. Example 1
The composition of the catalyst obtained in No. 3 is shown in Table 1.

[0027]

[Table 1]

Comparative Example 1 5.0 g of ammonium molybdate in an eggplant-shaped flask
Is dissolved in 14.5 ml of ion-exchanged water, and 20 g of an alumina carrier having a pore volume of 0.58 ml / g and a surface area of 267 m ₂ / g (substantially 1/16 inch columnar molded product made of γ-alumina) is dissolved in this solution. Was soaked. It was air-dried for 1 hour and baked in a muffle furnace at 470 ° C. for 5 hours. Further, 5.1 g of cobalt nitrate was immersed in an aqueous solution in which 14.5 ml of ion-exchanged water was dissolved to carry cobalt. After air drying 470
After firing for 5 hours at ℃, CoO (5% by weight) and MoO ₃ (1
A catalyst (Catalyst D) consisting of 7% by weight) and Al ₂ O ₃ (78% by weight) was obtained. Table 2 shows the physical properties of the catalyst D obtained in Comparative Example 1.
Shown in.

[0029]

[Table 2]

Catalysts A to D shown in the above Examples and Comparative Examples
Example 4 of hydrodesulfurization method of hydrocarbon oil using
10 to 10 and Comparative Examples 2 to 4.

Examples 4 to 6 and Comparative Example 2 (hydrodesulfurization reaction of light oil) Feed oil: LGO (specific gravity (15/4 ° C.) 0.851, sulfur content 1.35% by weight, nitrogen content 20 ppm, viscosity ( @ 30
℃) 5.499 cst) Reaction conditions: reaction temperature: 350 ° C., reaction pressure: 35 kg / cm ² liquid space velocity: 4 hr ⁻¹ device: high pressure flow reactor of fixed bed system catalyst: catalysts A, B, C, D Evaluation method: The sulfur content of the produced oil after 20 days of running under the above operating conditions was examined. The results are shown in Table 3.

[0032]

[Table 3]

Examples 7 and 8 and Comparative Example 3 (VGO hydrodesulfurization reaction) Feed oil: VGO (specific gravity (15/4 ° C.) 0.916, sulfur content 2.53% by weight, nitrogen content 780 ppm, viscosity ( @ 30
℃) 288 cst) Reaction conditions: reaction temperature: 350 ° C., reaction pressure: 52 kg / cm ² liquid space velocity: 0.4 hr ⁻¹ apparatus: high pressure flow type reaction apparatus by fixed bed system catalyst: catalysts A, B, D evaluation method : The sulfur content of the produced oil after 100 hours of running under the above operating conditions was examined. The results are shown in Table 4.

[0034]

[Table 4]

Examples 9 and 10 and Comparative Example 4 (Hydrodesulfurization of heavy oil) Feedstock: Atmospheric distillation residue of Kuwait crude oil (specific gravity (15
/ 4 ° C) 0.956, sulfur content 3.77% by weight, asphaltene 3.9% by weight, vanadium 48 ppm, nickel 14 ppm) Reaction conditions: reaction temperature: 360 ° C, reaction pressure: 150 kg / cm ² liquid space velocity: 1 0.0 hr ^-1 device: high pressure flow reactor by fixed bed system catalyst: catalysts A, B, D Evaluation method: The sulfur content of the produced oil after 100 hours of running under the above operating conditions was examined. The results are shown in Table 5.

[0036]

[Table 5]

[0037]

EFFECTS OF THE INVENTION According to the method of the present invention, a hydrogenation active component is supported on a composite carrier in which a part of the active components of molybdenum and tungsten are mixed in advance with alumina which is the main component of the carrier. By virtue of the affinity between the hydrogenation active component and the second component, it is possible to obtain a catalyst carrying the hydrogenation active component with dramatically higher dispersibility than the catalyst prepared by the conventional method. . Therefore, the catalyst obtained by the method of the present invention exhibits a significantly higher desulfurization activity for both feedstocks of petroleum fractions and residual oils than the conventional catalysts. It has a significant effect on the distillate feedstock.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazushi Usui 1-62-10 Iwana, Noda City, Chiba Prefecture

Claims (1)

[Claims] 1. A carrier containing at least one metal oxide selected from the group consisting of (A) alumina and (B) molybdenum and tungsten, and at least one selected from Group 6A metals of the Periodic Table and the Periodic Table. A method for producing a hydrotreating catalyst composition for a hydrocarbon oil, which comprises supporting at least one hydrogenation active component selected from Group 8 metals.