JP2000008050A - Catalyst for hydrotreatment and hydrotreatment of hydrocarbon oil using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst for hydrotreatment having high resistance to hydrogen sulfide inhibition and high activity and excellent in the ability to maintain the activity and to provide a method for hydrotreating a sulfur- containing hydrocarbon oil using the catalyst for hydrotreatment. SOLUTION: This catalyst for hydrotreatment has >=50 μmol/g total amount of Broensted acids and is obtained by supporting a hydrogenated active metal component on a carrier freed of the amount of a strong Broensted acid. The carrier contains at least one kind of metal component selected from the group consisting of alkali metals and alkaline earth metals in an amount of 0.01-8 wt.% based on the total weight of the carrier and expressed in terms of the amount of the metal. The hydrogenated active metal component is at least one kind of the active metal component selected from the group consisting of a group 6 metal of the periodic table and a group 8 metal of the same table. The method for hydrotreating a hydrocarbon oil comprises bringing the hydrocarbon oil into contact with hydrogen in the presence of the catalyst for hydrotreatment under hydrotreating conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrotreating catalyst and a method for hydrotreating a hydrocarbon oil using the same. More specifically, the present invention relates to a hydrotreating catalyst having high resistance to hydrogen sulfide, high activity, and The present invention relates to a hydrotreating catalyst excellent in activity maintaining ability and a method for hydrotreating a sulfur-containing hydrocarbon oil using the same.

[0002]

BACKGROUND ART Conventionally, catalysts for hydrotreating hydrocarbon oils,
In particular, as the hydrodesulfurization catalyst, a refractory inorganic oxide such as silica, alumina, magnesia or the like is used as a carrier, and this is used as a hydrogenation active metal component.
Those carrying a group metal are used. Molybdenum and tungsten are used as Group 6 metals in the Periodic Table, and cobalt and nickel are used as Group 8 metals in the Table. Combinations of these Group 6 metals and Group 8 metals, for example, molybdenum- Two or more hydrogenation-active metal components such as cobalt, molybdenum-nickel, tungsten-cobalt, tungsten-nickel, and molybdenum-cobalt-nickel have been used. However,
When desulfurizing a hydrocarbon oil having a high sulfur content using such a hydrogenation-active metal component, there has been a problem that as the concentration of hydrogen sulfide in the reaction atmosphere increases, the desulfurization activity decreases. In particular, it was pointed out that the activity of the molybdenum-nickel catalyst deteriorated.

In recent years, from the viewpoint of environmental protection measures,
It has become an issue to reduce the sulfur content of gas oil fractions such as light gas oil (LGO) and vacuum gas oil (VGO) to 0.05% by weight or less, and even more severe deep desulfurization has been required.
In order to achieve the task of reducing the sulfur content, 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyldibenzothiophene (2,4- The key is whether a desulfurization reaction such as DMDBT) can be performed and the reaction can be efficiently promoted in the presence of a large amount of hydrogen sulfide.

[0004] Therefore, the present inventors have previously improved the hydrogen sulfide inhibition resistance by causing the Bronsted acid sites of the support of the hydrotreating catalyst to interact with the hydrogenation active metal component. Further, it has been found that a high desulfurization activity is obtained, and a carrier having a Bronsted acid amount of 50 μmol / g or more is selected from at least one active metal component selected from Group 8 metals of the periodic table and a Group 6 metal of the same table. A hydrotreating catalyst supporting at least one active metal component has been proposed (Japanese Patent Application No. 9-333532). However, although control of Bronsted acid sites improves hydrogen sulfide inhibition resistance, strong acid sites on the carrier that do not interact with the hydrogenation-active metal component promote the formation of coking, maintaining high activity and activity retention ability. It is difficult to perform the treatment, and it has been necessary to further enhance the activity of activating and maintaining the activity.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a high sulfur-containing hydrocarbon oil which has excellent resistance to hydrogen sulfide generated in a large amount during hydrotreating, suppresses coking formation, maintains activity with high activity and maintains activity. It is an object of the present invention to provide a high-performance hydrotreating catalyst and a method for hydrotreating a hydrocarbon oil using the hydrotreating catalyst.

[0006]

Means for Solving the Problems Accordingly, the present inventors have:
In view of the development situation of advanced desulfurization catalysts to solve the above problems, the amount of Brönsted acid previously developed was 50 μmol /
After extensive studies on the hydrotreating catalyst using a carrier of g or more, strong Bronsted acid sites are removed by adding a metal component selected from the group consisting of alkali metals and alkaline earth metals to the carrier. As a result, they found that the hydrogen sulfide inhibition resistance was good and the activity maintaining ability was improved, and the present invention was completed based on these findings.

That is, a first aspect of the present invention is a hydrotreating catalyst comprising a hydrogenation-active metal component supported on a carrier having a total Bronsted acid content of 50 μmol / g or more, wherein the carrier is an alkali metal And at least one metal component selected from the group consisting of alkaline earth metals and 0.01% to 8% by weight as a metal amount based on the total weight of the carrier, wherein the hydrogenation-active metal component is selected from the sixth group of the periodic table. The present invention relates to a hydrotreating catalyst characterized in that the catalyst is at least one active metal component selected from the group consisting of group metals and group VIII metals.

A second aspect of the present invention is a hydrotreating catalyst comprising a hydrocarbon oil and a hydrogenation-active metal component supported on a carrier having a total Brönsted acid content of 50 μmol / g or more. Contains at least one metal component selected from the group consisting of alkali metals and alkaline earth metals in an amount of 0.01% by weight to 8% by weight based on the total weight of the carrier, and the hydrogenation-active metal component is cyclic. Contacting with hydrogen under hydrotreating conditions in the presence of a hydrotreating catalyst that is at least one active metal component selected from the group consisting of Group 6 metals and Group 8 metals. The present invention relates to a method for hydrotreating hydrocarbon oils.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The hydrotreating catalyst of the present invention is obtained by supporting at least one hydrogenation-active metal component on a carrier having a total Bronsted acid content of 50 μmol / g or more.

The carrier constituting the hydrotreating catalyst of the present invention contains at least one metal component selected from the group consisting of alkali metals and alkaline earth metals. Specifically, alumina, silica, boria, titania, zirconia, diiron trioxide, beryllium oxide, magnesia, calcium oxide, zinc oxide, thoria, chromium trioxide and the like, and composites thereof, for example, silica-alumina , Silica-magnesia, silica-zirconia, silica-tria, silica-beryllium oxide, silica-boria, alumina-zirconia, alumina-titania, alumina-boria, alumina-chromia, titania-zirconia, zeolite, kaolin, halosite,
Bentonite, adavalguite, bauxite, kaolinite, naclite, anoxite, etc., for at least one kind of carrier component selected from the group consisting of clay minerals and the like cross-linked, from the alkali metal and alkaline earth metal. At least one metal component selected from the group is added, and has a total Bronsted acid content of 50 μmol / g or more. As the alkali metal component, sodium, potassium and lithium are used, and as the alkaline earth metal component, calcium, magnesium, strontium and barium are usually used as oxides.

[0011] The content of the alkali metal component and the alkaline earth metal component is 0.0
It is 1% to 8% by weight, preferably 0.05% to 6% by weight. If the content does not reach 0.01% by weight, the effect on the distribution of Bronsted acid sites is small, and there is no effect of removing strong Bronsted acid sites, so that coking is easily generated and the activity maintaining ability is reduced. On the other hand, even if the content exceeds 8% by weight, a sufficient control effect on Bronsted acid sites accompanying an increase in the amount cannot be obtained.

The method of adding these alkali metal components and alkaline earth metal components (hereinafter referred to as "alkali metal components, etc." as necessary in the description of the production method) to the carrier is not particularly limited. Instead, a commonly used method may be used.

For example, a method in which a carrier is impregnated solely in a liquid phase using a solution of an alkali metal component or the like, and then a hydrogenation active metal component is supported. A method of impregnating a solution of an alkali metal component or the like in a liquid phase, a method of mixing a solution of an alkali metal component or the like and a solution of a hydrogenation active metal component and co-impregnating in a liquid phase, For example, when a raw material such as an alkali metal component is added and contained in a carrier, for example, when a silica-alumina carrier is produced using each alkoxide as a raw material, sodium methoxide, calcium methoxide, barium ethoxy is added to a solution of an alkoxide of silicon and aluminum. And a method of adding a predetermined amount of an alkoxide such as alkoxide.

By adding an alkali metal component and an alkaline earth metal component, strong Bronsted acid sites of the carrier component are selectively reduced or removed, and the generation of coking accompanying the decomposition of hydrocarbons can be suppressed. As a result, the activity maintaining ability of the hydrotreating catalyst is improved.

The carrier has a total Bronsted acid content of 50.
It is necessary to have at least μmol / g, preferably at least 80 μmol / g. If the total amount of Bronsted acid does not reach 50 μmol / g, resistance to hydrogen sulfide inhibition is inferior, so that there is a difficulty in performing a high degree of desulfurization in hydrotreating a sulfur-containing hydrocarbon oil. On the other hand, when the total amount of Bronsted acid exceeds 2000 μmol / g, the decomposition reaction of the hydrocarbon oil increases, so that the deterioration of the catalyst becomes remarkable due to the formation of coking and the like.

In particular, a special feature of the present invention is that the amount of strong Bronsted acid in the distribution of the amount of Bronsted acid contained in the catalyst carrier is reduced or eliminated.
Specifically, in the 2,6-dimethylpyridine-TPD profile, the amount of Bronsted acid in the range of 600 ° C. to 800 ° C. is 10% or less of the total amount of Bronsted acid, preferably 7%.
% Or less of the Brønsted acid content distribution.

The Brönsted acid is a type of solid acid which is defined as a proton donor. A specific site on the solid surface where a proton is donated is a Bronsted acid point. At such a Bronsted acid point, electrons are exchanged with peripheral reaction components to promote various reactions. In this specification, the amount of Bronsted acid is represented by the number of Bronsted acid points per unit weight of the carrier (μmol / g).

The amount of Bronsted acid in the catalyst carrier is controlled by controlling the rate of dropping each component solution to the solvent during the production of the carrier, controlling the pH change of the synthesis solution, controlling the rate of dropping water during hydrolysis, and the like. By adjusting the deposition rate of each component and controlling the dispersibility of each component in the resulting carrier, 5
It can be set to 0 μmol / g or more.

As a method for measuring the amount of Bronsted acid,
The following method was adopted in this specification. Insert 0.05 g of the catalyst support into a glass tube, and place
Degas for 1 hour at 00 ° C. After degassing, the mixture is heated to 200 ° C., and 2,6-dimethylpyridine (hereinafter, referred to as “2,6-DMPy”) is aerated to be adsorbed on the carrier. After adsorption, nitrogen gas was passed at 200 ° C. for about 1 hour,
Confirm that 2,6-DMPy is not contained in the exhaust gas. The carrier on which 2,6-DMPy is adsorbed is cooled to 800 ° C for 5 minutes.
2,6-DMPy was desorbed by heating at a rate of ° C./min, the desorption amount was measured by gas chromatography, mass spectrometry, conductivity titration, etc., and the desorption amount per unit weight of The amount of Steid acid (μmol / g).

The specific surface area and pore volume of the carrier used in the hydrotreating catalyst of the present invention are not particularly limited, but the hardly desulfurizable sulfur compound is effectively removed by hydrodesulfurization. Preferably, the specific surface area is 200 m ² / g or more, and the pore volume is 0.4 ml / g to 1.2 ml / g.

The hydrogenation active metal component of the hydrotreating catalyst of the present invention is at least one active metal component selected from the group consisting of metals belonging to Group 6 of the Periodic Table and metals belonging to Group 8 of the Periodic Table. Examples of the active metal component include Group 6 metals such as chromium, molybdenum and tungsten, and Group 8 metals such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum. Each of the components can be used alone or in combination.

As the hydrotreating catalyst of the present invention, a hydrogenation-active metal component comprising a combination of at least one selected from the group 6 metals and at least one selected from the group 8 metals, specifically, Molybdenum-cobalt, molybdenum-nickel, molybdenum-cobalt-nickel, and the like can be given. Further, it is preferable that these hydrogenation active metal components are supported on a carrier as oxides and / or sulfides.

Further, these hydrogenation-active metal components include manganese of Group 7 metal, zinc of Group 12 metal,
Group 4 tin, germanium and the like can also be added.

The supported amount of the hydrogenation-active metal component is 5% for the Group 6 metal as an oxide based on the total weight of the catalyst.
% To 40% by weight, preferably 10% to 30% by weight. If the supported amount is less than 5% by weight, the active points decrease, so that it becomes difficult to perform advanced desulfurization of the sulfur-containing hydrocarbon oil, and the hydrotreating of the hydrocarbon oil cannot proceed smoothly. On the other hand, when the content exceeds 40% by weight, the dispersibility of the active metal component is reduced, and as a result, the active sites are reduced, which hinders high-grade desulfurization. Further, for the Group 8 metal, 0.05
% To 20% by weight, preferably 0.1% to 15% by weight. If the supported amount is less than 0.05% by weight, the resistance to hydrogen sulfide inhibition is poor, while if it exceeds 20% by weight, the dispersibility of the active ingredient is reduced. Desulfurization may be difficult to achieve.

The process for producing the hydrotreating catalyst of the present invention comprises:
The method is not particularly limited, and a known method can be adopted. For example, when the hydrogenation-active metal component is supported by an impregnation method, nitrates, acetates, formates, ammonium salts, phosphates, oxidized salts of metals belonging to Group 6 and 8 of the Periodic Table. An impregnating solution obtained by dissolving a compound such as a product in a solvent is prepared, and an organic acid such as citric acid, tartaric acid, malic acid, acetic acid, and oxalic acid is added to the impregnating solution, and ammonia water is further added. The impregnating solution adjusted to about pH = 9 is added dropwise to the carrier with stirring to be impregnated.

Examples of the solvent include water, aqueous ammonia, alcohols, ethers, ketones, and aromatics. Preferred solvents are water, ammonia, acetone, methanol, n-propanol, i-propanol, n-butanol, i-butanol, pentanol, hexanol, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane and the like, especially Water is preferred.

The concentration of the bimetallic active metal component in the impregnating solution and the amount of the impregnating solution impregnated into the carrier are not particularly limited, and the ease of the impregnating operation, the drying operation and the like are taken into consideration. The amount of the hydrogenation-active metal component supported on the fired catalyst can be appropriately selected so as to be a desired value.

Next, the support impregnated with the bimetallic active metal component is formed by punching, extrusion, tumbling granulation, etc., and then dried by air drying, hot air drying, heat drying, freeze drying, or the like. And firing. The firing is performed at a temperature of 450 to 60.
It is preferable to carry out at 0 ° C. for 3 to 5 hours. If the calcination temperature is too high, oxide crystals of the supported active metal component precipitate, causing a decrease in surface area and pore volume, causing a decrease in activity as a catalyst. Since the ammonia and acetate ions contained in the components do not desorb and the active sites on the catalyst surface are not sufficiently exposed, the activity also decreases, so it is important to adjust the firing temperature and the firing time.

Further, by adding a phosphorus component to the hydrotreating catalyst of the present invention, the nitrogen compound inhibition resistance can be further improved. As the phosphorus component, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphomolybdic acid, phosphotungstic acid, ammonium phosphotungstate, or the like can be used, and is usually carried as an oxide. The content of the phosphorus component is 0.1 as phosphorus based on the total weight of the catalyst.
01 wt% to 8 wt%, preferably 0.05 wt% to
6% by weight. The method for adding the phosphorus component is not particularly limited. For example, a carrier is impregnated in a liquid phase alone with a phosphoric acid solution, and then the hydrogenation active metal is supported or the hydrogenation active metal is supported. The carrier can also be impregnated with a heteropolyacid (such as phosphomolybdic acid) of the component and the phosphorus component.

Next, a method for hydrotreating a hydrocarbon oil by using the hydrotreating catalyst of the present invention will be described.

The hydrotreating method of the present invention includes all reactions caused by the contact between hydrocarbon oil and hydrogen under hydrotreating conditions in the presence of the hydrotreating catalyst of the present invention, Specific examples include hydrodesulfurization, hydrodenitrogenation, hydrodearomatization, isomerization, and alkylation. Hydrotreating conditions can be arbitrarily selected based on the type of feed oil and the desired reaction.

The hydrocarbon oil used in the hydrotreating method of the present invention is not particularly limited, and any of them can be used. For example, a kerosene fraction, a normal distillation light oil, a vacuum Distilled gas oil, catalytic cracked gas oil, pyrolyzed gas oil, heavy cracked gas oil, atmospheric distillation residue oil and the like can be mentioned. Vacuum-distilled gas oil is a distillate containing a fraction having a boiling point in the range of about 370 ° C. to 610 ° C. obtained by vacuum distillation of atmospheric distillation residual oil, and has a considerable amount of sulfur, nitrogen and metal components. It contains. For example, a vacuum distilled light oil of Middle Eastern crude contains, for example, about 2% to 4% by weight of sulfur and about 0.05% to 0.2% by weight of nitrogen. Heavy cracked gas oil is cracked oil having a boiling point of about 200 ° C. or higher obtained by the thermal cracking of residual oil, and contains a considerable amount of both sulfur and nitrogen.

In carrying out the hydrotreating of the sulfur-containing hydrocarbon oil, the reaction conditions can be appropriately selected according to the type of the feed oil, the desired desulfurization rate and the desired denitrification rate. For example, reaction temperature; 200 ° C. to 500 ° C., reaction pressure: 5 kg / cm ² to
200 kg / cm ² , hydrogen gas to feed oil ratio; 50 liter / liter to 4000 liter / liter and liquid hourly space velocity (LHSV): 0.05 hr ^{−1 to} 10 hr ⁻¹ can be adopted. The hydrogen concentration in the hydrogen containing gas may range from about 60-100%.

In the deep desulfurization of the gas oil fraction, no particularly severe reaction conditions are required, and ordinary desulfurization conditions, for example, a temperature of 250 ° C. to 400 ° C., 5 kg / cm
Hydrogen pressure of ^{2 to} 60 kg / cm ² , 1 hr ^{-1 to} 5 hr ^-1
And a hydrogen / feedstock ratio of 50 liters / liter to 1000 liters / liter. Under these reaction conditions, 4-methyldibenzothiophene,
Hardly desulfurizable sulfur compounds such as 4,6-dimethyldibenzothiophene can be easily removed.

In the hydrodesulfurization unit, the catalyst for hydrotreating of the present invention can be used in any form of a fixed bed, a fluidized bed or a moving bed. Is preferred. Further, depending on the type of the hydrocarbon oil, the desired desulfurization rate, and the like, hydrodesulfurization can be performed by connecting two or more reactors in series. Further, the hydrotreating catalyst of the present invention is preferably subjected to pre-sulfurization by bringing it into contact with a sulfur-containing hydrocarbon oil, hydrogen sulfide, or a hydrocarbon oil containing a sulfur compound before the hydrotreatment.

As described above, the present invention provides a hydrotreating catalyst and a method for hydrotreating a hydrocarbon oil. In a preferred embodiment, the total amount of Bronsted acid is 50 μmol / g. And silica-alumina containing an oxide of a metal selected from the group consisting of sodium, potassium, calcium, magnesium and barium in a metal amount of 0.05 to 5% by weight based on the total weight of the carrier. A hydrotreating catalyst comprising a carrier supporting at least one of the Group 6 metal components of the periodic table and at least one of the Group 8 metal components of the same,
And a gas oil fraction in the presence of the above-mentioned hydrotreating catalyst at a temperature of 250 ° C to 400 ° C and a hydrogen pressure of 5 kg / cm.
^{2 to} 60 kg / cm ² , liquid hourly space velocity 1 hr ^{-1 to} 5 hr ^-1
And hydrogen / feed oil ratio 50 l / l to 100
It is possible to provide a hydrotreating method in which hydrogen is brought into contact with hydrogen under a reaction condition of 0 liter / liter.

[0037]

The present invention will be more specifically described below with reference to examples and comparative examples. However, the present invention is not limited by the examples and the like. The method of evaluating the performance of the sample oil and the catalyst used in the examples and the like will be described below.

The sulfur content of the sample oil (mainly 4,6-DMDBT) was 0.3% by weight.
Sample oil I was prepared by adding dimethyl disulfide (DMDS) and quinoline to the contained refined light gas oil (LGO-T). DMDS is added to simulate a substance that produces hydrogen sulfide in hydrocarbon oil.
Table 1 shows the composition of Sample Oil I.

Evaluation of catalyst performance Relative desulfurization activity (HDS) Sample oil I was hydrotreated under the hydrotreating conditions shown in Table 2 using each catalyst.
Based on the desulfurization activity after 00 hours, evaluation was made based on the relative desulfurization activities at the initial stage, after 30 hours and after 100 hours. The evaluation results in Table 3 are HDS (initial) and HDS (3
0HRS) and HDS (100HRS).

Production Example 1 Aluminum triisopropoxide (Al (i-OC ₃ H ₇ ) ₉ )
0.13 g and 2-methylpentane-2,4-diol (C
H ₃ · CH (OH) CH ₂ C (CH ₃ ) ₂ OH) was mixed and reacted at 80 ° C. for 5 hours with stirring, and then tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) was added. 69.3 g was added and reacted at 80 ° C. for 12 hours with further stirring. After the reaction, water 22
5.8 ml was added dropwise at a rate of 1 ml / min and hydrolyzed at 80 ° C. After the reaction, the mixture was dried at 90 ° C. and further calcined in an air stream at 600 ° C. for 5 hours to obtain silica-alumina having a silica content of 50% by weight.

Next, Mg-alumina was added to the obtained silica-alumina.
An aqueous solution of magnesium nitrate adjusted to a concentration of 1% by weight as O was impregnated by a pore filling method, dried at a temperature of 110 ° C. for 48 hours, and formed into a disk shape. This molded product was fired in an air stream at a temperature of 500 ° C. for 3 hours, and magnesia-silica-alumina (MgO-Si
O ₂ -Al ₂ O ₃ ) A ternary support was obtained.

The magnesia-silica-alumina ternary support has a 2,6-DMPy-TPD profile of 20.
0 ° C to 400 ° C, 400 ° C to 600 ° C and 600 ° C to
When the amount of Bronsted acid in each temperature range of three sections of 800 ° C. was measured, 200 ° C. to 400 ° C. and 400 ° C. to 6 ° C.
The amount of Bronsted acid at 00 ° C. is 57 μmol / g and 30 μmol / g, respectively, which are almost the same as Comparative Catalyst A, but the amount of strong Bronsted acid at 600 ° C. to 800 ° C. is 15 μmol / g of Comparative Catalyst A. On the other hand, in the case of the catalyst I, it was 5 μmol / g, which was 5.4 of the total amount of Bronsted acid.
% (14.2% for Comparative Catalyst A). 2,6-D
Table 3 shows the results of the MPy-TPD profile.

[0043] In this way a carrier prepared by nickel nitrate _{(Ni (NO 3) 2 ·} 6H 2 O) 10.38g of ammonium molybdate _{((NH 4) 6 Mo 7} O 24 · 4H 2 O) 13 0.08 g and citric acid 5.77 g were mixed with concentrated ammonia water and pure water 5
Dissolve in 4.9 g. The ratio of concentrated aqueous ammonia to pure water in the mixed solution was adjusted to pH with all the above solutes dissolved.
= 9. This impregnating solution was dropped and co-impregnated on the magnesia-silica-alumina carrier by a pore filling method. After impregnation, the temperature is further increased to 11
Dry at 0 ° C. for 48 hours, form into a disk,
It was calcined in an air stream at 00 ° C. for 3 hours to obtain a hydrotreating catalyst I. Table 3 shows the composition of the catalyst and the like.

Production Example 2 A sodium oxide-silica-alumina (Na ₂ O—SiO ₂ — containing 1% by weight of sodium oxide was prepared in the same manner as in Production Example 1 except that an aqueous solution of sodium hydroxide was used instead of magnesium nitrate. Al ₂ O ₃ ) A ternary carrier was prepared.

Preparation Example 3 A comparative catalyst A was prepared in the same manner as in Preparation Example 1 except that magnesium nitrate was not added to silica-alumina. Table 3 shows the composition of the catalyst and the like.

Example 1 The sample oil I shown in Table 1 was hydrotreated under the hydrotreating conditions shown in Table 2 using the catalyst I of Production Example 1 to obtain an initial desulfurization activity (HDS (initial)) of 30%. Time (HDS (30HRS)) and 1
After the treatment for 00 hours (HDS (100HRS)), the desulfurization activity was measured to evaluate the activity maintaining ability. Table 3 shows the evaluation results.

Example 2 A hydrogenation treatment was carried out in the same manner as in Example 1 except that the catalyst II obtained in Production Example 2 was used instead of the catalyst I, and the evaluation results shown in Table 3 were obtained.

Comparative Example 1 Comparative catalyst A was subjected to hydrotreating under the hydrotreating conditions shown in Table 2 in the same manner as in Example 1, and the catalyst performance was evaluated. Table 3 also shows the evaluation results.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

When the above Examples and Comparative Examples are compared, a silica-alumina carrier containing an alkali metal component and an alkaline earth metal component and having a total Bronsted acid content of 50 μmol / g or more has a 2,6-DMPy-TPD profile. Although the amounts of Bronsted acids at 200 ° C. to 400 ° C. and 400 ° C. to 600 ° C. are almost the same as Comparative Catalyst A, the amount of strong Bronsted acid appearing at 600 ° C. to 800 ° C. is extremely removed. It can be seen that the deterioration rate showing the activity maintaining ability was remarkably improved in the performance evaluation.

[0053]

According to the present invention, the amount of Bronsted acid is 50 μmol / g.
By adding an alkali metal component and an alkaline earth metal component to the above carrier, the amount of strong Bronsted acid can be removed, coking accompanying hydrocarbon decomposition is suppressed, and hydrogenation of sulfur-containing hydrocarbon oils is carried out. It is possible to provide a hydrotreating catalyst having high activity in desulfurization and having an activity maintaining ability for a long period of time.

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Claims (4)

[Claims] 1. The total amount of Bronsted acid is 50 μmol.
/ G or more of a carrier for supporting a hydrogenation-active metal component on a carrier, wherein the carrier comprises at least one metal component selected from the group consisting of alkali metals and alkaline earth metals. At least one active metal selected from the group consisting of metals belonging to Group 6 of the periodic table and metals belonging to Group 8 of the same Table, wherein the metal content is 0.01 to 8% by weight as a metal amount on a weight basis. A hydrotreating catalyst, which is a component. 2. According to the 2,6-dimethylpyridine-TPD profile of the carrier, the amount of Bronsted acid in the range of 600 ° C. to 800 ° C. is 10% of the total amount of Bronsted acid.
% Or less. 3. A method for hydrotreating a hydrocarbon oil, comprising contacting the hydrocarbon oil with hydrogen in the presence of the hydrotreating catalyst according to claim 1 or 2. 4. The method for hydrotreating a hydrocarbon oil according to claim 3, wherein the hydrocarbon oil is a light oil fraction.