JP2001353444A - Hydrogenation desulfurization catalyst for hydrocarbon oil and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst for hydrogenation desulfurization to decrease the sulfur content in hydrocarbon fractions obtained by fractionation of crude oil, particularly in naphtha, and to provide a catalyst which does not require preliminary sulfurization as a treating process prior to use and which shows high hydrogenation desulfurization activity at a low temperature. SOLUTION: The catalyst for hydrogenation desulfurization is prepared by depositing 1 to 30 mass% of alumina or silica alumina based on the catalyst, 1 to 3 mass% of sulfate groups in terms of the sulfur content and 0.05 to 10 mass% palladium on a carrier consisting of zirconium oxide or hydroxide. The catalyst has >=0.1 ml/g total pore volume, in which the proportion of pores having 1.4 to 2.1 nm pore diameter is 30 to 70 %. In addition to palladium, one or more kinds selected from platinum, rhenium, ruthenium, cobalt and molybdenum can be deposited by 0.05 to 10 mass% on the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst used for hydrodesulfurization treatment of hydrocarbon oil and for reducing the sulfur content of light hydrocarbon oil containing an organic sulfur compound. Specifically, in the hydrodesulfurization treatment using a solid superacid catalyst, the conventional desulfurization catalyst does not require a preliminary sulfurization treatment required as a pre-reaction treatment, and has an activity of reducing the sulfur content in hydrocarbon oil, It relates to a catalyst which can be obtained even at a relatively low reaction temperature. The present invention also relates to a method for producing such a catalyst.

[0002]

2. Description of the Related Art Various hydrocarbon fractions obtained by distillation or cracking of crude oil contain more or less sulfur compounds, and when these oils are used as fuels, sulfur oxides resulting therefrom are released. Pollutes the atmosphere. In recent years, gasoline and light oil used as fuels for automobile and aircraft engines have been required to further reduce sulfur due to environmental pollution.

[0003] Light hydrocarbon oils such as light naphtha currently used as a gasoline base material generally contain an organic sulfur compound in an amount of about 400 to 700 ppm.
m, or by using a hydrodesulfurization catalyst such as a Co-Mo system or a Ni-Mo system to reduce the sulfur content. The sulfur content is about 1 in the middle distillate such as light oil.
The sulfur content is reduced to 500 ppm or less by treating with a hydrodesulfurization catalyst, as in the case of naphtha desulfurization, but the sulfur content will be further reduced in the future by strengthening environmental regulations. Is required.

However, the hydrodesulfurization catalysts used so far do not exhibit a desulfurization activity high enough to sufficiently reduce the sulfur content in response to future regulations, and are even more active than conventional products. There is a demand for the emergence of desulfurization catalysts. In addition, conventional Co-Mo and Ni-
Mo-based desulfurization catalysts require preliminary sulfurization as a pretreatment for the hydrodesulfurization reaction, which is not only complicated but also economically disadvantageous.

[0005] As one solution to this problem,
Recently, an acidic catalyst based on sulfated zirconia has been disclosed (JP-A-11-197510). This catalyst
A solid acidic catalyst containing sulfated zirconia and a transition metal hydride such as platinum, having a specific surface area of at least 135 m ² / g, a pore volume of at least 0.16 ml / g, and an average fineness of at least 2 nm. And a hole radius.

The present inventors have also studied a hydrodesulfurization catalyst obtained by combining a sulfated zirconia with a platinum group metal, and have found a catalyst having a high isomerization performance as well as a desulfurization activity of light hydrocarbons, and have already proposed it (Japanese Patent Application No. Hei. 11-324242
issue). The catalyst contains zirconium oxide or zirconium hydroxide containing 1-3% by mass of sulfur as sulfur, and 0.05-10% by mass of palladium (or 0.05-10% by mass of platinum). Carried,
It is characterized by being stabilized by firing at 550 to 800 ° C. and having a specific surface area of 50 to 150 m ² / g.

The inventors of the present invention further studied and found that a specific solid superacid catalyst had excellent desulfurization activity even without pre-sulfurization as a pretreatment for the desulfurization reaction, and even in a comparatively low reaction temperature, the hydrocarbon solid oil catalyst had a high catalytic activity. It has been found that the sulfur content can be effectively reduced.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst used for hydrodesulfurization of a hydrocarbon oil by utilizing the above-mentioned new knowledge obtained by the inventors, and to provide a catalyst in a treatment step prior to use. An object of the present invention is to provide a hydrodesulfurization catalyst which does not require a certain presulfurization, has high hydrodesulfurization activity, and is effective at a relatively low temperature.

[0009]

The catalyst for hydrodesulfurization of a hydrocarbon oil according to the present invention is provided on a carrier comprising an oxide or hydroxide of zirconium on the basis of a catalyst.
1-30% by mass of alumina and sulfur content of sulfur
-3% by mass, and 0.05-10% by mass of palladium, and the total pore volume is 0.1 ml / g or more, among which pores having a pore size of 1.4-2.1 nm. Is 30 to 70%.

The catalyst may further support 0.05 to 10% by mass of one or more selected from platinum, rhenium, ruthenium, cobalt and molybdenum.

The hydrodesulfurization process for hydrocarbon oils using the catalyst of the present invention is characterized in that a hydrocarbon fraction containing an organic sulfur component is mixed with hydrogen together with a hydrogen partial pressure of 1 to 15 MPa and a temperature of 50 MPa.
Under the conditions of ３５０350 ° C., a liquid hourly space velocity of 0.1-115 hr ⁻¹ , and a hydrogen / oil ratio of 50〜1500 NL / L, a desulfurization reaction is performed by contacting the catalyst.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The carrier of the catalyst of the present invention is a zirconium oxide or hydroxide as described above. Zirconium hydroxide includes Zr (OH) ₄ , Zr (OH) ₂ , Zr
There are various forms such as (OH) _3, and any of them may be used. In general, zirconium oxide hydrate ZrO ₂ .xH ₂ O (where 0 <x ≦ 2) is preferable.

It is preferable from the viewpoint of catalyst strength that alumina or silica-alumina be contained in the support made of zirconium oxide or hydroxide. Its content is 1 to 30% by mass, preferably 3 to 25% by mass, based on the catalyst.
% By mass. If the content is less than 1% by mass, the catalyst strength is low and it is unsuitable as an industrial catalyst, while if it exceeds 30% by mass, the catalyst strength is sufficient but the activity of the desulfurization catalyst is low.

The solid superacid catalyst of the present invention preferably has an SCS, that is, a side crush strength (a value indicating the mechanical strength of the catalyst) of 0.5 kg / mm or more. If the SCS is less than 0.5 kg / mm, the catalyst strength is low, and the catalyst may be broken and powdered when the reactor is filled with the catalyst. When the catalyst particles are powdered, the pressure difference inside the device may increase, and the operation of the hydrotreating may not be continued.

Examples of the palladium compound used for supporting palladium on the carrier include metal chlorides, chlorides, sulfates, nitrates, acetates, and tetraamine palladium complexes. Preferred are chlorides, sulfates and nitrates.

[0016] The content of palladium is 0.1% on a catalyst basis.
The amount is from 0.05 to 10% by mass, preferably from 0.1 to 5% by mass. If the supported amount of palladium is less than 0.05% by mass, the desulfurization activity is not exhibited, and if it exceeds 10% by mass, the dispersibility of palladium which is an active metal is lowered, and the activity is rather lowered.

Examples of the treating agent that gives a sulfate group (SO ₄ ) to a carrier include sulfuric acid, ammonium sulfate, hydrogen sulfide, and the like.
Sulfurous acid gas and the like are mentioned. Those that are easy to use are sulfuric acid and ammonium sulfate. The amount of sulfate is sulfur (S)
The content is 1 to 3% by mass, preferably 1.5 to 2% by mass. If the amount of sulfate is less than 1% by mass as sulfur, the acidity of the catalyst, that is, the solid superacidity is weak,
Insufficient activity as a desulfurization catalyst. In addition, 3% by mass
If the amount exceeds the above range, the surface of the zirconia carrier is excessively covered with sulfate groups, and the active sites are crushed by laminating on the surface, so that the activity is rather lowered.

The sulfur content in the catalyst is measured by burning a sample in an oxygen stream, oxidizing S contained in the sample to SO ₂ , removing moisture and dust, and then using an infrared detector such as a solid detector. -It is performed by detecting using a state type detector. According to this analysis method, the amount of sulfur in the sample can be determined in the concentration range of 0.001 to 99.99%.

The hydrodesulfurization catalyst of the present invention has a total pore volume of 0.1 ml / g or more, preferably 0.1 to 0.25 ml / g, after calcination and stabilization at a predetermined temperature. It is necessary that the ratio of the pores having a pore diameter of 1.4 to 2.1 nm is 30 to 70%. If the total pore volume does not reach 0.1 ml / g, high catalytic activity cannot be obtained. If the volume of the pores having a pore diameter in the above range is less than 30% of the total pore volume, the desulfurization activity point is small, and sufficient desulfurization activity cannot be obtained. If it exceeds 70%, the desulfurization activity can be sufficiently obtained, but the strength of the catalyst decreases.
The preferred range is 35-65%.

The above pore diameter and pore volume can be measured and calculated by a nitrogen adsorption method using an ordinary surface area and pore volume measuring device.

In a preferred embodiment of the catalyst of the present invention, as described above, the catalyst containing palladium contains platinum, ruthenium,
The desulfurization activity is further enhanced by adding one or more metals selected from rhenium, cobalt and molybdenum. The amount of these metals added is
It is 0.05 to 10% by mass, preferably 0.05 to 5% by mass. If the amount is less than 0.05% by mass, the effect of improving the desulfurization activity is not recognized. If the amount exceeds 10% by mass, the dispersibility of the active metal is reduced, and the desulfurization activity may be rather reduced.

The solid superacid catalyst of the present invention has a physical property after the calcination stabilization treatment in which the abundance ratio between the monoclinic structure and the tetragonal structure in the crystal structure of zirconium oxide (ZrO ₂ ) of the carrier is as follows. Monoclinic / tetragonal = 20 / 80-0 /
It is preferably in the range of 100, more preferably 10/90 to 0/100. This is because the tetragonal structure has a higher activity as the catalyst carrier, and the higher the proportion of the monoclinic structure, the lower the catalytic activity. The abundance ratio between the monoclinic structure and the tetragonal structure in zirconium oxide was determined by measuring the X-ray diffraction peak of the catalyst,
It can be calculated from the integrated intensity ratio of the X-ray diffraction peak of 2θ = 28.2 (main peak of monoclinic structure) and 2θ = 30.2 (main peak of tetragonal structure) due to α-rays.

Further, the solid superacid catalyst of the present invention has a specific surface area of 50 to 20 after a predetermined calcination stabilization treatment.
It is preferably in the range of 0 m ² / g. More preferably, it is in the range of 50 to 150 m ² / g. Specific surface area is 50
If it is less than m ² / g, the dispersibility of the supported metal is low, and the number of active sites for hydrodesulfurization is reduced. Those with low specific surface area
The crystal structure of zirconium oxide also tends to have a monoclinic / tetragonal ratio greater than 20/80, which is not preferred from this viewpoint. If the specific surface area is low, it is difficult to secure the content of sulfate groups in the catalyst at 1% by mass or more by sulfur content, and solid superacidity does not appear. On the other hand, when the specific surface area exceeds 200 m ² / g, crystallization of the zirconium oxide does not progress, and the ratio of the zirconium oxide tetragonal structure therein is at a low level. It is not preferable. As the specific surface area, a value measured by the BET method is used.

There is no particular limitation on the method for producing the catalyst of the present invention. The method for providing sulfate and supporting palladium is not limited, and the order is arbitrary. And any of these methods may be used. (1) A zirconium hydroxide carrier first contains a sulfate group, which is dried, impregnated and supported with palladium metal, dried and calcined, and then mixed with an inorganic oxide such as alumina sol to form, dry, and form. Step of calcining (2) The active metal is first impregnated and supported on the zirconium hydroxide carrier, dried, then sulfated, dried and calcined, and then an inorganic oxide such as alumina sol is mixed. (3) Palladium metal is first impregnated and supported on the zirconium hydroxide carrier, and an inorganic oxide such as alumina sol is mixed with the zirconium hydroxide carrier. (4) A zirconium hydroxide carrier is first made to contain a sulfate group, an inorganic oxide such as alumina sol is mixed with the zirconium hydroxide carrier, molded, dried and calcined. (5) A zirconium hydroxide carrier is loaded with a sulfate group and a palladium metal at the same time, dried and fired, mixed with an inorganic oxide such as alumina sol, and formed. Drying and calcining step (6) First, an inorganic oxide such as alumina sol is mixed with the zirconium hydroxide support, molded and dried, then sulfated, dried again, and then impregnated with palladium metal Step of drying and firing after loading

When platinum, ruthenium, rhenium, cobalt or molybdenum, which is the second metal component, is used in addition to palladium, the loading can be carried out by the same method as that for loading palladium, and the firing stability can be improved. These metals may be introduced at any stage before the treatment. Of course, you may introduce simultaneously with palladium.

Hereinafter, the method for producing a catalyst of the present invention will be described in detail by taking the production step (1) as an example.

First, the raw material of the carrier made of zirconium hydroxide or oxide is subjected to sulfate treatment.
This sulfate treatment is carried out by adding a sulfate dissolved in water to a hydroxide or oxide of zirconium, followed by filtration and drying. As a treatment agent that gives a sulfate group,
Examples thereof include 0.1 to 5N sulfuric acid, 0.1 to 10 molar concentration of ammonium sulfate, hydrogen sulfide, and sulfurous acid gas. Preferred are sulfuric acid and ammonium sulfate as described above.

As a method of the sulfate group treatment, there are an impregnation method and a kneading method. The impregnation method is a method of impregnating a treating agent which is a liquid with a catalyst carrier in an equivalent amount of 1 to 10 times, filtering and drying.
Drying is performed, for example, by heating to 110 ° C. for 1 to 24 hours.
The kneading method is a method in which a solid state as a sulfate group treating agent is kneaded with a carrier and contained. As a kneading means, any kneading machine generally used for the production of a catalyst may be used. During kneading, a liquid can be added as a viscosity modifier. Liquids to be added include water, ethanol, isopropanol, acetone, methyl ethyl ketone, diethyl ketone,
Solvents such as methyl isobutyl ketone are exemplified. In this case, there are no particular restrictions on the order of addition of the sulfate treatment agent and the solvent, and the temperature and time of kneading are not limited as long as the catalyst of the present invention has the expected physical properties under the conditions.

Next, palladium metal is supported on the sulfate group-containing zirconia. Palladium is immersed in an aqueous solution of metal chloride, chloride, sulfate, nitrate, acetate, tetraamine palladium complex, etc.
It can be contained by drying. Drying is
For example, it is performed at a temperature of 110 ° C. for 1 to 24 hours. As another method, when kneading with the above-mentioned sulfate group treating agent, chloride, sulfate, nitrate and the like of palladium metal are also mixed, and by kneading, a method of simultaneously supporting the metal and sulfate group may be selected. it can.

The carrier supporting the sulfate group and the palladium metal is subjected to a calcination stabilization treatment. The firing stabilization process is
This is a treatment performed by heating in an oxidizing atmosphere at a temperature of 550 to 800 ° C., preferably 600 to 750 ° C. for 0.5 to 10 hours. If the calcination temperature is lower than 550 ° C., the proportion of zirconium hydroxide contained in the zirconium compound increases, and the proportion of the tetragonal crystals in the zirconium oxide decreases, so that the properties of the solid acid do not appear and the catalyst hydrogen Low desulfurization activity. On the other hand, when heat treatment is performed at a high temperature exceeding 800 ° C., the proportion of hydroxide decreases, but the proportion of monoclinic zirconium oxide increases and the hydrodesulfurization activity decreases. In addition, the sulfate groups are also eliminated from the catalyst, the sulfur content in the catalyst becomes less than 1% by mass, and the solid acid strength decreases. Further, sintering of a supported metal such as palladium also occurs, and the active sites of hydrodesulfurization decrease.

The reason why the stabilization treatment of the catalyst is carried out in an oxidizing atmosphere is that if it is carried out in a reducing atmosphere, the bonding state between a metal or metal compound such as palladium and a sulfate group changes, or the catalyst is caused by reductive decomposition. This is because the catalytic activity decreases due to the decrease in the sulfate group, which is considered to be the case.

The above-mentioned calcination stabilization treatment may be performed before or after carrying a metal such as palladium. Even when carried out before supporting the metal, the firing stabilization is performed in the range of 550 to 800 ° C., which is the temperature at which the crystalline state of the zirconium oxide having a tetragonal structure is obtained, and more preferably in the range of 600 to 750 ° C. Firing time is 0.5
A range from 10 hours to 10 hours is preferred. If the firing stabilization is performed first, then impregnated with a metal such as palladium,
Thereafter, a stabilization treatment for firing at a temperature of 300 to 700 ° C. may be further performed to activate the catalyst.

The palladium-supported sulfate-containing zirconia thus obtained is then mixed with alumina or silica-alumina serving as a binder to form a catalyst. Although various forms can be used as the alumina raw material, those in the form of aluminum hydroxide, boehmite, or pseudo-boehmite are preferable. As the silica raw material, silica sol is suitable. The production of the catalyst comprises mixing palladium-supported sulfate-containing zirconia with, for example, alumina sol, molding, drying, and then performing a firing stabilization treatment. Alternatively, the catalyst of the present invention can also be obtained by mixing palladium-containing sulfated zirconia and boehmite powder, adding water or other medium to give fluidity, performing a molding treatment, drying and calcining.

When alumina is used as the binder, as described in the above catalyst production methods (1) to (6),
After mixing alumina with zirconium hydroxide, perform a treatment to give sulfate, palladium metal, etc.,
The molding, drying and firing procedures may be used.

The shape of the catalyst is not particularly limited, and various shapes which can be usually taken by this type of catalyst, for example, a columnar shape or a four-leaf type obtained by tableting or extrusion molding can be adopted.

The production of a catalyst supporting platinum, ruthenium, rhenium, cobalt or molybdenum in addition to palladium, which is a preferred embodiment of the present invention, can be carried out in the same manner as the method for supporting palladium. That is, simultaneously or separately with palladium, the carrier is impregnated with an aqueous solution of a metal chloride, chloride, sulfate, nitrate, acetate, tetraamine complex, or the like, and dried. At the time of kneading with the sulfate treatment agent,
By kneading chlorides, sulfates, nitrates and the like of these metals, a method of giving a sulfate group and supporting the metal at the same time can be adopted.

The feedstock oil to be subjected to hydrodesulfurization using the solid superacid catalyst of the present invention includes hydrocarbons containing organic sulfur such as light naphtha, heavy naphtha, kerosene, and light oil distilled from a crude oil distillation apparatus. Oil is appropriate. A particularly suitable feedstock is light naphtha having an ASTM distillation temperature of 25-130 ° C, preferably 25-110 ° C. Regarding the content of organic sulfur in light naphtha, those having a content of 700 mass ppm or less, preferably about 10 to 500 mass ppm, can be desulfurized effectively.

The conditions for the hydrodesulfurization reaction of hydrocarbon oil using the catalyst of the present invention are as follows. Reaction temperature: 50-350 ° C, preferably 100-280
° C Hydrogen partial pressure: 1.0 to 15 MPa, preferably 1.4 to 5
MPa LHSV: 0.1 to 15 hr-1, preferably 1.0 to 8
hr-1 hydrogen / oil ratio: 50 to 1500 NL / L, preferably 100 to 1000 NL / L

When the reaction temperature is lower than 50 ° C., the activity of the catalyst is too low. On the other hand, when the reaction temperature is higher than 350 ° C., the decomposition of the hydrocarbon oil proceeds and the yield of the produced oil decreases. As seen in the examples below, it is an advantage of this catalyst that it exhibits high desulfurization activity at relatively low temperatures of 100-200 ° C. Other conditions, that is, the hydrogen partial pressure, the liquid hourly space velocity, and the hydrogen / oil ratio are almost the same as the conditions of the conventional desulfurization reaction of hydrocarbon oil.

The solid superacid catalyst of the present invention does not require pre-sulfurization, which is performed as a pre-reaction treatment for a conventional desulfurization catalyst, but instead stabilizes the catalytic activity, that is, removes the supported metal compound. For reduction to metal and activation of strong acid sites, reduction treatment is preferably performed. This reduction treatment is carried out by subjecting the catalyst to an atmosphere of hydrogen or an inert gas.
It is preferable to carry out drying by drying at a temperature of 0 to 500 ° C. for 1 to 24 hours, and then reducing at a temperature of 100 to 400 ° C. in a hydrogen gas atmosphere.

[0041]

EXAMPLES Examples 1 to 17 of the present invention (catalysts A to
J, N and P to T) and Comparative Examples 1 to 5 (production of catalysts K ^* , L ^* and O ^* and commercially available catalysts U ^* and V ^* )
The present invention will be described in detail by giving examples of hydrodesulfurization reactions using these catalysts. However, the present invention is not limited by these examples. (The asterisk indicates a comparative example.)

[0042] [Example 1] was dissolved catalyst A (1) Zr (OH) 4 1000g Preparation commercial zirconium oxychloride ZrOCl ₂ · 8H ₂ O in distilled water 4L, while stirring, 25% ammonia thereto Water NH ₃ aq. Was added dropwise to precipitate zirconium hydroxide Zr (OH) ₄ . PH of aqueous solution
Was adjusted to 9.0, and the precipitated zirconium hydroxide was separated by filtration. After filtration, wash well with distilled water, dry at 110 ° C. for 24 hours, and add zirconium hydroxide 4
90 g were obtained. (2) Preparation of SO ₄ / Zr (OH) ₄ 400 g of zirconium hydroxide prepared from zirconium oxychloride as described above was mixed with 4000 g of 1N sulfuric acid.
And stirred for 30 minutes. After stirring, the mixture was filtered and the solid was dried at 110 ° C. for 24 hours to obtain 452 g of sulfated zirconium hydroxide SO ₄ / Zr (OH) ₄ . (3) Preparation of Pd / SO ₄ / ZrO ₂ A solution of 1.8 g of palladium chloride PdCl ₂ dissolved in hydrochloric acid was charged with 190 g of zirconium hydroxide to which a sulfate group was given, and impregnated with a Pd salt. Thereafter, it is dried at 110 ° C. for 24 hours, and calcined in a muffle furnace at 600 ° C. for 3 hours to obtain a Pd-supported sulfate-containing zirconia catalyst material (P
d / SO ₄ / ZrO ₂ ) 135 g were obtained. (4) Pd / SO ₄ / ZrO ₂ —Al ₂ O ₃ 100 g of the catalyst raw material obtained by the above operation and 60 g of alumina sol were sufficiently mixed and passed through an extruder to a diameter of 1.6.
It was molded into a column of mm and dried at 110 ° C. all day and night. This was calcined again at 600 ° C. and stabilized to obtain 109 g of Catalyst A.

Example 2 Catalyst B The procedure of Example 1 was repeated except that 1.9 g of palladium sulfate was used instead of palladium chloride and 200 g of zirconium hydroxide containing a sulfate group was used.
Drying, molding and calcination were performed to obtain 151 g of Catalyst B.

Example 3 Catalyst C The procedure of Example 1 was repeated, except that 1.8 g of palladium nitrate was used instead of palladium chloride, and 166 g of zirconium hydroxide containing a sulfate group was used.
Drying, molding and calcination were performed to obtain 175 g of Catalyst C.

Example 4 Catalyst D Example 1 was the same as Example 1 except that 2.0 g of tetraamine palladium chloride monohydrate was used instead of palladium chloride, and 139 g of zirconium hydroxide containing a sulfate group was used. Impregnation, drying, molding and calcination were performed under the same conditions to obtain 149 g of Catalyst D.

Example 5 Catalyst E The impregnation and drying were carried out under the same conditions as in Example 1 except that 30 g of alumina sol was used in Example 1, and pellets having a diameter of 3 mm were produced using a tableting machine. This was calcined to obtain a catalyst E.

Example 6 Catalyst F A catalyst F was obtained by impregnation, drying, molding and calcining under the same conditions as in Example 1 except that 90 g of alumina sol was used.

Example 7 Catalyst G The catalyst G was obtained by impregnating, drying, molding and calcining under the same conditions as in Example 1 except that 120 g of alumina sol was used.

Example 8 Catalyst H The impregnation, drying, molding and calcination were carried out under the same conditions as in Example 1 except that 54 g of alumina sol and 6 g of silica sol were added, to obtain catalyst H. Was.

Example 9 Catalyst I In Example 1, impregnation was carried out under the same conditions as in Example 1 except that 36 g of alumina sol and 24 g of silica sol were added, and a tableting machine was used instead of an extruder. After drying and calcination, catalyst I was obtained.

Example 10 Catalyst J The impregnation, drying, molding and calcination were carried out under the same conditions as in Example 1 except that the alumina sol was changed to 108 g and the silica sol was further added to 12 g.
I got

[Comparative Example 1] Catalyst K ^* Impregnation, drying, molding and firing were performed under the same conditions as in Example 1 except that alumina was not mixed and a tableting machine was used. Thus, a catalyst K was obtained.

[Comparative Example 2] Catalyst L ^{* In} Example 1, 1.9 g of platinum chloride was used in place of palladium chloride, and 200 g of sulfate-containing zirconium hydroxide was used.
g, impregnation, drying,
Forming and calcining were performed to obtain a catalyst L ^* .

The production conditions and physical properties of the catalysts A to L are shown in Table 1. Table 1 catalyst preparation conditions and the physical properties (1) Catalyst A Catalyst B Catalyst C Catalyst D support material _{PdCl 2 PdSO 4 Pd (N0 3} ) 2 Pd (NH 3) 4 Cl 2 baking conditions 600 ℃ × 3h 600 ℃ × 3h 600 ℃ × 3h 600 ℃ × 3h Specific surface area (m ² / g) 134 133 138.4 132.4 Sulfur content (% by mass) 1.74 1.53 1.81 1.56 Metal element analysis value (% by mass) Pd 0.51 0.45 0.58 0.70 ZrO ₂ crystal structure ratio Amorphous / tetragonal 3.5 / 96.5 3.7 / 96.3 4.1 / 95.9 4.3 / 95.7 Inorganic metal oxide Alumina Alumina Alumina Alumina Content (% by mass) 10 10 10 10 Catalyst shape 1.6mmφ cylinder 1.6mmφ cylinder 1.6mmφ cylinder 1.6mmφ cylinder SCS ( (kg / mm) 0.6 0.5 0.6 0.6 Pore volume (ml / g) 0.154 0.151 0.157 0.153 Ratio of pore volume of 1.4 to 2.1 nm (%) 45.7 44.6 44.7 46.1

Table 1 Catalyst Production Conditions and Physical Properties (Part 2) Catalyst E Catalyst F Catalyst G Catalyst H Supported Material PdCl ₂ PdCl ₂ PdCl ₂ PdCl ₂ Firing Conditions 600 ° C. × 3h 600 ° C. × 3h 600 ° C. × 3h 600 ° C. × 3h Specific surface area (m2 / g) 116.1 146.1 161.0 141.7 Sulfur content (% by mass) 1.83 1.64 1.54 1.63 Metal element analysis value (% by mass) Pd 0.53 0.48 0.44 0.49 ZrO ₂ crystal structure ratio Monoclinic / tetragonal 3.5 / 96.5 3.7 /96.3 4.1 / 95.9 4.3 / 95.7 Inorganic oxide Alumina Alumina Alumina Silica / alumina (10:90) Content (% by mass) 5 15 20 10 Catalyst shape 3mmφ Heelette 1.6mmφ cylinder 1.6mmφ cylinder 1.6mmφ cylinder SCS (kg / mm ) 0.8 0.6 0.8 0.7 pore volume (ml / g) 0.130 0.178 0.202 0.170 proportion of Hosoanayo product of 1.4~2.1nm (%) 60.3 36.2 31.0 35.4

Table 1 Catalyst Production Conditions and Properties (Part 3) Catalyst I Catalyst J Catalyst K ^* Catalyst L ^* Supporting substance PdCl ₂ PdCl ₂ PdCl ₂ H ₂ PtCl ₆ Firing conditions 600 ° C × 3h 600 ° C × 3h 600 ° C × 3h 600 ° C × 3h Specific surface area (m2 / g) 119.1 137.2 101.1 132.4 Sulfur content (% by mass) 1.75 1.50 1.92 1.90 Metal element analysis value (% by mass) Pd 0.52 0.46 0.55 − Pt − − − 0.60 ZrO ₂ crystal structure ratio Monoclinic / tetragonal 3.5 / 96.5 3.7 / 96.3 3.5 / 96.5 4.3 / 95.7 Inorganic metal oxide silica / alumina 40:60) Silica / alumina (10:90) − Alumina content (% by mass) 10 20 0 10 Catalyst shape 3mmφ pellet 1.6mmφ cylinder 3mmφ pellet 1.6mmφ cylinder SCS (kg / mm) 0.9 0.8 <0.1 0.6 Pore volume (ml / g) 0.134 0.160 0.107 0.158 proportion of Hosoanayo product of 1.4~2.1nm (%) 57.5 40.1 76.8 the measurement of 45.9 specific surface area, high-precision fully automatic gas adsorption apparatus manufactured by Nippon Bell Co. " BELSOR P 28 "was used. The sulfur content was measured using a SC-132 sulfur analyzer from LECO.

Example 11 Catalyst M 1.5 g of palladium chloride PdCl ₂ was placed in 20 g of water, 30 cc of concentrated hydrochloric acid was added dropwise, and ultrasonic waves were dissolved for 10 minutes to obtain a first solution. Separately, chloroplatinic acid hexahydrate H
The ₂ PtCl ₆ · 6H ₂ O in 1.6g dissolved in water 10 g, to obtain a second solution. 172.9 g of the sulfate group-containing zirconium hydroxide prepared in Example 1 was added to the mixed solution of the first and second solutions, and impregnated with Pd salt and Pt salt.
Supported. Thereafter, alumina sol was mixed in the same manner as in step (4) of Example 1, and the mixture was molded, dried, and fired to obtain Pd / Pt / SO ₄ / ZrO ₂ —Al ₂ O ₃ .

Example 12 Catalyst N 1.5 g of palladium chloride PdCl ₂ was placed in 20 g of water, 30 cc of concentrated hydrochloric acid was added dropwise, and ultrasonic waves were dissolved for 10 minutes to obtain a first solution. Separately, chloroplatinic acid hexahydrate H
The ₂ PtCl ₆ · 6H ₂ O in 1.6g dissolved in water 10 g, to obtain a second solution. To a mixture of these solutions,
174.2 g of the above-mentioned sulfate group-containing zirconium hydroxide was added thereto, and impregnated with and supported Pd salts and Pt salts. After that, the alumina sol was mixed in the same manner as in step (4) of Example 1, and the mixture was molded, dried and calcined to obtain Pd / Pt / S
O ₄ / ZrO ₂ —Al ₂ O ₃ was obtained.

Comparative Example 3 2.2 g of catalyst O ^* palladium chloride PdCl ₂ was placed in 20 g of water.
30 cc of concentrated hydrochloric acid was added dropwise, and ultrasonic waves were dissolved for 10 minutes to obtain a first solution. Separately, chloroplatinic acid hexahydrate H ₂ P
The tCl ₆ · 6H ₂ O in 2.5g yield a second solution by dissolving in water 10g. Example 1 was added to a solution obtained by mixing these solutions.
170 g of the sulfate-containing zirconium hydroxide prepared in the above was added to impregnate the Pd salt and the Pt salt. Thereafter, drying and firing were performed in the same manner as in Example 1 to obtain Pd / Pt-supported sulfate-containing zirconia Pd / Pt / SO ₄ / ZrO ₂ . The obtained Pd / Pt-supported sulfate-containing zirconia 10
After mixing 210 g of alumina sol with 0 g and extrusion molding, 1 g
Drying was carried out at 10 ° C. all day and night, followed by baking at 600 ° C. for 3 hours to obtain Pd / Pt / SO ₄ / ZrO ₂ —Al ₂ O ₃ .

Example 13 Catalyst P Palladium chloride PdCl_Two1.5 g is put in 20 g of water,
30 cc of concentrated hydrochloric acid is dropped, and ultrasonic waves are dissolved for 10 minutes.
To obtain a first solution. Separately, rhenium oxide Re _TwoO₇1.
2 g was dissolved in 10 g of water to obtain a second solution. these
The solution obtained by mixing the solutions of
Add 170.0 g of ruconium, and add Pd salt and Re salt.
Impregnated. The following is the same as in step (4) of Example 1.
Alumina is mixed, molded, dried and fired,
Pd / Re / SO_Four/ ZrO_Two-Al_TwoO_ThreeI got

Example 14 Catalyst Q 1.5 g of palladium chloride PdCl ₂ was placed in 20 g of water.
30 cc of concentrated hydrochloric acid was added dropwise and ultrasonic waves were dissolved for 10 minutes to obtain a first solution. Separately, ruthenium chloride RuCl
₃ 1.9 g was dissolved in 10 g of water to obtain a second solution.
171.1 g of the above-mentioned sulfate group-containing zirconium hydroxide was added to a liquid obtained by mixing these solutions, and impregnated with a Pd salt and a Ru salt. Thereafter, molding, drying and calcination are performed in the same manner as in step (4) of Example 1, and Pd / Ru / SO ₄
/ To obtain a ZrO ₂ -Al ₂ O _3.

Example 15 Catalyst R 1.5 g of palladium chloride PdCl ₂ was placed in 20 g of water.
30 cc of concentrated hydrochloric acid was added dropwise and ultrasonic waves were dissolved for 10 minutes to obtain a first solution. Separately, ruthenium chloride RuCl
₃ 2.2 g was dissolved in 10 g of water to obtain a second solution.
169.5 g of the above-mentioned sulfate-containing zirconium hydroxide was added to a liquid obtained by mixing these solutions, and impregnated with a Pd salt and a Ru salt. Thereafter, molding, drying and calcination are performed in the same manner as in step (4) of Example 1, and Pd / Ru / SO ₄
/ To obtain a ZrO ₂ -Al ₂ O _3.

Example 16 Catalyst S 1.5 g of palladium chloride PdCl ₂ was placed in 20 g of water.
30 cc of concentrated hydrochloric acid was added dropwise and ultrasonic waves were dissolved for 10 minutes to obtain a first solution. Separately, a second solution was prepared by dissolving 4.5 g of cobalt nitrate hexahydrate Co (NO ₃ ) ₂ .6H ₂ O in 10 g of water. The above-mentioned sulfate-containing zirconium hydroxide of 170.9 was added to the mixed solution of the two solutions.
g and impregnated with Pd and Co salts. Thereafter, molding, drying and firing were performed in the same manner as in step (4) of Example 1 to obtain Pd / Co / SO ₄ / ZrO ₂ —Al ₂ O ₃ .

Example 17 Catalyst T Palladium chloride PdCl_Two1.5 g is put in 20 g of water,
30 cc of concentrated hydrochloric acid is dropped, and ultrasonic waves are dissolved for 10 minutes.
To obtain a first solution. Separately, ammo paramolybdate
Nium (NH_Four)₆Mo₇O_{twenty four}・ 4H_Two1.7 g of O in water 1
0 g to give a second solution. Mix two solutions
The sulfated zirconium hydroxide containing 17
0.4 g was impregnated with Pd salt and Mo salt. Less than
The lower part is molded, dried and dried in the same manner as in step (4) of Example 1.
And baking to produce Pd / Mo / SO _Four/ ZrO_Two-Al
_TwoO_ThreeI got

Comparative Example 4 Co-
A Mo-based, commercially available desulfurization catalyst U ^* was used.

Comparative Example 5 Co-
A Mo-based, commercially available desulfurization catalyst V ^* was used.

The production conditions and physical properties of the catalysts of Examples 11 to 17 and Comparative Example 3 are summarized in Table 2. Table 2 Catalyst Production Conditions and Properties (Part 4) Catalyst M Catalyst N Catalyst O ^* Catalyst P Supported Material PdCl ₂ / H ₂ PtCl ₆ PdCl ₂ / H ₂ PtCl ₆ PdCl ₂ / H ₂ PtCl ₆ PdCl ₂ / Re ₂ O ₃ Firing conditions 600 ℃ × 3h 600 ℃ × 3h 600 ℃ × 3h 600 ℃ × 3h Specific surface area (m ² / g) 149 144.9 191.1 143.5 Sulfur content (% by mass) 1.96 1.90 1.64 1.84 Metal element analysis value (% by mass) Pd 0.47 0.98 0.52 0.48 Pt 0.43 0.49 0.49 − Re − − − 0.48 ZrO ₂ crystal structure ratio Monoclinic / tetragonal 4.0 / 96.0 3.5 / 96.5 3.5 / 96.5 3.6 / 96.4 Inorganic oxide Alumina Alumina Alumina Alumina Content (% by mass) 10 10 35 10 Catalyst shape 1.6mmφ cylinder 1.6mmφ cylinder 1.6mmφ cylinder 1.6mmφ cylinder SCS (kg / mm) 0.6 0.6 1.0 0.6 Pore volume (ml / g) 0.156 0.160 0.245 0.153 1.4 ~ 2.1nm pore volume 45.5 44.4 22.7 46.7 Product occupation ratio (%)

Table 2 Catalyst Production Conditions and Properties (Part 5) Catalyst Q Catalyst R Catalyst S Catalyst T Carrying Material PdCl ₂ / RuCl ₃ PdCl ₂ / RuCl ₃ PdCl ₂ / Co (NO ₃ ) PdCl ₂ / (NH ₄ ) ₆ Mo ₇ 0 ₂₃ baking conditions 600 ℃ × 3h 600 ℃ × 3h 600 ℃ × 3h 600 ℃ × 3h specific surface area ^{(m 2 / g) 144 141.5} 140.0 144.6 sulfur (wt%) 2.11 2.04 1.74 1.64 metal element analysis ( Mass%) Pd 0.47 0.46 0.49 0.52 Ru 0.49 1.01 − − Co − − 0.49 − Mo − − − 0.49 ZrO ₂ crystal structure ratio Monoclinic / tetragonal 5.5 / 94.5 4.6 / 95.4 3.6 / 96.4 3.1 / 96.9 Inorganic oxide Alumina Alumina Alumina Alumina content (% by mass) 10 10 10 10 Catalyst shape 1.6 mmφ cylinder 1.6 mmφ cylinder 1.6 mmφ cylinder 1.6 mmφ cylinder SCS (kg / mm) 0.5 0.6 0.6 0.6 Pore volume (ml / g) 0.155 0.151 0.158 0.154 1.4 Pore volume up to 2.1 nm 46.6 44.3 47.0 45.5 Percentage of product (%)

[Example of use of catalyst] Evaluation method for hydrodesulfurization of hydrocarbon oil The catalyst was charged into a fixed bed flow type reactor having a catalyst filling capacity of 15 ml, and unwashed light naphtha was supplied as a raw material hydrocarbon oil. By performing the hydrodesulfurization reaction under the conditions of 3,
Catalysts A to J excluding catalyst K having an SCS of less than 0.5 kg / mm
And the desulfurization activity of LT was evaluated. Prior to filling,
Each catalyst was ground to 16-28 mesh. The commercial desulfurization catalysts of Comparative Examples 4 and 5 were used in the desulfurization reaction without performing preliminary sulfurization as pretreatment.

Table 3 Conditions for Hydrodesulfurization Reaction Reaction Conditions Reaction Temperature: 160 ° C. Hydrogen Partial Pressure: 3.0 MPa Liquid Space Velocity: 1 hr ⁻¹ Hydrogen / Oil Ratio: 300 NL / L Raw Material: Unwashed Light Naphtha (S Content: Properties of feed oil Density g / cm ³ (15 ° C) 0.6534 Distillation properties IBP ℃ 29.5 5% distillation temperature ℃ 39.5 10% distillation temperature ℃ 40.5 50% distillation temperature ° C 49.0 70% distillation temperature ° C 54.5 90% distillation temperature ° C 63.5 95% distillation temperature ° C 66.5 EP ° C 98.5 Sulfur mass ppm 384 Saturation volume% 98.53 Unsaturated Fraction volume% 0.07 aromatic content volume% 1.40

Table 4 shows the results of the hydrodesulfurization reaction together with the catalyst used. Table 4 Result of hydrodesulfurization reaction of light naphtha Catalyst composition Desulfurization rate (%) Catalyst A of Example 1 Pd / SO ₄ / ZrO ₂ .Al ₂ O ₃ 97.2 Catalyst B of Example 2 Pd / SO ₄ / ZrO ₂ .Al ₂ O ₃ 96.8 Catalyst C of Example 3 Pd / SO ₄ / ZrO ₂ .Al ₂ O ₃ 96.5 Catalyst D of Example 4 D Pd / SO ₄ / ZrO ₂ .Al ₂ O ₃ 96.0 catalyst _{E Pd / SO 4 / ZrO 2} · Al 2 O 3 98.5 catalyst _{F Pd / SO 4 / ZrO 2} · Al 2 O 3 97.0 example 7 example 6 example 5 Catalyst G Pd / SO ₄ / ZrO ₂ .Al ₂ O ₃ 95.0 Catalyst H Pd / SO ₄ / ZrO ₂ .Al ₂ O ₃ .SiO ₂ 96.7 Catalyst of Example 8 Catalyst I Pd / SO of Example 9 ₄ / ZrO ₂ .Al ₂ O ₃ .SiO ₂ 97.4 Catalyst J Pd / SO _{4 of} Example 10 / ZrO ₂ .Al ₂ O ₃ .SiO ₂ 95.9 Catalyst M Pd / Pt / SO of Example 11 ₄ / ZrO ₂ .Al ₂ O ₃ 98.5 Catalyst N Pd / Pt / SO ₄ / ZrO ₂ .Al ₂ O ₃ 98.9 of Example 12 Catalyst P Pd / Re / SO ₄ / ZrO _{2 of} Example 13・ Al ₂ O ₃ 98.7 Catalyst Q Pd of Example 14 / Ru / SO ₄ / ZrO ₂ .Al ₂ O ₃ 98.5 Catalyst R Pd / Ru / SO ₄ / ZrO ₂ .Al ₂ O ₃ 98.1 of Example 15 Catalyst S Pd / Co / SO of Example 16 ₄ / ZrO ₂ · Al ₂ O ₃ 98.5 Catalyst T Pd / Mo / SO ₄ / ZrO ₂ · Al ₂ O ₃ 98.8 of Example 17 Catalyst L ^* Pt / SO ₄ / ZrO ₂ · of Comparative Example 2 Al ₂ O ₃ 33.3 Catalyst O ^* Pd / Pt / SO ₄ / ZrO ₂ .Al ₂ O ₃ 63.7 of Comparative Example ₃ 63.7 Commercial Desulfurization Catalyst U ^* Co-Mo System of Comparative Example 4 50.8 Comparative Example 5 Commercial desulfurization catalyst V ^* Co-Mo system 46.0

From the above data, it can be seen that in Examples 1 to 17 using the catalyst according to the present invention, a high desulfurization rate of 95% or more could be achieved. Comparative Example 2 not carrying palladium (catalyst L ^* ), which is a constituent element of the catalyst of the present invention, and a ratio of a pore volume having a pore diameter of 1.4 to 2.1 nm of 30 to 70%. In Comparative Example 3 not satisfying (catalyst O ^* , 22.7%), the desulfurization rate was 63.7.
%, Which is lower than the desulfurization rate of the example.

Comparative Examples 4 and 5 using a commercially available Co—Mo-based desulfurization catalyst are the results of performing a desulfurization reaction without performing preliminary sulfurization as a pre-reaction treatment. Both rates are as low as about 50%.

[0074]

Industrial Applicability The solid acid catalyst having specific physical properties according to the present invention is used for hydrodesulfurization of a hydrocarbon oil to efficiently reduce sulfur contained in the hydrocarbon oil. can do. With conventional desulfurization catalysts,
While pre-sulfurization was essential as a pre-reaction treatment,
The catalyst of the present invention does not require pretreatment, and exhibits high desulfurization activity even when used directly. Further, the catalyst of the present invention shows high desulfurization activity even at the relatively low temperature of 160 ° C. mentioned in the above examples. As described above, when the catalyst of the present invention is applied to hydrodesulfurization of a hydrocarbon oil, it enables industrially advantageous hydrodesulfurization to be carried out.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10G 45/06 C10G 45/06 A 45/08 45/08 A 45/10 45/10 A (72) Invention Person Atsushi Oshio 1134-2 Gongendo, Satte City, Saitama Prefecture Cosmo Oil R & D Center (72) Inventor Kazuhiko Hagiwara 1134-2 Gongendo, Satte City, Saitama Prefecture Cosmo Oil R & D Center (72) Inventor Keishi Kawakami 1134-2 Gongendo, Satte-shi, Saitama Cosmo Oil Co., Ltd. Research and Development Center F-term (reference) 4G069 AA03 AA08 AA09 AA12 BA01A BA01B BA03A BA03B BA05A BA05B BB02A BB02B BB04A BB05C BB10A BB10BBCBC BCBC BC BC BC BC70B BC72A BC72B BC75A BC75B CC02 DA06 EA02Y EB14Y EC03Y EC07X EC07Y EC18X EC18Y EC22Y ED03 FA02 FB14 FB19 FB30 FB66 FB67 FB78 F C02 FC07 FC08 4H029 CA00 DA00

Claims (9)

[Claims] 1. A carrier comprising zirconium oxide or hydroxide, alumina or silica-alumina in an amount of 1 to 30% by mass and a sulfate group in a sulfur content of 1 to 30% by mass on a catalyst basis.
3% by mass, and 0.05 to 10% by mass of palladium, and the total pore volume is 0.1 ml / g or more, and among them, pores having a pore size of 1.4 to 2.1 nm A hydrodesulfurization catalyst for a hydrocarbon oil, wherein the catalyst accounts for 30 to 70%. 2. The catalyst according to claim 1, further comprising platinum.
One or more selected from rhenium, ruthenium, cobalt and molybdenum, from 0.05 to
A hydrodesulfurization catalyst, wherein the catalyst is supported by 10% by mass. 3. The method for producing a hydrodesulfurization catalyst according to claim 1, wherein the zirconium hydroxide support is treated with a treating agent that gives a sulfate group to the sulfate group to convert the sulfate group into a sulfur component. 1 to 3 mass%, and then impregnated with a palladium compound to make palladium 0.05 to 10 mass%.
After being supported and calcined and stabilized at a temperature of 550 to 800 ° C., alumina or silica-alumina was
0% by mass and mixed to form a catalyst.
A production method comprising firing and stabilizing at a temperature of 50 to 800 ° C. 4. The method for producing a hydrodesulfurization catalyst according to claim 1 or 2, wherein the palladium compound is impregnated into a zirconium hydroxide carrier to reduce the palladium content to 0.05 to 0.05%.
10% by mass, and then treated with a treating agent that gives a sulfate group to convert the sulfate group into a sulfur content, carry 1 to 3% by mass, stabilize the calcination at a temperature of 550 to 800 ° C.,
Alumina or silica-alumina is mixed so as to occupy 1 to 30% by mass of the catalyst, formed into a catalyst shape, and 550
A production method comprising firing and stabilizing at a temperature of about 800 ° C. 5. The method for producing a hydrodesulfurization catalyst according to claim 1 or 2, wherein the palladium compound is impregnated into a zirconium hydroxide support to reduce the palladium to 0.05 to 0.05%.
After supporting 10% by mass, alumina or silica-alumina is mixed with the mixture so as to occupy 1 to 30% by mass of the catalyst, molded, and then treated with a treating agent for providing a sulfate group, thereby reducing the sulfate group. 5 to 1% by weight of sulfur content
A production method comprising firing and stabilizing at a temperature of 50 to 800 ° C. 6. The method for producing a hydrodesulfurization catalyst according to claim 1, wherein the zirconium hydroxide support is treated with a treating agent which gives a sulfate group to the sulfate group to convert the sulfate group into a sulfur component. 1 to 30% by mass of the catalyst after supporting alumina or silica-alumina by 1 to 3% by mass.
, And then impregnated with a palladium compound to make palladium 0.05 to 10% by mass.
A production method comprising supporting and stabilizing by firing at a temperature of 550 to 800 ° C. 7. The method for producing a hydrodesulfurization catalyst according to claim 1, wherein the zirconium hydroxide support is treated with a treating agent that gives a sulfate group to the sulfur group to convert the sulfate group into a sulfur component. And palladium compound impregnated with 0.05 to
After supporting 10 mass% and stabilizing by calcination at a temperature of 550 to 800 ° C, alumina or silica-alumina is mixed to form 1 to 30 mass% of the catalyst and molded.
A production method comprising sintering to a temperature of 0 to 800 ° C. for stabilization. 8. The method for producing a hydrodesulfurization catalyst according to claim 1, wherein alumina or silica-alumina is added to the zirconium hydroxide support, and the catalyst is 1 to 3 times.
After mixing and shaping so as to occupy 0% by mass, the mixture is treated with a treating agent that gives a sulfate group, and the sulfate group is sulfur-supported by 1 to 3% by mass and subsequently impregnated with a palladium compound. By supporting 0.05 to 10% by mass of palladium and firing at a temperature of 550 to 800 ° C. for stabilization. 9. A method for producing the hydrodesulfurization catalyst according to claim 2, wherein the catalyst is selected from platinum, rhenium, ruthenium, cobalt and molybdenum. A production method comprising carrying out a step of supporting one or more kinds in an amount of 0.05 to 10% by mass on a catalyst basis simultaneously with or during any one of the steps prior to stabilization of calcination.