JPH07197038A - Production of hydrodesulfurization catalyst for hydrocarbon oil - Google Patents

Abstract

PURPOSE:To obtain the subject catalyst which can be produced by a low-temp. short-time impregnation of a carrier with a large amt. of a group VI metal together with phosphorus and a group VIII metal and which has an excellent desulfurization activity even in a depth desulfurization region. CONSTITUTION:This catalyst is prepd. by impregnating an inorg. oxide carrier contg. a crystalline aluminosilicate with a soln. contg. a condensed acid salt of a group VI metal, a salt of a group VIII metal, and phosphoric acid in amts. of the group VI metal, the group VIII metal, and phosphorus of 10-30wt.%, 1-15wt.%, and 0.1-15wt.%, respectively, in terms of oxides and based on the catalyst. The soln. is prepd. pref. at higher than 0 deg.C and lower than 100 deg.C.

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 hydrodesulfurization catalyst for hydrocarbon oil, and more particularly to a metal of Group VI, a metal of Group VIII and phosphorus of the Periodic Table at the same time and in a high loading amount. The present invention relates to a method for producing the catalyst that can be supported by.

[0002]

BACKGROUND OF THE INVENTION Hydrocarbon oils generally contain sulfur compounds, and when these oils are used as fuels, the sulfur present in the sulfur compounds is converted to sulfur oxides. And then released into the atmosphere. Therefore, in consideration of air pollution when burning, it is desirable that the sulfur content in the hydrocarbon oil be as low as possible. Hydrocarbon oil having a low sulfur content can be obtained by subjecting hydrocarbon oil to catalytic hydrodesulfurization treatment.

The catalyst conventionally used for this hydrodesulfurization treatment is a metal of Group VI of the periodic table (hereinafter, simply referred to as "V
A group I metal) and a Group VIII metal of the periodic table (hereinafter simply referred to as a Group VIII metal) as active metals supported on an oxide carrier such as alumina, magnesia, silica, etc. Is. At this time, generally, Mo or W is used as the Group VI metal, and the Group VIII metal is used.
Co or Ni is used as the group metal.

In order to improve the activity of this catalyst, phosphorus,
A technique of adding boron or the like has been reported (Japanese Patent Laid-Open No. Sho 5)
No. 2-1503). Further, a technique of mixing crystalline aluminosilicate into an inorganic oxide used as a carrier has also been reported (JP-A-56-2008).
(See Japanese Patent Publication No. 7). Moreover, techniques using both of them have been reported (Japanese Patent Laid-Open Nos. 61-126196 and 2-21.
4544).

On the other hand, as a method of supporting the above-mentioned active metal on a carrier, there is a method of impregnating with an aqueous solution of a salt of each metal (mainly ammonium salt or nitrate).
Due to the solubility relationship between the Group VI metal salt and phosphoric acid, it is difficult to prepare a catalyst in which a large amount of Group VI metal is supported by single-step impregnation. As a result, the two-step impregnation method of impregnating phosphorus and then impregnating the Group VI metal, or
The amount of Group VI metal carried must be kept low.

[0006] Further, as the regulation of sulfur content in commercial gas oil becomes stricter due to environmental problems (0.5
(% By weight → 0.05% by weight), further deep desulfurization is being demanded, and desulfurization treatment of the hardly desulfurizable substance is required.

Under such circumstances, Japanese Unexamined Patent Publication No. 4-2.
In Japanese Patent No. 65158, a Group VI metal is added at the same time as phosphorus.
Moreover, a method of supporting an amount exceeding 20% by weight is disclosed. However, this method requires considerably high temperature and long time when preparing the impregnating liquid, which is a negative factor in mass production.

The method of mixing crystalline aluminosilicate into the inorganic oxide used as the carrier is intended to obtain light oil by cracking heavy oil, and is used for deep desulfurization of light oil fractions. Didn't.

The present invention has been made in consideration of the circumstances of the prior art as described above, and the Group VI metal is not only phosphorus but also the Group VIII metal at the same time and with a high loading amount.
Moreover, it is an object of the present invention to provide a method for producing a hydrodesulfurization catalyst for hydrocarbon oil, which can be impregnated at a low temperature for a short time and exhibits an excellent desulfurization activity in a deep desulfurization region of a light oil fraction.

[0010]

Means for Solving the Problems As a result of repeated studies to achieve the above object, the present inventors have focused their attention on an inorganic polycondensate of a Group VI metal as a compound, and as a result of further studies. It was found that the above object can be achieved by using a solution of the condensed acid salt and crystalline aluminosilicate in combination.

That is, (1) by using an inorganic polycondensation salt of a Group VI metal as a starting material, the metal can be impregnated into the carrier at the same time as phosphorus and the Group VIII metal in a large amount. Impregnation can be carried out at room temperature and in a short time. (2) According to the catalyst produced by this method, these active components (Group VI metal, Group VIII metal and phosphorus) and the crystalline alumino in the carrier are used. It has been found that the interaction with silicate can sufficiently deal with the desulfurization treatment of the difficult-to-desulfurize substances, and particularly, the superior activity can be exhibited in the deep desulfurization region of the light oil fraction.

[0012] The present invention is based on the above findings and is characterized in that a V-containing inorganic oxide carrier containing crystalline aluminosilicate is used.
A solution containing a Group I metal polycondensate, a Group VIII metal salt and phosphoric acid is used as an oxide, and 10 to 30% by weight of the Group VI metal of the Periodic Table and the Group VIII metal of the Periodic Table are calculated as oxides. It is a gist of a method for producing a hydrodesulfurization catalyst for a hydrocarbon oil, which comprises impregnating and supporting so as to be 1 to 15% by weight and phosphorus to 0.1 to 15% by weight.

The present invention will be described in detail below. The carrier used in the present invention is an inorganic oxide containing a crystalline aluminosilicate. As this inorganic oxide, various ones can be used, for example, silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria,
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-
Examples thereof include magnesia-zirconia. Of these, alumina, silica-alumina, alumina-titania, alumina-boria, and alumina-zirconia are preferable, and [gamma] -alumina among alumina is particularly preferable. These inorganic oxides can be used alone or in combination of two or more kinds.

Various types of crystalline aluminosilicate can be used as the inorganic aluminosilicate contained in these inorganic oxides. Examples thereof include A-type zeolite, X-type zeolite, Y-type zeolite, stabilized Y-type zeolite, and ultra-stable Y-type. Zeolite,
Examples thereof include HY-type zeolite, L-type zeolite, ZSM-type zeolite and the like, and HY-type zeolite and stabilized Y-type zeolite are preferable. These crystalline aluminosilicates may be used alone or in combination of two or more.

If the content of the crystalline aluminosilicate in the carrier (that is, in the total amount of the inorganic oxide and the crystalline aluminosilicate) is too small, the effect of inclusion will not be exhibited, and if it is too large, the active metal will not be expressed. 1 to 20% by weight is preferable, and more preferably 2 to
It is 10% by weight.

The carrier of the present invention contains clay minerals such as montmorillonite, kaolin, halosite, bentonite, adabargite, bauxite, kaolinite, nacrite and anoxite, either alone or in combination of two or more. Can be made.

The specific surface area of the carrier comprising the above components is
Although not particularly limited, the object of the present invention (the VI
In order to obtain a catalyst exhibiting excellent desulfurization activity in the deep desulfurization region by impregnating a group metal, a Group VIII metal and phosphorus at the same time with a high loading amount and at a low temperature for a short time). , 250 m ² / g or more is preferable. Also,
The pore volume of the carrier is not particularly limited, but is preferably 0.3 to 1.2 cc / g for the same reason as above. Further, the average pore diameter of the inorganic oxide used for the carrier is not particularly limited, but is preferably 50 to 130 Å for the same reason as above.

As the inorganic polycondensate of the Group VI metal to be supported on the above carrier, various ones can be used, but inorganic polycondensates of chromium, molybdenum and tungsten are preferable, and heteropolyacids of molybdenum and tungsten are particularly preferable. Salt is preferred. Specifically, H ₃ (PMo ₁₂ O ₄₀ ) ・
Molybdophosphoric acid represented by 30H ₂ O, H ₃ (SiMo
₁₂ O ₄₀ ) .30H ₂ O molybdosilicic acid,
Examples thereof include tungstophosphoric acid represented by H ₃ (PW ₁₂ O ₄₀ ) · 30H ₂ O, and tungstosilic acid represented by H ₃ (SiW ₁₂ O ₄₀ ) · 30H ₂ O, preferably molybdophosphoric acid and molybdosilicic acid. And particularly preferably molybdophosphoric acid. These inorganic polycondensates can be used alone or in combination of two or more.

As the Group VIII metal salt to be supported together with the above-mentioned inorganic condensed salt of Group VI metal, various salts can be used, and salts of iron, cobalt, nickel, rhodium, palladium, osmium, iridium and platinum can be used. Particularly preferred are cobalt, nickel carbonates, acetates and phosphates. These Group VIII metal salts can be used alone or in combination of two or more kinds.

Examples of the phosphoric acid to be carried together with the above-mentioned inorganic condensed salt of Group VI metal and Group VIII metal salt include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid and polyphosphoric acid. Particularly preferred is orthophosphoric acid.

The solvent for dissolving each of the above-mentioned supported components is not particularly limited, and various solvents can be used, for example, water, alcohols, ethers, ketones, aromatics and the like. And preferably water, acetone, methanol, n-propanol, isopropanol, n-butanol, isobutanol, hexanol,
It is benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, etc., and particularly preferably water.

The proportion of each component dissolved in the above solvent is
The inorganic condensed acid salt of the Group VI metal is usually 10 to 30% by weight, preferably 1 in terms of oxide with respect to the calcined catalyst.
The amount is 8 to 25% by weight, and the amount of the Group VIII metal salt is 1 to 15% by weight, preferably 3 to 7% by weight.

The proportion of the inorganic condensation salt of a Group VI metal is 10
If it is less than wt%, the Group VIII metal salt tends to be difficult to dissolve, and if it exceeds 30 wt%, the surface area of the catalyst tends to be small and the catalytic activity tends to decrease. VII
If the proportion of the group I metal salt is less than 1% by weight, the catalytic activity is not sufficient, and if it exceeds 10% by weight, the entire catalyst surface is covered and the catalytic activity is likely to decrease.

The proportion of phosphoric acid is 0.1 to 15% by weight, preferably 1 to 7% by weight in terms of oxide, based on the calcined catalyst. If the proportion of phosphoric acid is too low, the technical effect of incorporating phosphoric acid will not be exhibited, and if it is too high, the pore volume of the catalyst after preparation will decrease too much, and the catalyst activity will tend to decrease.

If the amount of the solvent used is too small, the carrier cannot be sufficiently impregnated, and if the amount is too large, the dissolved active metal does not impregnate the carrier and adheres to the lip of the impregnation solution container. Since the desired loading amount cannot be obtained,
The amount is 50 to 150 g, preferably 70 to 90 g, relative to 100 g of the carrier.

In the present invention, the above components are dissolved in the above solvent to prepare a solution for impregnation. The temperature at this time may be higher than 0 ° C. and lower than 100 ° C., and the temperature should be within this range. For example, each of the above components can be well dissolved in the above solvent.

The above-prepared solution for impregnation is impregnated into the above carrier, and the above-mentioned respective components in the solution are supported on the above carrier. Although various conditions can be adopted as the impregnation condition, usually, the temperature is preferably higher than 0 ° C and lower than 100 ° C, more preferably 10 to 50 ° C, further preferably 15 to 30 ° C, and the impregnation time. Is preferably 15 minutes to 3 hours, more preferably 20 minutes to 2 hours,
More preferably, it is 30 minutes to 1 hour. If the temperature is too high, drying will occur during impregnation and the degree of dispersion will be biased. Moreover, it is preferable to stir during impregnation.

In the present invention, the catalyst is produced by thus supporting the above components on the carrier, drying the carrier, and calcining the carrier. The drying at this time is
It can be carried out by various drying methods such as air drying, hot air drying, heat drying and freeze drying. Further, firing can also be performed by various firing methods such as electric furnace firing, muffle furnace firing, alundum bath firing, electric tubular furnace firing, etc.
Usually, it is preferably carried out under air circulation in an electric furnace or in a muffle furnace.

The firing temperature may be appropriately selected and determined according to these firing methods, but when firing under air flow in an electric furnace or in a muffle furnace, 200 to 800 ° C., preferably 300 to 700 ° C. And particularly preferably 450 to 650
℃. If the firing temperature is too low, supporting of the active metal will be insufficient and poisoning substances will remain, and if it is too high, sintering will occur. The firing time is preferably 2 to 10 hours, particularly preferably 3 to 5 hours.

The shape of the catalyst produced as described above is not particularly limited and may be various shapes used in the usual catalyst shape of this kind. The oil is preferably a four-lobed type, and the light oil is preferably a cylindrical type. The size is usually 1/1 diameter
It is preferable that the length is 0 to 1/22 inch and the length is 3.2 to 3.6 inch.

When used in an actual process, the catalyst obtained in the present invention may of course be used alone, or may be mixed with a known catalyst or a known inorganic oxide carrier. In addition, before or after the above-mentioned drying, or after the above-mentioned firing, clay minerals such as montmorillonite, kaolin, halosite, bentonite, adabargite, bauxite, kaolinite, nacrite and anoxite are used alone or in combination of two or more. Can also be contained in combination.

Next, desulfurization treatment (including deep desulfurization treatment) by the catalyst obtained in the present invention will be explained. As the hydrocarbon oil to be treated, a light fraction or atmospheric distillation residue obtained by atmospheric distillation or vacuum distillation of crude oil, coker gas oil, solvent-depleted oil, tar sand oil, shale oil,
Examples include various hydrocarbon oils such as coal liquefied oil, catalytically cracked gas oil, thermally cracked gas oil, straight-run gas oil, coker gas oil, hydrotreated gas oil, desulfurized gas oil.

In the case of desulfurization by catalytic hydrotreating on a commercial scale, the catalyst obtained according to the invention (hereinafter simply referred to as "catalyst") is used as a fixed bed, moving bed or fluidized bed in a suitable reactor. Then, the hydrocarbon oil to be treated as described above is introduced into the reactor and treated under the following conditions to carry out desired desulfurization.

Most commonly, the catalyst is maintained as a fixed bed, with hydrocarbon oils passing downward through the fixed bed. The catalyst can be used in a single reactor,
It is also possible to use several reactors in series. In particular, when the feedstock is heavy, it is extremely preferable to use a multistage reactor.

As a preferable example of processing conditions, a hydrocarbon oil is used at a temperature of about 200 to 500 ° C., more preferably 25.
In the range of 0 to 400 ° C., the liquid hourly space velocity is about 0.05 to 5.
Contact with the catalyst at a hydrogen partial pressure of about 30 to 200 kg / cm ² G, more preferably 40 to 150 kg / cm ² G, in the range of ⁰ hr ⁻¹ , more preferably 0.1 to 4.0 hr ^−1. Let In this contact, the interaction between the group VI metal, the group VIII metal and phosphorus, which are the active components in the catalyst, and the crystalline aluminosilicate in the carrier is developed, and the hardly desulfurizable substance in the hydrocarbon oil is also contained. It can be easily desulfurized to realize deep desulfurization of hydrocarbon oils.

[0036]

【Example】

[Catalyst Production Example] The HY-type zeolite used in the following catalyst production examples (Examples and Comparative Examples) was SiO ₂ / Al.
₂ O ₃ molar ratio 6, Na ₂ O content 0.3 wt% or less, surface area 900 ~ 1100 (Langmuir, m
² / g) and ^{600~700 (BET, m 2 / g} ),
The crystal size was 0.7 to 1.0 μm.

Example 1 At room temperature, in an Erlenmeyer flask, 11 g of cobalt carbonate, 4 g of phosphoric acid and molybdophosphoric acid H ₃ (PMo ₁₂ O ₄₀ ).
38 g of 30H ₂ O was dissolved in 75 g of water and stirred to prepare an aqueous solution for impregnation. In an eggplant-shaped flask, this aqueous solution was added to an alumina carrier containing 5% by weight of HY-type zeolite (specific surface area: 372 m ² / g, pore volume: 0.65 cc / g).
Of 100 g (consisting essentially of γ-alumina). After impregnating at room temperature for 1 hour, it was air-dried and calcined at 500 ° C. for 4 hours in a muffle furnace to obtain a catalyst A.

Example 2 A catalyst B was produced in the same manner as in Example 1 except that 11 g of nickel carbonate was used instead of 11 g of cobalt carbonate.

Example 3 Tungstophosphoric acid H ₃ was used instead of 38 g of molybdophosphoric acid.
A catalyst C was produced in the same manner as in Example 1 except that 36 g of (PW ₁₂ O ₄₀ ) .30H ₂ O was used.

Example 4 A catalyst D was produced in the same manner as in Example 1 except that molybdophosphoric acid was changed to 28.5 g.

Example 5 A catalyst E was produced in the same manner as in Example 1 except that molybdophosphoric acid was changed to 47.5 g.

Example 6 A catalyst F was produced in the same manner as in Example 1 except that 6.2 g of phosphoric acid was used.

Example 7 A catalyst G was produced in the same manner as in Example 1 except that the HY-type zeolite added to the alumina carrier was changed to 10% by weight.

Example 8 A catalyst H was produced in the same manner as in Example 1 except that 20% by weight of HY-type zeolite was added to the alumina carrier.

Example 9 A catalyst I was produced in the same manner as in Example 3 except that 11 g of nickel carbonate was used instead of 11 g of cobalt carbonate.

Example 10 Catalyst J was produced in the same manner as in Example 1 except that cobalt carbonate was changed to 15.4 g.

Example 11 A catalyst K was produced in the same manner as in Example 1 except that the amount of cobalt carbonate was 8.8 g.

Example 12 21.6 g of cobalt acetate instead of 11 g of cobalt carbonate
A catalyst L was produced in the same manner as in Example 1 except that was used.

Comparative Example 1 At room temperature, in an Erlenmeyer flask, 32.7 g of ammonium molybdate was dissolved in 75 g of water, and ammonia water was added and stirred until the ammonium molybdate was completely dissolved. An aqueous solution was prepared. The first aqueous solution for impregnation was treated with a specific surface area of 33
6 m ² / g, pore volume 0.71 cc / g, average pore diameter 8
It was impregnated with 100 g of 5Å γ-alumina carrier. After impregnating at room temperature for 1 hour, air-drying and 500 ° C in a muffle furnace
Was baked for 4 hours.

On the other hand, at room temperature, 26 g of cobalt nitrate was dissolved in 70 g of water in an Erlenmeyer flask and stirred to prepare a second aqueous solution for impregnation. This second aqueous solution for impregnation was impregnated with the catalyst after calcination in the eggplant-shaped flask at room temperature, and the same drying and calcination as above were carried out to produce a catalyst M.

Comparative Example 2 Except that the carrier was the γ-alumina used in Comparative Example 1,
A catalyst N was produced in the same manner as in Example 1.

Comparative Example 3 A catalyst O was produced in the same manner as in Comparative Example 1, except that the HY-type zeolite-containing alumina used in Example 1 was used as the carrier.

Comparative Example 4 A catalyst P was produced in the same manner as in Example 1 except that the amount of molybdophosphoric acid was 15.2 g.

Comparative Example 5 A catalyst Q was produced in the same manner as in Example 1 except that the phosphoric acid was 19.4 g.

Comparative Example 6 4.2 g of phosphoric acid was dissolved in 75 g of water in an Erlenmeyer flask at room temperature and stirred to prepare a first aqueous solution for impregnation. This first impregnated aqueous solution was used in
100 g of the carrier used in 1. was impregnated. After impregnating at room temperature for 1 hour, it was air-dried and fired at 500 ° C. for 4 hours in a muffle furnace.

On the other hand, at room temperature, in an Erlenmeyer flask, 32.7 g of ammonium molybdate was dissolved in 65 g of water,
A second aqueous solution for impregnation was prepared by stirring. This second impregnating aqueous solution was impregnated with the catalyst after calcination in the eggplant-shaped flask at room temperature, and the same drying and calcination as described above were performed.

Further, at room temperature, 26 g of cobalt nitrate was dissolved in 60 g of water in an Erlenmeyer flask and stirred to prepare a third aqueous solution for impregnation. This third impregnating aqueous solution,
Catalyst R was prepared by impregnating the catalyst after the second calcination in the eggplant-shaped flask at room temperature and performing the same drying and calcination as above.

Comparative Example 7 At room temperature, in an Erlenmeyer flask, 32.7 g of ammonium molybdate was dissolved in 75 g of water and stirred to prepare a first aqueous solution for impregnation. 100 g of the carrier used in Example 1 was impregnated with this first impregnating aqueous solution in an eggplant-shaped flask. After impregnating at room temperature for 1 hour, it was air-dried and fired at 500 ° C. for 4 hours in a muffle furnace.

On the other hand, in an Erlenmeyer flask at room temperature, 4.2 g of phosphoric acid and 26 g of cobalt nitrate were dissolved in 70 g of water and stirred to prepare a second aqueous solution for impregnation. The second aqueous solution for impregnation was placed in an eggplant-shaped flask at room temperature,
The catalyst after calcination was impregnated, and the same drying and calcination as above were performed to prepare a catalyst S.

Comparative Example 8 At room temperature, in an Erlenmeyer flask, 32.7 g of ammonium molybdate, 26 g of cobalt nitrate and 4.2 g of phosphoric acid were dissolved in 75 g of water and stirred to prepare an aqueous solution for impregnation. This impregnating aqueous solution was added to the calcined catalyst in 3.
Attempts were made to prepare the catalyst such that 0% by weight CoO, 20.0% by weight MoO ₃ and 3.0% by weight P ₂ O ₅ were loaded, but the compounds were not completely soluble in the impregnation solution. Since it was present, impregnation became impossible.

As is clear from this result, it is understood that the conventional group VI compound such as ammonium molybdate, which has been typically used, cannot support the desired phosphorus amount and group VI metal amount.

Examples 1 to 12 and Comparative Examples 1 to 7 described above
The compositions of the catalysts A to S obtained in Example 1 are shown in Table 1, and the properties are shown in Table 2.
Shown in.

[0063]

[Table 1]

[0064]

[Table 2]

[Example of Desulfurization Treatment] Using the catalysts A to S obtained in Examples 1 to 12 and Comparative Examples 1 to 7 described above, the results of hydrodesulfurization treatment of light oil under the conditions shown in Table 3 are shown. , Table 4
~ Shown in Table 5. Since the catalyst Q obtained in Comparative Example 5 had a small pore volume and a small specific surface area, it lacked active sites and was not subjected to the test.

[0066]

[Table 3]

As the evaluation method, the reaction was carried out under the reaction conditions shown in Table 3, the sulfur content after 100-hour oil passage was obtained, and the reaction rate constant was obtained from this value based on the equation of Formula 1. Table 4
In Table 5, the value of the catalyst M is shown as 100.

[0068]

[Equation 1]

[0069]

[Table 4]

[0070]

[Table 5]

[0071]

EFFECTS OF THE INVENTION According to the present invention, since an inorganic condensed salt of a Group VI metal having a high solubility in an aqueous solution is used,
The Group VI metal can be supported at the same time as the Group VIII metal with a high supporting amount and at room temperature for a short time only by a single stage impregnation treatment. Further, according to the present invention, since phosphorus is simultaneously impregnated with these metal components, a catalyst having extremely excellent desulfurization activity can be produced. Further, according to the present invention, since the crystalline aluminosilicate contained in the carrier has an excellent effect on the hardly desulfurizable substance, the above Group VI metal, Group VIII metal,
By a synergistic action with phosphorus, it is possible to obtain a catalyst capable of significantly increasing the desulfurization specific activity determined from the rate constant under the same reaction conditions in the depth range of about 0.05% by weight of sulfur as compared with the conventional catalyst. it can. As described above, the present invention simplifies the process of catalyst production, and since the catalyst produced according to the present invention can provide fuel oil having a low sulfur content,
It can be said that this method is extremely effective in practice.

Front page continuation (72) Inventor Mitsugu Yumoto 1134-2 Gongendo, Satte City, Saitama Cosmo Research Institute Co., Ltd. Research and Development Center (72) Inventor Kazuo Ide 1134-2, Gongendo, Satte City, Saitama Prefecture Sumo Research Institute R & D Center (72) Inventor Etsuo Suzuki 1134-2 Gongendo, Satte City, Saitama Cosmo Research Institute R & D Center

Claims (2)

[Claims] 1. A solution containing a Group VI metal condensate of the Periodic Table, a Group VIII metal salt of the Periodic Table, and phosphoric acid on a crystalline aluminosilicate-containing inorganic oxide support, based on a catalyst, as an oxide. In conversion, Group VI metal of the periodic table is 10 to 30
% By weight, 1 to 15% by weight of Group VIII metal of the periodic table,
A method for producing a hydrodesulfurization catalyst for hydrocarbon oil, which comprises impregnating and supporting phosphorus in an amount of 0.1 to 15% by weight. 2. A solution containing a Group VI metal condensate of the Periodic Table, a Group VIII metal salt of the Periodic Table, and phosphoric acid is prepared at a temperature higher than 0 ° C. and lower than 100 ° C. The manufacturing method described.