JP2875148B2 - Method for producing hydrodesulfurization catalyst for hydrocarbon oil - Google Patents

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 oils, and more particularly to a method for supporting a Group VI metal of the periodic table simultaneously with phosphorus at a high loading. Related to manufacturing method.

[0002]

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

[0003] The catalyst conventionally used in this hydrodesulfurization treatment is a Group VI metal of the periodic table (hereinafter simply referred to as "V
A metal which is supported on an oxide carrier such as alumina, magnesia, silica or the like as an active metal comprising a group I metal) and a group VIII metal of the periodic table (hereinafter simply referred to as a "group VIII metal"). It is. At this time, Mo or W is generally used as the Group VI metal, and
Co or Ni is used as the group metal.

In order to improve the activity of this catalyst, phosphorus,
A technique for adding boron or the like has been reported (Japanese Patent Laid-Open No.
See JP-A-2-13503). Further, a technique of mixing a crystalline aluminosilicate into an inorganic oxide used as a carrier has been reported (JP-A-56-2008).
No. 7). In addition, techniques using both of them have been reported (JP-A-61-126196 and JP-A-2-21).
No. 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 an ammonium salt or a nitrate).
From the relationship between the solubility of the Group VI metal salt and phosphoric acid, it is difficult to prepare a catalyst in which a Group VI metal is supported in a high loading amount by one-stage impregnation. As a result, a two-stage impregnation method of impregnating with a Group VI metal after impregnating with phosphorus is performed,
The carrying amount of the Group VI metal must be kept low.

[0006] In addition, due to environmental problems, regulations on sulfur contained in commercial gas oil have become stricter (0.5%).
% By weight → 0.05% by weight), and further deep desulfurization is being demanded, and desulfurization treatment of hardly desulfurizable substances is required.

Under such circumstances, Japanese Patent Application Laid-Open No.
No. 65158, a Group VI metal is added simultaneously with phosphorus,
Moreover, a method for supporting an amount exceeding 20% by weight is disclosed. However, this method requires a considerably high temperature and a long time when preparing the impregnating liquid, which is a negative factor in mass production.

[0008] The above-mentioned technique of mixing a crystalline aluminosilicate into an inorganic oxide used as a carrier aims at obtaining light oil by decomposing heavy oil, and is used for deep desulfurization of a light oil fraction. I didn't.

The present invention has been made in view of the above-mentioned circumstances of the prior art, and impregnates a Group VI metal with phosphorus at a high loading amount, at a low temperature and in a short time. It is an object of the present invention to provide a method for producing a hydrodesulfurization catalyst for hydrocarbon oils, which exhibits excellent desulfurization activity in a deep desulfurization region of a gas oil fraction.

[0010]

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

That is, (1) If an inorganic condensate of the metal is used as a starting material for the metal of Group VI, a large amount of the metal can be impregnated simultaneously with the phosphorus into the carrier at room temperature and in a short time. (2) According to the catalyst produced by such a technique, an active component composed of these active components (Group VI metal and phosphorus) and a Group VIII metal to be loaded after the loading of these active components. It has also been found that the interaction with the crystalline aluminosilicate in the carrier makes it possible to sufficiently cope with difficult-to-desulfurize substances, and to exhibit more excellent activity especially in the deep desulfurization region of the gas oil fraction.

The present invention is based on the above-mentioned findings, and comprises the steps of: forming a first solution containing a metal condensate of Group VI of the Periodic Table and phosphoric acid on a crystalline aluminosilicate-containing inorganic oxide carrier; In terms of oxide, the Group VI metal is 10
-30% by weight and 0.1 to 15% by weight of phosphorus, and after drying and calcination, the second solution containing a metal salt of Group VIII of the periodic table was treated with an oxide on a catalyst basis. In conversion,
The gist of the present invention is a method for producing a hydrodesulfurization catalyst for hydrocarbon oils, which is impregnated and supported so that the Group VIII metal is 1 to 15% by weight, dried and calcined.

Hereinafter, the present invention will be described in detail. The carrier used in the present invention is an inorganic oxide containing a crystalline aluminosilicate. Various inorganic oxides can be used, for example, silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-tria,
Silica-berylia, silica-titania, silica-boria, alumina-zirconia, alumina-titania, alumina-boria, alumina-chromia, titania-zirconia, silica-alumina-tria, silica-alumina-
Zirconia, silica-alumina-magnesia, silica-
Magnesia-zirconia and the like can be mentioned, among which alumina, silica-alumina, alumina-titania, alumina-boria, and alumina-zirconia are preferable, and γ-alumina is particularly preferable among aluminas. These inorganic oxides can be used alone or in combination of two or more.

As the crystalline aluminosilicate to be contained in these inorganic oxides, various ones can be used. For example, A-type zeolite, X-type zeolite, Y-type zeolite, stabilized Y-type zeolite, ultra-stable Y-type Zeolite,
Examples include HY-type zeolites, L-type zeolites, and ZSM-type zeolites, and preferred are HY-type zeolites and stabilized Y-type zeolites. These crystalline aluminosilicates can also 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 the inclusion is not exhibited. 1 to 20% by weight, more preferably 2 to 20% by weight, since the dispersibility of
-10% by weight.

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

The specific surface area of the carrier comprising the above components is as follows:
Although not particularly limited, the object of the present invention (VI
Group metal and phosphorus at the same time, at a high loading, and at low temperature,
And it was impregnated in a short time, in order to achieve that) to obtain a catalyst exhibiting excellent hydrodesulfurization activity in deep desulfurization region, 250 meters ²
/ G or more is preferable. Also, the pore volume of the carrier,
Although not particularly limited, for the same reason as above, one having 0.3 to 1.2 cc / g is preferable. Further, the average pore diameter of the inorganic oxide used for the carrier is not particularly limited, but for the same reason as described above,
It is preferably 50 to 130 °.

As the inorganic condensate of the Group VI metal supported on the above-mentioned carrier, various ones can be used. Inorganic condensate of chromium, molybdenum and tungsten is preferable, and in particular, heteropolyacid of molybdenum and tungsten is used. Salts are preferred. Specifically, H ₃ (PMo ₁₂ O ₄₀ )
Molybdophosphoric acid represented by 30H ₂ O, H ₃ (SiMo
Molybdosilicic acid represented by ₁₂ O ₄₀ ) .30H ₂ O,
Tungstophosphoric acid represented by H ₃ (PW ₁₂ O ₄₀ ) · 30H ₂ O, tungsto silicic acid represented by H ₃ (SiW ₁₂ O ₄₀ ) · 30H ₂ O, and the like, preferably molybdophosphoric acid and molybdosilicic acid And particularly preferably molybdophosphoric acid. These inorganic condensed acid salts can be used alone or in combination of two or more.

Examples of the phosphoric acid supported simultaneously with the inorganic condensate of the Group VI metal include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, polyphosphoric acid, etc., and particularly preferred is orthophosphoric acid. It is.

As the Group VIII metal salt to be supported after the above-mentioned inorganic condensate of Group VI metal and phosphoric acid are simultaneously supported, various ones can be used, such as iron, cobalt, nickel, rhodium, palladium, and the like. Osmium, iridium, and platinum salts are preferred, and cobalt, nickel carbonate, acetate, and phosphate are particularly preferred. These VII
The Group I metal salts can be used alone or in combination of two or more.

The solvent for dissolving each of the above-mentioned components is not particularly limited in the first solution and the second solution, and various solvents can be used.
Water, alcohols, ethers, ketones, aromatics and the like, preferably water, acetone, methanol,
Examples thereof include n-propanol, isopropanol, n-butanol, isobutanol, hexanol, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, and dioxane, and particularly preferably water.

In each of the first and second solutions, the proportion of each component dissolved in the above-mentioned solvent is usually based on the amount of the oxide of the group VI metal inorganic condensate relative to the calcined catalyst. Is 10 to 30% by weight, preferably 18 to 25% by weight
The amount of phosphoric acid is 0.1 to 15% by weight, preferably 1 to 7% by weight, and the amount of the Group VIII metal salt is 1 to 15% by weight, preferably 3 to 7% by weight. Quantity.

When the proportion of the inorganic condensate of the Group VI metal is 10
If the amount is less than 10% by weight, the active site of the active metal is too small to obtain a deep desulfurization effect, and if it exceeds 30% by weight, the surface area of the catalyst tends to be small and the catalytic activity tends to decrease. If the proportion of phosphoric acid is too small, the technical effect of blending phosphoric acid will not be exhibited, and if it is too large, the pore volume of the catalyst after preparation will be too small, and the catalytic activity tends to decrease. If the proportion of the Group VIII 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 tends to decrease.

If the amount of the solvent used is too small for both the first solution and the second solution, the carrier cannot be sufficiently impregnated. If the amount is too large, the dissolved active metal does not impregnate the carrier. , Because it adheres to the rim of the impregnating solution container and the like, and a desired amount of support cannot be obtained, usually, the first solution and the second solution each have 50 wt.
１５０150 g, preferably 70-90 g.

In the present invention, the first and second solutions for impregnation are prepared by dissolving the above-mentioned components in the above-mentioned solvent, and the temperature at this time is set for both the first and second solutions. 0
The temperature may be higher than 100 ° C. and lower than 100 ° C. If the temperature is within this range, the above components can be dissolved well in the solvent.

The first solution and the second solution for impregnation prepared as described above are impregnated into the carrier in the order of the first and second solutions (actually, the first solution is impregnated with the first solution). , Dried and fired, then impregnated with the second solution, dried and fired), and the above components in these solutions are carried on the above-mentioned carrier. As the impregnation conditions, various conditions can be adopted for both the first solution and the second solution. Usually, the temperature is preferably higher than 0 ° C and lower than 100 ° C, more preferably 10 to 50 ° C, The temperature is preferably 15 to 30 ° C, and the impregnation time is preferably 15 minutes to 3 hours, more preferably 20 minutes to 2 hours, and still more preferably 30 minutes to 1 hour. If the temperature of both the first solution and the second solution is too high, drying occurs during the impregnation, and the degree of dispersion is biased. In addition, it is preferable to stir both the first and second solutions during the impregnation.

The drying after the impregnation can be performed by various drying methods such as air drying, hot air drying, heat drying, and freeze drying for both the first and second solutions. In addition, firing can be performed by various firing methods such as electric furnace firing, muffle furnace firing, alundum bath firing, and electric tubular furnace firing for both the first and second solutions. It is preferable to carry out under air circulation or in a muffle furnace.

The sintering temperature may be appropriately selected and determined according to the sintering method. In the case of sintering in an air flow in an electric furnace or in a muffle furnace, both the first and second solutions are used.
The temperature is from 00 to 800 ° C, preferably from 300 to 700 ° C, particularly preferably from 450 to 650 ° C. If the firing temperature is too low, the active metal is not sufficiently supported, and poisoning substances remain. If the firing temperature is too high, sintering occurs. The firing time is preferably 2 to 10 hours for both the first and second solutions,
Particularly, 3 to 5 hours are preferable.

The shape of the catalyst produced as described above is not particularly limited, and may be any of the various shapes used for ordinary catalysts of this type. For oil, a four-leaf type is preferable, and for light oil, a columnar shape is preferable. Usually, the diameter is 1/1
It is preferable that the length is about 0 to 1/22 inch and the length is about 3.2 to 3.6 inches.

When the catalyst obtained in the present invention is used in an actual process, it may of course be used alone, or may be mixed with a known catalyst or a known inorganic oxide carrier. Also, after the above-mentioned second solution impregnation, before or after drying, or after calcination, montmorillonite, kaolin, halothite, bentonite, adavalguite, bauxite,
Clay minerals such as kaolinite, nacrite, anoxite and the like can be contained alone or in combination of two or more.

Next, desulfurization treatment (including depth desulfurization treatment) using the catalyst obtained in the present invention will be described. The hydrocarbon oils to be treated include light fractions and atmospheric distillation residues obtained by atmospheric distillation or vacuum distillation of crude oil, coker gas oil, solvent de-historized oil, tar sand oil, shale oil,
Various hydrocarbon oils such as coal liquefied oil, catalytic cracked gas oil, pyrolyzed gas oil, straight run gas oil, coker gas oil, hydrotreated gas oil, and desulfurized gas oil.

In the case of desulfurization by catalytic hydrotreatment on a commercial scale, the catalyst obtained in the present invention (hereinafter simply referred to as "catalyst") is used as a fixed bed, a moving bed or a 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 perform desired desulfurization.

[0033] Most commonly, the catalyst is maintained as a fixed bed such that the hydrocarbon oil passes down 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 feed oil is heavy, it is extremely preferable to use a multi-stage reactor.

As a preferred example of the processing conditions, a hydrocarbon oil is used at a temperature of about 200 to 500 ° C., more preferably 25 ° C.
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 it. In this contact, an interaction between the active components of the group VI metal, the group VIII metal, and phosphorus, and the crystalline aluminosilicate in the carrier is expressed, and the difficult-to-desulfurize substances in the hydrocarbon oil are also reduced. Desulfurization can be easily performed, and deep desulfurization of hydrocarbon oil is realized.

[0035]

【Example】

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

Example 1 Molybdophosphoric acid [H ₃ (P
38 g of Mo ₁₂ O ₄₀ ) · 30H ₂ O] and 4 g of phosphoric acid were dissolved in 75 g of water and stirred to prepare a first solution for impregnation. This first solution is placed in an eggplant-shaped flask,
100 g of an alumina carrier (consisting essentially of γ-alumina) containing 5% by weight of HY type zeolite having a specific surface area of 372 m ² / g and a pore volume of 0.65 cc / g was impregnated. After impregnation at room temperature for 1 hour, air-dry and 500 ° C in a muffle furnace.
For 4 hours.

On the other hand, in an Erlenmeyer flask at room temperature, 26.9 g of cobalt nitrate was dissolved in 60 g of water and stirred to prepare a second solution for impregnation. This second solution was impregnated with 100 g of the fired one in the eggplant-shaped flask. After impregnating at room temperature for 1 hour, it was air-dried and calcined in a muffle furnace at 500 ° C. for 4 hours to obtain Catalyst A.

Example 2 11 g of nickel nitrate instead of 26.9 g of cobalt nitrate
Catalyst B was produced in the same manner as in Example 1 except that

Example 3 Tungstophosphoric acid H ₃ instead of 38 g of molybdophosphoric acid
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 the amount of 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 the amount of 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 the amount of phosphoric acid was changed to 6.2 g.

Example 7 A catalyst G was produced in the same manner as in Example 1 except that the amount of 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 the amount of HY-type zeolite added to the alumina carrier was changed to 20% by weight.

Example 9 Nickel nitrate was used instead of 26.9 g of cobalt nitrate.
Catalyst I was prepared in the same manner as in Example 3 except that 9 g was used.
Was manufactured.

Example 10 A catalyst J was produced in the same manner as in Example 1 except that the amount of cobalt nitrate was changed to 37.7 g.

Example 11 A catalyst K was produced in the same manner as in Example 1 except that the amount of cobalt nitrate was changed to 16.1 g.

Example 12 Instead of 26.9 g of cobalt nitrate, cobalt acetate was used.
Catalyst L was prepared in the same manner as in Example 1 except that 6 g of the catalyst L was used.
Was manufactured.

Comparative Example 1 In an Erlenmeyer flask at room temperature, 32.7 g of ammonium molybdate was dissolved in 75 g of water, and ammonia water was further added and stirred until the ammonium molybdate was completely dissolved. An aqueous solution was prepared. The first aqueous solution for impregnation is placed in an eggplant-shaped flask in a specific surface area of 33.
6 m ² / g, pore volume 0.71 cc / g, average pore diameter 8
It was impregnated into 100 g of a 5% γ-alumina carrier. After impregnation at room temperature for 1 hour, air-dry and 500 ° C in a muffle furnace.
For 4 hours.

On the other hand, in an Erlenmeyer flask at room temperature, 26 g of cobalt nitrate was dissolved in 70 g of water and stirred to prepare a second aqueous solution for impregnation. The second aqueous solution for impregnation was impregnated with the above-mentioned calcined catalyst in an eggplant-shaped flask at room temperature, and dried and calcined in the same manner as above to produce Catalyst M.

Comparative Example 2 Except that the carrier was γ-alumina used in Comparative Example 1,
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 support was HY-type zeolite-containing alumina used in Example 1.

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

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

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

On the other hand, in an Erlenmeyer flask at room temperature, 32.7 g of ammonium molybdate was dissolved in 65 g of water.
The mixture was stirred to prepare a second aqueous solution for impregnation. This second aqueous solution for impregnation was impregnated with the above-mentioned calcined catalyst in an eggplant-shaped flask at room temperature, and dried and calcined in the same manner as above.

Further, 26 g of cobalt nitrate was dissolved in 60 g of water at room temperature in an Erlenmeyer flask and stirred to prepare a third aqueous solution for impregnation. This third aqueous solution for impregnation is
At room temperature, the catalyst after the second baking was impregnated in an eggplant-shaped flask at room temperature, and dried and calcined in the same manner as above to prepare Catalyst R.

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

On the other hand, 4.2 g of phosphoric acid and 26 g of cobalt nitrate were dissolved in 70 g of water at room temperature in an Erlenmeyer flask, 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 the calcination was impregnated, dried and calcined in the same manner as above to prepare a catalyst S.

Comparative Example 8 In a conical flask at room temperature, 32.7 g of ammonium molybdate and 4.2 g of phosphoric acid were dissolved in 75 g of water and stirred to prepare a first aqueous solution for impregnation. On the other hand, 26 g of cobalt nitrate was dissolved in 75 g of water and stirred to prepare a second aqueous solution for impregnation. Using these first and second aqueous solutions for impregnation, impregnating the first aqueous solution for impregnation, drying and calcining, then impregnating the second aqueous solution for impregnation, drying,
So calcined, to the catalyst after calcination for the second time, 3.0% by weight of CoO, 20.0 wt% of MoO _3, and 3.0
An attempt was made to prepare the catalyst so that the amount of P ₂ O ₅ carried by weight% was reached. However, since the insoluble compound was present in the first aqueous solution for impregnation, the first aqueous solution for impregnation was not impregnated. It has become possible.

As is clear from the results, it has been found that the group VI compound such as ammonium molybdate, which has been typically used in the past, cannot support the desired amount of phosphorus and group VI metal.

Examples 1 to 12 and Comparative Examples 1 to 7
The compositions of catalysts A to S obtained in Table 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 P obtained in the above Examples 1 to 12 and Comparative Examples 1 to 7, the results of hydrodesulfurization treatment of light oil under the conditions shown in Table 3 are shown. , Table 4
To Table 5 below. Since the catalyst Q obtained in Comparative Example 5 had a small pore volume and a small specific surface area, it had poor active sites and was not subjected to the test.

[0066]

[Table 3]

The evaluation was carried out under the reaction conditions shown in Table 3 to determine the sulfur content after passing the oil for 100 hours, and to determine the reaction rate constant from this value based on the equation (1). Table 4
Table 5 shows the value of the catalyst M as 100.

[0068]

(Equation 1)

[0069]

[Table 4]

[0070]

[Table 5]

[0071]

According to the present invention, since an inorganic condensate of a Group VI metal having high solubility in an aqueous solution is used,
The Group VI metal can be supported at the same time as phosphorus by a single stage of impregnation at a high loading amount and at room temperature for a short time. Further, according to the present invention, since a Group VIII metal is also supported together with these, 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 non-desulfurizing substance, it is possible to obtain a synergistic effect with the above-mentioned Group VI metal, phosphorus and Group VIII metal. By the action, a catalyst capable of significantly increasing the specific activity of desulfurization determined from the rate constant under the same reaction conditions can be obtained in the depth range of about 0.05% by weight of sulfur as compared with the conventional catalyst under the same reaction conditions. As described above, the present invention can provide a fuel oil having a low sulfur content, and thus can be said to be a very effective method in practical use.

Continued on the front page (72) Inventor Mitsuru Yumoto 1134-2 Gondogendo, Satte City, Saitama Prefecture Cosmo Research Institute, Inc. R & D Center (72) Inventor Kazuo Dei 1134-2 Gondogendo, Satte City, Saitama Prefecture Cosmo Sogo Research and Development Center (72) Inventor Etsuo Suzuki 1134-2 Gongendo, Satte City, Saitama Prefecture Research and Development Center, Cosmo Research Institute, Inc. (56) References JP-A-59-69149 (JP, A) JP-A-7-197038 (JP, A) JP-A-6-277520 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) B01J 29/00 C10G 45/08 C10G 45/12

Claims (2)

(57) [Claims] 1. A first solution containing a metal condensate of Group VI of the periodic table and phosphoric acid on a crystalline aluminosilicate-containing inorganic oxide support, the catalyst being converted to a V-form in terms of oxide on a catalyst basis.
Group I metal is 10 to 30% by weight, phosphorus is 0.1 to 15% by weight
After being impregnated and supported, dried, and calcined, a second solution containing a Group VIII metal salt of the periodic table was prepared on the basis of a catalyst,
A method for producing a hydrodesulfurization catalyst for hydrocarbon oils, comprising impregnating and supporting the Group VIII metal in an amount of 1 to 15% by weight in terms of oxide, drying and calcining. 2. The method according to claim 1, wherein the first and second solutions are heated at a temperature above 0 ° C.
2. The composition is prepared at a temperature lower than 00 ° C.
Production method as described.