JP3060423B2 - 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 process for producing a hydrodesulfurization catalyst for hydrocarbon oils, and more particularly, to a hydrocarbon oil having a high loading of a Group 8 metal carbonate and having excellent desulfurization activity. The present invention relates to a method for producing a hydrodesulfurization catalyst for industrial use.

[0002]

2. Description of the Related Art Since hydrocarbon oils generally contain sulfur compounds, when such hydrocarbon oils are used as fuel, the sulfur present in the sulfur compounds is converted into sulfur compounds and discharged into the atmosphere. Pollutes the atmosphere. Therefore, to prevent air pollution, hydrocarbon oils used as fuels are:
It is desirable that the sulfur content be as low as possible. In particular, in recent years, where environmental degradation due to acid rain and nitrogen oxides is progressing on a global scale, in order to solve this environmental degradation problem, the sulfur content in hydrocarbon oils must be further reduced. Technology development is desired. Conventionally, hydrocarbon oils having a low sulfur content have been obtained by catalytic hydrodesulfurization of hydrocarbon oils. The catalyst used in the catalytic hydrodesulfurization is a catalyst in which a group 6 metal and a group 8 metal of the periodic table are used as active metals and supported on a support made of an oxide such as alumina, magnesia, and silica. Generally, Mo or W is used as the Group 6 metal, and Co or Ni is used as the Group 8 metal.

Conventionally, as a method for supporting these active metals on a carrier, a method of impregnating with an aqueous solution of various metal salts (mainly ammonium salts and nitrates) has been used. However, when a metal salt containing an atom such as N or Cl is used, a compound consisting of an atom such as N or Cl contained in the metal salt adversely affects the active metal in a catalyst preparation step such as drying and calcining. There are drawbacks.

On the other hand, carbonates composed of C and O atoms do not adversely affect active metals. An attempt to use a carbonate in an aqueous solution for impregnation has been made in JP-A-4-166231, and an aqueous solution comprising a carbonate of a metal belonging to Group 8 of the periodic table, an oxide of a metal belonging to Group 6 and phosphoric acid. According to US Pat. In this method, the pH is lowered by adding phosphoric acid in order to increase the solubility of the carbonate of a metal belonging to Group 8 of the periodic table, which has low solubility in water. However, if an attempt is made to prepare a Group 8 metal at a high loading, p
To lower H, a large amount of phosphoric acid needs to be added. As a result, the ratio of the Group 8 metal oxide / P ₂ O ₅ was suppressed to a low value, and there was a disadvantage that the catalytic activity was reduced.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the situation of the prior art described above, and does not include atoms such as N and Cl, and controls the amount of P ₂ O ₅ while controlling the amount of P ₂ O ₅ . It is an object of the present invention to provide a method for producing a hydrodesulfurization catalyst for hydrocarbon oils having a high loading of a group 6 metal carbonate and having excellent desulfurization activity.

[0006]

Means for Solving the Problems The inventors of the present invention have proposed a method for supporting a group 8 metal carbonate on a carrier in a high loading amount without using phosphoric acid or keeping the concentration of phosphoric acid low. As a result of diligent research, we focused on inorganic complex acid salts of Group 6 metals as Group 6 metal compounds, and as a result of further diligent research, used inorganic complex acid salts of Group 6 metals and carbonates of Group 8 metals in combination. Use the solution, and further use inorganic oxide and zeolite as carriers.
It has been found that the above object can be achieved by using a carrier contained therein , and based on this finding, the present invention has been completed.

That is, the present invention provides a support containing an inorganic oxide and a zeolite selected from HY-type zeolite and stabilized Y-type zeolite, comprising an inorganic complex acid salt of a Group 6 metal of the Periodic Table and a Periodic Table 8 It consists of carbonates of group metals and phosphoric acid, and the compounding ratio of phosphoric acid is
It is intended to provide a method for producing a hydrodesulfurization catalyst for hydrocarbon oils, which is impregnated with a solution containing 0.1 to 15% by weight of phosphoric acid . Hereinafter, the present invention will be described in detail.

The carrier used in the method for producing a hydrodesulfurization catalyst for hydrocarbon oils of the present invention contains an inorganic oxide .
You . Various inorganic oxides can be used, for example, silica, alumina, boria, chromia, magnesia,
Zirconia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titania, silica-boria, alumina-zirconia, alumina-titania, alumina-
Boria, alumina-chromia, titania-zirconia,
Examples include silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, and the like, or a mixture of one or more of these. Among these inorganic oxides, preferred are alumina, silica-alumina, alumina-titania, alumina-boria, and alumina-zirconia, and particularly preferred is γ-alumina. These inorganic oxides may be used alone or in combination of two or more.

Further, the carrier of the present invention, Ru is contained zeolite. As the zeolite, various zeolites can be used, for example, A type zeolite, X type zeolite, Y type zeolite, stabilized Y type zeolite, ultra stabilized Y type zeolite, HY type zeolite, L type zeolite, ZSM type Zeolite and the like, preferably H
Y-type zeolites and stabilized Y-type zeolites are exemplified.
These zeolites may be used alone or may be used alone.
A combination of more than one species may be used. The content of zeolite in the carrier is preferably 1 to 50% by weight.

[0010] The carrier or catalyst of the present invention may contain one or more clay minerals such as montmorillonite, kaolin, halosite, bentonite, adavalguite, bauxite, kaolinite, nacrite, and anoxite. The specific surface area of the support made of these inorganic oxides is not particularly limited, but is preferably 250 m ² / g or more. The pore volume of the carrier is not particularly limited, either, but is preferably 0.4 to 1.2 cc / g. The average pore diameter of the carrier is not particularly limited, but is preferably 50 to 130 A (angstrom).

In the method for producing a hydrodesulfurization catalyst for a hydrocarbon oil according to the present invention, the carrier comprises a solution comprising an inorganic complex acid salt of a metal belonging to Group 6 of the periodic table and a carbonate comprising a metal belonging to Group 8 of the periodic table. For impregnation. As the inorganic complex acid salt of a metal of Group 6 of the periodic table, various inorganic complex acid salts can be used, and an inorganic complex acid salt of a metal such as chromium, molybdenum and tungsten is preferable, and a heteropolyacid of a metal such as molybdenum and tungsten is particularly preferable. Specific examples of the inorganic composite salt, for example, molybdophosphoric acid represented by H ₃ [PMo ₁₂ O _40] · 30H ₂ O, H ₃ [SiMo ₁₂ O _40] · 30H
Molybdosilicate represented by ₂ O, H ₃ [PW ₁₂ O ₄₀ ]
Tungstophosphoric acid represented by 30H ₂ O, H ₃ [SiW
₁₂ O _40] · 30H ₂ such tungstosilicic acid represented by O and the like, preferably molybdophosphate, include molybdosilicic acid, particularly preferably include molybdophosphoric acid. These inorganic composite salts may be used alone or in combination of two or more.

As the carbonate of Group 8 metal of the periodic table, various ones can be used, and a carbonate of a metal such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum is preferable. Cobalt and nickel carbonates are preferred. These Group 8 metal carbonates may be used alone or in combination of two or more.

In the production method of the present invention, phosphoric acid is preferably added to a solution comprising the inorganic complex acid salt of a metal belonging to Group 6 of the periodic table and a carbonate of a metal belonging to Group 8 of the periodic table.
Examples of the phosphoric acid include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, and polyphosphoric acid.

The solvent for dissolving the inorganic complex acid salt of Group 6 metal of the periodic table, the carbonate of Group 8 metal of the periodic table, and the phosphoric acid to be added as necessary is not particularly limited, and various solvents can be used. Solvents can be used, for example, water, alcohols, ethers, ketones, and aromatics. Preferably, water, acetone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, Hexanol, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane and the like can be mentioned, and water is particularly preferable.

The mixing ratio of each component constituting the solution is as follows:
The inorganic complex acid salt of Group 6 metal is usually 10 to 25% by weight, preferably 15 to 2%, in terms of oxide based on the calcined catalyst.
0% by weight, and the carbonate of the Group 8 metal is usually 2 to 15% by weight, preferably 5 to 10% by weight. If the compounding ratio of the inorganic complex acid salt of the Group 6 metal is less than 10 % by weight, the carbonate of the Group 8 metal tends to be difficult to dissolve, and if it exceeds 25% by weight, the surface area of the catalyst becomes small and the catalytic activity becomes low. Tends to decrease. In addition, the group 8 metal carbonate is 2% by weight.
If it is less than 15%, the catalytic activity is not sufficient, and if it exceeds 15% by weight, the entire catalyst is covered, and the catalytic activity tends to decrease. Phosphoric acid is 0.1 to 15% by weight, preferably 3% by weight, in terms of oxide, based on the calcined catalyst.
~ 7% by weight. If the amount of phosphoric acid is too large, the catalytic activity decreases. Furthermore, the amount of the solvent used is based on 100 g of the carrier.
Usually, it is 50 to 150 g, preferably 70 to 90 g.

In the present invention, the carrier is impregnated with the solution. Various conditions can be adopted as the impregnation conditions. For example, the temperature is preferably from 10 to 50C, particularly preferably from 15 to 30C. During the impregnation, it is preferable to stir. Further, the impregnation time is preferably 30 minutes or more.

The catalyst of the present invention can be produced by drying and calcining the carrier impregnated with the above components and carrying the above components. Drying can be performed by various drying methods such as air drying, hot air drying, overheating drying, and freeze drying.
The firing temperature may be appropriately selected and determined.
The range of 0-550 degreeC is preferable, and especially 450-500 degreeC
Is preferable. The firing time is preferably 2 to 10 hours, and particularly preferably 3 to 5 hours.

The shape of the catalyst of the present invention is not particularly limited, and may be any of various shapes used for a normal catalyst, and the size is usually 1/10 to 1/22 inch. The shape is preferably a four-leaf type if the hydrocarbon oil is heavy oil, and a cylindrical type if the hydrocarbon oil is light oil.
When the catalyst of the present invention is used in an actual process, it may be used as a mixture with a known catalyst or a known inorganic oxide carrier.

The hydrocarbon oil used in the present invention includes a light fraction obtained by atmospheric distillation or vacuum distillation of crude oil, an atmospheric distillation residue, a vacuum distillation residue, coker gas oil, solvent-degraded oil, tar sand oil, shale Various hydrocarbon oils, such as oil and coal liquefied oil, may be mentioned. A commercial scale catalytic hydrodesulfurization unit uses a catalyst as a fixed, moving or fluidized bed of particles in a suitable reactor, introduces the oil to be treated into the reactor, and applies high The desired desulfurization is carried out by treating under the conditions of the hydrogen partial pressure. Most commonly, the catalyst is maintained as a fixed bed, with the oil passing down through the fixed bed. The catalyst can be used in a single reactor or in several successive reactors. Especially when the feedstock is heavy,
It is highly preferred to use a multi-stage reactor. As a preferred example of the reaction, the hydrocarbon oil is heated to about 200 to 500 ° C,
More preferably, in the range of 250 to 400 ° C., the liquid hourly space velocity is about 0.05 to 5.0 hr ⁻¹ , more preferably 0.1 to 5.0 hr ⁻¹ .
In the range of 4.0 hr ^-1 and hydrogen pressure of about 30-200.
kg / cm ² G, more preferably 40 to 150 kg / c
The catalyst is contacted under conditions in the range of m ² G.

[0020]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. An example of the catalyst preparation method is described in Example 1.
~ 2 . The HY-type zeolites used in Examples and Comparative Examples had a SiO ₂ / Al ₂ O ₃ molar ratio of 6, a Na ₂ O content of 0.3% by weight or less, and a surface area of 90 to 1100. (Langmuir, m ² / g) and 600-700 (BET, m ² / g), and the crystal size is 0 . It was 7 to 1.0 μm. Example 1 In an Erlenmeyer flask, 11 g of cobalt carbonate, 4 g of phosphoric acid,
Molybdophosphoric acid (H ₃ [PMo ₁₂ O ₄₀ ] ・ 30H ₂
O) HY type gel having a specific surface area of 321 m ² / g, a pore volume of 0.63 cc / g, and an average pore diameter of 79 A in an eggplant-shaped flask using an aqueous solution obtained by dissolving 38 g in 75 g of water and stirring.
Zeolite 5 wt% containing impregnated into γ- alumina responsible member 100 g. Impregnated at room temperature for 1 hour, dried (air dried), and calcined in a muffle furnace at 500 ° C. for 4 hours to obtain catalyst A
I got

[0021]

Embodiment2  Example 1 except that the amount of dissolved phosphoric acid was 6.8 g.
1Perform the same procedure as inBI got

Comparative Example 1 In an Erlenmeyer flask, 27 g of cobalt nitrate, 6 g of phosphoric acid,
25.5 g of ammonium molybdate was dissolved in 70 g of water, and a stirred aqueous solution was used in an eggplant-shaped flask.
Specific surface area 336 m ² / g, pore volume 0.71 cc / g,
Alumina carrier with an average pore size of 85A (substantially γ-aluminum
100 g). Includes 1 hour at room temperature
After soaking and drying (air drying), at 500 ° C in a muffle furnace
After calcining for 4 hours, catalyst C was obtained.

Comparative Example 2 The specific surface area of the support was 321 m ² / g, and the pore volume was 0.63.
Catalyst D was obtained in the same manner as in Comparative Example 1, except that γ-alumina containing 5% by weight of cc / g HY-type zeolite was used.

Comparative Example 3 In the eggplant-shaped flask, 23.5 g of ammonium molybdate was dissolved in 70 g of water in the carrier used in Comparative Example 1, and 100 g of the carrier was impregnated with this solution. Air-dry after impregnation for 1 hour,
The firing was performed at 500 ° C. for 4 hours. Further, an aqueous solution of 25 g of cobalt nitrate dissolved in 70 g of water was impregnated to carry cobalt. After air drying, calcined at 500 ° C for 4 hours
E was obtained.

Comparative Example 4 In an Erlenmeyer flask, a specific surface area of 336 m ² was obtained using an aqueous solution obtained by dissolving 38 g of molybdophosphoric acid in 75 g of water and stirring.
/ G of alumina support (consisting essentially of γ-alumina) with a pore volume of 0.71 cc / g. After impregnating for 1 hour, drying, and calcining at 500 ° C. for 4 hours, in order to carry cobalt, 11 g of cobalt carbonate was dissolved in a solution obtained by adding 4 g of phosphoric acid to 75 g of water. When it was not dissolved and phosphoric acid was added, it eventually became a gel-like substance and could not be impregnated. Therefore, it is difficult to support a large amount of cobalt carbonate unless molybdophosphoric acid is used. The compositions of catalysts A to E of Examples 1 and 2 and Comparative Examples 1 to 3 are shown in Table 1, and the properties thereof are shown in Display 2.

[0027]

[Table 1]

[0028]

[Table 2]

The catalysts A to A shown in the above Examples and Comparative ExamplesE
Table 3 shows examples of hydrodesulfurization reaction of gas oil using methane.
Was. Hydrodesulfurization reaction of light oil Raw material: LGO (specific gravity (15/4 ° C) 0.851 sulfur content 1.35 wt%, nitrogen content 20 ppm, viscosity (＠ 30 ° C) 5.499 cst) Reaction condition: reaction temperature 350 ° C Reaction pressure 35 kg / cm²  Liquid space velocity 4hr^-1  Apparatus High-pressure flow-type reactor with fixed-bed method Evaluation method: Sulfur content after passing oil for 100 hours under the above operating conditions
The weight was checked.

[0030]

[Table 3]

[0031]

According to the method for producing a catalyst of the present invention, since an inorganic complex acid salt of a Group 6 metal of the periodic table is used, its aqueous solution becomes acidic, and a carbonate of a Group 8 metal is dissolved. However, addition of an acidic substance such as phosphoric acid can be suppressed. Moreover, an inorganic acid at a high loading amount of metal in a single step impregnation
Thus, a catalyst having excellent desulfurization activity can be produced. The catalyst has a remarkably higher desulfurization specific activity determined from the rate constant under the same reaction conditions as the conventional catalyst. As described above, since the process of preparing the catalyst is simplified and a fuel oil having a low sulfur content can be produced, it is extremely useful in practical use.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Kazushi Usui 1-62-10 Iwana, Noda City, Chiba Prefecture (56) References JP-A-6-31176 (JP, A) (58) Fields investigated (Int .Cl. ⁷ , DB name) B01J 21/00-38/74 C10G 45/08

Claims (2)

(57) [Claims] 1. A support containing an inorganic oxide and a zeolite selected from HY-type zeolites and stabilized Y-type zeolites, an inorganic complex acid salt of a metal belonging to Group 6 of the periodic table and an inorganic complex acid salt of Group 8 of the periodic table.
It consists group metal carbonate and phosphoric acid, the mixing ratio of phosphoric acid
Phosphoric acid is 0.1 to 0.1% in terms of oxide based on the calcined catalyst.
A method for producing a hydrodesulfurization catalyst for hydrocarbon oils, comprising impregnating and supporting a solution of 15% by weight. 2. The method for producing a hydrodesulfurization catalyst for hydrocarbon oil according to claim 1, wherein the zeolite is a HY type zeolite.