JP2789489B2 - Hydrodesulfurization catalyst composition for hydrocarbon oil, method for producing the same, and hydrodesulfurization method using the same - Google Patents

Description

The present invention relates to a novel hydrodesulfurization catalyst composition having a remarkably improved desulfurization activity as compared with conventional catalysts, a method for producing the catalyst, and the catalyst. And a method for hydrodesulfurizing a hydrocarbon oil using the method.

(Prior Art) Hydrocarbon oils generally contain sulfur compounds, and when those oils are used as fuel, the sulfur present in the sulfur compounds is converted to sulfur oxides and discharged to the atmosphere. It is desirable that the hydrocarbon oil containing these sulfur compounds has as low a sulfur content as possible in consideration of the pollution of the atmosphere when burned. This can be achieved by catalytic hydrodesulfurization of hydrocarbon oils.

Recently, environmental problems such as acid rain and nitrogen oxides have been taken up on a global scale, and there is a demand for further removal of sulfur content exceeding the current technical level. Reducing the sulfur content in hydrocarbon oils can be achieved to some extent by harsh operating conditions, such as LHSV, temperature and pressure. However, such a method deposits carbonaceous material on the catalyst and rapidly reduces the activity of the catalyst. In particular, when the hydrocarbon oil is a light fraction, there are also adverse effects on properties such as hue stability and storage stability. Thus, there is a limit to the depth of desulfurization in operation. Therefore, the best strategy is to develop catalysts with significantly better desulfurization activity.

By the way, conventionally, as a general method for preparing a hydrodesulfurization catalyst, a so-called “impregnation” method of impregnating a carrier with an aqueous solution of a metal salt of Group 8 of the periodic table and a metal salt of Group 6B of the periodic table is used. Method, an aqueous solution in which alumina or alumina gel is dispersed, an aqueous solution of a metal salt of Group 6B of the periodic table and an aqueous solution of a metal salt of Group VIII of the periodic table are added, and a "coprecipitation method" in which a metal compound is precipitated, There is a "kneading method" in which heating and water removal are carried out while kneading a mixed paste of alumina, alumina gel, an aqueous solution of a metal salt of Group 6B of the Periodic Table and an aqueous solution of a metal salt of Group VIII of the Periodic Table ("Catalyst preparation"). Chemistry ", edited by Suzaki Ozaki, Kodansha Scientific, pp. 250-252).

However, it is difficult for these methods to support a relatively large amount of a metal compound on a carrier with good dispersibility. Even if excess catalyst metal compound is supported on the carrier,
There is a problem that there is a limit in improving the desulfurization activity of the catalyst in order to reduce the specific surface area of the catalyst. That is, until now, relatively containing a large amount of the active metal even if there is a description that it is possible, the limit value of the amount of metal can be used in reality most CoO content of about 5-8 wt-%, MoO ₃ content 19 ~ 20wt%
Met.

Considering the desulfurization rate, as long as a conventional catalyst is used,
For example, in the case of hydrodesulfurization of light oil, the sulfur content of the feed oil is 1.3 wt%
% Gas oil at a liquid hourly space velocity of 4 hr ^-1 , a reaction temperature of 350 ° C. and a hydrogenation pressure of 35 kg / cm ² under catalytic hydrodesulfurization conditions, the sulfur content of the produced oil is 0.13 to 0.19 wt% at most. That is the limit. In the case of hydrodesulfurization of vacuum gas oil (VGO), VGO with a sulfur content of 2.50 wt% of the feed oil is subjected to a liquid hourly space velocity of 0.4 hr.
^-1 , When the catalytic hydrodesulfurization is carried out under the reaction conditions of a reaction temperature of 350 ° C. and a hydrogenation pressure of 52 kg / cm ² , the limit of the sulfur content of the produced oil is 0.15 to 0.18 wt% at most. Furthermore, in the case of hydrodesulfurization of the residual oil under normal pressure, the sulfur content of the feedstock 3.8w
liquid space velocity of 1.0 hr ^-1 , reaction temperature of 361 ° C,
When performing catalytic hydrogenation desulfurization under the reaction conditions of the hydrogenation pressure 150 kg / cm ^2, the sulfur content of the product oil at most 0.9~1.0wt
% Is the limit.

The sulfur content of the produced oil is 0.05 to 0.08 wt% in light oil,
If it can be easily desulfurized without increasing the severity to 0.08 to 0.10 wt% for VGO and 0.6 to 0.8 wt% for normal pressure residual oil, there is no need to increase the severity of operation, so the life of the catalyst is extremely low. In addition to being economical, the use of these fuel oils has a great advantage in that air pollution can be suppressed.

(Problems to be Solved by the Invention) A problem to be solved by the present invention is that a large amount of active metal can be contained, and a large amount of the metal has a large surface area and severe operating conditions. Without developing a catalyst that exhibits extremely high desulfurization activity under normal operating conditions. It is a further object of the present invention to minimize the emission of sulfur compounds into the atmosphere due to the combustion of fuel oil and to suppress air pollution.

(Means for Solving the Problems) The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a composite of a metal oxide containing a Group 8 metal, a Group 6B metal and aluminum. , Group VIII metal content and
The group 6B metal content can be much higher than that of conventional hydrodesulfurization catalysts, and catalysts with different catalyst structures have been successfully developed. Since the catalyst of the present invention is a composite of a metal oxide having a completely different structure from the conventional catalyst, it has a high surface area in spite of the high metal content, and is used to hydrogenate hydrocarbon oil. In the case of desulfurization, the present invention provides an extremely useful technique that enables desulfurization at a deep depth and has a long catalyst life.

That is, the gist of the first invention is that (a) at least one compound selected from the group consisting of molybdenum and tungsten, (b) at least one compound of iron group, and (c) aluminum alkoxide in an organic solvent. At least one metal selected from the group consisting of molybdenum and tungsten, an iron group metal and A composite of a metal oxide containing aluminum,
The amount of at least one metal selected from the group consisting of molybdenum and tungsten is 40 to 60% by weight relative to the catalyst as an oxide, and the amount of iron group metal is 5 to 20% by weight relative to the catalyst as an oxide; 1.0-1.4kg / m side fracture strength
m, wherein the gist of the second invention is (a) at least one compound selected from the group consisting of molybdenum and tungsten, (b) ) At least one compound of the iron group;
And (c) mixing an aluminum alkoxide in an organic solvent, and drying and calcining an active ingredient produced by adding water simultaneously with or after the mixing, and selected from the group consisting of molybdenum and tungsten. At least one metal, a composite of a metal oxide containing an iron group metal and aluminum, wherein the amount of at least one metal selected from the group consisting of molybdenum and tungsten is 40% as an oxide relative to the catalyst.
~ 60% by weight, the amount of iron group metal is 5
The present invention relates to a method for producing a hydrodesulfurization catalyst composition for hydrocarbon oils having a side surface breaking strength of 1.1 to 1.4 kg / mm, and a gist of the third invention is a catalyst of the first invention. A method for hydrodesulfurizing a hydrocarbon oil, comprising using the composition to hydrodesulfurize a hydrocarbon oil.

 Next, the present invention will be described in detail.

First, a method for producing the hydrocarbon desulfurization catalyst composition of the present invention will be described.

The hydrodesulfurization catalyst composition for hydrocarbon oil of the present invention,
(A) at least one compound of Group 6B metal of the periodic table,
(B) at least one compound of Group 8 metals of the periodic table;
And (c) mixing the aluminum alkoxide in a solvent, drying the active ingredient resulting from the mixing,
This catalyst composition can be produced by calcining, and is a composite metal oxide substantially composed of a metal of Group 6B of the periodic table, a metal of Group VIII of the periodic table, and aluminum. The mixing of the three components (a), (b) and (c) is preferably performed by mixing two or three raw material solutions containing one or two of these components. "Method A", "Method B", "Method C" and "Method D" described later
Etc. The two-component compounds (a) and (b) may be any compounds as long as they are soluble in the solvent (water or organic solvent) used for preparing the raw material solution. The aluminum alkoxide as the component (c) is water or a mixed solution of water and an organic solvent (specifically, the volume ratio of the organic solvent / water is 0.
About 5-10 mixed solutions).

That is, the catalyst of the present invention can be prepared as follows.

"Method A": Aluminum alkoxide and Periodic Table 8
A mixed solution of at least one or more compounds of a group metal and an organic solvent capable of dissolving them is mixed and stirred for a certain period of time to form a homogeneous solution. Next, an aqueous solution of at least one compound of the Group 6B metal of the periodic table is added to this solution, and the active ingredient resulting from the mixing thereof is dried, followed by calcination.

"Method B": Aluminum alkoxide and Periodic Table 6B
A mixed solution of at least one or more compounds of a group metal and an organic solvent capable of dissolving them is mixed and stirred for a certain period of time to form a homogeneous solution. Next, an aqueous solution of at least one compound of Group 8 metal of the periodic table is added to this solution, and the active ingredient produced by mixing these is dried, followed by calcination.

"Method C": A solution prepared by dissolving an aluminum alkoxide in an organic solvent capable of dissolving the same in at least one compound of Group 6B metal of the periodic table and at least one compound of Group 8 metal of the periodic table. The compound can be produced by adding a mixed aqueous solution of the compounds, drying and calcining the active ingredient produced by the mixing.

"Method D": Aluminum alkoxide and Periodic Table No. 8
At least one compound of group metal and Periodic Table 6B
A mixed solution of at least one or more compounds of a group metal and an organic solvent capable of dissolving them is mixed and stirred for a certain period of time to form a homogeneous solution. It can be prepared by adding water to this solution, drying the resulting active ingredient and further baking.

In the present production method, an aluminum alkoxide is used as an essential component, but at least one selected from silicon, titanium, zirconium, boron, gallium, magnesium, and hafnium alkoxides can be used instead of part of the aluminum alkoxide. Any ratio may be used, but if used, 5 to 10 parts of alkoxides of silicon, titanium, zirconium, boron, gallium, magnesium, and hafnium are preferable for 90 to 95 parts of aluminum alkoxide in terms of oxide.

As the aluminum alkoxide, any alkoxide can be used, but an alkoxide having 1 to 5 carbon atoms in an alkoxy group is preferable from the viewpoint of ease of drying and the like.
Specific examples include aluminum methoxide, aluminum ethoxide, aluminum isopropoxide, aluminum-n-butoxide, aluminum-sec-butoxide and the like. As the aluminum alkoxide, a commercial product or a product prepared by a Ziegler method can be used.

Group 6B metal of the periodic table is preferably chromium, molybdenum, tungsten, more preferably molybdenum,
Use tungsten.

As the Group 8 metal of the periodic table, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, and more preferably, iron group metals cobalt and nickel are used.

The Group 6B metal compound and the Group 8 metal compound are
As described above, it is necessary to be soluble in an organic solvent or water, for example, nitrate, chloride, sulfate, acetate,
Acetyl acetonate, ammonium salts of these metal acids and the like are used.

An organic solvent capable of dissolving the alkoxide and the Group 6B metal compound or Group 8 metal compound is used to make them a uniform solution or to facilitate subsequent gelation and the like. As these organic solvents, alcohols, ethers, ketones, and aromatics can be used. Preferably, acetone, methanol, ethanol, n-propanol, iso
-Propanol, n-butanol, iso-butanol,
Hexanol, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane and the like can be used, and these can be used alone or in combination.

In a mixed solution of the aluminum alkoxide, the Group 6B metal compound or the Group VIII metal compound in Method A, Method B, Method C or Method D, and an organic solvent capable of dissolving the same, in the case of Method A, the aluminum alkoxide component is mixed with the aluminum alkoxide component. The mixing ratio of the two Group VIII metal compounds is about 50 to 98 wt% in terms of oxide, and about 2 to 50 wt%, preferably about 60 to 80 wt%, of the Group VIII metal compound.
20 to 40% by weight. In the case of Method B, similarly, in oxide conversion,
The aluminum alkoxide component is about 32-96 wt%, the Group 6B metal compound is about 4-68 wt%, preferably about 40-80 wt% and about 20-60 wt%. The amount of the organic solvent capable of dissolving them may be an amount sufficient to dissolve the aluminum alkoxide component, the Group 6B metal compound or the Group VIII metal compound. In addition, as for these mixing methods, a normal stirring method may be used, and sufficient stirring is performed until the mixture becomes uniform. The stirring conditions are preferably about 20 to 300 ° C., more preferably 50 to 200 ° C., and the time is usually about ten minutes to one hour, and usually a homogeneous solution is obtained.

Next, in methods A and B, a mixed solution of an alkoxide component, a Group 6B metal compound or a Group VIII metal compound, and an organic solvent capable of dissolving them (hereinafter, referred to as “organic solvent mixture”) is used. No. 6B not related to the metal used above
Aqueous solution of a Group 8 metal compound or a Group 8 metal compound
It is called "aqueous solution". ).

As the aqueous solution of the Group 6B metal compound, a solution obtained by dissolving ammonium paramolybdate, ammonium bichromate, ammonium paratungstate or the like in ion-exchanged water is preferably used.

The aqueous solution of the Group VIII metal compound is preferably cobalt nitrate hexahydrate, cobalt chloride hexahydrate, nickel nitrate 6
A hydrate or a solution obtained by dissolving nickel chloride hexahydrate or the like in ion-exchanged water is used.

The mixing of the aqueous solution or water with the organic solvent mixed solution in the methods A, B, C and D is preferably performed gradually, and more preferably a method by dropping. If mixed at the same time, the reaction will not be sufficiently performed. For this reason, the catalyst obtained by this method is not preferable because the distribution of each metal oxide becomes uneven. The temperature is about 20-300 ° C, preferably 50-200 ° C. The mixing ratio of the aqueous solution to the organic solvent mixed solution is such that the amount of the Group 6B metal is about 1.0 to 7.0, preferably about 2.0 to 4.0 based on the Group 8 metal in terms of oxide.

It is preferable to add an acid when mixing the aqueous solution with the organic solvent mixture or when preparing the aqueous solution. Examples of the acid include phosphoric acid, nitric acid, and hydrochloric acid, and the use of phosphoric acid is more preferable. This improves the solubility of the metal compound in the aqueous solution and increases the strength of the final catalyst composition. The addition ratio may be very small, and preferably about 0.5 to 5% by weight in terms of oxide based on the alumina derived from the aluminum alkoxide component. If the amount is too large, the activity is reduced, and the strength is not so high.

The active ingredient is produced by mixing the mixed solution with the organic solvent and the aqueous solution. Further, when the stirring is continued, a slurry is formed. As a method for extracting the active ingredient, any method can be used. For example, there is a method in which a solvent is removed at about 50 to 200 ° C. under reduced pressure using a rotary evaporator to obtain a dry gel. In addition, known means such as a method of extracting an active ingredient by filtration with filter paper can be used.

The dried gel having plasticity obtained by the above method is baked at a temperature of about 200 to 800 ° C. for about 1 to 24 hours, if necessary, and further, at about 150 to 700 ° C., if necessary.
Activated by performing a sulfidation treatment under the above conditions, and then used for the reaction.

The hydrodesulfurization catalyst for hydrocarbon oil of the present invention can be produced by the above method. This catalyst can contain a much higher amount of active metal than conventional ones, and has a high surface area and a high pore volume for a high amount of active metal.

The amount of active metal in this catalyst is based on the catalyst as oxide,
Group 6B metal is about 10-60% by weight, preferably about 15-55% by weight
More preferably, it is about 20-50% by weight, and the Group VIII metal is about 3-20% by weight, preferably about 5-18% by weight. If the amount is too small, a sufficient effect cannot be obtained. If the amount is too large, the catalyst strength becomes weak and notable activity cannot be obtained.

It is due to the above-mentioned production method and has a different structure from the conventional hydrodesulfurization catalyst. That is, the conventional one has a configuration in which the active metal is supported on a carrier such as alumina. For this reason, even if a large amount of the active metal is supported, the specific surface area is reduced. There was a limit. However, since the catalyst of the present invention adopts a production method based on the completely new concept described above, it does not have a concept of a carrier and is not in a form of supporting a metal. For example, aluminum, cobalt, and molybdenum metal oxides take the form of a metal oxide complex that is mixed together, or even if they are not mixed together, it is mainly composed of alumina and active metal oxide. Is considered to be coordinated in a complex form to enhance the activity.

This catalyst has an average pore diameter of about 73 to 108 °, for example, when molded into a cylindrical shape having a length of about 3.2 to 3.6 mm and a diameter of about 1.4 to 1.6 mm, a packed bulk density of about 0.76 to 0.80 g / ml, Breaking strength approx.
It has properties of 1.1-1.4 kg / mm (about 2.4-3.1 lbs / mm), which are not inferior to conventional hydrodesulfurization catalysts.

When this catalyst is used in an actual process, it may be used by mixing with a known catalyst or a known inorganic oxide carrier.

The hydrocarbon oil in the present invention means a light fraction obtained by atmospheric distillation or vacuum distillation of crude oil, an atmospheric distillation residue, and a vacuum distillation residue. Of course, coker gas oil, material deasphalted oil, tar sands Oils, shale oils, and coal liquefied oils are also included.

A commercial scale catalytic hydrotreating desulfurizer 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 temperature, high pressure and 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. Particularly when the feed oil is heavy oil, it is extremely preferable to use a multi-stage reactor. As a preferable example of the reaction, the hydrocarbon oil is heated at a temperature of about 200 to 500 ° C., more preferably 250 to 400 ° C., and the liquid hourly space velocity is about 0.05 to 5.0 hr ⁻¹ , more preferably 0.1 to 4.0 h.
In r ^-1 and the hydrogen pressure is about 30~200kg / cm ² G, more preferably is contacted with the catalyst under the conditions of 40~150kg / cm ² G.

(Effect of the Invention) Although the present catalyst can be prepared in a relatively simple process, the specific activity of desulfurization determined from the rate constant under the same reaction conditions is significantly higher than that of the conventional catalyst. Is shown. For example, in the case of gas oil (sulfur content of feedstock 1.3wt%),
Conventionally, the generated oil with 0.15 wt% at most was reduced to 0.07 wt%,
In the case of VGO (2.5 wt% sulfur content of the feedstock), the oil produced was
16% by weight to 0.08% by weight of heavy oil (sulfur
In the case of 3.8wt%), the conventional oil of 0.9wt% is 0.7wt
% Can be easily desulfurized without increasing the severity.
Therefore, the activity of the catalyst is also very stable over time. Therefore, there is no need to make the operating conditions severe even in long-term operation, and the economic effect is enormous. Furthermore, since it is possible to produce fuel oil having a low sulfur content, air pollution can be suppressed.

(Examples) Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Examples of the method for preparing the catalyst are shown in Examples 1 to 12.

Example 1 Aluminum-sec-butoxide 18 in an Erlenmeyer flask
0.9 g (0.7344 mol) and cobalt acetylacetonate 54.
A solution of 972 g (0.1875 mol) dissolved in 2000 cc of sec-butanol was stirred at 80 ° C. for 1 hour. Separately, 51.679 g (0.04182 mol) of ammonium paramolybdate was heated to about 80 ° C. in 280 g of ion-exchanged water and vigorously stirred to dissolve. When this aqueous solution was gradually added dropwise to the stirring sec-butanol solution, a purple gelatinous precipitate was formed. When stirring was continued, a purple milky white slurry was finally obtained. The slurry was further stirred at 80 ° C. for 3 hours.
The obtained slurry was separated by filtration with a filter, and then heated and concentrated to obtain a plastic gel, which was formed into a molded column having a diameter of 1.6 mm (1/16 inch) using an extruder. Spread this molded product on the evaporating dish, 500 ℃ in a muffle furnace,
For 4 hours heat treatment CoO (15 wt%) - MoO ₃ (45 wt%) - Al ₂ O ₃ composite metal oxide (40 wt%) (Catalyst A)
I got

Example 2 Aluminum-sec-butoxide 18 in an Erlenmeyer flask
0.9 g (0.7344 mol) and cobalt acetylacetonate 54.
A solution of 972 g (0.1875 mol) dissolved in 2000 cc of i-propanol was stirred at 80 ° C. for 1 hour. Separately, 51.679 g (0.04182 mol) of ammonium paramolybdate was heated to about 80 ° C. in 280 g of ion-exchanged water and vigorously stirred to dissolve. When this aqueous solution was gradually added dropwise to the stirring i-propanol solution, a purple gelatinous precipitate was formed. When the stirring was continued, a purple milky white slurry was finally obtained. The solution was further stirred at 80 ° C. for 3 hours. Put this slurry solution into a mold flask, and use a rotary evaporator to remove the solvent under reduced pressure at 100 ° C for 30 minutes to form a plastic gel, extrude this gel, and use a gel extruder to make the diameter 1.6 mm (1/16 inch). Was formed into a columnar product. Spread this molded product on the evaporating dish, 500 ℃ in a muffle furnace,
For 3 hours heat treatment CoO (15 wt%) - MoO ₃ (45 wt%) - Al ₂ O ₃ composite metal oxide (40 wt%) (Catalyst B)
I got

Example 3 A catalyst was prepared in the same manner as in Example 2, except that 150.0 g (0.7344 mol) of aluminum-i-propoxide was used instead of 180.9 g of aluminum-sec-butoxide. Consequently CoO (15 wt%) - MoO ₃ (45 wt%) - A
A composite metal oxide (catalyst C) of l ₂ O ₃ (40% by weight) was obtained.

Example 4 54.972 g (0.1875 mol) of cobalt acetylacetonate
Molybdenum acetylacetonate instead of 95.493
g (0.29278 mol) to ammonium molybdate 51.679 g
54.547 g of cobalt nitrate (0.187
4 mol) was prepared in the same manner as in Example 2. As a result, CoO (15 wt%) - MoO ₃ (45 wt%) - A
A composite metal oxide (catalyst D) of l ₂ O ₃ (40% by weight) was obtained.

Example 5 A catalyst was prepared in the same manner as in Example 2, except that 20.034 g (0.154 mol) of anhydrous cobaltous chloride was used instead of about 55 g of cobalt acetylacetonate. As a result, CoO (15 wt%) - MoO ₃ (45 _{wt%) - Al 2 O 3 (} 40
% By weight) of a composite metal oxide (catalyst E).

Example 6 Instead of 180.9 g of aluminum-sec-butoxide,
A catalyst was prepared in the same manner as in Example 2, except that 90.45 g (0.3672 mol) of aluminum-sec-butoxide and 64.930 g (0.31167 mol) of tetraethoxysilane were used. Consequently CoO (15 wt%) - MoO ₃ (45 wt%) - SiO ₂ (20
% By weight) -Al ₂ O ₃ (20% by weight) to obtain a composite metal oxide (catalyst F).

Example 7 Instead of 180.9 g of aluminum-sec-butoxide,
158.288 g (0.6426 mol) of aluminum-sec-butoxide
A catalyst was prepared in the same manner as in Example 2 except for using 16.232 g (0.07791 mol) of tetraethoxysilane.
As a result, CoO (15 wt%) - MoO ₃ (45 wt%) - SiO ₂
(5 wt%) - was obtained Al ₂ O ₃ composite metal oxide (35 wt%) (catalyst G).

Example 8 Aluminum-sec-butoxide 18 in an Erlenmeyer flask
A solution of 0.9 g (0.7344 mol) dissolved in 2000 cc of isopropanol was kept at 80 ° C. Separately, 54.399 g (0.04402 mol) of ammonium paramolybdate and 54.54 of cobalt nitrate
7 g (0.1874 mol) was vigorously stirred and dissolved at about 80 ° C. in 280 g of ion-exchanged water. When this aqueous solution and 3.202 g of phosphoric acid (having a phosphoric acid concentration of 85%) were gradually added dropwise to the above-mentioned isopropanol solution while stirring, a purple gelatinous precipitate was formed. A milky slurry was obtained. Subsequent operations were performed in the same manner as in Example 2. The catalyst, CoO (15 wt%) - MoO ₃ (45 wt%) - P ₂ O ₅ (2 wt%) - was obtained Al ₂ O ₃ composite metal oxide (38 wt%) (catalyst H) .

Example 9 Except that 16.653 g (0.05859 mol) of titanium isopropoxide was used instead of 16.232 g of tetraethoxysilane.
A catalyst was prepared in the same manner as in Example 7. As a result, CoO (15 wt%) - MoO ₃ (45 wt%) - TiO ₂ (5 wt%) - was obtained Al ₂ O ₃ composite metal oxide (35 wt%) (catalyst I).

Example 10 A catalyst was prepared in the same manner as in Example 7 except that 12.431 g (0.03799 mol) of zirconium-n-propoxide was used instead of 16.232 g of tetraethoxysilane. As a result, CoO (15 wt%) - MoO ₃ (45 wt%) - Z
and rO ₂ (5 wt%) - was obtained Al ₂ O ₃ composite metal oxide (35 wt%) (catalyst J).

Example 11 54.972 g of cobalt acetylacetonate was added to 29.40 g (0.0
937 mol), 51.679 g of ammonium paramolybdate, 36.
A catalyst was prepared in the same manner as in Example 2 except that 70 g (0.0297 mol) was used. As a result, CoO (10% by weight)
A composite metal oxide (catalyst K) of —MoO ₃ (40% by weight) —Al ₂ O ₃ (50% by weight) was obtained.

Example 12 39.60 g (0.1%) of 54.972 g of cobalt acetylacetonate
12 mol), 65.80 g of sec-butanol and 51.679 g of ammonium paramolybdate instead of i-propanol
(0.0532 mol) A catalyst was prepared in the same manner as in Example 2 except that the catalyst was used. As a result, CoO (10% by weight) -MoO
₃ (53 wt%) - was obtained Al ₂ O ₃ composite metal oxide (37 wt%) (catalyst L).

 The compositions of the catalysts of Examples 1 to 12 are shown in Table 1.

Comparative Example 1 In an eggplant-shaped flask, 4.7 g of ammonium made of molybdenum was ion-exchanged into 14.5 ml of ion-exchanged water on an alumina carrier (consisting essentially of γ-Al ₂ O ₃ ) having a pore volume of 0.7123 ml / g and a surface area of 336 m ² / g.
And the carrier was immersed in 20 g of this solution. After soaking for 1 hour, air-drying and baking in a muffle furnace at 500 ° C. for 10 hours. Furthermore, cobalt was supported by immersion in an aqueous solution in which 5 g of cobalt nitrate was dissolved in 14.5 ml of ion-exchanged water. After air drying, 1 at 500 ℃
Calcination was performed for 0 hour to obtain a catalyst. The composition of the resulting catalyst is CoO
(5 wt%) - MoO ₃ (15 _{wt%) - Al 2 O 3 (} 80 wt%)
(Catalyst M).

The surface area of this catalyst was 266 m ² / g, and the pore volume was 0.5478 cc / g.

Comparative Example 2 About 55.0 g of cobalt acetylacetonate was added to 3.150 g (0.0
0841 mol), about 51.7 g of ammonium paramolybdate in 2.
A catalyst was prepared in the same manner as in Example 2 except that the amount was changed to 47 g (0.00199 mol). As a result, CoO (2% by weight) -M
oO ₃ (5 wt%) - was obtained Al ₂ O ₃ composite metal oxide (93 wt%) (catalyst N).

Comparative Example 3 About 55.0 g of cobalt acetylacetonate was added to 109.9 g (0.3
085 mol), about 51.7 g of ammonium paramolybdate in 10
A catalyst was prepared in the same manner as in Example 2 except that the amount was 3.4 g (0.08367 mol) and aluminum-sec-butoxide was not used. As a result, CoO (25% by weight) -MoO ₃ (7
5% by weight) of a composite metal oxide (catalyst O).

Comparative Example 4 An attempt was made to prepare a catalyst containing 10% by weight and 35% by weight of cobalt and molybdenum based on the catalyst in terms of oxide in the conventional method (impregnation method). First, the pore volume of the alumina support
An attempt was made to dissolve ammonium paramolybdate in water equal to 0.7123 ml / g (surface area: 336 m ² / g), but it was insoluble even after heating and addition of ammonium. The same operation was performed on cobalt nitrate, but it was still insoluble.

Therefore, it is difficult to carry a large amount of active metal by the conventional method.

 Table 1 shows the compositions of the catalysts of Comparative Examples 1 to 3.

Examples 13 to 34 and Comparative Examples 5 to 13 show examples of hydrodesulfurization of hydrocarbon oils using the catalysts A to O shown in the above Examples and Comparative Examples.

Examples 13 to 19 and Comparative Examples 5 to 7 (Hydrodesulfurization reaction of light oil) Raw material: LGO (specific gravity (15/4 ° C) 0.851, sulfur content 1.35 wt
%, Nitrogen content 20ppm, viscosity (30 ℃) 5.499cSt) Reaction condition; reaction temperature: 350 ℃ reaction pressure: 35kg / cm ² liquid space velocity: 4hr ^-1 equipment: high pressure flow type reactor with fixed bed system catalyst : Catalysts A, B, C, E, H,
I, J, M, N, O Evaluation method: The sulfur content of the produced oil after passing for 100 hours or 60 days under the above operating conditions was examined. The results are shown in Table 2. In addition, Examples 13, 14, 15 and Comparative Example 5 in which oil was passed for 60 days
FIG. 1 shows the time-dependent changes of.

Examples 20 to 27 and Comparative Examples 8 to 10 (VGO hydrodesulfurization reaction) Raw material; LGO (specific gravity (15/4 ° C) 0.916, sulfur content 2.35 wt
%, Nitrogen content 780 ppm, viscosity (30 ° C) 28.8 cSt) Reaction conditions; reaction temperature: 350 ° C Reaction pressure: 52 kg / cm ² liquid space velocity: 0.4 hr ^-1 Equipment: High pressure flow type reactor with fixed bed system Medium: catalysts A, B, C, E, F,
H, I, J, M, N, O Evaluation method: The sulfur content of the produced oil after passing for 100 hours under the above operating conditions was examined. The results are shown in Table 3.

Examples 28 to 34, Comparative Examples 11 to 13 (Hydrodesulfurization reaction of heavy oil) Raw oil: Residual oil of Kuwaiti crude oil at atmospheric pressure (specific gravity (15/4 ° C) 0.956, sulfur content 3.77 wt%, Asphaltene 3.9
(wt%, vanadium 48ppm, nickel 14ppm) Reaction conditions; Reaction temperature: 361 ° C Reaction pressure: 150 kg / cm ² Hydrogen / hydrocarbon oil: 830 Nm ³ / Kl Hydrogen concentration: 90 mol% Liquid space velocity: 1.0 hr ^-1 High-pressure flow reactor with fixed bed catalyst: Catalysts A, B, C, D, J,
K, L, M, N, O Evaluation method: The sulfur content of the produced oil after passing for 100 hours under the above operating conditions was examined. The results are shown in Table 4.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the amount of residual sulfur and the number of operating days in Examples 13, 14, 15 and Comparative Example 5 of the present invention.

Continuation of front page (72) Inventor Katsumi Oki 1368 Shinmei, Satte-shi, Saitama (56) References JP-A-54-104493 (JP, A) JP-A-61-83603 (JP, A) 107946 (JP, A) JP-A-54-9185 (JP, A) JP-B-43-17659 (JP, B1) JP-B-55-44795 (JP, B2)

Claims (4)

(57) [Claims] 1. An organic solvent comprising: (a) at least one compound selected from the group consisting of molybdenum and tungsten; (b) at least one compound of the iron group; and (c) aluminum alkoxide. A metal oxide containing at least one metal selected from the group consisting of molybdenum and tungsten, an iron group metal and aluminum, obtained by drying and calcining an active ingredient produced by adding water simultaneously with or after mixing. Wherein the amount of at least one metal selected from the group consisting of molybdenum and tungsten is 40-60% by weight with respect to the catalyst as an oxide, and the amount of iron group metal is as an oxide with respect to the catalyst as an oxide. 5 to 20% by weight and a side fracture strength of 1.I to 1.4 kg / mm Catalyst composition. 2. A method comprising mixing (a) at least one compound selected from the group consisting of molybdenum and tungsten, (b) at least one compound of the iron group, and (c) aluminum alkoxide in an organic solvent. Drying and baking the active ingredient generated by adding water at the same time as or after mixing, at least one metal selected from the group consisting of molybdenum and tungsten, an iron group metal and a metal oxide containing aluminum A composite, wherein the amount of at least one metal selected from the group consisting of molybdenum and tungsten is 40 to 60% by weight based on the catalyst as an oxide, and the amount of iron group metal is 5 to 5% based on the catalyst as an oxide. A method for producing a hydrodesulfurization catalyst composition for a hydrocarbon oil having a weight percentage of 20% by weight and a side fracture strength of 1.1 to 1.4 kg / mm. 3. The carbonized material according to claim 2, wherein the aluminum alkoxide contains at least one selected from silicon, titanium, zirconium, boron, gallium, magnesium and hafnium alkoxides in addition to the aluminum alkoxide. A method for producing a hydrodesulfurization catalyst composition for hydrogen oil. 4. A method for hydrodesulfurizing a hydrocarbon oil, comprising using the catalyst composition according to claim 1 for hydrodesulfurization of a hydrocarbon oil.