JPH11179208A - Catalyst for hydrogenation of hydrocarbon oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst for hydrogenation of hydrocarbon oil having high desulfurization activity by carrying metallic components having hydrodesulfurization activity on a carrier in a highly dispersed state. SOLUTION: The catalyst has a carrier contg. alumina or an alumina-base inorg. oxide and 0.2-30 mass% zirconia based on the total amt. of the catalyst and has at least one of the group IV A metallic elements of the Periodic Table, at least one of the group VIII metallic elements of the Periodic Table and phosphorus carried on the carrier by 10-30 mass% (expressed in terms of oxide), 1-10 mass% (expressed in terms of oxide) and 1-7 mass% (expressed in terms of oxide), respectively, based on the total amt. of the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for hydrotreating hydrocarbon oils, and more particularly, to reducing the sulfur content of hydrocarbon oils when hydrotreating hydrocarbon oils. The present invention relates to a hydrocarbon oil hydrotreating catalyst having excellent activity.

[0002]

2. Description of the Related Art Since each oil fraction obtained by distillation or cracking of crude oil generally contains a sulfur compound, when such an oil is used as a fuel, sulfur present in the sulfur compound is converted into oxides or the like. Is converted to sulfur compounds and released into the atmosphere. Therefore, in order to prevent air pollution, it is desirable that the hydrocarbon oil used as the fuel oil has as small a sulfur content as possible. Particularly, in a situation where environmental destruction due to acid rain, nitrogen oxides, and the like has recently progressed on a global scale, in order to solve such environmental destruction problems, the sulfur content in hydrocarbon oils has been further reduced. The development of content technology is desired.

Conventionally, the reduction of the sulfur content in hydrocarbon oils has been carried out by catalytic hydrodesulfurization of hydrocarbon oils. The operating conditions of this catalytic hydrodesulfurization, for example, L
This has been achieved to some extent by making the HSV, temperature, pressure, etc. severe.

However, if catalytic hydrodesulfurization of a hydrocarbon oil is performed under such severe conditions, there is a problem that carbonaceous material is deposited on the catalyst and the activity of the catalyst is rapidly reduced. Furthermore, when the hydrocarbon oil is light, there is an adverse effect on properties such as hue stability and storage stability. in this way,
Desulfurization under severe conditions has its own practical limits. Therefore, the best way to further reduce the sulfur content in a hydrocarbon oil is to develop a hydrodesulfurization catalyst having remarkably superior desulfurization activity as compared with conventional ones.

[0005] Incidentally, catalysts conventionally used for hydrodesulfurization of hydrocarbon oils usually include a Group VIA metal (hereinafter simply referred to as a "Group VIA metal") of the Periodic Table and a Group VIII of the Periodic Table. Group metal (hereinafter simply referred to as "Group VIII metal")
And as active metals, these are alumina, magnesia,
It is supported on an oxide carrier such as silica. Here, in the present invention, the periodic table refers to the one described on the back of the cover of the third edition of the "Chemical Dictionary" popular edition issued by Morikita Publishing Co., Ltd.

However, according to the conventional catalyst as described above, although the sulfur content can be reduced to some extent, the desulfurization activity is not sufficient.

[0007] In order to increase the desulfurization activity of the hydrodesulfurization catalyst for hydrocarbon oils, it is necessary to carry the active metal in a highly dispersed state. Importantly, there is a need for a carrier that can further increase the dispersibility of the active metal than the carrier obtained by the above-described conventional technique.

[0008]

SUMMARY OF THE INVENTION The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems in the conventional hydrodesulfurization of hydrocarbon oils, and as a result, they have generally employed a catalyst carrier of this type. As a second component of the carrier, zirconia is contained as a second component of the carrier in a limited range to form a catalyst carrier, and the active metal component is supported on such a catalyst carrier, whereby the active metal component is highly advanced. The inventors have found that they can be dispersed, and have arrived at the present invention.

Accordingly, an object of the present invention is to provide a catalyst for hydrotreating a hydrocarbon oil having a hydrodesulfurization active metal component supported on a carrier in a highly dispersed state, and thus having a high desulfurization activity.

[0010]

The hydrocarbon oil hydrotreating catalyst according to the present invention comprises alumina or an inorganic oxide containing alumina as a main component and 0.2 to 30 mass% of the total amount of the catalyst.
On a support containing zirconia in the range of s%, (a) at least one selected from the group VIA metal elements of the periodic table is 10 to 30 mass% with respect to the total amount of the catalyst in terms of oxide;
(b) at least one selected from Group VIII metal elements of the Periodic Table, in terms of oxide, from 1 to 10 ma relative to the total amount of the catalyst;
ss% and (c) 1 to 7 mass% of phosphorus based on the total amount of the catalyst in terms of oxide.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The catalyst carrier used in the present invention contains alumina or an inorganic oxide containing alumina as a main component and zirconia, and may further contain zeolite, if necessary.

In the present invention, the term “alumina” or “inorganic oxide containing alumina as a main component” means 100% of the entire inorganic oxide.
mass%, the amount of alumina is 80 mass%
Above, preferably 90 mass% or more. Most preferred is 100 mass% alumina. According to the present invention, the alumina is preferably γ-alumina.

Zeolite generally belongs to the category of inorganic oxides. In the present invention, however, zeolite is not included in alumina or an inorganic oxide containing alumina as a main component. The term “inorganic oxide” means alumina or an oxide containing alumina as a main component and optionally containing zirconia, and the content of zeolite in the catalyst carrier is defined separately from alumina and zirconia.

Therefore, when alumina occupies 80 mass% or more of the inorganic oxide, the support made of such an inorganic oxide has a sufficiently large amount of basic hydroxyl groups thereon, and the active metal of Group VIA The element can be supported in a high dispersion. However, when the content of alumina in the inorganic oxide is less than 80 mass%,
The dispersibility of the group A element is deteriorated, and the group VIA element is agglomerated, and the resulting catalyst may have poor desulfurization activity.

In the present invention, zirconia, which is the second component of the carrier, is contained in the carrier in an amount of 0.2 with respect to the total amount of the catalyst.
３０30 mass%, preferably 0.5 to 25 mass%
%, More preferably in the range of 1 to 20 mass%. Zeolite, which is the third component of the support, is contained in the support in a range of 1 to 15 mass%, preferably 2 to 10 mass%, based on the total amount of the catalyst.

According to the present invention, the hydrodesulfurization active metal component is highly dispersed on the carrier by setting the content of zirconia in the carrier to an extremely limited range as described above with respect to the total amount of the catalyst. Thus, it is possible to obtain a hydrocarbon oil hydrotreating catalyst having a remarkably high desulfurization activity as compared with conventional catalysts.

When the content of zirconia in the carrier exceeds 30 mass% with respect to the total amount of the catalyst, the surface area of the catalyst is reduced to deteriorate the performance as a carrier, and when the content is less than 0.1 mass%. Is unable to highly disperse the active metal component in the resulting carrier,
The desired hydrotreating catalyst for hydrocarbon oils having high desulfurization activity cannot be obtained.

In the present invention, as a raw material for causing the carrier to contain zirconia, usually, a precursor which is converted into zirconia by firing is preferably used. As such a zirconia precursor, for example, nitrates, sulfates, chlorides, oxalates, acetates, and the like, which can be easily obtained industrially, are used. However, zirconia particles or fine particles may be used if necessary.

In order to make the carrier contain zirconia, for example, a water-soluble salt of zirconium such as zirconium nitrate is mixed with alumina or alumina gel, and the resulting paste is heated while being kneaded to have water suitable for extrusion molding. It is preferable to use a kneading method capable of controlling humidity.
However, it is not limited to this.

Zeolite is a patent that enhances the desulfurization activity of the resulting catalyst by highly dispersing an active metal on a carrier, and it includes 4-methyldibenzothiophene and 4,6- contained in hydrocarbon oil.
It is effective in desulfurizing difficult-to-desulfurize substances such as dimethyldibenzothiophene. However, if it is less than 1 mass%, the above effect cannot be sufficiently obtained. On the other hand, when the content of zeolite in the support exceeds 15 mass% with respect to the total amount of the catalyst, the dispersibility of the active metal is deteriorated.

In the present invention, various zeolites are used. Specific examples include, for example, A-type zeolite, X-type zeolite, Y-type zeolite, stabilized Y-type zeolite, ultra-stable Y-type zeolite, L-type zeolite, Z-type
SM type zeolite and the like can be mentioned. Above all,
According to the invention, Y-type zeolites or stabilized Y-type zeolites are preferred, and among the Y-type zeolites,
Particularly, HY type zeolite is preferable. However, these zeolites may be used alone or in combination of two or more.

In order to make the carrier contain zeolite, it is not particularly limited, but usually, zeolite particles are mixed with alumina or alumina gel, and the resulting paste is heated while kneading to form an extrudate. It is preferable to use a kneading method in which the humidity can be adjusted to have a suitable moisture.

According to the present invention, the specific surface area, the pore volume, and the average pore diameter of the carrier are not particularly limited. For example, it is possible to remove even the above-mentioned hardly desulfurizable substances. In order to obtain a suitable catalyst, the specific surface area should be 20
It is preferably at least 0 m ² / g, more preferably at least 250 m ² / g, and the pore volume is preferably in the range of 0.3 to 1.2 cc / g, particularly preferably 0.5 to 1.0 cc / g. It is preferably within the range. Further, the average pore size is preferably in the range of 50 to 130 °, and particularly preferably in the range of 50 to 100 °.

The catalyst according to the present invention thus contains alumina or an inorganic oxide containing alumina as a main component and zirconia and, if necessary, an active catalyst on a catalyst carrier which may contain zeolite. As a metal component, a Group VIA metal element is converted to an oxide in an amount of 10 to 3 with respect to the total amount of the catalyst.
0 mass%, 1 to 10 mass% of the group VIII metal element based on the total amount of the catalyst in terms of oxide, and 1 to 7 mass% of phosphorus based on the total amount of the catalyst in terms of oxide. is there.

In the present invention, the Group VIA metal component is preferably tungsten or molybdenum, particularly preferably molybdenum. These metal components are supported as oxides on the carrier.

As described above, the raw material for supporting the group VIA metal element as an oxide on a carrier is not particularly limited, but, for example, ammonium molybdate ((NH ₄ ) ₆ Mo _{7 O 24 · 4H 2 O)} , ammonium tungstate _{((NH 4) 10 W 12} O 41 · 5H 2
O), molybdenum oxide (MoO ₃ ), molybdophosphoric acid (H ₃ (PMo ₁₂ O ₄₀ ) .30H ₂ O), tungstophosphoric acid (H ₃ (PW ₁₂ O ₄₀ ) .30H ₂ O) and the like are used.
These compounds can be used alone or in combination of two or more.

As the Group VIII metal component to be supported on the catalyst carrier together with the Group VIA metal component, various ones are used. Usually, iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum and the like are preferable. In particular, cobalt or nickel is preferably used. These metal components are also usually supported on the carrier as oxides.

As described above, the raw material for supporting the group VIII metal component as an oxide on the carrier is not particularly limited, but, for example, nitrate, carbonate, acetate, phosphate and the like are preferably used. These compounds are also used alone or in combination of two or more.

Further, examples of the phosphorus component supported on the carrier together with the Group VIA metal and Group VIII metal include various phosphoric acids. Specifically, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, polyphosphoric acid and the like can be mentioned.
Orthophosphoric acid is preferably used. Phosphorus is also usually carried on the carrier as an oxide.

According to the invention, the preferred loadings of these active ingredients are, in terms of oxides, based on the weight of the catalyst.
The group VI metal component is 15 to 23 mass%;
Group metal component is 3 to 7 mass%, and phosphorus component is 2 to 2 mass%.
It is 5 mass%.

When a phosphorus-containing material is used as a raw material of the group VIA metal component or the group VIII metal component, the amount of phosphorus is also calculated as the amount of phosphorus component.

When the supported amount of the Group VIA metal component in the catalyst is less than 10 mass%, the sulfur content in the hydrocarbon oil cannot be efficiently desulfurized and removed, while the supported amount is 30 mass%. If the temperature exceeds the above range, the dispersibility of the active metal is deteriorated, and the desulfurization effect is saturated.

On the other hand, the loading amount of the Group VIII metal component is 1 ma
If it is less than ss%, the resulting catalyst cannot have the desired desulfurization activity, and therefore the sulfur content in the hydrocarbon oil cannot be efficiently removed. But,
Even if it is carried in excess of 10 mass%, the desulfurization activity is saturated, which is economically disadvantageous.

Next, the phosphorus component comprises a Group VI metal component and a VI
It is useful to increase the dispersibility of the Group II metal component on the support, increase the number of active sites, and increase the desulfurization activity of the resulting catalyst. When the supported amount of the phosphorus component is less than 1 mass%, the above effects cannot be obtained effectively. But 7
Even if it exceeds mass%, the above effect is saturated, so that it becomes uneconomical.

When the above-mentioned active component is supported on the carrier to obtain a catalyst, the preparation method is not particularly limited, and the catalyst according to the present invention can be prepared by any conventionally known method. For example, it can be easily prepared by an impregnation method.

That is, the compounds of the Group VI and Group VIII metal elements and phosphoric acid are dissolved in water to form an aqueous solution, which is impregnated into a carrier.
The catalyst according to the present invention can be obtained by heating and drying for up to 24 hours, and then heating and calcining at 400 to 550 ° C. for about 12 to 24 hours.

The properties of the catalyst according to the present invention thus obtained, that is, the specific surface area, the pore volume, and the average pore diameter are not particularly limited. In order to efficiently remove even the volatile substances, the specific surface area is 180 m ² / g or more, and the pore volume is
0.3 to 1.2 cc / g, and the average pore diameter is 60 to
It is preferably in the range of 120 °.

According to the present invention, the shape of the catalyst is not particularly limited, and various shapes usually used for this type of catalyst, for example, a columnar shape, a four-leaf type, etc. may be employed. Can be. The size is usually 1/10 of the diameter.
It is preferably about 1/22 inch and 3.2 to 3.6 inches long.

The catalyst according to the present invention may be used alone for the hydrotreating of hydrocarbon oils, may be used in combination with a conventionally known catalyst, and may be used in combination with a conventionally known carrier. May be used as a mixture. Further, in the case of performing a multi-stage hydrotreatment of hydrocarbon oil, it can be used in combination with another catalyst.

In the hydrotreating of a hydrocarbon oil using the catalyst of the present invention, the feedstock oil is not particularly limited, but is usually a catalytic cracking gas oil, a pyrolysis gas oil, a straight run gas oil, a coker gas oil, Hydrotreated gas oil, desulfurized gas oil and the like are preferred. However, these feedstocks may be used alone or in combination of two or more. Here, the desulfurized gas oil means a product oil that has already been desulfurized in the first stage during multi-stage processing.

The raw material oil has a boiling point of 150 ° C. (IBP (initial boiling point, initial boiling point) at the time of distillation, the same applies hereinafter) to 400 ° C. (EP at the time of distillation).
(End point, end point), the same applies hereinafter), preferably, IBP-EP is in the range of 200-380 ° C, particularly preferably in the range of 220-340 ° C, and sulfur content is 3 mass% or less, preferably , 2.5 mass% or less, and particularly preferably, 2.0 mass% or less.

The hydrodesulfurization reaction of the above feedstock using the catalyst of the present invention usually has a pressure (hydrogen partial pressure) of 30 to 80 kg.
/ Cm ² , preferably in the range of 35-60 kg / cm ² , at a temperature of 320-360 ° C., preferably 330
To 360 ° C, and the liquid hourly space velocity is 1.0 to 5.0 hr.
^-1 , preferably in the range of 1.0 to 2.0 hr ^-1 and a hydrogen / oil ratio of 100 to 400 L / L, preferably 20
It is performed under the condition of 0 to 300 L / L.

The pressure (hydrogen partial pressure) in the reaction is 30 kg
If it is less than / cm ² , it is not possible to remove even the hardly desulfurizable substance. However, even if the pressure exceeds 80 kg / cm ² , the efficiency of removing difficult-to-desulfurize substances is not only saturated, but also high-cost equipment capable of withstanding such a high-pressure reaction is required, which is uneconomical.

When the reaction temperature is lower than 320 ° C., even the hardly desulfurizable substance cannot be removed. However, when the reaction temperature is higher than 360 ° C., the efficiency of removing the hardly desulfurizable substance is saturated, so Economy.

When the liquid hourly space velocity exceeds 5.0 hr ^-1 , the contact time between the catalyst and the feedstock oil is too short, and it is not possible to remove even the hardly desulfurizable substances. However, 1.0h
If it is less than r ⁻¹ , not only the contact effect is saturated, but also the processing efficiency is low.

When the hydrodesulfurization reaction of the above feedstock using the catalyst of the present invention is carried out on a commercial scale, the catalyst is used as a fixed bed, a moving bed or a fluidized bed in a suitable reactor.
The feedstock may be introduced into the reactor and treated under predetermined conditions. Most commonly, the catalyst is maintained as a fixed bed and the feedstock is passed through the fixed bed from top to bottom. Here, the catalyst may be charged into a single reactor,
Moreover, you may fill and use a continuous several reactor.

[0047]

The present invention will be described below with reference to examples together with comparative examples, but the present invention is not limited to these examples. Table 1 shows the compositions of the catalysts prepared in Examples and Comparative Examples, and Table 2 shows their properties.

The properties, reaction conditions and catalyst pretreatment conditions of the straight-run gas oil (raw oil) subjected to the desulfurization reaction are as follows.

Straight run gas oil Specific gravity (15/4 ° C): 0.8567 Sulfur content: 1.364 mass% Nitrogen content: 150 ppm Boiling point (50% point): 315 ° C Viscosity (30 ° C): 6.608 cSt Reaction conditions Temperature: 330, 340, 350 ° C. Pressure (hydrogen partial pressure): 35 kg / cm ² Liquid space velocity: 1.5 hr ⁻¹ Device: High-pressure flow reactor with fixed bed system Pretreatment conditions for catalyst Pressure (hydrogen partial pressure): 35 kg / Cm ² atmosphere: under a mixed gas of hydrogen sulfide / hydrogen Temperature: step temperature rise 2 hours at 100 ° C. 2 hours at 250 ° C. 2 hours at 350 ° C.

Example 1 (Preparation of carrier) 1.5 kg (4 mol) of aluminum nitrate 9 hydrate and 2.5 kg (42 mol) of urea in 20 L of ion-exchanged water
mol)), and the resulting mixed aqueous solution was heated and stirred at 95 ° C. for 1.5 hours to obtain an alumina gel. Separately, zirconium nitrate (ZrO (NO ₃ ) ₂ ) is contained in ₂ L of ion-exchanged water.
28 g were dissolved to obtain an aqueous solution.

The alumina gel and the aqueous solution of zirconium nitrate were charged into a kneader and kneaded for 3 hours.
The mixture was heated to 0 ° C., and the amount of water was adjusted to an extent that the kneaded product could be extruded, that is, moisture was adjusted, and the mixture was molded by an extruder.

The obtained molded product was dried at 120 ° C. all day and night, and then calcined at 550 ° C. for 12 hours to obtain a specific surface area of 3
28 m ² / g, pore volume 0.62 cc / g, average pore diameter 6
3% of the carrier was obtained.

(Preparation of Catalyst) At room temperature, 11 g of cobalt carbonate, 4 g of orthophosphoric acid and 38 g of molybdophosphoric acid were dissolved in 77 g of ion-exchanged water in an Erlenmeyer flask and stirred to prepare an aqueous solution for impregnation. In an eggplant-shaped flask, 100 g of the carrier was impregnated with this aqueous solution at room temperature for 1 hour,
Air dried and calcined in a muffle furnace at 500 ° C for 4 hours,
A catalyst was prepared. A desulfurization reaction test was performed using this catalyst. The results are shown in Tables 3 and 6.

Example 2 In the kneading for preparing the carrier in Example 1, in addition to the alumina gel and the aqueous solution of zirconium nitrate, an HY-type zeolite (SiO ₂ / Al ₂ O ₃ molar ratio was 6; ₂ O content is 0.3 mass% or less and surface area is 900 to 1100 (Langmuir, m ² / g)
And a specific surface area of 373 m ² / g, and a pore size of 600 to 700 (BET, m ² / g) and a crystal size of 0.7 to 1.0 μm. volume
A carrier having 0.63 cc / g and an average pore diameter of 64 ° was obtained.

Using this carrier, a catalyst was prepared in the same manner as in Example 1, and a desulfurization reaction test was performed using the catalyst. Table 3 shows the results.

Example 3 A catalyst was prepared in the same manner as in Example 1 except that the carrier obtained in Example 1 was replaced with 12 g of nickel carbonate in place of 11 g of cobalt carbonate. Was used to perform a desulfurization reaction test. Table 4 shows the results.

Example 4 Using the carrier obtained in Example 2, a catalyst was prepared in the same manner as in Example 3, and a desulfurization reaction test was performed using the catalyst. Table 4 shows the results.

Example 5 The procedure of Example 1 was repeated, except that 6 g of nickel carbonate and 5.5 g of cobalt carbonate were used instead of 11 g of cobalt carbonate to prepare a catalyst using the carrier obtained in Example 1. A catalyst was prepared, and a desulfurization reaction test was performed using the catalyst. Table 5 shows the results.

Example 6 Using the carrier obtained in Example 2, a catalyst was prepared in the same manner as in Example 5, and a desulfurization reaction test was performed using the catalyst. Table 5 shows the results.

Example 7 The procedure of Example 1 was repeated, except that 8.4 g of zirconium nitrate was used in the preparation of the carrier in Example 1, and the specific surface area was 359 m ² / g, the pore volume was 0.63 cc / g, A carrier having an average pore diameter of 62 ° was obtained. Thereafter, a catalyst was prepared in the same manner as in Example 1, and a desulfurization reaction test was performed. Table 6 shows the results.

Example 8 In the same manner as in Example 1 except that 112 g of zirconium nitrate was used in the preparation of the carrier in Example 1, the specific surface area was 270 m ² / g, the pore volume was 0.59 cc / g, and the average fineness was small. A carrier having a pore size of 70 ° was obtained, and a catalyst was prepared in the same manner as in Example 1 and a desulfurization reaction test was performed. Table 6 shows the results.

Comparative Example 1 (Preparation of carrier) A specific surface area of 374 m ² / g and a pore volume of 0.64 c were obtained in the same manner as in Example 1 except that an aqueous solution of zirconium nitrate was not added to the alumina gel.
A carrier having c / g and an average pore diameter of 59 ° was obtained.

(Preparation of catalyst) At room temperature, 33 g of ammonium molybdate tetrahydrate and 28-30
An aqueous solution for impregnation was prepared by dissolving 10 g of mass% ammonia water (special grade reagent manufactured by Kanto Chemical Co., Ltd.) in 67 g of ion-exchanged water and stirring. This aqueous solution was impregnated with 100 g of the above-mentioned carrier at room temperature for 1 hour in an eggplant type flask, air-dried, and calcined in a muffle furnace at 500 ° C. for 4 hours to obtain an alumina carrier carrying molybdenum oxide.

Subsequently, 26 g of cobalt nitrate hexahydrate was dissolved in 77 g of ion-exchanged water in an Erlenmeyer flask at room temperature and stirred to prepare an aqueous solution for impregnation. This aqueous solution was impregnated with 100 g of the above-mentioned molybdenum oxide-supported alumina carrier in a eggplant-shaped flask at room temperature for 1 hour, air-dried, and calcined in a muffle furnace at 500 ° C. for 4 hours to obtain a catalyst.

A desulfurization reaction test was performed using this catalyst. Table 3 shows the results.

Comparative Example 2 Using the carrier obtained in Comparative Example 1, a catalyst was prepared in the same manner as in Example 1, and a desulfurization reaction test was performed using the catalyst. The results are shown in Tables 3 and 6.

Comparative Example 3 A catalyst was prepared in the same manner as in Comparative Example 1 except that 26 g of nickel nitrate hexahydrate was used instead of 26 g of cobalt nitrate hexahydrate. To perform a desulfurization reaction test. Table 4 shows the results.

Comparative Example 4 Using the carrier obtained in Comparative Example 1, a catalyst was prepared in the same manner as in Example 3, and a desulfurization reaction test was performed using the catalyst. Table 4 shows the results.

Comparative Example 5 The procedure of Comparative Example 1 was repeated, except that 13 g of nickel nitrate hexahydrate and 13 g of cobalt nitrate hexahydrate were used instead of 26 g of cobalt nitrate hexahydrate. A catalyst was prepared, and a desulfurization reaction test was performed using the catalyst. Table 5 shows the results.

Comparative Example 6 Using the carrier obtained in Comparative Example 1, a catalyst was prepared in the same manner as in Example 5, and a desulfurization reaction test was performed using the catalyst. Table 5 shows the results.

Comparative Example 7 In the preparation of the carrier in Example 1, 0.02 g of zirconium nitrate was used to obtain a carrier having a specific surface area of 370 m ² / g, a pore volume of 0.63 cc / g and an average pore diameter of 59 °. Hereinafter, a catalyst was produced in the same manner as in Example 1, and a desulfurization reaction test was performed using the catalyst. Table 6 shows the results.

Comparative Example 8 Except that 28 g of zirconium nitrate was replaced with 224 g in the preparation step of the carrier, and the resulting carrier (specific surface area 218 m 2 / g, pore volume 0.52 cc / g, average pore diameter 76 °) was used. A catalyst was prepared in the same manner as in Example 1, and a desulfurization reaction test was performed. Table 6 shows the results.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

Table 3 shows the relative activities of Comparative Example 2, Examples 1 and 2 when the desulfurization activity of the Co-Mo / alumina catalyst of Comparative Example 1 was set to 100%. By supporting P ₂ O ₅ as an active ingredient on
Shows a relative activity of 114%. On the other hand, the catalyst of Example 1 uses an alumina carrier containing zirconia and exhibits a relative activity of 130%. Furthermore, the relative activity of the catalyst of Example 2 reaches 140% by using a support containing zirconia and zeolite.

The improvement in the relative activity of the catalyst of the example with respect to the catalyst of the comparative example is more remarkable as the reaction temperature increases from 330 ° C. to 340 ° C., and further to 350 ° C. This fact indicates that zirconia works effectively in the ultra-deep desulfurization region where the sulfur content in the produced oil is 0.05 mass% or less.

[0078]

[Table 4]

Table 4 shows the relative activities of Comparative Example 4, Examples 3 and 4 when the desulfurization activity of the Ni-Mo / alumina catalyst of Comparative Example 3 was set to 100%, and the above-mentioned Co-Mo / alumina catalyst was used. As with the case, the catalyst shows higher relative activity with the loading of P ₂ O ₅ , zirconia and zeolite.

[0080]

[Table 5]

Table 5 shows the relative activities of Comparative Example 6, Examples 5 and 6 when the desulfurization activity of the Ni—Co—Mo / alumina catalyst of Comparative Example 5 was set to 100%.
As with the Mo / alumina catalyst, the catalyst exhibits higher activity with the loading of P ₂ O ₅ , zirconia and zeolite.

[0082]

[Table 6]

Table 6 shows the zirconia content dependence of the Co-Mo / alumina catalyst. When the desulfurization activity of the Co-Mo-P / alumina catalyst of Comparative Example 2 in which the carrier does not contain zirconia is defined as 100%, 1 shows the relative activities of catalysts containing zirconia in various proportions.

In the catalyst of Comparative Example 7, the content of zirconia in the carrier was only 0.1 mass% with respect to the total amount of the catalyst.
Comparative Example 2 in which the carrier does not contain zirconia
No improvement in the desulfurization activity is observed as compared with the catalyst of No.

However, according to the present invention, in the catalyst of Example 7 in which the content of zirconia in the carrier was 1.5 mass%, the desulfurization activity reached 112% (330 ° C.), and the effect of zirconia was remarkable. . In the catalyst of Example 1, the content of zirconia in the carrier was 5 mass%.
And the desulfurization activity is the highest. Further, as shown in the catalyst of Example 8, the catalyst having a zirconia content of 20 mass% in the support also has a relative activity of 107% (3%).
30 ° C.).

The presence of zirconia in the support thus significantly enhances the desulfurization activity, but when the content is excessive, the desulfurization activity is rather significantly reduced. That is,
The catalyst of Comparative Example 8 had a zirconia content of 40 mass% in the carrier, and had a lower activity than the catalyst of Comparative Example 2 containing no zirconia in the carrier, and had a relative activity of 8%.
7%.

As described above, according to the present invention, the hydrodesulfurization activity of a hydrocarbon oil can be significantly increased by including zirconia in a carrier only in a limited range.

[0088]

As described above, according to the present invention, zirconia is contained in the carrier only in a limited range with respect to the total amount of the catalyst, and the active metal is contained in such a carrier at a predetermined ratio. By supporting the catalyst, it is possible to obtain a catalyst exhibiting high activity in hydrodesulfurization of a hydrocarbon oil. Thus, by treating a hydrocarbon oil with such a catalyst, it has been conventionally difficult to obtain sulfur. A fuel oil having a small content can be provided.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takashi Fujikawa 1134-2, Gondogendo, Satte City, Saitama Prefecture Inside the R & D Center, Kosmo Research Institute, Inc. (72) Inventor Kazuo Dei 1134-2, Gongendo, Satte City, Saitama Prefecture Kosmo Research Institute R & D Center (72) Inventor Takashi Yoshizawa 1134-2 Gongendo, Satte City, Saitama Prefecture Cosmo Research Institute R & D Center

Claims (2)

[Claims] 1. A support containing zirconia in a range of 0.2 to 30 mass% based on the total amount of alumina or an inorganic oxide containing alumina as a main component and a catalyst, comprising: (a) a metal of Group VIA of the periodic table; At least one element selected from the elements is 10 to 30 m in terms of oxide with respect to the total amount of the catalyst.
(b) at least one metal element selected from Group VIII metal elements of the periodic table in an amount of 1 to 10 ma in terms of oxide based on the total amount of the catalyst.
ss%, and (c) 1 to 7 m of phosphorus based on the total amount of the catalyst in terms of oxide.
A hydrotreating catalyst for a hydrocarbon oil, wherein the catalyst carries an ass% of the catalyst. 2. The catalyst for hydrotreating hydrocarbon oil according to claim 1, wherein the carrier contains zeolite in a range of 1 to 15 mass% based on the total amount of the catalyst.