JPH11151441A - Hydrodesulfurizing catalyst, its production and hydrodesulfurizing method of heavy oil using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To high efficiently remove a sulfur compound in a heavy oil fraction through a long time and to high efficiently making the heavy oil fraction light in a catalytic hydrodesulfurization of the heavy oil fraction such as a vacuum gas oil fraction in an indirect desulfurizing device or a long residum in a direct desulfurizing device. SOLUTION: The hydrodesulfurizing catalyst of the heavy oil is composed of a base catalyst, which consists of 3-7 mass% at least one kind of a metal selected from iron group in periodic table expressed in terms of oxide, 10-30 mass% at least one kind of a metal selected from the group VIA in periodic table expressed in terms of oxide and the balance inorganic oxide carrier, and a modified catalyst, which consists of 15-100 mass% at least one kind of a metal selected from iron oxide, cobalt oxide, nickel oxide, chromium oxide, molybdenum oxide and tungsten oxide expressed in terms of oxide and the balance inorganic oxide carrier and has higher oxide concentration than that of the base catalyst, and is formed by applying 1-20 mass% modified catalyst per 100 mass% base body catalyst on the surface of the base catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the catalytic hydrodesulfurization of a vacuum gas oil (hereinafter referred to as VGO) fraction by an indirect desulfurizer or an atmospheric residue (hereinafter referred to as AR) fraction by a direct desulfurizer. A heavy oil hydrodesulfurization catalyst that can remove sulfur compounds in a heavy oil fraction for a long period of time at a high rate, and can also lighten the heavy oil fraction at a high rate, The present invention relates to a method for producing such a hydrodesulfurization catalyst and a method for hydrodesulfurizing heavy oil using such a hydrodesulfurization catalyst.

[0002]

2. Description of the Related Art Sulfur compounds are contained in heavy oil fractions such as VGO, which is a distillate obtained from a vacuum distillation unit, and AR, which is a bottom oil when crude oil is processed by an atmospheric distillation unit. Since these heavy oil fractions are used as fuels as they are at high concentrations, large amounts of sulfur oxides (SOx) are emitted into the atmosphere. Sulfur oxides have a direct and harmful effect on the human body and are one of the causative agents of acid rain.

Therefore, conventionally, as one of the processes for producing various petroleum products from crude oil, catalytic hydrodesulfurization treatment of heavy oil fractions by an indirect desulfurization unit or a direct desulfurization unit has been adopted. Removing sulfur compounds in the minute,
That is, although desulfurization treatment is performed, in this desulfurization,
Since the hydrocracking of the heavy oil fraction proceeds at the same time, higher value-added light fractions such as naphtha, kerosene, and gas oil are also produced.

[0004] Conventionally, a catalyst for hydrodesulfurization treatment for the purpose of removing sulfur compounds in VGO and AR and at the same time reducing the weight of the compounds is composed of a group VIA metal of the periodic table and an iron group metal as active components. And these are alumina, magnesia, a catalyst which is supported on an inorganic oxide carrier such as silica,
Usually, molybdenum is used as the Group VIA metal,
Further, cobalt or nickel is used as the iron group metal. Here, the Group VIA metal is an essential active component in the hydrodesulfurization catalyst, and it is considered that hydrodesulfurization activity is exhibited by sulfidizing this metal to form a sulfide.

Further, it has been conventionally known that it is effective to add phosphorus, boron or the like to the catalyst in order to improve the activity of the above-mentioned desulfurization catalyst (Japanese Patent Laid-Open No. 52-1982).
No. 13503). It is also known that the activity can be improved by adding zeolite to the carrier (Japanese Patent Application Laid-Open No. 56-20087).

[0006] The catalytic hydrodesulfurization treatment of heavy oil fractions is carried out in the reactor of an indirect desulfurization unit or direct desulfurization unit in the presence of the above-mentioned hydrodesulfurization catalyst. With an increase in demand for hydrodesulfurization, a hydrodesulfurization catalyst having high hydrocracking activity for heavy oil has been demanded. In fact, in indirect desulfurization, MHC was
The process (European Patent No. 0244106) has been commercialized.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have found that in a hydrodesulfurization process, a decomposition reaction is a main reaction field at a catalyst surface portion as compared with a desulfurization reaction. Therefore, in order to improve the hydrocracking activity of the conventional heavy oil hydrodesulfurization catalyst, if the active component effective for hydrocracking is coated on the outer surface of the catalyst, the desulfurization activity of the hydrodesulfurization catalyst will be improved. Since the addition of the active ingredient is limited to the outer surface portion of the catalyst as it is, it was found that only a small amount of the additive was required, the increase in catalyst cost could be suppressed, and the hydrocracking activity could be improved. The invention has been completed.

[0008] That is, the present invention relates to a VG using an indirect desulfurization apparatus.
In the catalytic hydrodesulfurization of O and AR using a direct desulfurization device, sulfur compounds in the heavy oil fraction can be removed at a high rate for a long time, and the heavy oil fraction can be removed at a high rate. An object of the present invention is to provide a hydrodesulfurization catalyst that can be lightened. Still another object of the present invention is to provide a method for producing such a hydrodesulfurization catalyst and a method for hydrodesulfurizing heavy oil using such a hydrodesulfurization catalyst.

[0009]

The hydrodesulfurization catalyst according to the present invention is characterized in that (a) at least one metal selected from the iron group of the periodic table is 3 to 7 mass% in terms of oxides,
A base catalyst comprising at least one metal selected from Group VIA in an amount of 10 to 30 mass% in terms of oxide and the balance being an inorganic oxide carrier; and (b) iron oxide, cobalt oxide, nickel oxide, chromium oxide, oxide At least one metal oxide selected from molybdenum and tungsten oxide is 15 to 100 mass% in terms of oxide, and the remainder is composed of an inorganic oxide carrier, and the concentration of the oxide is higher than the oxide concentration of the base catalyst. And the modified catalyst is coated on the surface of the base catalyst by 1 to 2 per 100 mass parts of the base catalyst.
It is characterized by being coated in the range of 0 mass part.

Here, the oxide concentration is determined by (metal oxide amount / (metal oxide amount + inorganic oxide carrier amount)) × 100 (mass%) in the base catalyst and the modified catalyst. When a plurality of metal oxides are present in the modification catalyst, the total amount of the metal oxides is defined as the amount of the metal oxide.

Such a hydrodesulfurization catalyst according to the present invention is obtained by suspending particles of a modified catalyst having a particle diameter in the range of 10 to 100 μm in water to form a slurry, coating the slurry on a base catalyst, and drying the slurry. In the method for producing a desulfurization catalyst, in which the modified catalyst is coated on the surface of the base catalyst, the mixture is calcined, and preferably, the mass ratio is 1.5 with respect to the saturated water absorption of the base catalyst. ~ 5
By using a slurry in which the particles of the modified catalyst are suspended in water in an amount ranging from 20 to 200 times the mass of the particles of the modified catalyst with respect to the particles of the modified catalyst. Can be.

Further, the method for hydrodesulfurization of heavy oil according to the present invention comprises a hydrogen partial pressure of 4 to 18 MPa and a temperature of 320 to 410 ° C.
And contacting the heavy oil with the catalyst under the reaction conditions of a liquid hourly space velocity of 0.1 to 4.0 hr ^-1 .

[0013]

DETAILED DESCRIPTION OF THE INVENTION The hydrodesulfurization catalyst according to the present invention comprises:
(a) At least one metal selected from the iron group of the periodic table is 3 to 7 mass% in terms of oxide, and at least one metal selected from group VIA in the periodic table is 10 in terms of oxide.
(B) iron oxide, cobalt oxide, nickel oxide,
At least one metal oxide selected from chromium oxide, molybdenum oxide and tungsten oxide is 15 to 100 mass% in terms of oxide, and the balance is an inorganic oxide carrier, and the oxide concentration is the oxide concentration of the base catalyst. Higher modified catalyst, the modified catalyst is provided on the surface of the base catalyst in an amount of 1 to 20 ma per 100 mass parts of the base catalyst.
It is characterized by being coated in the range of the ss portion.

The hydrodesulfurization catalyst according to the present invention has a multilayer structure comprising a base catalyst, which is a granular solid catalyst, and a modified catalyst coated on its surface.

In the catalyst having such a multilayer structure, the inorganic oxide carrier in the base catalyst may be any one as long as it has been conventionally used as a carrier for a hydrodesulfurization catalyst. . Accordingly, as such inorganic oxide carriers, for example, silica, alumina, boria, magnesia, 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, silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia,
Silica-magnesia-zirconia and the like can be mentioned, and these can be used alone or in combination of two or more.

However, according to the present invention, among these, alumina, silica-alumina, alumina-titania, alumina-boria, and the like are preferred as the preferable carrier for maximizing the desulfurization activity of the iron group metal and the group VIA metal. Or alumina-zirconia can be mentioned, and in particular, according to the present invention, alumina is preferably used.

According to the present invention, if necessary, A
Zeolite, Y zeolite, stabilized Y zeolite, ultra-stabilized Y zeolite, L zeolite, ZSM
Crystalline aluminosilicates such as -5 type zeolite, montmorillonite, kaolin, hallosite, bentonite,
Clay minerals such as adavalgite, bauxite, kaolinite, nacrite, anoxite and the like may be used alone or in combination of two or more kinds in the inorganic oxide carrier and used as the carrier.

In the present invention, a granular material is used as the carrier. The shape, specific surface area of such a granular carrier,
The pore volume, average pore diameter and the like are not particularly limited, but usually those having a particle diameter in the range of 0.2 to 5 mm are used. Here, the particle diameter refers to the maximum diameter when the particles are columnar.

Further, in the present invention, the carrier is VGO
In order to accelerate the hydrodesulfurization reaction of
The specific surface area is in the range of 200 to 400 m ² g ⁻¹ , particularly preferably in the range of 250 to 380 m ² g ⁻¹ . The pore volume is usually in the range of 0.4 to 1.2 cm ³ g ⁻¹ , and particularly preferably in the range of 0.5 to 1.0 cm ³ g ⁻¹ . The average pore diameter is usually in the range of 50 to 130 ° (angstrom), and particularly preferably in the range of 55 to 110 °.

Similarly, in the preparation of the modified catalyst, when an inorganic oxide carrier is used, the above-mentioned carrier is used. The carrier may be the same as or different from the carrier in the base catalyst. Is also good.

First, the preparation of the base catalyst will be described.
The method for preparing the base catalyst, which is a granular solid catalyst obtained by supporting the iron group metal and the group VIA metal on the support, is not particularly limited, and may be a conventionally known appropriate method. For example, the iron group metal and the group VIA metal may be supported on the carrier by a conventionally known impregnation method, coprecipitation method, kneading method, deposition method or the like.

For example, according to the impregnation method, the above-mentioned carrier is impregnated with a solution of a compound of the iron group metal and a compound of the group VIA metal having an appropriate concentration, dried, and then dried in air.
The temperature is in the range of 50 to 700 ° C, preferably 400 to 600 ° C, but is not limited thereto.
By calcining for about an hour, a base catalyst which is a granular solid catalyst can be prepared. The firing temperature in the air is about 350 to 700 ° C, preferably about 400 to 600 ° C.
° C and the time is about 1 to 10 hours.

However, if necessary, the support is first impregnated with a solution of an iron group metal compound at an appropriate concentration, dried, calcined in air, and then the support thus treated is treated with VIA VIA. It may be impregnated with a solution of an appropriate concentration of a compound of a group metal, dried, and then calcined in air. No. on the carrier
After supporting the VIA group metal, the iron group metal may be supported.

According to the present invention, in the preparation of the base catalyst, iron, cobalt or nickel is used as the iron group metal, but preferably cobalt or nickel is used. Various compounds can be used as these iron group metal compounds. For example, nitrates, sulfates, carbonates, acetates, oxalates, chlorides and the like are preferably used.

Accordingly, in preparing the base catalyst, examples of the iron compound include ferric nitrate, ferric chloride, and ferrous oxalate. Examples of the cobalt compound include cobalt nitrate and cobalt sulfate. , Cobalt carbonate, cobalt acetate, cobalt oxalate, cobalt chloride and the like, and as the nickel compound, for example,
Examples include nickel nitrate, nickel sulfate, nickel carbonate, nickel acetate, nickel oxalate, nickel chloride and the like.

As the Group VIA metal, chromium, molybdenum or tungsten is used. In particular, molybdenum or tungsten is preferably used. Various compounds of the group VIA metal can be used. Specific examples of the molybdenum compound include, for example, ammonium molybdate, molybdenum oxide, and molybdenum condensate. Further, specific examples of the tungsten compound include, for example, ammonium tungstate, tungsten oxide, and tungsten condensate.

As a solution of the above-mentioned metal compounds of the iron group and group VIA, an aqueous solution is usually preferably used. Therefore, in order to increase the water solubility of these compounds in aqueous solution, an acidic solution such as phosphoric acid is added to the aqueous solution. May be added. Here, taking phosphoric acid as an example, various phosphoric acids such as orthophosphoric acid, metaphosphoric acid, triphosphoric acid, and tetraphosphoric acid are used.
In addition, as a solvent for the solution of the compound, in addition to water, various solvents such as alcohols, ethers, ketones, aqueous solutions thereof, aromatic hydrocarbons, and the like, or a mixture of two or more kinds thereof Can also be used.

The amount of each of the metal compounds in the solution of the metal compound of the iron group and the metal compound of the group VIA is determined to be 3 to 7 mass in terms of oxide in the obtained base catalyst.
%, Preferably 4 to 6 mass%, and the amount of the Group VIA metal is 10 to 30 mass%, preferably 13 to
23 mass%, the inorganic oxide carrier is used so as to be the balance.

As described above, when phosphoric acid is added to the aqueous solution of the metal compound, the phosphoric acid is added to the base catalyst in the presence of P _2.
At O ₅ converted, 0.1～4Mass%, preferably, 1 to
It is used so as to be 3 mass%. The amount of the phosphoric acid is included in the amount of the inorganic oxide carrier.

In the present invention, when the iron group metal component in the base catalyst is less than 3 mass%, the obtained catalyst is not sufficient in the required hydrodesulfurization catalytic activity, while
If it exceeds mass%, it is considered that the compound (sulfide) under the use condition of the metal component is difficult to maintain a high dispersion state, but remarkable sintering (sintering) occurs and the catalytic activity is reduced. It tends to decrease. Similarly, when the Group VIA metal component is less than 10 mass%, the resulting catalyst is not sufficient in the required hydrodesulfurization catalytic activity, while the Group VIA metal component is a compound under the conditions of use of the metal component. In the state of (sulfide), it is considered that a high dispersion state can be maintained as compared with the iron group metal. However, when it exceeds 30 mass%, sintering (sintering) similarly occurs, The specific surface area of the catalyst becomes small, and high catalytic activity cannot be obtained.

In the present invention, the base catalyst is, as described above, a granular solid catalyst having a shape that does not cause a pressure difference before and after the catalyst layer under the reaction conditions.
Although not particularly limited, the particle diameter is 0.2 to 5 m in consideration of the distribution of the catalyst layer of a heavy oil fraction such as VGO or AR.
It is preferable that the particles are in the range of m. here,
The particle diameter means the maximum diameter when the particles are columnar.

In particular, according to the present invention, the base catalyst is desirably in a so-called pellet shape such as a columnar shape, a trilobe shape, or a tetralobe shape, and furthermore, a pressure difference occurs before and after the catalyst layer under the reaction conditions. The pellet diameter should be between 1/10 and 1 /
Preferably it is in the range of 36 inches. Here, the diameter of the pellet is the length of the thickest portion of the pellet except for the pellet having a cylindrical shape.

The hydrodesulfurization catalyst according to the present invention comprises at least one metal oxide selected from iron oxide, cobalt oxide, nickel oxide, chromium oxide, molybdenum oxide and tungsten oxide on the surface of the above-mentioned base catalyst. It can be obtained by coating a modified catalyst.

The method for preparing this modified catalyst is not particularly limited, either, and any conventionally known suitable method, for example, an impregnation method, a coprecipitation method, a kneading method, a deposition method, an ion exchange method, It can be prepared by various methods such as a thermal decomposition method and a thermal decomposition method. In addition, various iron compounds, cobalt compounds, nickel compounds, chromium compounds, molybdenum compounds, or tungsten compounds as described above are used as the compound species used in the preparation, depending on the preparation method of the modification catalyst.

For example, a modified catalyst composed of only at least one metal oxide selected from iron oxide, cobalt oxide, nickel oxide, chromium oxide, molybdenum oxide and tungsten oxide can be used in various compounds capable of producing the above oxide by firing. Can be obtained by firing at a high temperature in the air.

On the other hand, the modified catalyst comprising the metal oxide and the inorganic oxide carrier can be prepared, for example, by an impregnation method. Here, as described above, various inorganic oxides can be used as the inorganic oxide carrier, but usually, silica, alumina, silica-alumina and the like are preferably used.

To prepare the modified catalyst by the impregnation method,
For example, after the carrier is impregnated with the solution of the modifying compound, the carrier may be fired in the air. This firing temperature is usually 4
The temperature is in the range of 00 to 700 ° C, preferably 450 to 600 ° C, and the firing time is usually about 1 to 10 hours.
Whether the reduction treatment with hydrogen or the like after calcination is performed or not, there is no significant difference in catalytic performance.

The amount of the above-mentioned modified metal constituting the modified catalyst is as follows:
15 to 100% by mass, preferably 50 to 100% by mass, more preferably 70 to 100% by mass of the total amount in terms of oxides.
１００100 mass%, and the oxide concentration must be higher than the oxide concentration in the base catalyst.

In the modified catalyst, when the amount of the modified metal is less than 15 mass% in terms of oxide, the effect of increasing the hydrocracking activity of the obtained hydrodesulfurization catalyst cannot be obtained. Even when the oxide concentration in the modified catalyst is lower than the oxide concentration in the base catalyst, the effect of increasing the hydrocracking activity of the obtained hydrodesulfurization catalyst cannot be obtained.

In order to coat the modified catalyst on the surface of the base catalyst, the particle diameter of the modified catalyst is 10 to 100 μm.
m, preferably in the range of 30 to 80 μm. It is difficult to pulverize the modified catalyst into fine particles having a particle diameter of less than 10 μm. On the other hand, when the modified catalyst is a particle having a particle diameter of more than 100 μm, a coating effect, that is, a difference between the coated modified catalyst particles and the base catalyst is obtained. The effect of improving the concerted or cooperative decomposition activity is low, and the coated modified catalyst tends to peel off from the surface of the base catalyst.

In order to coat the modified catalyst on the surface of the base catalyst, the fine particles of the modified catalyst are suspended in water to form a slurry. The slurry is applied to the surface of the base catalyst, dried, and, if necessary, dried. The operation is repeated several times so that the resulting hydrodesulfurization catalyst has a predetermined ratio of the base catalyst and the modified catalyst.

In the hydrodesulfurization catalyst according to the present invention, the modified catalyst is used in an amount of 1 to 20 m per 100 mass parts of the base catalyst.
It is an ass part, preferably a 1 to 10 mass part, particularly preferably a 2 to 8 mass part. Base catalyst 100m
When the amount of the modified catalyst is less than 1 mass part per ass part, the effect of increasing the hydrocracking activity of the catalyst can hardly be obtained.

According to the present invention, when suspending the fine particles of the modified catalyst in water, the amount of water used for suspending the fine particles of the modified catalyst is determined by the maximum mass of water that can be absorbed by the base catalyst ( Hereinafter, simply referred to as saturated water absorption.)
The amount is preferably 5 to 5 times, and the ratio of the mass of water used for suspending the fine particles of the modified catalyst / the mass of the modified catalyst to be coated is in the range of 20 to 200.

For example, 50 g of base catalyst (30 g of water absorption)
On the other hand, when coating 2.5 g of the modified catalyst (5 mass parts per 100 mass parts of the base catalyst),
The amount of water satisfying the above requirements (the amount of water used for suspending the fine particles of the modified catalyst) is in the range of 50 to 150 g. The reason for defining the amount of water used to suspend the fine particles of the modified catalyst in this way is that when the concentration of the slurry is too high, the slurry cannot be coated uniformly on the base catalyst, and conversely, If the concentration is too small, it is necessary to repeat the coating operation unnecessarily many times.

The slurry in which the fine particles of the modified catalyst are suspended contains silica sol, alumina sol, zirconia sol, etc. as a binder in the obtained hydrodesulfurization catalyst so that the modified catalyst is not easily separated from the base catalyst. Is preferred. The amount of such a binder is usually 2 to 20 with respect to 100 mass parts of water in the slurry.
mass part, preferably in the range of 5 to 15 mass part. With respect to 100 mass parts of water in the slurry, when the amount of the binder is less than 2 mass parts, the effect as a binder is not sufficient. ,
As a result of being coated with the above-mentioned oxide constituting the binder, not only the desulfurization activity is reduced, but also the viscosity of the slurry is high, and the coating operation is difficult.

In order to charge the hydrodesulfurization catalyst of the present invention into a reactor of an indirect desulfurization unit or a direct desulfurization unit and use it for catalytic hydrodesulfurization of heavy oil, as in the conventional case, a reactor filled with the catalyst is used. Heavy oil as a feedstock may be introduced and treated under conventionally known conditions of high temperature, high pressure and substantial hydrogen partial pressure.

Most commonly, the hydrodesulfurization catalyst according to the invention is maintained in the reactor as a fixed bed, and the feedstock is passed through the fixed bed from top to bottom. The catalyst may be used after being filled in a single reactor, or the catalyst may be filled in each of a plurality of reactors connected in series. In particular, when the feed oil is AR, AR contains a high concentration of metals such as nickel and vanadium, so a multi-stage reactor combining a hydrodesulfurization catalyst with a catalyst system having a demetallation function is required. Preferably, it is used.

The reaction conditions are not particularly limited. For example, a 5% by volume distillation temperature is 240 ° C. or higher, 95 ° C.
Vacuum gas oil with a volume% distillation temperature of 450 ° C or higher (VG
O) When catalytically hydrodesulfurizing a fraction or an atmospheric residue (AR) having a 40% by volume distillation temperature of 450 ° C. or higher using the hydrodesulfurization catalyst according to the present invention, the hydrogen partial pressure is 4 to 18 MPa. ,
Preferably 4.5 to 16 MPa, feedstock temperature is 320 to 4
10 ° C., preferably 350-405 ° C., liquid hourly space velocity is 0.
The catalyst may be brought into contact with the catalyst of the present invention under the conditions of ¹ to 4.0 hr ^-1 , preferably 0.15 to 2.0 hr ^-1 .

When hydrodesulfurization of the above heavy oil is performed under such reaction conditions, the decomposition rate of the hydrodesulfurization catalyst according to the present invention is significantly larger than that of the conventional hydrodesulfurization catalyst.
The light fraction yield in commercial operation on actual equipment can be improved by 1.0% or more. This has a nominal capacity of 2800
In the kL / day apparatus, the yield of light components of about 10,000 kL / year is improved.

As described above, according to the present invention, the activity of the hydrocracking reaction is increased while the activity of the hydrodesulfurization reaction is maintained by coating the surface of the base catalyst with the modified catalyst having a high hydrolytic ability. Thus, it is possible to increase the production of soft components while removing sulfur compounds in the heavy oil fraction at a high rate over a long period of time.

Further, the hydrodesulfurization catalyst according to the present invention also has a feature that the initial hydrodesulfurization activity is higher than that of the conventional catalyst, so that the 90% vol. It can be effectively used for hydrodesulfurization of a kerosene fraction at 250 ° C. or lower and a gas oil fraction having a 90% by volume distillation temperature of 400 ° C. or lower.

[0052]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples.

(Preparation of base catalyst A) Base catalyst A1 (Preparation of alumina (columnar pellet) supporting 5 mass% CoO-15 mass% MoO ₃ ) 25 g of ion-exchanged water
In it, 10 g of molybdophosphoric acid 30 hydrate and orthophosphoric acid 1.
An aqueous solution in which 85 g and 8.0 g of cobalt acetate tetrahydrate are dissolved is impregnated into 36 g of cylindrical (1/16 inch) alumina pellets (manufactured by Nippon Ketjen Co., Ltd., surface area: 385 m ² g ^-1 ), and dried at room temperature. Then, it was calcined at 500 ° C. for 3 hours to obtain alumina supporting 5 mass% CoO-15 mass% MoO ₃ .

Preparation of Substrate Catalyst A2 (Preparation of alumina (tetralobular pellet) supporting 5 mass% CoO-15 mass% MoO ₃ ) In the preparation of the substrate catalyst A1, instead of the columnar (1/16 inch) alumina pellet, a four-lobe (1 / 20 inch) 5 mass% in the same manner as the base catalyst A1 except that alumina pellets (378 m ² g ⁻¹ surface area, manufactured by Nippon Ketjen) were used.
CoO-15 mass% MoO ₃ -supported alumina was obtained.

Base Catalyst A3 (Preparation of alumina supporting 5 mass% NiO-15 mass% MoO ₃ ) In the preparation of base catalyst A1, nickel acetate tetrahydrate was used instead of 8.0 g of cobalt acetate tetrahydrate.
Except that 8.0 g was used, 5
A mass% NiO-15 mass% MoO ₃ supported alumina was obtained.

Base Catalyst A4 (2.5 mass% CoO-2.5 mass% NiO-15
Preparation of Mass% MoO ₃ -Supported Alumina) Base Catalyst A1
Was prepared in the same manner as the base catalyst A1, except that 4.0 g of cobalt acetate tetrahydrate and 4.0 g of nickel acetate tetrahydrate were used instead of 8.0 g of cobalt acetate tetrahydrate.
2.5mass% CoO-2.5mass% NiO-15m
As% MoO ₃ -supported alumina was obtained.

Base Catalyst A5 (Preparation of 5 mass% CoO-15 mass MoO ₃ -Supported Alumina-Silica) In the preparation of the base catalyst A1, instead of cylindrical (1/16 inch) alumina pellets,
Cylindrical (1/16 inch) alumina-silica pellets (manufactured by Nippon Ketjen Co., containing ₂₀ mass% SiO ₂ ,
Except for using a surface area of 391 m ² g ^-1 ), the base catalyst A1 was used.
5 mass% CoO-15massMo
O ₃ supported alumina-silica was obtained.

Base Catalyst A6 (Preparation of alumina supporting 5 mass% CoO-20 mass% MoO ₃ ) In the preparation of base catalyst A1, 13.3 g of molybdophosphoric acid 30 hydrate and a columnar (1/16 inch)
Except that 33.5 g of alumina pellets were used, the base catalyst A was used.
5 mass% CoO-20 mass% in the same manner as 1.
MoO ₃ -supported alumina was obtained.

Base Catalyst A7 (Preparation of alumina supporting 2 mass% CoO-15 mass% MoO ₃ ) In the preparation of the base catalyst A1, 3.2 g of cobalt acetate tetrahydrate and 37.7 g of columnar (1/16 inch) alumina pellets were used. 2 mass% CoO-15 mass% MoO in the same manner as in the base catalyst A1 except that
₃ supported alumina was obtained.

Base Catalyst A8 (Preparation of 8 mass% CoO-15 mass% MoO ₃ -Supported Alumina) In the preparation of the base catalyst A1, 12.8 g of cobalt acetate tetrahydrate and 34.6 g of columnar (1/16 inch) alumina pellets were used. 8 mass% CoO-15 mass% Mo in the same manner as the base catalyst A1 except that
O ₃ supported alumina was obtained.

Base Catalyst A9 (Preparation of alumina supporting 5 mass% CoO-8 mass% MoO ₃ ) In the preparation of the base catalyst A1, 5.3 g of molybdophosphoric acid 30 hydrate and 39.4 g of cylindrical (1/16 inch) alumina pellets were used. 5 mass% CoO-8 mass% MoO in the same manner as the base catalyst A1 except that
₃ supported alumina was obtained.

Base Catalyst A10 (Preparation of alumina supporting 5 mass% CoO-35 mass% MoO ₃ ) In the preparation of the base catalyst A1, 23.3 g of molybdophosphoric acid 30 hydrate and a columnar (1/16 inch) were used.
Except that 28.7 g of alumina pellets were used, the base catalyst A was used.
5 mass% CoO-35 mass% in the same manner as 1.
MoO ₃ -supported alumina was obtained.

[0063] (Modified Preparation of Catalyst B) modified (Preparation of molybdenum oxide) catalyst B1 ammonium molybdate _{((NH 4) 6 Mo 7} O 24 · 4H 2 O ( molecular weight = 123
6)) 50 g was baked at 500 ° C. for 3 hours to obtain molybdenum oxide.

Modified catalyst B2 (Preparation of tungsten oxide) Tungstic acid (H ₂ WO ₄
(Molecular weight = 250) 50 g was baked at 500 ° C. for 3 hours to obtain tungsten oxide.

Modified catalyst B3 (Preparation of chromium oxide) Chromium nitrate nonahydrate (Cr (NO
_{3) 3} 9H ₂ O (molecular weight = 400)) to 50g was calcined for 3 hours at 500 ° C., to obtain a chromium oxide.

[0066] Modified catalysts B4 (Preparation of iron oxide) iron nitrate nonahydrate _{(Fe (NO 3) 3 ·} 9
50 g of H ₂ O (molecular weight = 404) was calcined at 500 ° C. for 3 hours to obtain iron oxide.

Modified catalyst B5 (Preparation of cobalt oxide) Cobalt nitrate hexahydrate (Co
_{(NO 3) 2 · 6H 2} O ( molecular weight = 291)) and 50 g 5
It was calcined at 00 ° C. for 3 hours to obtain cobalt oxide.

Modified catalyst B6 (Preparation of nickel oxide) Nickel nitrate hexahydrate (Ni
_{(NO 3) 2 · 6H 2} O ( molecular weight = 291)) and 50 g 5
It was calcined at 00 ° C. for 3 hours to obtain nickel oxide.

Modified Catalyst B7 (Preparation of alumina supporting 80 mass% MoO ₃ ) Molybdophosphoric acid ((NH ₄ ) ₆ Mo ₇ O ₂₄ .nH ₂ O (n = about 3)
0)) An aqueous solution obtained by dissolving 29.3 g in 50 g of ion-exchanged water until the water absorption reached 5.4 g in cylindrical (1/16 inch) alumina pellets (Nippon Ketjen Co., Ltd., surface area: 385 m ² · g ^-1 ). Impregnated and dried at room temperature. This operation was repeated several times until the aqueous solution disappeared, and calcined at 500 ° C. for 3 hours to obtain 80 mass% MoO ₃ supported alumina.

Modified Catalyst B8 (Preparation of alumina supporting 5 mass% MoO ₃ ) Molybdophosphoric acid ((NH ₄ ) ₆ Mo ₇ O ₂₄ .nH ₂ O (n = about 3)
0)) 53.5 g of columnar (1/16 inch) alumina pellets (Nippon Ketjen Co., Ltd., surface area: 385 m ² · g ^-1 ) was impregnated with an aqueous solution obtained by dissolving 3.8 g in 35 g of ion-exchanged water, and brought to room temperature. After drying, the mixture was calcined at 500 ° C. for 3 hours to obtain alumina supporting 5 mass% MoO ₃ .

(Raw material oil) The raw material oil used in the following Examples and Comparative Examples is as follows.

Raw oil R1 (vacuum gas oil (VGO)) Crude oil: Arabian heavy Density: 0.8990 g · cm ⁻³ (15 ° C.) Sulfur content: 3.06 mass% Metal content (Ni and V): 1.3 mass ppm Distillation properties: Distillation temperature 5% by volume = 306 ° C. 50% by volume = 404 ° C. 95% by volume = 510 ° C.

Raw oil R2 (normal pressure residual oil (AR)) Crude oil: Arabian light Density: 0.9724 g · cm ⁻³ (15 ° C.) Sulfur content: 3.25 mass% Metal content (Ni and V): 88 mass ppm Distillation properties: Distillation temperature 5% by volume = 404 ° C. 40% by volume = 493 ° C. 54% by volume = 538 ° C.

(Reaction conditions) The reaction conditions used in the following Examples and Comparative Examples are as follows.

Reaction conditions P1 Hydrogen partial pressure: 4.9 MPa Reaction temperature: 400 ° C. Liquid hourly space velocity: 0.66 hr ⁻¹ Hydrogen / oil ratio: 422 Nm ³ kL ⁻¹ (Note) This reaction condition is for hydrogenation of VGO fraction. This is for desulfurization.

Reaction condition P2 Hydrogen partial pressure: 0.3 MPa Reaction temperature: 390 ° C. Liquid hourly space velocity: 0.4 hr ⁻¹ Hydrogen / oil ratio: 997 Nm ³ kL ⁻¹ (Note) This reaction condition is hydrogenation of AR fraction. This is for desulfurization.

(Evaluation of Hydrodesulfurization Activity of Catalyst) The hydrodesulfurization activity of the catalyst was evaluated by a reaction rate constant k value derived from the following formula. Here, it is shown that the higher the k value, the better the catalytic activity.

K = [(1 / S concentration ^{n of} product oil ⁿ ) − (1 /
Feedstock S concentration ⁿ ) × Liquid space velocity Here, when the feedstock is VGO, n = 0.5, and when AR, n = 1.

(Evaluation of the hydrocracking activity of the catalyst) The hydrocracking activity of the catalyst was determined by the relative yield of a fraction of 343 ° C or lower obtained by gas chromatography distillation according to ASTM D2887. The higher the cracking activity, the higher the yield of the light fraction below 343 ° C.

An example of hydrodesulfurization / decomposition of the above feedstock under the above reaction conditions using a hydrodesulfurization catalyst M obtained by coating the surface of the base catalyst with a modified catalyst will be described below along with comparative examples. .

Example 1 Modified catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. (Saturated water absorption: 30 g) to prepare a hydrodesulfurization catalyst M1. Using 10 g of the hydrodesulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.

Example 2 Modified catalyst B2 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. This was coated to a saturated water absorption of 32 g) to prepare a hydrodesulfurization catalyst M2. This desulfurization catalyst 10
Using g, the feedstock R1 was subjected to catalytic hydrodesulfurization under the reaction conditions P1. Table 1 shows the results.

Example 3 Modified catalyst B3 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. (Saturated water absorption: 30 g) to prepare a desulfurization catalyst M3. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.

Example 4 The modified catalyst B4 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. (Saturated water absorption: 30 g) to prepare a desulfurization catalyst M4. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.

Example 5 The modified catalyst B5 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol, and this was suspended in the base catalyst A1 (50 g, (Saturated water absorption: 30 g) to prepare a desulfurization catalyst M5. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.

Example 6 Modified catalyst B6 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. (Saturated water absorption: 30 g) to prepare a desulfurization catalyst M6. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.

Example 7 Modified catalyst B7 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. (Saturated water absorption: 30 g) to prepare a desulfurization catalyst M7. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.

Example 8 Using 10 g of the desulfurization catalyst M1 prepared in Example 1, catalytic hydrodesulfurization was performed on a feedstock oil R2 under reaction conditions P2. Table 1 shows the results.

Comparative Example 1 Modified catalyst B8 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. (Saturated water absorption: 30 g) to prepare a desulfurization catalyst K1. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.

Comparative Example 2 Modified catalyst B1 (0.25 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. (Saturated water absorption: 30 g) to prepare a desulfurization catalyst K2. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.

Comparative Example 3 The modified catalyst B1 (14 g) sized to 55 to 73 μm was suspended in 300 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. 30 g) to prepare a desulfurization catalyst K3. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 1 shows the results.

Example 9 The modified catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol, and this was suspended in the base catalyst A2 (50 g, (Saturated water absorption: 32 g) to prepare a desulfurization catalyst N1. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.

Example 10 Modified catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. (Saturated water absorption: 29 g) to prepare a desulfurization catalyst N2. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.

Example 11 Modified catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. (Saturated water absorption: 33 g) to prepare a desulfurization catalyst N3. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.

Example 12 Modified catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol, and this was suspended in base catalyst A5 (50 g, (Saturated water absorption: 36 g) to prepare a desulfurization catalyst N4. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.

Example 13 Modified catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. (Saturated water absorption: 25 g) to prepare a desulfurization catalyst N5. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.

Example 14 Using 10 g of the desulfurization catalyst N1 prepared in Example 10,
The feed oil R2 was subjected to catalytic hydrodesulfurization under the reaction condition P2. Table 2 shows the results.

Comparative Example 4 Modified catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. The desulfurization catalyst L1 was prepared by coating with a saturated water absorption of 34 g). Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.

Comparative Example 5 Modified catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchange water containing 90 g of ion-exchanged water and 10 g of silica sol, and this was suspended in base catalyst A8 (50 g, After coating with a saturated water absorption of 28 g), a desulfurization catalyst L2 was prepared. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.

Comparative Example 6 Modified catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. (Saturated water absorption: 22 g) to prepare a desulfurization catalyst L3. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.

Comparative Example 7 Modified catalyst B1 (1.0 g) sized to 55 to 73 μm was suspended in 100 g of silica-sol-containing ion-exchanged water containing 90 g of ion-exchanged water and 10 g of silica sol. This was coated to a saturated water absorption of 18 g) to prepare a desulfurization catalyst L4. Using 10 g of the desulfurization catalyst, the raw oil R1 was subjected to catalytic hydrodesulfurization under the reaction condition P1. Table 2 shows the results.

Comparative Example 8 Using 10 g of the base catalyst A1 and the starting oil R1 under the reaction conditions P
In 1, catalytic hydrodesulfurization was performed. Table 2 shows the results.

COMPARATIVE EXAMPLE 9 Using 10 g of the base catalyst A1 and the starting oil R2 under the reaction conditions P
In 2, catalytic hydrodesulfurization was performed. Table 2 shows the results.

Comparative Example 10 Using 10 g of the base catalyst A3, the starting oil R2 was reacted under the reaction conditions P
In 2, catalytic hydrodesulfurization was performed. Table 2 shows the results.

[0105]

[Table 1]

[0106]

[Table 2]

[0107]

As described above, when the hydrodesulfurization catalyst of the present invention is used to hydrodesulfurize heavy oil fractions such as VGO and AR, the hydrodesulfurization catalyst is maintained at a high hydrodesulfurization activity. ,
Over the long term, it is possible to increase the production of light components by hydrocracking.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C10G 45/06 C10G 45/06 A 45/08 45/08 A (72) Inventor Mitsunori Tabata 1134-2 Gongendo, Satte City, Saitama Prefecture (72) Inventor Kazuo Dei 1134-2 Gongendo, Satte City, Saitama Prefecture Inventor Kazuo Dei (72) Inventor Takashi Yoshizawa Gongen, Satte City, Saitama Prefecture 1134-2 Kosmo Research Institute R & D Center

Claims (5)

[Claims] (A) at least one metal selected from the iron group of the periodic table is 3 to 7 mass% in terms of oxide; and at least one metal selected from group VIA of the periodic table is in terms of oxide. And (b) at least one metal oxide selected from iron oxide, cobalt oxide, nickel oxide, chromium oxide, molybdenum oxide, and tungsten oxide. Is 15 to 1 in oxide equivalent
00 mass% and the remainder consisted of an inorganic oxide carrier, and the modified catalyst had an oxide concentration higher than the oxide concentration of the base catalyst.
A hydrodesulfurization catalyst, which is coated in a range of 1 to 20 mass parts per mass part. 2. The hydrodesulfurization catalyst according to claim 1, wherein the iron group metal in the base catalyst is cobalt or nickel, and the group VIA metal is molybdenum. 3. The oxide concentration in the modified catalyst is from 50 to 10.
The hydrodesulfurization catalyst according to claim 1 or 2, wherein the content is in a range of 0 mass%. 4. A slurry in which particles of the modified catalyst having a particle size in the range of 10 to 100 μm are suspended in water to form a slurry. The method for producing a hydrodesulfurization catalyst according to any one of claims 1 to 3, wherein the modified catalyst is coated on the surface thereof, wherein the mass ratio is 1.5 with respect to the saturated water absorption of the base catalyst. ~ 5 times, and
20 to 20 by mass ratio with respect to the particles of the modified catalyst.
A method for producing a hydrodesulfurization catalyst, comprising suspending particles of the modified catalyst in water in an amount of 0 times the volume to form a slurry. 5. A hydrogen partial pressure of 4 to 18 MPa and a temperature of 320 to 4.
4. The hydrogen of heavy oil, wherein the heavy oil is brought into contact with the catalyst according to any one of claims 1 to 3 under reaction conditions of 10 ° C and a liquid hourly space velocity of 0.1 to 4.0 hr ^-1. Desulfurization treatment method.