JPH09117662A - Hydrocracking catalyst of heavy hydrocarbon oil and hydrocracking method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop a catalyst capable of realizing high hydrocracking activity without lowering the selectivity of an intermediate fraction such as kerosene or light gas oil from a heavy hydrocarbon oil and a hydrocracking method for manufacturing the intermediate fraction such as kerosene or light gas oil from the heave hydrocarbon oil at high conversion rate and high selectivity. SOLUTION: This hydrocracking catalyst consists of a carrier with a surface area of at least 100m<2> /g containing a laminar clay mineral composed mainly of Si and Mg and an amorphous metal oxide and at least one type of metal selected from the group VIA metals of the periodic table and at least, one type of metal selected from the group VIII metals of the table. The heavy hydrocarbon oil is brought into contact with hydrogen in the presence of this catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hydrocracking catalyst for heavy hydrocarbon oil and a method for hydrocracking heavy hydrocarbon oil using the catalyst.

[0002]

2. Description of the Related Art In recent years, the demand for kerosene and light oil, which are middle distillates, has been increasing in Japan, but the demand for heavy oil is expected to decrease in the long term. On the other hand, crude oil tends to increase in heavy crude oil, and a hydrocracker for producing middle distillates from heavy oil becomes more important. Also, from the perspective of environmental issues,
There is a need to reduce the sulfur content of middle distillates. Kerosene and gas oil obtained by hydrocracking of heavy oil have a low sulfur content, and hydrocracking is important also in this respect.

Conventionally, generally used hydrocracking catalysts are catalysts in which a metal having hydrogenation ability or a compound thereof is supported on a carrier made of an amorphous metal oxide or a carrier containing zeolite. In general, a catalyst using a carrier composed of an amorphous metal oxide has a high activity but a high selectivity for middle distillates, while a catalyst using a carrier containing zeolite has a high activity. The selectivity of middle distillates tends to be low.

Therefore, attempts have been made to improve the selectivity of the middle distillate by improving the zeolite. In JP-A-58-147495, hydrocracking is performed by using a catalyst containing an expanded pore zeolite consisting of steamed and then dealuminated faujasite zeolite and a hydrogenation component to select an intermediate fraction. A method of manufacturing the same is disclosed. In this method, the selectivity of middle distillates is improved as compared with the catalyst using the ordinary zeolite shown in the comparative example, but there is no description comparing with the catalyst containing no zeolite, and no zeolite is contained. It is estimated that the middle distillate selectivity is lower than that of the catalyst.

Further, in Japanese Unexamined Patent Publication (Kokai) No. 5-202366, a method for catalytically cracking petroleum hydrocarbons is characterized in that a composition containing a cation-exchange stevensite is used as a catalyst for catalytically cracking petroleum hydrocarbons. Is disclosed. However, the catalytic cracking described in this publication is a cracking method that does not use hydrogen,
Hydrocracking using hydrogen is a radically different cracking method.

US Pat. No. 5,023,221 discloses a hydrocracking catalyst for the selective production of middle distillates, which contains a hydrogenation component, magnesium silicate and an intercalated clay having cracking activity. . However, this patent does not describe an amorphous metal oxide as a constituent of the carrier, but discloses a finding about the effect of magnesium silicate and intercalated clay on the carrier of the amorphous metal oxide. Not not.

[0007]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a catalyst having excellent performance for producing middle distillates such as kerosene and light oil by hydrocracking heavy hydrocarbon oil, and a catalyst therefor. It is intended to provide a method for hydrocracking a heavy hydrocarbon oil used.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a carrier containing a layered clay mineral having a specific surface area and components and an amorphous metal oxide is used. The inventors have found that a catalyst containing an active metal has high selectivity for producing middle distillates such as kerosene and light oil from heavy hydrocarbon oil, and completed the present invention.

That is, the first invention of the present invention is to provide a carrier having a surface area of 100 m ² / g or more and containing a layered clay mineral containing Si and Mg as main components and an amorphous metal oxide, and a periodic table. It relates to a hydrocracking catalyst for heavy hydrocarbon oils, which comprises at least one metal selected from Group VIA metals and at least one metal selected from Group VIII metals.

The second invention of the present invention has a surface area of 1
A carrier containing a layered clay mineral containing Si and Mg as main components and having an amorphous metal oxide of at least 00 m ² / g, and at least one metal selected from Group VIA metals of the periodic table and Group VIII. It relates to a method for hydrocracking a heavy hydrocarbon oil, which comprises contacting the heavy hydrocarbon oil with hydrogen in the presence of a catalyst containing at least one metal selected from metals.

A third invention of the present invention is the method for hydrocracking heavy hydrocarbon oil according to claim 2, wherein the heavy hydrocarbon oil is vacuum gas oil.

A fourth invention of the present invention is the method for hydrocracking heavy hydrocarbon oil according to claim 2, wherein the heavy hydrocarbon oil is atmospheric distillation residual oil or vacuum distillation residual oil. And Hereinafter, the present invention will be described in detail.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The catalyst carrier used in the present invention has a surface area of 100 m ² / g or more and contains a layered clay mineral containing Si and Mg as main components and an amorphous metal oxide. For the definition, classification, structure, etc. of clay minerals, see the Clay Handbook (edited by the Japan Clay Society, Gihodo). Clay minerals are the main constituents of clay and are fine minerals that give plasticity to clay, most of which are Si,
It is a crystalline hydrous silicate mineral mainly composed of Al, Mg, Fe and the like. Many clay minerals are composed of a phyllosilicate having a structure in which a tetrahedron in which Si is tetracoordinated with O is two-dimensionally forming a layered lattice.

In the present invention, the layered clay mineral means a phyllosilicate mineral. The layered clay mineral is a tectosilicate mineral having a structure in which a tetrahedron in which Si is coordinated with O are three-dimensionally formed into a lattice, and a tetrahedron in which O is coordinated with Si is one-dimensional. Does not include inosilicate minerals with a structure that forms a linear or double-chained lattice, crystalline metallosilicates and zeolites that are classified as tectosilicates, attapulgite that is classified as inosilicates, sepiolite, It does not include palygorskite or chrysotile.

In the present invention, the layered clay mineral containing Si and Mg as main components used in the carrier excludes O which is always the largest in the elements constituting the clay mineral, and H which is often present as water and a hydroxyl group. The two most abundant elements based on the number of atoms are Si or Mg, which is a layered clay mineral. A small amount of components other than Si and Mg, such as A
1, Fe, alkali metal, alkaline earth metal, halogen, etc. may be contained.

Specific examples thereof include talc, stevensite, hectorite, saponite, vermiculite and the like. Among them, a tetrahedron layer mainly composed of tetrahedral tetrahedrons in which O is coordinated to Si is arranged in a plane, and an octahedral layer mainly composed of tetrahedral tetrahedrons in which O is coordinated to Mg from 6 is arranged in a plane, A three-layer structure in which two tetrahedral layers are arranged so as to sandwich an octahedral layer in a sandwich shape is preferable. Specific examples thereof include talc, stevensite having a 3-octahedral smectite structure, hectorite, and saponite.

Si and M used as the carrier in the present invention
It is particularly preferable that the layered clay mineral containing g as a main component has an ion exchange capacity. Specifically, they are stevensite, hectorite, and saponite. More preferred are stevensite and saponite, and particularly preferred is stevensite. Ion exchange capacity is 0.1 me
It is preferably q / g or more, more preferably 0.2 meq / g or more, and particularly preferably 0.4 meq / g or more.

Among the layered clay minerals containing Si and Mg as main components, stevensite, hectorite, and saponite will be described in more detail as examples of layered clay minerals having an ion exchange ability. Similar to talc, stevensite, hectorite, and saponite have a three-layer structure including a 3-octahedral layer. In general, clay minerals are non-stoichiometric compounds, and their compositions are complicated because they contain impurities. However, the ideal composition of stevensite is represented by Formula 1.

[0019]

## EQU1 ## Na _2x (Mg _6-x ) [Si ₄ ] ₂ O ₂₀ (OH) ₄ .nH ₂ O Formula 1

The stevensite has a defect in the Mg site of the 3-octahedral layer, and Na ions corresponding to the shortage of the electric charge exist between the layers. This Na ion is ion-exchangeable, and stevensite has an ion-exchange capacity. Equation 1
Therefore, the value of x is usually about 0 to 1. The ideal composition of hectorite is represented by Equation 2.

[0021]

Formula 2 Na _x (Mg _6-x Li _x ) [Si ₄ ] ₂ O ₂₀ (OH) ₄ · nH ₂ O Formula 2

In the hectorite, Li substitutes for the Mg site of the 3-octahedral layer, and Na ions corresponding to the shortage of the electric charge exist between the layers. This Na ion is ion-exchangeable, and hectorite has an ion-exchange ability. Equation 2
Therefore, the value of x is usually about 0 to 1. The ideal composition of saponite is represented by Equation 3.

[0023]

[Formula 3] Na _yx (Mg _6-x Al _x ) [Si _8-y Al _y ] O ₂₀ (OH) ₄ · nH ₂ O dashi y−x> O Formula 3

In the saponite, Al substitutes for the Si site of the tetrahedral layer and the Mg site of the 3-octahedral layer, and Na ions corresponding to the shortage of the electric charge exist between the layers. This Na ion can be ion-exchanged, and saponite has an ion-exchange ability. In Expression 3, the value of y is usually about 0 to 1 and the value of x is smaller than that.

The layered clay mineral containing Si and Mg as main components used in the present invention may be a natural product or a synthetic product, but a synthetic product is preferable. Generally, synthetic products tend to have higher purity and larger surface area. The surface area is 100
m ² / g or more is necessary, and preferably 20
0 m ² / g or more, more preferably 300 m ² / g or more, even more preferably 400 m ² / g or more and 700 m
² / g or less. If the surface area is less than 100 m ² / g, the effect of the present invention will not substantially appear.

Further, Si and M used in the present invention
The average pore diameter of the layered clay mineral containing g as a main component is preferably 1 nm or more and 10 nm or less, more preferably 2 nm or more and 8 nm or less, still more preferably 3 nm or more and 5 nm or less, as measured by a nitrogen adsorption method. .

At least a part of the cations of the ion-exchangeable layered clay mineral containing Si and Mg as the main components used in the present invention is preferably exchanged with ammonium ions or hydrogen ions. Ammonium ions are converted into hydrogen ions by desorption of ammonia by the baking treatment described later. The ion exchange rate is preferably 30% or more,
More preferably 50% or more, even more preferably 8
0% or more. Clay intercalation compounds obtained by intercalating various substances by utilizing the cation exchange ability are not preferred in the present invention.

The amorphous metal oxide used in the present invention is an amorphous and chemically stable metal oxide, and those usually used for hydrogenolysis can be used. Specific examples thereof include composite oxides such as silica / alumina and alumina / boria, and single oxides such as γ-alumina. Among these, complex oxides having acidity are preferable, and silica / alumina is particularly preferable.

The amount of the layered clay mineral containing Si and Mg as the main components used in the carrier of the present invention is 2-80 with respect to the carrier.
Mass% is preferable, 5-60 mass% is more preferable,
More preferably, it is 10 to 40% by mass. Further, the amount of the amorphous metal oxide used in the carrier of the present invention is preferably 20 to 98% by mass, and 40 to 95% by mass with respect to the carrier.
Is more preferable, and 60 to 90 mass% is even more preferable. Since the amorphous metal oxide also serves as a binder, it is usually unnecessary to add a binder.

Further, a small amount of the third component may be added to the carrier used in the present invention. However, the addition of zeolite or the like having a high decomposition activity has an unfavorable effect such as a decrease in middle distillate selectivity.

The carrier used in the present invention can be molded by any method. Specific examples include extrusion molding, tablet molding, and oil drop method. The carrier after molding is preferably baked. The firing temperature is 200-7
00 ° C is preferable, and 400 to 600 ° C is more preferable. Firing at high temperature may destroy the layered clay mineral.

The hydrocracking catalyst of the present invention comprises at least one metal selected from metals of Group VIII of the Periodic Table or a compound thereof and at least one selected from metals of Group VIA of the Periodic Table on the above carrier. The metal or the compound thereof is supported. The Group VIII metal of the periodic table specifically includes Fe, Co, Ni, Ru, Rh, Pd, Os and I.
r and Pt. Ni and Co are preferable, and Ni is more preferable. These metals may be used alone or in combination of two or more kinds. The Group VIA metal of the periodic table specifically includes Cr, Mo, W
Refers to. Mo and W are preferable, and W is more preferable. These metals may be used alone or in combination of two or more kinds.

With respect to the Group VIII metal of the periodic table, the amount of the metal supported is preferably in the range of 2 to 20% by mass, more preferably 5 to 15% by mass, and even more preferably 8 to 12% by mass, based on the whole catalyst. More particularly preferred. Regarding the Group VIA metal of the Periodic Table, the supported amount of the metal is preferably in the range of 3 to 30% by mass as an oxide based on the whole catalyst,
25% by mass is more preferable, and 10 to 20% by mass is particularly preferable. As a method for supporting these active metals, an impregnation method, a kneading method, or the like can be prepared, but an impregnation method is preferable, and an adsorption method, an evaporation dryness method,
The spray method is preferred. Further, a method of previously supporting all or part of the above metal by ion exchange or the like on the layered clay mineral is also effective.

In the hydrocracking method of the present invention, the reactor may be of any type, and may be a fixed bed, a fluidized bed, an expanded bed or a suspension bed, but a fixed bed is preferred. The reaction mode may be either a flow method or a batch method, but the flow method is preferable. When a fixed bed flow reactor is used, the hydrocracking catalyst of the present invention can be used alone, but it is preferable to charge the pretreatment catalyst in the preceding stage to carry out the reaction.

When the pretreatment catalyst is used, an ordinary catalyst used in the hydrodesulfurization treatment of petroleum distillate oil can be used as the pretreatment catalyst, but Mo is used as a stable amorphous metal oxide carrier. A catalyst supporting at least one metal selected from W, Ni and Co is preferable. A catalyst in which at least one metal selected from Ni and Co and at least one metal selected from Mo and W is supported on alumina or silica-alumina is more preferable. A catalyst in which Ni and / or Co and Mo are supported on alumina is particularly preferable. The supported amount of these metals is preferably in the range of 3 to 30 mass% as an oxide.

The pretreatment catalyst and hydrocracking catalyst used in the present invention are preferably subjected to sulfurization treatment before the reaction. The sulfurating treatment can be performed by a known method. Examples of the sulfiding agent used for the sulfiding treatment include hydrogen sulfide, carbon disulfide, dimethyl disulfide and the like.

The feed oil used in the hydrocracking method of the present invention is a heavy hydrocarbon oil having a boiling point of 250 to 600.
C. heavy hydrocarbon oils are preferred. Examples thereof include vacuum gas oil, atmospheric distillation residual oil, vacuum distillation residual oil, and the like. Especially, vacuum gas oil is preferable. The reaction temperature is preferably 300 to 500 ° C, more preferably 340 to 450 ° C, and particularly preferably 350 to 430 ° C. The reaction temperature here means the average temperature in the reactor. The reaction pressure is preferably 2 to 20 MPa, more preferably 3
˜15 MPa, more preferably 5˜13 M
Pa. The reaction pressure here means the total pressure in the reactor. The hydrogen gas used in the reaction may be pure hydrogen gas or a mixed gas containing hydrogen. For example, a gas rich in hydrogen gas obtained from a catalytic reforming device, a bleed gas from another hydrotreating device, or the like can be preferably used. Hydrogen purity of hydrogen gas used is 60% by volume
The above is preferable, more preferably 70% by volume or more, and particularly preferably 80% by volume or more.

LHSV (liquid hourly space velocity) is 0.05 to 10
h ^-1 are preferred, more preferably 0.1～5H ^-1, more particularly preferably 0.2~3h ^-1. The LHSV referred to here is a value with respect to the total amount of the pretreatment catalyst and the hydrocracking catalyst. Hydrogen / oil ratio is 20
Preferably 0~1500Nm ³ / m ^3, more preferably from 300~1000Nm ³ / m ^3, more especially preferably 400~800Nm ³ / m ^3.

[0039]

The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the scope of the examples. (Example 1) Na-type synthetic stevensite (trade name: I
ONITE-T, Mizusawa Chemical Co., Ltd.)
80 ° C with stirring in an ammonium nitrate aqueous solution,
Ion-exchanged for 3 hours and passed through. After repeating this operation 3 times, it was washed and dried. The surface area of this ammonium type ion-exchanged stevensite was 459 m ² / g. 70% by weight of silica and 30% by weight of alumina in a dry state
The silica-alumina hydrogel prepared as described above was filtered, washed, and kneaded. When kneading, the above-mentioned ion-exchanged stevensite was added. The amount added was adjusted to 10% by mass in the dry state. After kneading, extrusion molding was performed so that the diameter was 1/16 inch, drying and firing were performed to prepare a catalyst carrier.

On this carrier, Ni and W were loaded by an impregnation method so as to be 11% by mass and 20% by mass in terms of NiO and WO ₃ , respectively, and calcined to obtain a hydrocracking catalyst. Table 1 shows the properties of the catalyst.

67 cm ³ of a catalyst supporting Ni and Mo in γ-alumina at 5% by mass and 20% by mass in terms of NiO and MoO ₃ , respectively, was charged as a pretreatment catalyst at the inlet side of the fixed bed flow system reactor. Then, 133 cm ³ of the hydrocracking catalyst shown in Table 1 was filled at the outlet side thereof, followed by sulfurization treatment, and under the conditions shown in Table 3, the feedstock oil (vacuum gas oil) having the properties shown in Table 2 was hydrogenated. It was decomposed. Reaction temperature 380
After setting the temperature to 96 ° C. and holding for 96 hours, the conversion rate was measured. The conversion rate is defined by Equation 4.

[0042]

(Equation 4)

The reaction rate was calculated from the first-order reaction rate equation using this conversion rate. After that, the reaction temperature was changed so that the conversion rate was 60% and the temperature was held for 96 hours, and then the selectivity of kerosene and light oil was determined. The reaction results are shown in Table 4.

(Example 2) Instead of the Na-type synthetic stevensite, Mizuka Life (trade name, Mizusawa Chemical Industry Co., Ltd.), a silica magnesia-based mineral showing almost the same XRD (X-ray diffraction) peak pattern as smectite, was used. Ion exchange was performed in the same manner as in Example 1. The surface area of this Mizuka Life ion-exchanged to ammonium type was 550 m ² / g. The hydrocracking treatment was carried out in the same manner as in Example 1 except that the hydrocracking catalyst prepared in the same manner as in Example 1 was used in place of the ion-exchanged stevensite to use ion-exchanged Mizuka Life. The results are shown in Table 4.

(Example 3) Instead of Na-type synthetic stevensite, Na-type synthetic hectorite (trade name; IO
(NITE-H, Mizusawa Chemical Co., Ltd.) was ion-exchanged in the same manner as in Example 1. The surface area of the hectorite ion-exchanged to the ammonium type was 526 m ² / g. The hydrocracking treatment was performed in the same manner as in Example 1 except that the ion-exchanged hectorite was used in place of the ion-exchanged stevensite and the hydrocracking catalyst prepared in the same manner as in Example 1 was used. The results are shown in Table 4.

Example 4 In place of the Na-type synthetic stevensite, Na-type synthetic saponite (trade name; Smecton SA, Kunimine Industries Co., Ltd.) was ion-exchanged in the same manner as in Example 1. The surface area of this ammonium type ion-exchanged saponite was 366 m ² / g. A hydrocracking treatment was performed in the same manner as in Example 1 except that an ion-exchanged saponite was used instead of the ion-exchanged stevensite and the hydrocracking catalyst prepared in the same manner as in Example 1 was used. The results are shown in Table 4.

Comparative Example 1 Hydrocracking was carried out in the same manner as in Example 1 except that the catalyst prepared in the same manner as in Example 1 was used without adding stevensite. Table 4 shows the results
It was shown to.

(Comparative Example 2) Instead of the ion-exchanged stevensite, acid-type Y zeolite (SiO ₂ / Al ₂
O ₃ ratio 40, Tosoh Corporation) was used, and hydrocracking was performed in the same manner as in Example 1 except that the catalyst prepared in the same manner as in Example 1 was used. The results are shown in Table 4.

Comparative Example 3 Instead of the Na-type synthetic stevensite, Na-type natural sepiolite was ion-exchanged in the same manner as in Example 1. The surface area of this ammonium-type ion-exchanged sepiolite was 260 m ² / g. A hydrocracking treatment was carried out in the same manner as in Example 1 except that the ion-exchanged sepiolite was used in place of the ion-exchanged stevensite and the catalyst prepared in the same manner as in Example 1 was used. The results are shown in Table 4.

Comparative Example 4 Instead of the Na-type synthetic stevensite, Na-type montmorillonite was ion-exchanged in the same manner as in Example 1. The surface area of the ammonium type ion-exchanged montmorillonite was 45 m ² / g. The hydrogenolysis treatment was carried out in the same manner as in Example 1 except that ion-exchanged montmorillonite was used in place of the ion-exchanged stevensite and the catalyst prepared in the same manner as in Example 1 was used. The results are shown in Table 4.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

As is clear from Table 4, the catalysts of the present invention (catalysts of Examples 1 to 4) are heavy hydrocarbon oils to kerosene,
It can be seen that high hydrocracking activity can be realized without reducing the selectivity of middle distillates such as light oil. The hydrocracking method of the present invention (Examples 1 to 4) is an excellent method for producing middle distillates such as kerosene and light oil from heavy hydrocarbon oil with high conversion and high selectivity. I understand.

(Example 5) Na-type synthetic stevensite (trade name; IONITE-T, Mizusawa Chemical Industry Co., Ltd.)
Was placed in a 3.5 M ammonium nitrate aqueous solution and ion-exchanged at 80 ° C. for 3 hours with stirring to filter. This operation 3
After repeating the process once, it was washed and dried. The surface area of this ammonium-typed stevensite was 459 m ^2.
/ G. Separately filter and wash the alumina hydrogel,
I kneaded. When kneading, the above-mentioned ion-exchanged stevensite was added. The amount added was adjusted to 10% by mass in the dry state. After kneading, extrusion molding was performed so that the diameter was 1/16 inch, drying and firing were performed to prepare a catalyst carrier. Ni and W were carried on this carrier by an impregnation method so that they would be 11% by mass and 20% by mass, respectively, in terms of NiO and WO ₃ , and were calcined to obtain a hydrocracking catalyst. A hydrocracking treatment was carried out in the same manner as in Example 1 except that the hydrocracking catalyst was used.
Table 5 shows the results. The definition of the conversion rate is the same as that used in Examples 1 to 4.

(Comparative Example 5) A hydrocracking treatment was carried out in the same manner as in Example 1 except that the same catalyst as in Comparative Example 1 and the feedstock oil (normal pressure distillation residual oil) having the properties shown in Table 6 were used. . Table 5 shows the results
It was shown to.

(Example 6) Na-type synthetic stevensite (trade name: IONITE-T, Mizusawa Chemical Industry Co., Ltd.)
Was placed in a 3.5 M ammonium nitrate aqueous solution and ion-exchanged at 80 ° C. for 3 hours with stirring to filter. This operation 3
After repeating the process once, it was washed and dried. The surface area of this ammonium-typed stevensite was 459 m ^2.
/ G. Separately filter and wash the alumina hydrogel,
I kneaded. When kneading, the above-mentioned ion-exchanged stevensite was added. The amount added was adjusted to 10% by mass in the dry state. After kneading, extrusion molding was performed so that the diameter was 1/16 inch, drying and firing were performed to prepare a catalyst carrier. On this carrier, Ni and Mo were carried by the impregnation method so that they would be 5% by mass and 15% by mass, respectively, in terms of NiO and MoO ₃ , and baked to obtain a hydrocracking catalyst. Ni was added to γ-alumina as a pretreatment catalyst at the inlet side of the fixed bed flow system reactor.
The catalyst was loaded with 100 cm ³ of Ni and Mo so as to be 2% by mass and 5% by mass in terms of O and MoO ₃ , respectively.
After filling the outlet side with 100 cm ³ of the above-mentioned hydrocracking catalyst, it was subjected to sulfurization treatment, and under the reaction conditions shown in Table 7, the feedstock having the properties shown in Table 6 (atmospheric pressure distillation residual oil) was hydrocracked. Processed. The reaction temperature was set to 400 ° C., the temperature was maintained for 1500 hours, and then the conversion rate was measured. The conversion rate is defined by Equation 4. The results are shown in Table 8.

Comparative Example 6 A catalyst was prepared by the same preparation method as in Example 6 except that the same zeolite as that used in Comparative Example 2 was added instead of the synthetic stevensite. The amount of supported metal is 5% by mass in terms of NiO and MoO ₃ , respectively.
It was set to 15% by mass. A hydrocracking treatment was carried out in the same manner as in Example 6 except that the catalyst was used. The results are shown in Table 8.

Comparative Example 7 A catalyst was prepared by the same preparation method as in Example 6, but containing no layered clay mineral. The amount of supported metal was 5% by mass and 15% by mass in terms of NiO and MoO ₃ . A hydrocracking treatment was carried out in the same manner as in Example 6 except that the catalyst was used. The results are shown in Table 8.

[0061]

[Table 5]

[0062]

[Table 6]

[0063]

[Table 7]

[0064]

[Table 8]

As is clear from Table 5, it was found that under the same conditions, the catalyst of the present invention can obtain a high cracking activity and a high middle distillate yield. As is clear from Table 8, the decomposition activity (360 ° C ⁺ conversion) of the catalyst of the present invention (catalyst of Example 6) is lower than that of zeolite, but the yield of middle distillate is high.

[0066]

The catalyst of the present invention can realize high hydrocracking activity without deteriorating the selectivity of middle distillates such as kerosene and light oil from heavy hydrocarbon oils. Further, the hydrocracking method of the present invention is a high conversion rate from a heavy hydrocarbon oil, kerosene with a high selectivity,
It is an excellent method for producing middle distillates such as light oil.

Claims (4)

[Claims] 1. A carrier having a surface area of 100 m ² / g or more and containing a layered clay mineral containing Si and Mg as main components and an amorphous metal oxide, and at least one selected from Group VIA metals of the periodic table. A heavy hydrocarbon oil hydrocracking catalyst comprising at least one metal selected from the group consisting of metals and Group VIII metals. 2. A carrier having a surface area of 100 m ² / g or more and containing a layered clay mineral containing Si and Mg as main components and an amorphous metal oxide, and at least one selected from Group VIA metals of the periodic table. A method for hydrocracking a heavy hydrocarbon oil, which comprises contacting the heavy hydrocarbon oil with hydrogen in the presence of a catalyst containing one metal and at least one metal selected from Group VIII metals. 3. The method for hydrocracking a heavy hydrocarbon oil according to claim 2, wherein the heavy hydrocarbon oil is a vacuum gas oil. 4. The method for hydrocracking heavy hydrocarbon oil according to claim 2, wherein the heavy hydrocarbon oil is atmospheric distillation residual oil or vacuum distillation residual oil.