JP2651472B2 - Novel catalytic cracking catalyst composition and catalytic cracking method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalytic composition for catalytic cracking of hydrocarbon oils and a catalytic cracking method for hydrocarbon oils using the same. The present invention relates to a catalyst composition for catalytic cracking that can be carried out and a method for catalytically cracking a hydrocarbon oil using the composition.

[0002]

BACKGROUND OF THE INVENTION Generally, in petroleum refining technology, the most important issue is to produce catalytic cracked gasoline with a high octane number in good yield. Recently, however, due to the situation of crude oil and the market trend of petroleum products, atmospheric distillation has been considered. Utilization as an oil-whitening technology for decomposing residual oil or vacuum distillation residual oil (hereinafter referred to as residual oil) plays an important role. USYY is a catalyst for obtaining catalytic cracking gasoline having a high octane number.
A method using a catalyst comprising a stabilized Y zeolite such as zeolite (ultra-stable Y zeolite) and an inorganic oxide matrix has been proposed (JP-A-51-107294).
No. 54-161593. However, when catalytic cracking of hydrocarbon oil is carried out using a catalyst containing stabilized Y zeolite, there are problems such as that a large amount of olefin is contained in the gasoline fraction. On the other hand, as a catalyst aimed at improving the decomposability of residual oil, silica-alumina or boehmite is used as an inorganic oxide matrix, and Y or stabilized Y zeolite is mixed with these oxide matrices. A technique has been proposed for imparting activity to an inorganic oxide matrix (Japanese Patent Laid-Open No.
8-163439). However, also in this case, there is a problem that the olefin content in the gasoline fraction is increased, and also the production of coke and hydrogen is increased. In any case, the olefin content increases, which is not preferable in terms of gasoline quality. As a countermeasure, conventionally, the use of a catalyst in which zeolite is ion-exchanged with a rare earth element is used to reduce the olefin content.
When this catalyst is used, the octane number must be reduced.

[0003]

An object of the present invention is to provide a catalytic cracking catalyst composition which has a high octane value despite the low olefin content and can suppress the production of hydrogen and coke in the catalytic cracking of hydrocarbon oils, especially residual oils. It is another object of the present invention to provide a method for catalytically cracking a hydrocarbon oil using the catalyst composition.

[0004]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies in order to achieve the above-mentioned object, and as a result, have found that the stabilized Y zeolite disclosed in Japanese Patent Application No. 2-172500 can be thermally treated under certain conditions. Based on a loaded crystalline aluminosilicate, it is ion-exchanged with one active metal selected from the group consisting of a rare earth element, Mg and Ca, or a metal-modified type crystal having the metal supported thereon. We have found that a mixture of an aluminosilicate and an inorganic oxide matrix can be used, and have completed the present invention.

The catalyst composition of the present invention is characterized in that (A) the crystalline aluminosilicate is (a) bulk SiO ₂ / Al ₂ O by chemical composition analysis.
₃ molar ratio of 5 to 15, (b) the molar ratio to the total Al in the zeolite framework in Al is 0.3 to 0.6, (c) unit cell dimensions of less than 24.45A, the (d) alkali metal content 0.02% by weight or more and less than 1% by weight in terms of oxide. (E) In the pore distribution, characteristic peaks are shown around 50 ° and 180 °, and the pore volume of 100 ° or more is 10 to 10% of the total pore volume. (B) the crystalline aluminosilicate of (A) is at least one selected from the group consisting of rare earth elements, Mg and Ca
Ion-exchanged with or carried by the species of metal, said metal containing from 0.2% to 15% by weight as oxide, based on the metal-modified aluminosilicate, and A metal-modified crystalline aluminosilicate characterized by having a main X-ray diffraction pattern is included as an essential component. Further, the catalyst composition of the present invention is characterized by being a mixture of the above catalyst composition and an inorganic oxide matrix.
The catalytic cracking method of the present invention is characterized by catalytically cracking a hydrocarbon mixture boiling above the gasoline range using the mixed catalyst.

In the production of the crystalline aluminosilicate (A) (hereinafter referred to as heat shock crystalline aluminosilicate) in the catalyst composition of the present invention, the stabilized Y zeolite used as a starting material is a so-called Y zeolite. Is obtained by performing a high-temperature, steam treatment at least once or by performing a chemical treatment, and shows resistance to deterioration of crystallinity.

[0007] The stabilized Y zeolite is SiO ₂ / Al ₂
O ₃ molar ratio of 5 to 15 and unit cell size of about 24.50
Or more and less than 24.70%, preferably about 24.50 or more and less than 24.60%, and an alkali metal content of about 0.02% by weight or more and less than 1% by weight, preferably about 0.05% by weight in terms of oxide. It refers to Y zeolite in an amount of at least 0.8% by weight. Stable Y zeolite, natural faujasite and basically have the same crystal structure, composition formula expressed as _{oxides: 0.01~1.0R 2 / m O · Al} 2 O 3 · 5~ 15S
iO ₂ .5-8H ₂ O, where R is Na, K or other alkali metal or alkaline earth metal ion, and m is its valence. The stabilized Y zeolite of the raw material used here has a low R2 _{/ mO} content among them.
The coefficient is equivalent to 0.01 to 0.1.

The heat shock crystalline aluminosilicate can be obtained by subjecting the stabilized Y zeolite to a certain thermal load. Thermal load is about 600-
1200 ° C, preferably about 600-1000 ° C, about 5
The sintering may be carried out for about 300 minutes, preferably for about 5 to 100 minutes, and under such conditions that the crystallinity reduction rate of the stabilized Y zeolite is about 20%, preferably about 15% or less. If the temperature is too low, the desired product cannot be obtained. On the other hand, if the temperature is too high or the calcination time is too long, the crystal structure of the zeolite will collapse. Usually, firing is carried out at normal pressure in an electric furnace or a firing furnace under an air or nitrogen atmosphere.
It may be fired by leaving it in an electric furnace under an air or nitrogen atmosphere of 0.5 atm. Moderate humidity easily causes dealumination and can cause heat shock even at low temperatures. It is desirable that the crystal structure of the zeolite does not collapse as much as possible under heat shock conditions, and the crystallinity reduction rate of the stabilized Y zeolite is about 20% or less,
The reaction is preferably performed under a condition of about 15% or less.

The crystallinity of the stabilized Y zeolite is AST
MD-3906 (Standard Test Me)
the for for relative zeolite
Diffraction Intensities)
Required according to law. The standard sample was a Y-type zeolite (Si / Al ratio 5.0, unit cell size 24.58 °, N
a ₂ O content of 0.3% by weight), and is determined as the relative X-ray diffraction intensity ratio between the test sample and the standard sample. The crystallinity reduction rate of the stabilized Y zeolite due to heat shock can be obtained from the following equation.

(Equation 1) Upon applying the heat shock, the sample may be placed in a firing furnace after the above temperature is reached, or after the sample is placed in the firing furnace, the temperature may be gradually raised from room temperature to reach a predetermined temperature. The heating rate is not particularly limited.

Heat-shock crystalline aluminosilicate is obtained by heat-treating stabilized Y zeolite. However, if heat-shock crystalline aluminosilicate is directly produced by heat-treating Y zeolite, the crystal structure is destroyed. , Can not achieve the purpose. Although the reason is not necessarily clear, it is necessary to first heat the Y zeolite to produce stabilized Y zeolite, wait for the crystal structure to settle in that state, that is, to stabilize, and then perform another heat treatment. It is thought that.

[0011] Heat shock crystalline aluminosilicates can be prepared from bulk (total) SiO 2 by chemical composition analysis.
₂ / Al ₂ O ₃ molar ratio of about 5 to 15, preferably about 5
Twelve. The unit cell size is less than about 24.45 °, preferably less than 24.42 °. The measurement of the unit cell size can be calculated using the peak of X-ray diffraction in accordance with ASTM D-3942 / 85. If this value is too large, the hydrothermal resistance deteriorates.

The proportion of Al in the zeolite framework relative to the total Al molar ratio is about 0.3 to 0.6, preferably about 0.3
5 to 0.6. This value is calculated from the SiO ₂ / Al ₂ O ₃ molar ratio and the unit cell size by the chemical composition analysis according to the following formulas (1) to (3) (HK Beyer).
r et al. , J. et al. Chem. Soc. , Fraa
day Trans. 1,1985,81,2899
page).

N _Al = (a ₀ -2.425) /0.000068 (1) a ₀ : unit cell dimension [nm] N _Al : number of Al atoms per unit cell (Si / Al) calculation formula = (192-N _Al ) / N _Al (2) _{Al in} zeolite framework / total Al = (Si / Al) chemical composition analysis / (Si / Al) calculation formula (3)

The expression (2) is obtained from the fact that the number of (Si / Al) atoms per unit cell size of Y zeolite is 192. Bulk SiO ₂ / Al ₂ O ₃
When the molar ratio is the same, if the molar ratio of Al in the zeolite framework to the total Al is too small, the catalytic activity required for catalytic cracking is lost. In general, in the case of stabilized zeolite, since the extra-skeleton Al, that is, the amorphous Al ratio is high, the selectivity also shows a behavior close to that of an amorphous catalyst,
Hydrogen generation, coke production and the amount of olefins in gasoline increase. On the other hand, in the case of heat-shock crystalline aluminosilicate, when the proportion of extra-framework Al increases, the generation of hydrogen, the amount of coke produced, and the amount of olefin in gasoline decrease. Although the reason is not clear, it is considered that a new active site is generated by the reaction between the silica gel and the extra-skeleton Al during the preparation of the catalyst. If the Al molar ratio in the zeolite framework relative to the total Al is too large, the amount of olefin in gasoline decreases, but the hydrothermal resistance of the catalyst decreases and the amount of coke generated increases.

The content of the alkali metal or alkaline earth metal oxide is from about 0.02% by weight to about 1.0% by weight.
Less than about 0.05% by weight, preferably about 0.8% by weight
Is less than. When a large amount of an alkali metal or alkaline earth metal is present in the crystalline aluminosilicate, the decomposition activity of the catalyst is reduced, and nickel, which is a heavy metal contained in the base oil, especially heavy oil base oil, When vanadium or the like adheres, there is a problem that the activity is easily deteriorated. If the content of the alkali metal or alkaline earth metal oxide is less than 0.02% by weight, the crystal structure is likely to collapse, which is not preferable.

The ratio of the pore volume of 100 ° or more to the total pore volume is about 10 to 40%, preferably about 10 to 35%.
%. If this ratio is too small, the ratio of small pores becomes large, the reactivity becomes worse though the molecular diameter is large, the bottom resolution (heavy fraction resolution) 1 is lowered, and the product after decomposition is Since it is difficult to separate quickly, the amount of coke generated increases. Conversely, if it is too large, the ratio of large pores increases, the surface area decreases, and the reactivity deteriorates. The heat shock crystalline aluminosilicate has a pore distribution of about 50 ° and about 18 °.
It shows a characteristic peak near 0 ° and has a main X-ray diffraction pattern of Y zeolite. The pore distribution and the pore volume can be determined by applying the BET surface area measurement method and the capillary condensation method.

Heat shock crystalline aluminosilicates can be obtained by subjecting a stabilized Y zeolite to a constant thermal load, a major feature of which is that the unit cell size is less than about 24.45 ° and the stabilized Y About 2 of zeolite
It is smaller than 4.50 ° to less than 24.70 °, and the pore distribution is about 50 ° and about 180 °.
This is a point showing a characteristic peak near Å. And one more
As one of the features, ²⁷ Al-MAS (Magic An)
gleSpinning) NMR spectrum,
The heat-shock crystalline aluminosilicate exhibits three characteristic peaks (see FIG. 1), while the stabilized Y zeolite exhibits two peaks (see FIG. 2).
The horizontal axis in FIGS. 1 and 2 is Al (NO
₃ ) The shift value (ppm) from the peak of ₃ is shown, and the vertical axis is the spectrum intensity. 1 and 2, the peak indicates a peak due to tetracoordinate Al, that is, Al in the crystal lattice, the peak indicates a peak of pentacoordinate Al,
The peak is a peak due to hexacoordinate Al, that is, Al outside the crystal lattice. 5-coordinate Al appearing in this peak
Is, for example, Am. Chem. Soc. , 1986,
108, 6158 to 6162, it seems to be an unstable form of Al on the way from the four-coordinate Al in the crystal lattice to the six-coordinate Al out of the lattice. However, even though a long time has passed after the heat shock, the catalyst has a 5-coordinate Al peak, but is hidden by the peak indicating that the catalyst is in a hydrated state, and the 5-coordinate peak is not detected.
The hydration state here means that it is left at room temperature in the air for about 1 hour.
A weekly low level.

The metal-modified crystalline aluminosilicate of the present invention is characterized in that the crystalline aluminosilicate of (A) is at least one selected from the group consisting of rare earth elements, Mg and Ca.
Heat-shock crystalline aluminosilicate (hereinafter, abbreviated as ion-exchange or supported for simplicity) that has been ion-exchanged with or supported by the same metal
These are heat-shock metal ion-exchange crystalline aluminosilicate and heat-shock metal-carrying crystalline aluminosilicate, respectively, and are collectively referred to as heat-shock metal-modified crystalline aluminosilicate. As rare earth elements,
Scandium, yttrium, lanthanum, cerium, actinium, etc., and a mixture thereof may be used, preferably lanthanum. High-octane gasoline can be produced by ion exchange or loading with such a metal.

The ion exchange can be performed on the heat-shock crystalline aluminosilicate by a conventionally known method. In addition, loading can be performed by a conventionally known method. For example, chlorides such as lanthanum, magnesium, and calcium, nitrates, sulfates, acetates, and the like are used as the compounds of the above-mentioned metals, and an aqueous solution containing one or more of these metal compounds is dried with the above-mentioned dried product. Or immersed in these aqueous solutions, and further, if necessary, by heating. The metal to be ion-exchanged or supported is 0.2 to 15% by weight as an oxide based on the heat shock metal-modified crystalline aluminosilicate;
Preferably it is 0.5 to 8.0% by weight. If the amount of metal is too small, the effect does not appear, and if it is too large, the effect does not increase much.

Further, the heat shock metal-modified crystalline aluminosilicate substantially has the X-ray diffraction pattern shown in FIG. In FIG. 3, 1, 2 and 3 are peaks of the lattice spacing (d) showing the strongest diffraction, and are 14.1 ± 0.
2 °, 5.61 ± 0.1 ° and 3.72 ± 0.1 °. The X-ray diffraction diagram of FIG. 3 shows Table 1 as a representative example.
.

[0020]

[Table 1]

The catalyst composition of the present invention also includes a mixture of the above-mentioned heat shock metal-modified crystalline aluminosilicate and an inorganic oxide matrix. Examples of the inorganic oxide matrix include silica, alumina, boria, chromia, magnesia, zirconia, titania, silica-alumina, silica-magnesia, silica-zirconia, chromia-alumina, titania-alumina, titania-silica, titania-titanium. It is zirconia, alumina-zirconia or the like, or a mixture thereof, and may contain at least one kind of clay mineral such as montmorillonite, kaolin, halloysite, bentonite, attapulgite, and bauxite. A method for producing a mixture of the inorganic oxide matrix and the above-mentioned heat-shock metal-modified crystalline aluminosilicate can be performed by a usual method, and typically, as a suitable inorganic oxide matrix, for example, silica- Alumina hydrogel,
An aqueous slurry of silica sol or alumina sol is used, and the above-mentioned heat shock metal-modified crystalline aluminosilicate is added thereto, mixed well, stirred, and then spray-dried to obtain catalyst fine particles. In this case, the heat shock metal-modified crystalline aluminosilicate in the mixed catalyst composition is about 5 to 60% by weight, preferably about 1 to 60% by weight.
0 to 50% by weight, about 40 to 9 inorganic oxide matrix
5% by weight, preferably about 50 to 90% by weight, can be added and used. Therefore, the amount of active metal after mixing is about 0.0 as an oxide on a mixed catalyst basis.
1 to 9.0% by weight.

Further, in the catalytic cracking method of the present invention, a hydrocarbon mixture boiling above the gasoline range is catalytically cracked using a mixture of the above-mentioned heat shock metal-modified crystalline aluminosilicate and an inorganic oxide matrix. Is the way. The hydrocarbon mixture boiling above the gasoline range means a gas oil fraction obtained by normal or reduced pressure distillation of crude oil, a normal distillation residue and a reduced pressure distillation residue, and of course coker gas oil, solvent deasphalted oil, Solvent deasphalted asphalt, tar sand oil, shale oil oil, and coal liquefied oil are also included.

[0023] Catalytic cracking on a commercial scale usually involves two processes, a vertically mounted cracking reactor and a catalyst regenerator.
The above-mentioned catalyst composition is continuously circulated through a seed container. The hot regenerated catalyst exiting the catalyst regenerator is mixed with the cracked oil and directed upward in the cracking reactor. As a result, the deactivated catalyst is separated from the decomposition products by analyzing the carbonaceous material generally called coke on the catalyst, and is transferred to the catalyst regenerator after stripping. The cracked products are separated into dry gas, LPG, gasoline fraction and one or more heavy fractions such as light cycle oil (LCO), heavy cycle oil (HCO) or slurry oil. You. Of course, the cracking reaction can be further promoted by recycling these heavy fractions to the cracking reactor. The spent catalyst transferred to the catalyst regenerator is regenerated by removing the coke on the catalyst by air calcination, and is recycled again to the cracking reactor. The operating conditions are as follows: pressure is normal pressure to 5 kg / c.
m ² , preferably normal pressure to 3 kg / cm ² , temperature 400
The temperature is preferably from 600 to 600 ° C., preferably from 450 to 550 ° C., and the weight ratio of catalyst / raw material is from 2 to 20, preferably from 5 to 15.

[0024]

Example 1 (Production of heat shock crystalline aluminosilicate) Si
The O ₂ / Al ₂ O ₃ molar ratio is 7, the alkali metal content is 0.2 wt% in terms of oxide, and the unit cell size is about 24.58.
安定 stabilized Y zeolite in an electric furnace in an air atmosphere,
It was calcined at 800 ° C. for 10 minutes at normal pressure to obtain a crystalline aluminosilicate having excellent hydrothermal stability. When this product was analyzed, it had the physical properties shown in Table 2. In addition, the crystallinity was 112% after the heat shock (3.5% decrease in crystallinity) with respect to 116% of the stabilized Y zeolite of the raw material (assuming the standard Y zeolite was 100%). The pore distribution was as shown in FIG. This catalyst is designated as HZ-1.

[0025]

[Table 2]

(Production of Heat Shock Lanthanum Crystalline Aluminosilicate by Ion Exchange) The above-mentioned catalyst HZ-1 was treated with a 10-fold amount of 0.2N lanthanum chloride aqueous solution at 90 ° C. and 0.1%.
Ion exchange for 5 hours, then rinse with water, then 115
After drying at 16 ° C. for 16 hours, baking was performed at 550 ° C. for 3 hours. This zeolite showed the main X-ray diffraction pattern of Y zeolite.

(Preparation of catalyst composition) Next, 46.3 g of water
And 46.7 g of silica gel having a concentration of 30% by weight were stirred and mixed to adjust the pH to a predetermined value, and then kaolin was dried on a dry basis.
5 g, 24.5 g of the above-mentioned lanthanum crystalline aluminosilicate on a dry basis, and 74 g of water were further added and mixed with stirring. The resulting mixture was dried and atomized with a spray drier, and washed five times with 2000 ml of distilled water. Then 1
After drying at 15 ° C. for 16 hours, the catalyst composition of the present invention (hereinafter referred to as “the catalyst composition”)
Catalyst A) was obtained. The amount of lanthanum in this catalyst A was 1.3% by weight as an oxide based on the mixed catalyst.

Example 2 (Production of Heat Shock Crystalline Aluminosilicate) HZ-1 obtained in Example 1 was used. (Production of magnesium crystalline aluminosilicate by ion exchange) Instead of 0.2N lanthanum chloride aqueous solution, 0.1
Example 1 except that a 2N aqueous magnesium nitrate solution was used.
In the same manner as in the above, a magnesium crystalline aluminosilicate was obtained. (Preparation of catalyst composition) A catalyst composition of the present invention (hereinafter referred to as catalyst B) was prepared in the same manner as in Example 1 except that magnesium crystalline aluminosilicate was used instead of lanthanum crystalline aluminosilicate. Obtained. The amount of magnesium in this catalyst B was 0.2% by weight as an oxide based on the mixed catalyst.

Example 3 (Production of calcium crystalline aluminosilicate by ion exchange) [0029] 0.17 instead of 0.2N lanthanum chloride aqueous solution
A calcium crystalline aluminosilicate was obtained in the same manner as in Example 1 except that an N calcium nitrate aqueous solution was used. (Preparation of catalyst composition) A catalyst composition of the present invention (hereinafter referred to as catalyst C) was prepared in the same manner as in Example 1 except that calcium crystalline aluminosilicate was used instead of lanthanum crystalline aluminosilicate. Obtained. The amount of calcium in this catalyst C was 0.4% by weight as an oxide based on the mixed catalyst.

Comparative Example 1 A comparative catalyst composition (hereinafter referred to as Catalyst D) was prepared in the same manner as in Example 1 except that the stabilized Y zeolite used in Example 1 was used instead of the catalyst HZ-1. The amount of lanthanum in this catalyst D was 1.3% by weight as an oxide based on the mixed catalyst. Comparative Example 2 A comparative catalyst composition (hereinafter, referred to as catalyst E) was prepared in the same manner as in Example 2, except that the stabilized Y zeolite used in Example 1 was used instead of the catalyst HZ-1. The amount of magnesium in this catalyst E was 0.2% by weight as an oxide based on the mixed catalyst. Comparative Example 3 A comparative catalyst composition (hereinafter, referred to as catalyst F) was prepared in the same manner as in Example 3, except that the stabilized Y zeolite used in Example 1 was used instead of the catalyst HZ-1. The amount of calcium in this catalyst F was 0.4% by weight as an oxide based on the mixed catalyst.
Met.

[Bench Scale Plant Activity Test] A bench scale plant which is a scale down version of a commercial scale catalytic cracker and is a circulating fluidized bed reactor equipped with a cracking reactor and a catalyst regenerator. The catalytic cracking characteristics of the hydrocarbon oils were tested using the above catalysts A to G. Prior to the test, each test catalyst was treated at 785 ° C. for 6 hours in a 100% steam atmosphere for simulated equilibrium. The feed oil used was desulfurized vacuum gas oil. The test conditions were a reaction temperature of 500 ° C. and a catalyst circulation rate of 60 g / min.
The procedure was performed under the conditions of 12.5, and a result based on a conversion rate of 66% was selected from the four results obtained, and the selected results were compared. Table 3 shows this comparison.
It is shown in Table 4.

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

As described in detail above, the catalyst composition of the present invention contains a heat shock metal-modified crystalline aluminosilicate into which an active metal has been introduced after a specific thermal load has been applied to the stabilized Y zeolite. According to the present invention, it is possible to provide a high octane number gasoline having excellent catalytic cracking properties of hydrocarbon oils, especially residual oils, and low olefin content. Further, according to the catalyst composition of the present invention, which is a mixture of a heat shock crystalline aluminosilicate and an inorganic oxide matrix, the above-mentioned effect, that is, the resolving power of the residual oil is further improved, and the middle distillate corresponding to the light / light oil is obtained. (LCO) yield is high, and generation of hydrogen and coke can be suppressed. Moreover, the catalyst composition of the present invention using the above mixture has excellent hydrothermal stability, so that the catalyst life can be prolonged and makeup can be reduced. According to the catalytic cracking method of the present invention using the above catalyst composition, hydrocarbon oil boiling above the gasoline range can be catalytically cracked with high efficiency, and high octane number gasoline with a low olefin content can be produced. .

[Brief description of the drawings]

FIG. 1: Heat shock crystalline aluminosilicate ²⁷
It is a figure which shows the spectrum of Al-MAS NMR.

FIG. 2: ²⁷ Al-MAS NM of stabilized Y zeolite
It is a figure which shows the spectrum of R.

FIG. 3. Heat shock crystalline aluminosilicate (HZ)
It is a figure which shows the X-ray diffraction pattern in -1) copper K- (alpha) ray.

FIG. 4 is a view showing a pore distribution of a heat shock crystalline aluminosilicate.

Claims (3)

(57) [Claims] 1. The method of claim 1, wherein (A) the crystalline aluminosilicate is (a) bulk SiO ₂ / Al ₂ O by chemical composition analysis.
₃ molar ratio of 5 to 15, (b) the molar ratio to the total Al in the zeolite framework in Al is 0.3 to 0.6, (c) unit cell dimensions of less than 24.45A, the (d) alkali metal content 0.02% by weight or more and less than 1% by weight in terms of oxide (e) In the pore distribution, characteristic peaks are shown at around 50 ° and around 180 °, and the pore volume of 100 ° or more is 10 to 10% of the total pore volume. (B) the crystalline aluminosilicate of (A) is at least one selected from the group consisting of rare earth elements, Mg and Ca
Ion-exchanged with or carried by the species of metal, said metal containing from 0.2% to 15% by weight as oxide, based on the metal-modified aluminosilicate, and Carbonization characterized by containing a metal-modified crystalline aluminosilicate characterized by having a main X-ray diffraction pattern as an essential component
Catalyst composition for catalytic cracking of hydrogen oil . 2. A hydrocarbon, which is a mixture of the catalyst composition according to claim 1 and an inorganic oxide matrix.
Catalyst composition for catalytic cracking of oil . 3. Use of the catalyst composition according to claim 2,
A catalytic cracking method characterized by catalytically cracking a hydrocarbon mixture boiling above the gasoline range.