JPH04305248A - Novel catalyst composition for contact cracking and contact cracking method used therein - Google Patents

Abstract

PURPOSE:To provide the catalyst compsn. for contact cracking of hydrocarbon oils and more particularly residual oils which have a small amt. of olefin- component and high octane value and can suppress the formation of hydrogen and coke and the contact cracking method for hydrocarbon oils using this catalyst compsn. CONSTITUTION:This catalyst compsn. consists of metal modification type crystalline alumina silicate which is obtd. after the specific crystalline aluminosilicate formed by applying thermal load under specified conditions to stabilized Y zeolite is subjected to an ion exchange with an active metal of one kind among rare earth elements, Mg and Ca or is deposited with this metal or this salt and inorg. oxide matrix. This contact cracking method executes contact cracking of a hydrocarbon mixture which oils at the gasoline range or above by using the catalyst compsn. consisting of the above-mentioned salt and inorg. oxide matrix.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a catalyst composition for catalytic cracking of hydrocarbon oils and a method for catalytic cracking of hydrocarbon oils using the same, and more specifically to the production of gasoline with excellent residual oil decomposition properties and high octane number. The present invention relates to a catalyst composition for catalytic cracking that can be used for catalytic cracking, and a method for catalytically cracking hydrocarbon oil using the composition.

0002

[Technical background] In general, the most important issue in oil refining technology is to produce catalytic cracking gasoline with a high octane number in a high yield. Its use as a white oil technology that decomposes residual oil and vacuum distillation residual oil (hereinafter referred to as residual oil) plays an important role. As a catalyst for obtaining catalytic cracking gasoline with a high octane number, USY
A method using a catalyst consisting of a stabilized Y zeolite such as zeolite (ultra-stable Y zeolite) and an inorganic oxide matrix has been proposed (Japanese Patent Application Laid-Open No. 107294-1989).
No. 54-161593). However, when hydrocarbon oil is catalytically cracked using a catalyst containing stabilized Y zeolite, there are problems such as a large amount of olefins being contained in the gasoline fraction. On the other hand, catalysts aimed at improving the decomposition properties of residual oil use silica-alumina, boehmite, etc. as an inorganic oxide matrix, and mix Y or stabilized Y zeolite with these oxide matrices. , a technology for imparting activity to an inorganic oxide matrix has been proposed (Japanese Patent Application Laid-Open No.
8-163439). However, this also leads to an increase in the olefin content in the gasoline fraction, and
A problem arises in that the production of coke and hydrogen also increases. In either case, the olefin content increases, which is unfavorable in terms of gasoline quality. As a countermeasure for this, conventionally,
Although attempts are being made to reduce the olefin content by using a catalyst in which zeolite is ion-exchanged with a rare earth element, the use of this catalyst inevitably results in a reduction in the octane number.

0003

OBJECTS OF THE INVENTION The present invention provides a catalyst composition for catalytic cracking of hydrocarbon oils, particularly residual oils, which has a high octane number despite having a low olefin content and can suppress the production of hydrogen and coke; An object of the present invention is to provide a method for catalytic cracking of hydrocarbon oil using the catalyst composition.

0004

SUMMARY OF THE INVENTION As a result of intensive studies to achieve the above object, the present inventors have discovered that the stabilized Y zeolite disclosed in Japanese Patent Application No. 172500/1990 has been thermally stabilized under certain conditions. A metal-modified crystalline product in which a loaded crystalline aluminosilicate is ion-exchanged with one type of active metal selected from the group consisting of rare earth elements, Mg, and Ca, or the metal is supported on the loaded crystalline aluminosilicate. The present invention was completed based on the finding that a mixture of an aluminosilicate and an inorganic oxide matrix can be used.

The catalyst composition of the present invention is characterized in that (A) the crystalline aluminosilicate is composed of (a) bulk Si as determined by chemical composition analysis;
O2/Al2O3 molar ratio is 5 to 15, (b) molar ratio of Al in the zeolite skeleton to total Al is 0.3 to 0.6 (
c) Unit cell size is less than 24.45 Å, (d) Alkali metal content is 0.02% or more and 1% by weight in terms of oxide.
(e) Pore distribution around 50 Å and 180 Å
(B) the above (
The crystalline aluminosilicate of A) is ion-exchanged with at least one metal selected from the group consisting of rare earth elements, Mg, and Ca, or the metal is supported, and the metal is based on the metal-modified aluminosilicate. 0.2 as oxide
% to 15% by weight, and is characterized by containing as an essential component a metal-modified crystalline aluminosilicate characterized by having the main X-ray analysis pattern of (C)Y zeolite. . The catalyst composition of the present invention is also characterized in that it is a mixture of the above catalyst composition and an inorganic oxide matrix. The catalytic cracking method of the present invention is characterized in that this mixed catalyst is used to catalytically crack a hydrocarbon mixture that boils above the gasoline range.

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 so-called Y zeolite. It is obtained by subjecting it to high temperature and steam treatment at least once, or by chemical treatment, and shows resistance to deterioration of crystallinity.

[0007] Stabilized Y zeolite is SiO2/Al2
O3 molar ratio is 5 to 15, unit cell size is about 24.50
Å or more and less than 24.70 Å, preferably about 24.50 Å or more and less than 24.60 Å, and the alkali metal content is about 0.02% or more and less than 1% by weight in terms of oxide, preferably about 0.05% by weight. This refers to Y zeolite containing less than 0.8% by weight. Stabilized Y zeolite has basically the same crystal structure as natural faujasite, and is expressed as an oxide with the composition formula: 0.01-1.0R2/mO・Al2O3・5-15S
iO2.5-8H2O (wherein R is Na, K or other alkali metal ion or alkaline earth metal ion, and m is its valence). The stabilized Y zeolite used here has a low R2/mO content,
The above coefficient is equivalent to 0.01 to 0.1.

Heat shock crystalline aluminosilicate can be obtained by subjecting the stabilized Y zeolite to a certain thermal load. The thermal load is approximately 600-1
200°C, preferably about 600-1000°C, about 5-1000°C
300 minutes, preferably within the range of about 5 to 100 minutes,
and 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, and if the temperature is too high or the firing time is too long, the crystal structure of the zeolite will collapse. Usually, firing is carried out in an electric furnace or firing furnace at normal pressure in an air or nitrogen atmosphere, but the water vapor partial pressure is approximately 0 to 0.5.
It may be fired by leaving it in an electric furnace under atmospheric pressure air or nitrogen atmosphere. Moderate humidity tends to cause dealumination and can cause heat shock even at low temperatures. Under heat shock conditions, it is desirable to prevent the crystal structure of the zeolite from collapsing as much as possible, and the heat shock is carried out under conditions where the crystallinity reduction rate of the stabilized Y zeolite is about 20% or less, preferably about 15% or less. .

The crystallinity of stabilized Y zeolite is AST
MD-3906 (Standard Test
Method for Relative Z
eolite Diffraction Inte
nsities) method. The standard sample is
Y-type zeolite (Si/Al ratio 5.0, unit cell size 2
4.58 Å, Na2O content: 0.3% by weight), and is determined as the relative X-ray diffraction intensity ratio between the test sample and the standard sample. The rate of decrease in crystallinity of stabilized Y zeolite due to heat shock is calculated from the following equation.

[Equation 1] When applying a heat shock, the sample may be placed in a firing furnace after reaching the above temperature, or the sample may be placed in the firing furnace and then gradually raised from room temperature until the specified temperature is reached. The temperature increase rate is not particularly specified.

[0010] Heat-shock crystalline aluminosilicate is obtained by heat-treating stabilized Y zeolite, but when attempting to directly produce heat-shock crystalline aluminosilicate by heat-treating Y zeolite, the crystal structure collapses. , unable to achieve the goal. The reason for this is not necessarily clear, but it is necessary to heat-treat Y zeolite to first produce stabilized Y zeolite, wait for the crystal structure to settle down in that state, that is, to stabilize, and then heat-treat it again. This is thought to be for a reason.

[0011] Heat shock crystalline aluminosilicate is characterized by bulk (as a whole) SiO2 by chemical composition analysis.
/Al2O3 molar ratio is about 5-15, preferably about 5-1
It is 2. The unit cell dimension is less than about 24.45 Å, preferably less than 24.42 Å. Unit cell size measurements can be calculated using X-ray diffraction peaks according to ASTM D-3942/85. If this value is too large, hydrothermal resistance will deteriorate.

The proportion of Al in the zeolite framework to the total Al molar ratio is about 0.3 to 0.6, preferably about 0.3.
It is 5 to 0.6. This value is calculated by the following formulas (1) to (3) from the SiO2/Al2O3 molar ratio and unit cell size obtained from the above chemical composition analysis (H.K. Beye
r et al. , J. Chem. Soc. ,Fr
aaday Trans. 1, 1985, 81, 28
99 pages).

[Math. 2] NA1=(a0-2.425)/0.0008
68 (1) a0: Unit cell size [nm] NAl: Number of Al atoms per unit cell (Si/Al) calculation formula =
(192-NAl)/NAl (2) Al in zeolite framework/total Al= (Si/A
l) Chemical composition analysis/(Si/Al) calculation formula (3)

[
[0013] Equation (2) is obtained from the fact that the number of (Si/Al) atoms per unit cell size of Y zeolite is 192. When the bulk SiO2/Al2O3 molar ratio is the same, the A in the zeolite framework relative to the total Al
If the molar ratio of l is too small, the catalytic activity necessary for catalytic cracking will be lost. In general, in the case of stabilized zeolite, the extra-skeletal Al, that is, the amorphous Al ratio increases, so the selectivity also behaves similar to that of an amorphous catalyst, and the generation of hydrogen, the amount of coke produced, and the amount of olefins in gasoline increase. do. On the other hand, in the case of heat-shock crystalline aluminosilicate, when the ratio of extra-skeletal Al increases, the generation of hydrogen, the amount of coke produced, and the amount of olefins in gasoline conversely decrease. The reason for this is not clear, but it is thought that it is because new active sites are generated due to the reaction between silica gel and extra-skeletal Al during catalyst preparation. If the molar ratio of Al in the zeolite skeleton to the total Al is too large, the amount of olefins in gasoline will decrease, but the hydrothermal resistance of the catalyst will decrease and the amount of coke produced will also increase.

The content of the alkali metal or alkaline earth metal oxide is about 0.02% by weight or more and about 1.0% by weight.
less than about 0.05% by weight, preferably about 0.8% by weight
less than If a large amount of alkali metals or alkaline earth metals are present in the crystalline aluminosilicate, the decomposition activity of the catalyst will decrease, and the heavy metal nickel, which is contained in large amounts in feedstock oils, especially heavy oil feedstocks, will decrease. If vanadium or the like adheres, a problem arises in that it is likely to cause deterioration of activity. If the content of the alkali metal or alkaline earth metal oxide is less than 0.02% by weight, the crystal structure tends to collapse, which is not preferable.

The ratio of the pore volume of 100 Å or more to the total pore volume is about 10 to 40%, preferably about 10 to 35%.
%. If this ratio is too low, the ratio of small pores will increase, the reactivity of molecules with large molecules will deteriorate, the bottom resolution (heavy fraction resolution) 1 will decrease, and the products after decomposition will be more concentrated than active sites. Because it becomes difficult to leave quickly,
This leads to an increase in the amount of coke produced. Conversely, if the amount is too large, the ratio of large pores will increase, the surface area will decrease, and the reactivity will deteriorate. In addition, the heat shock crystalline aluminosilicate has a pore distribution of around 50 Å and around 180 Å.
It shows characteristic peaks in the vicinity and has the main X-ray diffraction pattern of Y zeolite. The pore distribution and pore volume can be determined by applying the BET surface area measurement method and the capillary condensation method.

Heat shock crystalline aluminosilicate is obtained by applying a certain thermal load to stabilized Y zeolite, and its major feature is that the unit cell size is less than about 24.45 Å, and the stabilized Y zeolite Approximately 24 of zeolite
．． It is smaller than 50 Å or more and less than 24.70 Å, and the pore distribution is around 50 Å and around 180 Å.
It is a point that shows a characteristic peak nearby. Furthermore, as another feature, 27Al-MAS (Magic An
According to the gle Spinning) NMR spectrum,
The heat-shocked crystalline aluminosilicate shows three characteristic peaks (see FIG. 1), whereas the stabilized Y zeolite shows two peaks (see FIG. 2). Note that the horizontal axis of FIGS. 1 and 2 represents the standard material Al(NO
3) The shift value (ppm) from the peak of 3 is shown, and the vertical axis is the spectral intensity. In FIGS. 1 and 2, the peak ■ indicates a peak due to four-coordinated Al, that is, the peak due to Al in the crystal lattice, and the peak ■ indicates a peak due to five-coordinated Al,
The peak ■ indicates a peak due to hexacoordinated Al, that is, Al outside the crystal lattice. The five-coordinated Al appearing in this peak ■ is, for example, described in J. Am. Chem. Soc. , 1986, 1
As described in No. 08, 6158-6162, this is considered to be a form of Al in an unstable state in the process of transitioning from 4-coordinated Al in the crystal lattice to 6-coordinated Al outside the lattice. but,
Even after a long period of time after heat shock, the 5-coordinated A remains on the catalyst.
Although the l peak exists, in the hydrated state it is hidden behind the ■ and ■ peaks, and the pentacoordination peak is no longer detected. The hydrated state here refers to approximately 1 hour after being left in the air at room temperature.
This refers to a state that is reached at low levels every week.

In the metal-modified crystalline aluminosilicate of the present invention, the crystalline aluminosilicate of (A) is combined with at least one element selected from the group consisting of rare earth elements, Mg, and Ca.
Heat-shocked crystalline aluminosilicate (hereinafter referred to as ion-exchanged or supported) that has been ion-exchanged with a seed metal or has the metal supported (hereinafter abbreviated as ion-exchanged or supported for simplicity).
These are respectively referred to as heat-shock metal ion-exchanged crystalline aluminosilicate and heat-shock metal-supported crystalline aluminosilicate, and collectively referred to as heat-shock metal-modified crystalline aluminosilicate. As rare earth elements,
These include scandium, yttrium, lanthanum, cerium, actinium, etc., and mixtures thereof may be used, with lanthanum being preferred. By ion exchange or support with such metals, high octane gasoline can be produced.

Ion exchange can be performed on heat-shocked crystalline aluminosilicate using conventionally known methods. Further, supporting can also be performed by a conventionally known method. For example, chlorides, nitrates, sulfates, acetates, etc. of lanthanum, magnesium, calcium, etc. are used as compounds of the above-mentioned metals, and an aqueous solution containing one or more of these metal compounds is added to the above-mentioned dried product. This can be carried out by impregnating the substrate with water, or by immersing it in these aqueous solutions, and further heating if necessary. The amount of the ion-exchanged or supported metal is 0.2 to 15% by weight as an oxide, preferably 0.5 to 8.0% by weight, based on the heat shock metal-modified crystalline aluminosilicate. If the amount of metal is too small, no effect will be produced, and if the amount is too large, the effect will not be as great.

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

[0020]

[Table 1]

The catalyst composition of the present invention also includes a mixture of the heat shock metal modified crystalline aluminosilicate described above 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- It is zirconia, alumina-zirconia, etc., or a mixture thereof, and can also contain at least one kind of clay mineral such as montmorillonite, kaolin, halloysite, bentonite, attapulgite, bauxite, etc. The mixture of these inorganic oxide matrices and the heat-shock metal-modified crystalline aluminosilicate described above can be produced by a conventional method. Typically, a suitable inorganic oxide matrix, such as silica alumina hydrogel,
Using an aqueous slurry of silica sol or alumina sol, the above-mentioned heat-shock metal-modified crystalline aluminosilicate is added thereto, thoroughly mixed and stirred, and then spray-dried to obtain fine catalyst 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
0 to 50% by weight, with an inorganic oxide matrix of about 40 to 9
It can be used in an amount of 5% by weight, preferably about 50 to 90% by weight. Therefore, the amount of active metal after mixing is approximately 0.0 as an oxide based on the mixed catalyst.
Contains 1 to 9.0% by weight.

Furthermore, the catalytic cracking method of the present invention uses the above-described mixture of heat-shock metal-modified crystalline aluminosilicate and an inorganic oxide matrix to catalytically crack hydrocarbon mixtures boiling above the gasoline range. It's a method. The hydrocarbon mixture that boils above the gasoline range means light oil fractions, atmospheric distillation residues, and vacuum distillation residues obtained by atmospheric or vacuum distillation of crude oil, and of course, coker light oil, solvent deasphalted oil, It also includes solvent-deasphalted asphalt, tar sand oil, shale oil, and liquefied coal oil.

Catalytic cracking on a commercial scale typically involves two vertically mounted cracking reactors and a catalyst regenerator.
This is done by continuously circulating the catalyst composition described above through the seed vessel. The hot regenerated catalyst emerging from the catalyst regenerator is mixed with the oil to be cracked and directed in an upward direction through the cracking reactor. As a result, the deactivated catalyst is separated from the cracked products by dissolving carbonaceous matter, commonly called coke, on the catalyst and, after stripping, is transferred to a catalyst regenerator. 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. Ru. Of course, it is also possible to further advance the cracking reaction by recycling these heavy fractions to the cracking reactor. The spent catalyst transferred to the catalyst regenerator is regenerated by removing coke on the catalyst by air calcination, and is recycled to the cracking reactor again. The operating conditions are normal pressure to 5 kg/c.
m2, preferably normal pressure to 3Kg/cm2, temperature 400
It is suitable that the temperature is 600°C to 600°C, preferably 450 to 550°C, and the catalyst/raw material weight ratio is 2 to 20, preferably 5 to 15.

[0024]

[Example] Example 1 (Production of heat shock crystalline aluminosilicate) Si
The O2/Al2O3 molar ratio is 7, the alkali metal content is 0.2 wt% in terms of oxide, and the unit cell size is approximately 24.58.
Å stabilized Y zeolite was heated in an electric furnace under an air atmosphere.
A crystalline aluminosilicate with excellent hydrothermal stability was obtained by firing at normal pressure and 800° C. for 10 minutes. When this product was analyzed, it had the physical property values shown in Table 2. Furthermore, the crystallinity of the stabilized Y zeolite as a raw material was 116% (regarding the standard Y zeolite as 100%), but after the heat shock it was 112% (crystallinity reduction rate 3.5%). The pore distribution was as shown in FIG. This catalyst is designated as HZ-1.

[0025]

[Table 2]

(Production of heat-shocked lanthanum crystalline aluminosilicate by ion exchange) The above catalyst HZ-1 was heated at 90° C. with 10 times the amount of 0.2N lanthanum chloride aqueous solution.
Ion exchange for 5 hours, then filtered and washed with water, then 115
After drying at 550°C for 16 hours, it was baked at 550°C for 3 hours. This zeolite showed the dominant X-ray diffraction pattern of Y zeolite.

(Preparation of catalyst composition) Next, 46.3 g of water
and 46.7 g of silica gel with a concentration of 30% by weight were stirred and mixed, and after adjusting to a predetermined pH, the kaolin was adjusted to 31.5 on a dry basis.
g, 24.5 g of the above 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 using a spray dryer.
Washed 5 times with 2000 ml of distilled water. Then 115
C. for 16 hours to obtain a catalyst composition of the present invention (hereinafter referred to as catalyst A). 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) 0.1% instead of 0.2N lanthanum chloride aqueous solution
Example 1 except that 2N magnesium nitrate aqueous solution was used.
Magnesium crystalline aluminosilicate was obtained in the same manner as above. (Preparation of catalyst composition) The 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 in place 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) In place of 0.2N lanthanum chloride aqueous solution, 0.17
A calcium crystalline aluminosilicate was obtained in the same manner as in Example 1 except that an aqueous N calcium nitrate solution was used. (Preparation of catalyst composition) The catalyst composition of the present invention (
Hereinafter, catalyst C) was 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 in place of catalyst HZ-1. The amount of lanthanum in 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 in place of catalyst HZ-1. The amount of magnesium in 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 in place of catalyst HZ-1. The amount of calcium in this catalyst F is 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 scaled-down version of a commercial-scale catalytic cracker and is a circulating fluidized bed reactor equipped with a cracking reactor and a catalyst regenerator, was used. The catalytic cracking characteristics of hydrocarbon oil were tested using the above catalysts A to G. Prior to testing, each test catalyst was treated in a 100% steam atmosphere at 785° C. for 6 hours for simulated equilibration. Desulfurized vacuum gas oil was used as the feedstock, and the test conditions were a reaction temperature of 500°C and a catalyst circulation rate of 60g/min.
2.5, and from among the four results obtained, the result based on a conversion rate of 66% was selected, and the selected results were compared. This comparison is shown in Tables 3 and 4.

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

Effects of the Invention As detailed above, the catalyst composition of the present invention contains a heat-shock metal-modified crystalline aluminosilicate into which an active metal is introduced after applying a specific thermal load to stabilized Y zeolite. According to the method, it is possible to provide a high octane number gasoline with excellent catalytic cracking properties of hydrocarbon oils, particularly residual oils, and a low olefin content. Furthermore, according to the catalyst composition of the present invention made of a mixture of a heat shock crystalline aluminosilicate and an inorganic oxide matrix, the above effect, that is, the ability to decompose residual oil is further improved, and the middle distillate equivalent to kerosene and gas oil can be reduced. (LCO) yield is high, and production of hydrogen and coke can be suppressed. Moreover, since the catalyst composition of the present invention made from the above mixture has excellent hydrothermal stability, the catalyst life can be extended and make-up can be reduced. According to the catalytic cracking method of the present invention using the above-mentioned catalyst composition, it is possible to catalytically crack hydrocarbon oil that boils above the gasoline range with high efficiency and to produce gasoline with a high octane number and low olefin content. .

[Brief explanation of the drawing]

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

[Figure 2] 27Al-MAS N of stabilized Y zeolite
FIG. 3 is a diagram showing an MR spectrum.

[Figure 3] Heat shock crystalline aluminosilicate (HZ
It is a figure showing the X-ray diffraction pattern with copper K-alpha ray of -1).

FIG. 4 is a diagram showing the pore distribution of heat-shocked crystalline aluminosilicate.

Claims (3)

[Claims] Claim 1: (A) Crystalline aluminosilicate is (a
) Bulk SiO2/Al2O3 molar ratio according to chemical composition analysis is 5 to 15, (b) total Al in the zeolite framework
(c) Unit cell size is less than 24.45 Å, (d) Alkali metal content is 0.02% by weight or more and less than 1% by weight in terms of oxide, (e) Fine Characteristic peaks near 50 Å and 180 Å in the pore distribution
(B) The crystalline aluminosilicate of (A) above is selected from the group consisting of rare earth elements, Mg and Ca. ion exchange with at least one metal, or support the metal, and the metal is 0.2% to 15% by weight as an oxide based on the metal-modified aluminosilicate.
and a metal-modified crystalline aluminosilicate characterized by having a main X-ray analysis pattern of (C)Y zeolite as an essential component. . 2. A catalyst composition for catalytic cracking, which is a mixture of the catalyst composition according to claim 1 and an inorganic oxide matrix. 3. A catalytic cracking process, characterized in that the catalyst composition according to claim 2 is used to catalytically crack hydrocarbon mixtures boiling above the gasoline range.