JP2547141B2 - Crystalline aluminosilicate, method for producing the same and catalyst for catalytic cracking of hydrocarbon oil 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 crystalline aluminosilicate, a method for producing the same, and a catalyst for catalytic cracking of hydrocarbon oil using the same, and more specifically, to a crystalline aluminosilicate excellent in hydrothermal stability. A method for producing the aluminosilicate by applying a predetermined thermal load to a stabilized Y zeolite, and using the aluminosilicate, which is excellent in decomposing residual oil,
The present invention relates to a catalytic cracking catalyst which is excellent in hydrogen and coke selectivity (that is, can effectively suppress the generation of hydrogen and coke) and can produce gasoline having a low olefin content.

[0002]

2. Description of the Related Art Generally, the role of a catalytic cracking process in petroleum refining is to produce a cracked gasoline in good yield by cracking a hydrocarbon oil in contact with a catalyst. At that time, a conventional vacuum gas oil (VGO) is mainly used as a raw material oil. However, recently, due to the crude oil situation and the market trend of petroleum products, atmospheric distillation residual oil and vacuum distillation residual oil (hereinafter referred to as residual oil) are also targeted for cracking, and not only gasoline fraction but also light cracked fraction (below , LCO) is being manufactured at the same time.

As a catalyst aiming at improving the decomposability of residual oil, silica-alumina, γ-alumina, boehmite, etc. are used as an inorganic oxide matrix, which is one of the constituents, and this is stabilized with Y. A mixture of zeolite and a mixture of an alumina-magnesia matrix and a crystalline aluminosilicate has been proposed (JP-A-58-163439, JP-A-1-111).
446).

[0004]

However, when the residual oil is catalytically cracked using a catalyst using silica-alumina or the like as a matrix, the production amount of hydrogen and coke increases, and the desired liquid product yield is increased. Not only the number decreases, but also the problem that the operation of the device becomes difficult occurs. Further, regarding the quality of gasoline, the olefin content is increased and the quality is inevitably deteriorated.

According to the present invention, in catalytic cracking of hydrocarbon oil, especially residual oil, the amount of olefins in gasoline is small, the product yield of gasoline and LCO can be increased, and the production of hydrogen and coke can be suppressed. Crystalline aluminosilicate having excellent hydrothermal stability, which is one component of a decomposition catalyst, and a method for producing the aluminosilicate from a stabilized Y zeolite as a raw material, and the above properties using the aluminosilicate. It is an object of the present invention to provide the above catalyst having

[0006]

Means and Actions for Solving the Problems The present inventors have
As a result of earnest studies to achieve the above object, a crystalline aluminosilicate obtained by applying a thermal load to a stabilized Y zeolite having a specific property under a certain condition is Al in the zeolite skeleton. Of the crystalline aluminosilicate and the inorganic oxide matrix exhibiting unique values in terms of the molar ratio to the total Al, the ignition weight loss rate, and the unit cell size, as a catalyst for catalytic cracking. When used, it decomposes hydrocarbon oils, especially residual oils, not only to reduce the olefin content, but also to increase the product yield of gasoline and LCO, and effectively suppress the formation of hydrogen and coke, and efficiently decompose them. The present invention has been completed based on the finding that it can be achieved.

That is, according to the present invention, [1] (A) the bulk SiO ₂ / Al ₂ O ₃ molar ratio by chemical composition analysis is 5
-11, (B) Unit lattice size is 24.45-24.55
Å, (C) The molar ratio of Al in the zeolite skeleton to the total Al is the value calculated by the formulas (1) to (3) shown in Formula 2,
0.3-0.9, (D) alkali metal content is 0.02-1 wt% in terms of oxide, (E) Y-zeolite main X-ray diffraction pattern, (F) ignition weight loss rate 0.5-2
0% by weight, a crystalline aluminosilicate, characterized in that

[0008]

[Equation 2]

The above equation (1) is based on H.264. K. Be
yer et al. , J. et al. Chem. Soc. , Fa
rayad Trans. 1,1985, (81), 2
The formula described in 899 is adopted.

[2] The SiO ₂ / Al ₂ O ₃ molar ratio is 5 to
11. Stabilized Y zeolite having a unit cell size of 24.50 to 24.72Å and an alkali metal content of 0.02 to 1% by weight in terms of oxide is 5 to 30 at 400 to 590 ° C.
A method for producing a crystalline aluminosilicate according to [1], which comprises firing for 0 minutes at a crystallinity reduction rate of the stabilized Y zeolite of 20% or less.

[3] A catalyst for catalytic cracking of hydrocarbon oil, comprising the crystalline aluminosilicate according to [1] and an inorganic oxide matrix, and the catalyst according to [4] and [3],
At least one metal selected from the group consisting of rare earth metals and alkaline earth metals is used on the basis of the catalyst of [3] (that is, on the basis of the total amount of the crystalline aluminosilicate and the inorganic oxide matrix). ), 0.01 as an oxide
A gist of the catalyst for catalytic cracking of hydrocarbon oil is characterized by containing 10 to 10% by weight.

The present invention will be described in detail below. The stabilized Y zeolite used as a starting material in the production of the crystalline aluminosilicate of the present invention is a so-called Y zeolite, which has been subjected to steam treatment at high temperature for several times, and then, if necessary, a mineral acid such as hydrochloric acid or hydroxylation. At least one of a base such as sodium, a salt such as potassium fluoride, or a chelating agent such as ethylenediaminetetraacetic acid (EDTA)
It is obtained by treating with seeds and exhibits resistance to deterioration of crystallinity. Of course, as the stabilized Y zeolite, Y zeolite may be ammonium hexafluorosilicate [(NH ₄ ) ₂ SiF ₆ ] or silicon tetrachloride (Si).
The compound obtained by treating with a silicon compound such as Cl ₄ ) may be used, or may be obtained by treating with a compound containing no silicon such as EDTA or phosgene (COCl ₂ ). There is no problem even if you use a thing.

The above-mentioned stabilized Y zeolite is SiO ₂ /
Al ₂ O ₃ molar ratio is 5 to 11, unit cell size is about 24.
50 to 24.72Å, preferably 24.55 to 24.7
It is 0Å, and the alkali metal content is about 0.
02 to 1% by weight, preferably about 0.05 to 0.8% by weight
Which means Y zeolite. The stabilized Y zeolite has basically the same crystal structure as that of natural faujasite, and has a composition formula represented by Chemical Formula 1 as an oxide.

[0014]

Embedded image

The stabilized Y zeolite used as the raw material in the present invention has a low content of R _{2 / m 2} O among them.
As shown in, the coefficient is equivalent to 0.002 to 0.2 . That is, the stabilized Y zeolite used in the present invention is a crystalline aluminosilicate having the properties shown in Table 1.

[0016]

[Table 1]

The crystalline aluminosilicate having the predetermined characteristics of the present invention can be obtained by subjecting the stabilized Y zeolite to a constant thermal load (hereinafter, also referred to as "heat shock"). . Thermal load is about 40
0 to 590 ° C, preferably about 450 to 560 ° C, about 5
The calcining 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% or less, preferably about 15% or less.

If the temperature is too low, the crystalline aluminosilicate having the above-mentioned predetermined properties cannot be obtained. On the contrary, if the temperature is too high or the firing time is too long, the crystal structure of the zeolite will be collapsed. A crystalline aluminosilicate having the above-mentioned predetermined properties cannot be obtained.

Usually, the above heat shock is carried out in an electric furnace or a firing furnace at atmospheric pressure under an atmosphere of air or nitrogen, but in an electric furnace under an atmosphere of air or nitrogen having a water vapor partial pressure of about 0 to 0.5 atm. You may leave and bake. It should be noted that moderate humidity easily causes dealumination, and heat shock can be generated even at a low temperature within the above temperature range.

The heat shock is preferably carried out under the conditions that the crystal structure of zeolite is not collapsed as much as possible, and the crystallinity reduction rate of the above-mentioned stabilized Y zeolite is about 2
It is performed under 0% or less, preferably about 15% or less. The crystallinity of the stabilized Y zeolite is ASTM D-390.
6 (Standard Test Method fo
r Relative Zeolite Diffra
It is obtained according to the method. That is, the standard sample is a Y-type zeolite (Si / A
L ratio of 5.0, unit cell size of 24.58Å, and Na ₂ O amount of 0.3% by weight), and is obtained as a relative X-ray diffraction intensity ratio between the test sample and the standard sample. The reduction rate of crystallinity of the stabilized Y zeolite by heat shock of the present invention is several 3
It is obtained from the formula shown in.

[0021]

(Equation 3)

In the above formula, the heat shock crystalline aluminosilicate means a crystalline aluminosilicate obtained by subjecting the stabilized Y zeolite to a heat shock.
The term "heat shock crystalline aluminosilicate" means this.

Upon application of heat shock, the stabilized Y zeolite as a raw material may be placed in the calcining furnace after reaching the above temperature, or after the stabilized Y zeolite is placed in the calcining furnace, the temperature is gradually increased from room temperature. The temperature may be raised to reach the predetermined temperature, and the temperature rising rate is not particularly limited.

The heat shock crystalline aluminosilicate is
As described below, mixed with an inorganic oxide matrix,
Although it is used for catalytic cracking of hydrocarbon oil, the heat shock is not particularly limited in its timing, but it is preferable that the mixing is before this mixing. The heat shock in the present invention is distinguished from the heat treatment under severe conditions for simulated equilibration performed prior to the catalyst performance evaluation test.

Further, the heat shock crystalline aluminosilicate of the present invention can be obtained by heat-treating stabilized Y zeolite, but if the heat shock crystalline aluminosilicate of the present invention is directly produced by heat treatment of Y zeolite. , The crystal structure collapses and the purpose cannot be achieved.
The reason for this is not clear in detail, but in order to obtain the heat shock crystalline aluminosilicate of the present invention, Y zeolite is heat-treated to first produce a stabilized zeolite, and the crystal structure is settled in that state, that is, It is presumed that it is necessary to wait for stabilization before performing heat treatment again.

The heat-shock crystalline aluminosilicate of the present invention can be obtained by the above, and has the following predetermined properties which have not hitherto been known. That is, bulk SiO ₂ / Al ₂ O by chemical composition analysis
_{The 3} molar ratio is about 5-11, preferably about 5.4-9. The unit lattice size is about 24.45 to 24.55.
Å, preferably about 24.45 to 24.53Å. The unit cell size can be measured according to ASTM D-3942 / 85, and can be calculated by using the peak of X-ray diffraction. If this value is too large, the hydrothermal resistance deteriorates. All Al
The molar ratio of Al in the zeolite skeleton to the value calculated from the above-mentioned formula (1) to (3) using the above-mentioned chemical composition analysis from the SiO ₂ / Al ₂ O ₃ molar ratio and the unit cell size. And about 0.3 to 0.9, preferably about 0.4.
.About.0.8 (see HK Beyer et a, supra).
l. , J. et al. Chem. Soc. , FaradayTra
ns. 1, 1985, (81), 2899). The molar ratio of Al in the zeolite skeleton to the total Al is
It can be calculated by other formulas, but when other formulas are used, the above values are not obtained.

When the bulk SiO ₂ / Al ₂ O ₃ molar ratio is the same, if the molar ratio of Al in the zeolite skeleton to the total Al is too small, the catalytic activity required for catalytic cracking is lost. When the ratio of Al outside the skeleton, that is, amorphous Al, becomes high, the selectivity also behaves like an amorphous catalyst,
Hydrogen generation, coke production, and olefin content in gasoline are increased. On the contrary, if the molar ratio of Al in the zeolite skeleton to the total Al is too large, the amount of olefins in gasoline decreases, but the problem of poor residual oil decomposability arises.

Further, the content of alkali metal or alkaline earth metal is about 0.02 to 1.0% by weight, preferably about 0.05 to 0.8% by weight in terms of oxide. If the content of alkali metal or alkaline earth metal is less than about 0.02% by weight in terms of oxide, the crystal structure is likely to collapse, which is not preferable. Further, when a large amount of alkali metal is present in the heat-shock crystalline aluminosilicate, the decomposition activity of the catalyst is reduced, and nickel, vanadium, etc., which are heavy metals contained in the feed oil, particularly heavy oil feed oil, are reduced. If adhered, there is a problem that activity deterioration is likely to occur.

The ignition weight reduction rate is about 0.5-2.
It is 0% by weight, preferably about 1-10% by weight. The ignition weight loss rate is measured by the formula shown in Formula 4.

[0030]

[Equation 4]

If this value is too large, the heat shock crystalline aluminosilicate tends to retain water, resulting in a decrease in hydrothermal stability. As a result, the life of the hydrocarbon oil decomposition catalyst of the present invention is shortened. There is a problem of causing.

The heat shock crystalline aluminosilicate of the present invention described above can be obtained by subjecting the stabilized Y zeolite to a constant thermal load, as described above. 24.45 ~ 24.5
5Å, which is about 24.50-2 of stabilized Y zeolite
It is smaller than 4.72Å, and the molar ratio of Al in the zeolite skeleton to all Al is about 0.3 to 0.9.
That is, the ignition weight reduction rate is about 0.5 to 20% by weight.

The characteristics of the heat shock crystalline aluminosilicate of the present invention are summarized in Table 2.

[0034]

[Table 2]

The heat shock crystalline aluminosilicate of the present invention substantially has the X-ray diffraction pattern shown in FIG. In FIG. 1, 1 and 2 are peaks of the lattice spacing (d) showing the strongest diffraction, which are 14.1 ± 0.
2Å, 5.61 ± 0.1Å and 3.72 ± 0.1Å. The X-ray diffraction diagram of FIG. 1 is shown in Table 3 as a typical example.
Has a value like.

[0036]

[Table 3]

The catalyst for catalytic cracking of hydrocarbon oils of the present invention is a mixture of the above heat shock crystalline aluminosilicate and an inorganic oxide matrix. Examples of the inorganic oxide matrix include silica, alumina, boria, chromina, magnesia, zirconia, titania, silica-
Alumina, silica-magnesia, silica-zirconia,
Chromia-alumina, titania-alumina, titania-
It may be silica, titania-zirconia, alumina-zirconia or the like, or a mixture thereof, and may further contain at least one clay mineral such as montmorillonite, kaolin, halloysite, bentonite, attapulgite and bauxite.

The above-mentioned mixture (that is, the catalyst of the present invention) can be produced by a conventional method, typically as a suitable inorganic oxide matrix, for example, silica-
It is possible to obtain catalyst fine particles by using an aqueous slurry of alumina hydrogel, silica sol or alumina sol, adding the heat shock crystalline aluminosilicate described above, thoroughly mixing and stirring, and then spray drying. In this case, the heat shock crystalline aluminosilicate in the mixed catalyst is about 5 to 60% by weight, preferably 10 to 50% by weight, and the inorganic oxide matrix is about 40 to 95% by weight, preferably about 50 to 90%. It can be used by adding it so that it becomes a weight% ratio. If the heat shock crystalline aluminosilicate is less than about 5% by weight, the effect as a catalyst for catalytic cracking of hydrocarbon oil cannot be obtained, and if it is more than about 60% by weight, the amount of the inorganic oxide matrix is relatively large. This is because the amount of the catalyst becomes too small and the strength of the catalyst decreases, which causes problems such as scattering of the catalyst and mixing in the product, which hinders the operation of the apparatus.

Another feature of the present invention is that the catalyst contains at least one metal selected from the group consisting of rare earth metals and alkaline earth metals. As rare earth metals, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium,
Gadolinium or the like is used, and these are used alone or in a mixture, and preferably lanthanum. As the alkaline earth metal, beryllium, magnesium, calcium, strontium, barium, and radium are used, and these are used alone or in a mixture, preferably magnesium or calcium alone or in a mixture. It is also possible to use a mixture of at least one of these rare earth elements and at least one of alkaline earth metals.

As a mode of containing the above-mentioned rare earth metal or alkaline earth metal in the above catalyst, a part or all of the heat shock crystalline aluminosilicate which is one of the constituents of the catalyst is replaced with the above metal. Ion exchange or heat shock crystalline aluminosilicate to carry the metal, so-called metal modified heat shock crystalline aluminosilicate, or the catalyst itself is ion-exchanged with the metal, Alternatively, a mode in which the metal is supported on the catalyst is adopted.

When the heat shock crystalline aluminosilicate or catalyst is ion-exchanged with the above metal, or when the heat shock crystalline aluminosilicate or catalyst is loaded with the above metal, it can be carried out by a conventionally known method. For example, in both cases of ion exchange and loading,
An aqueous solution containing one or more compounds such as chlorides such as lanthanum, magnesium, calcium, etc., nitrates, sulfates, acetates, etc. is impregnated into the heat-shock crystalline aluminosilicate or catalyst in a dry state, or It can be carried out by immersing these in an aqueous solution of and further heating if necessary.

In both cases of ion exchange and loading, the amount of the above metal is about 0. 0 as an oxide, based on the mixed catalyst of the crystalline aluminosilicate and the inorganic oxide matrix.
It is from 01 to 10% by weight, preferably about 0.05 to 7% by weight. By carrying out ion exchange or loading of the above-mentioned metals, gasoline having a low olefin content can be produced, but if the amount of metal is too small, this effect does not appear, and if it is too large, this effect does not improve so much.

To catalytically crack a hydrocarbon oil using the catalyst of the present invention detailed above, a hydrocarbon oil (hydrocarbon mixture) boiling above the boiling point range of gasoline is contacted with the catalyst of the present invention. Good. The hydrocarbon mixture boiling above the boiling point range of gasoline means a gas oil fraction obtained by atmospheric distillation or vacuum distillation of crude oil, atmospheric distillation residue oil and vacuum distillation residual oil, and of course, coker gas oil and solvent deasphalted oil. It also includes solvent deasphalted asphalt, tar sand oil, shale oil oil, and coal liquefied oil.

Catalytic cracking on a commercial scale is usually carried out in two vertically installed cracking reactors and catalyst regenerators.
It is carried out by continuously circulating the above-mentioned catalyst of the present invention in a catalytic cracking apparatus comprising a seed container. The hot regenerated catalyst exiting the catalyst regenerator is mixed with the hydrocarbon oil to be cracked and directed upward in the cracking reactor. As a result, the catalyst which is generally deactivated by depositing carbonaceous material called coke on the catalyst is separated from the decomposition products, stripped, and transferred to a catalyst regenerator. The spent catalyst transferred to the catalyst regenerator is regenerated by removing the coke on the catalyst by air calcination, and is recycled to the cracking reactor.

On the other hand, the decomposition products are dry gas and LP.
G, gasoline fraction, and, for example, light cycle oil (LC
O), heavy cycle oil (HCO) or slurry oil and separated into one or more heavy fractions. Of course, it is also possible to further promote the cracking reaction by recycling these heavy fractions to the cracking reactor.

As the operating conditions of the cracking reactor in the above catalytic cracking apparatus, the pressure is about normal pressure to 5 Kg / c.
m ² , the temperature is about 400 to 600 ° C., preferably about 450
~ 550 [deg.] C., catalyst / feedstock hydrocarbon oil weight ratio of about 2 to 2
Suitably 0, preferably about 4-15.

[0047]

EXAMPLES The contents of the present invention will be specifically described below in comparison with Examples. Example 1 (Production example of heat shock crystalline aluminosilicate) SiO ₂ / Al ₂ O ₃ molar ratio is 6, alkali metal content is 0.6 wt% in terms of oxide, and unit cell size is 24.6.
Stabilized Y zeolite of 3 Å in an electric furnace, air atmosphere,
A heat shock crystalline aluminosilicate was produced by baking at 540 ° C. for 10 minutes under normal pressure. When the product was analyzed, it showed the main X-ray diffraction pattern of Y zeolite and had the physical properties shown in Table 4. The crystallinity was 100% (15% decrease in crystallinity) after the heat shock, compared to 118% of the stabilized Y zeolite as the raw material (assuming 100% of the standard Y zeolite). This heat shock crystalline aluminosilicate is
-1.

[0048]

[Table 4]

Example 2 (Production Example of Heat Shock Crystalline Aluminosilicate) A heat shock crystalline aluminosilicate was produced in the same manner as in Example 1 except that the firing temperature was 480 ° C. When the product was analyzed, it showed the main X-ray diffraction pattern of Y zeolite and had the physical properties shown in Table 5. Further, the crystallinity was 105% (11% decrease in crystallinity) after heat shock on the same basis as in Example 1. This heat shock crystalline aluminosilicate is referred to as HZ-2.

[0050]

[Table 5]

Example 3 (Preparation example of catalyst) 46.3 g of water and 46.7 g of silica sol having a concentration of 30% by weight
After stirring and mixing to adjust the pH to a predetermined value, 30.8 g of kaolin on a dry basis, 17.5 g of HZ-1 obtained in Example 1 on a dry basis and 60 g of water were further added and mixed with stirring. The resulting mixture is dried and atomized with a spray dryer,
It was washed with 000 ml of distilled water. Then, it was dried in air at 115 ° C. for 16 hours to obtain a catalyst of the present invention (hereinafter referred to as catalyst A).

Example 4 (Preparation example of catalyst) The catalyst of the present invention (hereinafter referred to as catalyst B) was prepared in the same manner as in Example 3 except that HZ-2 obtained in Example 2 was used instead of HZ-1. Got

Example 5 (Catalyst Preparation Example) Catalyst A was immersed in 10 times amount of 0.1N lanthanum chloride solution at 70 ° C. for 2 hours for ion exchange, then filtered, washed with water, and then washed. After drying at 115 ° C. for 16 hours, a catalyst of the present invention (hereinafter referred to as catalyst C) was obtained. The amount of lanthanum in this catalyst C was 0. 0 based on the weight of the catalyst A as an oxide.
It was 43% by weight.

Example 6 (Catalyst Preparation Example) Except that the catalyst A was replaced by the catalyst B obtained in Example 4,
A catalyst of the present invention (hereinafter referred to as catalyst D) was obtained in the same manner as in Example 5. The amount of lanthanum in this catalyst D was 0.53% by weight based on the weight of the catalyst B as an oxide.

Comparative Example 1 A comparative catalyst (hereinafter referred to as catalyst E) was obtained in the same manner as in Example 3 except that the stabilized Y zeolite used in Example 1 was used instead of HZ-1.

Comparative Example 2 Except that the catalyst E obtained in Comparative Example 1 was used instead of the catalyst A.
A comparative composition (hereinafter referred to as catalyst F) was obtained in the same manner as in Example 5. The amount of lanthanum in this catalyst F is the amount of catalyst E
Was 0.25% by weight based on the weight of.

[Bench Scale Plant Test Example] A bench scale plant, which is a commercial scale catalytic cracking apparatus scaled down and is a circulating fluidized bed reactor equipped with a cracking reactor and a catalyst regenerator, is used. Then, catalytic cracking of hydrocarbon oil was tested using the above catalysts A to F. Prior to the test, each test catalyst was treated at 785 ° C. for 6 hours in a 100% steam atmosphere for simulated equilibration. Desulfurized vacuum gas oil was used as the feedstock, and the test conditions (cracking reactor conditions) were a reaction temperature of 500.
C., the catalyst circulation rate was 60 g / min, and the test was conducted under the conditions of catalyst / feed oil = 4, 7, 9.5, and 12.5, respectively. Results based on% were selected and a comparison was made on the selected results. Results of this comparison (ie product composition)
Are shown in Tables 6 and 7.

[0058]

[Table 6]

[0059]

[Table 7]

As is clear from Tables 6 and 7, when the catalyst of the present invention is used, the olefin content is lower and the amount of hydrogen and coke produced is lower than when the comparative catalyst is used. I understand. It can also be seen that this effect is particularly remarkable in the catalyst containing a rare earth metal.

[0061]

As described in detail above, the heat shock crystalline aluminosilicate of the present invention obtained by the production method of the present invention in which the stabilized Y zeolite is used as a raw material and the raw material is subjected to a specific thermal load. According to the catalyst of the present invention which is contained, it is possible to provide a gasoline which is excellent in catalytic cracking property of hydrocarbon oil, particularly residual oil, and has a low olefin content. Further, according to the catalyst of the present invention, the ability to decompose residual oil can be further improved, the yield of middle distillates (LCO) corresponding to gasoline and kerosene / light oil can be increased, and the production of hydrogen and coke is also effective. Can be suppressed.

[Brief description of drawings]

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsuru Oi 4-20-3-107 Hanaguri, Soka City, Saitama Prefecture (56) References JP-A-56-24051 (JP, A) JP-A-56-22624 (JP) , A) JP-A-51-146385 (JP, A) JP-A-3-45513 (JP, A)

Claims (4)

(57) [Claims] 1. (A) Bulk Si by chemical composition analysis
O ₂ / Al ₂ O ₃ molar ratio is 5 to 11, (B) unit cell size is 24.45 to 24.55Å, (C) molar ratio of Al in the zeolite skeleton to total Al is expressed by the following formula (1) to (3)
Calculated value by 0.3 to 0.9, (D) The alkali metal content is 0.02-1 in terms of oxide
%, A main X-ray diffraction pattern of (E) Y zeolite, and (F) a weight loss on ignition of 0.5 to 20% by weight, a crystalline aluminosilicate. 2. A SiO ₂ / Al ₂ O ₃ molar ratio of 5 to 1
1. Stabilized Y zeolite having a unit cell size of 24.50 to 24.72Å and an alkali metal content of 0.02 to 1% by weight in terms of oxide is 5 to 300 at 400 to 590C.
Min, and the rate of decrease in crystallinity of the stabilized Y zeolite 2
The method for producing a crystalline aluminosilicate according to claim 1, wherein the firing is performed at 0% or less. 3. A catalyst for catalytic cracking of hydrocarbon oils, which comprises the crystalline aluminosilicate according to claim 1 and an inorganic oxide matrix. 4. At least one metal selected from the group consisting of a rare earth metal and an alkaline earth metal is contained in an amount of 0.01 to 10% by weight as an oxide, based on the catalyst according to claim 3. The catalyst according to claim 3, wherein