JP3383374B2 - Catalyst composition for catalytic cracking of hydrocarbons and method for producing 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 catalyst composition for catalytic cracking of hydrocarbons and a method for producing the same, and more particularly to the production of coke and gas components for catalytic cracking of hydrocarbons, especially heavy oil. TECHNICAL FIELD The present invention relates to a catalyst composition having a small amount of heat, excellent resolution, and excellent abrasion resistance, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, various catalyst compositions for catalytic cracking of hydrocarbons have been proposed, and catalytic cracking catalyst compositions containing crystalline aluminosilicate zeolite and amorphous silica-alumina are also proposed. Various proposals have been made (for example, JP-B-49-30634 and JP-A-53-1).
No. 00985, JP-A-58-112053).

Japanese Patent Publication No. 49-30634 discloses silica-
A catalyst composition in which a crystalline aluminosilicate zeolite having a uniform pore size of 6 to 15Å and a silica-to-alumina molar ratio of greater than 3 is dispersed in an alumina matrix is described. Kaisho 53-100985
In No. 5, a catalyst containing crystalline aluminosilicate zeolite is mixed with a sol of an oxide selected from silica, alumina or silica-alumina to obtain a catalyst having excellent metal resistance and less generation of hydrogen and coke. Is disclosed. Further, JP-A-58-11
No. 2053 omits a washing step in the method for producing a catalyst and spray-drys a mixture of crystalline zeolite, a clay substance, and a colloidal binder selected from the group consisting of silica colloid, alumina colloid, and a mixture thereof. A method for producing the catalyst composition is disclosed.

However, these conventional catalyst compositions for catalytic cracking of hydrocarbons have a porous matrix material (matrix).
The decomposition activity is not taken into consideration at all, so when used for catalytic cracking of hydrocarbons, especially heavy oil such as residual oil, the cracking activity is low, and in order to increase the cracking activity, crystalline alumino, which is the active ingredient, is used. If the content of silicate zeolite is increased, there is a problem that coke and gas components are increased, which is not always satisfactory.

[0005]

OBJECT OF THE INVENTION The present invention is used for catalytic cracking of hydrocarbons, especially heavy oil such as vacuum gas oil, atmospheric residue oil, vacuum residue oil and the like, and has a high cracking activity, and moreover, it produces coke and gas components. It is an object to provide a low catalyst composition and a method for producing the same. Another object of the present invention is to provide a method for producing a catalyst composition having excellent wear resistance.

[0006]

SUMMARY OF THE INVENTION The present invention is a crystalline aluminosilicate zeolite and 4 measured by ²⁷ Al-MAS NMR.
The ratio (I ₄ / I ₆ ) of the strength (I ₄ ) of coordinated aluminum and the strength (I ₆ ) of hexacoordinated aluminum is 70/30 to 10
The present invention relates to a catalyst composition for catalytic cracking of hydrocarbons, which contains 0/0 of amorphous silica-alumina, and a method for producing the same.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below. The catalyst composition for catalytic cracking of hydrocarbons according to the present invention contains crystalline aluminosilicate zeolite and amorphous silica-alumina, and the amorphous silica-alumina has four coordinations measured by ²⁷ Al-MAS NMR. It is characterized in that the ratio of aluminum in the intensity I ₄ and 6-coordinate strength of the aluminum I ₆ (I ₄ / I ₆₎ is in the range of 70 / 30-100 / 0.

Here, the ratio (I ₄ / I ₆ ) of the strength I _{4 of four-} coordinated aluminum to the strength I ₆ of six-coordinated aluminum is
It is measured by ²⁷ Al-MAS NMR as follows. That is, the (I ₄ / I ₆ ) ratio in the present invention is determined by measuring ²⁷ Al-NMR spectrum at room temperature according to a conventional method after drying a sample of amorphous silica-alumina hydrate at 150 ° C. for 30 minutes. From the obtained NMR spectrum is + 50-
The peak intensity (peak area) due to 4-coordinate aluminum appearing around +80 ppm is I _4, and the peak intensity (peak area) due to 6-coordinate aluminum appearing near 0 ppm is I ₆ .

In the catalytic composition for catalytic cracking of the present invention,
When the I ₄ / I ₆ ratio is smaller than 70/30, the proportion of tetracoordinated aluminum in the amorphous silica-alumina is small, so that the amount of solid acid in the amorphous silica-alumina is small,
The desired resolution cannot be obtained. In order to impart a desired resolution to the matrix of the catalyst composition, it is desirable that the proportion of tetracoordinated aluminum in the amorphous silica-alumina is larger, and the I ₄ / I ₆ ratio is 90/10 or more. desirable. Further, the content of alumina in the amorphous silica-alumina is 1 to 40 wt% in addition to having a large amount of solid acid,
It is preferably in the range of 5 to 25 wt%.

The catalytic composition for catalytic cracking of the present invention contains 5 to 50 wt% of crystalline aluminosilicate zeolite, 5 to 95 wt% of the above-mentioned amorphous silica-alumina, calcium aluminate, activated alumina and the like. It may also contain a third component such as a metal scavenger or kaolin.

As the crystalline aluminosilicate zeolite, it is possible to use a zeolite which is usually used as a catalyst for catalytic cracking of hydrocarbons, and examples thereof include faujasite, zeolite A, ZSM, mordenite and the like. USY (ultra-stable Y-type zeolite), which is in the category of faujasite, is suitable.

Next, a method for producing the catalyst composition for catalytic cracking of hydrocarbons according to the present invention will be described. The catalyst composition of the present invention comprises a crystalline aluminosilicate zeolite and ²⁷ A
Amorphous having a ratio (I ₄ / I ₆ ) of the intensity (I ₄ ) of tetracoordinated aluminum and the intensity (I ₆ ) of hexacoordinated aluminum measured by 1-MAS NMR of 70/30 to 100/0. Silica-alumina hydrate and, if necessary, other clay, a metal scavenger, etc., are mixed, spray-dried, and optionally washed and dried. Amorphous silica-alumina hydrate acts as a binder. When the dealkalized silica-alumina hydrate is used as the binder, the washing step is not required in the catalyst production step. The amorphous silica-alumina hydrate having the above-mentioned properties used in the present invention may be in a gel state or a sol state, and a silica-alumina composite oxide sol is particularly preferable because it has a strong binding force. The silica-alumina composite oxide sol can be prepared, for example, according to Japanese Patent Application Laid-Open No. 5-132309 filed by the applicant. That is, a silicate of an alkali metal, ammonium or an organic base and an alkali-soluble aluminum compound are dispersed in seed particles, if desired, to obtain a pH of 10
It is prepared by simultaneously adding to the above alkaline aqueous solution and producing colloidal particles of silica-alumina composite oxide without controlling the pH of this reaction solution.

As a raw material for silica of the silica-alumina composite oxide, a silicate of alkali metal, ammonium or organic base is used. As alkali metal silicates,
Sodium silicate (water glass) and potassium silicate are used. Examples of the organic base of the organic base silicate include quaternary ammonium salts such as tetraethylammonium salt, amines such as monoethanolamine, diethanolamine, triethanolamine, and the like. Ammonium silicate or organic base silicate Include an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid solution.

As the alkali-soluble aluminum compound, sodium aluminosilicate, sodium aluminate or the like is used.

The amorphous silica-alumina composite oxide colloidal particles prepared by the above method are in a hydrate state.
²⁷ The intensity ratio (I ₄ / I ₆ ) of 4-coordinated aluminum and 6-coordinated aluminum measured by Al-MAS NMR is 70.
Since it is / 30 or more and the binding strength is very large, the catalyst composition prepared by mixing with the crystalline aluminosilicate zeolite has excellent wear resistance. The amorphous silica-alumina hydrate used in the present invention is not limited to the silica-alumina composite oxide sol obtained by the above method. Further, the catalyst composition of the present invention comprises a crystalline aluminosilicate zeolite and a predetermined (I ₄ / I ₆ )
A ratio of amorphous silica-alumina hydrate was mixed with the powder obtained by firing and other binder material, then spray dried,
If necessary, it can be obtained by washing and drying. Hereinafter, the present invention will be described more specifically with reference to examples.

[0016]

【Example】

Production Example 1 of Amorphous Silica-Alumina Commercially available silica sol having an average particle size of 5 mμ and a SiO ₂ concentration of 20% by weight [Catalyst Kasei Co., Ltd .: trade name Cataloid SI-
550, pH 11.0] (S-8) 1,220 g
15% aqueous ammonia was added to a mixture of 29,280 g of pure water and 29,280 g of pure water to adjust the pH of the reaction mother liquor to 11.4.
Warmed to 0 ° C. As SiO ₂ , 1.88 wt% sodium silicate aqueous solution 138, 659.6 g and as Al ₂ O ₃ 1.88 wt% sodium aluminate aqueous solution 7,
297.9 g was mixed, and this was subjected to sodium removal treatment using a cation exchange resin and added to the reaction mother liquor prepared above. The addition rate was 202.7 g / min, during which the temperature of the reaction solution was maintained at 60 ° C. After the addition is complete
The reaction solution is cooled to room temperature and the amorphous S having a pH of 10.7 is
iO ₂ · Al ₂ O ₃ to obtain a composite oxide sol. This was concentrated to 20% as SiO ₂ .Al ₂ O ₃ by ultrafiltration. The weight ratio of SiO ₂ and Al ₂ O ₃ in this concentrated amorphous SiO ₂ · Al ₂ O ₃ composite oxide sol (S-1) is SiO ₂
/ Al ₂ O ₃ = 96/4, the ratio (I ₄ ) of the intensity of four-coordinate Al ₂ O ₃ (I ₄ ) and the intensity of six-coordinate Al ₂ O ₃ (I ₆ ) by ²⁷ Al-MAS NMR. / I ₆ ) is I ₄ / I ₆ = 100/0
Met. FIG. 1 shows the ²⁷ Al-MAS NMR spectrum of the amorphous SiO ₂ · Al ₂ O ₃ composite oxide colloidal particles.
Shown in.

The amorphous SiO ₂ .Al ₂ O ₃ composite oxide colloidal particles were analyzed by ²⁷ Al-MAS NMR.
The ratio between the intensity of coordination Al ₂ O ₃ of the intensity (I ₄₎ and 6-coordinated _{Al 2 O 3 (I 6)} (I 4 / I 6) are dried for 30 minutes the sol at 0.99 ° C. under air atmosphere 270MHz sample
Measured by NMR (pulse angle: 45 ° pulse, waiting time:
What was measured for 2.5 seconds with a single pulse without ¹ H decoupling) was a spectrum range of Al ₂ O ₃ in each coordination (tetracoordinate Al ₂ O ₃ : around +50 to +80 ppm, 6
The coordinate ratio Al ₂ O ₃ (near 0 ppm) was subjected to waveform processing to obtain the area ratio. Aluminum sulfate (0 ppm) was used as a reference substance for chemical shift. The numerical values of I ₄ / I ₆ described below are obtained by the above method.

Production Example 2 of Amorphous Silica-Alumina The aqueous solution of sodium silicate used in Production Example 1 was used as 131
361.7g, 14.5 of sodium aluminate aqueous solution
An amorphous SiO ₂ · Al ₂ O ₃ composite oxide sol having a pH of 11.0 was obtained in the same manner as in Production Example 1 except that 95.7 g was mixed. The sol was subjected to ultrafiltration to obtain SiO ₂
Concentrated to 20% as Al ₂ O ₃ . Si of this concentrated amorphous SiO ₂ · Al ₂ O ₃ composite oxide sol (S-2)
The weight ratio of O ₂ and Al ₂ O ₃ is 93/7, and ²⁷ Al-MAS
Intensity (I ₄ ) of 4-coordinate Al ₂ O ₃ and 6-coordinate A by NMR
l ₂ ratio of the O ₃ of the intensity _{(I 6) (I 4 /} I 6) is I ₄ / I ₆ =
It was 100/0.

Production Example 3 of Amorphous Silica-Alumina In this Production Example and Production Example 4 which will be described later, the content of Al ₂ O ₃ is increased and the amorphous SiO that is not subjected to sodium removal treatment is used.
_{A 2} · Al ₂ O ₃ composite oxide sol was prepared. Production Example 1
A mixture (pH 10.7) of 1,084.5 g of the commercially available silica sol (S-8) used in 1. and 26,028 g of pure water was added at 60 ° C.
Warmed to. 116.766.0 g of a sodium silicate aqueous solution of 1.88 wt% as SiO ₂ and a sodium aluminate aqueous solution of 1,88 wt% of 1,88 wt% as Al ₂ O ₃
73.4 g were each added simultaneously to the reaction mother liquor prepared above. The addition rate is 162.2 for sodium silicate solution.
g / min, the sodium aluminate aqueous solution was 18.0 g / min, and the temperature of the reaction liquid was kept at 60 ° C. during that period. After the addition is complete, the reaction is cooled to room temperature and pH is 12.1
Amorphous SiO ₂ · Al ₂ O ₃ composite oxide sol was obtained. The sol was concentrated with an ultrafiltration membrane while adding pure water until it became 20% as SiO ₂ .Al ₂ O ₃ . SiO ₂ and Al ₂ O _{3 of the} obtained concentrated sol (S-3) (pH 10.5)
Is 82/18, and the ratio (I ₄ / I) of the intensity (I ₄ ) of tetracoordinate Al ₂ O _{3 and} the intensity (I ₆ ) of hexacoordinate Al ₂ O ₃ by ²⁷ Al-MAS NMR. ₆ ) is I ₄ / I ₆ = 100/0
Met.

Preparation Example 4 of Amorphous Silica-Alumina 103, 79
1.5 g (addition rate: 144.2 g / min), 25,947.9 g of sodium aluminate aqueous solution (addition rate: 3
6.0 g / min), except that p
An amorphous SiO ₂ · Al ₂ O ₃ composite oxide sol having H of 12.4 was obtained. While adding pure water to this sol, SiO ₂ · A
It was concentrated with an ultrafiltration membrane until it reached 20% as l ₂ O ₃ .
SiO of the obtained concentrated sol (S-4) (pH 10.6)
The weight ratio of ₂ and Al ₂ O ₃ is 76/24, and ²⁷ Al-MAS
Intensity (I ₄ ) of 4-coordinate Al ₂ O ₃ and 6-coordinate A by NMR
l ₂ ratio of the O ₃ of the intensity _{(I 6) (I 4 /} I 6) is I ₄ / I ₆ =
It was 100/0.

Production Example 5 of Amorphous Silica-Alumina 7.40% by weight of silicic acid solution as SiO ₂ (pH 4.0)
Add 20,000g of pure water to 448,000g and add 1
After aging for 65 minutes, add 15% aqueous ammonia to adjust the pH.
It was adjusted to 7.1, 20,000 g of pure water was added, and the mixture was aged for 120 minutes. During this time, the temperature was maintained at 37 ° C. Next, 1486.0 g of a 24 wt% aqueous solution of aluminum sulfate and 3467.4 g of a 22 wt% aqueous solution of sodium aluminate were simultaneously added to this solution as Al ₂ O ₃ . During this period, the pH of the reaction solution was maintained at 8.0 to 9.0, and finally reached pH 8.5. Add pure water to this
After adding 9,000 g and further aging for 120 minutes, a washing treatment was carried out to obtain an amorphous silica-alumina hydrogel. S of this silica-alumina hydrogel (S-5)
The weight ratio of iO ₂ and Al ₂ O ₃ is 87/13, ²⁷ Al-M
Intensity (I ₄ ) of 4-coordinated Al ₂ O ₃ and 6 by AS NMR
Coordination ratio of the intensities of the _{Al 2 O 3 (I 6)} (I 4 / I 6) is I ₄ /
I ₆ = 72/28.

Production Example 6 of Amorphous Silica-Alumina The aluminum sulfate aqueous solution used in Production Example 5 was 311.
0.7g, sodium aluminate aqueous solution 1842.7
Production Example 5 except that the reaction liquid during addition was maintained at pH 6.5 to 7.0 and finally reached pH 6.9.
Amorphous silica alumina hydrogel was obtained in the same manner as in. The weight ratio of SiO ₂ to Al ₂ O ₃ of this amorphous silica-alumina hydrogel (S-6) is 87/13, and ²⁷ Al-
The ratio (I ₄ / I ₆ ) of the intensity of 4-coordinate Al ₂ O ₃ (I ₄ ) and the intensity of 6-coordinate Al ₂ O ₃ (I ₆ ) by MAS NMR is I ₄
/ I ₆ = 50/50. The ²⁷ Al-MAS NMR spectrum of this amorphous silica-alumina hydrogel is shown in FIG.

Example 1 150 g (dry basis) of the amorphous SiO ₂ and Al ₂ O ₃ composite oxide sol (S-1) obtained in the above Production Example 1 was used, and 510 g of kaolinite clay (dry) was used. Standard), 40 g of activated alumina (dry basis), Y-type zeolite [previously ammonium ion exchanged to 0.3% Na ₂ O (dry)
wt%)] was mixed with 300 g (dry basis) and spray-dried to obtain spherical fine particles. The obtained catalyst composition was obtained by using amorphous SiO ₂ · Al ₂ O ₃ composite oxide sol (S-1) at a catalyst amount of 1 based on SiO ₂ · Al ₂ O ₃ dry standard.
5 wt%, kaolinite clay in a catalytic amount of 51 wt%, activated alumina in a catalytic amount of 4 wt%, and Y-type zeolite in a catalytic amount of 30 wt% were included. Using a rare earth chloride aqueous solution, 0.9 wt% of a rare earth element as RE ₂ O ₃ was ion exchange-supported with respect to the catalyst amount to obtain a target catalyst (C-1). In addition, in the same manner as this, using the kaolinite clay as a balance, amorphous SiO ₂ · Al ₂ O ₃
Catalysts (C-2) and (C-3) containing 25 wt% and 35 wt% of the composite oxide sol (S-1) were prepared.

[0024] Example 2 Example instead of 1 in the amorphous SiO ₂ · Al ₂ O ₃ composite oxide sol using (S-1), Preparation Example 2 in amorphous SiO ₂ · Al ₂ obtained A catalyst (C-4) was prepared in the same manner as the catalyst (C-2) except that the O ₃ composite oxide sol (S-2) was used.

Examples 3 and 4 Instead of the amorphous SiO ₂ · Al ₂ O ₃ composite oxide sol (S-1) used in Example 1, the amorphous SiO obtained in the above Production Examples 3 and 4 was used. ₂ · Al ₂ O ₃ complex oxide sol (S-3),
The catalysts shown in Table 2 were prepared in the same manner as in the preparation method of the catalyst (C-2), except that each of (S-4) was used to carry out sodium removal treatment using ammonium sulfate before the ion-exchange supporting treatment of rare earth elements. (C-5) and (C-6) were prepared.

Example 5 Instead of the amorphous SiO ₂ · Al ₂ O ₃ composite oxide sol (S-3) used in Example 3, the silica-alumina gel (S-5) obtained in Production Example 5 was used. 25% by weight of the catalytic amount is added,
The catalyst (C-5) shown in Table 2 was prepared in the same manner as the catalyst (C-5) except that the commercially available silica sol (S-8) used in Production Example 1 was added in a balance of kaolinite clay in an amount of 25% by weight of the catalytic amount. -7) was prepared.

Comparative Example 1 Instead of the silica-alumina gel (S-5) used in Example 5, the silica-alumina gel (S-) obtained in Production Example 6 was used.
6) was used in the same manner as the catalyst (C-7), except that Table 3 was used.
The catalyst (R-1) shown in was prepared.

Comparative Example 2 This comparative example shows a method for preparing a catalyst using a mixture of silica sol and alumina sol instead of the amorphous SiO ₂ .Al ₂ O ₃ composite oxide. The commercially available silica sol (S-8) used in Production Example 1 was subjected to sodium removal treatment using a cation exchange resin to obtain a low pH (pH 2.3) silica sol (SiO ₂ concentration 15% by weight). . This silica sol 2
32.5 g (dry basis) and commercially available alumina sol [Catalyst Kasei Kogyo KK: trade name Cataloid AS-2; Al ₂
O ₃ concentration 10%] 17.5 g (dry basis) was mixed (Si
The weight ratio of O ₂ and Al ₂ O ₃ is SiO ₂ / Al ₂ O ₃ = 93 /
7) Amorphous Si used in Example 1 was used (S-7).
The catalyst (R-2) shown in Table 3 was prepared in the same manner as the catalyst C-2 except that it was used instead of the O ₂ · Al ₂ O ₃ composite oxide sol (S-1).

Comparative Example 3 This comparative example shows a method for preparing a catalyst containing no amorphous SiO ₂ .Al ₂ O ₃ composite oxide. 250 g (dry basis) of the commercially available silica sol (S-8) used in Production Example 1 was used, and 410 g (dry basis) of kaolinite clay was used.
40 g of activated alumina (dry basis), Y-type zeolite [previously ammonium ion-exchanged to give Na ₂ O of 0.3
% (Dry wt%)] was mixed with 300 g (dry basis), and the mixture was spray-dried to obtain spherical fine particles.
The obtained catalyst composition contains S-8 in an amount of 25% by weight based on the catalytic amount,
Kaolinite clay was contained in a catalytic amount of 41% by weight, activated alumina was contained in a catalytic amount of 4% by weight, and Y-type zeolite was contained in a catalytic amount of 30% by weight. This is subjected to sodium removal treatment with ammonium sulfate, and with a rare earth chloride aqueous solution,
A catalyst (R-3) shown in Table 3 was prepared by carrying out ion exchange loading of 0.9% by weight of a rare earth element as RE ₂ O _{3 with} respect to the amount of the catalyst.

Example 6 Regarding the catalysts obtained in Examples 1 to 5 and Comparative Examples 1 to 3, ASTM MAT (Micro Activity T) was used.
The activity evaluation test according to est) was performed. In order to investigate the coke and gas generation of the metal deposition catalyst, the selectivity of gasoline, etc., the catalyst was prepared by adding nickel and vanadium to each catalyst at Ni + V (V / Ni = 2/1) in the following manner.
0 ppm was deposited. That is, each catalyst is preheated to 600 ° C.
After calcination for 2 hours, the catalyst was allowed to absorb a predetermined amount of a benzene solution of nickel naphthenate and vanadium naphthenate, dried at 110 ° C., and then calcined at 600 ° C. for 1.5 hours. After that, 77 catalysts were added for pseudo equilibration.
Steam treatment was performed at 0 ° C. for 6 hours, and firing was performed again at 600 ° C. for 1 hour. Using each catalyst thus pretreated, AST
The results of the activity evaluation test by M MAT are shown in the following table. The reaction conditions are as follows. Feedstock: Desulfurization atmospheric pressure residual oil Reaction temperature: 540 ° C. Space velocity: 40 hr ⁻¹ Catalyst / oil ratio: 4 (weight) Further, the wear resistance of each catalyst was evaluated as follows. That is, after each catalyst was calcined at 600 ° C. for 2 hours, it was brought into a fluidized state with air having a constant flow rate, and this state was maintained for 30 hours to calculate the ratio (% by weight) of the finely divided catalyst to the initial catalyst. The results are also shown in the following table.

[Table 1]

[Table 2]

[Table 3] * ¹ Conversion rate: 100- (LCO +
HCO) * ² to * ⁴ Cut Temp. Gasoline:
C5-216 ° C LCO: 216-343 ° C HCO: 343 ° C ⁺

[0031]

[Effect] The catalytic composition for catalytic cracking of the present invention has a 4-coordinate aluminum strength I ₄ and a 6-coordinate aluminum strength I ₆ measured by ²⁷ Al-MAS NMR as a matrix.
Since it contains amorphous silica-alumina having a ratio (I ₄ / I ₆ ) to 70/30 to 100/0, the amount of weak acid in the matrix itself increases. Therefore, as compared with a catalyst having a strong acid in the matrix, mild cracking occurs in catalytic cracking of heavy oil and the like, so that coke and gas components are less generated, and selectivity to gasoline and LCO is improved. Further, when the amorphous silica-alumina is used in the form of a composite oxide sol, since the binding force as a binder is strong, the wear resistance of the obtained catalyst is also improved.

[Brief description of drawings]

FIG. 1 shows a ²⁷ Al-MAS NMR spectrum of amorphous silica-alumina composite oxide colloidal particles (S-1) of Production Example 1.

FIG. 2 shows a ²⁷ Al-MAS NMR spectrum of amorphous silica-alumina hydrogel (S-6) of Production Example 6.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiroyasu Nishida 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Prefecture Inside the Wakamatsu Plant of Catalysis Chemicals Co., Ltd. (56) References Japanese Patent Publication No. 50-8996 (JP, B1) ) (58) Fields surveyed (Int.Cl. ⁷ , DB name) B01J 21/00-37/36 C10G 11 / 00,47 / 00

Claims (3)

(57) [Claims] 1. A ratio (I ₄ / I ₆ ) of the strength of a tetracoordinated aluminum (I ₄ ) and the strength of a hexacoordinated aluminum (I ₆ ) measured by ²⁷ Al-MASNMR to a crystalline aluminosilicate zeolite. Is 70/30 to 100/0
And a catalyst composition for catalytic cracking of hydrocarbons containing the amorphous silica-alumina. 2. The ratio (I ₄ / I ₆ ) of the strength I ₄ of tetracoordinated aluminum and the strength I ₆ of tetracoordinated aluminum measured by ²⁷ Al-MASNMR to the crystalline aluminosilicate zeolite is 70/30. A method for producing a catalyst composition for catalytic cracking of hydrocarbons, which comprises mixing with an amorphous silica-alumina hydrate having a concentration of ˜100 / 0. 3. The method for producing a catalyst composition for catalytic cracking of hydrocarbons according to claim 2, wherein the amorphous silica-alumina hydrate is a silica-alumina composite oxide sol.