JPH10245218A - Crystalline aluminosilicate and fluid catalystic cracking catalyst for hydrocarbon oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a crystalline aluminosilicate showing a characteristic peak in its<1> H-MASNMR spectrum, and to obtain a fluid catalystic cracking catalyst by using the aluminosilicate. SOLUTION: This crystalline aluminosilicate consists substantially of silicon, aluminum, alkali metal, oxygen and hydrogen, and shows the main X-ray diffraction patterns of Y zeolite, wherein a unit lattice dimension is <=24.60Å, an area ratio of Si-OH group peak to acidic OH group peak is >=0.8 by analysis using the Gaussian function and an alkali metal content is 0.02 to 5.0wt.% in terms of its oxide. The other objective catalyst consists of a mixture of the aluminosilicate and inorganic oxide matrix and may further contain 0.01 to 10wt.% of at least one selected from the group consisting of rare earth metals and alkali earth metals in terms of the oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a ¹ H-masnm
The present invention relates to a crystalline aluminosilicate exhibiting a characteristic peak in an R spectrum and a catalyst for fluid catalytic cracking of a hydrocarbon oil using the same.

[0002]

2. Description of the Related Art In petroleum refining technology, it is generally the most important issue to produce gasoline having a high octane number and kerosene and light oil in good yield. In order to produce gasoline for this purpose, a gas oil fraction obtained by atmospheric distillation or vacuum distillation of crude oil, an atmospheric distillation residue or a vacuum distillation residue is converted into X or Y zeolite or USY zeolite (ultrastable). (Y zeolite), and a catalytic decomposition method using a catalyst comprising an inorganic matrix.

[0003] Many catalysts have been proposed for the above-mentioned catalysts. For example, stabilized Y zeolite is disclosed in US Patent Nos. 3,293,192 and 3,402,996. Have been. However, in the case of catalytic cracking of hydrocarbon oil using a catalyst containing stabilized Y zeolite, the olefin content in the gasoline fraction increases, or the yield of the LCO fraction corresponding to kerosene / light oil decreases. There is a problem.

In order to solve this problem, there has been provided a catalyst in which Y or stabilized Y zeolite is modified with a rare earth metal. However, this catalyst has a disadvantage that the octane number is reduced even though the olefin content can be reduced.

[0005] Also, there has been provided a catalyst in which silica-alumina, γ-alumina, or the like is used as a matrix, and Y or stabilized Y zeolite is mixed with these matrices so that the matrix also has activity. But,
This catalyst has the disadvantage of increasing the production of undesired products hydrogen and coke.

On the other hand, in order to solve the above problem, the present inventors first applied a thermal load to stabilized Y zeolite to obtain a crystalline aluminosilicate having high hydrothermal stability (Japanese Patent Laid-Open No. 4-59616). No. 5-178610), which further suppresses the production of hydrogen and coke,
There is a need for a technique capable of obtaining a high yield of an LCO fraction corresponding to light oil.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a catalyst for catalytic cracking of hydrocarbon oil, which can suppress the production of hydrogen and coke and can improve the yield of LCO fraction equivalent to kerosene and gas oil. And a crystalline aluminosilicate having specific physical properties that can be produced.

[0008]

SUMMARY OF THE INVENTION The crystalline aluminosilicate of the present invention is a crystalline aluminosilicate substantially composed of silicon, aluminum, an alkali metal, oxygen, and hydrogen.
(B) having a main X-ray diffraction pattern of Y zeolite,
(C) ¹ H-MA with a unit cell size of 24.60 ° or less
The area ratio of the Si-OH group peak to the acidic OH group peak in the SNMR spectrum is 0.8 or more as analyzed by Gaussian function, and (D) the alkali metal content is 0.02 to 5% by mass in terms of oxide. It is characterized by the following. Further, the fluid catalytic cracking catalyst for hydrocarbon oils of the present invention is characterized by comprising a mixture of the crystalline aluminosilicate and an inorganic oxide matrix, and the catalyst comprises a rare earth metal,
At least one selected from the group consisting of alkaline earth metals
It is preferable that the content of the seed is 0.01 to 10% by mass in terms of oxide based on the catalyst.

The crystalline aluminosilicate of the present invention is substantially composed of Si, Al, an alkali metal, O and H,
It has the following characteristics.

(A) It has a main X-ray diffraction pattern of Y zeolite. The X-ray diffraction pattern is shown in Table 1 as a representative example.
. That is, the lattice spacing (d) at which the highest intensity was actually measured is 14.1 ± 0.2 °, 5.6.
1 ± 0.1 °, 3.72 ± 0.1 °.

[0011]

[Table 1]

(B) The unit cell size is about 24.6.
0 ° or less, preferably about 24.60 to 24.30.
Å, more preferably about 24.50 to 24.35Å. The measurement of the unit cell size is performed according to ASTM D-3942 /
85, and can be calculated using the peak of X-ray diffraction. If this value is too large, the hydrothermal stability decreases. When the hydrothermal stability is reduced, the activity becomes poor when used in a fluid catalytic cracking catalyst for hydrocarbon oil.

Further, (C) ¹ H-MAS (Magic)
The area ratio of the Si-OH group peak to the acidic OH group peak in the Angle Spinning (NMR) NMR spectrum analyzed by a Gaussian function (hereinafter may be simply referred to as “peak area ratio” or “area ratio”) is as follows:
0.8 or more. This peak area ratio is Si-OH group /
When crystalline aluminosilicates with acidic OH groups <0.8 are used in fluid catalytic cracking catalysts for hydrocarbon oils, the yields of the desired gasoline and LCO fractions decrease. Although the detailed reason for this is not clear, it is considered that the number of acid sites becomes too large, and the gasoline and LCO fraction undergoes overcracking.

The crystalline aluminosilicate according to the present invention comprises ¹ H
In the MAS NMR spectrum, generally, the following 5
One peak is shown. (1) H peak position of Si-OH group: about 2 ppm (2) H peak position of OH group bonded to extra-framework Al:
About 3 ppm (3) H peak position of acidic OH group in the super cage:
About 4 ppm (4) Peak position of H of acidic OH group in sodalite cage: about 5 ppm (5) Peak position of H of NH ₄ ion at ion exchange site: about 7 ppm

The peak area ratio in the present invention can be determined as follows. First, ¹ H-MAS NMR
Correct the baseline of the spectrum. Then, each peak is separated into five Gaussian functions. At this time, the function values are changed so that the sum of the five Gaussian functions is as close as possible to the original spectrum. The way to change is
Based on non-linear least squares method. The area intensity of each of the five Gaussian functions obtained by this separation is calculated. The area intensity of the Gaussian function can be obtained by the following equation from the half width and the peak height of the function.

[0016]

[Number 1] ^{S = (wI 2/2)} · (π / log2) 1/2 S: area intensity w: full width at half maximum I: peak height

The ratio between the areal strength of the acidic OH groups obtained by this calculation and the areal strength of the Si—OH groups is calculated. The result is the peak area ratio (Si-OH group) / (acid OH
Base). Here, the area intensity of the Si—OH group peak is the area of the Si—OH group peak of (1) among the above five peaks, and the area intensity of the acidic OH group is (3)
And (4).

(D) The alkali metal content is about 0.02 to 5% by mass in terms of oxide, preferably about 0.02% by mass.
2 to 2% by mass. If the content of the alkali metal is too large, when the crystalline aluminosilicate of the present invention is used for a fluid catalytic cracking catalyst for hydrocarbon oil, not only the decomposition activity is reduced, but also the metal resistance of the crystalline aluminosilicate is reduced. If nickel, vanadium, and the like, which are contained in a base oil, particularly a heavy oil base oil, adhere to the base oil, there is a problem that the activity tends to deteriorate. Conversely, if the content of the alkali metal is too small, the hydrothermal stability of the crystalline aluminosilicate decreases, and when used in a fluidized catalytic cracking catalyst for hydrocarbon oils, the problem is that the activity tends to deteriorate. Occurs.

The crystalline aluminosilicate of the present invention comprises:
Bulk _SiO 2 / _Al 2 _{O 3} molar ratio of about 5 to 15 by chemical composition analysis, preferably about 5 to 12.

The crystalline aluminosilicate of the present invention can be produced by a known production method of Y zeolite or stabilized Y zeolite. For example, (1) a method for producing Y zeolite or stabilized Y zeolite which is hydrothermally synthesized directly from a suitable silica source and alumina source, (2) a method for producing stabilized zeolite by treating Y zeolite with a chemical, (3) a method for producing stabilized Y zeolite by treating with Y zeolite steam; (4) a method for producing stabilized Y zeolite by treating Y zeolite at a high temperature; (5) the above (1) to (4). Any one of the above (2) to (4) to the Y zeolite or the stabilized Y zeolite produced by the method of
A method of further performing more than kinds of treatments can be used.

The direct synthesis method (1) is, for example, as follows:
(A) Suitable SiO ₂ / Al ₂ O ₃ , Na ₂ O / SiO
₂ , sodium, aluminum in a H ₂ O / Na ₂ O ratio,
Mix a mixture of silicate and water (e.g., a mixture of sodium metasilicate, sodium aluminate, colloidal silica, water) and allow 20-120 until a crystalline product is formed.
C. (see Japanese Patent Publication No. 49-24000), (b) solid reactive amorphous silica and specific SiO
₂ / Al ₂ O ₃ , Na ₂ O / SiO ₂ , H ₂ O / Na ₂
95-160 ° F by mixing with aqueous aluminosilicate of O ratio
At about 6 to 15 hours, and then inject steam to raise the temperature to 240 to 300 ° F. to increase the water content to no more than 15% based on the amount of water initially present. Maintain at 240-300 ° F. for 4-20 hours under pressure and quickly drop from this natural pressure to atmospheric pressure to reduce about 35
The method is carried out by using a known method such as a method of obtaining a temperature decrease of ° F (Japanese Patent Application Laid-Open No. 50-18399)
By appropriately controlling the production conditions, a crystalline aluminosilicate having the above characteristics can be obtained. In this direct synthesis method, an alkali metal is inevitably contained in the obtained crystalline aluminosilicate. Therefore, the content of the alkali metal is adjusted to the above range by ion exchange.

The method (2) for treating with a chemical is as follows.
The zeolite is converted to ammonium hexafluorosilicate [(NH ₄ ) ₂ SiF ₆ ] or silicon tetrachloride (SiC
l ₄₎ a method of or treated with a silicon compound, or with EDTA and phosgene (COCl ₂₎ does not contain silicon, such as compound treatment such as, by appropriately controlling the conditions, the above characteristics The resulting crystalline aluminosilicate can be obtained.

In the method (3) of treating with steam, the Y zeolite is treated at about 300 to 1200 ° C. in a steam atmosphere.
A method of treating at about 500 to 1000 ° C. for about 5 to 300 minutes, preferably for about 5 to 100 minutes,
By controlling the holding temperature, the holding time and the like within this range, a crystalline aluminosilicate having the above characteristics can be obtained.

In the above method (4), the Y zeolite is treated at a temperature of about 600 to 1200 ° C., preferably about 600 ° C.
At about 1000C for about 5 to 300 minutes, preferably about 5 to 300 minutes.
This is a method of treating for 100 minutes, and by appropriately controlling the holding temperature and the holding time within this range, a crystalline aluminosilicate having the above characteristics can be obtained. If the temperature and the holding time are out of the above ranges, the above characteristics cannot be obtained. This heat treatment is usually performed in an electric furnace or a baking furnace at normal pressure in an air or nitrogen atmosphere. The heat treatment may be performed by placing the raw material zeolite in the electric furnace or firing furnace after the temperature reaches the above-mentioned temperature, or by gradually increasing the temperature from room temperature after placing the raw material zeolite in the electric furnace or firing furnace. The temperature may be reached, and the heating rate is not particularly limited.

In the step (5), the Y zeolite or the stabilized Y zeolite produced by the method of the above (1) to (4) is further subjected to one or more kinds of treatments of the above (2) to (4). For example, a method in which the stabilized Y zeolite obtained in the above (2) is subjected to the steam treatment of the above (3), and the stabilized Y zeolite obtained in the above (3) is subjected to the high temperature treatment of the above (4). And a method in which the stabilized Y zeolite obtained in the above (3) is subjected to the chemical treatment of the above (2) and subsequently subjected to the high temperature treatment of the above (4).

The crystalline aluminosilicate of the present invention can be produced by any of the above-mentioned methods (1) to (5), but is preferably produced by the method of finally performing the high-temperature treatment of (4). .

The fluid catalytic cracking catalyst for hydrocarbon oils of the present invention is a mixture of the above 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-zirconia, alumina-zirconia, etc., or a mixture thereof, montmorillonite, kaolin, halloysite, bentonite, atavulgarite,
At least one kind of clay mineral such as bauxite can be mentioned.

The mixing ratio of the crystalline aluminosilicate and the inorganic oxide matrix in the catalyst of the present invention is not particularly limited. However, if the amount of the crystalline aluminosilicate is too small, the performance as a catalytic cracking of hydrocarbon oil can be obtained. If it is not possible, on the contrary, if it is too large, the amount of the inorganic oxide matrix becomes relatively small, the strength of the catalyst decreases, the scattering of the catalyst,
Since problems such as interfering with the product and interfering with the operation of the apparatus occur, the crystalline aluminosilicate is reduced to about 5 to 60%.
%, Preferably about 10 to 50% by weight, the inorganic oxide matrix is about 40 to 95% by weight, preferably about 50 to 50% by weight.
The proportion is 90% by mass.

The above-mentioned mixture can be produced by a usual method. Typically, an aqueous slurry of silica-alumina hydrogel, silica sol or alumina sol is used as a suitable inorganic oxide matrix, After adding an aluminosilicate and mixing and stirring well, it is spray-dried to obtain catalyst fine particles.

The catalyst of the present invention may contain at least one selected from the group consisting of rare earth metals and alkaline earth metals in an amount of 0.01 to 10% by mass in terms of oxide, based on the catalyst.
Preferably, the content is 0.05 to 7% by mass. By containing these rare earth metals and alkaline earth metals, the catalyst of the present invention improves the effect of producing gasoline having a low olefin content.However, if the amount of these metals is too small, this effect does not appear, and even if the amount is too large, This effect does not improve much.

The above-mentioned rare earth metal and alkaline earth metal may be contained in the above-mentioned catalyst by ion exchange of the above-mentioned crystalline aluminosilicate with these metals. These metals may be supported on a basic aluminosilicate, the catalyst itself may be ion-exchanged with these metals, or the catalyst may be supported on these metals. Preferably, the catalyst itself is ion-exchanged with these metals.

As the rare earth metal, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium and the like are used, and these are used alone or in a mixture, preferably lanthanum. As the alkaline earth metal, beryllium, magnesium, calcium, strontium, barium, and radium are used, and these are used alone or as a mixture, and preferably magnesium or calcium is used alone or as a mixture. At least one of these rare earth elements and at least one of the alkaline earth metals can be used in combination.

The above-mentioned crystalline aluminosilicate or catalyst can be ion-exchanged or supported by the above-mentioned metal by a conventionally known method. For example, in both cases of ion exchange and loading, an aqueous solution containing one or more compounds of chlorides such as lanthanum, magnesium, calcium, etc., nitrates, sulfates, acetates, etc. is prepared by drying a crystalline aluminosilicate in a dry state. Alternatively, it is carried out by impregnating in a catalyst, or by immersing them in an aqueous solution thereof and, if necessary, heating.

The catalytic cracking of hydrocarbon oil using the catalyst of the present invention can be carried out by a known catalytic cracking method. For example, the hydrocarbon oil boiling above the gasoline boiling range may be brought into contact with the catalyst of the present invention. Hydrocarbon oils boiling above the gasoline boiling range include light oil fractions obtained by atmospheric or vacuum distillation of crude oil, atmospheric distillation residue, vacuum distillation residue, coker gas oil, solvent deasphalted oil, solvent deasphalted oil. Bitumen asphalt, tar sand oil, shale oil oil, coal liquefied oil and the like are included.

[0035] Catalytic cracking on a commercial scale usually involves two cracks, a vertically installed cracking reactor and a catalyst regenerator.
The above-described catalyst of the present invention is continuously circulated through a catalytic cracking device comprising a kind of vessel. The hot regenerated catalyst coming out of the catalyst regenerator is mixed with the hydrocarbon oil to be cracked,
It is directed upward in the cracking reactor. As a result, the catalyst deactivated by the carbonaceous material generally called coke depositing on the catalyst is separated from the decomposition product,
After stripping, it is 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 again to the cracking reactor.

On the other hand, the decomposition products are dry gas, LP
G, gasoline fractions and, for example, light cycle oils (LC
O), one or more heavy fractions such as heavy cycle oil (HCO) or slurry oil. Of course, the cracking reaction can be further advanced by recirculating these heavy fractions to the cracking reactor.

The operating conditions of the cracking reactor in the above-mentioned catalytic cracking apparatus are as follows:
a, preferably normal pressure to 0.3 MPa, temperature about 400 to
600 ° C., preferably about 450-550 ° C., and the catalyst / feed hydrocarbon oil mass ratio is about 2-20, preferably about 4-1.
A value of 5 is suitable.

[0038]

【Example】

Example 1 (Preparation of crystalline _{aluminosilicate)} SiO 2 / _Al 2 _{O 3}
The molar ratio is 8, and the alkali metal content is 0.2 in terms of oxide.
Stabilized Y zeolite having a mass% of about 24.58 ° and a unit cell size of about 800.degree.
For 20 minutes to obtain a crystalline aluminosilicate. When this crystalline aluminosilicate was analyzed by XRD measurement, it showed a main X-ray diffraction pattern of Y zeolite indicated by reference symbol a in FIG. 1 and a unit cell size of 24.40 °.
Met. The crystallinity of the crystalline aluminosilicate is 70% with respect to 100% of the stabilized Y zeolite as the raw material.
Met.

(Measurement of ¹ H-MAS NMR spectrum)
The crystalline aluminosilicate obtained in Example 1 was replaced with ¹ H-MA
Analyzed by SNMR spectrum. For analysis,
After the adsorbed water adsorbed on the sample is sufficiently removed by vacuum evacuation, the sample is sealed in a sample tube filled with N ₂ gas, and 3.5 k
The ¹ H-MAS NMR spectrum was measured in the MAS state at Hz.

This result is indicated by reference numeral a in FIG. As is clear from the figure, the above crystalline aluminosilicate is
The peak at 2 ppm due to the i-OH group has a higher intensity than the peak at 4 ppm due to the acidic OH group. When this spectrum was analyzed, the peak area ratio was Si-OH group / acidic OH group ≒ 2.34.

(Preparation of Catalyst A) The above-mentioned crystalline aluminosilicate was mixed so that the content in the final catalyst was 35% by mass.
Further, kaolin was added to the silica sol so that the content in the final catalyst was 45% by mass, mixed and stirred, and then spray-dried with a spray drier to form fine particles. These fine particles are referred to as catalyst A.

Example 2 A crystalline aluminosilicate was prepared in the same manner as in Example 1 except that the heat treatment temperature in the electric furnace was changed to 750 ° C., and further, catalyst fine particles (catalyst B) were obtained.

The above crystalline aluminosilicate was prepared in Example 1
When the analysis was performed by XRD measurement in the same manner as described above,
1 shows a main X-ray diffraction pattern of Y zeolite indicated by a symbol b in FIG. 1, and the unit cell dimension was 24.43 °. The crystallinity of the crystalline aluminosilicate was 70% with respect to 100% of the stabilized Y zeolite as the raw material.

Further, as in Example 1, ¹ H-M
The result analyzed by the ASNMR spectrum is shown by the symbol b in FIG. As is clear from the figure, this crystalline aluminosilicate also has a 2 ppm peak caused by the Si-OH group more than a 4 ppm peak caused by the acidic OH group.
High strength. When this spectrum was analyzed, the peak area ratio was found to be Si—OH group / acidic OH.
The base was $ 0.96.

Example 3 The procedure of Example 1 was repeated, except that a stabilized Y zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 7 and an alkali metal content of 1.2% by mass in terms of oxide was used. A crystalline aluminosilicate was prepared.

The above crystalline aluminosilicate was prepared in Example 1.
When the analysis was performed by XRD measurement in the same manner as described above,
FIG. 1 shows a main X-ray diffraction pattern of Y zeolite indicated by a symbol c in FIG. 1 and a unit cell dimension was 24.48 °. The crystallinity of the crystalline aluminosilicate was 89% based on 100% of the stabilized Y zeolite as the raw material.

Further, in the same manner as in Example 1, ¹ H-M
The result analyzed by the ASNMR spectrum is shown by the symbol c in FIG. As is clear from the figure, this crystalline aluminosilicate also has a 2 ppm peak caused by the Si-OH group more than a 4 ppm peak caused by the acidic OH group.
High strength. When this spectrum was analyzed, the peak area ratio was found to be Si—OH group / acidic OH.
The base was $ 1.00.

Comparative Example 1 Example 1 was repeated except that the stabilized Y zeolite was used as it was.
In the same manner as described above, catalyst fine particles (catalyst C) were obtained. Stabilized Y
When the zeolite was analyzed by XRD measurement in the same manner as in Example 1, the main X-ray diffraction pattern of the Y zeolite indicated by the symbol d in FIG.
4.58４.

The results of analyzing the above stabilized Y zeolite by ¹ H-MAS NMR spectrum in the same manner as in Example 1 are shown by the symbol d in FIG. As is clear from the figure, this stabilized Y zeolite is
The peak at 2 ppm due to -OH groups is less intense than the peak at 4 ppm due to acidic OH groups. When the spectrum was analyzed, the peak area ratio was Si—OH group / acidic OH group ≒ 0.17.

Example 4, Comparative Example 2 (Micro-Activity Test) Using an ASTM-based fixed-bed Micro-activity Test apparatus, under the same hydrocarbon oil and the same reaction conditions, the catalyst A,
The catalytic cracking characteristics of B and C were tested. Prior to the test, each test catalyst was charged with 10% Ni and 10 V for simulated equilibration.
After carrying 00 mass ppm and 2000 mass ppm, 8
The treatment was performed at 00 ° C. for 6 hours in a 100% steam atmosphere. Vacuum distilled light oil was used as the hydrocarbon oil to be decomposed, and the test conditions were as follows. The microactivity test was performed using a fixed-bed test apparatus, and preferred conditions do not always correspond to the commercial-scale fluid catalytic cracking described in the text.

Reaction temperature: 500 ° C. Catalyst / hydrocarbon oil mass ratio: 2.3, 3.0, 3.8 Test time: 75 seconds

The results obtained were compared based on a conversion of 55%, and the results are shown in Table 2. As is clear from Table 2, the catalysts A and B have a higher yield of LCO corresponding to gasoline, kerosene and light oil, a lower yield of heavy distillate (HCO), and a lower hydrogen content than the catalyst C. And the coke yield has not increased. Moreover, the octane number of the obtained gasoline has not decreased. That is, when the catalytic cracking of the hydrocarbon oil is performed using the fluid catalytic cracking catalyst containing the crystalline aluminosilicate of the present invention, the production amount of hydrogen and coke is suppressed, and the LCO equivalent to the lamp / light oil is reduced. It turns out that it shows good performance that the yield is high.

[0053]

[Table 2]

Example 5 (Preparation of Catalyst D) The catalyst A obtained in Example 1 was immersed in a 10-fold amount of an aqueous 0.1N lanthanum chloride solution at 70 ° C. for 2 hours, subjected to ion exchange, and filtered. After washing with water and drying at 115 ° C. for 16 hours, catalyst fine particles were obtained. This is designated as catalyst D. The lanthanum content of Catalyst D was 1.2% by mass in terms of oxide based on Catalyst A.

Comparative Example 3 (Preparation of Catalyst E) Catalyst fine particles were obtained in the same manner as in Example 5 except that the catalyst C obtained in Comparative Example 1 was used. This is designated as catalyst E. The lanthanum content of Catalyst E was 1.3% by mass in terms of oxide based on Catalyst C.

(Bench Scale Plant Activity Test) A bench scale plant which is a scale down version of a commercial scale fluid catalytic cracking unit, which is a circulating fluidized bed reactor equipped with a cracking reactor and a catalyst regenerator, is used. Fluid catalytic cracking properties of catalysts D and E were tested. Prior to the test, each of the test catalysts was loaded with 650 mass ppm and 1250 mass ppm of Ni and V, respectively, for simulated equilibration, and then treated at 785 ° C. for 6 hours in a 100% steam atmosphere. Vacuum distilled light oil was used as the hydrocarbon oil to be decomposed, and the test conditions were as follows.

Reaction temperature: 500 ° C. Catalyst / hydrocarbon oil mass ratio: 4.0 to 13.0 Catalyst circulation amount: 60 g / min

The results obtained were compared on the basis of a conversion of 65%, and the results are shown in Table 3. As is evident from Table 3, Catalyst D has a higher LCO yield corresponding to kerosene and light oil, a lower yield of heavy fraction (HCO), and a lower yield of hydrogen and coke than Catalyst E. The rate has not increased. Moreover, the octane number of the obtained gasoline has not decreased. That is, when the fluid catalytic cracking of the hydrocarbon oil is performed using the fluid catalytic cracking catalyst containing the crystalline aluminosilicate of the present invention, the amount of hydrogen and coke generated is suppressed,
In addition, it can be seen that a good performance that the yield of LCO corresponding to the lamp / light oil is high is exhibited.

[0059]

[Table 3]

[0060]

According to the fluid catalytic cracking catalyst for hydrocarbon oils using the crystalline aluminosilicate having the characteristics of the present invention, the amount of undesired hydrogen and coke can be suppressed, while the amount of hydrogen and coke is suppressed. LCO fraction can be obtained in high yield.

[Brief description of the drawings]

FIG. 1 shows an X-ray diffraction pattern of a crystalline aluminosilicate of the present invention obtained in an example and an X-ray diffraction pattern of stabilized Y zeolite for comparison.

2 shows a ¹ H-MASNMR spectrum of the crystalline aluminosilicate of the present invention obtained in Example, a ¹ H-MASNMR spectrum of stable Y zeolite for comparison.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Mitsuru Oi 1134-2, Gongendo, Satte-shi, Saitama Prefecture Inside the R & D Center, Cosmo Research Institute, Inc. (72) Yoichi Ono 1134-2, Gongendo, Satte-shi, Saitama Cosmo Research Institute R & D Center

Claims (3)

[Claims] 1. A crystalline aluminosilicate consisting essentially of silicon, aluminum, alkali metal, oxygen and hydrogen, comprising: (A) a primary X-ray diffraction pattern of Y zeolite; (B) (C) Si-O in ¹ H-MAS NMR spectrum having a unit cell size of 24.60 ° or less
The area ratio of the H group peak to the acidic OH group peak is 0.8 or more as analyzed by Gaussian function, and (D) the alkali metal content is 0.02 to 5 in terms of oxide.
A crystalline aluminosilicate characterized by mass%. 2. A fluid catalytic cracking catalyst for hydrocarbon oils, comprising a mixture of the crystalline aluminosilicate according to claim 1 and an inorganic oxide matrix. 3. The catalyst according to claim 2, wherein the content of at least one selected from the group consisting of rare earth metals and alkaline earth metals is 0.01 to 10% by mass in terms of oxide based on the catalyst of claim 2. The fluidized catalytic cracking catalyst according to claim 2, wherein