JP2023037954A - Fluid catalytic cracking catalyst and method of producing same - Google Patents

Abstract

To provide a fluid catalytic cracking catalyst enabling improvement of the yield of propylene in fluid catalytic cracking and enabling suppression of the formation of naphthenes.SOLUTION: The fluid catalytic cracking catalyst is provided, including 10-30 mass% of a binder, 10-40 mass% of zeolites ion-exchanged with rare earth metals, 10-60 mass% of clay minerals, and 5-30 mass% of an active matrix, wherein the rare earth metal content is 0.5-1.2 mass% in terms of rare earth metal oxides (RE2O3), the binder is a silica binder, the zeolites are FAU-type zeolites with a lattice constant in the range of 2.438-2.460 nm, and the active matrix includes alumina-silica.SELECTED DRAWING: None

Description

The present invention relates to a fluid catalytic cracking catalyst and a method for producing the same.

Catalysts used for fluid catalytic cracking of hydrocarbon oils (hereinafter also referred to as "FCC catalysts") and their production methods have been developed for the purpose of increasing the yield of gasoline fractions in fluid catalytic cracking. ing.

For example, in Patent Document 1, for the purpose of providing a method for producing an FCC catalyst with high gasoline yield, low coke yield, and high abrasion strength, zeolite (ultra-stabilized Y-type zeolite, rare earth-exchanged ultra-stabilized Y-type zeolite, etc.), a binder (basic aluminum chloride), an inorganic oxide matrix (kaolin, etc.), and spray-drying a pH-adjusted slurry. ing. It also describes that spherical particles obtained by spray drying were washed with pure water, then washed with water containing ammonium sulfate, and dried to produce an FCC catalyst.

In the FCC catalyst composition described in Patent Document 2, Y-type zeolite contains yttrium to improve the production amount of light olefins (such as propylene).
Patent Documents 3 and 4 describe that the abrasion resistance of the FCC catalyst is improved by using a predetermined colloidal silica as a raw material of the FCC catalyst.

Patent Document 5 describes a step of mixing a predetermined rare earth metal-containing ultra-stable Y-type zeolite, a silica-based matrix-forming component, water, and optionally clay minerals and optionally additives to prepare a raw material slurry. A process for producing a fluid catalytic cracking catalyst is described comprising the steps of spray drying a slurry to obtain particles and contacting the particles with water containing an ammonium salt.

JP-A-2009-657 Japanese Patent Publication No. 2013-522025 Japanese Patent Publication No. 2019-528163 Japanese Patent Publication No. 2021-511200 Japanese Patent Application Laid-Open No. 2021-79378

However, conventional FCC catalysts have room for further improvement from the viewpoint of improving the yield of propylene in fluidized catalytic cracking and suppressing the formation of naphthenes.
SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an FCC catalyst capable of improving the yield of propylene and suppressing the formation of naphthenes in fluidized catalytic cracking, and a method for producing the same.

The present invention relates to, for example, the following [1] to [3].
[1]
10-30% by weight of a binder, 10-40% by weight of a zeolite ion-exchanged with rare earth metals, 10-60% by weight of clay minerals, and 5-30% by weight of an active matrix,
The content of the rare earth metal is 0.5 to 1.2% by mass in terms of rare earth metal oxide (RE ₂ O ₃ ),
The binder is a silica-based binder,
The zeolite is an FAU-type zeolite having a lattice constant in the range of 2.438 to 2.460 nm,
A fluid catalytic cracking catalyst, wherein said active matrix comprises alumina-silica.

[2]
(a) preparing a raw material slurry comprising a binder-forming component, a zeolite, clay minerals, and an active matrix-forming component;
(b) a step of spray-drying the raw material slurry to obtain particles;
(c) contacting the particles with an aqueous solution comprising a rare earth metal to ion exchange the zeolite with the rare earth metal;
The binder-forming component is a silica-based binder-forming component,
The zeolite is FAU-type zeolite having a lattice constant in the range of 2.438 to 2.460 nm,
A process for producing a fluid catalytic cracking catalyst, wherein said active matrix comprises alumina-silica.

[3]
A fluid catalytic cracking catalyst composition comprising the fluid catalytic cracking catalyst of [1] and a co-catalyst containing ZSM-5.

According to the present invention, when a catalytic cracking catalytic reaction is performed using a fluid catalytic cracking catalyst composition in which a ZSM-5 additive is added to a fluid catalytic cracking catalyst, the pyrene yield is improved and the product is cyclized. It is possible to suppress the generation of naphthenes by

The present invention will now be described in more detail.
[Fluid catalytic cracking catalyst]
The fluid catalytic cracking catalyst (FCC catalyst) according to the present invention comprises a binder, a rare earth metal ion-exchanged zeolite, clay minerals, and an active matrix.

<Binder>
As the binder (hereinafter also referred to as "binder"), a silica-based binder is used.
Silica-based binders are formed from silica, silica gel (including silica hydrogel), silica sol (including silica hydrosol), water glass (sodium silicate), silicic acid liquid, and the like. Examples of silica sol include sodium-type, lithium-type, acid-type colloidal silica, and the like. Of these, silica sol is preferred. When fluidized catalytic cracking is performed using the FCC catalyst, the formation of coke is suppressed because the binder is a silica-based binder.

The FCC catalyst of the present invention contains, for example, 10 to 30% by weight, preferably 12 to 26% by weight, more preferably 14 to 24% by weight of the binder.
Each component and raw material constituting the FCC catalyst of the present invention may contain water. ).

<Zeolite ion-exchanged with rare earth metal>
The details of the zeolite in the zeolite ion-exchanged with rare earth metals, that is, the zeolite before ion exchange will be described later.
Examples of the rare earth metals include cerium (Ce), lanthanum (La), praseodymium (Pr), and neodymium (Nd). These may be one kind or two or more kinds.

The FCC catalyst of the present invention contains, for example, 10 to 40 mass %, preferably 12 to 38 mass %, more preferably 14 to 36 mass % of the zeolite ion-exchanged with the rare earth metal. When the content is at least the lower limit, the resulting FCC catalyst exhibits sufficient activity. On the other hand, when the content is equal to or less than the above upper limit, it is possible to prevent excessive cracking and decrease in selectivity due to too high activity in the resulting FCC catalyst.

<Clay minerals>
Said clay minerals serving as bulking agents are clays and/or clay minerals, examples of which include kaolin, bentonite, kaolinite, halloysite, montmorillonite, etc. Among these, kaolin is preferred.

The FCC catalyst of the present invention contains, for example, 10 to 60% by mass, preferably 14 to 56% by mass, and more preferably 18 to 52% by mass of the clay minerals. When the content is at least the above lower limit, maintenance of the pore structure of the FCC catalyst, maintenance of the catalyst shape, abrasion resistance, fluidity, etc. are favorable. On the other hand, when the content is equal to or less than the upper limit, the activity of the FCC catalyst is good because the ratio of the zeolite component in the FCC catalyst is high.

<Activity matrix>
The active matrix comprises alumina-silica, and optionally an active matrix other than alumina-silica. Examples of active matrices other than alumina-silica include those containing materials with solid acids such as activated alumina (boehmite, gibbsite, etc.), silica-magnesia, alumina-magnesia, silica-magnesia-alumina. Solid acid indicates solid acidity in the temperature range where the catalyst is used. Solid acidity can be confirmed by, for example, temperature programmed desorption using ammonia, in situ FTIR (Fourier transform infrared ray) using ammonia or pyridine. absorption spectrum) method.

Since the active matrix contains alumina-silica, the hydrothermal resistance of the matrix is improved and a high matrix specific surface area can be maintained.
The active matrix preferably contains 10 mass % or more of alumina-silica, more preferably 15 to 65 mass %, and even more preferably 20 to 60 mass %.
The alumina-silica preferably contains 3 to 30% by weight of silica.

Active matrices that also function as metal scavengers include alumina particles, phosphorus-alumina particles, crystalline calcium aluminate, sepiolite, barium titanate, calcium stannate, strontium titanate, manganese oxide, magnesia, and magnesia-alumina. is mentioned.

As a raw material for the metal scavenger, a precursor substance such as boehmite that becomes alumina or the like by firing in an oxidizing atmosphere can also be used.
The FCC catalyst of the present invention contains, for example, 5 to 30% by weight, preferably 8 to 29% by weight, more preferably 10 to 28% by weight of the active matrix.

<Optional component>
The FCC catalysts of the present invention may optionally contain additives in addition to binders, rare earth metal ion-exchanged zeolites, clay minerals, and active matrices.
Examples of the additives include CO combustion promoting components (Pt, Pd), desulfurized oxide components (CeO ₂ , MgO), and the like.

(Rare earth metal content)
The FCC catalysts of the present invention contain rare earth metals. The content of the rare earth metal in the FCC catalyst of the present invention is 0.5 to 1.2% by mass, more preferably 0.6 to 1.1% by mass in terms of rare earth oxide (RE ₂ O ₃ ). %. When the rare earth metal content is within the above range, the FCC catalyst of the present invention has excellent hydrothermal resistance and excellent propylene yield.

[Method for producing fluid catalytic cracking catalyst]
The method for producing a fluid catalytic cracking catalyst (FCC catalyst) according to the present invention is
(a) preparing a raw material slurry comprising a binder-forming component, a zeolite, clay minerals, and an active matrix-forming component;
(b) a step of spray-drying the raw material slurry to obtain particles;
(c) contacting the particles with an aqueous solution containing a rare earth metal to ion-exchange the zeolite with the rare earth metal;

<<Step (a)>>
In step (a), a raw material slurry containing a binder-forming component, zeolite, clay minerals, and an active matrix-forming component is prepared.

As an embodiment of the step (a), for example, a raw material slurry is prepared by mixing a binder-forming component with zeolite, clay minerals, an active matrix-forming component, and optional additives. Each component may be added in the form of powder or may be added in the form of slurry. The order of adding each component does not matter.

(Binder forming component)
The binder-forming component is a component for forming a binder in the fluid catalytic cracking catalyst. A silica-based binder-forming component is used as the binder-forming component. Examples of silica-based binder-forming components include silica, silica gel (including silica hydrogel), silica sol (including silica hydrosol), water glass (sodium silicate), and silicic acid liquid. Colloidal silica of sodium type, lithium type, acid type, etc. can also be used for the silica sol. Of these, silica sol is preferred. A commercially available product may be used, or a silica sol may be prepared by adding acid to water glass.

(zeolite)
FAU-type zeolite is used as the zeolite. Examples of FAU-type zeolite include ultra-stable Y-type zeolite (USY) and rare-earth metal-exchanged ultra-stable Y-type zeolite (hereinafter also referred to as “REUSY”) obtained by introducing a rare earth metal into USY by ion exchange or the like. be done.

The lattice constant of the zeolite measured by the method employed in the examples described later is preferably in the range of 2.438 to 2.460 nm, more preferably in the range of 2.440 to 2.458 nm.
The lattice constant is determined by the X-ray diffraction method using anatase-type TiO ₂ as a standard material and by the interplanar spacing between the (553) plane and the (642) plane of the zeolite.

In a preferred embodiment of the step (a), after the clay minerals and active matrix-forming component are added to the binder-forming component, zeolite is added in the form of a slurry adjusted to a pH of 2.8-4.5. do. By doing so, it is possible to suppress the pH fluctuation of the zeolite-containing slurry due to the addition, and suppress the aggregation of the zeolite. The slurry can be prepared, for example, by adding the zeolite and acid to water. Examples of the acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, organic acids (eg, citric acid, formic acid, acetic acid, etc.).

(Clay minerals)
Specific examples and preferred embodiments of the clay minerals are as described above.

(active matrix-forming component)
Examples of the active matrix-forming component include, in addition to the specific examples of the active matrix described above, components that form an active matrix upon heating, such as aluminum hydroxide (gibbsite) and alumina hydrate (boehmite).

The raw material slurry may be prepared by mixing these components, optionally additives, and optionally water.
The raw material slurry contains, for example, 10 to 30 mass %, preferably 12 to 26 mass %, more preferably 14 to 24 mass % of the binder-forming component in terms of the amount of SiO ₂ (however, the raw material slurry contains The solid content (components other than the dispersion medium in the raw material slurry. The same shall apply hereinafter.) shall be 100% by mass.) is contained.

The raw material slurry contains, for example, 10 to 40% by mass, preferably 12 to 38% by mass, more preferably 14 to 36% by mass of the zeolite (where the solid content of the raw material slurry is 100% by mass). .

The raw material slurry contains, for example, 10 to 60% by mass, preferably 14 to 56% by mass, more preferably 18 to 52% by mass of the clay minerals (provided that the solid content of the raw material slurry is 100% by mass). contains.

The raw material slurry contains the active matrix-forming component in an amount of, for example, 5 to 30% by mass, preferably 8 to 29% by mass, more preferably 10 to 28% by mass (provided that the solid content of the raw material slurry is 100% by mass). )contains.

The raw material slurry contains water as a dispersion medium.
The raw material slurry may contain a small amount of components other than water, such as methanol, ethanol, and acetone, as a dispersion medium.
The solid content concentration of the raw material slurry is, for example, 10 to 50% by mass, preferably 20 to 40% by mass, from the viewpoint of carrying out spray drying of the raw material slurry without difficulty.

<<Step (b)>>
In the step (b), the raw material slurry is spray-dried to obtain particles (hereinafter also referred to as “spray-dried particles”).

Spray drying conditions may be appropriately changed depending on the solid content concentration, viscosity, etc. in the slurry, and the average particle size of the obtained catalyst is within the range of 50 to 90 μm, which is generally used as an FCC catalyst. It is not particularly limited as long as it is a condition. For example, the raw material slurry is filled in a slurry storage tank of a spray dryer, for example, by spraying the raw material slurry into a drying chamber in which an air flow (for example, air flow) adjusted to a range of 120 to 450 ° C. flows. (spray-dried particles) are obtained. Although the temperature of the air stream is lowered by the spray drying of the raw material slurry, the temperature at the outlet of the drying chamber is maintained in the range of, for example, 50 to 300° C. using a heater or the like.

The particle size of the spray-dried particles can be controlled by adjusting the concentration, viscosity, spray amount, spray pressure, nozzle diameter of the spray dryer, hot air temperature, etc. of the raw material slurry.
The spray-dried particles may also be washed (eg, washed with water) and dried.

<<Step (c)>>
In step (c), the spray-dried particles are contacted with an aqueous solution containing a rare earth metal to ion-exchange the zeolite in the spray-dried particles with the rare earth metal. An FCC catalyst is obtained by this step (c).

In step (c), preferably the spray-dried particles are suspended in water to form a suspension, and the suspension is contacted with an exchange aqueous solution containing the rare earth metal. The resulting solids (FCC catalyst) may then be separated, washed and dried. The temperature of the water is preferably 40-80°C. Alternatively, the suspension may be filtered, and the filtered solids may be suspended again in water to remove unnecessary soluble substances adhering to the spray-dried particles.

An aqueous solution containing a rare earth metal can be prepared, for example, by dissolving a salt of the rare earth metal (eg, LaCl ₃ ) in water.
The step (c) is performed so that the ion exchange rate with respect to the zeolite is in the range of 20% by mass or less. Specifically, the ion exchange capacity of the zeolite is calculated in advance from the amount of the zeolite, lattice constant, and chemical analysis, and the ion exchange rate is adjusted by the amount, concentration, etc. of the rare earth metal-containing aqueous solution to be brought into contact during ion exchange.

The ion exchange rate is preferably 5 to 20% by mass, more preferably 6 to 18% by mass.
The ion exchange rate as used herein means the occupancy rate of ion exchange sites in consideration of the valence of ion-exchanged rare earth ions with respect to the number of aluminum atoms in the zeolite framework.

When the zeolite is USY zeolite, the number of aluminum atoms in its framework can be calculated by Breck's formula (below), and the number of atoms contained in the unit cell is calculated as 192.
N _Al =115.2×(a ₀ −24.191)
where N _Al is the number of aluminum atoms in the framework and a ₀ is the lattice constant (Å).
The method for calculating the ion exchange rate is as follows.

From the chemical composition of USY zeolite obtained by fluorescent X-ray analysis, the amount of extra-framework aluminum atoms is calculated, and the amount of ion exchange sites contained in USY zeolite is calculated. From the amount of rare earth metal in the chemical composition of the USY zeolite into which the rare earth metal was introduced, which was obtained by fluorescent X-ray analysis after FCC catalyst preparation, considering the valence at the time of ion exchange, for example, ionization was performed using a _LaCl3 aqueous solution. When exchanged, as La ³⁺ , 3 atoms of aluminum atoms in the zeolite framework are occupied for 1 atom of La, and the rare earth metal introduced into the FCC catalyst by step (c) is all present at the ion exchange sites Calculate the ion exchange rate assuming that

Not only when the zeolite does not contain a rare earth metal, but also when using the REUSY as the zeolite and preparing the raw material slurry in step (a) or washing the spray-dried particles obtained in step (b) In addition, even if some rare earth metal ions are removed from REUSY (substituted with protons), the step (c) is performed to produce a fluid catalytic cracking catalyst containing a desired amount of rare earth metals. can do.

By the method for producing a fluid catalytic cracking catalyst according to the present invention including steps (a) to (c) as described above, the fluid catalytic cracking catalyst according to the present invention can be produced.

[Fluid catalytic cracking catalyst composition]
A fluid catalytic cracking catalyst composition according to the present invention comprises an FCC catalyst according to the present invention and a co-catalyst comprising ZSM-5.
As the auxiliary catalyst (additive) containing ZSM-5, if it is a commercial product, for example, additive (OCTUP-α, OCTUP-R) manufactured by Nikki Shokubai Kasei Co., Ltd., [0038 of JP 2013-522025] ] and the ZSM-5 additive or ZSM-5-containing additive described in paragraph . The content of the auxiliary catalyst in the catalyst composition is preferably 1 to 35% by mass, more preferably 5 to 25% by mass, when the content of the FCC catalyst according to the present invention is 100% by mass. is.

The FCC catalyst composition according to the present invention preferably has a specific surface area of 200 to 400 m ² /g, more preferably 250 to 350 m ² /g, as measured by the method employed in the examples below.

When the FCC catalyst composition according to the present invention is used for fluidized catalytic cracking, it is possible to improve the propylene selectivity, suppress the hydrogen transfer reaction in the FCC catalyst, and suppress the formation of i-paraffins and naphthenes. can. The reason for this is that the distance between acid sites in the catalyst is increased and the amount of acid sites per unit surface area is increased compared to catalysts in which the lattice constant of zeolite and the content of rare earth metals are larger than the ranges specified in the present invention. It is presumed that this is because the bimolecular reaction is suppressed, and the abstraction of hydrogen at the matrix acid site (Lewis acid site) is suppressed.

The present invention will be explained in more detail by way of examples.
[Method for measuring or evaluating catalyst, etc.]
(composition)
The content of each element contained in the zeolite and the catalysts obtained in Examples and the like was measured using a fluorescent X-ray analyzer (RIX 3000, manufactured by Rigaku Corporation).

(Lattice constant of zeolite)
The lattice constant of the zeolite was determined from the interplanar spacing between the (553) and (642) diffraction planes of the zeolite by the X-ray diffraction method under the following conditions using anatase TiO ₂ as a standard substance.

"Measurement condition"
After pulverizing and molding the catalyst obtained in Examples etc., it was set in an X-ray diffractometer (X-RAY DIFFRACT METER (RINT 1400) manufactured by Rigaku Co., Ltd.), tube voltage 30.0 kV, tube current 130.0 mA, Anticathode Cu, measurement range: start angle to end angle (2θ) 10.000° to 70.000°, scan speed 2.000°/min, divergence slit 1 deg, scattering slit 1 deg, receiving slit 0.15 mm It was measured.

(Specific surface area)
The specific surface areas of the catalysts of Examples and the like were measured by BELSORP-mini Ver2.5.6 manufactured by Microtrack Bell Co., Ltd. Specifically, nitrogen gas was adsorbed on the catalyst that had been heat-treated at 500° C. for 1 hour while being evacuated, and the specific surface area (m ² /g) was calculated by the BET method.

[Production Example 1]
~Preparation of alumina-silica slurry-1~
6280 g of aluminum sulfate aqueous solution (Al ₂ O ₃ concentration: 2.5 mass %) was added to 6530 g of sodium aluminate aqueous solution (Al ₂ O ₃ concentration: 5 mass %) and stirred at 65° C. for 1 hour to form an alumina slurry. Obtained. Then, the alumina slurry was washed with hot water to make the washed alumina cake contain Na ₂ O of 2% or less by dry mass and SO ₄ of 1% or less by dry mass. Next, pure water was added to the washed alumina cake to prepare a washed alumina slurry having an Al ₂ O ₃ concentration of 12.5%, and a 48% by mass sodium hydroxide aqueous solution was added to adjust the pH to 11.5. Then, the mixture was aged at 95° C. for 20 hours while stirring to obtain a slurry of crystalline boehmite (specific surface area: 178 m ² /g) (hereinafter “slurry A”).

A diluted water glass with a SiO ₂ concentration of 5% by mass was ion-exchanged with a cation exchange resin to prepare a desalted silicic acid solution with a pH of 2.67. A 15% by mass ammonia aqueous solution was added to 232.5 g of a 5% by mass desalted silicic acid solution to adjust the pH to 10.8. Slurry A: 3100 g (Al ₂ O ₃ concentration: 9% by mass) was added with the desalted silicic acid solution adjusted to pH 10.8 and stirred at room temperature for 30 minutes. Next, while stirring, aging is performed at 95° C. for 8 hours, and the amount of water is adjusted to prepare alumina-silica slurry-1 containing 4% by mass of silica in alumina-silica (solid concentration: 12% by mass). got

[Production Example 2]
~Preparation of alumina-silica slurry-2~
Alumina-silica slurry-2 (solid concentration: 10% by mass) containing 18% by mass of silica in alumina-silica was prepared in the same manner as in Production Example 1, except that the amount of the desalted silicic acid solution was changed to 1225 g. Obtained.

[Production Example 3]
~ Preparation of alumina slurry ~
Alumina (boehmite) slurry (solid content concentration: 10 mass %) was obtained.

[Production Example 4]
~Preparation of ultra-stable Y-type zeolite slurry-1~
Example 1 of JP-A-9-173853 was carried out by changing the firing temperature in the second firing process of zeolite from 670 ° C. to 810 ° C., ultra-stable Y-type zeolite-1 (lattice constant: 2.443 nm , SiO ₂ /Al ₂ O ₃ ratio: 7.1, ion exchange capacity: 2.251 mmol/g). Ultra-stable Y-type zeolite-1 and sulfuric acid were added to water to obtain ultra-stable Y-type zeolite slurry-1 (solid concentration: 33% by mass) having a pH of 3.9.

[Production Example 5]
~Preparation of ultra-stable Y-type zeolite slurry-2~
Ultra-stable Y-type zeolite-2 (lattice constant: 2.458 nm, SiO ₂ /Al ₂ O ₃ ratio: 5.4, ion exchange capacity: 3.731 mmol/g ). Ultra-stable Y-type zeolite-2 and sulfuric acid were added to water to obtain ultra-stable Y-type zeolite slurry-2 (solid concentration: 33% by mass) having a pH of 3.9.

[Example 1]
～FCC catalyst-1 preparation～
2941 g of water glass (SiO ₂ concentration: 17% by mass) and 1059 g of sulfuric acid (sulfuric acid concentration in aqueous sulfuric acid solution: 25% by mass) were simultaneously and continuously added to a vessel to prepare a silica binder solution with an SiO ₂ concentration of 12.5% by mass. 4000 g was prepared. To this silica binder solution, 893 g of kaolin (solid content concentration: 84% by mass), 195 g of aluminum hydroxide (crystal form: gibbsite, solid content concentration: 64% by mass) as an active matrix forming component, and crystalline boehmite (crystal form: 64% by mass) were added. 152 g of boehmite, solid content concentration: 82% by mass) and 2083 g of alumina silica slurry-1 (solid content concentration: 12% by mass) obtained in Production Example 1 are added. After adding 2273 g of Y-type zeolite slurry-1 (solid content concentration: 33% by mass) and stirring well, the resulting mixed slurry was dried using a spray dryer at an inlet temperature of 250 ° C. and an outlet temperature of 150 ° C. Spherical particles were obtained by spray drying in a stream of hot air.

The resulting spherical particles were suspended in 10 times the amount of warm water (60°C), then subjected to dehydration filtration, and after further adding 10 times the amount of warm water (60°C) to water, the suspension was further carried out, followed by addition of lanthanum chloride. By contacting with an aqueous solution, ion exchange was carried out so that the content of lanthanum in the FCC catalyst was 1.0% by mass in terms of La ₂ O ₃ . The ion exchange rate with respect to zeolite was 13.5% by mass. Thereafter, filtration was carried out, and the solid content was dried in a drier at 135° C. to obtain FCC catalyst-1.

[Example 2]
~Preparation of FCC catalyst-2~
2941 g of water glass (SiO ₂ concentration: 17% by mass) and 1059 g of sulfuric acid (sulfuric acid concentration: 25% by mass) were simultaneously and continuously added to a vessel to prepare 4000 g of a silica binder solution with an SiO ₂ concentration of 12.5% by mass. bottom. To this silica binder solution, 1042 g of kaolin (solid content concentration: 84% by mass), 156 g of aluminum hydroxide (crystal form: gypsite, solid content concentration: 64% by mass) as an active matrix, crystalline boehmite (crystal form: boehmite, 122 g of solid content concentration: 82 mass%), 500 g of the alumina-silica slurry-2 (solid content concentration: 10 mass%) obtained in Production Example 2 was added, and the ultra-stable Y obtained in Production Example 5 was added. After adding 2652 g of type zeolite slurry-2 (solid content concentration: 33% by mass) and stirring well, the resulting mixed slurry was treated with a spray dryer with an inlet temperature of 250 ° C. and an outlet temperature of 150 ° C. under the conditions of hot air flow. The spherical particles were obtained by spray-drying in the air.

The resulting spherical particles were suspended in 10 times the amount of warm water (60°C), then subjected to dehydration filtration, and after further adding 10 times the amount of warm water (60°C) to water, the suspension was further carried out, followed by addition of lanthanum chloride. By contacting with an aqueous solution, ion exchange was carried out so that the content of lanthanum in the FCC catalyst was 0.9% by mass in terms of La ₂ O ₃ . The ion exchange rate with respect to zeolite was 6.3% by mass. Thereafter, filtration was performed, and the solid content was dried in a drier at 135° C. to obtain FCC catalyst-2.

[Example 3]
～FCC catalyst-3 preparation～
2941 g of water glass (SiO ₂ concentration: 17% by mass) and 1059 g of sulfuric acid (sulfuric acid concentration: 25% by mass) were continuously added simultaneously to prepare 4000 g of a silica binder solution with an SiO ₂ concentration of 12.5% by mass. 1101 g of kaolin (solid content concentration: 84% by mass), 313 g of aluminum hydroxide (crystal form: gibbsite, solid content concentration: 64% by mass) as an active matrix, crystalline boehmite (crystal form: boehmite, 152 g of solid content concentration: 82% by mass), 3750 g of the alumina-silica slurry-2 (solid content concentration: 10% by mass) obtained in Production Example 2 was added, and the ultra-stable Y obtained in Production Example 4 was added. After adding 1136 g of type zeolite slurry-2 (solid content concentration: 33% by mass) and stirring well, this mixed slurry is sprayed into a hot air stream using a spray dryer at an inlet temperature of 250 ° C. and an outlet temperature of 150 ° C. and dried to obtain spherical particles.

The resulting spherical particles were suspended in 10 times the amount of warm water (60°C), then subjected to dehydration filtration, and after further adding 10 times the amount of warm water (60°C) to water, the suspension was further carried out, followed by addition of lanthanum chloride. By contacting with an aqueous solution, ion exchange was carried out so that the content of lanthanum in the FCC catalyst was 1.0% by mass in terms of La ₂ O ₃ . The ion exchange rate with respect to zeolite was 16.5% by mass. After that, filtration was carried out, and the solid content was dried in a drier at 135° C. to obtain FCC catalyst-3.

[Example 4]
～FCC catalyst-4 preparation～
FCC catalyst-4 was obtained by performing the same operation as in Example 1 except that ion exchange was carried out so that the content of lanthanum in the FCC catalyst was 0.6% by mass in terms of La ₂ O ₃ . rice field. The ion exchange rate with respect to zeolite was 8.2% by mass.

[Comparative Example 1]
~ FCC catalyst - R1 preparation ~
The same operation as in Example 1 was performed except that 1596 g of basic aluminum chloride aqueous solution (solid content concentration: 23.5% by mass) and 1042 g of kaolin (solid content concentration: 84% by mass) were used instead of the silica binder solution. to obtain FCC catalyst-R1.

[Comparative Example 2]
~ FCC catalyst - R2 preparation ~
FCC catalyst-R2 was obtained by performing the same operation as in Example 1 except that ion exchange was performed so that the content of lanthanum in the FCC catalyst was 2.0% by mass in terms of La ₂ O ₃ . rice field. The ion exchange rate with respect to zeolite was 27.5% by mass.

[Comparative Example 3]
~ FCC catalyst - R3 preparation ~
The same operation as in Example 3 was carried out except that 3750 g of the alumina (boehmite) slurry (solid content concentration: 10% by mass) obtained in Preparation Example 3 was used instead of alumina-silica slurry-2 to prepare an FCC catalyst. - gave R3.
The composition and physical properties of the FCC catalyst are summarized in Tables 1-1 and 1-2.

In Table 1-2, the fresh catalyst is the catalyst obtained in Examples or Comparative Examples, and the steam-treated catalyst is the fresh catalyst kept at 780° C. under 100% steam conditions for 13 hours. is a catalyst steamed at
The retention rate (%) is expressed as a percentage of various specific surface areas of the steam treatment catalyst/various specific surface areas of the fresh catalyst, and the higher the retention rate, the higher the hydrothermal resistance.

<Method for producing fluid catalytic cracking catalyst composition>
A fluid catalytic cracking catalyst composition was obtained by mixing an additive (OCTUP-α) manufactured by Nikki Shokubai Kasei Co., Ltd. as an additive containing ZSM-5 to the FCC catalyst obtained in Examples or Comparative Examples.

The obtained fluid catalytic cracking catalyst composition was subjected to a performance evaluation test of the catalyst composition using ACE-MAT (Advanced Cracking Evaluation-Micro Activity Test) under the same crude oil and the same reaction conditions. Table 2 shows the results of the performance evaluation test of each catalyst composition. However, prior to conducting these performance evaluation tests, steam treatment was performed at 780° C. for 13 hours in order to simulate hydrothermal deterioration in the catalyst regeneration tower.

(catalytic activity)
The reaction conditions and the like in the catalyst performance evaluation test are as follows.
Raw material oil: desulfurized vacuum gas oil (DSVGO) 100% by mass
Reaction temperature: 580°C
Space velocity based on catalyst mass (WHSV): 8h ^-1
Catalyst/oil ratio (hereinafter referred to as “C/O”): 5.0 (% by mass/% by mass)
1) Conversion rate: 100-(LCO; HCO + CLO) (% by mass)
2) Yield: Proportion of each product when C/O = 5.0 (% by mass)
3) Boiling point range of gasoline: 30-216°C (Gasoline)
4) Boiling point range of LCO: 216-343°C (LCO: Light Cycle Oil)
5) HCO + CLO boiling point range: 343 ° C + (HCO: Heavy Cycle Oil, CLO: Clarified Oil)
6) LPG (liquid petroleum gas)
7) Dry Gas: Methane, Ethane and Ethylene 8) Propylene: Included in LPG.
The reaction results are summarized in Table 2.

Claims (3)

10-30% by weight of a binder, 10-40% by weight of a zeolite ion-exchanged with rare earth metals, 10-60% by weight of clay minerals, and 5-30% by weight of an active matrix,
The content of the rare earth metal is 0.5 to 1.2% by mass in terms of rare earth metal oxide (RE ₂ O ₃ ),
The binder is a silica-based binder,
The zeolite is an FAU-type zeolite having a lattice constant in the range of 2.438 to 2.460 nm,
A fluid catalytic cracking catalyst, wherein said active matrix comprises alumina-silica. (a) preparing a raw material slurry comprising a binder-forming component, a zeolite, clay minerals, and an active matrix-forming component;
(b) a step of spray-drying the raw material slurry to obtain particles;
(c) contacting the particles with an aqueous solution comprising a rare earth metal to ion exchange the zeolite with the rare earth metal;
The binder-forming component is a silica-based binder-forming component,
The zeolite is FAU-type zeolite having a lattice constant in the range of 2.438 to 2.460 nm,
A process for producing a fluid catalytic cracking catalyst, wherein said active matrix comprises alumina-silica. A fluid catalytic cracking catalyst composition comprising the fluid catalytic cracking catalyst of claim 1 and a co-catalyst comprising ZSM-5.