JP7818922B2 - Fluid catalytic cracking catalyst and method for producing the same - Google Patents

Description

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

Various research and development efforts are being conducted on catalysts used in the fluid catalytic cracking of hydrocarbon oils (hereinafter also referred to as "FCC catalysts") and their manufacturing methods, with the aim of increasing the yield of gasoline fractions and improving wear resistance.

For example, Patent Document 1 discloses a method for producing an FCC catalyst that has a high gasoline yield, a low coke yield, and high attrition resistance. The method involves spray-drying a slurry obtained by mixing a zeolite (ultra-stable Y-type zeolite, rare earth-exchanged ultra-stable Y-type zeolite, etc.), a binder (basic aluminum chloride), and an inorganic oxide matrix (kaolin, etc.), and adjusting the pH. It also describes the production of an FCC catalyst by washing the spherical particles obtained by spray-drying with pure water, then with water containing ammonium sulfate, and drying the resulting mixture.

Patent Document 2 describes that the production of ethylene and propylene is increased by including phosphorus-modified submicron ZSM-5 in an FCC catalyst.
Patent Document 3 describes the use of an FCC catalyst containing an ultrastable Y-type zeolite in which some of the framework aluminum atoms are replaced with zirconia atoms and titanium atoms in a fluid catalytic cracking unit for producing light olefins and gasoline fuel.

Patent Document 4 describes that the yield of butylene is increased by using a Y zeolite containing barium ions in the ion exchange site III as an FCC catalyst.
Patent Documents 5 and 6 describe that the attrition resistance of an FCC catalyst can be improved by using colloidal silica as an FCC catalyst raw material.

Japanese Patent Application Laid-Open No. 2009-657 Special Publication No. 2015-518782 Special Publication No. 2017-534433 Special table 2018-536535 publication Special table 2019-528163 publication Special Publication No. 2021-511200

Recently, there has been a demand for an improvement in the propylene yield in fluid catalytic cracking, and there is still room for further improvement in conventional FCC catalysts.
Therefore, an object of the present invention is to provide an FCC catalyst that improves the propylene yield in a fluid catalytic cracking catalyst, and a method for producing the same.

The present invention relates to, for example, the following [1] to [3].
[1]
10 to 30% by weight of a binder, 10 to 40% by weight of a zeolite ion-exchanged with a rare earth metal, 10 to 60% by weight of clay minerals, and 5 to 30% by weight of an active matrix;
The binder is a silica-based binder formed from silica-based binder-forming components having a pH of less than 1.6,
The zeolite is an FAU-type zeolite,
The content of rare earth metal is 0.5 to 1.2 mass % in terms of rare earth metal oxide ( _{RE2O3 )} .
Fluid catalytic cracking catalyst.

[2]
(a) preparing a raw material slurry by mixing at least binder-forming components, zeolite, clay minerals, and active matrix-forming components;
(b) spray-drying the raw material slurry to obtain particles;
(c) contacting the particles with an aqueous solution containing rare earth metals to ion-exchange the zeolite with rare earth metals;
Including,
the binder-forming component is a silica-based binder-forming component having a pH of less than 1.6;
A method for producing a fluid catalytic cracking catalyst, wherein the zeolite is an FAU type zeolite.

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

According to the present invention, when fluid catalytic cracking is performed using a fluid catalytic cracking catalyst composition in which a ZSM-5 additive is added to a fluid catalytic cracking catalyst, the propylene yield can be improved.

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

<Binder>
As the binding agent (hereinafter also referred to as "binder"), a silica-based binding agent formed from silica-based binding agent-forming components having a pH of less than 1.6 is used.

The silica-based binder-forming components will be described in detail later.
The FCC catalyst of the present invention contains the binder in an amount of, for example, 10 to 30 mass %, preferably 12 to 26 mass %, and more preferably 14 to 24 mass %, calculated as SiO ₂ .

Note that although each component and raw material constituting the FCC catalyst of the present invention may contain water, the content of each component or the amount of each raw material used in the present invention is expressed as an amount excluding water (sometimes referred to as "solids concentration").

<Zeolite ion-exchanged with rare earth metals>
The zeolite in the zeolite ion-exchanged with rare earth metals, i.e., the zeolite before ion-exchange, will be described in detail later.

Examples of the rare earth metals include cerium (Ce), lanthanum (La), praseodymium (Pr), and neodymium (Nd). These may be used alone or in combination of two or more.

The FCC catalyst of the present invention contains the zeolite in an amount of, for example, 10 to 40% by mass, preferably 12 to 38% by mass, and more preferably 14 to 36% by mass. When the content is equal to or greater than the lower limit, the FCC catalyst exhibits sufficient reaction activity. On the other hand, when the content is equal to or less than the upper limit, excessive cracking and reduced selectivity due to excessive activity, as well as deterioration of the catalyst's attrition resistance and fluidity, can be prevented.

Note that while each component and raw material constituting the FCC catalyst of the present invention may contain water, the content of each component and the amount of each raw material used in this specification are expressed as the amount excluding water or as the solids concentration.

<Clay minerals>
The clay minerals that act as a bulking agent are clay and/or clay minerals, examples of which include kaolin, bentonite, kaolinite, halloysite, montmorillonite, etc., with kaolin being particularly preferred.

The FCC catalyst of the present invention contains the clay minerals in an amount of, for example, 10 to 60% by mass, preferably 14 to 56% by mass, and more preferably 18 to 52% by mass. When the content is at or above the lower limit, the FCC catalyst maintains its pore structure, catalyst shape, abrasion resistance, fluidity, and other properties. On the other hand, when the content is at or below the upper limit, the proportion of the zeolite component and active matrix in the FCC catalyst is high, resulting in good FCC catalyst activity.

Active Matrix
Examples of the active matrix include those containing a substance having a solid acid, such as activated alumina (boehmite, gibbsite, etc.), alumina-silica, silica-magnesia, alumina-magnesia, alumina-magnesia-silica, etc. A solid acid is one that exhibits solid acidity in the reaction temperature range of the catalyst, and methods for measuring the solid acidity include temperature programmed desorption using ammonia and in situ FTIR (Fourier transform infrared absorption spectroscopy) using ammonia or pyridine.

Examples of active matrices that also function as metal capture agents include alumina, phosphorus-alumina, crystalline calcium aluminate, sepiolite, barium titanate, calcium tin oxide, strontium titanate, manganese oxide, magnesia, and magnesia-alumina.
As the raw material for the metal capture agent, precursor substances such as aluminum hydroxide (gibbsite) and boehmite, which become alumina or the like when fired in an oxidizing atmosphere, can also be used.

The FCC catalyst of the present invention contains the active matrix in an amount of, for example, 5 to 30 mass%, preferably 8 to 29 mass%, and more preferably 10 to 28 mass%. When the content is above the lower limit, effects such as promoting the decomposition of high-molecular-weight substances and suppressing poisoning of the active component by capturing metals are exhibited. On the other hand, when the content is below the upper limit, deterioration of the attrition resistance and fluidity of the FCC catalyst can be prevented.

<Optional ingredients>
The FCC catalyst of the present invention may optionally contain additives in addition to the binder, rare earth metal ion-exchanged zeolite, clay minerals, and active matrix.
Examples of the additives include CO combustion promoting components (Pt, Pd), desulfurizing and deoxidizing components (CeO ₂ , MgO), and the like.

(Rare earth metal content)
The FCC catalyst of the present invention contains a rare earth metal. The content of _the rare earth metal in the FCC catalyst of the present invention is 0.5 to 1.2 mass%, more preferably 0.6 to 1.1 mass%, calculated as rare earth oxide ( _RE2O3 ). When the content of the rare earth metal is within this range, the FCC catalyst of the present invention has excellent hydrothermal resistance and an excellent propylene yield.

[Method of producing a fluid catalytic cracking catalyst]
The method for producing a fluid catalytic cracking catalyst (FCC catalyst) according to the present invention includes the steps of:
(a) preparing a raw material slurry by mixing at least binder-forming components, zeolite, clay minerals, and active matrix-forming components;
(b) spray-drying the raw material slurry to obtain particles;
(c) contacting the particles with an aqueous solution containing rare earth metals to ion-exchange the zeolite with rare earth metals;
Includes.

《Process (a)》
In the step (a), at least the binder-forming component, zeolite, clay minerals, and active matrix-forming component are mixed to prepare a raw material slurry containing these components.

One example of an embodiment of step (a) is to prepare a raw material slurry by mixing the binder-forming components with zeolite, clay minerals, active matrix-forming components, and optional additives. Each component may be added in powder form or in a slurried form. Furthermore, the order in which the components are added is not important, as long as a slurry can be prepared without causing gelation.

(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. The silica-based binder-forming component is usually prepared by mixing a silica source with an acid. Examples of the silica source include silica, silica gel (including silica hydrogel), silica sol (including silica hydrosol), and aqueous solutions of silicic acid (salts) (including orthosilicic acid (salts) and metasilicic acid (salts)) (e.g., water glass). For silica sol and silicate, colloidal silica of sodium type, potassium type, lithium type, acid type, etc. can be used. Of these, silica sol and aqueous solutions of silicic acid (salts) are preferred.

The acid may be an inorganic acid. Examples of inorganic acids include sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. Of these, sulfuric acid, hydrochloric acid, and nitric acid are preferred, and sulfuric acid is particularly preferred.

When preparing the silica-based binder-forming component by mixing a silica source and an acid, they are mixed in such a ratio that the molar ratio of hydrogen ions contained in the acid to silicon atoms in the silica source (hereinafter also referred to as "molar ratio ([H ⁺ ]/[SiO ₂ ])") is preferably 0.70 or more, more preferably 0.75 or more. The upper limit of the molar ratio is, for example, 2.0.

Furthermore, the pH of the binder-forming component is less than 1.6, preferably less than 1.5, and more preferably less than 1.3. By setting the pH of the binder-forming component within the above range, the propylene yield in fluid catalytic cracking can be improved. The lower limit of the pH is, for example, 0.1 or more, or may be 0.2 or more, or 0.3 or more. The temperature during pH measurement is 35 to 37°C (e.g., 36°C).

(Zeolite)
The zeolite used is an FAU-type zeolite. Examples of the 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"), which is obtained by introducing a rare-earth metal into USY by ion exchange or the like.

The lattice constant of the zeolite, measured by the method employed in the examples described below, 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 spacing between the diffraction planes (553) and (642) of the zeolite by X-ray diffraction using anatase TiO ₂ as a standard substance.

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

(Active Matrix-Forming Components)
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).

In a preferred embodiment of step (a), after adding the clay minerals and active matrix-forming components to the binder-forming components, the zeolite is added in the form of a slurry with a pH adjusted to 2.8 to 4.5. This suppresses pH fluctuations in the zeolite slurry when added to the raw material slurry, making the zeolite less likely to aggregate. The slurry can be prepared, for example, by adding the zeolite and an acid to water. Examples of acids include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and organic acids (such as citric acid, formic acid, and acetic acid).

Specific examples and preferred embodiments of each of the raw materials listed as components of the raw material slurry are as described above.
The raw material slurry may be prepared by adding additives and water in addition to these components.

The raw material slurry contains the binder-forming components in terms of the amount of _SiO2 , for example, 10 to 30% by mass, preferably 12 to 26% by mass, and more preferably 14 to 24% by mass (where the amount of solids in the raw material slurry (the same applies hereinafter to components other than the dispersion medium in the raw material slurry)) is taken as 100% by mass).

The raw material slurry contains the zeolite in an amount of, for example, 10 to 40% by mass, preferably 12 to 38% by mass, and more preferably 14 to 36% by mass (assuming 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, and more preferably 18 to 52% by mass of the clay minerals (assuming the solid content of the raw material slurry is 100% by mass).

The raw slurry contains, for example, 5 to 30% by mass, preferably 8 to 29% by mass, and more preferably 10 to 28% by mass of the active matrix (assuming the solid content of the raw slurry is 100% by mass).

The raw material slurry contains water as a dispersion medium.
The raw material slurry may contain small amounts of components other than water as a dispersion medium, such as methanol, ethanol, and acetone.
The solid content concentration of the raw material slurry is, for example, 10 to 50% by mass, preferably 20 to 40% by mass, so that the raw material slurry can be spray-dried 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 changed as appropriate depending on the solids concentration, viscosity, etc. of the raw material slurry, and are not particularly limited as long as the average particle size of the resulting spray-dried particles is in the range of 50 to 90 μm, similar to that of general FCC catalyst particles.

For example, the raw slurry is placed in a slurry storage tank of a spray dryer, and then sprayed into a drying chamber through which an air current (e.g., an air flow) set at a temperature in the range of 120 to 450°C flows, thereby obtaining particles (spray-dried particles). The temperature of the air current drops as the raw slurry is sprayed, but the temperature at the outlet of the drying chamber can be maintained in the range of 50 to 300°C, for example, by 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, with water) and dried.

《Process (c)》
In the step (c), the spray-dried particles are contacted with an aqueous solution containing a rare earth metal to introduce the rare earth metal into the zeolite in the spray-dried particles, and an FCC catalyst is obtained by this step (c).

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

The aqueous solution containing the rare earth metal can be prepared, for example, by dissolving a salt of the rare earth metal (for example, LaCl ₃ ) in water.
The step (c) is carried out so _that the concentration of the rare earth metal in the resulting fluid catalytic cracking catalyst is 0.5 to 1.2 mass%, preferably 0.6 to 1.1 mass%, calculated as rare earth metal oxide ( _RE2O3 ). The amount and concentration of the aqueous solution containing the rare earth metal are adjusted so that the target content of the rare earth metal oxide is achieved.

Not only when the zeolite does not contain rare earth metals, but also when the REUSY is used as the zeolite and some rare earth metal ions are removed from the REUSY (replaced with protons) during preparation of the raw material slurry in step (a) or during washing of the spray-dried particles obtained in step (b), a fluid catalytic cracking catalyst containing the desired amount of rare earth metals can be produced by performing step (c).

The fluid catalytic cracking catalyst according to the present invention can be produced by the method for producing the fluid catalytic cracking catalyst according to the present invention, which includes steps (a) to (c) described above.

[Fluid catalytic cracking catalyst composition]
The fluid catalytic cracking catalyst composition of the present invention comprises the FCC catalyst of the present invention and a co-catalyst comprising ZSM-5.

Commercially available auxiliary catalysts (additives) containing ZSM-5 include Additive (OCTUP-α) manufactured by JGC Catalysts and Chemicals Co., Ltd., and the ZSM-5 additives or ZSM-5-containing additives described in paragraph [0038] of JP2013-522025A. The content of the auxiliary catalyst in the catalyst composition is preferably 1 to 35% by mass, more preferably 5 to 25% by mass, relative to the FCC catalyst.

Here, the auxiliary catalyst containing ZSM-5 is not limited to the OCTUP-α, and any commercially available FCC catalyst containing ZSM-5 may be used instead.
The specific surface area of the FCC catalyst composition according to the present invention, measured by the method described below, is preferably 200 to 400 m ² /g, more preferably 250 to 350 m ² /g.

When the FCC catalyst composition of the present invention is used in fluid catalytic cracking, it can improve the yield of propylene. Because the hydrogen transfer reaction on the parent catalyst is suppressed, the yield of the olefin fraction that serves as the propylene source increases, making the effects of the auxiliary catalyst containing ZSM-5 more apparent. It is believed that the use of a specific binder changes the coating state of the zeolite to a different state than before, suppressing the hydrogen transfer reaction on the acid sites of the zeolite.

The present invention will be explained in more detail below using examples, but the present invention is not limited to these examples.

[Methods for measuring or evaluating catalysts, etc.]
(composition)
The content of each element contained in the zeolite and the catalysts obtained in the examples 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 by the spacing between the diffraction planes (553) and (642) of the zeolite by X-ray diffraction under the following conditions using anatase TiO ₂ as a standard substance.

<<Measurement conditions>>
The catalysts obtained in the examples and the like were pulverized and molded, and then set in an X-ray diffractometer (X-RAY DIFFRACT METER (RINT 1400) manufactured by Rigaku Corporation), and measurement was performed under the following conditions: 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, and receiving slit 0.15 mm.

(specific surface area)
The specific surface area of the catalysts in the examples was measured using a BELSORP-mini Ver. 2.5.6 manufactured by Microtrac-Bell Co., Ltd. Specifically, the catalyst was heat-treated at 500°C for 1 hour while evacuating to a vacuum, and nitrogen gas was adsorbed onto the catalyst, and the specific surface area ( ^m2 /g) was calculated by the BET method.

[Example 1]
～FCC catalyst-1 preparation～
2,647 g of water glass ( _SiO2 concentration: 17% by mass) and 1,598 g of sulfuric acid (sulfuric acid concentration: 25% by mass) were added simultaneously and continuously to prepare 4,245 g of silica hydrosol (an example of a silica binder) with a _SiO2 concentration of 10.6% by mass and a pH of 1.0 (measured at 35 to 37°C). The molar ratio ([H ⁺ ]/[ _SiO2 ]) was 1.09. To this silica hydrosol were added 923 g of kaolin (solids concentration: 84% by mass), 484 g of activated alumina (solids concentration: 62% by mass) as an active matrix-forming component, and 1731 g of an alumina-silica slurry (solids concentration: 12% by mass) containing 4% silica and having a pH adjusted to 3.0 with sulfuric acid. Furthermore, 2273 g of an ultra-stabilized Y-type zeolite slurry (solids concentration: 33% by mass) having a pH adjusted to 3.9 with sulfuric acid was added and stirred. The mixed slurry was then spray-dried to obtain spherical particles with an average particle size of 70 μm. The obtained spherical particles were washed with warm water (60°C), then subjected to ion exchange with an aqueous ammonium sulfate solution, and finally contacted with an aqueous lanthanum chloride solution to obtain an ion exchange such that the lanthanum content in the FCC catalyst was 1.0% by mass _, calculated as _La2O3 . The obtained washed cake was dried for 10 hours in a dryer maintained at an ambient temperature of 150°C, to obtain FCC catalyst-1. The resulting washed cake was dried for 10 hours in a dryer maintained at an atmospheric temperature of 150° C. to obtain FCC catalyst-1.

[Example 2]
～FCC catalyst-2 preparation～
FCC catalyst-2 was obtained in the same manner as in Example 1, except that, during the preparation of the silica hydrosol, 2647 g of water glass ( _SiO2 concentration: 17% by mass) and 2244 g of sulfuric acid (sulfuric acid concentration: 25% by mass) were simultaneously and continuously added (molar ratio ([H ⁺ ]/[ _SiO2 ]) was 1.53) to prepare 4891 g of silica hydrosol having a _SiO2 concentration of 9.2% by mass and a pH of 0.6.

[Example 3]
～FCC catalyst-3 preparation～
FCC catalyst-3 was obtained in the same manner as in Example 1, except that, during the preparation of the silica hydrosol, 2647 g of water glass ( _SiO2 concentration: 17% by mass) and 2585 g of sulfuric acid (sulfuric acid concentration: 25% by mass) were simultaneously and continuously added (molar ratio ([H ⁺ ]/[ _SiO2 ]) was 1.76) to prepare 5233 g of silica hydrosol having a _SiO2 concentration of 8.6% by mass and a pH of 0.4.

[Example 4]
~Preparation of FCC catalyst-4~
FCC catalyst-4 was obtained in the same manner as in Example 1, except that, during the preparation of the silica hydrosol, 2,647 g of water glass ( _SiO2 concentration: 17% by mass) and 1,266 g of sulfuric acid (sulfuric acid concentration: 25% by mass) were simultaneously and continuously added (molar ratio ([H ⁺ ]/[ _SiO2 ]) was 0.86) to prepare 3,913 g of silica hydrosol having a _SiO2 concentration of 11.5% by mass and a pH of 1.3.

[Comparative Example 1]
~FCC catalyst-R1 preparation~
FCC catalyst-R1 was obtained in the same manner as in Example 1, except that, in preparing the silica hydrosol, 2,647 g of water glass ( _SiO2 concentration: 17% by mass) and 953 g of sulfuric acid (sulfuric acid concentration: 25% by mass) were simultaneously and continuously added (molar ratio ([H ⁺ ]/[ _SiO2 ]) was 0.65) to prepare 3,600 g of silica hydrosol having a _SiO2 concentration of 12.5% by mass and a pH of 1.6.

[Comparative Example 2]
~FCC catalyst-R2 preparation~
FCC catalyst-R2 was obtained in the same manner as in Example 1, except that, during the preparation of the silica hydrosol, 2,647 g of water glass ( _SiO2 concentration: 17% by mass) and 762 g of sulfuric acid (sulfuric acid concentration: 25% by mass) were simultaneously and continuously added (molar ratio ([H ⁺ ]/[ _SiO2 ]) was 0.52) to prepare 3,409 g of silica hydrosol having a _SiO2 concentration of 13.1% by mass and a pH of 1.8.

[Comparative Example 3]
~FCC catalyst-R3 preparation~
Instead of silica hydrosol, 1596 g of a basic aluminum chloride aqueous solution (solid content concentration: 23.5 mass%) produced by the method described in the examples of JP 2021-121420 A was used, and the amount of kaolin (solid content concentration: 84 mass%) used was changed to 1012 g. FCC catalyst-R3 was obtained in the same manner as in Example 1, except that the amount of kaolin used was changed to 1012 g.

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 refers to the catalyst obtained in the examples or comparative examples, and the steam-treated catalyst refers to the catalyst that was steam-treated by holding the fresh catalyst at 810°C under 100% steam conditions for 12 hours.
The retention rate (%) is the ratio of the specific surface area of the steam-treated catalyst to the specific surface area of the fresh catalyst, expressed as a percentage. A high retention rate means high hydrothermal resistance.

<Method of producing a fluid catalytic cracking catalyst composition>
The FCC catalyst obtained in each of the Examples and Comparative Examples was mixed with 15% by mass of Additive (OCTUP-α) manufactured by JGC Catalysts and Chemicals Co., Ltd. as a ZSM-5-containing auxiliary catalyst to obtain a fluid catalytic cracking catalyst composition.

The resulting fluid catalytic cracking catalyst compositions were subjected to performance evaluation tests using the ACE-MAT (Advanced Cracking Evaluation-Micro Activity Test) under the same crude oil and reaction conditions. The results of the performance evaluation tests for each catalyst composition are shown in Table 2.

However, before carrying out these performance evaluation tests, a steam treatment was carried out in advance in a catalyst regeneration tower at 810° C. for 12 hours in order to simulate a state in which the catalyst had been subjected to hydrothermal degradation.
The operating conditions for the performance evaluation test were as follows:

Feedstock: 100% by mass of desulfurized vacuum gas oil (DSVGO)
Weight ratio of catalyst/throughput oil (hereinafter referred to as "C/O"): 5.0 (mass%/mass%)
Catalyst mass space velocity (WHSV): 8 ^h
Reaction temperature: 580°C
1) Conversion rate = 100-(LCO+HCO+CLO) (mass%)
2) Yield: The weight of each product when C/O = 5.0 was expressed as mass %.
3) Boiling point range of gasoline: 30 to 216°C (Gasoline)
4) Boiling point range of LCO: 216 to 343°C (LCO: Light Cycle Oil)
5) Boiling point range of HCO + CLO: 343°C + (HCO: Heavy Cycle Oil, CLO: Clarified Oil)
6) LPG (liquid petroleum gas)
7) Dry Gas: Methane, ethane and ethylene 8) Propylene: Found in LPG.

The reaction results are summarized in Table 2.

Claims (2)

a step (a) of preparing a raw material slurry by adding clay minerals and an active matrix-forming component to a silica-based binder-forming component having a pH of less than 1.6, and then adding a slurry of FAU-type zeolite having a pH of 2.8 to 4.5 ;
(b) 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;
A method for producing a fluid catalytic cracking catalyst, comprising:
the silica-based binder-forming component is at least one of silica, silica gel, silica sol, and an aqueous solution of silicic acid (salt);
The lattice constant of the FAU zeolite is 2.438 to 2.460 nm,
The method for producing a fluid catalytic cracking catalyst, wherein the clay minerals are added in the step (a) so that the clay minerals are contained in the fluid catalytic cracking catalyst in an amount of 10 to 60% by weight. a step (a) of preparing a raw material slurry by adding clay minerals and an active matrix-forming component to a silica-based binder-forming component having a pH of less than 1.6, and then adding a slurry of FAU-type zeolite having a pH of 2.8 to 4.5 ;
(b) 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 a rare earth metal to obtain a fluid catalytic cracking catalyst;
and (d) mixing the fluid catalytic cracking catalyst with a co-catalyst comprising ZSM-5;
the silica-based binder-forming component is at least one of silica, silica gel, silica sol, and an aqueous solution of silicic acid (salt);
The lattice constant of the FAU zeolite is 2.438 to 2.460 nm,
The method for producing a fluid catalytic cracking catalyst composition, wherein the clay minerals are added in the step (a) so that the clay minerals are contained in the fluid catalytic cracking catalyst in an amount of 10 to 60% by weight.