Fluid catalytic cracking catalyst and method for producing the same

Abstract

To provide a fluid catalytic cracking catalyst enhancing the yield of propylene in fluid catalytic cracking.SOLUTION: The fluid catalytic cracking catalyst includes in mass%: 10-30% of a binder, 10-40% of zeolite ion-exchanged by rare-earth metal, 10-60% of clay minerals and 5-30% of active matrix. The binder is a silica-based binder formed from a binder-forming component having pH of less than 1.6, and the zeolite is an FAU-type one. The content of the rare earth metal is in the range of 0.5 to 1.2 mass% in terms of rare-earth metal oxide (RE2O3).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a fluid catalytic cracking catalyst and a method for producing the same. [Background technology]

[0002] Various research and development efforts have been made on catalysts used in 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, improving wear resistance, etc.

[0003] 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, and that 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 that the spherical particles obtained by spray-drying were washed with pure water, then with water containing ammonium sulfate, and then dried to produce an FCC catalyst.

[0004] 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 substituted with zirconia atoms and titanium atoms in a fluid catalytic cracking unit for producing light olefins and gasoline fuel.

[0005] 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 a raw material for the FCC catalyst. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-657 [Patent Document 2] Special Publication No. 2015-518782 [Patent Document 3] Special Publication No. 2017-534433 [Patent Document 4] Special Publication No. 2018-536535 [Patent Document 5] Special Publication No. 2019-528163 [Patent Document 6] Special Publication No. 2021-511200 Summary of the Invention [Problem to be solved by the invention]

[0007] Recently, there has been a demand for improved 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. [Means for solving the problem]

[0008] The present invention relates to, for example, the following [1] to [3]. [1] The binder is 10 to 30% by mass, the rare earth metal ion-exchanged zeolite is 10 to 40% by mass, the clay minerals are 10 to 60% by mass, and the active matrix is ​​5 to 30% by mass, 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 metals is 0.5 to 1.2 mass% in terms of rare earth metal oxide (RE2O3). Fluid catalytic cracking catalyst.

[0009] [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; The zeolite is an FAU type zeolite. A method for producing a fluid catalytic cracking catalyst.

[0010] [3] A fluid catalytic cracking catalyst composition comprising the fluid catalytic cracking catalyst of [1] above and a co-catalyst containing ZSM-5. [Effects of the Invention]

[0011] According to the present invention, when fluid catalytic cracking is carried out 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. DETAILED DESCRIPTION OF THE INVENTION

[0012] 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.

[0013] <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.

[0014] 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, calculated as SiO2, of, for example, 10 to 30 mass %, preferably 12 to 26 mass %, and more preferably 14 to 24 mass %.

[0015] Although each component constituting the FCC catalyst of the present invention and its raw materials 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").

[0016] <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.

[0017] Examples of the rare earth metal include cerium (Ce), lanthanum (La), praseodymium (Pr), and neodymium (Nd), and these may be used alone or in combination of two or more.

[0018] The FCC catalyst of the present invention contains the zeolite in an amount of, for example, 10 to 40 mass%, preferably 12 to 38 mass%, and more preferably 14 to 36 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.

[0019] Although each component constituting the FCC catalyst of the present invention and its raw materials may contain water, the content of each component or the amount of each raw material used in this specification is expressed as the amount excluding water or as the solids concentration.

[0020] <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.

[0021] The FCC catalyst of the present invention contains the clay minerals in an amount of, for example, 10 to 60 mass%, preferably 14 to 56 mass%, and more preferably 18 to 52 mass%. When the content is equal to or greater than the lower limit, the FCC catalyst maintains its pore structure, catalyst shape, abrasion resistance, fluidity, etc., favorably. On the other hand, when the content is equal to or less than the upper limit, the proportions of the zeolite component and active matrix in the FCC catalyst are high, and the activity of the FCC catalyst is favorable.

[0022] 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 the solid acidity can be measured by temperature programmed desorption using ammonia or in situ Fourier transform infrared absorption spectroscopy (FTIR) using ammonia or pyridine.

[0023] Examples of active matrices that also function as metal scavengers 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.

[0024] 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 equal to or greater than 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 equal to or less than the upper limit, deterioration of the wear resistance and fluidity of the FCC catalyst can be prevented.

[0025] <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 (CeO2, MgO), and the like.

[0026] (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 the above range, the FCC catalyst of the present invention has excellent hydrothermal resistance and an excellent propylene yield.

[0027] [Method of manufacturing 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:

[0028] 《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.

[0029] In one embodiment of step (a), the binder-forming component is mixed with zeolite, clay minerals, an active matrix-forming component, and optional additives to prepare a raw material slurry. Each component may be added in powder form or in a slurried form. The order in which the components are added is not important, as long as a slurry can be prepared without causing gelation.

[0030] (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). As the 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.

[0031] The acid may be an inorganic acid, such as sulfuric acid, hydrochloric acid, nitric acid, or phosphoric acid, and among these, sulfuric acid, hydrochloric acid, and nitric acid are preferred, with sulfuric acid being particularly preferred.

[0032] When the silica source and the acid are mixed to prepare the silica-based binder-forming component, the molar ratio of hydrogen ions contained in the acid to silicon atoms in the silica source (hereinafter referred to as the "molar ratio ([H + ] / [SiO2]). They are mixed in a ratio such that the molar ratio is preferably 0.70 or more, more preferably 0.75 or more. The upper limit of the molar ratio is, for example, 2.0.

[0033] 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).

[0034] (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.

[0035] 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 TiO2 as a standard substance.

[0036] (clay minerals) Specific examples and preferred embodiments of the clay minerals are as described above.

[0037] (active matrix forming component) Examples of the active matrix-forming component include, in addition to the specific examples of the active matrix mentioned above, components that form an active matrix upon heating, such as aluminum hydroxide (gibbsite) and alumina hydrate (boehmite).

[0038] In a preferred embodiment of step (a), the clay minerals and active matrix-forming components are added to the binder-forming components, and then 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 the acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and organic acids (e.g., citric acid, formic acid, acetic acid, etc.).

[0039] 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.

[0040] The raw slurry contains the binder-forming components in terms of SiO2 content, for example, 10 to 30 mass %, preferably 12 to 26 mass %, and more preferably 14 to 24 mass % (where the amount of solids in the raw slurry (the same applies to components other than the dispersion medium in the raw slurry) is taken as 100 mass %).

[0041] The raw slurry contains the zeolite in an amount of, for example, 10 to 40 mass %, preferably 12 to 38 mass %, and more preferably 14 to 36 mass % (where the solid content in the raw slurry is taken as 100 mass %).

[0042] The raw slurry contains the clay minerals in an amount of, for example, 10 to 60 mass %, preferably 14 to 56 mass %, and more preferably 18 to 52 mass % (where the solid content in the raw slurry is taken as 100 mass %).

[0043] The raw slurry 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 % (where the solid content in the raw slurry is taken as 100 mass %).

[0044] 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 slurry is, for example, 10 to 50% by mass, and preferably 20 to 40% by mass, in order to perform spray drying of the raw slurry without difficulty.

[0045] 《Process (b)》 In the step (b), the raw material slurry is spray-dried to obtain particles (hereinafter also referred to as "spray-dried particles").

[0046] The spray-drying conditions may be appropriately changed depending on the solid content concentration, viscosity, etc. of the raw material slurry, and are not particularly limited as long as the conditions result in an average particle size of the resulting spray-dried particles in the range of 50 to 90 μm, similar to that of general FCC catalyst particles.

[0047] For example, particles (spray-dried particles) are obtained by placing the raw slurry in a slurry storage tank of a spray dryer and spraying the raw slurry into a drying chamber through which an air current (e.g., an air current) flows, the temperature of which is set in the range of, for example, 120 to 450° C. Although the temperature of the air current decreases as the raw slurry is sprayed, the temperature at the outlet of the drying chamber is maintained in the range of, for example, 50 to 300° C. by using a heater or the like.

[0048] 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.

[0049] 《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, thereby obtaining an FCC catalyst.

[0050] In the step (c), the spray-dried particles are preferably suspended in water to prepare a suspension, and the 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.

[0051] The aqueous solution containing the rare earth metal can be prepared, for example, by dissolving a salt of the rare earth metal (for example, LaCl3) in water. The step (c) is carried out so that the concentration of the rare earth metal in the obtained 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 rare earth metal oxide content is the desired amount.

[0052] 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 (substituted with protons) from the REUSY 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 a desired amount of rare earth metals can be produced by performing step (c).

[0053] The above-mentioned fluid catalytic cracking catalyst according to the present invention can be produced by the method for producing a fluid catalytic cracking catalyst according to the present invention, which includes the above steps (a) to (c).

[0054] [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.

[0055] Commercially available ZSM-5-containing auxiliary catalysts (additives) 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 JP-T-2013-522025. The content of the auxiliary catalyst in the catalyst composition is preferably 1 to 35 mass %, more preferably 5 to 25 mass %, relative to the FCC catalyst.

[0056] 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.

[0057] The use of the FCC catalyst composition of the present invention in fluid catalytic cracking can improve the yield of propylene. Because the hydrogen transfer reaction on the base catalyst is suppressed, the yield of the olefin fraction, which is the source of propylene, increases, and the effect of the auxiliary catalyst containing ZSM-5 becomes more pronounced. It is presumed that the use of a specific binder changes the coating state of the zeolite to a different state than before, thereby suppressing the hydrogen transfer reaction on the acid sites of the zeolite. [Example]

[0058] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0059] [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).

[0060] (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 TiO2 as a standard substance.

[0061] <<Measurement conditions>> The catalysts obtained in the examples and the like were crushed and molded, and then set in an X-ray diffractometer (X-RAY DIFFRACT METER (RINT 1400) manufactured by Rigaku Corporation) and measured 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, receiving slit 0.15 mm.

[0062] (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 Corporation. Specifically, the catalyst was heat-treated at 500°C for 1 hour while being evacuated to a vacuum, and nitrogen gas was adsorbed onto the catalyst, and the specific surface area (m 2 / g) was calculated.

[0063] [Example 1] ~FCC catalyst-1 preparation~ 2647 g of water glass (SiO2 concentration: 17% by mass) and 1598 g of sulfuric acid (sulfuric acid concentration: 25% by mass) were added simultaneously and continuously to prepare 4245 g of silica hydrosol (an example of a silica binder) with an SiO2 concentration of 10.6% by mass and a pH of 1.0 (measured at 35-37 °C). The molar ratio ([H + The SiO2 / SiO2 ratio was 1.09. To this silica hydrosol, 923 g of kaolin (solid content: 84 wt%), 484 g of activated alumina (solid content: 62 wt%) as an active matrix forming component, and 1731 g of an alumina-silica slurry (solid content: 12 wt%) containing 4% silica and adjusted to pH 3.0 with sulfuric acid were added. 2273 g of ultra-stabilized Y-type zeolite slurry (solid content: 33 wt%) adjusted to pH 3.9 with sulfuric acid were then added and stirred. The mixed slurry was then spray-dried to obtain spherical particles with an average particle size of 70 μm. The resulting 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 ion-exchange the lanthanum content in the FCC catalyst to 1.0 wt% La2O3. The obtained washed cake was dried for 10 hours in a dryer maintained at an atmospheric temperature of 150°C to obtain FCC catalyst-1. The obtained washed cake was dried for 10 hours in a dryer maintained at an atmospheric temperature of 150°C to obtain FCC catalyst-1.

[0064] [Example 2] ~FCC catalyst-2 preparation~ During the preparation of silica hydrosol, 2647 g of water glass (SiO concentration: 17% by mass) and 2244 g of sulfuric acid (sulfuric acid concentration: 25% by mass) were added simultaneously and continuously (molar ratio ([H +FCC catalyst-2 was obtained in the same manner as in Example 1, except that 4891 g of silica hydrosol having an SiO2 concentration of 9.2 mass% and a pH of 0.6 was prepared, with a SiO2 / [SiO2] ratio of 1.53).

[0065] [Example 3] ~FCC catalyst-3 preparation~ During the preparation of silica hydrosol, 2647 g of water glass (SiO concentration: 17% by mass) and 2585 g of sulfuric acid (sulfuric acid concentration: 25% by mass) were added simultaneously and continuously (molar ratio ([H + FCC catalyst-3 was obtained in the same manner as in Example 1, except that 5233 g of silica hydrosol having a SiO2 concentration of 8.6 mass% and a pH of 0.4 was prepared, with a SiO2 / [SiO2] ratio of 1.76).

[0066] [Example 4] ~FCC catalyst-4 preparation~ During the preparation of silica hydrosol, 2647 g of water glass (SiO concentration: 17% by mass) and 1266 g of sulfuric acid (sulfuric acid concentration: 25% by mass) were added simultaneously and continuously (molar ratio ([H + FCC catalyst-4 was obtained in the same manner as in Example 1, except that 3913 g of silica hydrosol having a SiO2 concentration of 11.5 mass % and a pH of 1.3 was prepared, with a SiO2 / [SiO2] ratio of 0.86).

[0067] [Comparative Example 1] ~FCC catalyst-R1 preparation~ During the preparation of silica hydrosol, 2647 g of water glass (SiO concentration: 17% by mass) and 953 g of sulfuric acid (sulfuric acid concentration: 25% by mass) were added simultaneously and continuously (molar ratio ([H + FCC catalyst-R1 was obtained in the same manner as in Example 1, except that 3600 g of silica hydrosol having a SiO2 concentration of 12.5 mass % and a pH of 1.6 was prepared, with a [SiO2 / [SiO2]] of 0.65).

[0068] Comparative Example 2 ~FCC catalyst-R2 preparation~ During the preparation of silica hydrosol, 2647 g of water glass (SiO concentration: 17% by mass) and 762 g of sulfuric acid (sulfuric acid concentration: 25% by mass) were added simultaneously and continuously (molar ratio ([H + FCC catalyst-R2 was obtained in the same manner as in Example 1, except that 3,409 g of silica hydrosol having a SiO2 concentration of 13.1 mass % and a pH of 1.8 was prepared, with a SiO2 / [SiO2] ratio of 0.52).

[0069] Comparative Example 3 ~FCC catalyst-R3 preparation~ FCC catalyst-R3 was obtained in the same manner as in Example 1, except that instead of silica hydrosol, 1596 g of a basic aluminum chloride aqueous solution (solid 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 concentration: 84 mass%) used was changed to 1012 g.

[0070] The composition and physical properties of FCC catalysts are summarized in Tables 1-1 and 1-2.

[0071] [Table 1-1]

[0072] [Table 1-2]

[0073] In Table 1-2, a fresh catalyst refers to a catalyst obtained in an example or comparative example, and a steam-treated catalyst refers to a 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.

[0074] <Method of producing a fluid catalytic cracking catalyst composition> The FCC catalyst obtained in the Examples or Comparative Examples was mixed with 15 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.

[0075] The obtained fluid catalytic cracking catalyst compositions were subjected to a performance evaluation test using the Advanced Cracking Evaluation-Micro Activity Test (ACE-MAT) under the same crude oil and the same reaction conditions. The results of the performance evaluation test for each catalyst composition are shown in Table 2.

[0076] However, before conducting these performance evaluation tests, the catalyst was subjected to steam treatment at 810°C for 12 hours in a catalyst regeneration tower in order to simulate the condition of hydrothermal degradation. The operating conditions for the performance evaluation test were as follows:

[0077] Feedstock: Desulfurized vacuum gas oil (DSVGO) 100% by mass Catalyst / throughput oil weight ratio (hereinafter referred to as "C / O"): 5.0 (mass% / mass%) Catalyst mass space velocity (WHSV): 8h -1 Reaction temperature: 580℃ 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: 30~216℃ (Gasoline) 4) Boiling point range of LCO: 216-343°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.

[0078] The reaction results are summarized in Table 2.

[0079] Table 2

Claims

1. A method for preparing a raw material slurry, comprising: (a) 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.

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 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.

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