CATALYST FOR FLUID CATALYTIC CRACKING AND METHOD FOR PRODUCING THE SAME

Abstract

A catalyst for fluid catalytic cracking is provided which contains faujasite-type zeolite, boehmite, a binder and clay minerals and which satisfies the following formulas (1) and (2) in powder X-ray diffraction analysis: A / B ≤ 1 .2 A / C ≤ 0.8 where in formulas (1) and (2), A is the integrated intensity of a diffraction peak assigned to the (020) plane of boehmite, B is the integrated intensity of a diffraction peak assigned to the (120) plane of boehmite, and C is the integrated intensity of a diffraction peak assigned to the (33 1) plane of the faujasite-type zeolite.

Description

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application is based on Japanese Patent Application No. 2024-056817, filed with the Japan Patent Office on March 29, 2024, the entire contents of which are hereby incorporated by reference. BACKGROUND 1. Technical field

[0002] The present disclosure relates to a catalyst for fluid catalytic cracking and a process for its production. 2. State of the art

[0003] For the purpose of increasing the yield of gasoline fractions in fluid catalytic cracking, various technologies have been developed regarding catalysts used in fluid catalytic cracking of hydrocarbon oils (hereinafter also referred to as "FCC catalysts" or "fluid catalytic cracking catalysts") and the process for producing them.

[0004] For example, one objective of the technology disclosed in JP-A-2011-088137 is to provide a catalytic cracking catalyst that can efficiently obtain a gasoline fraction in high yield by simultaneously improving the crackability of heavy fractions, reducing the amount of coke produced, and improving the gasoline yield in the catalytic cracking of hydrocarbon oils. Specifically, a catalyst for catalytic cracking of hydrocarbon oils containing boehmite, crystalline aluminosilicate, silica derived from silica sol, and clay minerals having an average diameter of 30 μm or less is disclosed.

[0005] Additionally, JP-T-2005-532146 discloses a zeolite-based catalyst for fluid catalytic cracking that passivates nickel and vanadium during catalytic cracking. According to the description of a process for producing the catalyst, microspheres containing kaolin, a binder, and dispersible boehmite alumina are first produced. The microspheres are then converted through a standard in-situ Y-zeolite growth process to produce a Y-containing catalyst. Furthermore, an FCC catalyst containing transition alumina derived from boehmite is produced by exchange with ammonium and then rare earth cations and appropriate calcination. SUMMARY

[0006] A catalyst for fluid catalytic cracking according to the present embodiment includes faujasite-type zeolite, boehmite, a binder, and clay minerals, and satisfies the following formulas (1) and (2) in powder X-ray diffraction analysis: A / B≤1.2 A / C≤0.8 where in formulas (1) and (2), A is the integrated intensity of a diffraction peak assigned to the (020) plane of boehmite, B is the integrated intensity of a diffraction peak assigned to the (120) plane of boehmite, and C is the integrated intensity of a diffraction peak assigned to the (331) plane of faujasite-type zeolite. DETAILED DESCRIPTION

[0007] In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the disclosed embodiments. However, it will be apparent that one or more embodiments may be practiced without these specific details.

[0008] Among the liquefied gases obtained by fluid catalytic cracking of hydrocarbon oils, olefins (e.g., propylene or butenes, which include 1-butene, 2-butene, and isobutene) are useful as feedstocks for the petrochemical industry. Therefore, catalysts capable of producing gasoline and these olefins in high yields are extremely useful industrially.

[0009] Therefore, it is an object of the present embodiment to provide an FCC catalyst capable of fluid catalytic cracking of hydrocarbons to have a high gasoline yield and a high LPG olefinity (i.e., a high proportion of propylene and butenes in LPG having 3 to 4 carbon atoms), and a process for producing the catalyst.

[0010] A catalyst for fluid catalytic cracking according to the present embodiment includes faujasite-type zeolite, boehmite, a binder, and clay minerals, and satisfies the following formulas (1) and (2) in powder X-ray diffraction analysis: A / B≤1.2 A / C≤0.8 where in formulas (1) and (2), A is the integrated intensity of a diffraction peak assigned to the (020) plane of boehmite, B is the integrated intensity of a diffraction peak assigned to the (120) plane of boehmite, and C is the integrated intensity of a diffraction peak assigned to the (331) plane of faujasite-type zeolite.

[0011] Furthermore, the method for producing the fluid catalytic cracking catalyst according to the present embodiment includes the following steps (α), (β), and (γ). In step (α), a boehmite crystal aggregate having the following properties (i) to (iv) is prepared. In step (β), a catalyst raw material slurry containing faujasite-type zeolite, the boehmite crystal aggregate, a binder-forming component, and clay minerals is prepared. In step (γ), the catalyst raw material slurry is spray-dried to form particles. (i) The boehmite crystals have a crystallite diameter of 10 to 70 nm. The crystallite diameter is calculated from a peak of the (020) plane in the X-ray diffraction measurement. (ii) The aggregate has a specific surface area of ​​40 to 150 m 2 / g. The specific surface area is measured using a nitrogen adsorption method. (iii) The aggregate has a d (mean diameter) of 2.0 to 10 µm on a volume basis in the particle size distribution. The mean diameter is measured by a laser diffraction / scattering method. (iv) A compact bulk density (CBD) of the aggregate is 0.20 to 0.50 g / ml.

[0012] By means of the FCC catalyst according to the present embodiment, it is possible to carry out fluid catalytic cracking of hydrocarbons to achieve high gasoline yield and high LPG olefinity.

[0013] In addition, it is possible to perform fluid catalytic cracking of hydrocarbons to achieve high gasoline yield and high LPG olefinity by means of the FCC catalyst which can be produced by the method for producing the FCC catalyst according to the present embodiment.

[0014] The present embodiment will be described in detail below. Catalyst for fluid catalytic cracking

[0015] The fluid catalytic cracking (FCC) catalyst (for hydrocarbon oils) according to the present embodiment contains faujasite-type zeolite, boehmite, a binder, and clay minerals, and has the physical properties described below. Catalyst componentsFaujasite-type zeolite

[0016] The FCC catalyst according to the present embodiment contains faujasite-type zeolite (hereinafter also referred to simply as “zeolite”).

[0017] As a faujasite-type zeolite, an ultrastable Y-type zeolite is preferred. Examples of ultrastable Y-type zeolites include ultrastable Y-type zeolite (USY) and rare earth metal-exchanged ultrastable Y-type zeolite (hereinafter also referred to as "REUSY"). REUSY, for example, is produced by incorporating a rare earth metal into the USY through ion exchange.

[0018] The zeolite content in the FCC catalyst of the present embodiment is, for example, 15 to 40 mass%. Here, the FCC catalyst of the present embodiment has sufficient activity when the content is equal to or greater than a lower limit. On the other hand, when the content is equal to or less than an upper limit, the FCC catalyst of the present embodiment can prevent overcracking, reduced gasoline selectivity, and reduced LPG olefinity caused by excessively high activity. The zeolite content is preferably 20 to 38 mass%, more preferably 22 to 35 mass%, and particularly preferably 24 to 34 mass%.

[0019] It should be noted that the components and raw materials constituting the FCC catalyst according to the present embodiment may contain water. In the present embodiment, the content of the components and the amount of each raw material used are expressed as amounts excluding water (may also be referred to as "solid content concentration"). Boehmite

[0020] The FCC catalyst according to the present embodiment contains boehmite. The boehmite is preferably an aggregate of boehmite crystals having the following properties (i) to (iv). (i) The crystallite diameter of the boehmite crystals is 10 to 70 nm, preferably 12 to 60 nm, more preferably 15 to 50 nm, even more preferably 18 to 35 nm, and particularly preferably 23 to 33 nm. The crystallite diameter is calculated from the peak of the (020) plane in the X-ray diffraction measurement. (ii) The specific surface area of ​​the aggregate is 40 to 150 m 2 / g, preferably 60 to 145 m 2 / g, more preferably 70 to 140 m 2 / g and even more preferably 80 to 120 m 2 / g. The specific surface area is measured by the nitrogen adsorption method. (iii) An average particle diameter of the aggregate is 2.0 to 10 µm, preferably 4.0 to 9.5 µm, and more preferably 6.0 to 9.0 µm. The average particle diameter is measured by the laser diffraction / scattering method. (iv) The compact bulk density (CBD) of the aggregate is 0.20 to 0.50 g / ml.

[0021] The above-mentioned boehmite preferably forms a house-of-cards structure. That is, the boehmite is preferably an aggregate of plate-like boehmite crystals. In this aggregate, the normal directions of the major faces of the plate-like boehmite crystals are not aligned in one direction. That is, the plate-like boehmite crystals are aggregated such that the normal lines of the major faces point in random directions. Gaps between the thus-formed boehmite crystals improve the diffusivity of feedstock oil molecules or product oil molecules. Therefore, an FCC reaction using the catalyst of the present embodiment exhibits high gasoline selectivity, high LPG olefinity, high bottom cracking ability, and low coke selectivity.

[0022] The fact that the boehmite forms the house-of-cards structure can be confirmed, for example, by observing the FCC catalyst according to the present embodiment with a scanning electron microscope (SEM) (for example, an S-5500 scanning electron microscope manufactured by Hitachi High-Tech Corporation). Observation conditions include, for example, an accelerating voltage of 30,000 volts and a magnification of 50,000 to 300,000 times.

[0023] The content of boehmite relative to Al2O3 in the FCC catalyst according to the present embodiment is, for example, 10 to 50 mass%. Here, when the content is equal to or greater than a lower limit, it is considered that the voids formed by the boehmite crystals in the aggregate of the boehmite crystals, as described below, can be sufficiently provided for the FCC catalyst. In this case, the FCC catalyst has good activity. On the other hand, when the content is equal to or less than an upper limit, the FCC catalyst has good wear resistance. The content of boehmite is preferably 13 to 45 mass%, more preferably 15 to 40 mass%, and particularly preferably 20 to 35 mass%. binder

[0024] The FCC catalyst according to the present embodiment contains a binder. The binder is typically a silica-based binder. The silica-based binder is formed from a silica-based binder-forming component described below. When the binder is a silica-based binder, coke formation during fluid catalytic cracking is suppressed.

[0025] The binder content in the FCC catalyst of the present embodiment is, for example, 10 to 30 mass%. Here, the FCC catalyst exhibits good wear resistance when the content is equal to or greater than a lower limit. On the other hand, a sufficient amount of active components such as zeolite can be blended when the content is equal to or less than an upper limit. Therefore, the FCC catalyst exhibits good activity. The binder content is preferably 12 to 26 mass%, and more preferably 14 to 24 mass%. Clay minerals

[0026] The FCC catalyst according to the present embodiment contains clay minerals. The clay minerals that act as extenders are clay and / or clay minerals. Examples of the clay minerals include kaolin, bentonite, halloysite, and montmorillonite. Among these exemplary clay minerals, kaolin is preferred.

[0027] The clay mineral content in the FCC catalyst according to the present embodiment is, for example, 15 to 50 mass%. Here, the FCC catalyst is good in terms of, for example, pore structure maintenance, catalyst shape maintenance, wear resistance, and flowability when the content is equal to or greater than a lower limit. On the other hand, a ratio of zeolite components in the FCC catalyst is high when the content is equal to or less than an upper limit. Therefore, the FCC catalyst has good activity. The clay mineral content is preferably 18 to 45 mass%, and more preferably 20 to 40 mass%. Rare earth metal

[0028] The FCC catalyst according to the present embodiment may contain a rare earth metal (RE). Examples of the rare earth metal include cerium (Ce), lanthanum (La), praseodymium (Pr), and neodymium (Nd). One of the exemplary rare earth metals may be used alone. Two or more rare earth metals may be used.

[0029] The rare earth element (RE) content relative to RE2O3 in the FCC catalyst according to the present embodiment is preferably 0.5 to 3.5 mass%. Here, the hydrothermal resistance of the zeolite is improved when the content is equal to or greater than a lower limit. Therefore, the FCC catalyst exhibits good activity. On the other hand, the amount of rare earth element used can be reduced when the content is equal to or less than an upper limit. Therefore, the FCC catalyst is excellent in terms of economic efficiency. The rare earth element (RE) content relative to RE2O3 is more preferably 0.7 to 3.0 mass%. additives

[0030] The FCC catalyst according to the present embodiment may contain components other than those described above to the extent that the effects of the present embodiment are not impaired. Examples of such components include silica-alumina, activated alumina, aluminum hydroxide (e.g., gibbsite), phosphorus-alumina particles, crystalline calcium aluminate, sepiolite, barium titanate, calcium stannate, strontium titanate, manganese oxide, magnesium oxide, and magnesium oxide-alumina. In addition, CO combustion-promoting components (Pt and Pd) or desulfurizing oxide components (cerium oxide and magnesium oxide), for example, may be contained in the FCC catalyst. Catalyst propertiesFormulas (1) and (2)

[0031] The FCC catalyst according to the present embodiment satisfies the following formulas (1) and (2) in powder X-ray diffraction analysis. A / B≤1.2 [in the formula, A is the integrated intensity of the diffraction peak assigned to the (020) plane of boehmite and B is the integrated intensity of the diffraction peak assigned to the (120) plane of boehmite] A / C≤0.8 [In the formula, A is the integrated intensity of the diffraction peak assigned to the (020) plane of boehmite and C is the integrated intensity of the diffraction peak assigned to the (331) plane of the faujasite-type zeolite]

[0032] The values ​​of A / B and A / C can be determined by performing powder X-ray diffraction analysis using the following method or an equivalent method. (Method for calculating A / B and A / C)

[0033] A sample is subjected to X-ray diffraction analysis using an X-ray diffraction device (e.g., MiniFlex, manufactured by Rigaku Corporation) under the following conditions. Scan axis: 2θ / θ Radiation source: CuKα Measurement method: continuous Voltage: 40 kV Current: 15 mA Measuring range: from start angle 2θ = 5° to end angle 2θ = 90° Scanning width: 0.020° Scanning speed: 10,000° / min

[0034] From an obtained X-ray diffraction pattern, the integrated intensity (A), the integrated intensity (B), and the integrated intensity (C) are calculated using analysis software (e.g., PDXL2, manufactured by Rigaku Corporation). The integrated intensity (A) is the integrated intensity of the diffraction peak assigned to the (020) plane of boehmite (2θ = 14.0 to 15.0°). The integrated intensity (B) is the integrated intensity of the diffraction peak assigned to the (120) plane of boehmite (2θ = 28.0 to 28.5°). The integrated intensity (C) is the integrated intensity of the diffraction peak assigned to the (33 1) plane of the ultrastable Y-type zeolite (2θ = 15.5 to 16.0°). From these integrated intensity values, the values ​​for A / B and A / C are calculated.

[0035] A / B is preferably 1.1 or less. A lower limit of A / B may be, for example, 0.9. The A / B can be increased or decreased, for example, by adjusting the hydrothermal treatment temperature, the hydrothermal treatment time, the amount of the inorganic basic compound, or the ratio of gibbsite raw material to pseudo-boehmite when the boehmite to be blended into the FCC catalyst is produced by hydrothermal treatment.

[0036] Although this is not necessarily clear, it is assumed that the smaller the value of A / B, the smaller the amount of stacked aggregates where the (020) planes of the plate-like boehmite crystals in the catalyst are in contact with each other. Therefore, it is assumed that instead, the proportion of aggregates containing the plate-like boehmite crystals randomly combined like a house of cards is high.

[0037] Furthermore, the value of A / C is preferably 0.9 or more, more preferably 1.1 or more, and even more preferably 1.3 or more. An upper limit of A / C may be, for example, 1.5. The A / C tends to correspond to a ratio of the boehmite content to the zeolite content in the FCC catalyst and the degree of crystallinity of the boehmite crystals.

[0038] Here, the smaller the A / B value and the larger the A / C value, the higher the gasoline selectivity and LPG olefinity of the FCC catalyst according to the present embodiment tend to be. The reason for this is not necessarily clear. However, since the A / C value is large, it is considered that fully grown boehmite crystals reduce acidic sites and increase gasoline selectivity. Here, acidic sites may cause coke formation. Then, it is considered that acidic sites are particularly abundant in amorphous components containing insufficiently grown crystals. In addition, it is considered that a large amount of aggregate of boehmite crystals with large crystal gaps exists because the A / B value is small. In this case, the diffusivity of the starting oil molecules and the product oil molecules increases, and the desorption of the reaction molecules is promoted.Therefore, the reaction molecules are less susceptible to excessive hydrogen transfer reactions at the acidic sites of the zeolite. This is expected to suppress the reduction of olefins. Specific surface

[0039] A specific surface area of ​​the FCC catalyst according to the present embodiment is preferably 200 to 350 m 2 / g and more preferably 200 to 300 m 2 / g. The specific surface area is measured by the nitrogen adsorption method. Matrix-specific surface

[0040] In the present embodiment, a matrix-specific surface area after a pseudo-equilibrium treatment is preferably 10 to 40 m 2 / g and more preferably 20 to 39 m 2 / g. The matrix specific surface area is determined by a t-plot analysis of a nitrogen adsorption isotherm obtained by measuring the FCC catalyst according to the present embodiment after the pseudo-equilibrium treatment under the following conditions. Note that the matrix specific surface area is the specific surface area of ​​the FCC catalyst excluding the zeolite. (Pseudo-equilibrium treatment conditions)

[0041] The FCC catalyst contains 1000 ppm (based on the mass of the catalyst) of nickel and 2000 ppm (based on the mass of the catalyst) of vanadium. The FCC catalyst is then steamed for 13 hours at 780 °C.

[0042] The smaller the matrix specific surface area after the pseudo-equilibrium treatment, the higher the gasoline yield of the FCC catalyst according to the present embodiment tends to be. The reason for this is not entirely clear. However, it is assumed that the fully grown boehmite crystals reduce the number of strongly acidic sites, which cause coke formation. On the other hand, the specific surface area of ​​the boehmite crystals is assumed to decrease as crystal growth progresses.

[0043] The FCC catalyst according to the present embodiment preferably satisfies the following formula (3). (1−(matrix-specific surface area after pseudo-equilibrium treatment) / (matrix-specific surface area before pseudo-equilibrium treatment))×100%≥40%

[0044] (In the formula, the matrix specific surface area after the pseudo-equilibrium treatment is determined by the t-plot analysis of the nitrogen adsorption isotherm obtained by measuring the FCC catalyst after the pseudo-equilibrium treatment described above. The matrix specific surface area before the pseudo-equilibrium treatment is determined by the t-plot analysis of the nitrogen adsorption isotherm obtained by measuring the FCC catalyst before the pseudo-equilibrium treatment described above.)

[0045] The left side of formula (3) is also referred to as the "reduction rate of the matrix specific surface area by pseudo-equilibrium" or simply the "reduction rate." The reduction rate is more preferably 45% or more, and an upper limit of the reduction rate can be, for example, 65%.

[0046] Here, a value of the reduction rate can be increased or decreased, for example, by adjusting the temperature of the hydrothermal treatment, the time of the hydrothermal treatment, the amount of the inorganic basic compound, or the ratio of the gibbsite raw material to the pseudo-boehmite when the boehmite to be mixed into the FCC catalyst is produced by the hydrothermal treatment.

[0047] The higher the reduction rate, the higher the LPG olefinity of the FCC catalyst according to the present embodiment tends to be. The reason for this is not necessarily clear. However, the more the specific surface area of ​​the boehmite is reduced by the pseudo-equilibrium treatment before undergoing the FCC reaction, the more inactive the boehmite is after the pseudo-equilibrium treatment. Therefore, it is assumed that the boehmite effectively acts as a passage for the diffusion of the reaction molecules.

[0048] The FCC catalyst according to the present embodiment preferably satisfies the following formula (4). (matrix-specific surface area after pseudo-equilibrium treatment) / (pore volume)≤120 m2 / ml

[0049] [In the formula, the matrix specific surface area after pseudo-equilibrium treatment is determined by t-plot analysis of the nitrogen adsorption isotherm obtained by measuring the FCC catalyst after the pseudo-equilibrium treatment described above. The pore volume is the volume of pores with a pore diameter of 4.0 to 10,000 nm, obtained by measuring the FCC catalyst after the pseudo-equilibrium treatment described above by mercury intrusion porosimetry (mercury contact angle: 140 degrees, surface tension: 480 dyn / cm).]

[0050] A value of the left side of formula (4) is more preferably 115 m 2 / ml or less. A lower limit of the left side can, for example, be 95 m 2 / ml.

[0051] The value of the left side of formula (4) can be increased or decreased, for example, by adjusting the temperature of the hydrothermal treatment, the time of the hydrothermal treatment, the amount of the inorganic basic compound, or the ratio of the gibbsite raw material to the pseudo-boehmite when the boehmite to be mixed into the FCC catalyst is produced by the hydrothermal treatment.

[0052] The smaller the value of the left side of equation (4), i.e., the matrix specific surface area per pore volume after pseudo-equilibrium treatment, the higher the gasoline yield of the FCC catalyst according to the present embodiment tends to be. The reason for this is not necessarily clear. Although the pore volume of the FCC catalysts is large, the specific surface area is small. It is believed that this allows the large-volume pores to effectively function as a passage for the diffusion of the reactant molecules. Process for producing a catalyst for fluid catalytic cracking

[0053] The method for producing the fluid catalytic cracking (FCC) catalyst (for hydrocarbon oils) according to the present embodiment includes the following steps (α), (β), and (γ). In step (α), a boehmite crystal aggregate having predetermined properties is prepared. In step (β), a catalyst raw material slurry containing the faujasite-type zeolite, the boehmite crystal aggregate, and the binder-forming component is prepared. In step (γ), the catalyst raw material slurry is spray-dried. (Step (α))

[0054] The step (α) is a step for preparing the aggregate of boehmite crystals (hereinafter also referred to as “aggregated boehmite (a)”) having the following properties (i) to (iv). (i) The crystallite diameter of the boehmite crystals is 10 to 70 nm. The crystallite diameter is calculated from the peak of the (020) plane in the X-ray diffraction measurement. (ii) The specific surface area of ​​the aggregate is 40 to 150 m 2 / g. The specific surface area is measured by the nitrogen adsorption method. (iii) The average particle diameter of the aggregate is 2.0 to 10 µm. The average particle diameter is measured by the laser diffraction / scattering method. (iv) The compact bulk density (CBD) of the aggregate is 0.20 to 0.50 g / ml. Each physical property is described in detail. (i) Crystallite diameter

[0055] The crystallite diameter of the boehmite crystals forming the aggregated boehmite (a) is 10 to 70 nm. The crystallite diameter is calculated from the peak of the (020) plane in the X-ray diffraction measurement.

[0056] Aggregated boehmite (a) with a crystallite diameter within this range is suitable as a catalyst material. For example, an FCC catalyst with excellent catalyst performance can be produced using aggregated boehmite (a) as a matrix component.

[0057] On the other hand, aggregated boehmite (a) with a crystallite diameter excessively larger than this range is considered an unsuitable catalyst material. For example, if the FCC catalyst is produced using aggregated boehmite (a) with an excessively large crystallite diameter as a matrix component, the catalyst performance or wear resistance may be significantly deteriorated.

[0058] The crystallite diameter is preferably 12 to 50 nm, more preferably 15 to 40 nm, even more preferably 18 to 35 nm, and particularly preferably 23 to 33 nm. The crystallite diameter is determined by the following method or an equivalent method. Method for calculating the crystallite diameter

[0059] A powder of the aggregated boehmite (a) is prepared. For example, if the aggregated boehmite (a) is in the form of a slurry, the slurry is dried at 130 °C for 12 hours. The residue is then ground in a mortar. This collects the powder.

[0060] The powder is then pulverized in a mortar. This prepares the sample. The X-ray diffraction pattern of the sample is obtained using an X-ray diffraction device (e.g., MiniFlex, manufactured by Rigaku Corporation). The half-width of the peak of the (020) plane of the boehmite in the obtained X-ray diffraction pattern is then measured. A value calculated using the following Scherrer formula is used as the crystallite diameter. D = Kλ / βcosθ D: Crystallite diameter (nm) K: Scherrer constant (K = 0.94 in this disclosure) λ: X-ray wavelength (0.15418 nm, CuKα) β: Half-width (rad) θ: reflection angle

[0061] The crystallite diameter can be adjusted, for example, in a production process described below by changing the time of the hydrothermal treatment, by changing the ratio of aluminum and the inorganic basic compound during the hydrothermal treatment, or by changing the mixing ratio of gibbsite and pseudo-boehmite.

[0062] It should be noted that a gibbsite peak may be observed to the extent that the effects of the present embodiment are not impaired in the above-mentioned X-ray diffraction pattern. When the gibbsite peak is observed, the ratio of the integrated intensity of the (002) plane of gibbsite to the integrated intensity of the (020) plane of boehmite in X-ray diffraction analysis is preferably 10% or less, more preferably 5% or less, and particularly preferably 1% or less. The integrated intensity in X-ray diffraction analysis can be determined by analyzing the X-ray diffraction pattern obtained by the above-mentioned method using X-ray diffraction analysis software (for example, PDXL2, manufactured by Rigaku Corporation). The gibbsite content can be adjusted, for example, by changing the temperature or time of the hydrothermal treatment. (ii) Specific surface area

[0063] The specific surface area of ​​aggregated boehmite (a) is 40 to 150 m 2 / g. The specific surface area is measured by the nitrogen adsorption method (a method described below or an equivalent method). If the specific surface area is within this range, the aggregated boehmite (a) is suitable as a catalyst material. The specific surface area is preferably 60 to 145 m 2 / g, more preferably 70 to 140 m 2 / g and even more preferably 80 to 120 m 2 / g. Method for measuring the specific surface area by Nitrogen adsorption process

[0064] First, the powder of aggregated boehmite (a) is prepared. For example, if the aggregated boehmite (a) is in the form of a slurry, the slurry is dried at 130 °C for 12 hours, and the residue is then ground in a mortar. This collects the powder.

[0065] The powder collected in a magnetic crucible is then fired at 600 °C for 2 hours. The fired powder is then placed in a desiccator and cooled to room temperature. This prepares the test sample. The specific surface area of ​​the collected 0.3 g sample is then measured using a BET single-point method using a fully automated surface area measurement device.

[0066] For example, in the production process described below, the specific surface area can be adjusted by changing the time of hydrothermal treatment, by changing the ratio of aluminum and the inorganic basic compound during the hydrothermal treatment, or by changing the mixing ratio of gibbsite and pseudo-boehmite. (iii) Average particle diameter

[0067] The average particle diameter of the aggregated boehmite (a) is 2.0 to 10 µm. The average particle diameter can be adjusted, for example, in the production process described below by adjusting the blade tip speed of a stirring blade when stirring the raw materials or a holding temperature during the hydrothermal treatment. The average particle diameter is preferably 4.0 to 9.5 µm, and more preferably 6.0 to 9.0 µm. Method for measuring the average particle diameter

[0068] When measuring using a laser diffraction / scattering particle size distribution analyzer (e.g., LA-950V2, manufactured by HORIBA, Ltd.), the sample is added to a solvent (water) so that the light transmittance is in the range of 70 to 95%. The particle size distribution is measured under conditions of a circulation rate of 5.0 l / min, 1-minute ultrasonic irradiation repeated 15 times, and a refractive index of 1.66 or equivalent. 50 (mean diameter) on a volume basis is used as the average particle diameter. (iv) Compact bulk density (CBD)

[0069] The compact bulk density (CBD) of aggregated boehmite (a) is 0.20 to 0.50 g / ml. With such a low CBD, aggregated boehmite (a) is considered to have plate-like boehmite crystals forming a house-of-cards structure. That is, the CBD in aggregated boehmite (a) is small. Therefore, the gaps between the plate-like boehmite crystals forming a house-of-cards structure are considered to be large. Therefore, when aggregated boehmite (a) is used as an FCC catalyst material, large gaps are expected to form in the FCC catalyst. In this case, the starting oil and the product oil easily diffuse. Therefore, it is expected to improve catalyst performance, such as the conversion rate. The CBD is preferably 0.25 to 0.40 g / ml, and more preferably 0.30 to 0.40 g / ml. Method for measuring CBD

[0070] First, the powder of aggregated boehmite (a) is prepared. For example, if the aggregated boehmite (a) is in the form of a slurry, the slurry is dried at 130 °C for 12 hours. The aggregated boehmite (a) is then ground in a mortar. This collects the powder.

[0071] Then, 25 g of this weighed powder sample is transferred into a 250 ml graduated cylinder. The graduated cylinder is attached to a Tyler sieve shaker. The sample is filled by tapping it against the Tyler sieve shaker over a period of 15 minutes. The graduated cylinder is removed from the Tyler sieve shaker. After the sample surface has been smoothed, a fill volume is read. The CBD is calculated from the weight of the powder sample and the fill volume of the powder sample.

[0072] The CBD can be adjusted, for example, by changing the mixing ratio of gibbsite and pseudo-boehmite in the production process described below. The production process of aggregated boehmite (a) will be described later. In step (α), aggregated boehmite (a) can be produced as a powder. Alternatively, aggregated boehmite (a) can be produced as a slurry. Aggregated boehmite (a) is preferably produced as a slurry. (Step (β))

[0073] In step (β), the faujasite-type zeolite, the aggregated boehmite (a) prepared in step (α), the binder-forming component, water, the clay minerals and, if necessary, additives are mixed together to produce the slurry of catalyst raw material.

[0074] The faujasite-type zeolite, the aggregated boehmite (a), the binder-forming component, the clay minerals, and the additives can be added as a powder or as a slurry. Furthermore, the order of adding the components is irrelevant as long as the slurry can be prepared without causing gelation. Faujasite-type zeolite

[0075] Details of the faujasite-type zeolite are as described above. Aggregated boehmite (a)

[0076] Details of the aggregated boehmite (a) are as described above. Binder-forming component

[0077] The binder-forming component is typically the silica-based binder-forming component. The binder-forming component is prepared by mixing a silica source with an acid.

[0078] Examples of the silica source include silicon dioxide, silica gel (including silicon dioxide hydrogel), silicon dioxide sol (including silicon dioxide hydrosol), and an aqueous solution (e.g., water glass) of silicic acid (salt) (including orthosilicic acid (salt) and metasilicic acid (salt)). For example, sodium-type, potassium-type, lithium-type, or acid-type colloidal silicon dioxide can be used as the silica sol and silicate salt. Of these, an aqueous solution of the silica sol and an aqueous solution of the silicic acid (salt) are preferred. Examples of acids include an inorganic acid. Examples of inorganic acids include sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, and of these, sulfuric acid, hydrochloric acid, and nitric acid are preferred, and sulfuric acid is particularly preferred. Clay minerals

[0079] Details of the clay minerals are as described above. additives

[0080] The catalyst raw material slurry may contain additives to such an extent that the effects of the present embodiment are not impaired. Details of the additives are as described above. Slurry of catalyst raw material

[0081] A ratio of each component in the slurry of catalyst raw material is appropriately adjusted to correspond to the content of each component in the FCC catalyst according to the present embodiment as described above.

[0082] The catalyst raw material slurry contains water as a dispersion medium. The catalyst raw material slurry may contain a small amount of a component other than water as a dispersion medium, such as methanol, ethanol, or acetone.

[0083] From the perspective of smooth spray-drying of the catalyst raw material slurry and the like, the solid content concentration of the catalyst raw material slurry is preferably 20 to 40 mass%, and more preferably 25 to 35 mass%. A temperature of the catalyst raw material slurry is preferably 20 to 80°C, and more preferably 30 to 70°C. A viscosity of the catalyst raw material slurry is preferably 100 to 10,000 mPa·s, and more preferably 200 to 8,000 mPa·s. (Step (γ))

[0084] In the step (γ), the slurry of catalyst raw material produced in the step (β) is spray-dried to obtain the particles (hereinafter also referred to as “spray-dried particles”).

[0085] Spray-drying conditions can be adjusted accordingly, for example, depending on the solid content concentration or the viscosity of the catalyst raw material slurry. Spray-drying conditions are not particularly limited, as long as the average particle diameter of the resulting spray-dried particles is adjusted to an average range of 50 to 90 µm, similar to that of general FCC catalyst particles.

[0086] For example, the catalyst raw material slurry placed in a slurry tank of a spray dryer is sprayed into a drying chamber through which an air stream (e.g., an air stream) flows. The temperature of the air stream is adjusted, for example, to a range of 120 to 600°C. This results in particles (spray-dried particles) being obtained. The temperature of the air stream is lowered by spraying the catalyst raw material slurry. However, a temperature at an outlet of the drying chamber is maintained in a range of 50 to 300°C, for example, by means of a heater or the like.

[0087] The particle diameter of the spray-dried particles can be controlled by adjusting the concentration, viscosity, spray rate, or spray pressure of the catalyst raw material slurry to be sprayed, or by adjusting the nozzle size or hot air temperature of the spray dryer. Furthermore, the spray-dried particles can be washed (e.g., with water) and then dried. From a washability perspective, the water temperature is preferably 40 to 80°C.

[0088] The resulting spray-dried particles can be used directly as an FCC catalyst according to the present embodiment. However, it is preferable that the spray-dried particles obtained in step (γ) be subjected to a step (δ) of contacting the dried particles with water containing an ammonium salt and a step (ε) of drying the particles subjected to step (δ), and then used as an FCC catalyst according to the present embodiment. (Step (8))

[0089] In step (δ), the spray-dried particles obtained in step (γ) are brought into contact with the water containing an ammonium salt.

[0090] Examples of the ammonium salt include ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium oxalate and ammonium acetate, with ammonium sulfate being preferred among them.

[0091] Examples of aspects of step (δ) include a step of separating particles from a slurry obtained by dispersing the spray-dried particles obtained in step (γ) in the water containing an ammonium salt, and a step of pouring the water containing an ammonium salt onto the spray-dried particles obtained in step (y).

[0092] From the point of view of removing sulfate ions and the like originating from the ammonium salt, the spray-dried particles brought into contact with the water containing an ammonium salt may be washed with water and then dried.

[0093] The temperature of the water used in step (δ) is preferably 40 to 80°C, for example, from the perspective of washability. In step (δ), the spray-dried particles obtained in step (γ) were contacted with water containing an ammonium salt and then with an aqueous solution containing a rare earth metal. This allows the rare earth metal to be incorporated into the zeolite in the spray-dried particles.

[0094] In step (δ), the spray-dried particles are preferably suspended in water to form a suspension. The suspension is contacted with the aqueous solution containing the rare earth metal to be ion-exchanged. The resulting solid content (FCC catalyst) can then be separated, washed, and dried. The water temperature is preferably 40 to 80°C. Furthermore, the solid content separated by filtration of the suspension can be resuspended in water. This allows for the removal of undesirable soluble substances present in the spray-dried particles.

[0095] The aqueous solution containing the rare earth metal is prepared, for example, by dissolving a rare earth metal salt (e.g., LaCl3) in water. The concentration of the rare earth metal in the fluid catalytic cracking catalyst obtained in step (δ) is 0.5 to 3.5 mass%, and preferably 0.7 to 3.0 mass%, based on rare earth metal oxide (RE2O3). The amount or concentration of the aqueous solution containing the rare earth metal is adjusted so that the rare earth metal oxide content has a desired value.

[0096] When the ultrastable Y-type zeolite is USY, a fluid catalytic cracking catalyst containing a desired amount of the rare earth metal can be produced in step (δ). In addition, when the catalyst raw material slurry is prepared using REUSY in step (β) or when the spray-dried particles containing the REUSY obtained in step (γ) are washed, even if some of the rare earth metal ions are removed from the REUSY (replaced by protons), the fluid catalytic cracking catalyst containing a desired amount of the rare earth metal can be produced in step (δ). (Step (ε))

[0097] Step (ε) is a step for drying the spray-dried particles that have undergone step (δ). Drying can be carried out, for example, by heating the spray-dried particles that have undergone step (δ) in a dryer at 90 to 200 °C for 0.5 to 24 hours. Process for producing aggregated boehmite (a)

[0098] The above-mentioned aggregated boehmite (a) can be produced, for example, by a process including a step (A) of producing an aggregated boehmite slurry. Furthermore, the aggregated boehmite (a) can be produced by a process including a step (B) of drying the aggregated boehmite slurry produced in step (A). Step (A)

[0099] In step (A), the slurry of aggregated boehmite is produced, for example, by a process including the following first, second and third steps.

[0100] In the first step, 75 to 95 parts by mass of gibbsite, based on Al2O3, 5 to 25 parts by mass of pseudo-boehmite powder, based on Al2O3 (where the total amount of gibbsite and pseudo-boehmite, based on Al2O3, is 100 parts by mass), and water are mixed so that the pH is not 7.0 or less to prepare a mixed liquid (1). The d 50(mean diameter) of the gibbsite is 0.5 µm or more and less than 70 µm. The mean diameter is determined on a volume basis from the particle size distribution measured by the laser diffraction / scattering method. The pseudo-boehmite powder is not flocculated. The crystallite diameter of the pseudo-boehmite powder is 2 to 6 nm. The crystal size is calculated from the peak of the (020) plane in the X-ray diffraction measurement. Furthermore, the d 50 (Mean diameter) of the pseudo-boehmite powder is 5 to 100 µm. The mean diameter is determined on a volume basis from the particle size distribution measured by the laser diffraction / scattering method.

[0101] In the second step, the inorganic basic compound is added to the mixed liquid (1) to prepare a mixed liquid (2) having a pH of 9 to 12.

[0102] In the third step, while stirring the mixed liquid (2), the temperature of the mixed liquid (2) is increased at a rate of 15 to 60 °C / hour. The mixed liquid (2) is then hydrothermally treated at 150 to 190 °C for 1 to 24 hours. (First step)

[0103] The first step is a step to prepare the mixed liquid (1) by mixing gibbsite, pseudo-boehmite and water.

[0104] An average particle diameter of the gibbsite, ie the d 50 (mean diameter) on a volume basis in the particle size distribution is 0.5 µm or more and less than 70 µm. In this case, it is difficult to control the reaction if the d 50 smaller than this range. Conversely, gibbsite settles quickly when suspended in water, if the d 50 larger than this range. Therefore, handling is difficult. The d 50is preferably 1.0 µm or more and less than 65 µm, and more preferably 2.0 µm or more and less than 60 µm. From the perspective of being able to shorten the time of the hydrothermal treatment, the d 50 more preferably 2.0 µm or more and less than 55 µm.

[0105] Examples of commercially available gibbsite include "C-303" (manufactured by Sumitomo Chemical Co., Ltd.) and "C-12" (manufactured by Sumitomo Chemical Co., Ltd.). The gibbsite can be pulverized appropriately so that the d50 is within the above range and used. For example, the gibbsite can be pulverized using a ball mill, an attritor, a bead mill, a colloid mill, or a high-shear mixer. Method for measuring particle size distribution

[0106] A method for measuring the d 50, ie the average particle diameter, of gibbsite is the same as the method described above for measuring the average particle diameter of aggregated boehmite (a).

[0107] Pseudo-boehmite is assumed to act as a seed crystal during hydrothermal treatment. The crystallite diameter is 2 to 6 nm. If the crystallite diameter is smaller than this range, the hydrothermal treatment takes a long time. Therefore, a crystallite diameter that is too small is not preferred. If the crystallite diameter is larger than this range, the reaction is difficult to control.

[0108] A method for calculating the crystallite diameter of pseudo-boehmite is the same as the method for calculating the crystallite diameter of aggregated boehmite (a) described above. The average particle diameter of pseudo-boehmite, i.e., the d 50(mean diameter) on a volume basis in the particle size distribution is 5 to 100 µm. Here, the aggregated boehmite (a) acts as a seed crystal when the d 50 lies in this range while remaining in the form of an aggregate. Therefore, it is difficult to flocculate the aggregated boehmite (a) when the aggregated boehmite (a) comes into contact with the acid. This makes it possible to produce the aggregated boehmite (a) that has a small CBD. Conversely, the CBD of the resulting aggregate of boehmite crystals is large when the d 50 is smaller than this range. If the d 50 larger than this range, the pseudo-boehmite does not function as a seed crystal. 50 is preferably 40 to 70 µm.

[0109] An example of a commercially available pseudo-boehmite is "Catapal-A" (manufactured by Sasol). The pseudo-boehmite used can be pulverized in advance so that the 50within the above-mentioned range. For example, pseudo-boehmite can be pulverized using a ball mill, attritor, bead mill, colloid mill, or high-shear mixer.

[0110] The procedure for measuring the d 50 The method for measuring the average particle diameter of pseudo-boehmite is the same as the method for measuring the average particle diameter of aggregated boehmite (a) described above. When pseudo-boehmite powder, gibbsite, and water are mixed to prepare the mixed liquid (1), the pseudo-boehmite powder, which has aggregates solidified by drying, acts as a seed crystal, compared to when pseudo-boehmite slurry, gibbsite, and water are mixed. Therefore, aggregated boehmite can be produced.

[0111] The pseudo-boehmite is mixed with gibbsite and water without flocculation. Due to the non-flocculation of the pseudo-boehmite, an aggregate of pseudo-boehmite acts as a seed crystal. Therefore, the resulting boehmite also aggregates. Aggregated boehmite (a), which has a house-of-cards structure, is then formed. Therefore, the CBD is considered to be reduced. Furthermore, due to the non-flocculation of the pseudo-boehmite, the step can be shortened. Therefore, excellent economic efficiency and productivity are achieved industrially.

[0112] The water used is preferably ion-exchanged water. The mixing ratio of gibbsite and pseudo-boehmite, i.e., "(mass of gibbsite):(mass of pseudo-boehmite)", is "75 to 95:25 to 5" based on Al2O3 (where the sum of both is 100). Here, the CBD of the boehmite obtained from the boehmite slurry is large when the amount of gibbsite is too small (an amount of pseudo-boehmite is too large). Conversely, when the amount of gibbsite is too large (the amount of pseudo-boehmite is too small), the crystallite diameter of the obtained boehmite is large. On the other hand, the specific surface area of ​​the obtained boehmite is small. This “(mass of gibbsite):(mass of pseudo-boehmite)” is preferably “75 to 90:25 to 10” and more preferably “80 to 90:20 to 10”.

[0113] The mixed liquid (1), prepared by mixing gibbsite, pseudo-boehmite, and water, is usually a slurry. When the gibbsite, pseudo-boehmite, and water are mixed to prepare the mixed liquid (1), the temperature is usually 5 to 90 °C, and preferably 15 to 80 °C.

[0114] These components are mixed so that the pH of the mixed liquid (1) is not 7.0 or less. The mixed liquid (1) is used in the next step. This prevents the pseudo-boehmite from flocculating under acidic conditions. That is, the pseudo-boehmite acts as a seed crystal while remaining in the form of an aggregate. Therefore, aggregated boehmite (a) with a low CBD is obtained. (Second step)

[0115] The second step is a step of preparing the mixed liquid (2) having a pH of 9 to 12 by adding the inorganic basic compound to the mixed liquid (1).

[0116] Examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, and calcium hydroxide. Sodium hydroxide is preferred. The mixed liquid (2) is usually a slurry.

[0117] The specific inorganic basic compound and its amount are selected so that the pH of the resulting mixed liquid (2) at 60°C is preferably 9 to 12. Here, if the pH is lower than this lower limit, the dissolution and reprecipitation of gibbsite or pseudo-boehmite may not proceed sufficiently during the hydrothermal treatment. In this case, a slurry containing not only the desired boehmite but also gibbsite is obtained. Therefore, a pH that is too low is not preferable. When the inorganic basic compound is added to the mixed liquid (1) to prepare the mixed liquid (2), the temperature is normally 5 to 90°C, and preferably 15 to 80°C. (Third step)

[0118] The third step is a step of obtaining the slurry of aggregated boehmite by subjecting the mixed liquid (2) obtained in the second step to the hydrothermal treatment.

[0119] The temperature of the hydrothermal treatment is usually 140 to 190 °C, preferably 150 to 190 °C. The time of the hydrothermal treatment is usually 1 to 24 hours, preferably 15 to 18 hours. On the other hand, if the hydrothermal treatment temperature is lower than this range or if the hydrothermal treatment time is shorter than this range, the hydrothermal reaction may not proceed sufficiently. In this case, the boehmite yield decreases.

[0120] Furthermore, a temperature rise rate (i.e., a rate at which the temperature of the mixed liquid (2) obtained in the second step is raised to the above-mentioned hydrothermal treatment temperature) is usually 15 to 60 °C / hour, and preferably 20 to 40 °C / hour. On the other hand, if the temperature rise rate is higher than this range, the hydrothermal reaction may not proceed sufficiently. In this case, the yield of boehmite decreases.

[0121] The mixed liquid (2) can be hydrothermally treated under autogenous pressure. An autoclave is typically used for hydrothermal treatment. The autoclave is preferably equipped with a stirring blade. By stirring the mixed liquid (2), the mixed liquid (2) can be hydrothermally treated more uniformly.

[0122] Preferably, the mixed liquid (2) is stirred under gentle conditions. For example, the mixed liquid (2) is preferably stirred at a low blade tip speed. Stirring under gentle conditions makes it difficult to flocculate the aggregated boehmite, even if the resulting aggregated boehmite comes into contact with acid or undergoes pulverization. On the other hand, if the mixed liquid (2) is stirred at, for example, an excessively high blade tip speed, the resulting boehmite may not be sufficiently aggregated. In this case, the CBD may increase. (Fourth step)

[0123] The step (A) of producing the slurry of aggregated boehmite may, if necessary, include a fourth step which involves washing the slurry obtained in the third step.

[0124] In the fourth step, the slurry obtained in the third step is dewatered. The resulting solids are washed with water (preferably ion-exchanged water). The resulting washed cake is suspended in a liquid medium (preferably water, such as ion-exchanged water). In this way, a washed slurry of aggregated boehmite is produced.

[0125] The temperature of the water used for washing is preferably set between 40 and 90 °C. The fourth step allows for the removal of impurities (e.g., sodium or sulfate). Furthermore, the washed cake can be resuspended in a solvent such as water. This allows the concentration of the slurry to be adjusted to a desired value. (Slurry of aggregated boehmite)

[0126] For example, the aggregated boehmite slurry is produced by the above-mentioned step (A). The concentration of boehmite relative to alumina (Al2O3) in the aggregated boehmite slurry produced in the above-mentioned step (A) is, for example, 5.0 to 30 mass%, preferably 8.0 to 25 mass%, and more preferably 10 to 20 mass%.

[0127] The concentration of boehmite can be adjusted by increasing or decreasing the amount of water contained in the aggregated boehmite slurry. The aggregated boehmite slurry may contain additives to such an extent that the effects of the present embodiment are not impaired. The slurry may not contain any additives.

[0128] Examples of additives include inorganic acids (which include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and boric acid), inorganic bases (which include sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonium hydroxide), organic acids (which include formic acid, acetic acid, citric acid, malic acid, tartaric acid, gluconic acid, succinic acid, oxalic acid and lactic acid) and thickeners (which include polyvinyl alcohol, methylcellulose, gum arabic, diatomaceous earth, bentonite, polyacrylamide, polyethylene oxide, polyacrylic acid esters and locust bean gum).

[0129] If the additives are included, they can be added in a conventional manner in the first to fourth step stages. However, when the additives are added in the first to third step stages, an amount of the additives, excluding the inorganic basic compound added in the second step, is preferably 1 mass% or less based on a total content (ie, 100 mass%) of gibbsite and boehmite relative to aluminum (aluminum oxide (Al2O3)) in the raw materials, from the viewpoint of promoting the dissolution of gibbsite as a raw material and the growth of boehmite crystals. Step (B)

[0130] In step (B), the aggregated boehmite slurry produced in step (A) is dried. This yields aggregated boehmite (a).

[0131] The aggregated boehmite slurry can be washed with water before drying. The temperature of the wash water is preferably 40 to 90 °C. Drying can be carried out, for example, by heating the aggregated boehmite slurry after washing at 90 to 200 °C for 0.5 to 24 hours.

[0132] The resulting dried material is preferably pulverized. Pulverization can be carried out by a conventionally known method, for example, using a mortar. Furthermore, drying can be carried out by spray-drying the aggregated boehmite slurry. In this case, the concentration of the aggregated boehmite slurry can be adjusted, for example, to 5 to 30 mass percent based on Al2O3 by adding water.

[0133] For example, the aggregated boehmite slurry, which is placed in the slurry tank of the spray dryer, is sprayed into the drying chamber, through which the air stream (e.g., air flow) flows. The temperature of the air stream is adjusted, for example, in the range of 120 to 600 °C. This produces the particles (spray-dried particles). The temperature of the air stream is lowered by spraying the aggregated boehmite slurry. However, the temperature at the outlet of the drying chamber is maintained in the range of 50 to 300 °C, for example, by means of a heater or the like.

[0134] The particle diameter of the spray-dried particles can be controlled by adjusting, for example, the concentration, viscosity, spray amount or spray pressure of the aggregated boehmite slurry to be sprayed or the nozzle size or hot air temperature of the spray dryer. Examples

[0135] The present embodiment will be described in more detail using the examples shown below. However, the present embodiment is not limited to these examples. Measurement methods

[0136] In the examples and comparative examples, the properties were measured using the following methods. Measurement of boehmite (measurement sample)

[0137] Powders obtained in Step 2 of the Production Examples and Step 2 of the Comparative Production Examples were used as measurement samples. However, slurries obtained in Step 3 of the Production Examples and Step 3 of the Comparative Production Examples were used as measurement samples to determine the average particle diameter (particle size distribution (d 50 )) to eat. (Average particle diameter (Particle size distribution (d 50 )))

[0138] The particle size distribution of the sample was measured using a laser diffraction / scattering particle size distribution analyzer (LA-950V2) manufactured by HORIBA, Ltd. Specifically, the sample was added to the solvent (water) so that the light transmittance ranged from 70 to 95%. The particle size distribution was measured under conditions of a circulation rate of 5.0 L / min, 1-minute ultrasonic irradiation repeated 15 times, and a refractive index of 1.66. (Crystal structure and crystallite diameter)

[0139] The sample, pulverized in the mortar, was subjected to X-ray diffraction analysis using an X-ray diffraction device (MiniFlex, manufactured by Rigaku Corporation). The measurement conditions were such that one scan axis was set at 2θ / θ. CuKα was used as the radiation source. In addition, the X-ray diffraction analysis was performed using a continuous measurement method under the conditions of voltage 40 kV, current 15 mA, start angle 2θ = 5°, end angle 2θ = 90°, scan width 0.020°, and scan speed 10,000° / min.

[0140] A crystal structure was identified by comparing the X-ray diffraction pattern of the sample with a PDF-2 2023 database of the International Centre for Diffraction Data using PDXL2 software manufactured by Rigaku Corporation. Furthermore, the crystallite diameter was calculated from the peak of the (020) plane of boehmite using the above-mentioned method when the sample was identified as boehmite. (Confirmation of crystal form and aggregate)

[0141] The sample was examined with a scanning electron microscope (SEM). It was confirmed that the crystals formed the aggregate. Note that the scanning electron microscope used was an S-5500 scanning electron microscope manufactured by Hitachi High-Tech Corporation. The magnification was set at 50,000 to 300,000 times. Winroof 2018 STANDARD, manufactured by Mitani Corporation, was used as image analysis software. (Specific surface)

[0142] The sample collected in the magnetic crucible was fired for 2 hours at 600 °C. The sample was then placed in a desiccator and cooled to room temperature. A specific surface area (m 2 / g) of 0.3 g of the weighed sample was measured by the BET single-point method using a fully automatic surface area measuring device (Macsorb-1220, manufactured by Mountec Co., Ltd.). (CBD)

[0143] 25 g of the weighed sample was transferred into a 250 ml graduated cylinder. The graduated cylinder was attached to a Tyler sieve shaker. The sample was filled by tapping it against the Tyler sieve shaker over a period of 15 minutes, and then the cylinder was removed from the Tyler sieve shaker. After the sample surface was smoothed, the CBD was calculated from the measured fill volume. Measurement of the catalyst for fluid catalytic cracking (measurement sample)

[0144] The fluid catalytic cracking catalysts obtained in Examples and Comparative Examples were used as measurement samples. (Specific surface)

[0145] The specific surface area of ​​the fluid catalytic cracking catalyst was measured using a method similar to the method for measuring the specific surface area of ​​boehmite. (Powder X-ray diffraction analysis)

[0146] The sample, pulverized in the mortar, was subjected to X-ray diffraction analysis using an X-ray diffraction device (MiniFlex, manufactured by Rigaku Corporation). The measurement conditions were such that the scan axis was set to 2θ / θ. CuKα was used as the radiation source. In addition, X-ray diffraction analysis was performed using the continuous measurement method under the conditions of voltage 40 kV, current 15 mA, start angle 2θ = 5°, end angle 2θ = 90°, scan width 0.020°, and scan speed 10,000° / min.

[0147] The integrated intensities were calculated using PDXL2 software manufactured by Rigaku Corporation. The A / B and A / C values ​​were calculated from the integrated intensity (A) of the diffraction peak (2θ = 14.0 to 15.0°) assigned to the (020) plane of boehmite, the integrated intensity (B) of the diffraction peak (2θ = 28.0 to 28.5°) assigned to the (120) plane of boehmite, and the integrated intensity (C) of the diffraction peak (2θ = 15.5 to 16.0°) assigned to the (33 1) plane of the ultrastable Y-type zeolite. (Matrix-specific surface)

[0148] The matrix specific surface area of ​​the fluid catalytic cracking catalyst was measured before and after pseudo-equilibrium treatment in a catalyst performance evaluation test described below.

[0149] The sample collected in the magnetic crucible was fired at 600 °C for 2 hours. The sample was then placed in a desiccator and cooled to room temperature. Subsequently, the adsorption amount of the weighed sample was measured using a fully automated nitrogen adsorption / desorption measuring device (BELSORP-mini, manufactured by MicrotracBEL Corp.). The resulting adsorption isotherm was analyzed using a t-plot method using BELMaster software, manufactured by MicrotracBEL Corp., to determine the matrix-specific surface area.

[0150] In addition, the reduction rate of the matrix specific surface area was calculated by pseudo-equilibrium using the following formula. Reduction rate of the matrix-specific surface area after pseudo-equilibrium treatment (%) = (1 − (matrix-specific surface area after pseudo-equilibrium treatment) / (matrix-specific surface area before pseudo-equilibrium treatment)) × 100% (pore volume)

[0151] The pore volume of the fluid catalytic cracking catalyst after the pseudo-equilibrium treatment was measured by mercury intrusion porosimetry. The sample collected in a magnetic crucible was heated to 500 °C for 1 hour. The sample was then placed in a desiccator and cooled to room temperature. This resulted in the sample. The pore volume (ml / g) of the catalyst, which had a pore diameter of 4.0 to 10,000 nm, was then measured by mercury intrusion porosimetry (Poremaster GT-60, manufactured by Quantachrome Corporation, mercury contact angle: 140 degrees, surface tension: 480 dyn / cm). Furthermore, a ratio (m 2 / ml) of the matrix-specific surface (m 2 / g) after the pseudo-equilibrium treatment to the pore volume (ml / g). Production Example 1 (Step 1: Production of aggregated boehmite by hydrothermal treatment)

[0152] 0.12 kg pseudo-boehmite powder (1) (Catapal-A, manufactured by Sasol, concentration based on Al2O3 71.2 mass%, d 50 (mean diameter) on a volume basis 57 µm), 0.72 kg of gibbsite powder (1) (C-303, manufactured by Sumitomo Chemical Co., Ltd., concentration based on Al2O3 66.6 mass%, d 50(average diameter) on a volume basis: 6.1 µm) and 3.15 kg of ion-exchanged water were mixed. This resulted in a slurry containing 14 mass% boehmite based on Al2O3. While stirring the slurry, 20 g of a 48 mass% sodium hydroxide aqueous solution was added to the slurry. Thus, a uniform slurry (1) was obtained, which had a pH value of 11.8 (pH value measured at 60 °C; the same applies to other production examples and comparative production examples).

[0153] The slurry (1) was placed in a 5-liter autoclave reactor and heated to 170 °C at a temperature rise rate of 25 °C / hour while stirring at a blade tip speed of 0.7 m / s. The slurry (1) was then held at 170 °C under autogenous pressure for 4 hours. The slurry (1) was further stirred and allowed to cool naturally. This yielded a slurry (2). (Step 2: Washing boehmite)

[0154] 4.0 kg of the slurry (2) obtained in step 1 was dewatered using a flat-plate filtration device under reduced pressure. Then, the slurry (2) was flow-washed with 20 liters of ion-exchanged water at 60°C. Thus, a washed cake (1) was obtained. A portion of the washed cake (1) was placed on a stainless steel tray and dried at 130°C for 12 hours. Thereafter, the washed cake (1) was thoroughly ground in a mortar. Thus, a powder (1) was obtained. The obtained powder (1) was measured by the method described above. It was confirmed that the powder (1) was the aggregate of plate-shaped boehmite crystals. The production conditions and measurement results are shown in Table 1. (Step 3: Preparation of a slurry of aggregated boehmite)

[0155] The washed cake (1) was suspended in pure water. The pH of the washed cake (1) was then adjusted to 3.0 with sulfuric acid. Thus, an aggregated boehmite slurry (hereinafter referred to as aggregated boehmite slurry (1)) with a concentration of 15 mass% based on Al2O3 was obtained. Production example 2

[0156] The holding time in the autoclave reactor was changed from 4 hours to 2 hours. Other means and conditions were the same as in steps 1 and 2 of Production Example 1. Thus, a washed cake (2) and a powder (2) were obtained. It was confirmed that the powder (2) was an aggregate of plate-shaped boehmite crystals.

[0157] The production conditions and measurement results are shown in Table 1. The washed cake (1) was converted into the washed cake (2). The means and conditions other than these were the same as those in Step 3 of Production Example 1. Thus, an aggregated boehmite slurry (hereinafter referred to as "aggregated boehmite slurry (2)") with a concentration of 15 mass% based on Al2O3 was obtained. Production example 3

[0158] The holding time in the autoclave reactor was changed from 4 hours to 14 hours. The other means and conditions were the same as those in steps 1 and 2 of Production Example 1. Thus, a washed cake (3) and a powder (3) were obtained. It was confirmed that the powder (3) was an aggregate of plate-shaped boehmite crystals.

[0159] The production conditions and measurement results are shown in Table 1. The washed cake (1) was converted into the washed cake (3). The means and conditions other than these were the same as those in Step 3 of Production Example 1. Thus, an aggregated boehmite slurry (hereinafter referred to as "aggregated boehmite slurry (3)") with a concentration of 15 mass% based on Al2O3 was obtained. Production example 4

[0160] The heating temperature (holding temperature) was changed from 170°C to 160°C. Furthermore, the holding time was changed from 4 hours to 5 hours. Furthermore, the blade tip speed was changed from 0.7 m / s to 1.4 m / s. The means and conditions other than these were the same as those in Production Example 1. Thus, a powder (4) was obtained. It was confirmed that the powder (4) was an aggregate of plate-shaped boehmite crystals. The production conditions and measurement results are shown in Table 1. Production example 5

[0161] The gibbsite powder (1) was replaced by a gibbsite powder (2) (B-52, manufactured by Nippon Light Metal Co., Ltd., concentration based on Al2O3 65.0 mass%, d 50(average diameter) on a volume basis 52 µm). Furthermore, the heating temperature (holding temperature) was changed from 170 °C to 160 °C. Furthermore, the holding time was changed from 4 hours to 5 hours. The means and conditions other than these were the same as those in Production Example 1. Thus, a powder (5) was obtained. It was confirmed that the powder (5) was the aggregate of plate-shaped boehmite crystals. The production conditions and measurement results are shown in Table 1. Comparative production example 1

[0162] 9.09 kg of an aqueous sodium aluminate solution containing 22 mass% based on Al2O3 was placed in a 200 l steam-jacketed tank. 50.7 kg of ion-exchanged water was then added to the tank. Subsequently, 231 g of an aqueous sodium gluconate solution containing 26 mass% was added to this solution. The resulting solution was heated with stirring until the temperature of the solution reached 60 °C. Thus, a mixed solution of sodium aluminate and sodium gluconate was obtained.

[0163] Separately from the mixed solution, 14.29 kg of an aqueous aluminum sulfate solution with a concentration of 7 mass% based on Al2O3 was diluted with 25.71 kg of ion-exchanged water. The diluted aqueous solution was then heated until its temperature reached 60 °C. Thus, the aqueous aluminum sulfate solution was prepared.

[0164] Subsequently, while stirring the mixed solution of sodium aluminate and sodium gluconate, the aqueous aluminum sulfate solution was added to the mixed solution over a period of 10 minutes. During stirring, the temperature of the mixed solution was maintained at 60°C. Thus, an alumina hydrate slurry having a concentration of 3.0 mass% based on Al2O3 was prepared. At this time, the pH of the slurry was 7.2. The obtained alumina hydrate slurry was aged with stirring at 60°C for 60 minutes. Subsequently, the aged alumina hydrate slurry was dewatered using a flat-plate filtration device under reduced pressure. After that, the alumina hydrate slurry was washed with 100 L of ion-exchanged water at 60°C.The ion-exchanged water was added to a cake (c1) obtained by washing so that the concentration of alumina hydrate was 12 mass% based on Al2O3 to prepare a suspension. A pseudo-boehmite slurry (cl) was obtained.

[0165] A small amount of an analytical sample was extracted from this slurry and analyzed. As a result, the particles in the slurry became pseudo-boehmite particles. The crystallite diameter was 3.9 nm. The d 50 (mean diameter) on a volume basis was 4.4 µm.

[0166] 1.40 kg of pseudo-boehmite slurry (c1), 0.72 kg of gibbsite powder (1), and 1.99 kg of ion-exchanged water were mixed. Thus, a slurry with a pseudo-boehmite concentration of 14 mass% based on Al2O3 was prepared. While stirring the slurry, 20 g of a 48 mass% sodium hydroxide aqueous solution was added to the slurry. This resulted in a uniform slurry with a pH of 11.8.

[0167] Subsequently, the heating temperature (holding temperature) was changed from 170°C to 160°C. The holding time was changed from 4 hours to 5 hours. The means and conditions other than these were the same as those in Production Example 1. A powder (c1) produced in this manner was measured. It was confirmed that the powder (c1) was a dispersion of plate-shaped boehmite crystals. The production conditions and measurement results are shown in Table 1. Comparative production example 2

[0168] The amount of pseudo-boehmite powder (1) was changed to 0.24 kg. The amount of gibbsite powder (1) was changed to 0.59 kg. The heating temperature (holding temperature) was changed from 170 °C to 160 °C. The holding time was changed from 4 hours to 5 hours. The means and conditions other than these were the same as those in Production Example 1. A powder (c2) produced in this way was measured. It was confirmed that the powder (c2) was a dispersion of plate-shaped boehmite crystals. The production conditions and measurement results are shown in Table 1. Comparative production example 3

[0169] The heating temperature (holding temperature) was changed from 160°C to 120°C. The holding time was changed from 4 hours to 5 hours. The means and conditions other than these were the same as those in Production Example 1. A powder (c3) produced in this way was measured. In the X-ray diffraction pattern of the powder (c3), the diffraction pattern of gibbsite and the diffraction pattern of boehmite were mixed. The integrated intensity of the (002) plane of gibbsite was 24% of the integrated intensity of the (020) plane of boehmite. It was confirmed that the powder (c3) was a mixture of boehmite and gibbsite. The production conditions and measurement results are shown in Table 1. Comparative production example 4

[0170] While mixing the pseudo-boehmite powder (1), the gibbsite powder (1), and the ion-exchanged water, 23.3 g of a SiO2 source (water glass, manufactured by JGC Catalysts and Chemicals Ltd., SiO2 concentration 24 mass%) was further mixed. The concentration of the SiO2 source was adjusted to 2.0 mass% in terms of SiO2, based on a total amount (relative to Al2O3) of pseudo-boehmite powder (1) and gibbsite powder (1) as a reference (100 mass%). The heating temperature (holding temperature) was changed from 170°C to 160°C. The holding time was changed from 4 hours to 5 hours. The means and conditions other than these were the same as those in Production Example 1. A powder (c4) produced in this way was measured. The powder (c4) was confirmed to be gibbsite. The production conditions and measurement results are shown in Table 1. Comparative production example 5

[0171] While mixing the pseudo-boehmite powder (1), the gibbsite powder (1), and the ion-exchanged water, 5.6 g of tartaric acid (L(+)-tartaric acid, manufactured by Kanto Chemical Co., Inc., special grade) was further added. The concentration of tartaric acid was adjusted to 1.0 mass% based on the total amount (based on Al2O3) of pseudo-boehmite powder (1) and gibbsite powder (1) as a reference (100 mass%). The heating temperature (holding temperature) was changed from 170°C to 160°C. The holding time was changed from 4 hours to 5 hours. The means and conditions other than these were the same as those in Production Example 1. The powder (c5) thus produced was measured. It was confirmed that the powder (c5) was gibbsite. The production conditions and measurement results are shown in Table 1. [Table 1] Production example 1 Production example 2 Production example 3 Production example 4 Production example 5 Compare Production Example 1 Comparing Production Example 2 Comparing Production Example 3 Comparing Production Example 4 Compare Production Example 5 Slurry of aggregated boehmite (1) (2) (3) Manufacturing conditions Raw materials Ratio of pseudo-boehmite powders parts by mass 15 15 15 15 15 15 30 15 15 15 Gibbsite powder ratio parts by mass 85 85 85 85 85 85 70 85 85 85 d 50 Gibbsitpulvers µm 6,1 6,1 6,1 6,1 6,1 6,1 6,1 6,1 6,1 6,1 Crystallite diameter of pseudo-bohmites nm 2,7 2,7 2,7 2,7 2,7 3,9 2,7 2,7 2,7 2,7 d 50 Pseudo-Bohmits µm 57 57 57 57 57 4,4 57 57 57 57 Additional component (amount added based on Al2O3) No additives No additives No additives No additives No additives No additives No additives No additives SiO2 2.0 mass% No additives Hydrothermal conditions pH value of the slurry before hydrothermal treatment 11,8 11,8 11,8 11,8 11,8 11,7 11,5 11,8 11,9 11,4 Blade tip speed m / s 0,7 0,7 0,7 1,4 0,7 0,7 0,7 0,7 0,7 0,7 Holding temperature ℃ 170 170 170 160 160 160 160 160 160 160 Holding time h 4 2 14 5 5 5 5 5 5 5 Temperature rise rate ℃ / h 25 25 25 25 25 25 25 25 25 25 Physical properties Crystallite diameter nm 28 21 35 27 29 21 24 - - - Particle size distribution (d 50 ) µm 7 7 6 7 8 7 7 - - - Specific surface area m 2 / g 107 121 99 102 98 103 111 - - - CBD g / ml 0,31 0,3 0,37 0,3 0,38 0,65 0,3153 - - - Crystalliform - Boehmite Boehmite Boehmite Boehmite Boehmite Boehmite Boehmite Boehmite+Gibbsite Gibbsite Gibbsite Production of the catalyst for fluid catalytic crackingExample 1Production of the catalyst for fluid catalytic cracking (1)

[0172] 2,941 g of water glass (SiO2 concentration 17 mass%) and 1,059 g of sulfuric acid with a concentration of 25 mass% were simultaneously and continuously added to a vessel to prepare 4,000 g of silica binder solution with a SiO2 concentration of 12.5 mass%. 706 g of kaolin (solid concentration 85 mass%), 4167 g of the aggregated boehmite slurry (1) (Al2O3 concentration 15 mass%) obtained as crystalline boehmite in Production Example 1, and 1014 g of ultrastable Y-type zeolite powder (solid concentration 74 mass%) (manufactured by JGC Catalysts and Chemicals Ltd., UCS 2,445 nm, and SiO2 / Al2O3 molar ratio 7.1, determined by fluorescence X-ray measurement) were added to this silica binder solution and thoroughly stirred. Thus, a mixed slurry was prepared. The solid concentration of the prepared mixed slurry was 25.0%.The slurry temperature was 39 °C. The slurry viscosity was 800 mPa s.

[0173] The mixed slurry was formed into droplets and spray-dried using a spray dryer under conditions of an inlet temperature of 250 °C and an outlet temperature of 150 °C. Spherical spray-dried particles with an average particle diameter of 70 µm were obtained.

[0174] The resulting spray-dried particles were washed with warm water. Subsequently, the spray-dried particles were subjected to ion exchange treatment using an aqueous ammonium sulfate solution. The spray-dried particles were further washed with warm water. Furthermore, the spray-dried particles were subjected to ion exchange treatment using an aqueous rare earth chloride solution (LaCl3) to a concentration of 1.0 mass % based on RE2O3. Thereafter, the resulting catalyst particles were dried for 10 hours in a dryer at an atmosphere of 150 °C. Thus, a fluid catalytic cracking catalyst (1) was obtained. The composition and physical properties of the catalyst (1) are shown in Table 2. Example 2Production of the catalyst for fluid catalytic cracking (2)

[0175] The aggregated boehmite slurry (1) was replaced with 4.167 g of the aggregated boehmite slurry (2) (Al2O3 concentration 15 mass%) obtained in Production Example 2. The means and conditions other than these were the same as those in Example 1. Thus, a fluid catalytic cracking catalyst (2) was obtained. The composition and physical properties of the catalyst (2) are shown in Table 2. Example 3 Production of the catalyst for fluid catalytic cracking (3)

[0176] The aggregated boehmite slurry (1) was replaced with 4.167 g of the aggregated boehmite slurry (3) (Al2O3 concentration 15 mass%) obtained in Production Example 3. The means and conditions other than these were the same as those in Example 1. Thus, a fluid catalytic cracking catalyst (3) was obtained. The composition and physical properties of the catalyst (3) are shown in Table 2. Example 4 Production of the catalyst for fluid catalytic cracking (4)

[0177] The amount of ultrastable Y-type zeolite powder was changed to 845 g, and the amount of kaolin was changed to 853 g. The other agents and conditions were the same as those in Example 1. Thus, a fluid catalytic cracking catalyst (4) was obtained. The composition and physical properties of the catalyst (4) are shown in Table 2. Example 5 Production of the catalyst for fluid catalytic cracking (5)

[0178] Further, 833 g of microcrystalline boehmite slurry (manufactured by JGC Catalysts and Chemicals Ltd., Al2O3 concentration 15.0 mass%, crystallite diameter 3 nm) and 833 g of gibbsite slurry (manufactured by JGC Catalysts and Chemicals Ltd., Al2O3 concentration 15.0 mass%) were used as raw materials for the mixed slurry. Furthermore, the amount of aggregated boehmite slurry (1) was changed to 2500 g. The means and conditions other than these were the same as those in Example 1. Thus, a fluid catalytic cracking catalyst (5) was obtained. The composition and physical properties of the catalyst (5) are shown in Table 2. Comparative Example 1 Production of the catalyst for fluid catalytic cracking (c1)

[0179] The aggregated boehmite slurry (1) was changed into 4167 g of microcrystalline boehmite slurry (manufactured by JGC Catalysts and Chemicals Ltd., Al2O3 concentration: 15.0 mass%, crystallite diameter: 3 nm, dispersion medium: water, boehmite crystals dispersed without aggregation). The means and conditions other than these were the same as those in Example 1. Thus, a fluid catalytic cracking catalyst (c1) was obtained. The composition and physical properties of the catalyst (c1) are shown in Table 2. Comparative Example 2 Production of the catalyst for fluid catalytic cracking (c2)

[0180] The aggregated boehmite slurry (1) was changed into 4.167 g of highly dispersed crystalline boehmite slurry (manufactured by JGC Catalysts and Chemicals Ltd., Al2O3 concentration: 15.0 mass%, crystallite diameter: 23 nm, dispersion medium: water, mean diameter: 0.29 µm, boehmite crystals dispersed without aggregation). The means and conditions other than these were the same as those in Example 1. Thus, a fluid catalytic cracking catalyst (c2) was obtained. The composition and physical properties of the catalyst (c2) are shown in Table 2. Comparative Example 3 Production of the catalyst for fluid catalytic cracking (c3)

[0181] Further, 1667 g of microcrystalline boehmite slurry (manufactured by JGC Catalysts and Chemicals Ltd., Al2O3 concentration: 15.0 mass%, crystallite diameter: 3 nm, dispersion medium: water, boehmite crystals are dispersed without aggregation) and 833 g of gibbsite (manufactured by JGC Catalysts and Chemicals Ltd., Al2O3 concentration: 15.0 mass%) were used as raw materials for the mixed slurry. The amount of the aggregated boehmite slurry (1) was changed to 1667 g. The means and conditions other than these were the same as those in Example 1. Thus, a fluid catalytic cracking catalyst (c3) was obtained. The composition and physical properties of the catalyst (c3) are shown in Table 2. Evaluation of the catalyst for fluid catalytic cracking

[0182] Using the same crude oil and under the same reaction conditions, the fluid catalytic cracking catalyst performance evaluation test was conducted for examples and comparative examples. An advanced microactivity cracking evaluation test (ACE-MAT, manufactured by Kayser Technology, Inc., Model R+) was used for the test. The results are presented in Table 2.

[0183] However, before these performance evaluation tests, pseudo-equilibrium treatment was carried out on the catalyst using nickel and vanadium in advance to simulate a state where the catalyst had undergone hydrothermal degradation in a catalyst regeneration tower. Specifically, a toluene solution containing nickel octylate and vanadium octylate was absorbed into the catalyst so that the nickel concentration was 1,000 ppm and the vanadium concentration was 2,000 ppm. The nickel concentration was calculated by dividing the nickel mass by the catalyst mass. The vanadium concentration was calculated by dividing the vanadium mass by the catalyst mass. The catalyst was then fired at 600°C for 1.5 hours to deposit. Afterward, the catalyst was further steamed at 780°C for 13 hours. Thus, the pseudo-equilibrium treatment was carried out. Operating conditions

[0184] The reaction conditions for the catalyst performance evaluation test are as follows. Feedstock: Desulfurized atmospheric residual oil (DSAR) + desulfurized vacuum gas oil (DSVGO) (50 + 50) from crude oil Mass ratio of catalyst / oil flow (C / O): 3.75 and 5.0 (mass% / mass%) Reaction temperature: 520°C 1) Conversion rate = 100 - (LCO + HCO) (mass%) 2) Boiling point range of gasoline: 30 to 216 °C 3) Boiling point range of light cycle oil (LCO): 216 to 343 °C 4) Boiling point range of heavy cycle oil (HCO): 343 °C+ 5) Liquefied petroleum gas (LPG) 6) LPG olefinity: Proportion (mass ratio) of propylene and butenes in LPG that have 3 to 4 carbon atoms.

[0185] Selectivity at a conversion rate of 73%: A simple regression line was plotted between the conversion rate at C / O = 3.75 and the yield of each component, and the conversion rate at C / O = 5.0 and the yield of each component. The selectivity of each component at a conversion rate of 73% was calculated from the simple regression line.

[0186] The foregoing detailed description has been presented for purposes of illustration and description. Many modifications and variations are possible in light of the above teachings. It is not intended to be exhaustive of the subject matter described herein or to limit it to the precise form disclosed. Although the subject matter has been described in language specific to structural features and / or methodological acts, it is to be understood that the subject matter defined in the appended claims is not necessarily limited to the specific features or acts described above. Rather, the specific features and acts described above are disclosed as example forms of practicing the appended claims. QUOTES CONTAINED IN THE DESCRIPTION

[0000] This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Cited patent literature

[0000] JP 2024-056817

[0001] JP-A-201 1-088137

[0004] JP-T-2005-532146

[0005]

Claims

[1] Catalyst for fluid catalytic cracking comprising faujasite-type zeolite, boehmite, a binder and clay minerals, and satisfying the following formulas (1) and (2) in powder X-ray diffraction analysis: A / B≤1.2 A / C≥0.8 where in formulas (1) and (2) A is the integrated intensity of a diffraction peak associated with the (020) plane of boehmite, B is the integrated intensity of a diffraction peak associated with the (120) plane of boehmite, and C is the integrated intensity of a diffraction peak associated with the (331) plane of faujasite-type zeolite. [2] Catalyst for fluid catalytic cracking according to claim 1, wherein a matrix-specific surface area, determined by t-plot analysis of a nitrogen adsorption isotherm, obtained by measuring the catalyst for fluid catalytic cracking after a pseudo-equilibrium treatment, 10 to 40 m 2 / g is and The pseudo-equilibrium treatment involves vaporizing the catalyst for fluid catalytic cracking, which contains 1,000 ppm nickel and 2,000 ppm vanadium, at 780 °C for 13 hours. [3] Catalyst for fluid catalytic cracking according to claim 1, which satisfies the following formula (3): (1−(matrix-specific surface area after pseudo-equilibrium treatment) / (matrix-specific surface area before pseudo-equilibrium treatment))×100%≥40% In formula (3), the matrix-specific surface area after pseudo-equilibrium treatment is a matrix-specific surface area determined by t-plot analysis of the nitrogen adsorption isotherm obtained by measuring the catalyst for fluid catalytic cracking after the pseudo-equilibrium treatment. The matrix-specific surface area before pseudo-equilibrium treatment is a matrix-specific surface area determined by t-plot analysis of the nitrogen adsorption isotherm, obtained by measuring the catalyst for fluid catalytic cracking before pseudo-equilibrium treatment, and The pseudo-equilibrium treatment involves vaporizing the catalyst for fluid catalytic cracking, which contains 1,000 ppm nickel and 2,000 ppm vanadium, at 780 °C for 13 hours. [4] Catalyst for fluid catalytic cracking according to claim 1, which satisfies the following formula (4): (matrix-specific surface area after pseudo-equilibrium treatment) / (pore volume)≤120 m2 / ml In formula (4), the matrix-specific surface area after pseudo-equilibrium treatment is a matrix-specific surface area determined by t-plot analysis of the nitrogen adsorption isotherm obtained by measuring the catalyst for fluid catalytic cracking after the pseudo-equilibrium treatment. The pore volume is a volume of pores exhibiting a pore diameter of 4.0 to 10,000 nm, obtained by measuring the catalyst for fluid catalytic cracking after pseudo-equilibrium treatment by mercury intrusion porosimetry, and The pseudo-equilibrium treatment involves vaporizing the catalyst for fluid catalytic cracking, which contains 1,000 ppm nickel and 2,000 ppm vanadium, at 780 °C for 13 hours. [5] Catalyst for fluid catalytic cracking according to claim 1, wherein the boehmite forms a house of cards structure. [6] Catalyst for fluid catalytic cracking according to claim 1, wherein the boehmite is an aggregate of boehmite crystals having the following properties (i) to (iv): (i) a crystallite diameter calculated from a peak of the (020) plane of the boehmite crystal in an X-ray diffraction measurement, which is 10 to 70 nm; (ii) a specific surface area of ​​the aggregate, measured by a nitrogen adsorption method, which is 40 to 150 m² 2 / g is; (iii) a d 50 mean diameter on a volume basis of the aggregate in the particle size distribution, measured by a laser diffraction / scattering method, which is 2.0 to 10 µm; and (iv) a compact bulk density (CBD) of the aggregate, which is 0.20 to 0.50 g / ml. [7] Catalyst for fluid catalytic cracking according to claim 1, wherein the content of boehmite is 5 to 50 wt% based on Al2O3. [8] Catalyst for fluid catalytic cracking according to claim 1, wherein the faujasite-type zeolite is an ultrastable Y-type zeolite. [9] Catalyst for fluid catalytic cracking according to claim 1, wherein the faujasite-type zeolite content is 20 to 40 wt%. [10] Catalyst for fluid catalytic cracking according to claim 1, comprising 0.5 to 3.5 wt% rare earth metal RE based on oxide RE2O3. [11] Catalyst for fluid catalytic cracking according to claim 1, wherein the clay mineral content is 15 to 50 wt%. [12] Catalyst for fluid catalytic cracking according to claim 1, wherein a specific surface area, measured by a nitrogen adsorption method, is 200 to 350 m² 2 / g. [13] Method for producing a catalyst for fluid catalytic cracking, the method comprising the following steps α, β and γ in this order: a step α to produce an aggregate of boehmite crystals having the following properties (i) to (iv): (i) a crystallite diameter calculated from a peak of the (020) plane of the boehmite crystal in an X-ray diffraction measurement, which is 10 to 70 nm; (ii) a specific surface area of ​​the aggregate, measured by a nitrogen adsorption method, which is 40 to 150 m² 2 / g is; (iii) a d 50 mean diameter on a volume basis of the aggregate in the particle size distribution, measured by a laser diffraction / scattering method, which is 2.0 to 10 µm; and (iv) a compact bulk density (CBD) of the aggregate, which is 0.20 to 0.50 g / ml; a step β to produce a slurry of catalyst raw material containing faujasite-type zeolite, the boehmite crystal aggregate, a binder-forming component and clay minerals; and a step γ to spray-dry the slurry of catalyst raw material to form particles. [14] Method for producing the catalyst for fluid catalytic cracking according to claim 13, wherein Step α comprises a first step, a second step, and a third step in that order: a first step to mix gibbsite, non-flocculated pseudo-boehmite and water, so that there is no pH of 7.0 or less, to produce a mixed liquid 1; a total amount of gibbsite and pseudo-boehmite in the mixed liquid is 1,100 parts by mass based on Al2O3, a quantity of gibbsite in the mixed liquid 1 is 75 to 95 parts by mass based on Al2O3, a quantity of pseudo-boehmite in the mixed liquid is 1.5 to 25 parts by mass based on Al2O3, a mean diameter d 50on a volume basis of the gibbsite in the particle size distribution, measured by the laser diffraction / scattering method, is 1.0 to 1.5 µm or more and less than 70 µm, a crystallite diameter, calculated from the peak of the (020) plane of the pseudo-boehmite in the X-ray diffraction measurement, which is 2 to 6 nm, and a d 50 mean diameter on a volume basis of the pseudo-Boehmite in the particle size distribution, measured by the laser diffraction / scattering method, which is 5 to 100 µm; a second step to add an inorganic basic compound to the mixed liquid 1 to produce a mixed liquid 2 having a pH of 9 to 12; and a third step to increase the temperature of the mixed liquid 2 at a rate of 15 to 60 °C / hour and to hydrothermally treat the mixed liquid 2 at 150 to 190 °C for 1 to 24 hours, while stirring the mixed liquid 2, to produce a slurry of the aggregate of boehmite crystals. [15] Method for producing the catalyst for fluid catalytic cracking according to claim 13, wherein in step β the slurry of the catalyst raw material has a solids content concentration of 20 to 40 wt%, a temperature of the slurry of the catalyst raw material is 20 to 80 °C and a viscosity of the slurry of the catalyst raw material is 100 to 10,000 mPa·s.