Fluid catalytic cracking catalyst and method for producing the same

Abstract

To provide a fluid catalytic cracking catalyst capable of performing the fluid catalytic cracking of hydrocarbon with high gasoline yield and high LPG olefinicity.SOLUTION: There is provided a fluid catalytic cracking catalyst which comprises a faujasite-type zeolite, boehmite, a binder and clay minerals and satisfies A / B≤1.2 and A / C≥0.8 in powder X-ray diffraction analysis. [wherein, A is the integrated intensity of the XRD diffraction peak attributed to the (020) plane of boehmite, B is that attributed to the (120) plane of boehmite and C is that attributed to the (331) plane of the faujasite-type zeolite.]SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Various catalysts used in the fluid catalytic cracking of hydrocarbon oils (hereinafter also referred to as "FCC catalysts" or "fluid catalytic cracking catalysts") and methods for producing them have been developed with the aim of increasing the yield of gasoline fractions in fluid catalytic cracking.

[0003] For example, Patent Document 1 discloses a catalytic cracking catalyst for hydrocarbon oils that contains boehmite, crystalline aluminosilicate, silicon oxide derived from silica sol, and clay minerals, each having a median diameter of 30 μm or less, for the purpose of providing a catalytic cracking catalyst that improves the cracking ability of heavy fractions in the catalytic cracking of hydrocarbon oils, while at the same time reducing the amount of coke produced and improving gasoline yield, thereby enabling efficient high yields of gasoline fractions.

[0004] Furthermore, Patent Document 2 discloses a zeolite-based fluid catalytic cracking catalyst that passivates nickel and vanadium during catalytic cracking, and describes a method for producing the catalyst as follows: It is first made from microspheres containing kaolin, a binder, and dispersible boehmite alumina; The microspheres are then converted to Y-containing catalysts using standard in situ Y zeolite growth procedures; Exchange with ammonium and rare earth cations followed by appropriate calcination produces an FCC catalyst containing transition alumina derived from boehmite; It is stated that: [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-88137 [Patent Document 2] Special Publication No. 2005-532146 Summary of the Invention [Problem to be solved by the invention]

[0006] Among the LPG obtained by fluid catalytic cracking of hydrocarbon oils, olefins (propylene, butenes (1-butene, 2-butene, isobutene)) are useful as raw materials in the petrochemical industry, and therefore a catalyst that can produce these olefins in high yields along with gasoline would be extremely useful industrially.

[0007] Therefore, an object of the present invention is to provide an FCC catalyst capable of performing fluid catalytic cracking of hydrocarbons with a high gasoline yield and high LPG olefinicity (i.e., a high proportion of propylene and butenes in LPG having 3 to 4 carbon atoms), and a method for producing the same. [Means for solving the problem]

[0008] The fluid catalytic cracking catalyst according to the present invention comprises: The composition comprises faujasite-type zeolite, boehmite, a binder, and clay minerals, In powder X-ray diffraction analysis, the following formulas (1) and (2) are satisfied. A / B≦1.2 …(1) (wherein A is the integrated intensity of the diffraction peak attributable to the (020) plane of boehmite, and B is the integrated intensity of the diffraction peak attributable to the (120) plane of boehmite.) A / C≧0.8 …(2) (wherein A is the integrated intensity of the diffraction peak attributable to the (020) plane of boehmite, and C is the integrated intensity of the diffraction peak attributable to the (331) plane of faujasite-type zeolite.)

[0009] The method for producing a fluid catalytic cracking catalyst according to the present invention further comprises the steps of: A step (α) of preparing a boehmite crystal aggregate having the following properties (i) to (iv): A step (β) of preparing a catalyst raw material slurry containing faujasite-type zeolite, the boehmite crystal aggregates, a binder-forming component, and clay minerals; and a step (γ) of spray-drying the catalyst raw material slurry to obtain particles; Includes: (i) The boehmite crystals have a crystallite diameter of 10 to 70 nm calculated from the peak of the (020) plane in X-ray diffraction measurement. (ii) the specific surface area of ​​the aggregates, as measured by a nitrogen adsorption method, is 40 to 150 m 2 / g. (iii) the volume-based d in the particle size distribution of the aggregate measured by a laser diffraction / scattering method 50 (median diameter) is 2.0 to 10 μm. (iv) The CBD (Compact Bulk Density) of the aggregate is 0.20 to 0.50 g / ml. [Effects of the Invention]

[0010] The FCC catalyst of the present invention can be used to carry out fluid catalytic cracking of hydrocarbons, which allows for high gasoline yields and high LPG olefinicity.

[0011] Furthermore, the method for producing an FCC catalyst of the present invention makes it possible to produce an FCC catalyst capable of fluid catalytic cracking of hydrocarbons, which allows for a high gasoline yield and a high LPG olefinicity. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the present invention will be described in detail. [Flowing contact decomposition catalyst] The fluid catalytic cracking catalyst (FCC catalyst) (for hydrocarbon oils) according to the present invention contains faujasite-type zeolite, boehmite, a binder, and clay minerals, and has the physical properties described below.

[0013] <Catalyst component> <Faujasite-type zeolite> The FCC catalyst of the present invention contains a faujasite-type zeolite (hereinafter also simply referred to as "zeolite").

[0014] As the faujasite type zeolite, ultra-stable Y type zeolite is preferred. Examples of such ultra-stable Y-type zeolites include ultra-stable Y-type zeolite (USY) and rare earth metal-exchanged ultra-stable Y-type zeolite (hereinafter also referred to as "REUSY"), which is obtained by introducing rare earth metals into USY by ion exchange or the like.

[0015] The zeolite content in the FCC catalyst of the present invention is, for example, 15 to 40% by mass. Here, when the content is equal to or greater than the lower limit, the FCC catalyst of the present invention exhibits sufficient activity. On the other hand, when the content is equal to or less than the upper limit, the FCC catalyst of the present invention can prevent overcracking, reduced gasoline selectivity, and reduced LPG olefin selectivity due to excessive activity. The zeolite content is preferably 20 to 38% by mass, more preferably 22 to 35% by mass, and particularly preferably 24 to 34% by mass.

[0016] Although each component constituting the FCC catalyst of the present invention and its raw materials may contain water, the content of each component and the amount of each raw material used in the present invention are expressed as an amount excluding water (sometimes referred to as "solid concentration").

[0017] Boehmite The FCC catalyst of the present invention comprises boehmite. This boehmite is preferably an aggregate of boehmite crystals having the following properties (i) to (iv). (i) The crystallite diameter of the boehmite crystals calculated from the peak of the (020) plane in X-ray diffraction measurement 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. (ii) The specific surface area of ​​the aggregates, as measured by the nitrogen adsorption method, is 40 to 150 m 2 / g, preferably 60 to 145 m 2 / g, more preferably 70 to 140m 2 / g, more preferably 80 to 120m 2 / g. (iii) The aggregates have an average particle size of 2.0 to 10 μm, preferably 4.0 to 9.5 μm, and more preferably 6.0 to 9.0 μm, as measured by a laser diffraction / scattering method. (iv) The CBD (Compact Bulk Density) of the aggregate is 0.20 to 0.50 g / ml.

[0018] The boehmite preferably has a house-of-cards structure. That is, the boehmite is preferably an aggregate of plate-like boehmite crystals, and in the aggregate, the normal direction of each plate-like boehmite crystal is randomly oriented rather than aligned in one direction. The resulting gaps between the boehmite crystals improve the diffusibility of feedstock oil molecules and product oil molecules, and when an FCC reaction is carried out using the catalyst of the present invention, high gasoline selectivity, high LPG olefin selectivity, and further, high bottom resolution and low coke selectivity are exhibited.

[0019] The fact that the boehmite forms a house-of-cards structure can be confirmed, for example, by observing the FCC catalyst of the present invention using a scanning electron microscope (SEM) (e.g., a scanning electron microscope S-5500 manufactured by Hitachi High-Technologies Corporation) at an acceleration voltage of 30,000 volts and a magnification of 50,000 to 300,000 times.

[0020] The boehmite content in the FCC catalyst of the present invention, calculated as Al2O3, is, for example, 10 to 50 mass%. When the content is equal to or greater than the lower limit, it is believed that the gaps formed by the boehmite crystals in the boehmite crystal aggregates described below can be sufficiently provided to the FCC catalyst, resulting in good FCC catalyst activity. On the other hand, when the content is equal to or less than the upper limit, the FCC catalyst has good abrasion resistance. The boehmite content is preferably 13 to 45 mass%, more preferably 15 to 40 mass%, and particularly preferably 20 to 35 mass%.

[0021] Binder The FCC catalyst of the present invention comprises a binder. This binder is usually a silica-based binder, and the silica-based binder is formed from the silica-based binder-forming components described below. When the binder is a silica-based binder, coke formation during fluid catalytic cracking is suppressed.

[0022] The binder content in the FCC catalyst of the present invention is, for example, 10 to 30% by mass. Here, if the content is equal to or greater than the lower limit, the FCC catalyst has good wear resistance. On the other hand, if the content is equal to or less than the upper limit, a sufficient amount of active components such as zeolite can be blended, and the activity of the FCC catalyst is good. The binder content is preferably 12 to 26% by mass, more preferably 14 to 24% by mass.

[0023] Clay minerals The FCC catalyst of the present invention comprises clay minerals. The clay minerals that act as a bulking agent are clay and / or clay minerals, examples of which include kaolin, bentonite, halloysite, montmorillonite, etc., with kaolin being preferred among these.

[0024] The clay mineral content in the FCC catalyst of the present invention is, for example, 15 to 50 mass%. Here, if the content is equal to or greater than the lower limit, the FCC catalyst maintains its pore structure, catalyst shape, abrasion resistance, fluidity, and the like, and is excellent. On the other hand, if the content is equal to or less than the upper limit, the ratio of the zeolite component in the FCC catalyst is high, and therefore the activity of the FCC catalyst is excellent. The clay mineral content is preferably 18 to 45 mass%, more preferably 20 to 40 mass%.

[0025] Rare Earth Metals The FCC catalyst of the present invention may contain rare earth metals (RE). Examples of the rare earth metal include cerium (Ce), lanthanum (La), praseodymium (Pr), and neodymium (Nd), and these may be used alone or in combination of two or more.

[0026] The content of rare earth metals (RE) in the FCC catalyst of the present invention, calculated as RE2O3, is preferably 0.5 to 3.5% by mass. When the content is equal to or greater than the lower limit, the hydrothermal resistance of the zeolite is improved, resulting in good FCC catalyst activity. On the other hand, when the content is equal to or less than the upper limit, the amount of rare earth metal used can be reduced, resulting in excellent economic efficiency of the FCC catalyst. The content of rare earth metals (RE) calculated as RE2O3 is more preferably 0.7 to 3.0% by mass.

[0027] Additives The FCC catalyst of the present invention may contain components other than those mentioned above, such as silica-alumina, activated alumina, aluminum hydroxide (e.g., gibbsite), phosphorus-alumina particles, crystalline calcium aluminate, sepiolite, barium titanate, calcium stannate, strontium titanate, manganese oxide, magnesia, magnesia-alumina, and further, for example, CO combustion promoting components (Pt, Pd), desulfurization components (ceria, magnesia), etc., within the scope of the present invention.

[0028] <Catalyst properties> Formulas (1) and (2) The FCC catalyst of the present invention satisfies the following formulas (1) and (2) in powder X-ray diffraction analysis. A / B≦1.2 …(1) (wherein A is the integrated intensity of the diffraction peak attributable to the (020) plane of boehmite, and B is the integrated intensity of the diffraction peak attributable to the (120) plane of boehmite.) A / C≧0.8 …(2) (wherein A is the integrated intensity of the diffraction peak attributable to the (020) plane of boehmite, and C is the integrated intensity of the diffraction peak attributable to the (331) plane of faujasite-type zeolite.) The values ​​of A / B and A / C can be determined by powder X-ray diffraction analysis using the following method or an equivalent method.

[0029] (Calculation method for A / B and A / C) The measurement sample is subjected to X-ray diffraction analysis using an X-ray diffractometer (for example, MiniFlex manufactured by Rigaku Corporation) under the following conditions. Operation axis: 2θ / θ Source: CuKα Measurement method: Continuous Voltage: 40kV Current: 15mA Measurement range: from start angle 2θ=5° to end angle 2θ=90° Sampling width: 0.020° Scan speed: 10,000° / min

[0030] From the obtained X-ray diffraction pattern, analytical software (for example, PDXL2 manufactured by Rigaku Corporation) is used to calculate 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 (331) plane of ultra-stable Y-type zeolite, and the values ​​of A / B and A / C are calculated from these values.

[0031] A / B is preferably 1.1 or less, and the lower limit thereof may be, for example, 0.9. This A / B can be increased or decreased by, for example, adjusting the hydrothermal treatment temperature, hydrothermal treatment time, amount of inorganic basic compound, ratio of gibbsite raw material to pseudo-boehmite, etc. when preparing boehmite to be blended in the FCC catalyst by hydrothermal treatment.

[0032] Although it is not entirely clear, it is thought that a smaller value of A / B indicates that the catalyst contains fewer stacked aggregates in which the 020 faces of the plate-like boehmite crystals are in contact, and instead, the proportion of aggregates in which the plate-like boehmite crystals are randomly combined in a house-of-cards shape is higher.

[0033] 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, and the upper limit may be, for example, 1.5. This A / C tends to correspond to the ratio of the boehmite content to the zeolite content in the FCC catalyst and the degree of crystallinity of the boehmite crystals.

[0034] Here, the smaller the A / B value and the larger the A / C value, the higher the gasoline selectivity and LPG olefinicity of the FCC catalyst of the present invention. The reasons for this are not entirely clear, but a large A / C value means that the boehmite crystals have grown sufficiently, reducing the acid sites that cause coke formation (acid sites are thought to be particularly abundant in amorphous components with insufficient crystal growth), thereby increasing gasoline selectivity. A small A / B value also means that there are many boehmite crystal aggregates with large intercrystalline gaps, which increases the diffusivity of feedstock oil molecules and product oil molecules and promotes the desorption of reactant molecules. This makes it difficult for the reactant molecules to undergo excessive hydrogen transfer reactions at the zeolite acid sites, thereby suppressing the loss of olefins.

[0035] 《Specific surface area》 The specific surface area of ​​the FCC catalyst of the present invention, as measured by a nitrogen adsorption method, is preferably 200 to 350 m 2 / g, more preferably 200 to 300m 2 / g.

[0036] <Matrix specific surface area> The matrix specific surface area after pseudo-equilibration treatment, i.e., the matrix specific surface area obtained by t-plot analysis of the nitrogen adsorption isotherm measured for the FCC catalyst of the present invention after pseudo-equilibration treatment under the following conditions, is preferably 10 to 40 m 2 / g, more preferably 20 to 39 m 2 / g. The matrix specific surface area is the specific surface area of ​​the FCC catalyst excluding the zeolite.

[0037] (Pseudo-equilibration treatment conditions) The FCC catalyst is loaded with 1000 ppm (based on the mass of the catalyst) of nickel and 2000 ppm (based on the mass of the catalyst) of vanadium, and then subjected to a steaming treatment at 780° C. for 13 hours.

[0038] The smaller the specific surface area of ​​the matrix after pseudo-equilibration treatment, the higher the gasoline yield of the FCC catalyst of the present invention tends to be. The reason for this is not entirely clear, but it is thought that this is because, while the strong acid sites that cause coke formation decrease as the boehmite crystals grow sufficiently, the specific surface area of ​​the boehmite crystals decreases as the crystal growth progresses.

[0039] The FCC catalyst of the present invention preferably satisfies the following formula (3): (1-(specific surface area of ​​matrix after pseudo-equilibration treatment) / (specific surface area of ​​matrix before pseudo-equilibration treatment)) × 100% ≧ 40% ... (3) [wherein the matrix specific surface area after pseudo-equilibration treatment is the matrix specific surface area determined by t-plot analysis of the nitrogen adsorption isotherm measured for the FCC catalyst after the pseudo-equilibration treatment described above, and The matrix specific surface area before the pseudo-equilibration treatment is the matrix specific surface area determined by t-plot analysis of the nitrogen adsorption isotherm measured for the FCC catalyst before the pseudo-equilibration treatment described above.

[0040] The left side of equation (3) is also referred to as the “reduction rate of the matrix specific surface area due to pseudo-equilibrium,” or simply as the “reduction rate.” This reduction rate is more preferably 45% or more, and the upper limit may be, for example, 65%.

[0041] Here, the value of the reduction rate can be increased or decreased by adjusting, for example, the hydrothermal treatment temperature, hydrothermal treatment time, amount of inorganic basic compound, ratio of gibbsite raw material to pseudo-boehmite, etc. when preparing boehmite to be blended in the FCC catalyst by hydrothermal treatment.

[0042] The larger this reduction rate, the higher the LPG olefinicity of the FCC catalyst of the present invention tends to be. The reason for this is not entirely clear, but it is thought that the boehmite is so inactive after pseudo-equilibration that the specific surface area is reduced by the pseudo-equilibration treatment before use in the reaction, and therefore functions efficiently as a path for diffusing reactant molecules.

[0043] The FCC catalyst of the present invention preferably satisfies the following formula (4): (Matrix specific surface area after pseudo-equilibration treatment) / pore volume ≦ 120 m 2 / ml …(4) [wherein the matrix specific surface area after pseudo-equilibration treatment is the matrix specific surface area determined by t-plot analysis of the nitrogen adsorption isotherm measured for the FCC catalyst after the pseudo-equilibration treatment described above, and The pore volume is the volume of pores with a diameter of 4.0 to 10,000 nm measured by mercury porosimetry (mercury contact angle: 140 degrees, surface tension: 480 dyn / cm) for the FCC catalyst after the pseudo-equilibration treatment described above. The value of the left side of equation (4) is preferably 115 m 2 / ml or less, and the lower limit is, for example, 95m 2 / ml may also be used.

[0044] The value of the left side of formula (4) can be increased or decreased by adjusting the hydrothermal treatment temperature, hydrothermal treatment time, amount of inorganic basic compound, ratio of gibbsite raw material to pseudo-boehmite, etc., when preparing boehmite to be blended in an FCC catalyst by hydrothermal treatment.

[0045] The smaller the value of the left side of equation (4), i.e., the specific surface area of ​​the matrix per pore volume after pseudo-equilibrium treatment, the higher the gasoline yield of the FCC catalyst of the present invention tends to be. The reason for this is not entirely clear, but it is thought that the large pore volume, combined with the small specific surface area, allows the large pores to function efficiently as paths for diffusing reactant molecules.

[0046] [Manufacturing method of flowing contact decomposition catalyst] The method for producing a fluid catalytic cracking catalyst (FCC catalyst) (for hydrocarbon oils) according to the present invention includes the steps of: Step (α) of preparing boehmite crystal aggregates having predetermined properties; A step (β) of preparing a catalyst raw material slurry containing faujasite-type zeolite, the boehmite crystal aggregates, and a binder-forming component; and A step (γ) of spray-drying the catalyst raw material slurry The present invention is characterized in that it includes:

[0047] (Engineering (α)) Step (α) is a step of preparing an aggregate of boehmite crystals (hereinafter also referred to as “aggregated boehmite (a)”) having the following properties (i) to (iv): (i) The boehmite crystals have a crystallite diameter of 10 to 70 nm calculated from the peak of the (020) plane in X-ray diffraction measurement. (ii) the specific surface area of ​​the aggregates, as measured by a nitrogen adsorption method, is 40 to 150 m 2 / g. (iii) The aggregates have an average particle size of 2.0 to 10 μm as measured by a laser diffraction / scattering method. (iv) The CBD (Compact Bulk Density) of the aggregate is 0.20 to 0.50 g / ml.

[0048] Each physical property will be described in detail. <(i) Crystal diameter> The boehmite crystals constituting the aggregated boehmite (a) have a crystallite diameter of 10 to 70 nm calculated from the peak of the (020) plane in X-ray diffraction measurement.

[0049] Agglomerated boehmite (a) with a crystallite size in this range is suitable as a catalyst material. For example, by using this agglomerated boehmite (a) as a matrix component, an FCC catalyst with excellent catalytic performance can be produced.

[0050] On the other hand, agglomerated boehmite (a) having a crystallite size excessively larger than this range is considered unsuitable as a catalyst material. For example, an FCC catalyst produced using agglomerated boehmite (a) having an excessively large crystallite size as a matrix component may have significantly inferior catalytic performance or attrition resistance.

[0051] The crystallite size is preferably 12 to 50 nm, more preferably 15 to 40 nm, still more preferably 18 to 35 nm, and particularly preferably 23 to 33 nm. The crystallite size can be determined by the following method or an equivalent method.

[0052] <<Calculation method for crystallite size>> A powder of agglomerated boehmite (a) is prepared. If the agglomerated boehmite (a) is in the form of a slurry, for example, the slurry is dried at 130°C for 12 hours, and then the residue is ground in a mortar to obtain a powder.

[0053] Next, this powder is pulverized in a mortar to prepare a measurement sample. An X-ray diffraction pattern is obtained for this sample using an X-ray diffractometer (e.g., MiniFlex, manufactured by Rigaku Corporation). The full width at half maximum of the peak of the (020) plane of boehmite in the obtained X-ray diffraction pattern is measured, and the value calculated by the following Scherrer formula is used as the crystallite diameter. D=Kλ / βcosθ D: Crystallite diameter (nm) K: Scherrer constant (in the present invention, K=0.94) λ: X-ray wavelength (0.15418nm, CuKα) β: Full width at half maximum (rad) θ: reflection angle

[0054] The crystallite size can be adjusted, for example, by changing the time of hydrothermal treatment in the production method described below, by changing the ratio of aluminum to the inorganic basic compound during the hydrothermal treatment, or by changing the mixing ratio of gibbsite to pseudo-boehmite.

[0055] In the X-ray diffraction pattern described above, a gibbsite peak may be observed as long as it does not impair the effects of the present invention. When a 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 is preferably 10% or less, more preferably 5% or less, and particularly preferably 1% or less. The integrated intensity of the X-ray diffraction can be determined by analyzing the X-ray diffraction pattern obtained by the above method using X-ray diffraction analysis software (e.g., PDXL2, manufactured by Rigaku Corporation). The gibbsite content can be adjusted, for example, by changing the temperature and time of the hydrothermal treatment.

[0056] <(ii) Specific surface area> The specific surface area of ​​the agglomerated boehmite (a) measured by the nitrogen adsorption method (the method described below or an equivalent method) is 40 to 150 m 2 When the specific surface area is in this range, the agglomerated boehmite (a) is useful as a catalyst material. This specific surface area is preferably 60 to 145 m 2 / g, more preferably 70 to 140m 2 / g, more preferably 80 to 120m 2 / g.

[0057] <Method for measuring specific surface area using nitrogen adsorption method> First, a powder of agglomerated boehmite (a) is prepared. If the agglomerated boehmite (a) is in the form of a slurry, for example, the slurry is dried at 130°C for 12 hours, and then the residue is ground in a mortar to obtain a powder.

[0058] Next, this powder is placed in a porcelain crucible and fired at 600°C for 2 hours, then placed in a desiccator and cooled to room temperature to prepare a measurement sample. Next, 0.3 g of this sample is taken and its specific surface area is measured using a fully automatic surface area measuring device by the BET single-point method.

[0059] The specific surface area can be adjusted, for example, by changing the time of hydrothermal treatment in the production method described below, by changing the ratio of aluminum to the inorganic basic compound during the hydrothermal treatment, or by changing the mixing ratio of gibbsite to pseudo-boehmite.

[0060] <(iii) Average Particle Size> The average particle size of the agglomerated boehmite (a) is 2.0 to 10 μm. This average particle size can be adjusted, for example, by adjusting the tip speed of the stirring blade when stirring the raw materials in the production method described below, adjusting the holding temperature during hydrothermal treatment, etc. This average particle size is preferably 4.0 to 9.5 μm, more preferably 6.0 to 9.0 μm.

[0061] <Method for measuring average particle size> Using a laser diffraction / scattering particle size distribution analyzer (e.g., HORIBA, Ltd. LA-950V2), the sample is placed in a solvent (water) so that the light transmittance is in the range of 70 to 95%, and the particle size distribution is measured under the following conditions: circulation rate 5.0 L / min, ultrasonic irradiation 1 minute, repetition number 15 times, refractive index 1.66, or equivalent conditions. The volume-based d 50 (Median diameter) is used as the average particle diameter.

[0062] <(iv)CBD(Compact Bulk Density)> The CBD (Compact Bulk Density) of the agglomerated boehmite (a) is 0.20 to 0.50 g / ml. Agglomerated boehmite (a) with such a small CBD is thought to form a house-of-cards structure. Since the agglomerated boehmite (a) has a small CBD and is thought to have large gaps between the plate-like boehmite crystals that form the house-of-cards structure, using this as a material for an FCC catalyst is thought to form large gaps in the FCC catalyst, facilitating the diffusion of feedstock oil and product oil and improving catalytic performance such as conversion. The CBD is preferably 0.25 to 0.40 g / ml, more preferably 0.30 to 0.40 g / ml.

[0063] <<How to measure CBD>> First, a powder of agglomerated boehmite (a) is prepared. If the agglomerated boehmite (a) is in the form of a slurry, for example, the slurry is dried at 130°C for 12 hours and then ground in a mortar to obtain a powder.

[0064] Next, 25 g of this powder sample is weighed and transferred to a 250 ml measuring cylinder, and the measuring cylinder is attached to a Tyler type sieve shaker. The sample is tapped and filled in the Tyler type sieve shaker for 15 minutes, and the measuring cylinder is removed, the sample surface is flattened, the filled volume is read, and the CBD is calculated.

[0065] CBD can be adjusted, for example, by changing the mixing ratio of gibbsite and pseudoboehmite in the production method described below. The method for producing the agglomerated boehmite (a) will be described later. In step (α), the agglomerated boehmite (a) may be prepared in the form of a powder or a slurry, and is preferably prepared in the form of a slurry.

[0066] (Engineering (β)) In step (β), a catalyst raw material slurry is produced by mixing faujasite-type zeolite, the agglomerated boehmite (a) prepared in step (α), binder-forming components, water, clay minerals, and optionally additives.

[0067] The faujasite-type zeolite, the agglomerated boehmite (a), the binder-forming component, the clay minerals, and the additives may be added in the form of powder or slurry, and the order of adding the components is not important as long as a slurry can be prepared without causing gelation.

[0068] <Faujasite-type zeolite> The details of the faujasite-type zeolite are as described above.

[0069] Agglomerated boehmite (a) The details of the agglomerated boehmite (a) are as described above.

[0070] <Binder-forming component> The binder-forming component is usually a silica-based binder-forming component and is prepared by mixing a silica source with an acid. Examples of this silica source include silica, silica gel (including silica hydrogel), silica sol (including silica hydrosol), and aqueous solutions of silicic acid (salts) (including orthosilicic acid (salts) and metasilicic acid (salts)) (e.g., water glass). As the silica sol and silicate, colloidal silica of sodium type, potassium type, lithium type, acid type, etc. can be used. Of these, silica sol and aqueous solutions of silicic acid (salts) are preferred. The acid may be an inorganic acid, such as sulfuric acid, hydrochloric acid, nitric acid, or phosphoric acid, and among these, sulfuric acid, hydrochloric acid, and nitric acid are preferred, with sulfuric acid being particularly preferred.

[0071] Clay minerals Details of the clay minerals are as described above.

[0072] Additives The catalyst raw material slurry may contain additives as long as the effects of the present invention are not impaired. Details of the additives are as described above.

[0073] <Catalyst raw material slurry> The proportion of each component in the catalyst raw material slurry is appropriately set so as to correspond to the content of each component in the FCC catalyst of the present invention described above.

[0074] The catalyst raw material slurry contains water as a dispersion medium. The catalyst raw material slurry may contain small amounts of components other than water as a dispersion medium, such as methanol, ethanol, and acetone.

[0075] From the viewpoint of easily carrying out spray drying of the catalyst raw material slurry, the solids concentration of the catalyst raw material slurry is preferably 20 to 40 mass %, and more preferably 25 to 35 mass %, the temperature of the catalyst raw material slurry is preferably 20 to 80°C, and more preferably 30 to 70°C, and the viscosity of the catalyst raw material slurry is preferably 100 to 10,000 mPa s, and more preferably 200 to 8000 mPa s.

[0076] (engineering (γ)) In step (γ), the catalyst raw material slurry produced in step (β) is spray-dried to obtain particles (hereinafter also referred to as “spray-dried particles”).

[0077] The spray-drying conditions may be appropriately changed depending on the solids concentration, viscosity, etc. of the catalyst raw material slurry, and are not particularly limited as long as the conditions result in an average particle size of the resulting spray-dried particles in the range of 50 to 90 μm, similar to that of general FCC catalyst particles.

[0078] For example, particles (spray-dried particles) are obtained by placing the catalyst raw material slurry in a slurry storage tank of a spray dryer and spraying the catalyst raw material slurry into a drying chamber through which an air current (e.g., an air current) flows, the temperature of which is set in the range of 120 to 600° C. Although the temperature of the air current decreases as the catalyst raw material slurry is sprayed, the temperature at the outlet of the drying chamber is maintained in the range of 50 to 300° C., for example, by using a heater or the like.

[0079] The particle size of the spray-dried particles can be controlled by adjusting the concentration, viscosity, spray amount, spray pressure, nozzle diameter of the spray dryer, hot air temperature, etc. of the catalyst raw material slurry to be sprayed. The spray-dried particles may be washed (for example, with water) and then dried. The temperature of the water is preferably 40 to 80°C from the viewpoint of washing properties.

[0080] The resulting spray-dried particles may be used as an FCC catalyst of the present invention as is, but preferably, the spray-dried particles obtained in step (γ) are subjected to step (δ) of contacting with water containing an ammonium salt, and step (ε) of drying the particles that have been subjected to step (δ), before being used as an FCC catalyst of the present invention.

[0081] (Engineering (δ)) In step (δ), the spray-dried particles obtained in step (γ) are contacted with water containing an ammonium salt.

[0082] Examples of the ammonium salt include ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium oxalate, and ammonium acetate, with ammonium sulfate being preferred.

[0083] Examples of embodiments of step (δ) include: Dispersing the spray-dried particles obtained in step (γ) in water containing an ammonium salt and separating the particles from the resulting slurry; and A step of pouring water containing an ammonium salt onto the spray-dried particles obtained in step (γ). Examples include:

[0084] From the viewpoint of removing sulfate ions and the like derived from the ammonium salt, the spray-dried particles that have been brought into contact with water containing the ammonium salt may be washed with water and then dried.

[0085] The temperature of the water used in step (δ) is preferably 40 to 80°C, for example, from the viewpoint of cleaning properties. In step (δ), the spray-dried particles obtained in step (γ) may be contacted with water containing an ammonium salt, and then with an aqueous solution containing a rare earth metal, thereby introducing the rare earth metal into the zeolite in the spray-dried particles.

[0086] In step (δ), the spray-dried particles are preferably suspended in water to prepare a suspension, and the suspension is then contacted with an aqueous solution containing a rare earth metal to be ion-exchanged. The resulting solid (FCC catalyst) may then be separated, washed, and dried. The temperature of the water is preferably 40 to 80°C. Alternatively, the suspension may be filtered, and the filtered solid may be resuspended in water to remove unnecessary soluble substances present in the spray-dried particles.

[0087] An aqueous solution containing a rare earth metal can be prepared, for example, by dissolving a salt of the rare earth metal (for example, LaCl3) in water. Step (δ) is carried out so that the concentration of rare earth metals in the resulting fluid catalytic cracking catalyst is 0.5 to 3.5 mass%, preferably 0.7 to 3.0 mass%, calculated as rare earth metal oxides (RE2O3). The amount and concentration of the aqueous solution containing the rare earth metals are adjusted to achieve the desired content of rare earth metal oxides.

[0088] Not only when the ultra-stable Y-type zeolite is USY, but also when REUSY is used and some rare earth metal ions are removed (substituted with protons) from REUSY during preparation of the catalyst raw material slurry in step (β) or during washing of the spray-dried particles obtained in step (γ), a fluid catalytic cracking catalyst containing a desired amount of rare earth metal can be produced by performing step (δ).

[0089] (Engineering (ε)) Step (ε) is a step of drying the spray-dried particles that have been subjected to step (δ). Drying may be carried out, for example, by heating the spray-dried particles that have been subjected to step (δ) at 90 to 200° C. for 0.5 to 24 hours using, for example, a dryer.

[0090] [Manufacturing method of agglomerated polytope (a)] The above-mentioned agglomerated boehmite (a) can be produced, for example, by a method including a step (A) of producing an agglomerated boehmite slurry, and may also be produced by a method including a step (B) of drying the agglomerated boehmite slurry produced in the step (A).

[0091] <Engineering (A)> In step (A), for example, The volume-based d in particle size distribution measured by laser diffraction and scattering method 50 75 to 95 parts by mass of gibbsite having a (median diameter) of 0.5 μm or more and less than 70 μm, calculated as Al2O3, The crystallite diameter calculated from the (020) plane peak in X-ray diffraction measurement is 2 to 6 nm, and the volume-based d in the particle size distribution measured by laser diffraction / scattering method is 0.01 to 0.02. 50 5 to 25 parts by mass, in terms of Al2O3, of pseudo-boehmite powder having a (median diameter) of 5 to 100 μm and not subjected to peptization treatment (where the total amount of gibbsite and pseudo-boehmite in terms of Al2O3 is 100 parts by mass), and A first step of preparing a mixed solution (1) by mixing water so that the pH does not become 7.0 or less; a second step of adding an inorganic basic compound to the mixed solution (1) to prepare a mixed solution (2) having a pH of 9 to 12; a third step of hydrothermally treating the mixed solution (2) at 150 to 190°C for 1 to 24 hours while heating the mixed solution (2) at a rate of 15 to 60°C / hour and stirring the mixture; The agglomerated boehmite slurry is produced by a method comprising:

[0092] (First Project) The first step is a step of mixing gibbsite, pseudo-boehmite, and water to prepare a mixed solution (1).

[0093] The average particle size of this gibbsite, i.e., the volume-based d 50 (median diameter) is 0.5 μm or more and less than 70 μm. 50 However, if the value is too small, it is difficult to control the reaction. 50 However, if the d is too large, the gibbsite settles quickly when suspended in water, making it difficult to handle. 50is preferably 1.0 μm or more and less than 65 μm, more preferably 2.0 μm or more and less than 60 μm. 50 More preferably, it is 2.0 μm or more and less than 55 μm.

[0094] Examples of commercially available gibbsite include "C-303" (manufactured by Sumitomo Chemical Co., Ltd.) and "C-12" (manufactured by Sumitomo Chemical Co., Ltd.). 50 The powder may be ground appropriately so that the particle size falls within the above range. The grinding may be carried out using a ball mill, an attritor, a bead mill, a colloid mill, a high-shear mixer, or the like.

[0095] <Method for measuring particle size distribution> Gibbsite d 50 That is, the method for measuring the average particle size is the same as the method for measuring the average particle size of the agglomerated boehmite (a) described above.

[0096] Pseudo-boehmite is thought to function as a seed crystal during hydrothermal treatment, and its crystallite diameter is 2 to 6 nm. If the crystallite diameter is smaller than this range, the hydrothermal treatment takes a long time, which is undesirable, and if it is too large, it is difficult to control the reaction.

[0097] The method for calculating the crystallite diameter of pseudo-boehmite is the same as the method for calculating the crystallite diameter of the agglomerated boehmite (a) described above. The average particle size of this pseudo-boehmite, i.e., the volume-based d 50 (median diameter) is 5 to 100 μm. 50 When d is in this range, the aggregates function as seed crystals, so they are difficult to peptize even when contacted with an acid, and it is possible to produce aggregated boehmite (a) with a small CBD. 50 However, if the value is too small, the CBD of the resulting boehmite crystal aggregates will be large. 50 If d is too large, the pseudo-boehmite does not function as a seed crystal. 50 is preferably 40 to 70 μm.

[0098] An example of a commercially available pseudo-boehmite is "Catapal-A" (manufactured by Sasol). Pseudoboehmite is d 50 The powder may be ground appropriately so that the particle size falls within the above range. The grinding may be carried out using a ball mill, an attritor, a bead mill, a colloid mill, a high-shear mixer, or the like.

[0099] Pseudoboehmite d 50 That is, the method for measuring the average particle size is the same as the method for measuring the average particle size of the agglomerated boehmite (a) described above. When the mixed solution (1) is prepared by mixing pseudo-boehmite powder, gibbsite, and water, the pseudo-boehmite powder, which has agglomerates strengthened by drying, functions as seed crystals, making it possible to prepare agglomerated boehmite, compared to the case where pseudo-boehmite slurry, gibbsite, and water are mixed.

[0100] This pseudo-boehmite is mixed with gibbsite and water without peptization. By not peptizing the pseudo-boehmite, the pseudo-boehmite aggregates function as seed crystals, and the resulting boehmite also aggregates to form boehmite aggregates (a) with a house-of-cards structure, which is thought to result in a smaller CBD. Furthermore, by not peptizing the pseudo-boehmite, the process can be shortened, resulting in excellent industrial economy and productivity.

[0101] 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 "75-95:25-5" in terms of Al2O3 (provided that the sum of both is 100). Here, if the amount of gibbsite is too small (the amount of pseudo-boehmite is too large), the CBD of the boehmite obtained from the boehmite slurry will be large. Conversely, if the amount of gibbsite is too large (the amount of pseudo-boehmite is too small), the resulting boehmite will have a large crystallite diameter and a small specific surface area. This "mass of gibbsite:mass of pseudo-boehmite" is preferably "75-90:25-10", more preferably "80-90:20-10".

[0102] The mixture (1) obtained by mixing gibbsite, pseudo-boehmite, and water is usually a slurry. The temperature when preparing the mixed liquid (1) by mixing gibbsite, pseudo-boehmite, and water is usually 5 to 90°C, and preferably 15 to 80°C.

[0103] These components are mixed so that the pH of the mixed solution (1) does not become 7.0 or less, and is used in the next step. In this way, the pseudo-boehmite does not undergo peptization under acidic conditions, and functions as a seed crystal while remaining in a state of agglomeration, and agglomerated boehmite (a) with a small CBD is obtained.

[0104] (Second Project) The second step is a step of adding an inorganic basic compound to the mixed solution (1) to prepare a mixed solution (2) having a pH of 9 to 12.

[0105] Examples of inorganic basic compounds include sodium hydroxide, potassium hydroxide, calcium hydroxide, etc., with sodium hydroxide being preferred. The mixed liquid (2) is usually a slurry.

[0106] The type and amount of the inorganic basic compound are adjusted so that the pH of the resulting mixed solution (2), preferably the pH at 60°C, is 9 to 12. Here, if the pH is lower than this lower limit, dissolution and reprecipitation of gibbsite and pseudo-boehmite do not proceed during the hydrothermal treatment, and a slurry containing not only the desired boehmite but also gibbsite is obtained, which is not preferred. The temperature when preparing the mixed solution (2) by adding the inorganic basic compound to the mixed solution (1) is usually 5 to 90°C, preferably 15 to 80°C.

[0107] (Third Project) The third step is a step of hydrothermally treating the mixed liquid (2) obtained in the second step to obtain an agglomerated boehmite slurry.

[0108] The heat treatment temperature is usually 140 to 190°C, preferably 150 to 190°C. The heat treatment time is usually 1 to 24 hours, preferably 1.5 to 18 hours. On the other hand, if the heat treatment temperature is excessively lower than this range, or if the heat treatment time is excessively shorter than this range, the hydrothermal reaction does not proceed sufficiently, resulting in a reduced yield of boehmite.

[0109] The temperature increase rate (that is, the rate at which the mixed liquid (2) obtained in the second step is increased in temperature to the above-mentioned heat 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 excessively higher than this range, the hydrothermal reaction does not proceed sufficiently, resulting in a reduced yield of boehmite.

[0110] The hydrothermal treatment may be carried out under autogenous pressure. An autoclave is usually used for the hydrothermal treatment. This autoclave is preferably equipped with a stirring blade. The hydrothermal treatment can be carried out more uniformly by stirring the mixture (2) with the stirring blade.

[0111] The stirring is preferably carried out under gentle conditions, for example, at a low impeller tip speed, which makes it possible to obtain agglomerated boehmite that is difficult to deflocculate even when brought into contact with an acid or subjected to a pulverization treatment. On the other hand, if stirring is performed at an excessively high impeller tip speed, the resulting boehmite may not aggregate, resulting in a large CBD.

[0112] (Fourth Project) The step (A) of producing an agglomerated boehmite slurry may optionally include a fourth step of washing the slurry obtained in the third step.

[0113] In the fourth step, the slurry obtained in the third step is dehydrated, the obtained solid content is washed with water (preferably ion-exchanged water), and the obtained washed cake is suspended in a liquid medium (preferably water such as ion-exchanged water) to prepare a washed agglomerated boehmite slurry.

[0114] The temperature of the water used for washing is preferably set to 40 to 90°C. By carrying out the fourth step, impurities (sodium, sulfate, etc.) can be removed. In addition, by suspending the washed cake again in water, etc., the slurry can be adjusted to a desired concentration.

[0115] (agglutination ベーマイトスラリー) For example, an agglomerated boehmite slurry is produced by the above-mentioned step (A). The alumina (Al2O3) equivalent concentration of the agglomerated boehmite slurry produced in the above step (A) is, for example, 5.0 to 30 mass %, preferably 8.0 to 25 mass %, and more preferably 10 to 20 mass %.

[0116] The concentration can be adjusted by increasing or decreasing the amount of water contained in the agglomerated boehmite slurry. This agglomerated boehmite slurry may contain additives within the range that does not impair the effects of the present invention, or may not contain any additives.

[0117] Examples of additives include inorganic acids (sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid, etc.), inorganic bases (sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, etc.), organic acids (formic acid, acetic acid, citric acid, malic acid, tartaric acid, gluconic acid, succinic acid, oxalic acid, lactic acid, etc.), thickeners (polyvinyl alcohol, methyl cellulose, gum arabic, diatomaceous earth, bentonite, polyacrylamide, polyethylene oxide, polyacrylic acid esters, locust bean gum, etc.).

[0118] When additives are included, they can be added by a conventional method in the stages of the first to fourth steps. However, when additives are added in the stages of the first to third steps, the amount of additives excluding the inorganic basic compound added in the second step is preferably 1% by mass or less based on the content of aluminum (equivalent to alumina (Al2O3)) in the raw materials (i.e., 100% by mass), from the viewpoint of promoting dissolution of the raw material gibbsite and growth of boehmite crystals.

[0119] <Engineering (B)> In step (B), the agglomerated boehmite slurry produced in step (A) is dried to obtain agglomerated boehmite (a).

[0120] The agglomerated boehmite slurry may be washed with water before drying. The temperature of the water is preferably 40 to 90°C. Drying may be carried out, for example, by heating the washed agglomerated boehmite slurry at, for example, 90 to 200° C. for 0.5 to 24 hours.

[0121] The dried product is preferably pulverized by a conventional method such as using a mortar. Alternatively, the drying may be carried out by spray drying the agglomerated boehmite slurry. In this case, the concentration of the agglomerated boehmite slurry may be adjusted by adding water to, for example, 5 to 30 mass % in terms of Al2O3.

[0122] For example, particles (spray-dried particles) are obtained by placing the agglomerated boehmite slurry in a slurry storage tank of a spray dryer and spraying the agglomerated boehmite slurry into a drying chamber through which an air current (e.g., an air flow) set at a temperature in the range of, for example, 120 to 600° C. Although the temperature of the air current decreases as the agglomerated boehmite slurry is sprayed, the temperature at the outlet of the drying chamber is maintained in the range of, for example, 50 to 300° C. by using a heater or the like.

[0123] The particle size of the spray-dried particles can be controlled by adjusting the concentration, viscosity, spray amount, spray pressure, nozzle diameter of the spray dryer, hot air temperature, etc. of the agglomerated boehmite slurry to be sprayed. [Example]

[0124] The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples. [Measurement method] In the examples, various measurements were carried out by the following methods.

[0125] <Measurement of boehmite> (Measurement sample) The powders obtained in step 2 of the Production Example and Comparative Production Example were measured for average particle diameter (particle size distribution (d 50 The slurries obtained in step 3 of the Production Examples and Comparative Production Examples were used as measurement samples for the average particle diameter (particle size distribution (d 50 )) was used as a measurement sample.

[0126] (Average particle diameter (particle size distribution (d 50 ))) The particle size distribution of the measurement sample was measured using a laser diffraction / scattering particle size distribution analyzer (LA-950V2) manufactured by Horiba, Ltd. Specifically, the measurement sample was placed in a solvent (water) so that the light transmittance was in the range of 70 to 95%, and the measurement was carried out at a circulation rate of 5.0 L / min, ultrasonic irradiation for 1 minute, repeated 15 times, and a refractive index of 1.66.

[0127] (Crystalline structure and crystallite size) The measurement sample was crushed in a mortar and subjected to X-ray diffraction analysis using an X-ray diffractometer (MiniFlex, manufactured by Rigaku Corporation). The measurement conditions were as follows: the operating axis was set to 2θ / θ, a CuKα source was used, and the measurement was performed continuously with a voltage of 40 kV and a current of 15 mA, starting from an angle of 2θ = 5° to an end angle of 2θ = 90°, with a sampling width of 0.020°, and a scan rate of 10,000° / min.

[0128] The crystal structure was identified by comparing the X-ray diffraction pattern of the measured sample with the International Centre for Diffraction Data database PDF-2 2023 using PDXL2 software manufactured by Rigaku Corporation. Furthermore, when the measured sample was identified as boehmite, the crystallite size was calculated from the peak of the (020) plane of boehmite using the method described above.

[0129] (Confirmation of crystal shape and aggregates) The measurement sample was observed using a scanning electron microscope (SEM) to confirm that the crystals formed aggregates. The scanning electron microscope used was a Hitachi High-Technologies Corporation S-5500, with a magnification of 50,000 to 300,000 times. The image analysis software used was Winroof 2018 STANDARD, manufactured by Mitani Corporation.

[0130] (specific surface area) The measurement sample was placed in a porcelain crucible, fired at 600°C for 2 hours, and then placed in a desiccator and cooled to room temperature. Next, 0.3 g of the measurement sample was weighed, and the specific surface area (m 2 / g) was measured by the BET single-point method.

[0131] (CBD) 25 g of the sample was weighed out and transferred to a 250 ml measuring cylinder, which was then attached to a Tyler sieve shaker. The sample was filled by tapping on the Tyler sieve shaker for 15 minutes, the measuring cylinder was removed, the sample surface was flattened, and the filled volume was read to calculate the CBD.

[0132] <Measurement of fluid catalytic cracking catalyst> (Measurement sample) The fluid catalytic cracking catalysts obtained in the examples and comparative examples were used as measurement samples.

[0133] (specific surface area) The specific surface area of ​​the fluid catalytic cracking catalyst was measured by the same method as used to measure the specific surface area of ​​the boehmite.

[0134] (Powder X-ray diffraction analysis) The measurement sample was crushed in a mortar and subjected to X-ray diffraction analysis using an X-ray diffractometer (MiniFlex, manufactured by Rigaku Corporation). The measurement conditions were as follows: the operating axis was set to 2θ / θ, a CuKα source was used, and the measurement was performed continuously with a voltage of 40 kV and a current of 15 mA, starting from an angle of 2θ = 5° to an end angle of 2θ = 90°, with a sampling width of 0.020°, and a scan rate of 10,000° / min.

[0135] 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 (331) plane of ultra-stable Y-type zeolite.

[0136] (Matrix specific surface area) The matrix specific surface area of ​​the fluid catalytic cracking catalyst was measured before and after pseudo-equilibrium treatment in the catalyst performance evaluation test described below.

[0137] The measurement sample was placed in a porcelain crucible and sintered at 600°C for 2 hours. It was then placed in a desiccator and cooled to room temperature. The sample was then weighed and the adsorption amount was measured using a fully automated nitrogen adsorption / desorption analyzer (Microtrack-Bell, BELSORP mini). The resulting adsorption isotherm was analyzed using the t-plot method with Microtrack-Bell's BELMaster software to determine the matrix specific surface area.

[0138] Furthermore, the reduction rate of the matrix specific surface area due to pseudo-equilibration was calculated using the following formula. Reduction rate (%) of matrix specific surface area due to pseudo-equilibration = (1 - (specific surface area of ​​matrix after pseudo-equilibration treatment) / (specific surface area of ​​matrix before pseudo-equilibration treatment)) × 100%

[0139] (pore volume) The pore volume of the fluid catalytic cracking catalyst after the pseudo-equilibration treatment was measured by mercury porosimetry. The measurement sample was collected in a porcelain crucible, heated at 500°C for 1 hour, and then placed in a desiccator to cool to room temperature. After obtaining a measurement sample, the volume (ml / g) of pores in the catalyst with a pore diameter of 4.0 to 10,000 nm was measured by mercury intrusion porosimetry (Quantachrome Poremaster GT-60, mercury contact angle: 140 degrees, surface tension: 480 dyn / cm). In addition, the matrix specific surface area (m) after pseudo-equilibrium treatment relative to this pore volume (ml / g) 2 / g) ratio (m 2 / ml) was calculated.

[0140] [Manufacturing Example 1] (Step 1: Preparation of agglomerated boehmite by hydrothermal treatment) Pseudoboehmite powder (1) (Sasol Catapal-A, Al2O3 equivalent concentration 71.2 mass%, volume-based d 50 0.12 kg of gibbsite powder (1) (Sumitomo Chemical Co., Ltd. C-303, Al2O3 equivalent concentration 66.6 mass%, volume-based d 50 0.72 kg of cellulose acetate (median diameter: 6.1 μm) was mixed with 3.15 kg of ion-exchanged water to prepare a slurry with an Al2O3-equivalent concentration of 14 mass %. While stirring the slurry, 20 g of a 48 mass % aqueous sodium hydroxide solution was added to obtain a uniform slurry (1) with a pH of 11.8 (pH measured at 60°C; the same applies to other production examples and comparative production examples).

[0141] The slurry (1) was placed in a 5 L autoclave reactor, and while stirring at a tip speed of 0.7 m / s, the mixture was heated to 170°C at a temperature increase rate of 25°C / hour, maintained at autogenous pressure for 4 hours, and then naturally cooled while continuing to stir, to obtain a slurry (2).

[0142] (Step 2: Washing the boehmite) 4.0 kg of the slurry (2) obtained in step 1 was dehydrated under reduced pressure using a plate filter and then washed with 20 L of ion-exchanged water at 60°C to obtain a washed cake (1). A portion of the washed cake (1) was placed on a stainless steel tray and dried at 130°C for 12 hours, and then thoroughly ground in a mortar to obtain a powder (1). The obtained powder (1) was measured using the method described above. It was confirmed that the powder (1) was an aggregate of plate-like boehmite crystals. The manufacturing conditions and measurement results are shown in Table 1.

[0143] (Step 3: Preparation of agglomerated boehmite slurry) The washed cake (1) was suspended in pure water, and then the pH was adjusted to 3.0 with sulfuric acid to obtain a slurry of agglomerated boehmite (hereinafter referred to as agglomerated boehmite slurry (1)) having an Al2O3 concentration of 15 mass %.

[0144] [Manufacturing Example 2] A washed cake (2) and powder (2) were obtained in the same manner as in steps 1 and 2 of Production Example 1, except that the retention time in the autoclave reactor was changed from 4 hours to 2 hours. It was confirmed that powder (2) was an aggregate of plate-like boehmite crystals.

[0145] The manufacturing conditions and measurement results are shown in Table 1. A slurry of agglomerated boehmite having an Al2O3 concentration of 15 mass% (hereinafter referred to as "agglomerated boehmite slurry (2)") was obtained in the same manner as in step 3 of Production Example 1, except that the washed cake (1) was changed to the washed cake (2).

[0146] [Manufacturing Example 3] A washed cake (3) and powder (3) were obtained in the same manner as in steps 1 and 2 of Production Example 1, except that the retention time in the autoclave reactor was changed from 4 hours to 14 hours. It was confirmed that powder (3) was an aggregate of plate-like boehmite crystals.

[0147] The manufacturing conditions and measurement results are shown in Table 1. A slurry of agglomerated boehmite having an Al2O3 concentration of 15 mass% (hereinafter referred to as "agglomerated boehmite slurry (3)") was obtained in the same manner as in step 3 of Production Example 1, except that the washed cake (1) was changed to the washed cake (3).

[0148] [Manufacturing Example 4] Powder (4) was obtained in the same manner as in Production Example 1, except that the heating temperature (holding temperature) was changed from 170°C to 160°C, the holding time was changed from 4 hours to 5 hours, and the impeller tip speed was changed from 0.7 m / s to 1.4 m / s. Powder (4) was confirmed to be an aggregate of plate-like boehmite crystals. The production conditions and measurement results are shown in Table 1.

[0149] [Manufacturing Example 5] Gibbsite powder (1) was mixed with gibbsite powder (2) (B-52 manufactured by Nippon Light Metal Co., Ltd., Al2O3 equivalent concentration 65.0 mass%, d 50 Powder (5) was obtained in the same manner as in Production Example 1, except that the temperature (median diameter) was changed to 52 μm, the heating temperature (holding temperature) was changed from 170° C. to 160° C., and the holding time was changed from 4 hours to 5 hours. Powder (5) was confirmed to be an aggregate of plate-like boehmite crystals. The production conditions and measurement results are shown in Table 1.

[0150] [Comparative Manufacturing Example 1] A 200 L steam-jacketed tank was charged with 9.09 kg of sodium aluminate solution with an Al2O3 equivalent concentration of 22 mass%, and 50.7 kg of ion-exchanged water was added. Next, 231 g of sodium gluconate solution with a concentration of 26 mass% was added to this solution, and the mixture was heated to 60°C with stirring to obtain a mixed solution of sodium aluminate and sodium gluconate.

[0151] Separately from this mixed solution, 14.29 kg of an aqueous aluminum sulfate solution having a concentration of 7 mass % in terms of Al2O3 was diluted with 25.71 kg of ion-exchanged water and then heated to 60°C to prepare an aqueous aluminum sulfate solution.

[0152] Next, while stirring a mixed solution of sodium aluminate and sodium gluconate at 60°C, an aqueous aluminum sulfate solution was added over 10 minutes to prepare an alumina hydrate slurry with an Al2O3 equivalent concentration of 3.0% by mass. The pH of the slurry was 7.2. The resulting alumina hydrate slurry was aged at 60°C for 60 minutes while stirring. The aged alumina hydrate slurry was then dehydrated under reduced pressure using a plate filter and washed with 100 L of ion-exchanged water at 60°C. The cake (c1) obtained after washing was suspended in ion-exchanged water to a concentration of 12% by mass in terms of Al2O3, yielding pseudo-boehmite slurry (c1).

[0153] A small amount of the sample was extracted from the slurry and analyzed. The particles in the slurry were found to be pseudo-boehmite particles, with a crystallite diameter of 3.9 nm and a volume-based d 50 The median diameter was 4.4 μm.

[0154] 1.40 kg of pseudoboehmite slurry (c1), 0.72 kg of gibbsite powder (1), and 1.99 kg of ion-exchanged water were mixed to prepare a slurry with an Al2O3 equivalent concentration of 14 mass%. While stirring the slurry, 20 g of a 48 mass% sodium hydroxide aqueous solution was added to obtain a uniform slurry with a pH of 11.8.

[0155] Powder (c1) was produced and measured in the same manner as in Production Example 1, except that the heating temperature (holding temperature) was changed from 170°C to 160°C and the holding time was changed from 4 hours to 5 hours. Powder (c1) was confirmed to be a dispersion of plate-like boehmite crystals. The production conditions and measurement results are shown in Table 1.

[0156] [Comparative Manufacturing Example 2] Powder (c2) was produced and measured in the same manner as in Production Example 1, except that the amount of pseudoboehmite 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, and the holding time was changed from 4 hours to 5 hours. Powder (c2) was confirmed to be a dispersion of plate-like boehmite crystals. The production conditions and measurement results are shown in Table 1.

[0157] [Comparative Manufacturing Example 3] Powder (c3) was produced and measured in the same manner as in Production Example 1, except that the heating temperature (holding temperature) was changed from 160°C to 120°C and the holding time was changed from 4 hours to 5 hours. The X-ray diffraction pattern of powder (c3) was a mixture of gibbsite and boehmite, and the integrated intensity of the gibbsite (002) plane was 24% of the integrated intensity of the boehmite (020) plane, confirming that powder (c3) was a mixture of boehmite and gibbsite. The production conditions and measurement results are shown in Table 1.

[0158] [Comparative Manufacturing Example 4] When mixing the pseudo-boehmite powder (1), the gibbsite powder (1), and the ion-exchanged water, 23.3 g of an SiO source (water glass, SiO concentration 24% by mass, manufactured by JGC Catalysts and Chemicals Co., Ltd.) was further added to the mixture so that the SiO content was 2.0% by mass, based on the total amount (AlO equivalent) of the pseudo-boehmite powder (1) and the gibbsite powder (1) (100% by mass). The heating temperature (retention temperature) was changed from 170°C to 160°C, and the retention time was changed from 4 hours to 5 hours. Powder (c4) was produced and measured in the same manner as in Production Example 1. Powder (c4) was confirmed to be gibbsite. The production conditions and measurement results are shown in Table 1.

[0159] [Comparative Manufacturing Example 5] When mixing the pseudoboehmite powder (1), the gibbsite powder (1), and the ion-exchanged water, 5.6 g of tartaric acid (Kanto Chemical Co., Ltd., L(+)-tartaric acid, special grade) was further added to the mixture so that the total amount of the pseudoboehmite powder (1) and the gibbsite powder (1) (calculated as Al2O3) was 1.0 mass% based on 100 mass%. The heating temperature (holding temperature) was changed from 170°C to 160°C, and the holding time was changed from 4 hours to 5 hours. Powder (c5) was produced and measured in the same manner as in Production Example 1. Powder (c5) was confirmed to be gibbsite. The production conditions and measurement results are shown in Table 1.

[0160] [Table 1]

[0161] [Production of fluid catalytic cracking catalyst] [Example 1] <Production of fluid catalytic cracking catalyst (1)> 2941 g of water glass (SiO concentration 17 mass%) and 1059 g of sulfuric acid with a concentration of 25 mass% were simultaneously and continuously added to a container to prepare 4000 g of a silica binder solution with an SiO concentration of 12.5 mass%. Kaolin (solid concentration 85% by mass) 706g, As crystalline boehmite, 4167 g of the agglomerated boehmite slurry (1) (AlO concentration 15 mass%) obtained in Production Example 1 was used, and 1014 g of ultra-stabilized Y-type zeolite powder (JGC Catalysts and Chemicals Co., Ltd., UCS 2.445 nm, SiO2 / Al2O3 molar ratio 7.1 as determined by X-ray fluorescence analysis) (solid content 74% by mass) was added and thoroughly stirred to prepare a mixed slurry. The solid content of the prepared mixed slurry was 25.0%, the temperature was 39°C, and the viscosity was 800 mPa s.

[0162] This mixed slurry was formed into droplets and spray-dried in a spray dryer with an inlet temperature of 250°C and an outlet temperature of 150°C to obtain spherical particles with an average particle size of 70 µm.

[0163] The resulting spray-dried particles were washed with warm water, then ion-exchanged with an aqueous ammonium sulfate solution and washed with warm water. Furthermore, an aqueous rare earth metal chloride (LaCl) solution was used to perform an ion-exchange treatment so that the REO concentration was 1.0 mass%. The catalyst particles were then dried in a dryer at 150°C for 10 hours to obtain a fluid catalytic cracking catalyst (1). The composition and physical properties of the catalyst (1) are shown in Table 2.

[0164] [Example 2] <Production of fluid catalytic cracking catalyst (2)> A fluid catalytic cracking catalyst (2) was obtained in the same manner as in Example 1, except that the agglomerated boehmite slurry (1) was changed to 4,167 g of the agglomerated boehmite slurry (2) (AlO concentration: 15% by mass) obtained in Production Example 2. The composition and physical properties of the catalyst (2) are shown in Table 2.

[0165] [Example 3] <Production of fluid catalytic cracking catalyst (3)> A fluid catalytic cracking catalyst (3) was obtained in the same manner as in Example 1, except that the agglomerated boehmite slurry (1) was changed to 4,167 g of the agglomerated boehmite slurry (3) (AlO concentration: 15% by mass) obtained in Production Example 3. The composition and physical properties of the catalyst (3) are shown in Table 2.

[0166] [Example 4] <Production of fluid catalytic cracking catalyst (4)> A fluid catalytic cracking catalyst (4) was obtained in the same manner as in Example 1, except that the amount of ultra-stable Y-type zeolite powder was changed to 845 g and the amount of kaolin was changed to 853 g. The composition and physical properties of the catalyst (4) are shown in Table 2.

[0167] [Example 5] <Production of fluid catalytic cracking catalyst (5)> A fluid catalytic cracking catalyst (5) was obtained in the same manner as in Example 1, except that 833 g of a microcrystalline boehmite slurry (manufactured by JGC Catalysts and Chemicals Co., Ltd., AlO concentration 15.0 mass%, crystallite size 3 nm) and 833 g of a gibbsite slurry (manufactured by JGC Catalysts and Chemicals Co., Ltd., AlO concentration 15.0 mass%) were further used as raw materials for the mixed slurry, and the amount of agglomerated boehmite slurry (1) was changed to 2500 g. The composition and physical properties of catalyst (5) are shown in Table 2.

[0168] [Comparative Example 1] <Production of fluid catalytic cracking catalyst (c1)> A fluid catalytic cracking catalyst (c1) was obtained in the same manner as in Example 1, except that the agglomerated boehmite slurry (1) was replaced with 4,167 g of a microcrystalline boehmite slurry (manufactured by JGC Catalysts and Chemicals Co., Ltd., Al2O3 concentration: 15.0 mass%, crystallite diameter: 3 nm, dispersion medium: water, boehmite crystals were dispersed without agglomeration). The composition and physical properties of the catalyst (c1) are shown in Table 2.

[0169] Comparative Example 2 <Production of fluid catalytic cracking catalyst (c2)> A fluid catalytic cracking catalyst (c2) was obtained in the same manner as in Example 1, except that the agglomerated boehmite slurry (1) was replaced with 4,167 g of a highly dispersed crystalline boehmite slurry (manufactured by JGC Catalysts and Chemicals Co., Ltd., AlO concentration: 15.0 mass%, crystallite size: 23 nm, dispersion medium: water, median size: 0.29 μm, boehmite crystals were dispersed without agglomeration). The composition and physical properties of the catalyst (c2) are shown in Table 2.

[0170] Comparative Example 3 <Production of fluid catalytic cracking catalyst (c3)> A fluid catalytic cracking catalyst (c3) was obtained in the same manner as in Example 1, except that the amount of agglomerated boehmite slurry (1667 g) was changed to 1667 g using 1667 g of microcrystalline boehmite slurry (manufactured by JGC Catalysts and Chemicals Co., Ltd., Al2O3 concentration: 15.0 mass%, crystallite diameter: 3 nm, dispersion medium: water, boehmite crystals were dispersed without agglomeration) and 833 g of gibbsite (manufactured by JGC Catalysts and Chemicals Co., Ltd., Al2O3 concentration: 15.0 mass%) as raw materials for the mixed slurry. The composition and physical properties of catalyst (c3) are shown in Table 2.

[0171] [Evaluation of Fluid Catalytic Cracking Catalysts] For each of the fluid catalytic cracking catalysts in the examples and comparative examples, a performance evaluation test was carried out using ACE-MAT (Model R+, Advanced Cracking Evaluation-Micro Activity Test, manufactured by Kayser) under the same crude oil and the same reaction conditions. The results are shown in Table 2.

[0172] However, before conducting these performance evaluation tests, in order to simulate the condition of hydrothermal degradation in a catalyst regeneration tower, the catalyst was first absorbed into a toluene solution of nickel octylate and vanadium octylate so that the nickel concentration was 1000 ppm (the mass of nickel divided by the mass of the catalyst) and the vanadium concentration was 2000 ppm (the mass of vanadium divided by the mass of the catalyst), and the catalyst was baked at 600°C for 1.5 hours to deposit the nickel and vanadium.The catalyst was then steamed at 780°C for 13 hours to perform a pseudo-equilibrium treatment.

[0173] <Operating conditions> The reaction conditions in the catalyst performance evaluation test are as follows: Feedstock: Desulfurized atmospheric residue (DSAR) of crude oil + desulfurized vacuum gas oil (DSVGO) (50+50) Catalyst / through oil mass ratio (C / O): 3.75 and 5.0 (mass% / mass%) Reaction temperature: 520℃ 1) Conversion rate=100-(LCO+HCO) (mass%) 2) Boiling point range of gasoline: 30~216℃ 3) Boiling point range of LCO: 216-343°C (LCO: Light Cycle Oil) 4) Boiling point range of HCO: 343°C+ (HCO: Heavy Cycle Oil) 5) LPG (liquid petroleum gas) 6) LPG Olefinicity: The ratio (mass ratio) of propylene and butenes in LPG with 3 to 4 carbon atoms Selectivity at 73% conversion: A simple regression line was created from the conversions and the yields of each component at C / O=3.75 and 5.0, and the selectivity of each component at 73% conversion was calculated.

[0174] [Table 2]

Claims

1. The composition comprises faujasite-type zeolite, boehmite, a binder, and clay minerals, A fluid catalytic cracking catalyst that satisfies the following formulas (1) and (2) in powder X-ray diffraction analysis. A / B≦1.2…(1) (wherein A is the integrated intensity of the diffraction peak attributable to the (020) plane of boehmite, and B is the integrated intensity of the diffraction peak attributable to the (120) plane of boehmite.) A / C≧0.8…(2) (wherein A is the integrated intensity of the diffraction peak attributable to the (020) plane of boehmite, and C is the integrated intensity of the diffraction peak attributable to the (331) plane of faujasite-type zeolite.)

2. The matrix specific surface area, determined by t-plot analysis of the nitrogen adsorption isotherm measured for the fluid catalytic cracking catalyst after pseudo-equilibrium treatment under the following conditions, is 10 to 40 m 2 2. The fluid catalytic cracking catalyst of claim 1, wherein the catalyst has a molecular weight of 1.001 or more. Pseudo-equilibration treatment Equilibration treatment conditions: 1000 ppm of nickel and 2000 ppm of vanadium were supported on the fluid catalytic cracking catalyst, and then steaming treatment was carried out at 780° C. for 13 hours.

3. The fluid catalytic cracking catalyst according to claim 1, which satisfies the following formula (3): (1 - (specific surface area of ​​matrix after pseudo-equilibration treatment) / (specific surface area of ​​matrix before pseudo-equilibration treatment)) × 100% ≧ 40% (3) [wherein the formula, the matrix specific surface area after pseudo-equilibration treatment is the matrix specific surface area determined by t-plot analysis of the nitrogen adsorption isotherm measured for the fluid catalytic cracking catalyst after pseudo-equilibration treatment under the following conditions: The matrix specific surface area before pseudo-equilibration treatment is a matrix specific surface area determined by t-plot analysis of the nitrogen adsorption isotherm measured for the fluid catalytic cracking catalyst before the pseudo-equilibration treatment. Pseudo-equilibration treatment conditions: 1000 ppm of nickel and 2000 ppm of vanadium were supported on the fluid catalytic cracking catalyst, and then the catalyst was subjected to steaming treatment at 780°C for 13 hours.

4. The fluid catalytic cracking catalyst according to claim 1, which satisfies the following formula (4): (matrix specific surface area after pseudo-equilibration treatment) / pore volume≦120 m 2 / ml … (4) [wherein the formula, the matrix specific surface area after pseudo-equilibration treatment is the matrix specific surface area determined by t-plot analysis of the nitrogen adsorption isotherm measured for the fluid catalytic cracking catalyst after pseudo-equilibration treatment under the following conditions: The pore volume is the volume of pores having a pore diameter of 4.0 to 10,000 nm measured by mercury porosimetry for the fluid catalytic cracking catalyst after pseudo-equilibration treatment under the following conditions. Pseudo-equilibration treatment conditions: 1000 ppm of nickel and 2000 ppm of vanadium were supported on the fluid catalytic cracking catalyst, and then the catalyst was subjected to steaming treatment at 780°C for 13 hours.

5. 2. The fluid catalytic cracking catalyst of claim 1, wherein the boehmite forms a house-of-cards structure.

6. 2. The fluid catalytic cracking catalyst according to claim 1, wherein the boehmite is a boehmite crystal aggregate having the following properties (i) to (iv): (i) The boehmite crystals have a crystallite diameter of 10 to 70 nm calculated from the peak of the (020) plane in X-ray diffraction measurement. (ii) the specific surface area of ​​the aggregates, as measured by a nitrogen adsorption method, is 40 to 150 m 2 / g. (iii) the volume-based d in the particle size distribution of the aggregate measured by a laser diffraction / scattering method 50 The median diameter is 2.0 to 10 μm. (iv) The CBD (Compact Bulk Density) of the aggregate is 0.20 to 0.50 g / ml.

7. The Al of the boehmite 2 O 3 The fluid catalytic cracking catalyst according to claim 1, wherein the converted content is 5 to 50 mass %.

8. 2. The fluid catalytic cracking catalyst according to claim 1, wherein the faujasite-type zeolite is an ultra-stable Y-type zeolite.

9. 2. The fluid catalytic cracking catalyst according to claim 1, wherein the content of the faujasite-type zeolite is 20 to 40 mass %.

10. Rare earth metals (RE) are converted into oxides (RE 2 O 3 2. The fluid catalytic cracking catalyst according to claim 1, wherein the content is 0.5 to 3.5 mass% in terms of carbon monoxide.

11. 2. The fluid catalytic cracking catalyst according to claim 1, wherein the content of the clay minerals is 15 to 50 mass %.

12. Specific surface area measured by nitrogen adsorption method is 200 to 350 m 2 2. The fluid catalytic cracking catalyst of claim 1, wherein the catalyst has a molecular weight of 1.001 or more.

13. a step (α) of preparing a boehmite crystal aggregate having the following properties (i) to (iv): A step (β) of preparing a catalyst raw material slurry containing faujasite-type zeolite, the boehmite crystal aggregates, a binder-forming component, and clay minerals; and a step (γ) of spray-drying the catalyst raw material slurry to obtain particles; A method for producing a fluid catalytic cracking catalyst comprising: (i) The boehmite crystals have a crystallite diameter of 10 to 70 nm calculated from the peak of the (020) plane in X-ray diffraction measurement. (ii) the specific surface area of ​​the aggregates, as measured by a nitrogen adsorption method, is 40 to 150 m 2 / g. (iii) the volume-based d in the particle size distribution of the aggregate measured by a laser diffraction / scattering method 50 The median diameter is 2.0 to 10 μm. (iv) The CBD (Compact Bulk Density) of the aggregate is 0.20 to 0.50 g / ml.

14. The step (α) is Volume-based d in particle size distribution measured by laser diffraction / scattering method 50 Gibbsite having a median diameter of 0.5 μm or more and less than 70 μm is used as Al 2 O 3 Converted to 75 to 95 parts by mass, The crystallite diameter calculated from the peak of the (020) plane in X-ray diffraction measurement is 2 to 6 nm, and the volume-based d 50 The powder of pseudo-boehmite having a median diameter of 5 to 100 μm and not subjected to peptization treatment is mixed with Al 2 O 3 5 to 25 parts by mass (however, the Al content of gibbsite and pseudo-boehmite is 2 O 3 The total amount converted is 100 parts by mass.) A first step of preparing a mixed solution (1) by mixing water so that the pH does not become 7.0 or less; a second step of adding an inorganic basic compound to the mixed solution (1) to prepare a mixed solution (2) having a pH of 9 to 12; a third step of hydrothermally treating the mixed solution (2) at 150 to 190°C for 1 to 24 hours while heating the mixed solution (2) at a rate of 15 to 60°C / hour and stirring the mixture; producing a slurry of boehmite crystal aggregates by a method comprising:

14. The method for producing the fluid catalytic cracking catalyst of claim 13, comprising:

15. 14. The method for producing a fluid catalytic cracking catalyst according to claim 13, wherein in the step (β), the catalyst raw material slurry has a solids concentration of 20 to 40 mass%, a temperature of 20 to 80°C, and a viscosity of 100 to 10,000 mPa s.

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