Fluid catalytic cracking catalyst and method for producing the same

Abstract

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

Description

[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 fluid catalytic cracking of hydrocarbon oils (hereinafter also referred to as "FCC 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 method for producing an FCC catalyst that has a high gasoline yield, a low coke yield, and high attrition resistance, and involves spray-drying a slurry obtained by mixing a zeolite (ultra-stable Y-type zeolite, rare earth-exchanged ultra-stable Y-type zeolite, etc.), a binder (basic aluminum chloride), and an inorganic oxide matrix (kaolin, etc.), and adjusting the pH. It also describes the production of an FCC catalyst by washing the spherical particles obtained by spray-drying with pure water, then with water containing ammonium sulfate, and drying the resulting mixture.

[0004] In the FCC catalyst composition described in Patent Document 2, the amount of light olefins (propylene, etc.) produced is improved by incorporating yttrium into Y-type zeolite. Patent Documents 3 and 4 describe that the attrition resistance of an FCC catalyst can be improved by using a specific colloidal silica as a raw material for the FCC catalyst.

[0005] Patent Document 5 describes a method for producing a fluid catalytic cracking catalyst, which includes the steps of preparing a raw material slurry by mixing a predetermined rare earth metal-containing ultra-stable Y-type zeolite, a silica-based matrix-forming component, water, and optionally clay minerals and optionally additives; spray-drying the raw material slurry to obtain particles; and contacting the particles with water containing an ammonium salt. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-657 [Patent Document 2] Special Publication No. 2013-522025 [Patent Document 3] Special Publication No. 2019-528163 [Patent Document 4] Special Publication No. 2021-511200 [Patent Document 5] Japanese Patent Publication No. 2021-79378 Summary of the Invention [Problem to be solved by the invention]

[0007] However, conventional FCC catalysts have room for further improvement in terms of improving the propylene yield and suppressing the formation of naphthenes in fluid catalytic cracking. Therefore, an object of the present invention is to provide an FCC catalyst that can improve the propylene yield and suppress the formation of naphthenes in fluid catalytic cracking, and a method for producing the same. [Means for solving the problem]

[0008] The present invention relates to, for example, the following [1] to [3]. [1] The binder comprises 10 to 30 mass % of a binder, 10 to 40 mass % of a zeolite ion-exchanged with a rare earth metal, 10 to 60 mass % of a clay mineral, and 5 to 30 mass % of an active matrix; The content of rare earth metals is 0.5 to 1.2 mass% in terms of rare earth metal oxide (RE2O3), the binder is a silica-based binder; The zeolite is an FAU-type zeolite having a lattice constant in the range of 2.438 to 2.460 nm, The active matrix comprises alumina-silica Fluid catalytic cracking catalyst.

[0009] [2] (a) preparing a raw material slurry containing binder-forming components, zeolite, clay minerals, and active matrix-forming components; (b) spray-drying the raw material slurry to obtain particles; (c) contacting the particles with an aqueous solution containing a rare earth metal to ion-exchange the zeolite with the rare earth metal; Including, the binder-forming component is a silica-based binder-forming component, The zeolite is an FAU-type zeolite having a lattice constant in the range of 2.438 to 2.460 nm, The active matrix comprises alumina-silica A method for producing a fluid catalytic cracking catalyst.

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

[0011] According to the present invention, when a catalytic cracking reaction is carried out using a fluid catalytic cracking catalyst composition in which a ZSM-5 additive is added to a fluid catalytic cracking catalyst, the propylene yield is improved and the production of naphthenes due to cyclization of the product can be suppressed. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will now be described in further detail. [Fluid catalytic cracking catalyst] The fluid catalytic cracking catalyst (FCC catalyst) of the present invention comprises a binder, a rare earth metal ion-exchanged zeolite, clay minerals, and an active matrix.

[0013] <Binder> As the binding agent (hereinafter also referred to as "binder"), a silica-based binding agent is used. Silica-based binders are formed from silica, silica gel (including silica hydrogel), silica sol (including silica hydrosol), water glass (sodium silicate), silicic acid liquid, etc. Examples of silica sol include colloidal silica of sodium type, lithium type, acid type, etc. Of these, silica sol is preferred. When fluid catalytic cracking is performed using the FCC catalyst, the formation of coke is suppressed because the binder is a silica-based binder.

[0014] The FCC catalyst of the present invention contains the binder in an amount of, for example, 10 to 30 mass %, preferably 12 to 26 mass %, and more preferably 14 to 24 mass %. Although each component constituting the FCC catalyst of the present invention and its raw materials may contain water, the content of each component or the amount of each raw material used in the present invention is expressed as an amount excluding water (sometimes referred to as "solids concentration").

[0015] <Zeolite ion-exchanged with rare earth metals> The zeolite in the zeolite ion-exchanged with rare earth metals, i.e., the zeolite before ion-exchange, will be described in detail later. Examples of the rare earth metal include cerium (Ce), lanthanum (La), praseodymium (Pr), and neodymium (Nd), and these may be used alone or in combination of two or more.

[0016] The FCC catalyst of the present invention contains the rare earth metal ion-exchanged zeolite in an amount of, for example, 10 to 40 mass%, preferably 12 to 38 mass%, and more preferably 14 to 36 mass%. When the content is equal to or greater than the lower limit, the resulting FCC catalyst exhibits sufficient activity. On the other hand, when the content is equal to or less than the upper limit, the resulting FCC catalyst can be prevented from over-cracking and reduced selectivity due to excessive activity.

[0017] <Clay minerals> The clay minerals that act as a bulking agent are clay and / or clay minerals, examples of which include kaolin, bentonite, kaolinite, halloysite, montmorillonite, etc., with kaolin being preferred among these.

[0018] The FCC catalyst of the present invention contains the clay minerals in an amount of, for example, 10 to 60 mass%, preferably 14 to 56 mass%, and more preferably 18 to 52 mass%. When the content is equal to or greater than the lower limit, the FCC catalyst maintains its pore structure, catalyst shape, abrasion resistance, and fluidity. On the other hand, when the content is equal to or less than the upper limit, the proportion of the zeolite component in the FCC catalyst is high, and the activity of the FCC catalyst is therefore good.

[0019] <Activity Matrix> The active matrix includes alumina-silica and optionally includes an active matrix other than alumina-silica. Examples of active matrices other than alumina-silica include those containing substances having solid acidity, such as activated alumina (boehmite, gibbsite, etc.), silica-magnesia, alumina-magnesia, and silica-magnesia-alumina. A solid acid is one that exhibits solid acidity in the temperature range in which the catalyst is used, and the solid acidity can be confirmed, for example, by temperature-programmed desorption using ammonia or in situ FTIR (Fourier transform infrared absorption spectroscopy) using ammonia or pyridine.

[0020] Since the active matrix contains alumina-silica, the hydrothermal resistance of the matrix is ​​improved, and the specific surface area of ​​the matrix can be kept high. The active matrix preferably contains 10% by mass or more of alumina-silica, more preferably 15 to 65% by mass, and even more preferably 20 to 60% by mass. The alumina-silica preferably contains 3 to 30% by mass of silica.

[0021] Active matrices that also function as metal scavengers include alumina particles, phosphorus-alumina particles, crystalline calcium aluminate, sepiolite, barium titanate, calcium stannate, strontium titanate, manganese oxide, magnesia, and magnesia-alumina.

[0022] As a raw material for the metal capture agent, a precursor substance such as boehmite, which becomes alumina or the like when fired in an oxidizing atmosphere, can also be used. The FCC catalyst of the present invention contains the active matrix in an amount of, for example, 5 to 30 mass %, preferably 8 to 29 mass %, and more preferably 10 to 28 mass %.

[0023] <Optional ingredients> The FCC catalyst of the present invention may optionally contain additives in addition to the binder, rare earth metal ion-exchanged zeolite, clay minerals, and active matrix. Examples of the additives include CO combustion promoting components (Pt, Pd), desulfurizing and deoxidizing components (CeO2, MgO), and the like.

[0024] (Rare earth metal content) The FCC catalyst of the present invention contains a rare earth metal. The content of the rare earth metal in the FCC catalyst of the present invention is 0.5 to 1.2 mass%, more preferably 0.6 to 1.1 mass%, calculated as rare earth oxide (RE2O3). When the content of the rare earth metal is within the above range, the FCC catalyst of the present invention has excellent hydrothermal resistance and an excellent propylene yield.

[0025] [Method of manufacturing fluid catalytic cracking catalyst] The method for producing a fluid catalytic cracking catalyst (FCC catalyst) according to the present invention includes the steps of: (a) preparing a raw material slurry containing binder-forming components, zeolite, clay minerals, and active matrix-forming components; (b) spray-drying the raw material slurry to obtain particles; (c) contacting the particles with an aqueous solution containing a rare earth metal to ion-exchange the zeolite with the rare earth metal; The present invention is characterized in that it includes:

[0026] 《Process (a)》 In the step (a), a raw material slurry containing binder-forming components, zeolite, clay minerals, and active matrix-forming components is prepared.

[0027] In the step (a), for example, a raw material slurry is prepared by mixing the binder-forming components with the zeolite, clay minerals, active matrix-forming components, and optional additives. Each component may be added in powder form or in a slurry form. The order in which the components are added is not important.

[0028] (Binder-forming component) The binder-forming component is a component for forming a binder in the fluid catalytic cracking catalyst. A silica-based binder-forming component is used as the binder-forming component. Examples of silica-based binder-forming components include silica, silica gel (including silica hydrogel), silica sol (including silica hydrosol), water glass (sodium silicate), and silicic acid liquid. Colloidal silica such as sodium type, lithium type, and acid type can also be used as the silica sol. Of these, silica sol is preferred. Commercially available products may be used, or the silica sol may be prepared by adding acid to water glass.

[0029] (Zeolite) The zeolite used is an FAU type zeolite. Examples of the FAU type zeolite include ultra-stable Y type zeolite (USY) and rare earth metal-exchanged ultra-stable Y type zeolite (hereinafter also referred to as "REUSY"), which is obtained by introducing a rare earth metal into USY by ion exchange or the like.

[0030] The lattice constant of the zeolite, measured by the method employed in the examples described below, is preferably in the range of 2.438 to 2.460 nm, more preferably in the range of 2.440 to 2.458 nm. The lattice constant of the zeolite was determined by X-ray diffraction using anatase-type TiO2 as a standard material. It is determined by the spacing between the (553) and (642) diffraction planes of the light.

[0031] In a preferred embodiment of step (a), after adding the clay minerals and active matrix-forming components to the binder-forming components, the zeolite is added in the form of a slurry adjusted to a pH of 2.8 to 4.5. This prevents the pH of the zeolite-containing slurry from fluctuating due to the addition, thereby preventing zeolite aggregation. The slurry can be prepared, for example, by adding the zeolite and an acid to water. Examples of the acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and organic acids (e.g., citric acid, formic acid, acetic acid, etc.).

[0032] (clay minerals) Specific examples and preferred embodiments of the clay minerals are as described above.

[0033] (active matrix forming component) Examples of the active matrix-forming component include, in addition to the specific examples of the active matrix mentioned above, components that form an active matrix upon heating, such as aluminum hydroxide (gibbsite) and alumina hydrate (boehmite).

[0034] The raw material slurry may be prepared by mixing these components with optional additives and optional water. The raw slurry contains the binder-forming components, converted into the amount of SiO2, in an amount of, for example, 10 to 30 mass %, preferably 12 to 26 mass %, and more preferably 14 to 24 mass % (where the amount of solids in the raw slurry (components other than the dispersion medium in the raw slurry; the same applies hereinafter) is taken as 100 mass %).

[0035] The raw slurry contains the zeolite in an amount of, for example, 10 to 40 mass %, preferably 12 to 38 mass %, and more preferably 14 to 36 mass % (where the solid content of the raw slurry is taken as 100 mass %).

[0036] The raw slurry contains the clay minerals in an amount of, for example, 10 to 60 mass %, preferably 14 to 56 mass %, and more preferably 18 to 52 mass % (where the solid content of the raw slurry is taken as 100 mass %).

[0037] The raw slurry contains the active matrix-forming component in an amount of, for example, 5 to 30 mass %, preferably 8 to 29 mass %, and more preferably 10 to 28 mass % (where the solid content of the raw slurry is taken as 100 mass %).

[0038] The raw material slurry contains water as a dispersion medium. The raw material slurry may contain a small amount of components other than water as a dispersion medium, such as methanol, ethanol, acetone, etc. The solid content concentration of the raw slurry is, for example, 10 to 50 mass %, and preferably 20 to 40 mass %, from the viewpoint of easily carrying out spray drying of the raw slurry.

[0039] 《Process (b)》 In the step (b), the raw material slurry is spray-dried to obtain particles (hereinafter also referred to as "spray-dried particles").

[0040] The spray-drying conditions may be appropriately changed depending on the solids concentration, viscosity, etc. of the slurry, and are not particularly limited as long as the average particle size of the resulting catalyst falls within the range of 50 to 90 μm, which is the range used for general FCC catalysts. For example, the raw slurry is filled into a slurry storage tank of a spray dryer, and the raw slurry is sprayed into a drying chamber through which an airflow (e.g., an airflow) adjusted to, for example, a temperature in the range of 120 to 450°C flows, thereby obtaining particles (spray-dried particles). The temperature of the airflow decreases as the raw slurry is spray-dried, but the temperature at the outlet of the drying chamber is maintained in the range of, for example, 50 to 300°C using a heater or the like.

[0041] 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, and the like of the raw material slurry. The spray-dried particles may also be washed (eg, with water) and dried.

[0042] 《Process (c)》 In the step (c), the spray-dried particles are contacted with an aqueous solution containing a rare earth metal to ion-exchange the zeolite in the spray-dried particles with the rare earth metal, thereby obtaining an FCC catalyst.

[0043] In step (c), the spray-dried particles are preferably suspended in water to prepare a suspension, and the suspension is then contacted with an aqueous solution containing a rare earth metal. 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 adhering to the spray-dried particles.

[0044] The aqueous solution containing the rare earth metal can be prepared, for example, by dissolving a salt of the rare earth metal (for example, LaCl3) in water. Step (c) is carried out so that the ion exchange rate relative to the zeolite is 20% by mass or less. Specifically, the ion exchange capacity of the zeolite is calculated in advance from the amount, lattice constant, and chemical analysis of the zeolite, and the ion exchange rate is adjusted by the amount, concentration, etc. of the aqueous solution containing a rare earth metal that is contacted during ion exchange.

[0045] The ion exchange rate is preferably 5 to 20% by mass, and more preferably 6 to 18% by mass. The ion exchange rate here means the occupancy rate of ion exchange sites, taking into consideration the valence of the rare earth ions exchanged, relative to the number of aluminum atoms in the zeolite framework.

[0046] When the zeolite is a USY zeolite, the number of aluminum atoms in the framework can be calculated by Breck's formula (below), and the number of atoms contained in the unit cell is calculated as 192. N Al =115.2×(a0-24.191) where N Al is the number of aluminum atoms in the framework, and a0 is the lattice constant (Å). The ion exchange rate is calculated as follows.

[0047] The amount of aluminum atoms outside the framework is calculated from the chemical composition of the USY zeolite obtained by X-ray fluorescence analysis, and the amount of ion exchange sites contained in the USY zeolite is calculated. From the amount of rare earth metal in the chemical composition of the USY zeolite into which rare earth metals have been introduced, obtained by X-ray fluorescence analysis after preparing the FCC catalyst, the amount of ion exchange sites is calculated by taking into account the valence at the time of ion exchange. For example, when ion exchange is performed using an aqueous solution of LaCl3, the amount of La 3+ The ion exchange rate is calculated assuming that 3 aluminum atoms in the zeolite framework are occupied by 1 La atom, and that all of the rare earth metals introduced into the FCC catalyst in step (c) are present at the ion exchange sites.

[0048] Not only when the zeolite does not contain rare earth metals, but also when the REUSY is used as the zeolite and some rare earth metal ions are removed (substituted with protons) from the REUSY during preparation of the raw material slurry in step (a) or during washing of the spray-dried particles obtained in step (b), a fluid catalytic cracking catalyst containing a desired amount of rare earth metals can be produced by performing step (c).

[0049] The above-mentioned fluid catalytic cracking catalyst according to the present invention can be produced by the method for producing a fluid catalytic cracking catalyst according to the present invention, which includes the above steps (a) to (c).

[0050] [Fluid catalytic cracking catalyst composition] The fluid catalytic cracking catalyst composition of the present invention comprises the FCC catalyst of the present invention and a co-catalyst comprising ZSM-5. Commercially available ZSM-5-containing auxiliary catalysts (additives) include, for example, additives (OCTUP-α, OCTUP-R) manufactured by JGC Catalysts and Chemicals Co., Ltd., and the ZSM-5 additives or ZSM-5-containing additives described in paragraph

[0038] of JP-T-2013-522025. The content of the auxiliary catalyst in the catalyst composition is preferably 1 to 35% by mass, more preferably 5 to 25% by mass, based on 100% by mass of the FCC catalyst according to the present invention.

[0051] The specific surface area of ​​the FCC catalyst composition according to the present invention, as measured by the method employed in the examples described below, is preferably 200 to 400 m 2 / g, more preferably 250 to 350 m 2 / g.

[0052] When the FCC catalyst composition of the present invention is used in fluid catalytic cracking, it is possible to improve propylene selectivity, suppress hydrogen transfer reactions in the FCC catalyst, and inhibit the production of i-paraffins and naphthenes. This is presumably because, compared to catalysts in which the zeolite lattice constant and rare earth metal content are greater than the ranges specified in the present invention, the distance between acid sites in the catalyst increases and the number of acid sites per unit surface area decreases, thereby inhibiting bimolecular reactions and hydrogen abstraction at matrix acid sites (Lewis acid sites). [Example]

[0053] The present invention will now be described in more detail with reference to examples. [Methods for measuring or evaluating catalysts, etc.] (composition) The content of each element contained in the zeolite and the catalysts obtained in the examples was measured using a fluorescent X-ray analyzer (RIX 3000, manufactured by Rigaku Corporation).

[0054] (Lattice constant of zeolite) The lattice constant of the zeolite was determined by the spacing between the diffraction planes (553) and (642) of the zeolite by X-ray diffraction under the following conditions using anatase TiO2 as a standard substance.

[0055] <<Measurement conditions>> The catalysts obtained in the examples and the like were crushed and molded, and then set in an X-ray diffractometer (X-RAY DIFFRACT METER (RINT 1400) manufactured by Rigaku Corporation) and measured under the following conditions: tube voltage 30.0 kV, tube current 130.0 mA, anticathode Cu, measurement range: start angle to end angle (2θ) 10,000° to 70,000°, scan speed 2,000° / min, divergence slit 1 deg, scattering slit 1 deg, receiving slit 0.15 mm.

[0056] (specific surface area) The specific surface area of ​​the catalysts in the examples was measured using a BELSORP-mini Ver. 2.5.6 manufactured by Microtrac-Bell Corporation. Specifically, the catalyst was heat-treated at 500°C for 1 hour while being evacuated to a vacuum, and nitrogen gas was adsorbed onto the catalyst, and the specific surface area (m 2 / g) was calculated.

[0057] [Manufacturing Example 1] Preparation of alumina-silica slurry 1 6280 g of an aluminum sulfate aqueous solution (Al2O3 concentration: 2.5 mass%) was added to 6530 g of a sodium aluminate aqueous solution (Al2O3 concentration: 5 mass%) and stirred at 65°C for 1 hour to obtain an alumina slurry. The alumina slurry was then washed with warm water to adjust the Na2O content of the washed alumina cake to 2% or less by dry mass and the SO4 content to 1% or less by dry mass. Pure water was then added to the washed alumina cake to prepare a washed alumina slurry with an Al2O3 concentration of 12.5%, and a 48 mass% aqueous sodium hydroxide solution was added to adjust the pH to 11.5. The mixture was then aged at 95°C for 20 hours with stirring to obtain crystalline boehmite (specific surface area: 178 m 2 / g) slurry (hereinafter referred to as "slurry A").

[0058] Diluted water glass with an SiO2 concentration of 5% by mass was subjected to ion exchange using a cation exchange resin to prepare a desalted silicic acid solution with a pH of 2.67. 232.5 g of the 5% by mass desalted silicic acid solution was added with a 15% by mass aqueous ammonia solution to adjust the pH to 10.8. 3100 g of Slurry A (Al2O3 concentration: 9% by mass) was added to the desalted silicic acid solution with a pH adjusted to 10.8, and the mixture was stirred at room temperature for 30 minutes. The mixture was then aged at 95°C for 8 hours while stirring, and the amount of water was adjusted to obtain Alumina-Silica Slurry-1 (solid concentration: 12% by mass), which contains 4% by mass of silica in the alumina-silica.

[0059] [Manufacturing Example 2] Preparation of alumina-silica slurry 2 Alumina-silica slurry-2 (solid content: 10% by mass) containing 18% by mass of silica in alumina-silica was obtained in the same manner as in Production Example 1, except that the amount of desalted silicic acid liquid was changed to 1225 g.

[0060] [Manufacturing Example 3] ~Preparation of alumina slurry~ An alumina (boehmite) slurry (solid content concentration: 10% by mass) was obtained in the same manner as in the production method for slurry A in Production Example 1, except that the washed alumina slurry was prepared so that the solid content concentration of the washed alumina cake was 10% by weight.

[0061] [Manufacturing Example 4] ~Preparation of Ultra-Stabilized Y-Type Zeolite Slurry-1~ Example 1 of JP-A-9-173853 was carried out, except that the calcination temperature in the second calcination step of the zeolite was changed from 670°C to 810°C, to obtain ultra-stable Y-type zeolite-1 (lattice constant: 2.443 nm, SiO2 / Al2O3 ratio: 7.1, ion exchange capacity: 2.251 mmol / g). Ultra-stable Y-type zeolite-1 and sulfuric acid were added to water to obtain ultra-stable Y-type zeolite slurry-1 (solid content: 33% by mass) with a pH of 3.9.

[0062] [Manufacturing Example 5] ~Preparation of Ultra-Stabilized Y-Type Zeolite Slurry-2~ Ultrastable Y-type zeolite-2 (lattice constant: 2.458 nm, SiO / AlO ratio: 5.4, ion exchange capacity: 3.731 mmol / g) was obtained according to Example 1 of JP-A-9-173853. Ultrastable Y-type zeolite-2 and sulfuric acid were added to water to obtain ultrastable Y-type zeolite slurry-2 (solid concentration: 33% by mass) with a pH of 3.9.

[0063] [Example 1] ~FCC catalyst-1 preparation~ 2941 g of water glass (SiO2 concentration: 17 mass%) and 1059 g of sulfuric acid (sulfuric acid concentration in sulfuric acid aqueous solution: 25 mass%) were simultaneously and continuously added to a container to prepare 4000 g of silica binder solution with an SiO2 concentration of 12.5 mass%. To this silica binder solution, 893 g of kaolin (solid content: 84% by mass), 195 g of aluminum hydroxide (crystal form: gibbsite, solid content: 64% by mass) as active matrix-forming components, 152 g of crystalline boehmite (crystal form: boehmite, solid content: 82% by mass), and 2083 g of alumina-silica slurry-1 (solid content: 12% by mass) obtained in Production Example 1 were added, and then 2273 g of ultra-stabilized Y-type zeolite slurry-1 (solid content: 33% by mass) obtained in Production Example 4 was added and stirred well.The resulting mixed slurry was then spray-dried in a hot air stream using a spray dryer under conditions of an inlet temperature of 250°C and an outlet temperature of 150°C, to obtain spherical particles.

[0064] The resulting spherical particles were suspended in 10 times the amount of hot water (60°C), dehydrated, filtered, and then poured over 10 times the amount of hot water (60°C), after which they were suspended again and contacted with an aqueous lanthanum chloride solution to carry out ion exchange so that the lanthanum content in the FCC catalyst was 1.0 mass% in terms of La2O3. The ion exchange rate relative to the zeolite was 13.5 mass%. The solids were then filtered and dried in a dryer at 135°C to obtain FCC catalyst-1.

[0065] [Example 2] ~FCC catalyst-2 preparation~ 2941 g of water glass (SiO2 concentration: 17 mass%) and 1059 g of sulfuric acid (sulfuric acid concentration: 25 mass%) were simultaneously and continuously added to a container to prepare 4000 g of a silica binder solution with an SiO2 concentration of 12.5 mass%. To this silica binder solution, 1042 g of kaolin (solid content: 84% by mass), 156 g of aluminum hydroxide (crystal form: gypsum, solid content: 64% by mass) as an active matrix, 122 g of crystalline boehmite (crystal form: boehmite, solid content: 82% by mass), 500 g of alumina-silica slurry-2 (solid content: 10% by mass) obtained in Production Example 2, and 2652 g of ultra-stabilized Y-type zeolite slurry-2 (solid content: 33% by mass) obtained in Production Example 5 were added and stirred thoroughly. The resulting mixed slurry was then spray-dried in a hot air stream using a spray dryer at an inlet temperature of 250°C and an outlet temperature of 150°C to obtain spherical particles.

[0066] The resulting spherical particles were suspended in 10 times the amount of hot water (60°C), dehydrated, filtered, and then poured over 10 times the amount of hot water (60°C), after which they were suspended again and contacted with an aqueous lanthanum chloride solution to carry out ion exchange so that the lanthanum content in the FCC catalyst was 0.9 mass% in terms of La2O3. The ion exchange rate relative to the zeolite was 6.3 mass%. The solids were then filtered and dried in a dryer at 135°C to obtain FCC catalyst-2.

[0067] [Example 3] ~FCC catalyst-3 preparation~ 2941 g of water glass (SiO2 concentration: 17 mass%) and 1059 g of sulfuric acid (sulfuric acid concentration: 25 mass%) were added simultaneously and continuously to prepare 4000 g of a silica binder solution with an SiO2 concentration of 12.5 mass%. To this silica binder solution, 1101 g of kaolin (solid content: 84% by mass), 313 g of aluminum hydroxide (crystal form: gibbsite, solid content: 64% by mass) as an active matrix, 152 g of crystalline boehmite (crystal form: boehmite, solid content: 82% by mass), 3750 g of alumina-silica slurry-2 (solid content: 10% by mass) obtained in Production Example 2, and 1136 g of ultra-stabilized Y-type zeolite slurry-2 (solid content: 33% by mass) obtained in Production Example 4 were added and stirred thoroughly. After that, this mixed slurry was sprayed into a hot air stream using a spray dryer at an inlet temperature of 250°C and an outlet temperature of 150°C and dried to obtain spherical particles.

[0068] The resulting spherical particles were suspended in 10 times the amount of hot water (60°C), dehydrated, filtered, and then poured over 10 times the amount of hot water (60°C), after which they were suspended again and contacted with an aqueous lanthanum chloride solution to carry out ion exchange so that the lanthanum content in the FCC catalyst was 1.0 mass% in terms of La2O3. The ion exchange rate relative to the zeolite was 16.5 mass%. The solids were then filtered and dried in a dryer at 135°C to obtain FCC catalyst-3.

[0069] [Example 4] ~FCC catalyst-4 preparation~ The same procedure as in Example 1 was carried out, except that ion exchange was carried out so that the lanthanum content in the FCC catalyst was 0.6 mass% in terms of La2O3, to obtain FCC catalyst-4. The ion exchange rate with respect to the zeolite was 8.2 mass%.

[0070] [Comparative Example 1] ~FCC catalyst-R1 preparation~ The same operation as in Example 1 was carried out, except that 1596 g of a basic aluminum chloride aqueous solution (solid content: 23.5 mass%) and 1042 g of kaolin (solid content: 84 mass%) were used instead of the silica binder solution, to obtain FCC catalyst-R1.

[0071] Comparative Example 2 ~FCC catalyst-R2 preparation~ FCC catalyst-R2 was obtained by carrying out the same operation as in Example 1, except that ion exchange was carried out so that the lanthanum content in the FCC catalyst was 2.0 mass% in terms of La2O3. The ion exchange rate with respect to the zeolite was 27.5 mass%.

[0072] Comparative Example 3 ~FCC catalyst-R3 preparation~ The same operation as in Example 3 was carried out except that 3750 g of the alumina (boehmite) slurry (solid content: 10 mass%) obtained in Preparation Example 3 was used instead of the alumina-silica slurry-2, to obtain FCC catalyst-R3. The composition and physical properties of FCC catalysts are summarized in Tables 1-1 and 1-2.

[0073] [Table 1-1]

[0074] [Table 1-2]

[0075] In Table 1-2, fresh catalyst refers to the catalyst obtained in the examples or comparative examples, and steam-treated catalyst refers to the catalyst obtained by steam-treating the fresh catalyst under conditions of 780°C and 100% steam for 13 hours. The retention rate (%) is the ratio of the specific surface area of ​​the steam-treated catalyst to the specific surface area of ​​the fresh catalyst expressed as a percentage, and a high retention rate means high hydrothermal resistance.

[0076] <Method of producing a fluid catalytic cracking catalyst composition> The FCC catalyst obtained in the Examples or Comparative Examples was mixed with an additive (OCTUP-α) manufactured by JGC Catalysts and Chemicals Co., Ltd., which contained ZSM-5, to obtain a fluid catalytic cracking catalyst composition.

[0077] The obtained fluid catalytic cracking catalyst compositions were subjected to performance evaluation tests using the Advanced Cracking Evaluation-Micro Activity Test (ACE-MAT) under the same crude oil and the same reaction conditions. The results of the performance evaluation tests for each catalyst composition are shown in Table 2. However, prior to these performance evaluation tests, the catalyst compositions were subjected to steam treatment at 780°C for 13 hours in order to simulate the condition of hydrothermal degradation in a catalyst regeneration tower.

[0078] (Catalytic activity) The reaction conditions in the catalyst performance evaluation test are as follows: Feedstock: Desulfurized vacuum gas oil (DSVGO) 100% by mass Reaction temperature: 580℃ Catalyst mass space velocity (WHSV): 8h -1 Catalyst / oil ratio (hereinafter referred to as "C / O"): 5.0 (mass% / mass%) 1) Conversion rate: 100-(LCO;HCO+CLO) (mass%) 2) Yield: Proportion of each product (mass%) when C / O = 5.0 3) Boiling point range of gasoline: 30~216℃ (Gasoline) 4) Boiling point range of LCO: 216-343°C (LCO: Light Cycle Oil) 5) Boiling point range of HCO + CLO: 343℃+ (HCO: Heavy Cycle Oil, CLO: Clarified Oil) 6) LPG (liquid petroleum gas) 7) Dry Gas: Methane, Ethane and Ethylene 8) Propylene: Found in LPG. The reaction results are summarized in Table 2.

[0079] [Table 2]

Claims

1. A catalyst comprising 10 to 30 mass% of a silica-based binder, 10 to 40 mass% of a rare earth metal ion-exchanged FAU-type zeolite, 10 to 60 mass% of clay minerals, and 5 to 30 mass% of an active matrix containing alumina-silica, The rare earth metal is a rare earth metal oxide (RE 2 O 3 ) is contained in an amount of 0.5 to 1.2 mass % in terms of The lattice constant of the FAU zeolite is 2.438 to 2.460 nm, The alumina-silica fluid catalytic cracking catalyst contains 3 to 30 mass % of silica.

2. A method for producing a raw material slurry comprising: (a) a silica-based binder-forming component; an FAU-type zeolite having a lattice constant of 2.438 to 2.460 nm; clay minerals; and an active matrix-forming component containing alumina-silica; (b) spray-drying the raw material slurry to obtain particles; and (c) contacting the particles with an aqueous solution containing a rare earth metal to ion-exchange the zeolite with the rare earth metal; The method for producing a fluid catalytic cracking catalyst, wherein the alumina-silica contains 3 to 30 mass % of silica.

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

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