Silica-alumina powder, method for producing silica-alumina powder, fluid catalytic cracking catalyst, and method for producing the same

Abstract

To provide silica-alumina powder used as a fluidized catalytic cracking catalyst to enhance decomposition performance of bottom fractions and coke, a method for producing the same, and a fluidized catalytic cracking catalyst containing the silica-alumina powder.SOLUTION: A non-zeolitic silica-alumina powder has the following characteristics: the silica (SiO2) content is in the range of 5 to 30 mass%; the pore volume measured by using the nitrogen adsorption isotherm is in the range of 0.70 to 1.20 ml / g; the silica-alumina has an acidity that is measured by IR monitoring of the thermal desorption of pyridine, and has Bronsted acid with Lewis acid content being in the range of 200 to 400 μmol / g; and the BET specific surface area ranges from 350 to 550 m2 / g. A fluidized catalytic cracking catalyst contains the silica-alumina powder.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing silica-alumina powder used in a fluid catalytic cracking catalyst and the obtained silica-alumina powder. More specifically, the present invention relates to a fluid catalytic cracking catalyst having high cracking performance for heavy hydrocarbon oil fractions containing silica-alumina (hereinafter also simply referred to as "bottom") and coke, and a method for producing the same.

Background Art

[0002] A fluid catalytic cracking (FCC) catalyst used in a process for fluid catalytic cracking of a feedstock oil (hydrocarbon oil), for example, atmospheric distillation residue oil, contains zeolite which is a solid acid. Further, a matrix component such as silica-alumina having cracking activity of hydrocarbon oil is added to the fluid catalytic cracking catalyst for the purpose of imparting abrasion resistance when used in a fluidized state.

[0003] Silica-alumina generally means a mixture or composite oxide of silica and alumina. The mixture of silica and alumina means a physically mixed product of silica and alumina without chemical bonding. In this case, the mixture of silica and alumina has Lewis acid derived from alumina. On the other hand, the composite oxide of silica and alumina means a product in which silica and alumina are mixed through chemical bonding. In this case, the composite oxide of silica and alumina has Bronsted acid derived from its crystal structure.

[0004] Silica-alumina is characterized in that the nature of the acid changes depending on whether silica and alumina are chemically bonded. Silica-alumina has been used in various catalytic reactions for a long time by taking advantage of the above characteristics. Further, it is produced by various methods.

[0005] For example, Patent Document 1 discloses a method for producing an alkali aluminosilicate that is partially crystallized by mixing a raw material containing silica and alumina with an alkali metal hydroxide and a solid reagent. It is a method of heating until a solid phase is obtained, performing mixing and crystallization simultaneously, and continuing mixing until redispersion occurs.

[0006] Further, Patent Document 2 discloses a method for producing a silica-alumina hydrogel catalyst. It is a method of reacting sodium silicate and an acidic aluminum salt in a solution to produce a silica-alumina gel.

[0007] Further, Patent Document 3 discloses a method for producing an amorphous aluminosilicate. It is a method of adding an aqueous solution of an alkali metal aluminate to an aqueous solution of an alkali metal silicate salt at a temperature of 15 to 100°C under strong stirring and performing a heat treatment at a temperature of 70 to 100°C.

[0008] Further, Patent Document 4 discloses a method for producing a catalyst in an oligomerization method of an olefin using a silica-alumina catalyst. The method for producing the catalyst includes a step of mixing at least one alumina compound that is partially soluble in an acidic medium with at least one silica compound that is completely soluble in the reaction mixture, or a combination of at least one silica compound and at least one alumina compound that are both completely soluble in the reaction mixture to form a solid precursor of the catalyst, and a step of calcining the solid obtained in the step in moist air for 4 to 7 hours and performing a hydrothermal treatment.

[0009] Further, Patent Document 5 discloses an aluminosilicate having a large cesium ion adsorption capacity and a method for producing the same. It is an aluminosilicate represented by the following formula (I): xNa2O·Al2O3·mSiO2·nH2O···(I) (wherein x is 0.12 ≦ x ≦ 1.3, m is 5.0 ≦ m ≦ 15.0, and n is 5 ≦ n ≦ 15), and the Na2O content is 1.5 to 11.0% by weight, and more than 50% of the aluminum atoms are four-coordinate aluminum atoms.

[0010] In addition, Patent Document 6 discloses a method for producing an alkali metal aluminosilicate composition. In this method, a predetermined amount of sodium sulfate is supplied during the reaction of sodium silicate and aluminum sulfate in an aqueous medium.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Non-Patent Documents

[0012]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0013] Since silica alumina has solid acid, it is used in various catalytic reactions such as fluid catalytic cracking catalysts and hydrocracking catalysts. In particular, in fluid catalytic cracking, a catalyst with higher decomposition of the bottom fraction is required. However, the techniques disclosed in Patent Documents 1 to 6 above do not describe the decomposition performance of the bottom fraction.

[0014] The object of the present invention is to provide a silica-alumina powder used in a fluid catalytic cracking catalyst, which can enhance the cracking performance of bottom fractions and coke, a method for producing the same, a fluid catalytic cracking catalyst containing the silica-alumina powder, and a method for producing the same.

Means for Solving the Problems

[0015] The silica-alumina powder of the present invention is a non-zeolite-based silica-alumina powder and has the following characteristics: · The silica (SiO2) content ranges from 5 to 30% by mass; · The pore volume measured using the nitrogen adsorption isotherm ranges from 0.70 to 1.20 ml / g; · The acidity of the silica-alumina is measured by IR monitoring of the thermal desorption of pyridine Shi and has Bronsted acid, and the amount of Lewis acid ranges from 200 to 400 μmol / g; · The BET specific surface area ranges from 350 to 550 m 2 / g.

[0016] The silica-alumina powder of the present invention preferably further has an ammonia desorption amount as the acid amount calculated from NH3-TPD measurement in the range of 500 to 700 μmol / g, and the ratio of the acid amount at a desorption temperature of 400 to 500 °C is 10% or more based on the total acid amount.

[0017] The method for producing the silica-alumina powder proposed by the present invention is (A) A step of mixing an aqueous solution containing an alumina hydrate and an aqueous solution containing a silica precursor to prepare an aqueous solution A containing the silica-alumina precursor; (B) A step of adjusting the pH of the aqueous solution A containing the silica-alumina precursor obtained in the step (A) to the range of 9.0 to 11.0, and then performing heat treatment in the temperature range of 80 to 100 °C for 0.5 to 12 hours; (C) A step of cooling the aqueous solution heat-treated in the step (B), separating the solid matter, washing it, drying it, or further calcining it to obtain silica-alumina powder. The method includes the above steps.

[0018] The fluid catalytic cracking catalyst according to the present invention is a fluid catalytic cracking catalyst containing any of the above silica-alumina powders.

[0019] In addition, the method for producing a fluid catalytic cracking catalyst according to the present invention is (1) A step of mixing any of the above silica-alumina powders, a binder component, a clay component as an extender, a zeolite component, and an additive to obtain a mixed slurry; (2) A step of spray-drying the mixed slurry obtained in the step (1) to obtain dried particles; (3) A step of washing and drying the dried particles obtained in the step (2) to obtain a fluid catalytic cracking catalyst. It includes these steps.

[0020] The method for producing a fluid catalytic cracking catalyst according to the present invention further includes, instead of the step (3), (4) A step of washing and drying the dried particles obtained in the step (2), and then performing rare earth metal exchange to obtain a fluid catalytic cracking catalyst subjected to rare earth metal exchange. It is preferably included.

Advantages of the Invention

[0021] According to the present invention, a silica-alumina powder that can be used in a fluid catalytic cracking catalyst to enhance the cracking performance of bottom fractions and coke can be obtained. Therefore, the fluid catalytic cracking catalyst containing the silica-alumina powder can be used in the fluid catalytic cracking of hydrocarbon oils, and the cracking performance of bottom fractions and coke is improved, and useful cracking products can be recovered with a high yield.

Embodiments for Carrying Out the Invention

[0022] The inventors mixed alumina hydrate with sodium silicate or a silica sol precursor, such as silicate or silicic acid (or colloidal silica) obtained by adding an acid to silicate, etc., and the resulting silica-alumina powder has the characteristics of a large specific surface area and different acidic properties and acid strength distribution, etc. Furthermore, it has been found that the fluid catalytic cracking catalyst containing the silica-alumina powder of the present invention is excellent in the decomposability of heavy fractions (bottoms), and particularly excellent in coke / bottom selectivity and gasoline selectivity.

[0023] <Silica-alumina powder> The silica-alumina powder of the present invention is non-zeolite-based and has the following characteristics: · The silica (SiO2) content ranges from 5 to 30% by mass; · The pore volume measured using the nitrogen adsorption isotherm ranges from 0.70 to 1.20 ml / g; · The acidity of the silica-alumina is measured by IR monitoring of the thermal desorption of pyridine, has Bronsted acid, and the amount of Lewis acid ranges from 200 to 400 μmol / g; · The BET specific surface area ranges from 350 to 550 m 2 / g.

[0024] In the silica-alumina powder according to the present invention, the ammonia desorption amount as the acid amount calculated from NH3-TPD measurement ranges from 500 to 700 μmol / g, and preferably, the ratio of the acid amount at the desorption temperature of 400 to 500 °C is 10% or more with respect to the total acid amount.

[0025] The silica-alumina powder according to the present invention is a non-zeolite substance. The silica component contained in the powder ranges from 5 to 30% by mass. Preferably, it ranges from 7 to 28% by mass, and more preferably from 10 to 25% by mass. If it is less than 5% by mass, the performance may be insufficient because the specific surface area and the acid amount are low. On the other hand, if it exceeds 30% by mass, the specific surface area and the acid amount decrease, the performance also decreases, the SiO2 content increases, and the bulk density (ABD) and abrasion resistance of the catalyst deteriorate, which is not preferable.

[0026] <Pyridine Adsorption FT-IR Measurement> After molding 30 mg of silica alumina powder into a 20 mm Φ disk, it was placed in an IR cell connected to a vacuum line and subjected to vacuum evacuation treatment at 500 °C for 1 hour. After the pretreatment, the temperature was lowered to 150 °C, and the IR spectra of the sample disk before and after the introduction of pyridine vapor were measured with a FT / IR-4600 manufactured by JASCO Corporation. The quantification of Bronsted acid sites and Lewis acid sites was carried out based on the method described in Non-Patent Document 1.

[0027] <NH3-TPD Measurement> The amount of ammonia desorbed as the acid amount was measured by the ammonia temperature-programmed desorption method (NH3-TPD method). That is, using BELCAT―B (registered trademark) manufactured by Microtrac BEL Japan, Inc., 0.2 g of the sample was placed in the measurement cell, and it was subjected to evacuation treatment at 500 °C for 1 hour. Then, the temperature was set to 100 °C, and ammonia gas was introduced and adsorbed at 100 °C for 0.5 hour. Next, after performing evacuation treatment again at 100 °C for 0.5 hour, while flowing He gas at 50 ml per minute, the amount of ammonia desorbed as the temperature was raised from 100 °C to 500 °C at a rate of 10 °C per minute was measured. The strong acid ratio is defined as the ratio of the acid amount at 400 - 500 °C to the acid amount in the entire region (100 - 500 °C). Strong acid ratio (%) = acid amount (400 - 500 °C) / acid amount (100 - 500 °C) × 100

[0028] <Abrasion Resistance Test Method> The abrasion resistance (Attrition Resistance) was measured by the abrasion resistance index (CCIC Attrition Index, CAI) measured by the method described in Non-Patent Document 2.

[0029] <Measurement Method of Bulk Density (ABD)> The bulk density (ABD) can be measured by using a 25 ml cylinder to measure the weight of the sample and calculating the bulk density from the weight per unit volume.

[0030] <Pore Distribution Measurement> Using a BELSORP-mini II manufactured by MicrotracBEL, N2 adsorption measurements were performed on a silica-alumina sample powder that had been pretreated at 500 °C for 1 hour in an inert gas atmosphere. From the obtained N2 adsorption isotherm, the pore volume of the silica-alumina was calculated using the BJH method.

[0031] <BET specific surface area measurement> For the silica-alumina sample powder that had been pretreated at 500 °C for 1 hour in an inert gas atmosphere, the adsorption and desorption amounts of N2 were measured using a MacSorb-1220 manufactured by Mountech. From the obtained N2 desorption amount, the specific surface area was calculated based on the BET one-point method. The specific surface area of the silica-alumina according to the present invention is 350 to 550 m 2 / g. Preferably, it is in the range of 400 to 500 m 2 / g.

[0032] <Method for producing silica-alumina powder> Silica-alumina Powder The production method of (A) A step of mixing an aqueous solution containing an alumina hydrate and an aqueous solution containing a silica precursor to prepare an aqueous solution A containing a silica-alumina precursor. (B) After adjusting the pH of the aqueous solution A containing the silica-alumina precursor obtained in the step (A) to the range of 9.0 to 11.0, heat treatment is performed in the temperature range of 80 to 100 °C for 0.5 to 12 hours. (C) A step of cooling the aqueous solution heat-treated in the step (B), separating the solid matter, washing it, drying it, or further firing it to obtain silica-alumina powder. including.

[0033] <Alumina hydrate> As the alumina hydrate Al2O3·nH2O, boehmite, pseudo-boehmite, and amorphous or substantially amorphous alumina gels are more preferred. Mixtures combining these are also all available for use. Usually, boehmite is described as the alumina monohydrate (AlOOH) of the formula Al2O3·nH2O, which encompasses various materials with different degrees of hydration and textures. Although the differences in such materials are unclear, when n exceeds 2, it is maximally hydrated gel-like boehmite, when n is between 1 and 2, it is pseudo-boehmite or microcrystalline boehmite, then there is crystalline boehmite, and finally when n is close to 1, boehmite crystallizes into large crystals. The form of the alumina monohydrate varies greatly between the acicular and prismatic forms. Between these two forms, a series of various forms such as combinations of chains, boat shapes, and plates may be used. Regarding the preparation and / or shaping of solids based on transition alumina obtained from alumina monohydrate as a substrate, it is described in many patents (for example, JP-A-46-7164, US Patent No. 3864461, JP-A-53-119800, JP-A-62-230612, etc.).

[0034] <Method for Preparing Alumina Hydrate> Relatively pure alumina hydrate may be used in powder form, and the powder may be amorphous or crystalline, and the crystalline powder may contain an amorphous portion. Also, the alumina hydrate may be added in the form of an aqueous suspension or dispersion. The aqueous suspension or dispersion of alumina hydrate used in the preparation of the silica-alumina powder in the method of the present invention may be capable of gelling or coagulating. As is well known to those skilled in the art, an acidic aqueous dispersion or suspension may be prepared by peptizing the alumina hydrate in water or an aqueous alumina hydrate solution. The aqueous dispersion or suspension of alumina used may be an aqueous suspension or dispersion of boehmite composed of fine or ultrafine colloidal particles. In particular, the fine or ultrafine boehmite used in the present invention may be obtained according to French Patent No. 1261182, French Patent No. 1381282, or Japanese Patent Laid-Open No. 55-116622. Aqueous suspensions or dispersions obtained from pseudoboehmite, amorphous alumina gel, aluminum hydroxide gel, or crystalline alumina hydrogel can also be used.

[0035] Aluminum monohydrate may be obtained from various commercially available aluminum sources (PURAL®, CATAPAL®, DISPERAL®, and DISPAL® commercially available from SASOL, HIQ® commercially available from ALCOA, etc.). Alternatively, aluminum monohydrate may be obtained by partial dehydration or precipitation of aluminum trihydrate by a conventional method using a method known to those skilled in the art. When the alumina is in gel form, peptization is carried out with water or an acidic aqueous solution. In the case of precipitation, for example, at least one of aluminum chloride, aluminum sulfate, and aluminum nitrate may be used as an acid source. The basic aluminum source may be selected from basic aluminum salts such as sodium aluminate and potassium aluminate. Examples of precipitants that can be used include sodium hydroxide, sodium carbonate, potassium hydroxide, and ammonia. The precipitant is selected so that it precipitates together with the above-mentioned alumina source. Depending on the acidity or basicity of the raw material aluminum compound, a base or an acid (hydrochloric acid, sulfuric acid, sodium hydroxide, etc.), or a basic or acidic aluminum compound as described above is used to precipitate the aluminum hydrate. These two reagents may be aluminum sulfate and sodium aluminate. Regarding the preparation of aluminum alpha monohydrate using aluminum sulfate and sodium aluminate, it is described, for example, in JP-A-53-119800. Boehmite may be prepared by reacting an alkaline aluminate solution with a mineral acid solution using the method described in JP-A-46-007164. It may also be prepared as described in French Patent No. 1357830. Amorphous alumina gel may be prepared using the method described in Alcoa Paper, 1972, 19, 9, and in particular, may be prepared by the reaction of an aluminate or an aluminum salt, the hydrolysis of an aluminum alcoholate, or the hydrolysis of a basic aluminum salt. Aluminum hydroxide gel may be prepared by mixing an acidic aluminum source and a base, or a basic aluminum source and an acid, using the methods described in U.S. Patent Nos. 3268295, 3245919, or WO 00 / 01617, and precipitating aluminum monohydrate. This mixing process is carried out without backmixing.Ultra-fine hydrargillite may be prepared by gelling alumina in the form of a cake at a temperature of ambient temperature to 60 °C, particularly using the method described in US Patent No. 1,371,808.

[0036] As a source of an alumina compound that is partially soluble in an acidic medium, an aqueous suspension or dispersion of ultra-high-purity boehmite or pseudo-boehmite prepared by using a method of reacting an alkali aluminate with anhydrous carbon dioxide to obtain a precipitate of amorphous hydroxycarbonate aluminum may also be used. This precipitate is obtained by filtration and subsequent washing. Such a method is described in US Patent No. 3,268,295. Next, 1) in the first step, the washed amorphous hydroxycarbonate aluminum precipitate is mixed with a solution of an acid, a base, a salt, or a mixture thereof (pour the solution into the hydroxycarbonate to obtain a mixture with a medium pH of less than 11); 2) in the second step, the obtained reaction mixture is heated at a temperature of less than 90 °C for 5 minutes or more; 3) in the third step, the medium obtained in the second step is heated to 90 to 250 °C. The dispersion or suspension of boehmite or pseudo-boehmite obtained by using this method has an alkali content of less than 0.005% by mass as indicated by the ratio of alkali metal oxide / Al2O3. The size of the alumina particles serving as the alumina source varies greatly and is usually 1 to 100 μm.

[0037] <Source of silica compound> In an embodiment of step (A) of the method for preparing the silica-alumina powder according to the present invention, a silica precursor is mixed with an alumina compound. The source of the silica compound added to the alumina hydrate is preferably selected from the group consisting of silicic acid, colloidal silicic acid solution, water-soluble silicate, cationic silicon salt (such as sodium metasilicate hydrate), Ludox (registered trademark, ammonia type or alkali type), and quaternary ammonium silicate salt. The preparation of the colloidal silicic acid solution may be carried out using methods known to those skilled in the art. As the source of this completely soluble silicon compound, an orthosilicic acid solution (H2SiO4, H2O) prepared by ion-exchanging a water-soluble alkali silicate on a resin may also be used.

[0038] <Process (A)> · Mixing an aqueous solution containing an alumina hydrate and an aqueous solution containing a silica precursor to prepare an aqueous solution A containing a silica-alumina precursor Combining a silica compound that is completely soluble in an alumina compound, or a partially soluble silica compound and an alumina compound corresponds to bringing alumina chemical species and silica chemical species having specific sizes and chemical reactivities into contact in the mixture of this step (A) and controlling the interaction between the chemical species. Controlling the interaction in this way contributes to enhancing the homogeneity of the silica-alumina powder of the present invention. In this preparation method, at any step before the hydrothermal treatment, the interaction activity between the silica chemical species and the alumina chemical species may be controlled according to the chemical properties of the alumina compound and the silica compound used in the preparation of the silica-alumina powder. In a non-limiting example, a partially soluble alumina compound of the hydrated aluminum type, Al2O3·nH2O (boehmite), may be mixed with a completely soluble silica compound of the de-cationized orthosilicic acid type in an aqueous medium under controlled various synthesis conditions (pH, temperature, etc.), or during the molding process, after machining, a partially soluble alumina compound of the alumina hydrate type, Al2O3·nH2O (boehmite), may be mixed with a commercially available completely soluble silica (Ludox (registered trademark)) colloidal solution. Following the mixing in step (A) of the silica-alumina powder preparation method, hydrothermal treatment is performed in the presence of water (vapor phase or liquid phase), and finally, the homogeneity at the micrometer level (or nanometer level) between the alumina chemical species and the silica chemical species necessary to obtain the acidity and texture characteristics of the silica-alumina powder used in the fluid catalytic cracking of the present invention is achieved.

[0039] In the formulation of this step (A), the temperature of the aqueous solution is preferably carried out in the range of 10 to 60 °C. If formulated at a temperature lower than this range, the acid amount and acid strength of the silica-alumina may be insufficient, and if formulated at a high temperature, the alumina compound grows, causing a decrease in specific surface area and acid amount, which is not preferable.

[0040] When performing this step (A), an alumina compound that is partially soluble in an acidic medium is 150 to 600 m 2It is effective to select from the group of alumina compounds of the general formula Al2O3·nH2O (n ≦ 5) having a specific surface area of / g. In particular, hydrated alumina compounds such as boehmite, pseudo-boehmite, amorphous or substantially amorphous alumina gel may be used.

[0041] At the stage before adding a compound containing part or all of silicon, it applies to all of hydrated alumina powder, spray-dried hydrated alumina powder, dispersion and suspension of hydrated alumina, and combinations thereof.

[0042] For the purpose of increasing the diameter of the mesopores of the finally obtained silica alumina powder, as disclosed in U.S. Patent No. 4,066,574, an aqueous suspension or dispersion of an alumina component such as alumina monohydrate (an alumina compound partially soluble in an acidic medium) is prepared to obtain the mixture of this step (A), and then the mixture is neutralized with a basic solution (such as ammonia), and finally this is added simultaneously or sequentially to a completely soluble silica compound (such as a deionized orthosilicic acid solution). This suspension is vigorously stirred for mechanical homogenization, and after optionally adjusting the dry matter content by filtration and re-homogenization, the product is heat-treated and optionally shaped simultaneously or sequentially therewith.

[0043] Hereinafter, in the description of the above method, the first "homogenization" of the mixture is often carried out by mechanical treatment. For example, when using a product containing a solid fraction in a state such as a liquid such as a suspension, powder, or filtration precipitate, the product is strongly stirred and dispersed. Mechanical homogenization of the dispersion is widely known to those skilled in the art. Homogenization may be carried out by mechanical methods known to those skilled in the art, for example, using a batch reactor, a continuous mixer, or a mill. Mixing may be carried out in a plug flow reactor, particularly in a static reactor. A Lightning reactor can also be used. A colloidal mill such as an Ultraturrax (registered trademark) turbine or a Staro (registered trademark) turbine, or a Staro (registered trademark) colloidal mill may be used. A commercially available IKA (registered trademark) colloidal mill may also be used.

[0044] <Step (B)> · After adjusting the pH of the aqueous solution A containing the silica-alumina precursor obtained in the step (A) to the range of 9.0 to 11.0, it is heat-treated in the temperature range of 80 to 100 °C for the range of 0.5 to 12 hours. In the step (B) of the method for preparing the silica-alumina powder of the present invention, by adjusting the pH of the aqueous solution A obtained in the above step (A) to the range of 9.0 to 11.0 and then heat-treating it in the temperature range of 80 to 100 °C for the range of 0.5 to 12 hours, the homogeneity of the silica-alumina powder can be ensured. The pH of the aqueous solution A in this step is in the range of 9.0 to 11.0, preferably 9.5 to 10.5. If the pH deviates excessively from the range of 9.0 to 11.0, the specific surface area and the acid amount will decrease, which is not preferable. Also, the temperature of the aqueous solution is preferably in the temperature range of 80 to 100 °C. If it is less than 80 °C, the reaction of the silica-alumina precursor will be insufficient, and the acid amount and acid strength will decrease. If it exceeds 100 °C, the particle growth of silica-alumina will proceed, and the specific surface area and acid amount will decrease, which is not preferable. That is, the solid obtained in the above step (A) is brought into contact with water (vapor phase or liquid phase) for hydrothermal treatment. The hydrothermal treatment may be performed at any stage of the preparation. Although the mobility of the silica component may be improved by this treatment, the present invention is not limited thereto. The heat treatment time has no further effect even if it exceeds 12 hours.

[0045] <Step (C)> · A step of cooling the aqueous solution heat-treated in the step (B), separating the solid matter, washing it, drying it, or further firing it to obtain silica-alumina powder.

[0046] <Method for Producing Fluid Catalytic Cracking Catalyst> (1) A step of mixing the silica-alumina powder, a binder component, a clay component (filler), a zeolite component, and an additive to obtain a mixed slurry. (2) A step of spray-drying the mixed slurry obtained in the step (1) to obtain dry particles. (3) A step of washing and drying the dry particles obtained in the step (2) to obtain a fluid catalytic cracking catalyst. It is a method for producing a fluid catalytic cracking catalyst including the above steps. Alternatively, instead of step (3), (4) A step of washing and drying the dried particles obtained in the step (2), and then performing rare earth metal exchange to obtain a fluid catalytic cracking catalyst subjected to rare earth metal exchange. It is a method for producing a fluid catalytic cracking catalyst including this.

[0047] The method for producing a fluid catalytic cracking catalyst can be carried out by the methods described in JP-A-2020-032350 and JP-A-2020-032352.

Example

[0048] Examples are shown below to specifically explain this example, but the present invention is not limited by these examples. In this example, alumina particles prepared by the neutralization method were used, but the alumina particles applicable to this application can be various alumina particles as described above.

[0049] (Example 1) Preparation of Pseudoboehmite Slurry 9.09 kg of an aqueous sodium aluminate solution (manufactured by JGC Catalysts & Chemicals Ltd.) with an Al2O3 concentration equivalent of 22% by mass was placed in a 100 L tank with a steam jacket, diluted with pure water to 40.00 kg, and then 60.0 g of sodium gluconate with a concentration of 99% by mass (manufactured by Fuso Chemical Industry Co., Ltd.) was added. While stirring, it was heated to 60°C to prepare an aqueous sodium aluminate solution (L1) containing 5% by mass of sodium gluconate. Also, an aqueous aluminum sulfate solution (manufactured by JGC Catalysts & Chemicals Ltd. ) with an Al2O3 concentration equivalent of 7% by mass was diluted with 25.71 kg of ion-exchanged water, and an aqueous aluminum sulfate solution (L2) heated to 60°C was prepared. Next, while stirring the aqueous sodium aluminate solution (L1), the aqueous aluminum sulfate solution (L2) was added thereto over 10 minutes to prepare a precursor of a boehmite slurry. The obtained mixed slurry was aged at 60°C for 60 minutes while stirring, then dehydrated with a flat filter, and then the filter residue was washed with warm water at 60°C to obtain a washed cake. The washed cake was reslurried to a solid content concentration of 15% by mass to obtain a pseudo-boehmite slurry.

[0050] Preparation of Silica Alumina No. S1 To 100 kg of the pseudo-boehmite slurry (15% by mass in terms of Al2O3 concentration) heated to 45°C, 15.60 kg of water glass (No. 3 water glass adjusted to 24% by mass in terms of SiO2, medium-purity sol manufactured by Fuji Chemical Industry Co., Ltd.) was added to obtain a suspension slurry containing 20% by mass of SiO2. After adjusting the temperature of this suspension slurry to 45°C, sulfuric acid (concentration: 25% by mass) was added to adjust the pH to 10.0. Then, the obtained suspension slurry was heated to 95°C and held for 1 hour, and then cooled to 60°C or lower. The obtained slurry was filtered, then washed with warm water at 60°C and an aqueous ammonium sulfate solution, and the washed cake was dried at 150°C to obtain silica alumina No. S1. The properties of silica alumina No. S1 are shown in Table 1.

[0051] Preparation of Fluid Catalytic Cracking Catalyst No. C1 Water glass (No. 3 water glass adjusted to 17.5% by mass in terms of SiO2) and sulfuric acid (adjusted to a concentration of 25% by mass) were continuously added simultaneously to prepare a silica hydrosol containing 12.5% by mass of SiO2. To 4000 g of this silica hydrosol, 737.6 g of kaolin (solid content concentration: 83% by mass), 533.3 g of activated alumina powder (solid content concentration: 75% by mass), 2407 g of silica alumina No. S1 slurry (solid content concentration: 16% by mass) adjusted to pH 3.0 with sulfuric acid, and 783.7 g of Y-type zeolite powder (solid content concentration: 77% by mass) were added to prepare a mixed slurry. After adjusting this catalyst slurry to 40°C, spray drying was performed using a spray dryer with an inlet temperature of 250°C and an outlet temperature of 150°C as droplets to obtain dried particles with an average particle diameter of 70 μm. These dried particles were washed with warm water, and then ion-exchanged with an aqueous ammonium sulfate solution and a rare earth metal chloride aqueous solution followed by washing with warm water, and ion-exchanged so that RE2O3 became 1.8 mass%. The obtained washed cake was dried in a dryer maintained at an atmospheric temperature of 150°C for 10 hours to obtain fluid catalytic cracking catalyst No. C1. The catalyst composition and catalyst properties of fluid catalytic cracking catalyst No. C1 are shown in Table 2.

[0052] (Example 2) Preparation of Silica Alumina No. S2 Silica alumina No. S2 was obtained in the same manner as in Example 1, except that 11.03 kg of water glass was added to 100 kg of pseudo-boehmite slurry heated to 45°C to obtain a suspension slurry containing 15 mass% of SiO2. The properties of silica alumina No. S2 are shown in Table 1.

[0053] Preparation of Fluid Catalytic Cracking Catalyst No. C2 Fluid catalytic cracking catalyst No. C2 was obtained in the same manner as in Example 1, except that silica alumina No. S2 was used as the silica alumina slurry. The catalyst composition and catalyst properties of fluid catalytic cracking catalyst No. C2 are shown in Table 2.

[0054] (Example 3) Preparation of Silica Alumina No. S3 Silica alumina No. S3 was obtained in the same manner as in Example 1, except that 20.83 kg of water glass was added to 100 kg of pseudo-boehmite slurry heated to 45°C to obtain a suspension slurry containing 25 mass% of SiO2. The properties of silica alumina No. S3 are shown in Table 1.

[0055] Preparation of Fluid Catalytic Cracking Catalyst No. C3 Fluid catalytic cracking catalyst No. C3 was obtained in the same manner as in Example 1, except that silica alumina No. S3 was used as the silica alumina slurry. The catalyst composition and catalyst properties of fluid catalytic cracking catalyst No. C3 are shown in Table 2.

[0056] (Example 4) Preparation of Silica Alumina No. S4 A silica-alumina No. S4 was obtained in the same manner as in Example 1, except that a suspension slurry containing 20% by mass of SiO2 was adjusted to 45°C, sulfuric acid (concentration: 25% by mass) was added, and the pH was adjusted to 9.5. The properties of silica-alumina No. S4 are shown in Table 1.

[0057] Preparation of Fluid Catalytic Cracking Catalyst No. C4 A fluid catalytic cracking catalyst No. C4 was obtained in the same manner as in Example 1, except that silica-alumina No. S4 was used as the silica-alumina slurry. The catalyst composition and catalyst properties of fluid catalytic cracking catalyst No. C4 are shown in Table 2.

[0058] (Example 5) Preparation of Silica Alumina No. S5 A silica-alumina No. S5 was obtained in the same manner as in Example 1, except that a suspension slurry containing 20% by mass of SiO2 was adjusted to 45°C, sulfuric acid (concentration: 25% by mass) was added, and the pH was adjusted to 10.5. The properties of silica-alumina No. S5 are shown in Table 1.

[0059] Preparation of Fluid Catalytic Cracking Catalyst No. C5 A fluid catalytic cracking catalyst No. C5 was obtained in the same manner as in Example 1, except that silica-alumina No. S5 was used as the silica-alumina slurry. The catalyst composition and catalyst properties of fluid catalytic cracking catalyst No. C5 are shown in Table 2.

[0060] (Comparative Example 1) Preparation of Silica Alumina No. SA A silica-alumina No. SA was obtained in the same manner as in Example 1, except that 1.93 kg of water glass was added to 100 kg of pseudoboehmite slurry heated to 45°C to obtain a suspension slurry containing 3% by mass of SiO2. The properties of silica-alumina No. SA are shown in Table 1.

[0061] Preparation of Fluid Catalytic Cracking Catalyst No. CA A fluid catalytic cracking catalyst No. CA was obtained in the same manner as in Example 1, except that silica alumina No. SA was used as the silica alumina slurry. The catalyst composition and catalyst properties of the fluid catalytic cracking catalyst No. CA are shown in Table 2.

[0062] (Comparative Example 2) Preparation of Silica Alumina No. SB Silica alumina No. SB was obtained in the same manner as in Example 1, except that 41.7 kg of water glass was added to 100 kg of pseudoboehmite slurry heated to 45°C to obtain a suspension slurry containing 40 mass% of SiO2. The properties of silica alumina No. SB are shown in Table 1.

[0063] Preparation of Fluid Catalytic Cracking Catalyst No. CB A fluid catalytic cracking catalyst No. CB was obtained in the same manner as in Example 1, except that silica alumina No. SB was used as the silica alumina slurry. The catalyst composition and catalyst properties of the fluid catalytic cracking catalyst No. CB are shown in Table 2.

[0064] (Comparative Example 3) Preparation of Silica Alumina No. SC Silica alumina No. SC was obtained in the same manner as in Example 1, except that sulfuric acid (concentration 25 mass%) was not added to the suspension slurry containing 20 mass% of SiO2 and the pH of the suspension slurry at 45°C was adjusted to 11.5. The properties of silica alumina No. SC are shown in Table 1.

[0065] Preparation of Fluid Catalytic Cracking Catalyst No. CC A fluid catalytic cracking catalyst No. CC was obtained in the same manner as in Example 1, except that silica alumina No. SC was used as the silica alumina slurry. The catalyst composition and catalyst properties of the fluid catalytic cracking catalyst No. CC are shown in Table 2.

[0066] (Comparative Example 4) Preparation of Silica Alumina No. SD Silica alumina No. SD was obtained in the same manner as in Example 1, except that the suspension slurry containing 20 mass% of SiO2 was adjusted to 45°C, sulfuric acid (concentration 25 mass%) was added, and the pH was adjusted to 8.5. The properties of silica alumina No. SD are shown in Table 1.

[0067] Preparation of Fluid Catalytic Cracking Catalyst No. CD A fluid catalytic cracking catalyst No. CD was obtained in the same manner as in Example 1, except that silica alumina No. SD was used as the silica alumina slurry. The catalyst composition and catalyst properties of the fluid catalytic cracking catalyst No. CD are shown in Table 2.

[0068] (Comparative Example 5) Preparation of Silica Alumina No. SE Silica alumina No. SE was obtained in the same manner as in Example 1, except that the suspension slurry adjusted to pH 10.0 was heated to 60 °C and held for 1 hour. The properties of silica alumina No. SE are shown in Table 1.

[0069] Preparation of Fluid Catalytic Cracking Catalyst No. CE A fluid catalytic cracking catalyst No. CE was obtained in the same manner as in Example 1, except that silica alumina No. SE was used as the silica alumina slurry. The catalyst composition and catalyst properties of the fluid catalytic cracking catalyst No. CE are shown in Table 2.

[0070] [Catalyst Activity Evaluation Test] For the catalysts of each example and comparative example, a performance evaluation test of the catalyst was carried out using ACE-MAT (Advanced Cracking Evaluation Micro Activity Test) under the same crude oil and the same reaction conditions. However, before performing these performance evaluation tests, 1000 mass ppm (the mass of nickel divided by the mass of the catalyst) and 2000 mass ppm (the mass of vanadium divided by the mass of the catalyst) of nickel and vanadium were respectively deposited on the surface of each catalyst in advance, and then steaming was carried out for pseudo-equilibration treatment.

[0071] The operating conditions in the activity evaluation test are as follows. Feedstock oil: Desulfurized atmospheric residue oil (DSAR) of crude oil Mass ratio of catalyst / throughput (C / O): 5.0 Reaction temperature: 520 °C 1) Conversion rate = 100 - (LCO + HCO) 2) Boiling point range of gasoline: 30~216°C 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)

[0072] The results of the activity evaluation test are as shown in Table 3. Compared with the catalyst of the comparative example, the catalyst of the inventive example can be evaluated as a catalytic cracking catalyst with excellent conversion rate, excellent Coke yield and excellent HCO yield.

[0073]

Table 1

[0074]

Table 2

[0075]

Table 3

Claims

1. It is non-zeolite-based, The silica (SiO ２ ) content is 5 to 30% by mass, The pore volume measured using the nitrogen adsorption isotherm is 0.70 to 1.20 ml / g, When the thermal desorption of pyridine from silica-alumina is monitored by IR, Bronsted acid is present and the amount of Lewis acid is 200 to 400 μmol / g, The BET specific surface area is 420 to 550 m ２ / g, When measured by NH₃-TPD, the ammonia desorption amount at 100 to 500 °C is 500 to 700 μmol / g, When measured by NH₃-TPD, the ratio of the ammonia desorption amount at 400 to 500 °C to the ammonia desorption amount at 100 to 500 °C is 10% or more, a silica-alumina powder.

2. It is non-zeolite-based, The silica (SiO₂) content is 5 to 30% by mass, The pore volume measured using the nitrogen adsorption isotherm is 0.70 to 1.20 ml / g, When the thermal desorption of pyridine from silica-alumina is monitored by IR, Bronsted acid is present and the amount of Lewis acid is 200 to 400 μmol / g, The BET specific surface area is 350 to 550 m² / g, NH ３ -TPD measurement, when the ammonia desorption amount at 100 to 500 °C is 500 to 700 μmol / g, When measured by NH₃-TPD, the ratio of the ammonia desorption amount at 400 to 500 °C to the ammonia desorption amount at 100 to 500 °C is 10% or more, silica-alumina powder for fluid catalytic cracking catalyst.

3. A step A of preparing an aqueous solution A containing a silica-alumina precursor by mixing an aqueous solution containing an alumina hydrate having a specific surface area of 150 to 600 m² / g and an aqueous solution containing a silica precursor so that the silica component in the silica-alumina powder is contained in an amount of 5 to 30% by mass in terms of SiO₂, After adjusting the pH of the aqueous solution A to the range of 9.5 to 11.0, a heat treatment step B is performed in the temperature range of 95 to 100 °C for 0.5 to 12 hours. A step C of cooling the aqueous solution heat-treated in the step B, separating the solid matter, and then washing and drying the solid matter is provided. The alumina hydrate is at least one of boehmite, pseudo-boehmite, and amorphous alumina gel. The silica precursor is at least one of silicic acid, colloidal silicate solution, water-soluble silicate, cationic silicon salt, Ludox (registered trademark, ammonia type or alkali type), and quaternary ammonium silicate. The temperature of the aqueous solution containing the alumina hydrate is 10 to 60 °C. A method for producing silica-alumina powder, wherein the temperature of the aqueous solution containing the silica precursor is 10 to 60 °C.

4. A method for producing a fluid catalytic cracking catalyst, comprising a step of adding the silica-alumina powder according to Claim 2.

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