Catalytic cracking catalyst containing large particle size sol and use thereof

Abstract

A catalytic cracking catalyst containing a large particle sol and a method for producing the same. The catalytic cracking catalyst contains, based on its total weight, 15-50 wt% of β zeolite, 10-75 wt% of clay, and 10-50 wt% of a large particle sol. The pore distribution is measured by a low-temperature nitrogen adsorption method, and the total pore volume is 0.200 mL / g or more. The pore volume of mesopores having a parameter of 4-50 nm accounts for 60% or more of the total pore volume. The large particle sol contains 10-40 wt% Al 2 O 3 , 50 to 85% by weight P 2 O 5 , and 0.2 to 10 wt.% SiO 2 Including P 2 O 5 :Al 2 O 3 The mass ratio of SiO is (1.5~5.0):1. 2 :Al 2 O 3 The mass ratio of is (0.01-0.3):1, and the average particle size distribution of the sol is concentrated at 20-50 nm. The preparation method includes the following steps: mix an aluminum source with deionized water to obtain a first slurry, mix the first slurry with a phosphorus source to obtain a second slurry, add silica sol to the second slurry to obtain a third slurry, and age the third slurry to obtain a large particle size sol. The large particle size sol is uniformly mixed with clay and β zeolite to obtain a fourth slurry, and the fourth slurry is dried and calcined. This catalyst is applied in the catalytic cracking process, which can significantly improve the yield and selectivity of C4 olefins.

Description

Detailed Description of the Invention

[0001] [Technical field] The present invention is in the field of refining industry. In particular, the present invention relates to a catalytic cracking catalyst containing a large particle size sol and a method for preparing the same.

[0002] [Background art] The conversion of refinery oil into basic chemical feedstocks such as olefins and aromatics has become the mainstream of the industry, and catalytic cracking is one of the key technologies to maximize the production of low-carbon olefins from crude oil. Statistics show that nearly 70% of the world's C4 olefins come from catalytic crackers. The technology of producing C4 olefin fractions through catalytic crackers has the advantages of low investment and low cost, so many companies are trying to obtain higher C4 olefin yields from the catalytic cracking process. The use of catalytic cracking catalysts or assistants is the most direct and economical way to improve the C4 olefin yield.

[0003] The main active components of catalytic cracking catalysts or assistants for improving C4 olefin yield include Y-type molecular sieves, ZSM-5 molecular sieves, and beta zeolites. Among them, beta zeolites are considered to be the main active components of catalysts for improving C4 olefin yield because of their unique structure that combines acid catalyst properties and structural selectivity. Binders are also one of the main components of catalytic cracking catalysts or assistants, and can improve the activity and hydrothermal stability of the catalyst in synergy with the active components while ensuring the wear resistance of the catalyst. The most common binders include alumina sol, silica sol, and acidified pseudoboehmite.

[0004] US6355591 discloses a catalytic cracking additive comprising 4-20% by weight of aluminum phosphate, 1-40% by weight of ZSM-5, beta zeolite and mixtures thereof, and 40-90% by weight of clay, which can increase the yield of liquefied gas.

[0005] CN1055105C discloses a cracking catalyst for increasing the yield of isobutylene and isopentylene. The cracking catalyst comprises 6-30% by weight of a five-membered ring high silica zeolite containing phosphorus and rare earth, 5-20% by weight of USY zeolite, 1-5% by weight of β zeolite, 30-60% by weight of clay, and 15-30% by weight of inorganic oxide. The catalyst is characterized by its ability to increase the yield of isobutylene and isopentylene under catalytic cracking process conditions and co-produce high octane gasoline.

[0006] CN103785456A discloses a cracking aid for increasing low-carbon olefin concentration, the cracking aid includes a modified β molecular sieve, a phosphorus-aluminum inorganic binder with a first clay, and other inorganic binders with or without a second clay and a group VIII metal additive; the phosphorus-aluminum inorganic binder with a first clay includes an aluminum component, a phosphorus component and a first clay; the β molecular sieve modified by phosphorus and transition metal includes a phosphorus content of 1-10 wt% (calculated as P2O5) and a metal content of 0.5-10 wt% (calculated as metal oxide). The cracking catalyst composition is used for catalytic cracking of petroleum hydrocarbons, and can increase the yield of catalytically cracked liquefied gas and increase the concentration of low-carbon olefins in the liquefied gas, especially the concentration of isobutylene, while increasing the ratio of ethylene to dry gas and increasing the octane number of gasoline; the heavy oil conversion ability of the main catalyst is not affected by the addition of a large proportion of the assistant.

[0007] Although the existing catalytic cracking catalysts or catalysts for enhancing the production of low-carbon olefins can achieve the purpose of enhancing the production of C4 olefins to a certain extent, the following problems remain: the increase in the yield of C4 olefins mainly depends on the increase in the yield of liquefied gas, but the concentration of C4 olefins in the liquefied gas does not change significantly, and the selectivity of C4 olefins is low; the catalyst or catalysts do not have abundant mesoporous and macroporous structures, which is not conducive to the rapid diffusion of C4 olefins generated in the catalytic cracking process, leading to continuous secondary reactions of low-carbon olefins such as C4 olefins, resulting in a decrease in the yield and selectivity of C4 olefins.

[0008] Therefore, in order to solve the above problems, the object of the present invention is to provide a catalytic cracking catalyst / auxiliary having abundant mesoporous structure and a preparation method thereof, so as to further improve the yield and selectivity of C4 olefins.

[0009] Summary of the Invention Meanwhile, the present invention provides a large particle sol comprising (on a dry basis) 10-40 wt. % Al2O3, 50-85 wt. % P2O5, and 0.2-10 wt. % SiO2, wherein the mass ratio of P2O5:Al2O3 is (1.5-5.0):1, and the mass ratio of SiO2:Al2O3 is (0.01-0.3):1, preferably (0.05-0.3):1; the average particle size of the large particle sol is in the range of 20-50 nm, for example, the large particle sol having an average particle size distribution of 20-50 nm accounts for 60% or more of the total amount.

[0010] The present invention further provides a catalytic cracking catalyst containing a large particle size sol for increasing the yield of low carbon olefins, comprising (based on the dry weight of the catalytic cracking catalyst) 15-50 wt% β zeolite and / or ZSM-5 zeolite, 10-75 wt% clay, and 10-50 wt% of the large particle size sol. The pore distribution is determined by a low-temperature nitrogen adsorption method. The total pore volume of the catalytic cracking catalyst is 0.200 mL / g or more, and the pore volume of mesopores with pore diameters of 4-50 nm accounts for 60% or more of the total pore volume.

[0011] In one embodiment, the catalytic cracking catalyst according to the present invention can be used as a catalytic cracking aid.

[0012] In one embodiment, the catalytic cracking catalyst according to the present invention comprises 20-40 wt % beta zeolite, 20-65 wt % clay, and 15-45 wt % large particle size sol.

[0013] In one embodiment, the catalytic cracking catalyst comprises 20-50 wt % ZSM-5 zeolite, 10-70 wt % clay, and 10-45 wt % large particle size sol.

[0014] In one embodiment, the catalytic cracking catalyst according to the present invention comprises 25-45 wt % ZSM-5 zeolite, 20-60 wt % clay, and 15-40 wt % large particle size sol.

[0015] In one embodiment, the large particle sol contains 15-35 wt % Al2O3, 55-80 wt % P2O5, and 0.5-8.0 wt % SiO2, the mass ratio of P2O5:Al2O is (2.0-4.5):1, the mass ratio of SiO2:Al2O3 is (0.05-0.25):1, and the large particle sol having an average particle size distribution of 25-45 nm accounts for 60% or more of the total amount.

[0016] In one embodiment, the catalytic cracking catalyst has a total pore volume of 0.200-0.300 mL / g.

[0017] In one embodiment, in the catalytic cracking catalyst according to the present invention, the pore volume of mesopores having a size of 4 to 50 nm accounts for 65 to 85% of the total pore volume.

[0018] In one embodiment, the beta zeolite is selected from the group consisting of H-type beta zeolite, Na-type beta zeolite, phosphorus-modified beta zeolite, and metal-modified beta zeolite, or any combination thereof, and the molar ratio of SiO2 to Al2O3 in the beta zeolite is 20-50.

[0019] In one embodiment, the beta zeolite is an H-type beta zeolite.

[0020] In one embodiment, the metal in the metal modified beta zeolite is selected from the group consisting of La, Ce, Pr, Zr, Ti, Fe, Cu, and Mg.

[0021] In one embodiment, the ZSM-5 zeolite is selected from the group consisting of HZSM-5 zeolites, ZSM-5 zeolites containing phosphorus and / or iron, ZSM-5 zeolites containing phosphorus and / or rare earths, modified ZSM-5 zeolites, or any combination thereof.

[0022] In one embodiment, the modified ZSM-5 zeolite is selected from the group consisting of Zn, Cu, Mg, Zr, Ti or B modified ZSM-5 zeolites.

[0023] In one embodiment, the clay is selected from the group consisting of kaolin, rectorite, diatomaceous earth, montmorillonite, bentonite, sepiolite, or a combination thereof.

[0024] In another aspect, the present invention provides a method for producing the catalytic cracking catalyst of the present invention, comprising the steps of: (1) First, a large particle sol is prepared by the following procedure: (1a) mixing an aluminum source with deionized water and stirring at room temperature for 30 minutes or more to obtain a first slurry having a solid content of 5 to 25% by weight; (1b) mixing the first slurry with a phosphorus source and stirring at a temperature of 60°C or less for 30 minutes or more to obtain a second slurry having a solid content of 15 to 50% by weight; (1c) adding silica sol to the second slurry, mixing, and stirring at a temperature of 60°C or less for 30 minutes or more to obtain a third slurry having a solid content of 15 to 50% by weight; (1d) The third slurry is allowed to stand at 20 to 60°C for 1 to 72 hours for aging treatment to obtain a large particle size sol; wherein the mass ratio of the amount of the phosphorus source (calculated as P2O5) to the amount of the aluminum source is (1.5-5.0):1, and the mass ratio of the amount of the silica sol (calculated as SiO2) to the amount of the aluminum source (calculated as Al2O3) is (0.01-0.3):1; (2) Next, the clay, the beta zeolite and the large particle size sol are mixed thoroughly and uniformly to obtain a fourth slurry; wherein the solid content of the obtained fourth slurry is 10-50% by weight; and the fourth slurry is sprayed, shaped, dried and calcined to obtain the catalytic cracking catalyst, wherein the weight ratio of the β zeolite and / or ZSM-5 zeolite, the clay and the large particle size sol is (15-50):(10-75):(10-50) on a dry basis.

[0025] In one embodiment, the weight ratio of the ZSM-5 zeolite, the clay, and the large particle size sol on a dry basis is (20-50):(10-70):(10-45).

[0026] In one embodiment, according to the production method of the present invention, in step (1a), the mixing and stirring continues for 30 to 60 minutes.

[0027] In one embodiment, according to the production method of the present invention, step (1b) is carried out at a temperature of 35-55° C., and the mixing and stirring continues for 30-90 minutes.

[0028] In one embodiment, according to the production method of the present invention, step (1c) is carried out at a temperature of 35-55° C., and the mixing and stirring continues for 30-90 minutes.

[0029] In one embodiment, according to the production method of the present invention, the aluminum source is one or more selected from the group consisting of pseudoboehmite, alumina, boehmite, gibbsite, and diaspore.

[0030] In one embodiment, according to the production method of the present invention, the phosphorus source is one or more selected from phosphoric acid, phosphorous acid, and hypophosphorous acid.

[0031] In one embodiment, according to the production method of the present invention, the clay is one or more selected from the group consisting of kaolin, rectorite, diatomaceous earth, montmorillonite, bentonite, and sepiolite.

[0032] In one embodiment, according to the production method of the present invention, the β zeolite is selected from the group consisting of H-type β zeolite, Na-type β zeolite, phosphorus-modified β zeolite, and metal-modified β zeolite, or any combination thereof, and the molar ratio of SiO2 to Al2O3 in the β zeolite is 20 to 50.

[0033] In one embodiment, according to the production method of the present invention, the ZSM-5 zeolite is selected from the group consisting of HZSM-5 zeolite, ZSM-5 zeolite containing phosphorus and / or iron, ZSM-5 zeolite containing phosphorus and / or rare earth, modified ZSM-5 zeolite, or any combination thereof.

[0034] In one embodiment, according to the production method of the present invention, the modified ZSM-5 zeolite is selected from the group consisting of Zn, Cu, Mg, Zr, Ti or B modified ZSM-5 zeolite.

[0035] In another aspect, the present invention provides a large particle size sol comprising, based on its dry weight, 10-40 wt. % Al2O3, 50-85 wt. % P2O5, and 0.2-10 wt. % SiO2, wherein the mass ratio of P2O5:Al2O3 is (1.5-5.0):1 and the mass ratio of SiO2:Al2O3 is (0.01-0.3):1, and the average particle size is 20-50 nm, preferably prepared by the following method: (1a) mixing an aluminum source with deionized water and stirring at room temperature for at least 30 minutes to obtain a first slurry having a solid content of 5 to 25% by weight; (1b) mixing the first slurry with a phosphorus source and stirring at a temperature of 60°C or less for 30 minutes or more to obtain a second slurry having a solid content of 15 to 50% by weight; (1c) adding silica sol to the second slurry, mixing and stirring at a temperature of 60°C or less for 30 minutes or more to obtain a third slurry having a solid content of 15 to 50% by weight; (1d) The third slurry is allowed to stand at 20 to 60° C. for 1 to 72 hours for aging treatment, thereby obtaining a large particle size sol.

[0036] As described above, the catalytic cracking catalyst prepared according to the method of the present invention contains a large particle size sol rich in mesoporous structure formed by the accumulation of colloidal particles with large particle size and uniform particle size distribution. Therefore, by using the catalytic cracking catalyst containing the large particle size sol according to the present invention in the catalytic cracking process, the yield of low carbon olefins is relatively high. Since the low carbon olefins can diffuse quickly through the mesoporous structure rich in the catalyst, continuous secondary reactions can be avoided, thereby achieving an improvement in the yield and selectivity of low carbon olefins. In addition, the large particle size sol contained in the catalytic cracking catalyst of the present invention is dispersed on the molecular sieve and clay, which can further improve the binding property of the catalyst and improve the wear resistance, i.e., strength, of the catalyst.

[0037] [Figure Description] FIG. 1 is a TEM image of catalytic cracking catalyst A1 prepared according to Example 1.

[0038] FIG. 2 is a TEM image of catalytic cracking catalyst DA3 prepared according to Comparative Example 3.

[0039] FIG. 3 is a graph of the pore size distribution of catalytic cracking catalysts prepared according to Example and Comparative Example 3.

[0040] FIG. 4 is a TEM image of catalytic cracking catalyst ZA1 prepared according to Example Z1.

[0041] FIG. 5 is a graph of the pore size distribution of catalytic cracking catalysts prepared according to Example Z2 and Comparative Example Z3.

[0042] Detailed Description of the Invention The following figures and examples are used to explain the present invention in detail. The features and advantages of the present invention will become more apparent through these descriptions.

[0043] Furthermore, the technical features contained in the different embodiments of the present invention described below can be combined with each other unless they are mutually inconsistent.

[0044] In one embodiment, the present invention provides a catalytic cracking catalyst for increasing the yield of low carbon olefins. The catalytic cracking catalyst comprises, based on the dry weight of the catalytic cracking catalyst, 15-50 wt% β zeolite, 10-75 wt% clay, and 10-50 wt% of a large particle sol containing 10-40 wt% Al2O3, 50-85 wt% P2O5, and 0.2-10 wt% SiO2, where the mass ratio of P2O5:Al2O is (1.5-5.0):1, and the mass ratio of SiO2:Al2O3 is (0.01-0.3):1, and the large particle sol having an average particle size distribution in the range of 20-50 nm accounts for 60% or more of the total amount; the pore distribution is determined by low-temperature nitrogen adsorption method, and the total pore volume of the catalytic cracking catalyst is 0.200 mL / g or more, and the pore volume of mesopores of 4-50 nm accounts for 60% or more of the total pore volume. This catalytic cracking catalyst has a significant effect on increasing the yield of C4 olefins.

[0045] The catalytic cracking catalyst according to the present invention preferably comprises 20-40% by weight of β zeolite, 20-65% by weight of clay, and 15-45% by weight of large particle sol. The large particle sol preferably comprises 15-35% by weight of Al2O3, 55-80% by weight of P2O5, and 0.5-8.0% by weight of SiO2, and the mass ratio of P2O5:Al2O is preferably (2.0-4.5):1, and the mass ratio of SiO2:Al2O3 is preferably (0.05-0.25):1. The large particle sol having an average particle size distribution in the range of 25-45 nm can account for 60% or more of the total amount. The total pore volume of the catalytic cracking catalyst according to the present invention can reach 0.200-0.300 mL / g, and the pore volume of 4-50 nm mesopores accounts for 65-85% of the total pore volume.

[0046] The β zeolite contained in the catalytic cracking catalyst of the present invention is selected from the group consisting of H-type β zeolite, Na-type β zeolite, phosphorus-modified β zeolite and metal-modified β zeolite, or any combination thereof, preferably H-type β zeolite. The metal in the metal-modified β zeolite contained in the catalytic cracking catalyst of the present invention can be, for example, a rare earth metal selected from the group consisting of La, Ce, Pr, Zr, Ti, Fe, Cu, Mg, etc. The clay contained in the catalytic cracking catalyst of the present invention can be, for example, a clay selected from the group consisting of kaolin, rectorite, diatomaceous earth, montmorillonite, bentonite, sepiolite, or any combination thereof, and can be various clays suitable for catalyst production well known to those skilled in the art.

[0047] In a second aspect, the present invention provides a catalytic cracking catalyst for increasing the yield of low carbon olefins; the catalytic cracking catalyst comprises, based on the dry weight of the catalytic cracking catalyst, 20-50 wt.% ZSM-5 zeolite, 10-70 wt.% clay, and 10-45 wt.% large particle sol; the large particle sol comprises, based on the dry weight, 10-40 wt.% Al2O3, 50-85 wt.% P2O5, and 0.2-10 wt.% SiO2. The mass ratio of P2O5:Al2O is (1.5-5.0):1, and the mass ratio of SiO2:Al2O3 is (0.01-0.3):1; the number of colloidal particles having an average particle size in the range of 20-50 nm in the large particle size sol accounts for 60% or more of the total amount; the total pore volume of the catalytic cracking catalyst determined by a low-temperature nitrogen adsorption method is 0.200 mL / g or more, and the pore volume of mesopores with a size of 4-50 nm accounts for 60% or more of the total pore volume. This catalytic cracking catalyst can improve the yield of propylene.

[0048] The catalytic cracking catalyst according to the second aspect of the present invention preferably comprises 25-45% by weight of ZSM-5 zeolite, 20-60% by weight of clay, and 15-40% by weight of large particle sol, the large particle sol comprises, on a dry weight basis, 15-35% by weight of Al2O3, 55-80% by weight of P2O5, and 0.5-8.0% by weight of SiO2, the mass ratio of P2O5:Al2O is preferably (2.0-4.5):1, the mass ratio of SiO2:Al2O3 is preferably (0.05-0.25):1, the number of colloidal particles having an average particle size in the range of 25-45 nm in the large sol accounts for 60% or more of the total amount; the total pore volume of the catalytic cracking catalyst can reach 0.200-0.300 mL / g, and the pore volume of mesopores of 4-50 nm can account for 65-85% of the total pore volume.

[0049] The ZSM-5 zeolite contained in the catalytic cracking catalyst according to the second aspect of the present invention may be selected from the group consisting of HZSM-5 zeolite, ZSM-5 zeolite containing phosphorus and / or iron, ZSM-5 zeolite containing phosphorus and / or rare earth, modified ZSM-5 zeolite, or any combination thereof, and the modified ZSM-5 zeolite may be selected from the group consisting of Zn, Cu, Mg, Zr, Ti or B modified ZSM-5 zeolite. The clay contained in the catalytic cracking catalyst according to the present invention may be, for example, selected from the group consisting of kaolin, rectorite, diatomaceous earth, montmorillonite, bentonite, sepiolite, or any combination thereof, and may be various clays suitable for catalyst production well known to those skilled in the art.

[0050] In another aspect, the present invention provides a method for preparing the catalytic cracking catalyst, comprising the steps of: (1) First, a large particle sol is prepared by the following procedure: (1a) mixing an aluminum source with deionized water and stirring at room temperature for at least 30 minutes to obtain a first slurry having a solid content of 5 to 25% by weight; (1b) mixing the first slurry with a phosphorus source and stirring at a temperature of 60°C or less for 30 minutes or more to obtain a second slurry having a solid content of 15 to 50% by weight; (1c) adding silica sol to the second slurry, mixing and stirring at a temperature of 60°C or less for 30 minutes or more to obtain a third slurry having a solid content of 15 to 50% by weight; (1d) The third slurry is allowed to stand at 20 to 60°C for 1 to 72 hours for aging treatment to obtain a large particle size sol; wherein the mass ratio of the amount of the phosphorus source (calculated as P2O5) to the amount of the aluminum source is (1.5-5.0):1, and the mass ratio of the amount of the silica sol (calculated as SiO2) to the amount of the aluminum source (calculated as Al2O3) is (0.01-0.3):1; (2) Next, the clay, β zeolite and / or ZSM-5 zeolite, and the large particle sol are thoroughly and uniformly mixed to obtain a fourth slurry having a solid content of 10-50% by weight; the fourth slurry is sprayed, shaped, dried and calcined to obtain the catalytic cracking catalyst, in which, based on the dry weight, the weight ratio of the β zeolite and / or ZSM-5 zeolite, the clay, and the large particle sol is (15-50):(10-75):(10-50).

[0051] According to one embodiment of the present invention, in the production method of the present invention, the aluminum source used in step (1a) is one or more selected from the group consisting of pseudoboehmite, alumina, aluminum nitrate, aluminum isopropoxide, boehmite, gibbsite, and diaspore. The time for mixing and stirring the aluminum source and deionized water is preferably within the range of 30 to 60 minutes.

[0052] According to one embodiment of the present invention, in the production method of the present invention, the phosphorus source used in step (1b) is one or more selected from the group consisting of phosphoric acid, phosphorous acid, and hypophosphorous acid. Preferably, the first slurry prepared in step (1a) and the phosphorus source are mixed and stirred at a temperature of 35 to 55°C, and the mixing and stirring time is preferably 30 to 90 minutes.

[0053] According to one embodiment of the present invention, in the production method of the present invention, the selected aluminum source is preferably capable of interacting with the selected phosphorus source to form different forms of aluminum phosphate.

[0054] According to one embodiment of the present invention, in the production method of the present invention, step (1c) is preferably carried out at a temperature of 35 to 55°C, and the mixing and stirring time of the second slurry prepared in step (1b) and the silica sol is preferably 30 to 90 minutes.

[0055] According to one embodiment of the present invention, in the manufacturing method of the present invention, without being limited by known theories, it is believed that OH on the surface of the aluminum source absorbs H+ in phosphoric acid to form positively charged colloidal particles. The positively charged colloidal particles lead to the formation of a large number of colloidal particles with an average particle size of 20-50 nm. The addition of silica sol particles can suppress further aggregation of the colloidal particles and improve the stability of the colloidal structure.

[0056] According to one embodiment of the present invention, in the production process of the present invention, the selection of clay and beta zeolite used in step (2) is as described above for the catalytic cracking catalyst of the present invention.

[0057] According to one embodiment of the present invention, in the production method of the present invention, the forming and drying carried out in step (2) refers to granulation and drying of the catalyst, which is a technique well known to those skilled in the art. In the production of catalytic cracking catalysts, spray forming and drying are generally used, and the temperature of the sprayed exhaust gas is controlled to 100 to 250°C. The calcination process is also well known to those skilled in the art, and can be carried out, for example, in a muffle furnace. The calcination is carried out under the following conditions: the temperature is 350 to 800°C, preferably 400 to 650°C, and the calcination time is 0.5 to 6 hours, preferably 1 to 4 hours. The calcination can be carried out in any atmosphere, for example, air or an inert atmosphere, and the inert atmosphere includes an inert gas including nitrogen, helium, argon, etc.

[0058] When the catalytic cracking catalyst according to the present invention is used in a catalytic cracking process, the catalytic cracking catalyst can be added separately to a catalytic cracking reactor or mixed with other catalytic cracking catalysts. For example, the catalytic cracking catalyst according to the present invention can be used as a catalytic cracking aid. When the catalytic cracking catalyst according to the present invention is mixed with other catalytic cracking catalysts, the amount of the catalytic cracking catalyst according to the present invention is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, based on the total amount of the catalytic cracking catalyst according to the present invention and the other catalytic cracking catalyst. Examples of other catalytic cracking catalysts include catalytic cracking catalysts containing Y-type molecular sieves.

[0059] In general, compared with the prior art, the catalytic cracking catalyst according to the present invention has a rich mesoporous structure due to the use of the large particle size sol of the present invention, and the pore volume of the mesopores of 4-50 nm accounts for more than 60% of the total pore volume, which is favorable to improving the diffusion ability of the feed molecules and product molecules when used in the catalytic cracking process, thereby significantly improving the yield and selectivity of low-carbon olefins.

[0060] Specifically, the rich mesoporous structure of the catalytic cracking catalyst according to the present invention is mainly derived from the pore structure generated by the accumulation of colloidal particles of the large particle size sol contained therein. The large particle size sol contained in the catalytic cracking catalyst according to the present invention has functions in at least two aspects: on the one hand, the large particle size sol is dispersed on the surface of the zeolite molecular sieve and clay, and fully exerts the binding property to increase the strength of the catalyst; on the other hand, the colloidal particles are accumulated to form a pore structure, and since the colloidal particle size of the large particle size sol of the present invention is concentrated in the range of 20 to 50 nm, a rich mesoporous structure can be formed by the accumulation of large particle size particles. In contrast, conventional sols such as alumina sol and acidified pseudoboehmite generally have a particle size smaller than 5 nm, and when particles with a particle size smaller than this are accumulated, a rich mesoporous structure cannot be formed and may even clog the pore structure of the molecular sieve.

[0061] Furthermore, according to the TEM images and average particle size distributions shown in Figures 1, 2 and 4, the particle size distribution of aluminum phosphate sol prepared by conventional techniques is non-uniform and the particle size is small, typically less than 10 nm. In contrast, the large particle size sol prepared by the method of the present invention has a large particle size (20 to 50 nm) and a uniform distribution, which solves the problem of the unclear mesoporous structure of the catalyst caused by the small particle size and non-uniform distribution of conventional aluminum phosphate sol.

[0062] The present invention is further illustrated through the following examples, which are intended to help those skilled in the art to better understand the nature of the present invention and the advantageous effects provided by it, but the examples should not be construed as limiting the scope of the present invention in any way.

[0063] [Example] The raw materials used in the following Examples and Comparative Examples are as follows: Kaolin was from Suzhou Kaolin Company, with a solid content of 76 wt%; Pseudoboehmite was from Shandong Aluminum Company, with a solid content of 62 wt%; The silica sol had a solid content of 27 wt % and a pH of 2–3; The H-type β zeolite had a solid content of 75 wt%, SiO2 / Al2O3 molar ratio = 25, and Na2O content of 0.15 wt%; The H-type ZSM-5 zeolite had a SiO2 / Al2O3 molar ratio = 42, a Na2O content of 3.5 wt%, and a solid content of 80 wt%; The phosphorus-modified ZSM-5 zeolite had a SiO2 / Al2O3 molar ratio = 45, a Na2O content of 0.12 wt%, a P2O5 content of 2.1 wt%, and a solid content of 83 wt%; Phosphoric acid was manufactured by Beijing Chemical Works, analytical grade specifications, and had a mass concentration of 85%.

[0064] Specific surface area and pore volume analysis: Measured by low-temperature static nitrogen adsorption capacity method using an automatic adsorption apparatus ASAP 2405N V1.01 manufactured by Micromeritics, USA. The sample was 1.33 x 10 -2 The sample is vacuum degassed at 300°C and 77.4K for 4 hours, and N2 is used as the adsorption medium to measure the adsorption / desorption isotherm of the sample at 77.4K. The specific surface area of ​​the sample is calculated according to the BET equation, and the volume of N2 adsorbed by the sample at a relative pressure of p / p0=0.98 is calculated; the volume is then converted to the volume of liquid nitrogen, i.e., the total pore volume; the micropore volume is calculated according to the t-plot method; the difference between these two volumes is the volume of mesopores and macropores with a size of 2-100 nm, and the pore volume of mesopores with a size of 4-50 nm is calculated by the peak split fitting method. The pore size distribution is calculated using the data of the BJH desorption pore size distribution.

[0065] Measurement of colloid particle size: Analysis is performed using a JEOL (JEOL Ltd.) JEM-2000FX-II transmission electron microscope. The average particle size of colloid particles is determined by randomly measuring the projections of 50 colloid particles in the TEM image of the sample and taking the average of the maximum circumference diameter.

[0066] Catalyst strength: The catalyst is placed in a fixed device and blown with constant airflow for 5 hours. The average wear rate of the last 4 hours, excluding the first hour, is the wear index of the catalyst (unit: % / hour). The method and standard are: Airlift method Q / SYLS0518-2002.

[0067] Evaluation of catalytic cracking catalyst: The catalytic cracking catalyst was aged in a fixed bed aging apparatus at 800°C for 17 hours with 100% steam by volume, and then evaluated in an ACE apparatus. The properties of the reaction feedstock oil are shown in Table 4, the reaction temperature was 500°C, the catalyst / oil weight ratio was 6, and the WHSV was 16s. -1 Conversion rate=gasoline yield+liquefied gas yield+carbonized gas yield+coke yield, C4 olefin selectivity=C4 olefin yield / conversion rate.

[0068] The following Examples 1 to 5 are examples in which a large particle sol was prepared according to the method of the present invention.

[0069] Example 1 First, 493 g of pseudoboehmite was mixed with 1,546 g of deionized water and stirred at room temperature (25°C) for 60 minutes to obtain a first slurry with a solid content of 15 wt%. Next, 727 g of 85 wt% phosphoric acid solution was added to the first slurry and stirred at 45°C for 60 minutes to obtain a second slurry with a solid content of 33 wt%. Next, 283 g of silica sol was added to the second slurry and stirred continuously at 45°C for 45 minutes to obtain a third slurry with a solid content of 33 wt%. Finally, the third slurry was left to stand at 45°C for 48 hours to obtain a large particle size sol A1 according to the method of the present invention.

[0070] Example 2 First, 413 g of pseudoboehmite was mixed with 868 g of deionized water and stirred at room temperature for 90 minutes to obtain a first slurry with a solid content of 15 wt%. Then, 839 g of 85 wt% phosphoric acid solution was added to the first slurry and stirred at 50°C for 60 minutes to obtain a second slurry with a solid content of 38 wt%. Then, 114 g of silica sol was added to the second slurry and stirred continuously at 50°C for 30 minutes to obtain a third slurry with a solid content of 38 wt%. Finally, the third slurry was left to stand at 50°C for 12 hours to obtain a large particle size sol A2 according to the method of the present invention.

[0071] Example 3 First, 363 g of pseudoboehmite was mixed with 1,888 g of deionized water and stirred at room temperature for 60 minutes to obtain a first slurry with a solid content of 10 wt%. Then, 885 g of 85 wt% phosphoric acid solution was added to the first slurry and stirred at 55°C for 60 minutes to obtain a second slurry with a solid content of 31 wt%. Then, 83 g of silica sol was added to the second slurry and stirred continuously at 55°C for 60 minutes to obtain a third slurry with a solid content of 31 wt%. Finally, the third slurry was left to stand at 40°C for 24 hours to obtain a large particle size sol A3 according to the method of the present invention.

[0072] Example 4 First, 299 g of pseudoboehmite was mixed with 2,017 g of deionized water and stirred at room temperature for 45 minutes to obtain a first slurry with a solid content of 8 wt%. Then, 911 g of 85 wt% phosphoric acid solution was added to the first slurry and stirred at 50°C for 90 minutes to obtain a second slurry with a solid content of 30 wt%. Then, 151 g of silica sol was added to the second slurry and stirred continuously at 50°C for 30 minutes to obtain a third slurry with a solid content of 30 wt%. Finally, the third slurry was left to stand at 35°C for 24 hours to obtain a large particle size sol A4 according to the method of the present invention.

[0073] Example 5 First, 268 g of pseudoboehmite was mixed with 3,059 g of deionized water and stirred at room temperature for 60 minutes to obtain a first slurry with a solid content of 5 wt%. Then, 979 g of 85 wt% phosphoric acid solution was added to the first slurry and stirred at 60°C for 90 minutes to obtain a second slurry with a solid content of 23 wt%. Then, 6 g of silica sol was added to the second slurry and stirred continuously at 60°C for 30 minutes to obtain a third slurry with a solid content of 23 wt%. Finally, the third slurry was left to stand at 60°C for 12 hours to obtain a large particle size sol A5 according to the method of the present invention.

[0074] Comparative Example 1 A comparative sol was prepared according to the method of Example 1, except that no silica sol was added.

[0075] First, 534 g of pseudoboehmite was mixed with 1,674 g of deionized water and stirred at room temperature for 60 minutes to obtain a first slurry with a solid content of 15 wt %. Next, 787 g of an 85 wt % phosphoric acid solution was added to the first slurry and stirred at 45° C. for 60 minutes to obtain a second slurry with a solid content of 33 wt %. This second slurry was left to stand at 45° C. for 48 hours to obtain a comparative sol DA1.

[0076] Comparative Example 2 A comparative sol was prepared according to the method of Example 1, except that no aging treatment was carried out.

[0077] First, 493 g of pseudoboehmite was mixed with 1,546 g of deionized water and stirred at room temperature for 60 minutes to obtain a first slurry with a solid content of 15 wt%. Then, 727 g of an 85 wt% phosphoric acid solution was added to the first slurry and stirred at 45°C for 60 minutes to obtain a second slurry with a solid content of 33 wt%. Then, 283 g of silica sol was added to the second slurry and stirred continuously at 45°C for 45 minutes to obtain a third slurry with a solid content of 33 wt%; thus, comparative sol DA2 was obtained.

[0078] Comparative Example 3 A comparative sol was prepared according to the method of Example 1 of CN1417296A, in which the difference from the above-mentioned Examples 1 to 5 is that no silica sol was added and no aging treatment was performed.

[0079] 534 g of pseudoboehmite was mixed with 1,674 g of deionized water and stirred at room temperature for 30 minutes, and then 787 g of 85 wt % phosphoric acid solution was added to the slurry under stirring. After stirring at 70° C. for 45 minutes, a colorless and transparent phosphorus-containing alumina sol, i.e., comparative sol DA3, was obtained.

[0080] The physicochemical properties of the sols obtained in Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1. TEM images of the sols obtained in Example 1 and Comparative Example 3 are shown in Figs.

[0081] [Table 1]

[0082] As can be seen from Table 1 and Figures 1 and 2, the sol obtained according to the production method of the present invention has a larger sol particle size and a more uniform distribution of the sol particle size compared to the comparative example, which is helpful in forming a mesoporous structure and improving the yield and selectivity of C4 olefins.

[0083] The following Examples 6 to 10 are examples of producing catalytic cracking catalysts containing a large particle size sol according to the present invention.

[0084] Example 6 Add 428g of kaolin and 1,604g of decationized water to a slurrying tank and slurried for 60 minutes, then add 286g of H-type β zeolite slurry (wherein the slurry contains 167g of H (hydrogen type) β zeolite and has a solid content of 35% by weight) and stir for 30 minutes; finally add 227g of the large particle sol (A1) obtained in Example 1 and stir for 15 minutes to obtain a slurry with a solid content of 19.7% by weight. Then, the obtained slurry is spray-formed and dried, and calcined at 500°C for 2 hours to obtain a catalytic cracking catalyst C1 containing a large particle sol according to the present invention.

[0085] Example 7 349g of kaolin and 976g of decationized water were added to a slurrying tank, and the mixture was slurried for 60 minutes. Then, 289g of the large particle sol (A2) obtained in Example 2 was added, and the mixture was stirred continuously for 60 minutes. Finally, 329g of H-type β zeolite slurry (wherein the slurry contained 167g of H-type β zeolite and had a solid content of 38% by weight) was added, and the mixture was stirred for 30 minutes to obtain a slurry with a total solid content of 25.7% by weight. The obtained slurry was then spray-formed and dried, and calcined at 550°C for 1.5 hours to obtain a catalytic cracking catalyst C2 containing a large particle sol according to the present invention.

[0086] Example 8 296g of kaolin, 403g of the large particle sol (A3) obtained in Example 3, and 647g of decationized water were mixed to form a slurry, and stirred for 90 minutes. Then, 500g of H-β zeolite slurry (wherein the slurry contained 200g of H-β zeolite and had a solid content of 30 wt%) was added to the above slurry, and stirred for 60 minutes to obtain a slurry with a total solid content of 32.3 wt%. Then, the obtained slurry was spray-formed and dried, and calcined at 600°C for 1.0 hour to obtain a catalytic cracking catalyst C3 containing a large particle sol according to the present invention.

[0087] Example 9 543g of β-zeolite slurry (wherein the slurry contained 253g of H-β-zeolite and had a solid content of 35wt%) was mixed with 500g of the large particle sol (A4) obtained in Example 4, and stirred for 60 minutes. Then, 800g of kaolin slurry (wherein the slurry contained 211g of kaolin and had a solid content of 20wt%) was added to the slurry, and stirred continuously for 60 minutes to obtain a slurry with a solid content of 27.1wt%. Then, the obtained slurry was spray-formed and dried, and calcined at 500°C for 2.0 hours to obtain a catalytic cracking catalyst C4 containing a large particle sol according to the present invention.

[0088] Example 10 99g of kaolin and 276g of decationized water were added to a slurry tank, and the slurry was made for 60 minutes. Then, 643g of H-β zeolite slurry (wherein the slurry contained 300g of H-β zeolite and had a solid content of 35% by weight) was added and stirred for 30 minutes. Finally, 870g of the large particle sol (A5) obtained in Example 5 was added and stirred for 30 minutes to obtain a slurry with a solid content of 26.5% by weight. The obtained slurry was then spray-formed and dried, and calcined at 450°C for 2 hours to obtain a catalytic cracking catalyst C5 containing a large particle sol according to the present invention.

[0089] [Comparative Examples 4 to 6] In Comparative Examples 4 to 6, catalytic cracking catalysts were produced according to the method of Example 6, except that the large particle size sol (A1) prepared in Example 1 used in Example 6 was replaced with the sol (DA1) prepared in Comparative Example 1, the sol (DA2) prepared in Comparative Example 2, or the sol (DA3) prepared in Comparative Example 3. Thus, catalytic cracking catalysts DC1 to DC3 were obtained.

[0090] The physicochemical properties of the catalysts obtained in Examples 6 to 10 and Comparative Examples 4 to 6 are shown in Table 2. The pore size distribution of the catalysts is shown in FIG.

[0091] [Table 2]

[0092] As can be seen from Table 2 and FIG. 3, compared with the comparative example, the catalytic cracking catalyst containing the large particle size sol produced according to the method of the present invention has a significantly increased total pore volume, i.e., a rich pore structure, and the proportion of mesopores of 4 to 50 nm is significantly increased, reaching 60% or more of the total pore volume.

[0093] [Examples 11 to 15 and Comparative Examples 7 to 9] In the following Examples 11 to 15 and Comparative Examples 7 to 9, the catalytic cracking performance and the ability to improve the C4 olefin yield of the catalyst containing the large particle sol of the present invention and the comparative catalyst were evaluated, respectively.

[0094] Catalysts C1-C5 containing large particle sol produced according to the method of the present invention and catalysts DC1-DC3 produced in the comparative examples were mixed with an industrial catalyst (trade name HSC, provided by Sinopec Catalyst Co.Ltd. Qilu Branch, main properties are shown in Table 3) in a mass ratio of 2:8 to obtain a catalyst mixture. This catalyst mixture was aged in 100% steam at 800°C for 17 hours in a fixed bed aging apparatus. Then, evaluation was performed in an ACE apparatus. The properties of the feedstock oil used in the evaluation are shown in Table 4. The reaction temperature, catalyst / oil ratio, weight space velocity, and evaluation results are shown in Table 5. Here, conversion rate = gasoline yield + liquefied gas yield + dry gas yield + coke yield; C4 olefin selectivity = C4 olefin yield / conversion rate.

[0095] [Table 3]

[0096] [Table 4]

[0097] [Table 5]

[0098] As can be seen from Table 5, compared with the comparative examples, when a catalytic cracking catalyst containing a large particle sol produced in the examples of the present invention is used in the catalytic cracking reaction of hydrocarbon oil, the yield of C4 olefins in the catalytic cracking reaction product is improved and the C4 olefin selectivity is significantly improved.

[0099] [Example Z1] First, 483 g of pseudoboehmite and 1,514 g of deionized water were mixed and stirred at room temperature for 60 minutes to obtain a first slurry with a solid content of 15 wt%. Then, 736 g of 85 wt% phosphoric acid solution was added to the first slurry and stirred at 45°C for 60 minutes to obtain a second slurry with a solid content of 34 wt%. Then, 277 g of silica sol was added to the second slurry and stirred continuously at 45°C for 45 minutes to obtain a third slurry with a solid content of 33 wt%. Finally, the third slurry was left to stand at 45°C for 24 hours to obtain a large particle size sol ZA1 prepared according to the method of the present invention.

[0100] [Example Z2] First, 399 g of pseudoboehmite and 1,250 g of deionized water were mixed and stirred at room temperature for 90 minutes to obtain a first slurry with a solid content of 15 wt%. Then, 851 g of 85 wt% phosphoric acid solution was added to the first slurry and stirred at 50°C for 60 minutes to obtain a second slurry with a solid content of 39 wt%. Then, 110 g of silica sol was added to the second slurry and stirred continuously at 50°C for 60 minutes to obtain a third slurry with a solid content of 38 wt%. Finally, the third slurry was left to stand at 50°C for 24 hours to obtain a large particle size sol ZA2 prepared according to the method of the present invention.

[0101] [Example Z3] First, 352 g of pseudoboehmite and 1,831 g of deionized water were mixed and stirred at room temperature for 60 minutes to obtain a first slurry with a solid content of 10 wt%. Next, 894 g of an 85 wt% phosphoric acid solution was added to the first slurry and stirred at 55°C for 60 minutes to obtain a second slurry with a solid content of 31 wt%. Next, 81 g of silica sol was added to the second slurry and stirred continuously at 55°C for 60 minutes to obtain a third slurry with a solid content of 31 wt%. Finally, the third slurry was left to stand at 40°C for 24 hours to obtain a large particle size sol ZA3 prepared according to the method of the present invention.

[0102] [Example Z4] First, 291 g of pseudoboehmite and 1,967 g of deionized water were mixed and stirred at room temperature for 45 minutes to obtain a first slurry with a solid content of 8 wt%. Next, 917 g of 85 wt% phosphoric acid solution was added to the first slurry and stirred at 50°C for 90 minutes to obtain a second slurry with a solid content of 30 wt%. Next, 147 g of silica sol was added to the second slurry and stirred continuously at 50°C for 30 minutes to obtain a third slurry with a solid content of 30 wt%. Finally, the third slurry was left to stand at 35°C for 48 hours to obtain a large particle size sol ZA4 prepared according to the method of the present invention.

[0103] [Example Z5] First, 277 g of pseudoboehmite and 3,163 g of deionized water were mixed and stirred at room temperature for 60 minutes to obtain a first slurry with a solid content of 5 wt%. Next, 972 g of 85 wt% phosphoric acid solution was added to the first slurry and stirred at 60°C for 90 minutes to obtain a second slurry with a solid content of 23 wt%. Next, 6 g of silica sol was added to the second slurry and stirred continuously at 60°C for 30 minutes to obtain a third slurry with a solid content of 23 wt%. Finally, the third slurry was left to stand at 60°C for 12 hours to obtain a large particle size sol ZA5 prepared according to the method of the present invention.

[0104] [Comparative example Z1] A comparative sol was prepared according to the method of Example Z2, except that no silica sol was added.

[0105] First, 411 g of pseudoboehmite and 1,288 g of deionized water were mixed and stirred at room temperature for 60 minutes to obtain a first slurry with a solid content of 15 wt%. Next, 877 g of an 85 wt% phosphoric acid solution was added to the first slurry and stirred at 45°C for 60 minutes to obtain a second slurry with a solid content of 39 wt%. This second slurry was left to stand at 45°C for 48 hours to obtain a comparative sol DZA1.

[0106] [Comparative Example Z2] A comparative sol was prepared according to the method of Example Z2, except that no aging treatment was performed.

[0107] First, 386 g of pseudoboehmite and 1,211 g of deionized water were mixed and stirred at room temperature for 60 minutes to obtain a first slurry with a solid content of 15 wt%. Next, 824 g of an 85 wt% phosphoric acid solution was added to the first slurry and stirred at 45°C for 60 minutes to obtain a second slurry with a solid content of 39 wt%. Next, 222 g of silica sol was added to the second slurry and stirred continuously at 45°C for 45 minutes to obtain a third slurry with a solid content of 38 wt%. In this way, a comparative sol DZA2 was obtained.

[0108] [Comparative Example Z3] A comparative sol was prepared according to the method of Example 1 of CN1417296A with reference to the preparation method of Comparative Example 3. The difference from the above Examples Z1 to Z5 is that no silica sol was added and no aging treatment was performed.

[0109] 534 g of pseudoboehmite and 1,674 g of deionized water were mixed and stirred at room temperature for 30 minutes. 787 g of 85 wt % phosphoric acid solution was added to the slurry while stirring. After stirring at 70°C for 45 minutes, a colorless and transparent phosphorus-containing alumina sol with a solid content of 33% was obtained, which was designated as comparative sol DZA3.

[0110] The physicochemical properties of the sols obtained in Examples Z1 to Z5 and Comparative Examples Z1 to Z3 are shown in Table Z1. TEM images of the sols obtained in Example Z1 and Comparative Example Z3 are shown in Figures 4 and 2, respectively.

[0111] [Table 6]

[0112] As can be seen from Table Z1, Figure 4 and Figure 2, compared with the comparative example, the sol obtained according to the preparation method of the present invention has a larger particle size and a more uniform particle size distribution, which is conducive to the formation of mesoporous structure, which is less likely to block the flow path of the molecular sieve, so that propylene can diffuse quickly and avoid secondary reactions, and therefore the yield and selectivity of propylene are improved.

[0113] The following Examples Z6 to Z10 are examples of producing catalytic cracking catalysts containing a large particle size sol according to the present invention.

[0114] [Example Z6] 355g of kaolin and 1,145g of decationized water were added to a slurry tank, and slurried for 60 minutes, after which 400g of HZSM-5 zeolite slurry (wherein the slurry contained 175g of HZSM-5 zeolite and had a solid content of 35% by weight) was added, stirred for 30 minutes, and finally 273g of the large particle sol (ZA1) obtained in Example Z1 was added, and stirred for 15 minutes. The solid content of the obtained slurry was 23.0% by weight. The obtained slurry was then spray-formed and dried, and calcined at 500°C for 2 hours to obtain a catalytic cracking catalyst ZC1 containing a large particle sol according to the present invention.

[0115] [Example Z7] 237g of kaolin and 888g of deionized water were added to a slurry tank and slurried for 60 minutes, then 368g of the large particle sol (ZA2) obtained in Example Z2 was added and stirred continuously for 60 minutes, and finally 474g of HZSM-5 zeolite slurry (wherein the slurry contained 225g of HZSM-5 zeolite and had a solid content of 38 wt%) was added and stirred for 30 minutes. The total solid content of the obtained slurry was 25.4 wt%. The obtained slurry was then spray-formed and dried, and calcined at 550°C for 1.5 hours to obtain catalytic cracking catalyst ZC2 containing large particle sol according to the present invention.

[0116] [Example Z8] 197g of kaolin, 469g of the large particle sol (ZA3) obtained in Example Z3, and 683g of deionized water were mixed to form a slurry, and stirred for 90 minutes. Then, 667g of phosphorus-modified ZSM-5 zeolite slurry (wherein the slurry contained 241g of phosphorus-modified ZSM-5 zeolite and had a solid content of 30 wt%) was added to the slurry, and stirred for 60 minutes. The total solid content of the obtained slurry was 31.4 wt%. Then, the obtained slurry was spray-formed and dried, and calcined at 600°C for 1.0 hour to obtain a catalytic cracking catalyst ZC3 containing a large particle sol according to the present invention.

[0117] [Example Z9] 643g of phosphorus-modified ZSM-5 zeolite slurry (wherein the slurry contained 271g of phosphorus-modified ZSM-5 zeolite and had a solid content of 35wt%) was mixed with 583g of the large particle sol (ZA4) obtained in Example Z4, and stirred for 60 minutes. Then, 500g of kaolin slurry (wherein the slurry contained 132g of kaolin and had a solid content of 20wt%) was added to the slurry, and stirred continuously for 60 minutes. The solid content of the obtained slurry was 29.0wt%. Then, the obtained slurry was spray-formed and dried, and calcined at 500°C for 2 hours to obtain a catalytic cracking catalyst ZC4 containing a large particle sol according to the present invention.

[0118] [Example Z10] 66g of kaolin and 247g of deionized water were added to the slurry tank and slurried for 60 minutes; then 714g of ZSM-5 zeolite slurry (wherein the slurry contained 313g of ZSM-5 zeolite and had a solid content of 35wt%) was added and stirred for 30 minutes; finally, 870g of the large particle sol (ZA5) obtained in the above Example Z5 was added and stirred for 30 minutes. The solid content of the obtained slurry was 26.5wt%. The obtained slurry was then spray-formed and dried, and calcined at 450°C for 2 hours to obtain the catalytic cracking catalyst ZC5 containing the large particle sol according to the present invention.

[0119] [Comparative Examples Z4 to Z6] In Comparative Examples Z4 to Z6, the sol (DZA1) prepared in Comparative Example Z1, the sol (DZA2) prepared in Comparative Example Z2, and the sol (DZA3) prepared in Comparative Example Z3 were used instead of the large particle sol (ZA2) (prepared in Example Z2) used in Example Z7. The catalytic cracking catalysts were produced according to the method of Example Z7. Thus, comparative catalytic cracking catalysts DZC1 to DZC3 were obtained.

[0120] The physicochemical properties of the catalysts obtained in Examples Z6 to Z10 and Comparative Examples Z4 to Z6 are shown in Table Z2. The pore size distribution of the catalysts is shown in FIG.

[0121] [Table 7]

[0122] As can be seen from Table Z2 and FIG. 5, compared with the comparative example, the catalytic cracking catalyst containing the large particle size sol prepared according to the method of the present invention has a significantly increased total pore volume, that is, it has a rich pore structure, and the proportion of mesopores of 4 to 50 nm is significantly increased, reaching more than 60% of the total pore volume.

[0123] [Examples Z11 to Z15 and Comparative Examples Z7 to Z9] In the following Examples Z11 to Z15 and Comparative Examples Z7 to Z9, the catalytic cracking performance and the propylene yield increasing ability of the catalyst containing the large particle size sol according to the present invention and the comparative catalyst were evaluated, respectively.

[0124] Catalysts ZC1-ZC5 containing large particle size sol prepared according to the method of the present invention and catalysts DZC1-DZC3 prepared in comparative examples were mixed with HSC industrial catalyst (provided by Qilu branch of Sinopec Catalyst Co. Ltd., main properties are shown in Table Z3) in a mass ratio of 5:95 to obtain a catalyst mixture. The catalyst mixture was aged in 100% steam at 800 °C for 17 hours in a fixed bed aging apparatus. Then, evaluation was performed in an ACE apparatus. The properties of the feedstock oil used in the evaluation are shown in Table Z4. The reaction temperature, catalyst / oil ratio and evaluation results are shown in Table Z5. Here, conversion rate = gasoline yield + liquefied gas yield + dry gas yield + coke yield; propylene selectivity = propylene yield / conversion rate.

[0125] [Table 8]

[0126] [Table 9]

[0127] [Table 10]

[0128] As can be seen from Table Z5, compared with the comparative examples, when the catalytic cracking catalyst containing the large particle sol produced in the examples of the present invention is used in the catalytic cracking reaction of hydrocarbon oil, the propylene yield in the catalytic cracking reaction product is significantly increased and the propylene selectivity is significantly increased.

[0129] The present invention has been illustrated in combination with the preferred embodiments as described above. These embodiments are merely exemplary and illustrative. Based on this, various substitutions and improvements can be made to the present application, all of which are within the protection scope of the present invention. [Brief description of the drawings]

[0130] [Figure 1]FIG. 1 is a TEM image of catalytic cracking catalyst A1 prepared according to Example 1. [Diagram 2] FIG. 2 is a TEM image of catalytic cracking catalyst DA3 prepared according to Comparative Example 3. [Diagram 3] FIG. 3 is a graph of the pore size distribution of catalytic cracking catalysts prepared according to Example and Comparative Example 3. [Figure 4] FIG. 4 is a TEM image of catalytic cracking catalyst ZA1 prepared according to Example Z1. [Diagram 5] FIG. 5 is a graph of the pore size distribution of catalytic cracking catalysts prepared according to Example Z2 and Comparative Example Z3.

Claims

1. 10 to 40 wt. % Al based on the dry weight of the large particle sol ２ O ３ , 50 to 85 wt.% P ２ O ５ and 0.2 to 10 wt. % SiO ２ A large particle sol comprising P ２ O ５ :Al ２ O ３ The mass ratio of SiO is (1.5-5.0):

1. ２ :Al ２ O ３ The mass ratio of the above is (0.01 to 0.3):1, and the average particle size of the large particle sol is in the range of 20 to 50 nm.

2. 15 to 35 wt. % Al on a dry basis ２ O ３ , 55 to 80 wt.% P ２ O ５ and 0.5 to 8.0 wt. % SiO ２ P ２ O ５ :Al ２ The mass ratio of O is (2.0 to 4.5):1, SiO ２ :Al ２ O ３ 2. The large particle sol according to claim 1, wherein the mass ratio of

3. 2. The large particle sol according to claim 1, having an average particle size distribution in the range of 3.25 to 45 nm.

4. A composition for use in catalytic cracking, comprising, based on the dry weight of the composition, 15 to 50 wt % of beta zeolite and / or ZSM-5 zeolite, 10 to 75 wt % of clay, and 10 to 50 wt % of the large particle sol according to claim 1.

5. 5. The composition of claim 4, comprising, based on the dry weight of the composition, 20 to 40% by weight of beta zeolite, 20 to 65% by weight of clay, and 15 to 45% by weight of large particle size sol.

6. The beta zeolite is selected from the group consisting of H-type beta zeolite, Na-type beta zeolite, phosphorus- and / or metal-modified beta zeolite, and metal-modified beta zeolite, or any combination thereof, and is preferably H-type beta zeolite, and SiO in the beta zeolite. ２ Al ２ O ３ The composition of claim 4, wherein the molar ratio to is 20 to 50.

7. The composition according to claim 6, wherein the metal in the metal-modified β zeolite is one or more selected from the group consisting of La, Ce, Pr, Zr, Ti, Fe, Cu, and Mg.

8. 5. The composition of claim 4, wherein the ZSM-5 zeolite is selected from the group consisting of HZSM-5 zeolite, ZSM-5 zeolite containing phosphorus and / or iron, ZSM-5 zeolite containing phosphorus and / or rare earth, and modified ZSM-5 zeolite, and the modified ZSM-5 zeolite is selected from the group consisting of Zn, Cu, Mg, Zr, Ti, or B modified ZSM-5 zeolite.

9. 5. The composition of claim 4, wherein the clay is one or more selected from the group consisting of kaolin, rectorite, diatomaceous earth, montmorillonite, bentonite, and sepiolite.

10. A catalytic cracking catalyst produced by drying and calcining the composition according to claim 4, wherein the pore size distribution is determined by a low-temperature nitrogen adsorption method, the total pore volume of the catalytic cracking catalyst is 0.200 mL / g or more, and the pore volume of mesopores having pore diameters of 4 to 50 nm accounts for 60% or more of the total pore volume.

11. 11. The catalytic cracking catalyst according to claim 10, wherein the pore size distribution is determined by low-temperature nitrogen adsorption and the total pore volume of the catalytic cracking catalyst is 0.200 to 0.300 mL / g.

12. The catalytic cracking catalyst according to claim 10, wherein the pore volume of mesopores having a pore diameter of 4 to 50 nm in the catalytic cracking catalyst accounts for 65 to 85% of the total pore volume.

13. A method for producing the catalytic cracking catalyst according to any one of claims 10 to 12, using the composition according to any one of claims 4 to 9, comprising the following steps: (1) A large particle sol is prepared by the following steps: (1a) mixing an aluminum source with deionized water and stirring at room temperature for at least 30 minutes to obtain a first slurry having a solids content of 5 to 25 wt%; (1b) mixing the first slurry with a phosphorus source and stirring at a temperature of 60°C or less for 30 minutes or more to obtain a second slurry having a solid content of 15 to 50 wt%; (1c) adding silica sol to the second slurry, mixing, and stirring at a temperature of 60°C or less for 30 minutes or more to obtain a third slurry having a solid content of 15 to 50% by weight; (1d) The third slurry is allowed to stand at 20 to 60°C for 1 to 72 hours for aging treatment to obtain a large particle size sol; Here, P relative to the amount of aluminum source ２ O ５ The mass ratio of the amount of phosphorus source calculated as: (1.5-5.0):1, and Al ２ O ３ SiO relative to the amount of aluminum source calculated as ２ The mass ratio of the amount of silica sol calculated as: (0.01-0.3):1; (2) uniformly mixing clay, β zeolite and / or ZSM-5 zeolite, and the large particle size sol to obtain a fourth slurry having a solid content of 10 to 50% by weight; spray-forming, drying, and calcining the fourth slurry to obtain the catalytic cracking catalyst, wherein the weight ratio of the β zeolite, the clay, and the large particle size sol is (15 to 50):(10 to 75):(10 to 50) on a dry basis; or the weight ratio of the ZSM-5 zeolite, the clay, and the large particle size sol is (20 to 50):(10 to 70):(10 to 45) on a dry basis.

14. 14. The method of claim 13, wherein in step (1a), the mixing and stirring continues for 30 to 60 minutes.

15. 14. The method of claim 13, wherein step (1b) is carried out at a temperature of 35 to 55°C and the mixing and stirring lasts for 30 to 90 minutes.

16. 14. The method of claim 13, wherein step (1c) is carried out at a temperature of 35 to 55°C and the mixing and stirring lasts for 30 to 90 minutes.

17. 14. The method of claim 13, wherein the aluminum source is one or more selected from the group consisting of pseudoboehmite, alumina, boehmite, gibbsite, and diaspore; the phosphorus source is one or more selected from the group consisting of phosphoric acid, phosphorous acid, and hypophosphorous acid; and the clay is one or more selected from the group consisting of kaolin, rectorite, diatomaceous earth, montmorillonite, bentonite, and sepiolite.

18. The beta zeolite is selected from the group consisting of H-type beta zeolite, Na-type beta zeolite, phosphorus-modified beta zeolite, and metal-modified beta zeolite, or any combination thereof, and SiO in the beta zeolite ２ Al ２ O ３ The molar ratio to 14. The method of claim 13, wherein the ZSM-5 zeolite is selected from the group consisting of HZSM-5 zeolite, ZSM-5 zeolite containing phosphorus and / or iron, ZSM-5 zeolite containing phosphorus and / or rare earth, modified ZSM-5 zeolite, or any combination thereof; and the modified ZSM-5 zeolite is selected from the group consisting of Zn, Cu, Mg, Zr, Ti, or B modified ZSM-5 zeolite.

19. 10 to 40 wt. % Al based on dry weight ２ O ３ , 50 to 85 wt.% P ２ O ５ and 0.2 to 10 wt. % SiO ２ A large particle sol comprising P ２ O ５ :Al ２ O ３ The mass ratio of SiO is (1.5-5.0):

1. ２ :Al ２ O ３ The mass ratio of the large particle sol is (0.01-0.3):1; the average particle size of the large particle sol is 20-50 nm, and the large particle sol is prepared by the following method: (1a) mixing an aluminum source with deionized water and stirring at room temperature for at least 30 minutes to obtain a first slurry having a solids content of 5 to 25 wt%; (1b) mixing the first slurry with a phosphorus source and stirring at a temperature of 60°C or less for 30 minutes or more to obtain a second slurry having a solid content of 15 to 50 wt%; (1c) adding silica sol to the second slurry, mixing, and stirring at a temperature of 60°C or less for 30 minutes or more to obtain a third slurry having a solid content of 15 to 50% by weight; (1d) The third slurry is left to stand at 20 to 60° C. for 1 to 72 hours for aging treatment to obtain a large particle size sol.

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