Catalytic decomposition agent containing phosphorus-modified molecular sieves, method for producing the same, production system, and use thereof

Abstract

A catalytic cracking agent having an active component consisting of phosphorus-modified molecular sieve and non-phosphorus-modified molecular sieve, or an active component consisting of only phosphorus-modified molecular sieve. When the active component consists of phosphorus-modified molecular sieve and non-phosphorus-modified molecular sieve, the D value of phosphorus in the catalytic cracking agent measured by electron probe microanalyzer (EPMA) is 65% or more, preferably 68% or more, and when the active component consists of only phosphorus-modified molecular sieve, the D value of phosphorus in the catalytic cracking agent measured by electron probe microanalyzer (EPMA) is 82% or more, preferably 84% or more.

Description

Technical Field

[0001] The present invention relates to a cracking catalyst containing a phosphorus-modified molecular sieve, a method for producing the same, a production system thereof, and use thereof. More specifically, the present invention relates to a cracking catalyst containing a phosphorus-modified MFI structure molecular sieve, or a cracking promoter containing a phosphorus-modified MFI structure molecular sieve, a method for producing the same in a short step, a production system thereof, and use thereof.

Background Art

[0002] ZSM-5 molecular sieve / zeolite having an MFI structure is a zeolite / molecular sieve catalyst material developed by Mobil Corporation in the United States in 1972 and is widely used. The ZSM-5 molecular sieve has a three-dimensional cross-channel structure. The channels along the a-axis are straight channels with a cross-sectional dimension of 0.54×0.56 nm and are substantially circular. The channels along the b-axis are zigzag channels with a cross-sectional dimension of 0.51×0.56 nm and are elliptical. The ZSM-5 molecular sieve has an aperture composed of 10-membered rings and is located between small-pore zeolites and large-pore zeolites in terms of the aperture size, so it has a unique shape-selective catalytic effect. The ZSM-5 molecular sieve has a unique pore channel structure, good shape-selective catalysis and isomerization performance, high thermal stability and hydrothermal stability, a large specific surface area, a wide variation range of the silica-alumina ratio, a unique surface acidity, and relatively low carbon formation. It is widely used as a catalyst and a catalyst carrier and has achieved success in production processes such as alkylation, isomerization, disproportionation, catalytic cracking, methanol-gasoline, and methanol-olefin. The ZSM-5 molecular sieve has been introduced into catalytic cracking and C4 hydrocarbon catalytic cracking, shows excellent catalytic performance, and can greatly improve the yield of light olefins by utilizing its molecular shape selectivity.

[0003] Since 1983, ZSM-5 molecular sieves have been used as catalytic cracking octane-enhancing catalysts in catalytic cracking processes with the aim of improving the octane number and selectivity of lower carbon olefins in catalytic cracked gasoline. US3758403 was the first to report the production of an FCC catalyst using ZSM-5 as the active ingredient to increase propylene production together with REY. US5997728 discloses the use of unmodified ZSM-5 molecular sieves as an additive to increase propylene production. However, the yield of these propylenes was not high. While ZSM-5 molecular sieves have good shape selectivity and isomerization properties, their drawback is low hydrothermal stability, making them prone to deactivation under harsh high-temperature hydrothermal conditions and reducing catalytic performance.

[0004] In the 1980s, Mobil Corporation discovered that phosphorus could improve the hydrothermal stability of ZSM-5 molecular sieves, and simultaneously, that the modification of ZSM-5 molecular sieves with phosphorus could increase the yield of lower carbon olefins. Conventional additives typically contain phosphorus-activated ZSM-5, which selectively converts primary decomposition products (e.g., gasoline olefins) to C3 and C4 olefins. ZSM-5 molecular sieves can be modified after synthesis by introducing an appropriate amount of inorganic phosphorus compound, which can stabilize framework aluminum under severe hydrothermal conditions.

[0005] CN106994364A discloses a process for phosphorus-modified ZSM-5 molecular sieves. This process involves first mixing one or more phosphorus-containing compounds selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium phosphate with a ZSM-5 molecular sieve with a high alkali metal ion content to obtain a mixture having a phosphorus loading of at least 0.1% by weight (as P2O5). This mixture is then dried and calcined, followed by ammonium exchange and water washing steps to reduce the alkali metal ion content to 0.10% by weight or less, and then drying and hydrothermal aging steps at 400-1000°C under 100% water vapor. The phosphorus-containing ZSM-5 molecular sieves obtained by this process have a high total acid content, excellent decomposition conversion rate and propylene selectivity, and a relatively high liquefaction gas yield.

[0006] CN1506161A discloses a method for modifying hierarchical ZSM-5 molecular sieves. This method involves producing hierarchical ZSM-5 molecular sieves according to the conventional process of synthesis → filtration → ammonium exchange → drying → calcination, and then modifying the hierarchical ZSM-5 molecular sieves with phosphoric acid, drying and calcining to obtain phosphorus-modified hierarchical ZSM-5 molecular sieves, with the P2O5 loading typically ranging from 1 to 7% by weight. However, phosphoric acid or ammonium phosphate salts self-aggregate during the calcination process, forming phosphorus species in different aggregate states. In the hydrothermal treatment process, only the phosphate groups that have entered the pores interact with the framework aluminum to retain the B acid center, reducing the distribution of phosphorus species.

[0007] Modifying ZSM-5 molecular sieves with an appropriate amount of inorganic phosphorus compound can delay the dealuminization of the framework and improve its hydrothermal stability, as the phosphorus atoms bond to the distorted 4-coordinate framework aluminum to form weak B acid centers. However, modifying ZSM-5 molecular sieves with an excess of inorganic phosphorus compound clogs the pore channels of the molecular sieve, reducing pore volume and specific surface area, and occupying a large number of strong B acid centers. Furthermore, in prior art, phosphoric acid or ammonium phosphate salts self-polymerize during the calcination process to form phosphorus species in different aggregate states, resulting in insufficient coordination between phosphorus and framework aluminum, relatively low phosphorus utilization efficiency, and phosphorus modification not always yielding satisfactory improvements in hydrothermal stability. Therefore, there is an urgent need for novel techniques to promote coordination between phosphorus and framework aluminum, improve the hydrothermal stability of phosphorus-modified ZSM-5 molecular sieves, and further enhance their decomposition activity.

[0008] In this specification, catalytic cracking catalysts and catalytic cracking aids are collectively referred to as catalytic cracking agents. The difference between them lies in their active ingredients. Generally, a catalytic cracking agent containing only phosphorus-modified molecular sieves represents a catalytic cracking aid, while a catalytic cracking agent containing phosphorus-modified molecular sieves and at least one non-phosphorus-modified molecular sieve (i.e., an un-phosphorus-modified molecular sieve) represents a catalytic cracking catalyst.

[0009] In the prior art industrial production, the methods for producing catalytic cracking catalysts or catalytic cracking aids are similar (see Figures 1 and 2), and include the process of producing the final product of the catalytic cracking catalyst or catalytic cracking aid by phosphorus modification (impregnation with a phosphorus-containing solution) of an MFI structure molecular sieve, drying (flash drying), and a first calcination, mixing and molding of raw materials (including phosphorus-modified MFI structure molecular sieves and other molecular sieves (optional), inorganic binders, etc.), and a second calcination. In existing technology, two calcination steps are required to improve the hydrothermal stability of the phosphorus-exchange-modified MFI structure molecular sieve, resulting in high manufacturing costs and a relatively complex manufacturing method. [Overview of the project]

[0010] Aiming to address the problems of the prior art, namely the complex phosphorus reforming methods resulting from the need to improve the hydrothermal stability of molecular sieves such as MFI structure molecular sieves in catalytic cracking catalysts or catalytic cracking aids, and the relatively complex manufacturing methods of catalytic cracking catalysts or catalytic cracking aids, one objective of the present invention is to provide a simplified manufacturing method for catalytic cracking catalysts or catalytic cracking aids and the catalytic cracking catalyst or catalytic cracking aid obtained thereby (collectively referred to as catalytic cracking agents in the present invention). A second objective of the present invention is to provide a manufacturing system for the manufacturing process of the simplified method described above.

[0011] To achieve the above objective, the present invention provides a method for producing a catalytic decomposition agent (catalytic decomposition catalyst or catalytic decomposition aid), the method being (1) A process of mixing the following components as raw materials, forming the raw materials into a slurry, and molding it into a molded body: phosphorus-modified molecular sieve (e.g., phosphorus-modified MFI structure molecular sieve), optionally non-phosphorus-modified molecular sieve (e.g., FAU structure molecular sieve such as Y-type molecular sieve), inorganic binder, and optionally a second clay; (2) A step of subjecting the molded body to hydrothermal firing under atmospheric conditions in which external pressure is applied and an aqueous solution is added externally; The above-mentioned phosphorus-modified molecular sieve is obtained by impregnating (exchanging) a molecular sieve at a temperature of 0 to 150°C with an aqueous solution of a phosphorus-containing compound at a temperature of 0 to 150°C; The above hydrothermal firing process is carried out in an atmosphere containing 1-100% water vapor at a temperature of 200-800°C and a gauge pressure of 0.01-1.0 MPa.

[0012] To achieve the above objectives, the present invention further comprises a phosphorus-modified molecular sieve (e.g., a phosphorus-modified MFI structure molecular sieve) and a non-phosphorus-modified molecular sieve (e.g., a FAU structure molecular sieve such as a Y-type molecular sieve), or a phosphorus-modified molecular sieve alone. When the above active ingredient consists of a phosphorus-modified molecular sieve (e.g., a phosphorus-modified MFI structure molecular sieve) and a non-phosphorus-modified molecular sieve (e.g., a FAU structure molecular sieve such as a Y-type molecular sieve), the D value of phosphorus in the above catalytic decomposition agent measured by an electron probe microanalyzer (EPMA) is 65% or higher, preferably 68% or higher, or The present invention further provides an agent in which, when the above active ingredient consists solely of a phosphorus-modified molecular sieve (for example, a phosphorus-modified MFI structure molecular sieve), the D value of phosphorus in the catalytic decomposition agent measured by an electron probe microanalyzer (EPMA) is 82% or higher, preferably 84% or higher.

[0013] In the present invention, the catalytic decomposition agent or catalytic decomposition catalyst contains the following on a dry basis: 1-25% by weight of non-phosphorus modified molecular sieves (e.g., FAU structure molecular sieves such as Y-type molecular sieves); 5-50% by weight phosphorus-modified molecular sieves (e.g., phosphorus-modified MFI structure molecular sieves); 1-60% by weight of an inorganic binder; and, Optionally, 0-60% by weight of a second clay.

[0014] In the present invention, the catalytic decomposition agent or catalytic decomposition aid contains the following on a dry basis: 5-75% by weight of phosphorus-modified molecular sieves (e.g., phosphorus-modified MFI structure molecular sieves) without non-phosphorus-modified molecular sieves; 1-40% by weight of an inorganic binder; and, Optionally, 0-65% by weight of a second clay.

[0015] In the present invention, non-phosphorus-modified molecular sieves (for example, FAU structure molecular sieves such as Y-type molecular sieves) include at least one of PSRY molecular sieves, rare earth-containing PSRY molecular sieves, USY molecular sieves, rare earth-containing USY molecular sieves, REY molecular sieves, REHY molecular sieves, and HY molecular sieves.

[0016] In the present invention, the inorganic binder comprises at least one of pseudoboehmite, alumina sol, silica-alumina sol, water glass, and phosphorus-aluminum inorganic binder, preferably the inorganic binder contains a phosphorus-aluminum inorganic binder, and more preferably the inorganic binder is a phosphorus-aluminum inorganic binder. The phosphorus-aluminum inorganic binder is a phosphorus-aluminate binder and / or a first clay-containing phosphorus-aluminum inorganic binder. If the phosphorus-aluminum inorganic binder is a phosphorus-aluminate binder and / or a first clay-containing phosphorus-aluminum inorganic binder, the first clay-containing phosphorus-aluminum inorganic binder is based on a dry basis and contains 15-40% by weight of aluminum component (as Al2O3), 45-80% by weight of phosphorus component (as P2O5), and more than 0% and less than or equal to 40% by weight of a first clay, and the first clay-containing phosphorus-aluminum inorganic binder has a P / Al weight ratio of 1.0-6.0, a pH of 1-3.5, and a solids content of 15-60% by weight, and the first clay contains at least one of kaolin, sepiolite, attapulgite, rectolite, montmorillonite, and diatomaceous earth. The second clay is selected from at least one of kaolin, sepiolite, attapulgite, rectolite, montmorillonite, glagelite, halloysite, hydrotalcite, bentonite, and diatomaceous earth.

[0017] In the production method of the present invention, the phosphorus-containing compound used for phosphorus modification may be selected from organophosphorus compounds and / or inorganic phosphorus compounds. For example, organophosphorus compounds may be selected from trimethylphosphate, triphenylphosphine, trimethylphosphine, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium hydroxide, triphenylethylphosphonium bromide, triphenylbutylphosphonium bromide, triphenylbenzylphosphonium bromide, hexamethyl phosphate triamide, dibenzyldiethylphosphoramidite, and 1,3-bis((triethyl-phosphanyl)methyl)benzene. Inorganic phosphorus compounds may be selected from, for example, phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and boron phosphate.

[0018] In the manufacturing method of the present invention, the Na2O content in the phosphorus-modified molecular sieve is less than 0.1% by weight. The phosphorus-modified molecular sieve is a microporous ZSM-5 molecular sieve or a hierarchical ZSM-5 molecular sieve. The microporous ZSM-5 molecular sieve has a silica / alumina molar ratio of 15 to 1000, preferably 20 to 200. The hierarchical ZSM-5 molecular sieve has a mesoporous volume ratio of more than 10% to the total pore volume, an average pore diameter of 2 to 20 nm, and a silica / alumina molar ratio of 15 to 1000, preferably 20 to 200. In the manufacturing method of the present invention, when the molecular sieve to be phosphorus-modified is impregnated and exchanged with an aqueous solution of a phosphorus-containing compound, the molar ratio of the phosphorus-containing compound (as phosphorus) to the molecular sieve to be phosphorus-modified (as aluminum) is 0.01 to 2, preferably 0.1 to 1.5, and more preferably 0.2 to 1.5. During the impregnation and exchange, the weight ratio of water to molecular sieve is 0.5 to 1. Better results can be obtained by performing the above impregnation and exchange at a higher temperature, namely, better dispersion of phosphorus species, making it easier for phosphorus to move into the crystalline voids of the molecular sieve, and making it easier for it to bond with framework aluminum during the subsequent pressurized calcination of the catalyst raw material, further improving the coordination between phosphorus and framework aluminum, and ultimately contributing to improved hydrothermal stability of the molecular sieve. Therefore, it is preferable to perform the above impregnation and exchange at a higher temperature, preferably 50 to 150°C, more preferably 70 to 130°C, for 0.5 to 40 hours.

[0019] In the manufacturing method of the present invention, the atmospheric conditions have a gauge pressure of 0.01 to 1.0 MPa, for example 0.1 to 0.8 MPa, preferably 0.3 to 0.6 MPa, and contain 1% to 100% water vapor, for example 30% to 100% water vapor, preferably 60% to 100% water vapor; the hydrothermal calcination treatment is carried out at 200 to 800°C, preferably 300 to 500°C. The externally applied pressure refers to applying a constant external pressure during the hydrothermal calcination process of the auxiliary raw materials. For example, this can be done by introducing an inert gas from the outside to maintain a constant back pressure. The amount of water added externally is to satisfy the requirement that the atmospheric conditions contain 1% to 100% water vapor.

[0020] In this invention, for example, "containing 1 to 100% water vapor" refers to an air atmosphere having a moisture content of at least 1% or a 100% water vapor atmosphere (pure water vapor atmosphere).

[0021] In the present invention, a particular embodiment relating to the composition of the inorganic binder, based on the total amount of catalytic cracking catalyst or catalytic cracking aid, comprises 3 to 39% by weight on a dry basis of phosphorus-aluminum inorganic binder and 1 to 30% by weight on a dry basis of other inorganic binders, the other inorganic binders including pseudoboehmite, alumina sol, silica-alumina sol and water glass.

[0022] In the manufacturing method of the present invention, preferably, the first clay-containing phosphorus-aluminum inorganic binder is manufactured by the following steps: a step of slurring an alumina source, the first clay, and water and dispersing them in a slurry having a solid content of 5 to 48% by weight, wherein the alumina source is aluminum hydroxide that can be papillated with acid and / or alumina, and the amount of the first clay used, based on dry weight, is more than 0 parts by weight and 40 parts by weight or less, relative to 15 to 40 parts by weight of the alumina source as Al2O3; a step of adding concentrated phosphoric acid to the slurry under stirring according to a weight ratio of P / Al = 1 to 6, and reacting the resulting mixed slurry at 50 to 99°C for 15 to 90 minutes; where P in P / Al is the weight of elemental phosphorus in the phosphoric acid, and Al is the weight of elemental aluminum in the alumina source.

[0023] In the present invention, the above-mentioned shaping is pelletization by spray drying, and fine spheres having a diameter of 1 to 150 μm are produced by the above-mentioned shaping. This shaping operation is well known to those skilled in the art and will not be described in detail herein.

[0024] The present invention also provides a catalytic cracking catalyst produced by the above method.

[0025] The present invention also provides a catalytic cracking promoter produced by the above method.

[0026] The present invention further provides a method for catalytic cracking of hydrocarbon oil. The method includes a step of reacting the hydrocarbon oil by contacting it with the catalytic cracking agent (catalytic cracking catalyst or catalytic cracking promoter) of the present invention under catalytic cracking conditions.

[0027] The present invention further provides a method for catalytic cracking of hydrocarbon oil. The method includes a step of reacting the hydrocarbon oil by contacting it with a mixture containing the catalytic cracking promoter and the catalytic cracking catalyst of the present invention; in the mixture, the content of the catalytic cracking promoter is 0.1 to 30% by weight.

[0028] The catalytic cracking conditions include that the reaction temperature is 500 to 800 °C; and the hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric gas oil, vacuum gas oil, straight-run gas oil, propane light / heavy deasphalted oil, coker gas oil, and coal liquefaction products.

[0029] The present invention further provides a production system for a catalytic cracking agent (catalytic cracking catalyst or catalytic cracking promoter). The production system is mainly composed of a phosphorus reforming device, a raw material mixing device, a shaping device, and a hydrothermal pressure calcination device.

[0030] The phosphorus modification apparatus is used for the operation of impregnating and exchanging molecular sieves to be phosphorus modified with a solution of phosphorus-containing compounds, and includes equipment for introducing the solution of phosphorus-containing compounds. The raw material mixing apparatus receives the raw materials. The raw materials include impregnated (e.g., impregnated and exchanged) phosphorus-modified molecular sieves obtained from the phosphorus modification apparatus, a phosphorus-aluminum inorganic binder from a phosphorus-aluminum inorganic binder processing apparatus, optionally non-phosphorus-modified molecular sieves (e.g., FAU structure molecular sieves such as Y-type molecular sieves), and optionally clay. The molding apparatus may be a spray-drying molding apparatus. The pressurized hydrothermal firing apparatus is equipped with an aqueous solution inlet and a gas pressurized fitting to satisfy the conditions for pressurized hydrothermal firing of the molded body.

[0031] Figure 3 shows a schematic flowchart of the method for producing the catalytic cracking catalyst of the present invention. As can be seen from Figure 3, in the phosphorus modification apparatus for MFI structure molecular sieves, phosphorus-modified MFI structure molecular sieves are obtained by impregnating and exchanging the MFI structure molecular sieves with an aqueous solution containing phosphorus. In the raw material mixing apparatus, the phosphorus-modified MFI structure molecular sieves, Y-type molecular sieves, an inorganic binder, and an optionally added second clay are mixed to form a slurry, which is then molded (for example, by spray drying); and the resulting molded body is subjected to hydrothermal calcination under an atmospheric condition in which external pressure is applied and an aqueous solution is added externally.

[0032] Figure 4 shows a schematic flowchart of the method for producing the catalytic decomposition aid of the present invention. As can be seen from Figure 4, in the phosphorus modification apparatus for MFI structure molecular sieves, phosphorus-modified MFI structure molecular sieves are obtained by impregnating the MFI structure molecular sieves with an aqueous solution containing phosphorus. In the raw material mixing apparatus, raw materials including phosphorus-modified MFI structure molecular sieves, an inorganic binder, and optionally added second clay are mixed and formed into a slurry, which is then molded (for example, by spray drying); and the resulting molded body is subjected to pressurized hydrothermal firing under atmospheric conditions where external pressure is applied and an aqueous solution is added externally.

[0033] In this invention, quantities such as percentages are expressed by weight unless otherwise specified.

[0034] In this invention, unless otherwise specified, the total weight percentage of the components of the composition is 100% by weight.

[0035] In this invention, the D value represents the uniformity of the distribution of phosphorus atoms in the catalyst or auxiliary agent. The closer the D value is to 100%, the more uniform the distribution. Specifically, an arbitrary cross-section of a catalytic decomposition agent (usually in the shape of microspheres (e.g., with a diameter of 1 to 150 μm)) is randomly selected, 20 small squares with a side length of 10 nm are selected on the cross-section, and the phosphorus content (number of atoms / number of atoms) in each small square is obtained by electron probe microanalysis (EPMA). The ratio of the minimum phosphorus content of the 20 squares to the average phosphorus content of the 20 squares is taken as the d value of that cross-section, and the average of the d values ​​of five cross-sections spaced more than 50 nm apart is taken as the D value of the catalytic decomposition agent.

[0036] The manufacturing method provided by the present invention optimizes and shortens the flow steps for producing catalytic cracking catalysts or catalytic cracking aids, thereby reducing manufacturing costs. The catalytic cracking catalysts or catalytic cracking aids provided by the present invention exhibit excellent decomposition conversion rates, superior lower carbon olefin yields, and higher liquefaction gas yields in catalytic cracking reactions of petroleum hydrocarbons.

[0037] This invention provides the following technical solutions. 1. A method for producing a catalytic cracking catalyst, comprising the steps of: mixing a phosphorus-modified MFI structure molecular sieve, a Y-type molecular sieve, an inorganic binder, and an optionally added second clay, forming a slurry, and molding it into a molded body; and performing a hydrothermal calcination treatment on the molded body under atmospheric conditions in which external pressure is applied and an aqueous solution is added from the outside, wherein the phosphorus-modified MFI structure molecular sieve is obtained by contacting an MFI structure molecular sieve with a temperature of 0 to 150°C with an aqueous solution of a phosphorus-containing compound with a temperature of 0 to 150°C by impregnation, and the hydrothermal calcination treatment is performed under atmospheric conditions containing 1 to 100% water vapor, at a temperature of 200 to 800°C, and under a gauge pressure of 0.01 to 1.0 MPa.

[0038] 2. A method for producing technical solution 1, wherein, on a dry basis, the catalytic cracking catalyst contains 1-25% by weight of a Y-type molecular sieve, 5-50% by weight of a phosphorus-modified MFI structure molecular sieve, 1-60% by weight of an inorganic binder, and optionally 0-60% by weight of a second clay.

[0039] 3. A method for manufacturing technical solution 1, wherein the above-mentioned Y-type molecular sieve is selected from at least one of PSRY molecular sieve, rare earth-containing PSRY molecular sieve, USY molecular sieve, rare earth-containing USY molecular sieve, REY molecular sieve, REHY molecular sieve, and HY molecular sieve.

[0040] 4. A method for producing technical solution 1 or 2, wherein the inorganic binder is selected from or comprises at least one of pseudoboehmite, alumina sol, silica-alumina sol, water glass, and phosphorus-aluminum inorganic binder; preferably comprising phosphorus-aluminum inorganic binder, and more preferably phosphorus-aluminum inorganic binder.

[0041] 5. A method for manufacturing technical solution 4, wherein the phosphorus-aluminum inorganic binder is a phosphoraluminate binder and / or a first clay-containing phosphorus-aluminum inorganic binder.

[0042] 6. A method for producing technical solution 5, wherein the first clay-containing phosphorus-aluminum inorganic binder is based on a dry basis, and the first clay-containing phosphorus-aluminum inorganic binder contains 15-40% by weight of aluminum component (as Al2O3), 45-80% by weight of phosphorus component (as P2O5), and more than 0% and less than or equal to 40% by weight of the first clay, the first clay-containing phosphorus-aluminum inorganic binder has a P / Al weight ratio of 1.0-6.0, a pH of 1-3.5, and a solids content of 15-60% by weight, and the first clay contains at least one of kaolin, sepiolite, attapulgite, rectolite, montmorillonite, and diatomaceous earth.

[0043] 7. A method for producing technical solution 1, wherein the second clay is selected from at least one of kaolin, sepiolite, attapulgite, rectolite, montmorillonite, glagelite, halloysite, hydrotalcite, bentonite, and diatomaceous earth.

[0044] 8. A method for producing technical solution 1, wherein, based on the total amount of the catalytic cracking catalyst, the inorganic binder comprises, on a dry basis, 3 to 39% by weight of a phosphorus-aluminum inorganic binder and 1 to 30% by weight of at least one inorganic binder selected from pseudoboehmite, alumina sol, silica alumina sol and water glass.

[0045] 9. The method for producing the above-mentioned first clay-containing phosphorus-aluminum inorganic binder, comprising the steps of: slurring an alumina source, a first clay, and water to disperse them in a slurry having a solid content of 5-48% by weight, wherein the alumina source is aluminum hydroxide that can be papillated with acid and / or alumina, and the amount of the first clay used, based on dry weight, is more than 0 parts by weight and 40 parts by weight or less, relative to 15-40 parts by weight of the alumina source as Al2O3; adding concentrated phosphoric acid to the slurry under stirring according to a weight ratio of P / Al = 1-6, and reacting the resulting mixed slurry at 50-99°C for 15-90 minutes; where P in P / Al is the weight of elemental phosphorus in the phosphoric acid, and Al is the weight of elemental aluminum in the alumina source; the method for producing technical solution 5.

[0046] 10. A manufacturing method for technical solution 1, wherein the above molding is pelletization by spray drying.

[0047] 11. A method for manufacturing technical solution 1, wherein the atmospheric conditions have a gauge pressure of 0.01 to 1.0 MPa, preferably 0.3 to 0.6 MPa, and contain 30% to 100% water vapor, preferably 60% to 100% water vapor; and the hydrothermal firing treatment is carried out at 200 to 800°C, preferably 300 to 500°C.

[0048] 12. A method for producing technical solution 1, wherein the phosphorus-containing compound is selected from organophosphorus compounds and / or inorganic phosphorus compounds.

[0049] 13. A method for producing technical solution 12, wherein the organophosphorus compound is selected from trimethylphosphate, triphenylphosphine, trimethylphosphine, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium hydroxide, triphenylethylphosphonium bromide, triphenylbutylphosphonium bromide, triphenylbenzylphosphonium bromide, hexamethylphosphate triamide, dibenzyldiethylphosphoramidite, and 1,3-bis((triethyl-phosphanyl)methyl)benzene; and the inorganic phosphorus compound is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and boron phosphate.

[0050] 14. In MFI structure molecular sieves, the amount of Na2O is less than 0.1% by weight. Manufacturing method for technical solution 1.

[0051] 15. A method for producing the phosphorus-modified MFI structure molecular sieve, which is a microporous ZSM-5 molecular sieve or a hierarchical ZSM-5 molecular sieve, according to technical solution 1.

[0052] 16. Microporous ZSM-5 molecular sieves have a silica / alumina molar ratio of 15-1000, preferably 20-200; and hierarchical ZSM-5 molecular sieves have a mesoporation volume ratio of over 10% to total pore volume, an average pore diameter of 2-20 nm, and a silica / alumina molar ratio of 15-1000, preferably 20-200, according to the catalytic cracking catalyst of technical solution 15.

[0053] 17. A method for producing technical solution 1, wherein the molar ratio of the phosphorus-containing compound (as phosphorus) to the MFI structure molecular sieve (as aluminum) is 0.01 to 2; preferably 0.1 to 1.5; more preferably 0.2 to 1.5.

[0054] 18. A method for manufacturing technical solution 1, wherein contact is carried out at a temperature of 50 to 150°C, preferably 70 to 130°C, with a water / molecular sieve weight ratio of 0.5 to 1 for 0.5 to 40 hours.

[0055] 19. A catalytic cracking catalyst obtained from any of the manufacturing methods described in Technical Solution 1 to 18.

[0056] 20. A method for catalytic cracking of a hydrocarbon oil, comprising the step of reacting the hydrocarbon oil by contacting it with a catalytic cracking catalyst of technical solution 19 under catalytic cracking conditions.

[0057] 21. A technical solution of 20, comprising: catalytic cracking conditions, the reaction temperature being 500-800°C; and the hydrocarbon oil being one or more selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric diesel, vacuum diesel, straight-run diesel, propane light / heavy deasphaltized oil, coker diesel, and coal liquefaction products.

[0058] 22. A catalytic decomposition agent manufacturing system mainly consisting of a phosphorus modifier for MFI structure molecular sieves, a raw material mixing device, a molding device, and a pressurized hydrothermal calcination device.

[0059] 23. A technical solution 22 manufacturing system for phosphorus modification of MFI structure molecular sieves, including a device for introducing a solution of phosphorus-containing compounds.

[0060] 24. A manufacturing system for a catalyst, comprising a raw material mixing apparatus that receives raw materials for producing a catalyst, comprising impregnated and replaced phosphorus-modified molecular sieves obtained from a phosphorus-modifying apparatus for MFI structure molecular sieves, phosphorus-aluminum inorganic binder from a phosphorus-aluminum inorganic binder processing apparatus, Y-type molecular sieves, and optionally added clay.

[0061] 25. A manufacturing system for technical solution 22, wherein the molding apparatus is a spray-drying molding apparatus.

[0062] 26. A manufacturing system for technical solution 22, wherein the above-mentioned pressurized hydrothermal firing apparatus is equipped with a water inlet and a gas pressurizing fitting.

[0063] 27. A method for producing a catalytic decomposition aid, comprising the steps of: mixing a phosphorus-modified MFI structure molecular sieve obtained by impregnating an MFI structure molecular sieve having a temperature of 0 to 150°C with an aqueous solution of a phosphorus-containing compound having a temperature of 0 to 150°C with an inorganic binder and an optionally added second clay, slurring the resulting mixture and forming it into a molded body; and subjecting the molded body to a hydrothermal firing treatment under atmospheric conditions in which external pressure is applied and an aqueous solution is added externally, wherein the hydrothermal firing treatment is carried out at a temperature of 200 to 800°C, a gauge pressure of 0.01 to 1.0 MPa, and in an atmosphere containing 1 to 100% water vapor.

[0064] 28. A method for producing technical solution 27, wherein, on a dry basis, the catalytic decomposition aid contains 5-75% by weight of a phosphorus-modified MFI structure molecular sieve, 1-40% by weight of an inorganic binder, and 0-65% by weight of a second clay.

[0065] 29. A method for producing the technical solution 27, wherein the phosphorus-containing compound is selected from organophosphorus compounds and / or inorganic phosphorus compounds.

[0066] 30. A method for producing technical solution 27, wherein the organophosphorus compound is selected from trimethylphosphate, triphenylphosphine, trimethylphosphite, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium hydroxide, triphenylethylphosphonium bromide, triphenylbutylphosphonium bromide, triphenylbenzylphosphonium bromide, hexamethylphosphate triamide, dibenzyldiethylphosphoramidite, and 1,3-bis((triethyl-phosphanyl)methyl)benzene; and the inorganic phosphorus compound is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and boron phosphate.

[0067] 31. A method for producing the technical solution 27 in which Na2O is less than 0.1% by weight in an MFI structure molecular sieve.

[0068] 32. A method for producing a phosphorus-modified MFI structure molecular sieve, which is a microporous ZSM-5 molecular sieve or a hierarchical ZSM-5 molecular sieve, according to technical solution 27.

[0069] 33. A method for producing the technical solution 32, wherein the microporous ZSM-5 molecular sieve has a silica / alumina molar ratio of 15 to 1000, preferably 20 to 200; and the hierarchical ZSM-5 molecular sieve has a mesoporation volume ratio of more than 10% to the total pore volume, an average pore diameter of 2 to 20 nm, and a silica / alumina molar ratio of 15 to 1000, preferably 20 to 200.

[0070] 34. A method for producing technical solution 27, wherein the molar ratio of a phosphorus-containing compound (as phosphorus) to an MFI structure molecular sieve (as aluminum) is 0.01 to 2; preferably 0.1 to 1.5; more preferably 0.2 to 1.5.

[0071] 35. A method for producing technical solution 27, wherein the impregnation treatment described above is carried out at a temperature of 50 to 150°C, preferably 70 to 130°C, with a water / molecular sieve weight ratio of 0.5 to 1 for 0.5 to 40 hours.

[0072] 36. A method for producing technical solution 27, wherein the inorganic binder is selected from or contains at least one of pseudoboehmite, alumina sol, silica-alumina sol, water glass, and phosphorus-aluminum inorganic binder; the preferred inorganic binder contains phosphorus-aluminum inorganic binder, and the more preferred inorganic binder is phosphorus-aluminum inorganic binder.

[0073] 37. A method for producing technical solution 36, wherein the phosphorus-aluminum inorganic binder is a phosphoraluminate binder and / or a first clay-containing phosphorus-aluminum inorganic binder.

[0074] 38. A method for producing technical solution 37, wherein the first clay-containing phosphorus-aluminum inorganic binder is based on a dry basis, and the first clay-containing phosphorus-aluminum inorganic binder contains 15-40% by weight of aluminum component (as Al2O3), 45-80% by weight of phosphorus component (as P2O5), and more than 0% and less than or equal to 40% by weight of the first clay, the first clay-containing phosphorus-aluminum inorganic binder has a P / Al weight ratio of 1.0-6.0, a pH of 1-3.5, and a solids content of 15-60% by weight, and the first clay contains at least one of kaolin, sepiolite, attapulgite, rectolite, montmorillonite, and diatomaceous earth.

[0075] 39. A method for producing technical solution 27, wherein the second clay is selected from at least one of kaolin, sepiolite, attapulgite, rectolite, montmorillonite, glagelite, halloysite, hydrotalcite, bentonite, and diatomaceous earth.

[0076] 40. A method for producing technical solution 36, wherein the inorganic binder comprises, on a dry basis, 3 to 39% by weight of a phosphorus-aluminum inorganic binder and 1 to 30% by weight of at least one inorganic binder selected from pseudoboehmite, alumina sol, silica alumina sol and water glass, based on the total amount of catalytic decomposition aids.

[0077] 41. The method for producing the above-mentioned first clay-containing phosphorus-aluminum inorganic binder, comprising the steps of: slurring an alumina source, a first clay, and water to disperse them in a slurry having a solid content of 5 to 48% by weight, wherein the alumina source is aluminum hydroxide that can be papillated with acid and / or alumina, and the amount of the first clay used, based on dry weight, is more than 0 parts by weight and 40 parts by weight or less, relative to 15 to 40 parts by weight of the alumina source as Al2O3; adding concentrated phosphoric acid to the slurry under stirring according to a weight ratio of P / Al = 1 to 6, and reacting the resulting mixed slurry at 50 to 99°C for 15 to 90 minutes; where P in P / Al is the weight of elemental phosphorus in the phosphoric acid, and Al is the weight of elemental aluminum in the alumina source; the method for producing the technical solution 37.

[0078] 42. A manufacturing method for technical solution 27, wherein the molding described above is performed by spray drying.

[0079] 43. A method for manufacturing technical solution 27, wherein the atmospheric conditions have a gauge pressure of 0.01 to 1.0 MPa, preferably 0.3 to 0.6 MPa, and contain 30% to 100% water vapor, preferably 60% to 100% water vapor; and the hydrothermal firing treatment is carried out at 200 to 800°C, preferably 300 to 500°C.

[0080] 44. A catalytic decomposition aid obtained from any of the manufacturing methods described in technical solutions 27-43.

[0081] 45. A method for catalytic cracking of a hydrocarbon oil, comprising the step of reacting the hydrocarbon oil by contacting it with a catalytic cracking aid of technical solution 44 under catalytic cracking conditions.

[0082] 46. ​​A method for producing technical solution 45, comprising the step of reacting a hydrocarbon oil with a mixture containing a catalytic cracking aid and a catalytic cracking catalyst under catalytic cracking conditions; wherein the content of the catalytic cracking aid in the mixture is 0.1 to 30% by weight.

[0083] 47. A method for producing technical solution 45 or 46, comprising: catalytic cracking conditions, the reaction temperature being 500-800°C; and the hydrocarbon oil being one or more selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric diesel, vacuum diesel, straight-run diesel, propane light / heavy deasphaltized oil, coker diesel, and coal liquefaction products.

[0084] 48. A catalytic cracking aid manufacturing system mainly consisting of a phosphorus modifier for MFI structure molecular sieves, a raw material mixing device, a molding device, and a pressurized hydrothermal calcination device.

[0085] 49. A technical solution 48 manufacturing system for phosphorus modification of MFI structure molecular sieves, including a device for introducing a solution of phosphorus-containing compounds.

[0086] 50. A manufacturing system for technical solution 22 in which a raw material mixing device receives raw materials for producing an auxiliary, comprising impregnated phosphorus-modified molecular sieves obtained from a phosphorus-modifying device for MFI structure molecular sieves, phosphorus-aluminum inorganic binder from a phosphorus-aluminum inorganic binder processing device, and optionally added clay.

[0087] 51. A manufacturing system for technical solution 48, wherein the molding apparatus is a spray-drying molding apparatus.

[0088] 52. A manufacturing system for the technical solution 48, wherein the above-mentioned pressurized hydrothermal calcination apparatus is equipped with an aqueous solution inlet and a gas pressurizing fitting.

[0089] The present invention also provides the following group of technical solutions: 1. A catalytic decomposition agent, The active ingredient consists of phosphorus-modified molecular sieves and non-phosphorus-modified molecular sieves, or the active ingredient consists solely of phosphorus-modified molecular sieves. When the above active ingredient consists of phosphorus-modified molecular sieves and non-phosphorus-modified molecular sieves, the D value of phosphorus in the above catalytic decomposition agent measured by an electron probe microanalyzer (EPMA) is 65% or higher, preferably 68% or higher, or When the above active ingredient consists solely of phosphorus-modified molecular sieves, the D value of phosphorus in the above catalytic decomposition agent measured by an electron probe microanalyzer (EPMA) is 82% or higher, preferably 84% or higher. For example, a catalytic decomposition agent (usually in the shape of microspheres, e.g., with a diameter of 1 to 150 μm) has its D value determined by randomly selecting an arbitrary cross-section, choosing 20 small squares with a side length of 10 nm on the cross-section, obtaining the phosphorus content (number of atoms / number of atoms) for 20 small squares by electron probe microanalysis (EPMA), taking the ratio of the minimum phosphorus content of 20 to the average phosphorus content of 20 as the d value of that cross-section, and taking the average of the d values ​​of five cross-sections spaced more than 50 nm apart as the D value of the catalytic decomposition agent.

[0090] Specifically, the upper limit of the D value for phosphorus in the catalytic decomposition agent is 100%.

[0091] When the active ingredient consists of phosphorus-modified molecular sieves and non-phosphorus-modified molecular sieves, the D-value of phosphorus in the catalytic decomposition agent is less than 100%, for example, less than 90%, for example, less than 80%. Or, when the active ingredient consists only of phosphorus-modified molecular sieves, the D-value of phosphorus in the catalytic decomposition agent is less than 100%, for example, less than 99%, for example, less than 98%.

[0092] 2. The above-mentioned phosphorus-modified molecular sieve is a phosphorus-modified MFI structure molecular sieve, for example, a phosphorus-modified ZSM-5 molecular sieve; The catalytic decomposition agent according to the solution, wherein the non-phosphorus-modified molecular sieve is a FAU structure molecular sieve, for example, a Y-type molecular sieve.

[0093] 3. The catalytic decomposition agent is a catalytic decomposition catalyst having an active component consisting of a phosphorus-modified molecular sieve (for example, a phosphorus-modified MFI structure molecular sieve such as a phosphorus-modified ZSM-5 molecular sieve) and a non-phosphorus-modified molecular sieve (for example, a FAU structure molecular sieve such as a Y-type molecular sieve). A catalytic decomposition agent according to any one of the solutions 1 to 2, wherein the phosphorus D value of the catalyst measured by an electron probe microanalyzer (EPMA) is 65% or higher, preferably 68% or higher.

[0094] 4. The above catalytic decomposition agent is a catalytic decomposition aid having an active ingredient consisting of a phosphorus-modified molecular sieve. A catalytic decomposition agent according to any one of the solutions 1 to 2, wherein the D value of the phosphorus in the auxiliary agent measured by an electron probe microanalyzer (EPMA) is 82% or higher, preferably 84% or higher.

[0095] 5. The above catalytic decomposition agent, based on dryness, 1-25% by weight of non-phosphorus modified molecular sieves; 5-50% by weight phosphorus-modified molecular sieves; 1-60% by weight of an inorganic binder; and, A catalytic decomposition agent according to any of the solutions 1 to 2 above, optionally containing 0 to 60% by weight of a second clay.

[0096] 6. The above catalytic decomposition agent, based on dryness, 5-75% by weight of phosphorus-modified molecular sieves (excluding non-phosphorus-modified molecular sieves); 1 to 40 grams of inorganic binder; and, A catalytic decomposition agent according to any of the solutions 1 to 2 above, optionally containing 0 to 65% by weight of a second clay.

[0097] 7. The catalytic decomposition agent according to any of the above solutions, wherein the non-phosphorus-modified molecular sieve is at least one of PSRY molecular sieve, rare earth-containing PSRY molecular sieve, USY molecular sieve, rare earth-containing USY molecular sieve, REY molecular sieve, REHY molecular sieve, and HY molecular sieve.

[0098] 8. The inorganic binder described above comprises at least one of pseudoboehmite, alumina sol, silica-alumina sol, water glass, and phosphorus-aluminum inorganic binder. Preferably, the inorganic binder contains a phosphorus-aluminum inorganic binder. A catalytic decomposition agent according to any of the above solutions, more preferably the inorganic binder being a phosphorus-aluminum inorganic binder.

[0099] 9. The catalytic decomposition agent according to any of the above solutions, wherein the phosphorus-aluminum inorganic binder is a phosphorus aluminate binder and / or a first clay-containing phosphorus-aluminum inorganic binder.

[0100] 10. The above first clay-containing phosphorus-aluminum inorganic binder is based on a dry standard. The above-mentioned first clay-containing phosphorus-aluminum inorganic binder contains 15-40% by weight of aluminum component (as Al2O3), 45-80% by weight of phosphorus component (as P2O5), and more than 0% and less than or equal to 40% by weight of the first clay. The above-mentioned first clay-containing phosphorus-aluminum inorganic binder has a P / Al weight ratio of 1.0 to 6.0, a pH of 1 to 3.5, and a solids content of 15 to 60% by weight. The catalytic decomposition agent according to any of the above solutions, wherein the first clay comprises at least one of kaolin, sepiolite, attapulgite, rectolite, montmorillonite, and diatomaceous earth.

[0101] 11. The catalytic decomposition agent according to any of the solutions, wherein the second clay is selected from at least one of kaolin, sepiolite, attapulgite, rectolite, montmorillonite, glagelite, halloysite, hydrotalcite, bentonite, and diatomaceous earth.

[0102] 12. A catalytic decomposition agent according to any of the solutions, wherein, based on the total amount of the catalytic decomposition catalyst, the inorganic binder comprises, on a dry basis, 3 to 39% by weight of a phosphorus-aluminum inorganic binder and 1 to 30% by weight of at least one inorganic binder selected from pseudoboehmite, alumina sol, silica alumina sol, and water glass.

[0103] 13. (1) A process of mixing the following components as raw materials, forming the raw materials into a slurry, and molding it into a molded body: phosphorus-modified molecular sieve, optionally non-phosphorus-modified molecular sieve, inorganic binder, and optionally a second clay; (2) A step of subjecting the molded body to hydrothermal firing under atmospheric conditions in which external pressure is applied and an aqueous solution is added externally; The above-mentioned phosphorus-modified molecular sieve is obtained by impregnating a phosphorus-modified molecular sieve at a temperature of 0 to 150°C with an aqueous solution of a phosphorus-containing compound at a temperature of 0 to 150°C; The above hydrothermal calcination treatment is performed in a 100% water vapor atmosphere or in an air atmosphere with a moisture content of at least 1%, at a temperature of 200 to 800°C and a gauge pressure of 0.01 to 1.0 MPa, in a method for producing a catalytic decomposition agent according to any of the above solutions.

[0104] 14. The phosphorus-modified molecular sieve described above is a microporous ZSM-5 molecular sieve or a hierarchical ZSM-5 molecular sieve. Preferably, the above-mentioned micropore ZSM-5 molecular sieve has a silica / alumina molar ratio of 15 to 1000, preferably 20 to 200; Preferably, the hierarchical ZSM-5 molecular sieve has a ratio of mesopore volume to total pore volume of more than 10%, an average pore diameter of 2 to 20 nm, and a silica / alumina molar ratio of 15 to 1000, preferably 20 to 200, according to any of the above solutions.

[0105] 15. The method according to any of the above solutions, wherein the molar ratio of the phosphorus-containing compound (as phosphorus) to the phosphorus-modified molecular sieve (as aluminum) is 0.01 to 2, preferably 0.1 to 1.5, and more preferably 0.2 to 1.5.

[0106] 16. The phosphorus-containing compound is selected from organophosphorus compounds and / or inorganic phosphorus compounds. Preferably, the organophosphorus compound is selected from trimethylphosphate, triphenylphosphine, trimethylphosphine, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium hydroxide, triphenylethylphosphonium bromide, triphenylbutylphosphonium bromide, triphenylbenzylphosphonium bromide, hexamethyl phosphate triamide, dibenzyldiethylphosphoramidite, and 1,3-bis((triethyl-phosphanyl)methyl)benzene; Preferably, the inorganic phosphorus compound is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and boron phosphate, according to any of the above solutions.

[0107] 17. The method according to any of the above solutions, wherein the phosphorus-modified molecular sieve contains less than 0.1% by weight of Na2O.

[0108] 18. In the above method, the first clay-containing phosphorus-aluminum inorganic binder is produced by the following steps: A step comprising: slurring an alumina source, a first clay, and water to disperse them in a slurry having a solid content of 5-48% by weight, wherein the alumina source is aluminum hydroxide that can be papillated with acid and / or alumina, and the amount of the first clay used, based on dry weight, is greater than 0 parts by weight and less than or equal to 40 parts by weight, relative to 15-40 parts by weight of the alumina source as Al2O3; adding concentrated phosphoric acid to the slurry under stirring according to a weight ratio of P / Al = 1-6, and reacting the resulting mixed slurry at 50-99°C for 15-90 minutes; The method according to any of the above solutions, wherein P in P / Al is the weight of elemental phosphorus in phosphoric acid, and Al is the weight of elemental aluminum in the alumina source.

[0109] 19. A method according to any of the above solutions, wherein the molding is pelletization by spray drying.

[0110] 20. The conditions for the above hydrothermal firing treatment are: The gauge pressure is 0.1 to 0.8 MPa, preferably 0.3 to 0.6 MPa; The atmosphere is a 100% water vapor atmosphere or an air atmosphere with a moisture content of at least 30%, preferably a 100% water vapor atmosphere or an air atmosphere with a moisture content of at least 60%; The temperature is 200-800°C, preferably 300-500°C; The conditions for the above contact by impregnation are: The water / molecular sieve weight ratio is 0.5-1; The temperature is 50-150°C, preferably 70-130°C; A method according to any of the above solutions, wherein the duration is between 0.5 and 40 hours.

[0111] 21. A catalytic decomposition agent according to any of the above solutions 1 to 12, manufactured by the method described in any of the above solutions 13 to 20.

[0112] 22. A method for catalytic cracking of hydrocarbon oils, A method comprising the step of reacting the above-mentioned hydrocarbon oil with a catalytic decomposition agent described in any of the above solutions under catalytic decomposition conditions.

[0113] 23. The above method includes a step of reacting the hydrocarbon oil by contacting a mixture containing a catalytic cracking aid and a catalytic cracking catalyst described in any of the above solutions under catalytic cracking conditions, A method for catalytically cracking a hydrocarbon oil according to any of the above solutions, wherein the content of the catalytic cracking aid in the above mixture is 0.1 to 30% by weight.

[0114] 24. The above contact decomposition conditions are: The reaction temperature is 500-800°C. The above hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric diesel, vacuum diesel, straight-run diesel, propane light / heavy deasphaltized oil, coker diesel, and coal liquefaction products. A method for catalytic cracking of hydrocarbon oil as described in any of the above solutions.

[0115] 25. A manufacturing system for catalytic decomposition agents, The above system mainly consists of a phosphorus reformer, a raw material mixing device, a molding device, and a pressurized hydrothermal calcination device; Preferably, the phosphorus modifier includes equipment for introducing a solution of phosphorus-containing compounds, and / or the raw material mixer receives raw materials, the raw materials comprising impregnated (e.g., impregnated and exchanged) phosphorus-modified molecular sieves obtained from the phosphorus modifier, a phosphorus-aluminum inorganic binder from a phosphorus-aluminum inorganic binder processing apparatus, optionally a non-phosphorus-modified molecular sieve, and optionally clay, and / or the molding apparatus is a spray-drying molding apparatus, and / or the pressurized hydrothermal firing apparatus comprises an aqueous solution inlet and a gas pressurized fitting. [Brief explanation of the drawing]

[0116] [Figure 1] This is a flowchart for manufacturing conventional catalysts using prior art. [Figure 2] This is a flowchart for manufacturing conventional additives using prior art. [Figure 3] This is a flowchart for manufacturing a catalyst, as provided by the present invention. [Figure 4] This is a flowchart for manufacturing an auxiliary agent provided by the present invention. Detailed description of the invention

[0117] The present invention will be further described below with specific examples, but the present invention is not limited thereto.

[0118] Unless otherwise specified, the instruments and reagents used in the embodiments of this invention are all commonly used by those skilled in the art.

[0119] The effect of the catalytic cracking catalyst or catalytic cracking aid of the present invention on the yield of lower carbon olefins in the catalytic cracking of petroleum hydrocarbons was evaluated using a microreaction apparatus.

[0120] The prepared catalytic cracking catalyst / catalytic cracking aid samples were aged in a fixed-bed aging apparatus at 800°C and 100% steam for 17 hours, and then evaluated using a microreaction apparatus. The feedstock oil was VGO or naphtha. The evaluation conditions included: reaction temperature 620°C, regeneration temperature 620°C, and agent (catalyst / aid)-oil ratio of 3.2. Microreactivity was measured according to the ASTM D5154-2010 standard method.

[0121] The D-value of phosphorus in the sample cross-section was quantitatively analyzed using EPMA (JXA-8230 type electron probe microanalyzer). Specifically, five cross-sections of the sample were randomly selected with an interval of more than 50 nm between them. Twenty squares with a side length of 10 nm were selected on each cross-section, and the phosphorus content (number of atoms / number of atoms) within each square was obtained by electron probe microanalysis (EPMA). The ratio of the minimum phosphorus content of the 20 squares to the average phosphorus content was taken as the d-value of that cross-section, and the average of the d-values ​​of the five cross-sections was taken as the D-value of the phosphorus in the sample to determine the D-value.

[0122] The properties of some of the raw materials used in the examples are as follows:

[0123] [Table 1]

[0124] Binder 1, the phosphorus-aluminum inorganic binder used in the examples, was prepared as follows: 1.91 kg of pseudoboehmite (containing Al2O3, 1.19 kg), 0.56 kg of kaolin (0.5 kg on a dry basis), and 3.27 kg of decationized water were mixed and stirred for 30 minutes to form a slurry. Under stirring, 5.37 kg of concentrated phosphoric acid (85% by mass) was added to the slurry, with a phosphoric acid addition rate of 0.04 kg of phosphoric acid / min / kg of alumina source. The mixture was heated to 70°C and reacted at this temperature for 45 minutes to produce the phosphorus-aluminum inorganic binder. The proportions of the materials are shown in Table 1.

[0125] Binders 2, 3, and 4, which are phosphorus-aluminum inorganic binders, were also manufactured according to the method described above, but with different material proportions, which are shown in Table 1.

[0126] [Table 2]

[0127] [Table 3]

[0128] Examples F1.X to F24.X (X=1 or 2, the same applies hereafter) provide catalytic cracking catalysts of the present invention, and Comparative Examples F1 to F17 illustrate catalytic cracking catalysts for comparison. Of these, the MFI structure molecular sieves in Examples F1.X to F10.X are microporous ZSM-5 molecular sieves, and the MFI structure molecular sieves in Examples F11.X to F20.X are hierarchical ZSM-5 molecular sieves. Comparative Example F8 is a comparative catalytic cracking catalyst containing a microporous ZSM-5 MFI structure molecular sieve manufactured by the prior art, and Comparative Example F16 is a comparative catalytic cracking catalyst containing a hierarchical ZSM-5 MFI structure molecular sieve manufactured by the prior art.

[0129] (Example F1.1) 16.2 g of diammonium hydrogen phosphate (Tianjin Guangfu Science and Technology Development Co., Ltd., analytically pure, the same applies hereafter) was dissolved in 60 g of deionized water, and the mixture was stirred for 0.5 hours to obtain an aqueous solution containing phosphorus. 113 g of HZSM-5 molecular sieve (provided by Changling Division of Sinopec Catalyst Company, with a relative crystallinity of 91.1%, a silica / alumina molar ratio of 24.1, a Na2O content of 0.039 wt%, and a specific surface area of ​​353 m²) was dissolved. 2A solution containing 0.177 mL / g (with a total pore volume of 0.177 mL / g, the same applies hereafter) was added to the above solution and modified by impregnation (i.e., impregnation at 20°C for 2 hours). Y-type molecular sieves (PSRY molecular sieves), kaolin, and pseudoboehmite were mixed into the obtained mixture. Decationized water and alumina sol were added, and the resulting mixture was stirred for 120 minutes to obtain a slurry with a solid content of 30% by weight. Hydrochloric acid was added to adjust the pH of the slurry to 3.0, and stirring was continued for 45 minutes. Binder 1, a phosphorus-aluminum inorganic binder, was added, and the resulting mixture was stirred for 30 minutes. Microspheres (diameter 1-150 μm) were produced by spray drying the obtained slurry. These microspheres were treated at 500°C for 0.5 hours under external pressure with water added (i.e., in a 50% water vapor atmosphere at a pressure of 0.5 MPa) to produce a catalytic cracking catalyst sample, which was designated CFZY1.1. Its composition consisted of 40% phosphorus-modified ZSM-5 molecular sieve, 10% PSRY molecular sieve, 23% kaolin, 18% binder 1, 5% pseudoboehmite (as Al2O3), and 4% alumina sol (as Al2O3).

[0130] To illustrate the catalytic cracking reaction effect of the catalytic cracking catalyst provided in this disclosure, the reaction performance of the 100% equilibrium catalyst and the equilibrium catalyst incorporating the catalytic cracking catalyst CFZY1.1 prepared in Example F1.1 was evaluated using a fixed-bed microreaction apparatus.

[0131] Catalyst CFZY1.1 was aged at 800°C for 17 hours in a 100% water vapor atmosphere. The aged CFZY1.1 was mixed with an industrial FCC equilibrium catalyst (an industrial brand DVR-3 FCC equilibrium catalyst with a diesel microactivity of 63). The equilibrium catalyst and catalyst mixture were charged into a fixed-bed microreactor, and the feedstock oils shown in Table 2 were catalytically cracked. The evaluation conditions included: a reaction temperature of 620°C, a regeneration temperature of 620°C, and a catalyst-to-oil ratio of 3.2. The reaction results, including the blank test agent, are shown in Table 3.

[0132] (Example F1.2) This example was carried out in the same manner as in Example F1.1, except for the preparation of the phosphorus-modified molecular sieve. Diammonium hydrogen phosphate, HZSM-5 molecular sieve, and water were mixed and stirred to form a slurry. This slurry was heated to 100°C and maintained for 2 hours to prepare a catalytic cracking catalyst sample, which was designated CFZY1.2.

[0133] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0134] (Comparative Example F1) In this example, a comparative catalytic cracking catalyst sample was prepared in the same manner as in Example F1.1, except that the firing conditions were set to atmospheric pressure (gauge pressure: 0 MPa) and the firing was performed in a muffle furnace in an air atmosphere at a temperature of 550°C. This sample was designated DCFZY1.

[0135] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0136] (Example F2.1) In this example, a catalytic cracking catalyst sample was prepared in the same manner as in Example F1.1, except that 16.2 g of diammonium hydrogen phosphate was dissolved in 120 g of deionized water at 50°C, the mixture was stirred for 0.5 hours to obtain an aqueous solution containing phosphorus, 113 g of HZSM-5 molecular sieve was added, the sample was modified by impregnation at 20°C for 2 hours, and then subjected to pressurized hydrothermal calcination at 600°C for 2 hours under conditions of external pressure and external addition of water (i.e., in a 30% water vapor atmosphere under a pressure of 0.5 MPa), and this sample was designated CFZY2.1.

[0137] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0138] (Example F2.2) In this example, a catalytic cracking catalyst sample was prepared in the same manner as in Example F2.1, except that diammonium hydrogen phosphate, HZSM-5 molecular sieve, and water were mixed and stirred to form a slurry, and this slurry was heated to 70°C and maintained for 2 hours. This sample was designated CFZY2.2.

[0139] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0140] (Comparative Example F2) In this example, a catalytic cracking catalyst comparison sample was prepared in the same manner as in Example F2.1, except that the firing conditions were set to atmospheric pressure (gauge pressure: 0 MPa) and the firing was performed in an air atmosphere at a temperature of 550°C using a muffle furnace. This sample was designated DCFZY2.

[0141] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0142] (Example F3.1) In this example, a catalytic cracking catalyst sample was prepared in the same manner as in Example F1.1, except that 10.4 g of phosphoric acid was dissolved in 60 g of deionized water at room temperature, the mixture was stirred for 2 hours to obtain an aqueous solution containing phosphorus, 113 g of HZSM-5 molecular sieve was added, and the sample was modified by impregnation at 20°C for 4 hours, followed by pressurized hydrothermal calcination at 400°C for 2 hours under external pressure (i.e., in a 100% water vapor atmosphere at a pressure of 0.3 MPa). This sample was designated CFZY3.1.

[0143] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0144] (Example F3.2) In this example, a catalytic cracking catalyst sample was prepared in the same manner as in Example F3.1, except that an aqueous solution of a phosphorus-containing compound at a temperature of 80°C was brought into contact with an HZSM-5 molecular sieve heated to 80°C and mixed for 4 hours. This sample was designated CFZY3.2.

[0145] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0146] (Comparative Example F3) In this example, a comparative catalytic cracking catalyst sample was prepared in the same manner as in Example F3.1, except that the firing conditions were set to atmospheric pressure (gauge pressure: 0 MPa) and the firing was performed in a muffle furnace in an air atmosphere at a temperature of 550°C. This sample was designated DCFZY3.

[0147] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0148] (Example F4.1) In this example, a catalytic cracking catalyst sample was prepared in the same manner as in Example F1.1, except that 8.1 g of diammonium hydrogen phosphate was dissolved in 120 g of deionized water at room temperature, the mixture was stirred for 0.5 hours to obtain an aqueous solution containing phosphorus, 113 g of HZSM-5 molecular sieve was added, the sample was modified by impregnation at 20°C for 2 hours, and then subjected to pressurized hydrothermal calcination at 300°C for 2 hours under conditions of external pressure and external addition of water (i.e., in a 100% water vapor atmosphere under a pressure of 0.4 MPa), and this sample was designated CFZY4.1.

[0149] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0150] (Example F4.2) In this example, a catalytic cracking catalyst sample was prepared in the same manner as in Example F4.1, except that ammonium dihydrogen phosphate, HZSM-5 molecular sieve, and water were mixed and stirred to form a slurry, and this slurry was heated to 90°C and maintained for 2 hours. This sample was designated CFZY4.2.

[0151] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0152] (Comparative Example F4) In this example, a comparative catalytic cracking catalyst sample was prepared in the same manner as in Example F4.1, except that the firing conditions were set to atmospheric pressure (gauge pressure: 0 MPa) and the firing was performed in a muffle furnace in an air atmosphere at a temperature of 550°C. This sample was designated DCFZY4.

[0153] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0154] (Example F5.1) In this example, a catalytic cracking catalyst sample was prepared in the same manner as in Example F1.1, except that 8.5 g of trimethyl phosphate was dissolved in 80 g of deionized water at 90°C, the mixture was stirred for 1 hour to obtain an aqueous solution containing phosphorus, 113 g of HZSM-5 molecular sieve was added, and the sample was modified by impregnation at 20°C for 8 hours, followed by pressurized hydrothermal calcination at 500°C for 4 hours under external pressure (i.e., in an 80% water vapor atmosphere at a pressure of 0.8 MPa). This sample was designated as CFZY5.1.

[0155] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0156] (Example F5.2) In this example, a catalytic cracking catalyst sample was prepared in the same manner as in Example F5.1, except that trimethyl phosphate, HZSM-5 molecular sieve, and water were mixed and stirred to form a slurry, and this slurry was heated to 120°C and maintained for 8 hours. This sample was designated CFZY5.2.

[0157] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0158] (Comparative Example F5) In this example, a catalytic cracking catalyst comparison sample was prepared in the same manner as in Example F5.1, except that the firing conditions were set to atmospheric pressure (gauge pressure: 0 MPa) and the firing was performed in an air atmosphere using a muffle furnace at a temperature of 550°C. This sample was designated DCFZY5.

[0159] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0160] (Example F6.1) In this example, a catalytic cracking catalyst sample was prepared in the same manner as in Example F1.1, except that 11.6 g of boron phosphate was dissolved in 100 g of deionized water at 100°C, the mixture was stirred for 3 hours to obtain an aqueous solution containing phosphorus, 113 g of HZSM-5 molecular sieve was added, the sample was modified by impregnation at 20°C for 2 hours, and then subjected to pressurized hydrothermal calcination at 400°C for 4 hours under external pressure (i.e., in a 100% water vapor atmosphere at a pressure of 0.3 MPa). This sample was designated CFZY6.1.

[0161] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0162] (Example F6.2) In this example, a catalytic cracking catalyst sample was prepared in the same manner as in Example F6.1, except that boron phosphate, HZSM-5 molecular sieve, and water were mixed and stirred to form a slurry, and this slurry was heated to 150°C and maintained for 2 hours. This sample was designated CFZY6.2.

[0163] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0164] (Comparative example F6) In this example, a comparative catalytic cracking catalyst sample was prepared in the same manner as in Example F6.1, except that the firing conditions were set to atmospheric pressure (gauge pressure: 0 MPa) and the firing was performed in a muffle furnace in an air atmosphere at a temperature of 550°C. This sample was designated DCFZY6.

[0165] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0166] (Example F7.1) In this example, a catalytic cracking catalyst sample was prepared in the same manner as in Example F1.1, except that 14.2 g of triphenylphosphine was dissolved in 80 g of deionized water at 100°C, the mixture was stirred for 2 hours to obtain an aqueous solution containing phosphorus, 113 g of HZSM-5 molecular sieve was added, and the sample was modified by impregnation at 20°C for 4 hours, followed by pressurized hydrothermal calcination at 600°C for 2 hours under external pressure (i.e., in a 30% water vapor atmosphere at a pressure of 1 MPa). This sample was designated CFZY7.1.

[0167] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0168] (Example F7.2) In this example, a catalytic cracking catalyst sample was prepared in the same manner as in Example F7.1, except that boron phosphate, HZSM-5 molecular sieve, and water were mixed and stirred to form a slurry, and this slurry was heated to 150°C and maintained for 2 hours. This sample was designated CFZY7.2.

[0169] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0170] (Comparative Example F7) In this example, a catalytic cracking catalyst comparison sample was prepared in the same manner as in Example F7.1, except that the firing conditions were set to atmospheric pressure (gauge pressure: 0 MPa) and the firing was performed in a muffle furnace in an air atmosphere at a temperature of 550°C. This sample was designated DCFZY7.

[0171] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0172] (Comparative example F8) Comparative Example F8 shows a phosphorus-containing modified ZSM-5 comparative sample obtained using a currently industry-standard method.

[0173] This example was carried out in the same manner as in Example F1.2, except for the following conditions: 16.2 g of diammonium hydrogen phosphate was dissolved in 60 g of deionized water, and the mixture was stirred for 0.5 hours to obtain an aqueous solution containing phosphorus; 113 g of HZSM-5 molecular sieve was added to the solution and modified by impregnation (i.e., impregnation at 100°C for 2 hours); the resulting mixture was dried in an oven at 110°C, and then calcined in a muffle furnace at 550°C in an air atmosphere under normal pressure (gauge pressure: 0 MPa) to produce a phosphorus-modified ZSM-5 molecular sieve sample; this sample was mixed with kaolin and pseudoboehmite; decationized water and alumina sol were added, and the resulting mixture was stirred for 120 minutes to obtain a slurry with a solid content of 30% by weight. After adding hydrochloric acid to adjust the pH of the slurry to 3.0, stirring was continued for 45 minutes, then binder 1, a phosphorus-aluminum inorganic binder, was added, and the resulting mixture was stirred for 30 minutes. The resulting slurry was then molded by spray drying to produce microspheres (diameter 1-150 μm). These microspheres were calcined at 500°C for 1 hour to produce a comparative sample of the catalytic cracking catalyst, which was designated DCFZY8.

[0174] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0175] (Example F8.1) In this example, a catalytic cracking catalyst was prepared in the same manner as in Example F1.1, except that the phosphorus-aluminum inorganic binder was replaced with binder 2, and this was designated CFZY8.1.

[0176] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0177] (Example F8.2) In this example, a catalytic cracking catalyst was prepared in the same manner as in Example F1.2, except that the phosphorus-aluminum inorganic binder was replaced with binder 2, and this was designated CFZY8.2.

[0178] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0179] (Example F9.1) In this example, a catalytic cracking catalyst was prepared in the same manner as in Example F5.1, except that the phosphorus-aluminum inorganic binder was replaced with binder 3, and this was designated CFZY9.1.

[0180] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0181] (Example F9.2) In this example, a catalytic cracking catalyst was prepared in the same manner as in Example F1.2, except that the phosphorus-aluminum inorganic binder was replaced with binder 3, and this was designated CFZY9.2.

[0182] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0183] (Example F10.1) In this example, a catalytic cracking catalyst was prepared in the same manner as in Example F1.1, except that the phosphorus-aluminum inorganic binder was replaced with binder 4, and this was designated CFZY10.1.

[0184] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0185] (Example F10.2) In this example, a catalytic cracking catalyst was prepared in the same manner as in Example F1.2, except that the phosphorus-aluminum inorganic binder was replaced with binder 4, and this was designated CFZY10.2.

[0186] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0187] Examples F11.X to F20.X illustrate the production of catalytic cracking catalysts using the phosphorus-modified ZSM-5 molecular sieve according to the present invention.

[0188] (Examples F11.1 to F17.1) Examples F11.1 to F17.1 used HZSM-5 molecular sieves, which were supplied by the Changling Division of Sinopec Catalyst Company and had a relative crystallinity of 88.6%, a silica / alumina molar ratio of 20.8, a Na2O content of 0.017 wt%, and a specific surface area of ​​373 m². 2 Catalytic cracking catalyst samples were prepared sequentially according to Examples F1.1 to F17.1, except that they were replaced with (a total pore volume of 0.256 mL / g, a pore volume of 0.119 mL / g, and an average pore diameter of 5.8 nm; the same applies hereafter), and these were designated as CFZY11.1 to CFZY17.1.

[0189] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0190] (Examples F11.2 to F17.2) Examples F11.2 to F17.2 were prepared by sequentially manufacturing catalytic cracking catalyst samples corresponding to Examples F1.2 to F7.2, except that the HZSM-5 molecular sieve was replaced with a hierarchical ZSM-5 molecular sieve. These samples were designated CFZY11.2 to CFZY17.2.

[0191] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0192] (Comparative example F9~Comparative example F15) Comparative Examples F9 to F15 were prepared by sequentially manufacturing catalytic cracking catalyst samples corresponding to Comparative Examples F1 to F7, except that the HZSM-5 molecular sieve was replaced with a hierarchical ZSM-5 molecular sieve. These were designated DCFZY9 to DCFZY15.

[0193] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0194] (Comparative Example F16) Comparative Example F16 illustrates a currently industry-standard method and the phosphorus-containing modified hierarchical ZSM-5 comparative sample obtained therefrom. In this example, a catalytic cracking catalyst comparative sample was prepared in the same manner as in Comparative Example F8, except that the HZSM-5 molecular sieve was replaced with a hierarchical ZSM-5 molecular sieve, and this was designated DCFZY16.

[0195] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0196] (Example F18.1) In this example, a catalytic cracking catalyst was prepared in the same manner as in Example F11.1, except that the phosphorus-aluminum inorganic binder was replaced with binder 2, and this was designated CFZY18.1.

[0197] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0198] (Example F18.2) In this example, a catalytic cracking catalyst was prepared in the same manner as in Example F11.2, except that the phosphorus-aluminum inorganic binder was replaced with binder 2, and this was designated CFZY18.2.

[0199] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0200] (Example F19.1) In this example, a catalytic cracking catalyst was prepared in the same manner as in Example F11.1, except that the phosphorus-aluminum inorganic binder was replaced with binder 3, and this was designated CFZY19.1.

[0201] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0202] (Example F19.2) In this example, a catalytic cracking catalyst was prepared in the same manner as in Example F11.2, except that the phosphorus-aluminum inorganic binder was replaced with binder 3, and this was designated CFZY19.2.

[0203] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0204] (Example F20.1) In this example, a catalytic cracking catalyst was prepared in the same manner as in Example F11.1, except that the phosphorus-aluminum inorganic binder was replaced with binder 4, and this was designated CFZY20.1.

[0205] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0206] (Example F20.2) In this example, a catalytic cracking catalyst was prepared in the same manner as in Example F11.2, except that the phosphorus-aluminum inorganic binder was replaced with binder 4, and this was designated CFZY20.2.

[0207] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0208] In Examples F21.1, F22.1, and Comparative Example F17, a different Y-type molecular sieve, the commercially available HRY-1 molecular sieve, was used.

[0209] (Example F21.1) In this example, the catalyst sample was prepared in the same manner as in Example F1.1, except that the Y-type molecular sieve (PSRY) was replaced with HRY-1, and this sample was designated CFZY21.1. To write it down.

[0210] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0211] (Example F22.1) In this example, the catalyst sample was prepared in the same manner as in F11.1, except that the Y-type molecular sieve (PSRY) was replaced with HRY-1, and this was designated as CFZY22.1.

[0212] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0213] (Comparative Example F17) In this example, the catalyst sample was prepared in the same manner as in Example F1.1, except that the Y-type molecular sieve (PSRY) was replaced with HRY-1, and this was designated DCFZY17.

[0214] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0215] In Examples F23.1 and F24.1, the amounts of pseudo-boehmite and alumina sol were increased and replaced with a phosphorus-aluminum inorganic binder.

[0216] (Example F23.1) In this example, a catalytic decomposition aid sample was prepared in the same manner as in Example F1.1, except that the amounts of pseudo-boehmite and alumina sol were increased and replaced with Binder 1, which is a phosphorus-aluminum inorganic binder. This sample was designated CFZY23.1.

[0217] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0218] (Example F24.1) In this example, a catalytic decomposition aid sample was prepared in the same manner as in Example F11.1, except that the amounts of pseudo-boehmite and alumina sol were increased and replaced with Binder 1, which is a phosphorus-aluminum inorganic binder. This sample was designated CFZY24.1.

[0219] The evaluation was carried out in the same manner as in Example F1.1, and the results are shown in Table 3.

[0220] [Table 4-1]

[0221] [Table 4-2]

[0222] [Table 4-3]

[0223] [Table 4-4]

[0224] Examples E1.X to E22.X provide catalytic decomposition aids of the present invention, and Comparative Examples E1 to E16 illustrate comparative catalytic decomposition aids. Examples E1.X to E10.X and E21.1 use porous ZSM-5 molecular sieves, while Examples E11.X to E20.X and E22.1 use hierarchical ZSM-5 molecular sieves. Comparative Example E8 was a comparative catalytic decomposition aid containing microporous ZSM-5 molecular sieves manufactured by the prior art. Comparative Example E16 was a comparative catalytic decomposition aid containing hierarchical ZSM-5 molecular sieves manufactured by the prior art.

[0225] (Example E1.1) 16.2 g of diammonium hydrogen phosphate (Tianjin Guangfu Science and Technology Development Co., Ltd., analytically pure, the same applies hereafter) was dissolved in 60 g of deionized water, and the mixture was stirred for 0.5 hours to obtain an aqueous solution containing phosphorus. 113 g of HZSM-5 molecular sieve (provided by Changling Division of Sinopec Catalyst Company, with a relative crystallinity of 91.1%, a silica / alumina molar ratio of 24.1, a Na2O content of 0.039 wt%, and a specific surface area of ​​353 m²) was dissolved. 2A solution containing 0.177 mL / g (with a total pore volume of 0.177 mL / g, the same applies hereafter) was added to the above solution and modified by impregnation (i.e., impregnation at 20°C for 2 hours). Kaolin and pseudoboehmite were mixed into the resulting mixture. Decationized water and alumina sol were added, and the resulting mixture was stirred for 120 minutes to obtain a slurry with a solid content of 30% by weight. Hydrochloric acid was added to adjust the pH of the slurry to 3.0, and stirring was continued for 45 minutes. Binder 1, a phosphorus-aluminum inorganic binder, was added, and the resulting mixture was stirred for 30 minutes. Microspheres (diameter 1-150 μm) were produced by spray drying the resulting slurry. These microspheres were treated at 500°C for 0.5 hours under external pressure with water added (i.e., in a 50% water vapor atmosphere under a pressure of 0.5 MPa) to produce a sample of catalytic decomposition aid, which was designated CEZ1.1. Its composition consisted of 50% molecular sieve, 23% kaolin, 18% binder 1, 5% pseudoboehmite (as Al2O3), and 4% alumina sol (as Al2O3).

[0226] To illustrate the catalytic cracking reaction effect of the catalytic cracking aids provided in this disclosure, the reaction performance of a 100% equilibrium catalyst and an equilibrium catalyst incorporating the catalytic cracking aid CEZ1.1 prepared in Example E1.1 was evaluated using a fixed-bed microreaction apparatus.

[0227] The additive CEZ1.1 was aged at 800°C for 17 hours in a 100% steam atmosphere. The aged CEZ1.1 was mixed with an industrial FCC equilibrium catalyst (an industrial brand DVR-3 FCC equilibrium catalyst with a diesel microactivity of 63). The mixture of the equilibrium catalyst and the additive was charged into a fixed-bed microreactor, and the feedstock oils shown in Table 2 were catalytically cracked. The evaluation conditions included: a reaction temperature of 620°C, a regeneration temperature of 620°C, and a catalyst-to-oil ratio of 3.2. The reaction results, including the blank test agent, are shown in Table 4.

[0228] (Example E1.2) This example was carried out in the same manner as in Example E1.1, except for the preparation of the phosphorus-modified molecular sieve. Diammonium hydrogen phosphate, HZSM-5 molecular sieve, and water were mixed and stirred to form a slurry, and this slurry was heated to 100°C and maintained for 2 hours to prepare a catalytic cracking aid sample, which was designated CEZ1.2.

[0229] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0230] (Comparative Example E1) In this example, a comparative sample of catalytic decomposition aids was prepared in the same manner as in Example E1.1, except that the firing conditions were set to atmospheric pressure (gauge pressure: 0 MPa) and the firing was carried out in an air atmosphere at a temperature of 550°C using a muffle furnace. This sample was designated DCEZ1.

[0231] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0232] (Example E2.1) In this example, a catalytic decomposition aid sample was prepared in the same manner as in Example E1.1, except that 16.2 g of diammonium hydrogen phosphate was dissolved in 120 g of deionized water at 50°C, the mixture was stirred for 0.5 hours to obtain an aqueous solution containing phosphorus, 113 g of HZSM-5 molecular sieve was added, the sample was modified by impregnation at 20°C for 2 hours, and then subjected to pressurized hydrothermal calcination at 600°C for 2 hours under conditions of external pressure and external addition of water (i.e., in a 30% water vapor atmosphere under a pressure of 0.5 MPa), and this sample was designated CEZ2.1.

[0233] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0234] (Example E2.2) In this example, a catalytic decomposition aid sample was prepared in the same manner as in Example E2.1, except that diammonium hydrogen phosphate, HZSM-5 molecular sieve, and water were mixed and stirred to form a slurry, and this slurry was heated to 70°C and maintained for 2 hours. This sample was designated CEZ2.2.

[0235] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0236] (Comparative example E2) In this example, a comparative sample of catalytic decomposition aids was prepared in the same manner as in Example E2.1, except that the firing conditions were set to atmospheric pressure (gauge pressure: 0 MPa) and the firing was performed in an air atmosphere using a muffle furnace at a temperature of 550°C. This sample was designated DCEZ2.

[0237] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0238] (Example E3.1) In this example, a catalytic decomposition aid sample was prepared in the same manner as in Example E1.1, except that 10.4 g of phosphoric acid was dissolved in 60 g of deionized water at room temperature, the mixture was stirred for 2 hours to obtain an aqueous solution containing phosphorus, 113 g of HZSM-5 molecular sieve was added, the mixture was modified by impregnation at 20°C for 4 hours, and then subjected to pressurized hydrothermal calcination at 400°C for 2 hours under conditions of external pressure and external addition of water (i.e., in a 100% water vapor atmosphere at a pressure of 0.3 MPa), and this sample was designated CEZ3.1.

[0239] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0240] (Example E3.2) In this example, a catalytic decomposition aid sample was prepared in the same manner as in Example E3.1, except that an aqueous solution of a phosphorus-containing compound at a temperature of 80°C was brought into contact with an HZSM-5 molecular sieve heated to 80°C and mixed for 4 hours. This sample was designated CEZ3.2.

[0241] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0242] (Comparative example E3) In this example, a comparative sample of catalytic decomposition aids was prepared in the same manner as in Example E3.1, except that the firing conditions were set to atmospheric pressure (gauge pressure: 0 MPa) and the firing was performed in an air atmosphere using a muffle furnace at a temperature of 550°C. This sample was designated DCEZ3.

[0243] The evaluation was carried out in the same manner as in Example E1.1, and the results are shown in Table 4.

[0244] (Example E4.1) In this example, 8.1 g of diammonium hydrogen phosphate was dissolved in 120 g of deionized water at room temperature, and the mixture was stirred for 0.5 h to obtain an aqueous solution containing phosphorus. Then, 113 g of HZSM-5 molecular sieve was added, and the modification was carried out by the impregnation method at 20 °C for 2 h. A catalytic cracking aid sample was produced in the same manner as in Example E1.1 except that hydrothermal calcination treatment was carried out at 300 °C for 2 h under the condition of adding external pressure to externally add water (that is, in a 100% steam atmosphere under a pressure of 0.4 MPa), and this was designated as CEZ4.1.

[0245] The evaluation was carried out in the same manner as in Example E1.1, and the results are shown in Table 4.

[0246] (Example E4.2) In this example, a catalytic cracking aid sample was produced in the same manner as in Example E4. except that ammonium dihydrogen phosphate, HZSM-5 molecular sieve and water were mixed and stirred to form a slurry, and this slurry was heated to 90 °C and maintained for 2 h, and this was designated as CEZ4.2.

[0247] The evaluation was carried out in the same manner as in Example E1.1, and the results are shown in Table 4.

[0248] (Comparative Example E4) In this example, a comparative sample of the catalytic cracking aid was produced in the same manner as in Example E4.1 except that the firing condition was normal pressure (gauge pressure: 0 MPa), and firing was carried out at a temperature of 550 °C in an air atmosphere using a muffle furnace, and this was designated as DCEZ4.

[0249] The evaluation was carried out in the same manner as in Example E1.1, and the results are shown in Table 4.

[0250] (Example E5.1) In this example, a catalytic decomposition aid sample was prepared in the same manner as in Example E1.1, except that 8.5 g of trimethyl phosphate was dissolved in 80 g of deionized water at 90°C, the mixture was stirred for 1 hour to obtain an aqueous solution containing phosphorus, 113 g of HZSM-5 molecular sieve was added, the mixture was modified by impregnation at 20°C for 8 hours, and then subjected to pressurized hydrothermal calcination at 500°C for 4 hours under external pressure (i.e., in an 80% water vapor atmosphere at a pressure of 0.8 MPa), and this sample was designated as CEZ5.1.

[0251] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0252] (Example E5.2) In this example, a catalytic decomposition aid sample was prepared in the same manner as in Example E5.1, except that trimethyl phosphate, HZSM-5 molecular sieve, and water were mixed and stirred to form a slurry, and this slurry was heated to 120°C and maintained for 8 hours. This sample was designated CEZ5.2.

[0253] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0254] (Comparative Example E5) In this example, a comparative sample of catalytic decomposition aids was prepared in the same manner as in Example E5.1, except that the firing conditions were set to atmospheric pressure (gauge pressure: 0 MPa) and the firing was carried out in an air atmosphere at a temperature of 550°C using a muffle furnace. This sample was designated DCEZ5.

[0255] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0256] (Example E6.1) In this example, a catalytic decomposition aid sample was prepared in the same manner as in Example E1.1, except that 11.6 g of boron phosphate was dissolved in 100 g of deionized water at 100°C, the mixture was stirred for 3 hours to obtain an aqueous solution containing phosphorus, 113 g of HZSM-5 molecular sieve was added, the sample was modified by impregnation at 20°C for 2 hours, and then subjected to pressurized hydrothermal calcination at 400°C for 4 hours under external pressure (i.e., in a 100% water vapor atmosphere under a pressure of 0.3 MPa), and this sample was designated CEZ6.1.

[0257] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0258] (Example E6.2) In this example, a catalytic decomposition aid sample was prepared in the same manner as in Example E6.1, except that boron phosphate, HZSM-5 molecular sieve, and water were mixed and stirred to form a slurry, and this slurry was heated to 150°C and maintained for 2 hours. This sample was designated CEZ6.2.

[0259] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0260] (Comparative example E6) In this example, a comparative sample of catalytic decomposition aids was prepared in the same manner as in Example E6.1, except that the firing conditions were set to atmospheric pressure (gauge pressure: 0 MPa) and the firing was carried out in an air atmosphere at a temperature of 550°C using a muffle furnace. This sample was designated DCEZ6.

[0261] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0262] (Example E7.1) In this example, 14.2 g of triphenylphosphine was dissolved in 80 g of deionized water at 100 °C, and the mixture was stirred for 2 hours to obtain an aqueous solution containing phosphorus. Then, 113 g of HZSM-5 molecular sieve was added, and modification was carried out by the impregnation method at 20 °C for 4 hours. A catalytic cracking aid sample was prepared in the same manner as in Example E1.1 except that hydrothermal calcination treatment was carried out at 600 °C for 2 hours under the condition of adding external pressure to externally add water (that is, in a 30% water vapor atmosphere under a pressure of 1 MPa), and this was designated as CEZ7.1.

[0263] Evaluation was carried out in the same manner as in Example E1.1, and the results are shown in Table 4.

[0264] (Example E7.2) In this example, a catalytic cracking aid sample was prepared in the same manner as in Example E7.1 except that boron phosphate, HZSM-5 molecular sieve and water were mixed and stirred to form a slurry, and this slurry was heated to 150 °C and maintained for 2 hours, and this was designated as CEZ7.2.

[0265] Evaluation was carried out in the same manner as in Example E1.1, and the results are shown in Table 4.

[0266] (Comparative Example E7) In this example, a comparative sample of catalytic cracking aid was prepared in the same manner as in Example E7.1 except that the firing condition was normal pressure (gauge pressure: 0 MPa), and firing was carried out at a temperature of 550 °C in an air atmosphere using a muffle furnace, and this was designated as DCEZ7.

[0267] Evaluation was carried out in the same manner as in Example E1.1, and the results are shown in Table 4.

[0268] (Comparative Example E8) Comparative Example E8 shows the current industry-common method and the phosphorus-containing modified ZSM-5 comparative sample obtained thereby.

[0269] This example was carried out in the same manner as in Example E1.2, except for the following conditions: 16.2 g of diammonium hydrogen phosphate was dissolved in 60 g of deionized water, and the mixture was stirred for 0.5 hours to obtain an aqueous solution containing phosphorus; 113 g of HZSM-5 molecular sieve was added to the solution and modified by impregnation (i.e., impregnation at 100°C for 2 hours); the resulting mixture was dried in an oven at 110°C, and then calcined in a muffle furnace at 550°C in an air atmosphere under normal pressure (gauge pressure: 0 MPa) to produce a phosphorus-modified ZSM-5 molecular sieve sample; this sample was mixed with kaolin and pseudoboehmite; decationized water and alumina sol were added, and the resulting mixture was stirred for 120 minutes to obtain a slurry with a solid content of 30% by weight. After adding hydrochloric acid to adjust the pH of the slurry to 3.0, stirring was continued for 45 minutes, then binder 1, a phosphorus-aluminum inorganic binder, was added, and the resulting mixture was stirred for 30 minutes. The resulting slurry was then molded by spray drying to produce microspheres (diameter 1-150 μm). These microspheres were calcined at 500°C for 1 hour to produce a comparative sample of catalytic decomposition aids, which was designated DCEZ8.

[0270] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0271] (Example E8.1) In this example, a catalytic decomposition aid was prepared in the same manner as in Example E1.1, except that the phosphorus-aluminum inorganic binder was replaced with binder 2, and this was designated CEZ8.1.

[0272] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0273] (Example E8.2) In this example, a catalytic decomposition aid was prepared in the same manner as in Example E1.2, except that the phosphorus-aluminum inorganic binder was replaced with binder 2, and this was designated CEZ8.2.

[0274] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0275] (Example E9.1) In this example, a catalytic decomposition aid was prepared in the same manner as in Example E1.1, except that the phosphorus-aluminum inorganic binder was replaced with binder 3, and this was designated CEZ9.1.

[0276] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0277] (Example E9.2) In this example, a catalytic decomposition aid was prepared in the same manner as in Example E1.2, except that the phosphorus-aluminum inorganic binder was replaced with binder 3, and this was designated CEZ9.2.

[0278] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0279] (Example E10.1) In this example, a catalytic decomposition aid was prepared in the same manner as in Example E1.1, except that the phosphorus-aluminum inorganic binder was replaced with binder 4, and this was designated CEZ10.1. Evaluation was performed in the same manner as in Example E5.1, and the results are shown in Table 4.

[0280] (Example E10.2) In this example, a catalytic decomposition aid was prepared in the same manner as in Example E1.2, except that the phosphorus-aluminum inorganic binder was replaced with binder 4, and this was designated CEZ10.2.

[0281] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0282] Examples E11.X to E20.X illustrate the production of catalytic cracking aids using the phosphorus-modified ZSM-5 molecular sieve of the present invention.

[0283] (Examples E11.1 to E17.1) Examples E11.1 to E17.1 used HZSM-5 molecular sieves, which were supplied by the Changling Division of Sinopec Catalyst Company and had a relative crystallinity of 88.6%, a silica / alumina molar ratio of 20.8, a Na2O content of 0.017 wt%, and a specific surface area of ​​373 m². 2 Except for replacing the values ​​with (a total pore volume of 0.256 mL / g, a pore volume of 0.119 mL / g, and an average pore diameter of 5.8 nm, the same applies hereafter), catalytic decomposition aid samples were prepared sequentially corresponding to Examples E1.1 to E7.1, and these were designated CEZ11.1 to CEZ17.1. Evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0284] (Examples E11.2 to E17.2) Examples E11.2 to E17.2 were prepared by sequentially manufacturing catalytic decomposition aid samples corresponding to Examples E1.2 to E7.2, except that the HZSM-5 molecular sieve was replaced with a hierarchical ZSM-5 molecular sieve. These were designated CEZ11.2 to CEZ17.2.

[0285] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0286] (Comparative Examples E9 to E15) Comparative Examples E9 to E15 were prepared by sequentially producing catalytic decomposition aid samples corresponding to Comparative Examples E1 to E7, except that the HZSM-5 molecular sieve was replaced with a hierarchical ZSM-5 molecular sieve. These are designated DCEZ9 to DCEZ15.

[0287] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0288] (Comparative example E16) Comparative Example E16 illustrates a currently industry-standard method and the phosphorus-containing modified hierarchical ZSM-5 comparative sample obtained therefrom. In this example, a catalytic cracking aid comparative sample was prepared in the same manner as in Comparative Example E8, except that the HZSM-5 molecular sieve was replaced with a hierarchical ZSM-5 molecular sieve, and this was designated DCEZ16.

[0289] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0290] (Example E18.1) In this example, a catalytic decomposition aid was prepared in the same manner as in Example E11.1, except that the phosphorus-aluminum inorganic binder was replaced with binder 2, and this was designated CEZ18.1.

[0291] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0292] (Example E18.2) In this example, a catalytic decomposition aid was prepared in the same manner as in Example E11.2, except that the phosphorus-aluminum inorganic binder was replaced with binder 2, and this was designated CEZ18.2.

[0293] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0294] (Example E19.1) In this example, a catalytic decomposition aid was prepared in the same manner as in Example E11.1, except that the phosphorus-aluminum inorganic binder was replaced with binder 3, and this was designated CEZ19.1.

[0295] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0296] (Example E19.2) In this example, a catalytic decomposition aid was prepared in the same manner as in Example E11.2, except that the phosphorus-aluminum inorganic binder was replaced with binder 3, and this was designated CEZ19.2.

[0297] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0298] (Example E20.1) In this example, a catalytic decomposition aid was prepared in the same manner as in Example E11.1, except that the phosphorus-aluminum inorganic binder was replaced with binder 4, and this was designated CEZ20.1.

[0299] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0300] (Example E20.2) In this example, a catalytic decomposition aid was prepared in the same manner as in Example E11.2, except that the phosphorus-aluminum inorganic binder was replaced with binder 4, and this was designated CEZ20.2.

[0301] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0302] (Example E21.1) In this example, a catalytic decomposition aid sample was prepared in the same manner as in Example E1.1, except that the amounts of pseudo-boehmite and alumina sol were increased and replaced with Binder 1, which is a phosphorus-aluminum inorganic binder. This sample was designated CEZ21.1.

[0303] (Example E21.2) In this example, a catalytic decomposition aid sample was prepared in the same manner as in Example E11.1, except that the amounts of pseudo-boehmite and alumina sol were increased and replaced with Binder 1, which is a phosphorus-aluminum inorganic binder. This sample was designated CEZ21.2.

[0304] The evaluation was performed in the same manner as in Example E1.1, and the results are shown in Table 4.

[0305] [Table 5-1]

[0306] [Table 5-2]

[0307] [Table 5-3]

[0308] Although preferred embodiments of the present invention have been described in detail above, the present invention is not limited to the specific details of the above embodiments. Within the scope of the technical idea of ​​the present invention, various simple modifications can be made to the technical solutions of the present invention. All of these simple modifications fall within the scope of protection of the present invention.

[0309] Furthermore, it should be noted that each specific technical feature described in the embodiments above can be combined in any suitable manner, provided that no contradictions arise. To avoid unnecessary repetition, various possible combinations are not described in the detailed description of the invention.

[0310] Furthermore, various combinations of different embodiments of the present invention can be arbitrarily combined as long as they do not contradict the spirit of the present invention, and these should also be considered as part of the disclosure of the present invention.

Claims

1. A catalytic decomposition agent, The active ingredient consists of phosphorus-modified molecular sieves and non-phosphorus-modified molecular sieves, or the active ingredient consists solely of phosphorus-modified molecular sieves. When the above active ingredient consists of phosphorus-modified molecular sieves and non-phosphorus-modified molecular sieves, the D value of phosphorus in the above catalytic decomposition agent measured by an electron probe microanalyzer (EPMA) is 65% or higher, preferably 68% or higher, or A catalytic decomposition agent in which the above active ingredient consists solely of phosphorus-modified molecular sieves, and the D value of phosphorus in the catalytic decomposition agent measured by an electron probe microanalyzer (EPMA) is 82% or higher, preferably 84% or higher.

2. The above-mentioned phosphorus-modified molecular sieve is a phosphorus-modified MFI structure molecular sieve, for example, a phosphorus-modified ZSM-5 molecular sieve; The catalytic decomposition agent according to claim 1, wherein the non-phosphorus-modified molecular sieve is a FAU structure molecular sieve, for example, a Y-type molecular sieve.

3. The catalytic decomposition agent is a catalytic decomposition catalyst having an active component consisting of a phosphorus-modified molecular sieve (for example, a phosphorus-modified MFI structure molecular sieve such as a phosphorus-modified ZSM-5 molecular sieve) and a non-phosphorus-modified molecular sieve (for example, a FAU structure molecular sieve such as a Y-type molecular sieve). The catalytic decomposition agent according to any one of claims 1 to 2, wherein the phosphorus D value of the catalyst measured by an electron probe microanalyzer (EPMA) is 65% or more, preferably 68% or more.

4. The above catalytic decomposition agent is a catalytic decomposition aid having an active ingredient consisting of a phosphorus-modified molecular sieve (for example, a phosphorus-modified MFI structure molecular sieve such as phosphorus-modified ZSM-5 molecular sieve), The catalytic decomposition agent according to any one of claims 1 to 2, wherein the phosphorus D value of the above-mentioned auxiliary agent measured by an electron probe microanalyzer (EPMA) is 82% or more, preferably 84% or more.

5. The above catalytic decomposition agent, when measured by dryness, 1-25% by weight of non-phosphorus modified molecular sieves; 5-50% by weight phosphorus-modified molecular sieves; 1 to 60% by weight of an inorganic binder; and, The catalytic decomposition agent according to any one of claims 1 to 2, optionally containing 0 to 60% by weight of a second clay.

6. The above catalytic decomposition agent, when measured by dryness, 5-75% by weight of phosphorus-modified molecular sieves (excluding non-phosphorus-modified molecular sieves); 1 to 40 grams of inorganic binder; and, The catalytic decomposition agent according to any one of claims 1 to 2, optionally containing 0 to 65% by weight of a second clay.

7. The catalytic decomposition agent according to any one of claims 1 to 5, wherein the non-phosphorus modified molecular sieve is at least one of PSRY molecular sieve, rare earth-containing PSRY molecular sieve, USY molecular sieve, rare earth-containing USY molecular sieve, REY molecular sieve, REHY molecular sieve, and HY molecular sieve.

8. The inorganic binder described above includes at least one of pseudoboehmite, alumina sol, silica-alumina sol, water glass, and phosphorus-aluminum inorganic binder. Preferably, the inorganic binder contains a phosphorus-aluminum inorganic binder. The catalytic decomposition agent according to any one of claims 5 to 6, more preferably the inorganic binder being a phosphorus-aluminum inorganic binder.

9. The catalytic decomposition agent according to claim 8, wherein the phosphorus-aluminum inorganic binder is a phosphorus aluminate binder and / or a first clay-containing phosphorus-aluminum inorganic binder.

10. The first clay-containing phosphorus-aluminum inorganic binder described above is based on a dry standard. The above-mentioned first clay-containing phosphorus-aluminum inorganic binder contains 15-40% by weight of aluminum component (Al ２ O ３ (as) 45-80% by weight of phosphorus component (P ２ O ５ (as), and containing a first clay that is more than 0% by weight and less than or equal to 40%, The above-mentioned first clay-containing phosphorus-aluminum inorganic binder has a P / Al weight ratio of 1.0 to 6.0, a pH of 1 to 3.5, and a solid content of 15 to 60% by weight. The catalytic decomposition agent according to claim 9, wherein the first clay comprises at least one of kaolin, sepiolite, attapulgite, rectolite, montmorillonite, and diatomaceous earth.

11. The contact decomposition agent according to any one of claims 5 to 6, wherein the second clay is selected from at least one of kaolin, sepiolite, attapulgite, rectolite, montmorillonite, glagelite, halloysite, hydrotalcite, bentonite, and diatomaceous earth.

12. The catalytic decomposition agent according to any one of claims 5 to 6 and 8 to 10, wherein the inorganic binder comprises, on a dry basis, 3 to 39% by weight of a phosphorus-aluminum inorganic binder and 1 to 30% by weight of at least one inorganic binder selected from pseudoboehmite, alumina sol, silica alumina sol, and water glass.

13. (1) A process of mixing the following components as raw materials, forming the raw materials into a slurry, and molding it into a molded body: phosphorus-modified molecular sieve, optionally non-phosphorus-modified molecular sieve, inorganic binder, and optionally a second clay; (2) A step of subjecting a molded body to hydrothermal firing under atmospheric conditions in which external pressure is applied and an aqueous solution is added externally; The above phosphorus-modified molecular sieve is obtained by impregnating a phosphorus-modified molecular sieve at a temperature of 0 to 150°C with an aqueous solution of a phosphorus-containing compound at a temperature of 0 to 150°C; A method for producing a catalytic decomposition agent according to any one of claims 1 to 12, wherein the above hydrothermal calcination treatment is carried out in a 100% water vapor atmosphere or in an air atmosphere with a moisture content of at least 1%, at a temperature of 200 to 800°C and a gauge pressure of 0.01 to 1.0 MPa.

14. The phosphorus-modified molecular sieve described above is a microporous ZSM-5 molecular sieve or a hierarchical ZSM-5 molecular sieve. Preferably, the above-mentioned micropore ZSM-5 molecular sieve has a silica / alumina molar ratio of 15 to 1000, preferably 20 to 200; Preferably, the hierarchical ZSM-5 molecular sieve has a ratio of mesopore volume to total pore volume of more than 10%, an average pore diameter of 2 to 20 nm, and a silica / alumina molar ratio of 15 to 1000, preferably 20 to 200, according to the method of claim 13.

15. The method according to any one of claims 13 to 14, wherein the molar ratio of the phosphorus-containing compound (as phosphorus) to the phosphorus-modified molecular sieve (as aluminum) is 0.01 to 2, preferably 0.1 to 1.5, and more preferably 0.2 to 1.

5.

16. The above phosphorus-containing compound is selected from organophosphorus compounds and / or inorganic phosphorus compounds. Preferably, the organophosphorus compound is selected from trimethylphosphate, triphenylphosphine, trimethylphosphine, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium hydroxide, triphenylethylphosphonium bromide, triphenylbutylphosphonium bromide, triphenylbenzylphosphonium bromide, hexamethyl phosphate triamide, dibenzyldiethylphosphoramidite, and 1,3-bis((triethyl-phosphanyl)methyl)benzene; Preferably, the inorganic phosphorus compound is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and boron phosphate, according to any one of claims 13 to 15.

17. In the phosphorus-modified molecular sieve described above, Na ２ The method according to any one of claims 13 to 16, wherein the amount of O is less than 0.1% by weight.

18. In the above method, the first clay-containing phosphorus-aluminum inorganic binder is produced by the following steps: A step of slurrying an alumina source, a first clay, and water to disperse them in a slurry having a solid content of 5 to 48% by weight, wherein the alumina source is aluminum hydroxide that can be papillated with acid and / or alumina, Al ２ O ３ The process involves using 15 to 40 parts by weight of alumina source, with the amount of first clay used based on dry weight being more than 0 parts by weight and 40 parts by weight or less; adding concentrated phosphoric acid to the slurry under stirring according to a weight ratio of P / Al = 1 to 6; and reacting the resulting mixed slurry at 50 to 99°C for 15 to 90 minutes; The method according to any one of claims 13 to 17, wherein P in P / Al is the weight of elemental phosphorus in phosphoric acid, and Al is the weight of elemental aluminum in an alumina source.

19. The method according to any one of claims 13 to 18, wherein the molding described above is pelletization by spray drying.

20. The conditions for the above hydrothermal calcination treatment are: The gauge pressure is 0.1 to 0.8 MPa, preferably 0.3 to 0.6 MPa; The atmosphere is a 100% water vapor atmosphere or an air atmosphere with a moisture content of at least 30%, preferably a 100% water vapor atmosphere or an air atmosphere with a moisture content of at least 60%; The temperature is 200 to 800°C, preferably 300 to 500°C; The conditions for the above contact by impregnation are: The water / molecular sieve weight ratio is 0.5 to 1; The temperature is 50 to 150°C, preferably 70 to 130°C; The method according to any one of claims 13 to 19, wherein the time is 0.5 to 40 hours.

21. A method for catalytic cracking of hydrocarbon oils, A method comprising the step of reacting the above-mentioned hydrocarbon oil with a catalytic cracking agent according to any one of claims 1 to 12 under catalytic cracking conditions.

22. The above method includes a step of reacting the hydrocarbon oil by contacting a mixture containing the catalytic cracking aid described in claim 4 and the catalytic cracking catalyst described in claim 3 under catalytic cracking conditions, The method for catalytic cracking a hydrocarbon oil according to claim 21, wherein the content of the catalytic cracking aid in the above mixture is 0.1 to 30% by weight.

23. The above contact decomposition conditions are: The reaction temperature is 500 to 800°C. The above hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric diesel, vacuum diesel, straight-run diesel, propane light / heavy deasphaltized oil, coker diesel, and coal liquefaction products. A method for catalytic cracking of a hydrocarbon oil according to claim 21.

24. A production system for a catalytic decomposition agent according to any one of claims 1 to 12, The above system consists of a phosphorus reformer, a raw material mixing device, a molding device, and a pressurized hydrothermal calcination device; A manufacturing system comprising: a phosphorus modifier including equipment for introducing a solution of phosphorus-containing compounds; a raw material mixer receiving raw materials, the raw materials comprising impregnated (e.g., impregnated and exchanged) phosphorus-modified molecular sieves obtained from the phosphorus modifier, a phosphorus-aluminum inorganic binder from a phosphorus-aluminum inorganic binder processing apparatus, optionally a non-phosphorus-modified molecular sieve, and optionally clay; a molding apparatus being a spray-drying molding apparatus; and a pressurized hydrothermal firing apparatus comprising an aqueous solution inlet and a gas pressurized fitting.

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