A rapid bed heavy oil conversion method

Abstract

The present invention relates to a fast bed heavy oil conversion method, comprising contacting and reacting heavy oil with a catalytic cracking catalyst in a fast bed reactor, wherein the catalytic cracking catalyst comprises a phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve and a porous oxide support having a weak Br acid, the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve having a closed hollow structure, and the average grain size of the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve crystals is 0.2-3.0 μm. The method of the present invention can significantly improve the yield of light olefins converted from heavy oil.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrocarbon oil conversion and relates to a heavy oil catalytic cracking method. Background Art

[0002] Light olefins, such as ethylene and propylene, are essential organic chemical raw materials and are considered the cornerstone of the modern chemical industry. With the growing demand for light olefins and their expanding applications, the development and research of efficient methods for their production have become increasingly important. Catalytic cracking is one of the most promising technologies for light olefin production. This technology allows for flexible adjustment of product distribution, lowers reaction temperatures, and reduces energy consumption. Currently, the feedstocks used in catalytic cracking to produce light olefins are diverse. Heavy crude oil reserves account for approximately 50% of the world's recoverable reserves. As crude oil resources worldwide become increasingly heavier, refineries are facing pressure to achieve heavier and lower-quality feedstocks, lighter and cleaner products, and cleaner and less carbon-intensive refining processes. Therefore, a key technical challenge facing the catalytic cracking industry is how to efficiently convert heavy oil into high-value-added, light petrochemical products demanded by the market.

[0003] One heavy oil catalytic cracking process is the DCC process, which uses a dilute phase riser + dense phase bed to convert heavy oil into light olefins, but its propylene selectivity is difficult to further improve. In order to achieve high-selectivity cracking of inferior heavy oil, WO2020015603A1 provides a hydrocarbon oil catalytic cracking method using a new reactor with a special structure. Figure 1 , known as the RTC process. Compared to the currently industrialized DCC process, the feedstock molecules in the RTC reactor essentially all undergo cracking reactions within the uniformly heated fast bed reactor. The reactor contains a high catalyst content, approaching a "quasi-dense phase" process. This significantly increases the proportion of catalytic cracking reactions and reduces the proportion of thermal cracking reactions, which helps improve cracking selectivity. The uniformity of the reactor's axial linear velocity also stabilizes the flow state. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a rapid-bed heavy oil catalytic cracking method that can significantly increase the yield of light olefins. Another technical problem to be solved by the present invention is to provide a heavy oil catalytic cracking catalyst suitable for a rapid-bed reactor and a method for preparing the catalyst. This catalyst has a multi-level pore structure and a matrix with specific acidic properties, which can match the step-by-step cracking of heavy oil macromolecules. Its use in the heavy oil catalytic cracking process can improve the yield of light olefins.

[0005] The present invention provides a fast-bed heavy oil catalytic cracking method, comprising: allowing heavy oil to contact and react with a catalytic cracking catalyst in a fast-bed reactor, wherein the catalytic cracking catalyst comprises a phosphorus-containing hollow multi-level porous ZSM-5 molecular sieve and a carrier having a weak Br acid. The content of the phosphorus-containing hollow multi-level porous ZSM-5 molecular sieve is 25-60% by weight, the total content of the carrier is 40-75% by weight, and the content of the porous oxide having a weak Br acid is 1-30% by weight, based on the dry weight of the catalytic cracking catalyst.

[0006] The porous oxide having weak Br acid has a total Br acid content of 5-15 μmol / g and a strong Br acid content of 0.5-2.5 μmol / g;

[0007] The phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve has a closed hollow structure, which refers to a structure with a completely closed shell and an internal cavity of a hollow structure. The average grain size of the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve grains is 0.2-3.0 μm, and the ratio of the bulk silicon-aluminum molar ratio to the surface silicon-aluminum molar ratio is 1.0-1.5; the phosphorus-aluminum molar ratio of the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve is 0.1-1.5; the total specific surface area of the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve is 340-400 m 2 / g, mesopore specific surface area is 40-150m 2 / g, the mesoporous specific surface area of the phosphorus-containing hollow ZSM-5 multi-level porous molecular sieve accounts for 15-40% of the total specific surface area, the proportion of strong Br acid to the total Br acid is 65-80%, and the proportion of strong L acid to the total L acid is 50-75%.

[0008] Preferably, the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve has an N2 adsorption-desorption curve that exhibits an H4-type hysteresis loop.

[0009] For the N2 adsorption and desorption method, please refer to the literature "Solid Catalyst Research Methods" or "Modern Catalysis Research Methods".

[0010] Optionally, the phosphorus-to-aluminum molar ratio of the phosphorus-containing hollow ZSM-5 hierarchical pore molecular sieve is 0.2-1.3. In the present invention, the phosphorus-to-aluminum molar ratio of the phosphorus-containing hollow ZSM-5 hierarchical pore molecular sieve is obtained by XRF fluorescence detection, and the content of each component is also obtained by XRF fluorescence detection.

[0011] Optionally, the average grain size of the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve grains is 0.4-2.7 μm, for example, 0.6-2.5 μm. In the present invention, the grain size refers to the size of the widest part of the grain, which can be obtained by measuring the size of the widest part of the grain projection surface in the SEM or TEM image of the sample. The average grain size is obtained by selecting any 10 molecular sieves in the SEM or TEM image and calculating their average value.

[0012] The ratio of the bulk silicon-aluminum molar ratio to the surface silicon-aluminum molar ratio of the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve grains is 1.1-1.4, and the relative crystallinity is 75-90%. The bulk silicon-aluminum molar ratio is calculated as SiO2 / Al2O3, and the surface silicon-aluminum molar ratio is calculated as SiO2 / Al2O3. The bulk silicon-aluminum molar ratio refers to the silicon-aluminum molar ratio of the entire ZSM-5 nanocrystalline material, which is determined by the XRF method, and the surface silicon-aluminum molar ratio is determined by the XPS method. The specific testing method is well known to those skilled in the art and will not be repeated here. The bulk silicon-aluminum molar ratio is 15-200. In the present invention, the relative crystallinity of the molecular sieve is based on the XRD standard ZSM-5 molecular sieve standard sample of the China Petrochemical Research Institute, and the crystallinity of this standard sample is regarded as 100%.

[0013] Optionally, the total specific surface area of the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve before phosphorus modification is 340-420 m 2 / g, mesopore specific surface area is 40-150m 2 / g, the mesopore specific surface area accounts for 20-40% of the total specific surface area. The total specific surface area and mesopore specific surface area in the present invention are obtained by BET analysis, which can be found in the literature "Solid Catalyst Research Methods" or "Modern Catalysis Research Methods".

[0014] Optionally, the strong Br acid content of the phosphorus-containing hollow ZSM-5 hierarchical pore molecular sieve accounts for 70-80% of the total Br acid content, and the strong L acid content accounts for 55-70% of the total L acid content.

[0015] The strong Br acid content and the total Br acid content were prepared by pyridine infrared acid method, and the strong L acid content and the total L acid content were prepared by pyridine infrared acid method.

[0016] Optionally, the carrier includes other carriers, and the other carriers are selected from one or more of natural clay, alumina carrier, silica carrier and aluminum phosphate carrier.

[0017] In one embodiment, the alumina carrier is one or more of aluminum sol, acidified pseudo-boehmite, hydrated alumina and activated alumina; and the aluminum phosphate carrier is aluminum phosphate gel.

[0018] The silicon oxide carrier can be one or more of neutral silica sol, acidic silica sol or alkaline silica sol.

[0019] In a specific embodiment of the present invention, the porous oxide support having a weak B acid is a modified silicon-based matrix; the silicon-based matrix is preferably present in an amount of 1-20% by weight, based on the dry weight of the catalytic cracking catalyst. The modified silicon-based matrix comprises a silicon-based matrix and a modifier; the modifier is one or more of boron oxide, aluminum oxide, magnesium oxide, and zirconium oxide, and the modifier content, calculated as oxide, is 5-40% by weight, and the silicon oxide content is 60-95% by weight, based on the weight of the modified silicon-based matrix. The modified silicon-based matrix is obtained by modifying the silicon oxide support by adding a metal salt solution. The silicon oxide can be derived from one or more of neutral silica sol, acidic silica sol, or alkaline silica sol. The maximum mesopore diameter of the modified silicon-based matrix is preferably 3 nm to 20 nm.

[0020] The modified silicon-based matrix can be obtained by adding a metal salt solution to the silicon-based matrix for modification; a method for preparing the modified silicon-based matrix includes:

[0021] (1) preparing a modifying element salt solution with a concentration of 10-50 wt%, wherein the modifier element is one or more of boron, aluminum, magnesium, and zirconium;

[0022] (2) adding a modified element salt solution to a silicon-based matrix, and adding ammonia water to adjust the pH value to 6-7; the silicon-based matrix can be one or more of neutral silica sol, acidic silica sol or alkaline silica sol; the neutral silica sol, acidic silica sol or alkaline silica sol, respectively, can have an SiO2 content of 10-40% by weight.

[0023] (3) Filtration, drying, and calcination. The calcination temperature may be 400-600°C, and the calcination time may be 1-5 hours.

[0024] Preferably, the modified silicon-based matrix has a most probable mesopore distribution of 3 nm to 15 nm, a total Br acid content of 5 to 15 μmol / g, and a strong Br acid content of 0.5 to 2.5 μmol / g.

[0025] According to the present invention, based on the dry basis weight of the catalytic cracking catalyst, the content of the phosphorus-containing hollow ZSM-5 multi-level porous molecular sieve in the catalytic cracking catalyst is 30-55 weight%, the content of the carrier is 45-70 weight%, and the content of the porous oxide support having weak B acid is 3-15 weight%.

[0026] Optionally, based on the dry weight of the catalytic cracking catalyst, the phosphorus-containing hollow multi-level pore ZSM-5 molecular sieve comprises 30-55% by weight, the carrier comprises 45-70% by weight, and the modified silicon-based matrix comprises 1-20% by weight. The other carriers comprise 25-69% by weight. The modified silicon-based matrix preferably has a maximum mesopore diameter of 3 nm to 20 nm.

[0027] In a specific embodiment of the present invention, based on the dry weight of the catalytic cracking catalyst, the catalytic cracking catalyst contains 20-50 weight% of the phosphorus-containing hollow ZSM-5 hierarchical pore molecular sieve, 20-50 weight% of clay, 5-30 weight% of acidified pseudo-boehmite, 3-20 weight% of aluminum sol and 2-25 weight% of a porous oxide having a weak B acid. Furthermore, based on the dry weight of the catalytic cracking catalyst, on a dry basis, the catalytic cracking catalyst includes 30-55 weight % such as 40-50 weight % of the phosphorus-containing hollow ZSM-5 hierarchical pore molecular sieve, 10-30 weight % of clay such as 15-25 weight % of clay, 5-20 weight % such as 8-15 weight % of pseudo-boehmite (abbreviated as diaspore), 5-25 weight % such as 10-20 weight % of aluminum sol and 2-25 weight % such as 5-25 weight % or 5-20 weight % or such as 2-15 weight % such as 5-10 weight % of the porous oxide support having weak B acid.

[0028] In a specific embodiment of the present invention, the content of sodium oxide in the catalytic cracking catalyst is preferably 0.15 wt% or less, based on the dry weight of the catalytic cracking catalyst.

[0029] The catalytic cracking catalyst can be prepared by the following preparation method, comprising: spray drying and calcining a slurry formed by a carrier comprising a porous oxide having weak B acid, a phosphorus-containing hollow ZSM-5 hierarchical pore molecular sieve, and water.

[0030] One embodiment of the method for preparing the catalytic cracking catalyst of the present invention comprises mixing a porous oxide support containing a weak Br(II) acid, another support, a phosphorus-containing hollow ZSM-5 hierarchical pore molecular sieve, and water, followed by slurrying, spray drying, and calcination. Spray drying is a commonly used method by those skilled in the art, and can simultaneously dry the material and shape the catalyst. Spray drying is well known to those skilled in the art, and the specific method is not described here in detail.

[0031] In one embodiment, the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve can be prepared by a method comprising the following steps:

[0032] (1) mixing a first organosilicon source and a first solvent at 30-50° C. and stirring for 0.5-5 hours, then heating to 70-100° C. and stirring for 2-10 hours, and mixing the obtained mixed liquid with a first template at 20-30° C. and mixing for 0.5-3.0 hours to obtain a first mixed product;

[0033] (2) mixing a first alkali metal hydroxide, calculated as alkali metal oxide, a second solvent, and a first aluminum source, calculated as Al2O3, at a molar ratio of (1.5-5):(60-350):1 at 20-80°C for 0.5-2.0 hours to obtain a second mixed product;

[0034] (3) mixing the first mixed product and the second mixed product and performing dynamic crystallization, taking out the obtained solid and performing a second roasting to obtain a first solid product;

[0035] (4) mixing the first solid product with a first solution containing an alkali, heating the mixture to a reaction temperature at a heating rate of 1-5°C / min, and reacting the mixture at the reaction temperature for 10-90 minutes to obtain a second solid product; wherein the reaction temperature is 60-90°C, and the content of the alkali in the first solution containing an alkali is 0.45-2 mol / L;

[0036] (5) subjecting the second solid product to a first ammonium exchange to obtain a third solid product;

[0037] (6) Mixing the third solid product with a second solution containing a phosphorus source, and subjecting the obtained first slurry to a second drying and a third roasting.

[0038] In another embodiment, the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve can also be prepared by a method comprising the following steps:

[0039] S1. Mixing a second template, a second inorganic silicon source, and a third solvent at 30-50° C. for 0.5-3.0 hours, and subjecting the obtained third mixed product to a first hydrothermal treatment and a second hydrothermal treatment in sequence to obtain a fourth mixed product; wherein the conditions of the first hydrothermal treatment include: a temperature of 80-150° C. and a time of 1-6 hours; and the conditions of the second hydrothermal treatment include: a temperature of 160-180° C. and a time of 4-60 hours;

[0040] S2. Mixing a second alkali metal hydroxide, calculated as alkali metal oxide, a fourth solvent, and a second aluminum source, calculated as Al2O3, in a molar ratio of (1.5-5):(60-350):1 at 20-80°C for 0.5-2.0 hours to obtain a fifth mixed product;

[0041] S3, mixing the fourth mixed product and the fifth mixed product, subjecting the obtained mixture to a third hydrothermal treatment, taking out the obtained solid and subjecting it to a fourth roasting to obtain a fourth solid product;

[0042] S4. Mixing the fourth solid product with the second alkali-containing solution, heating the mixture to a reaction temperature at a heating rate of 1-5°C / min, and reacting the mixture at the reaction temperature for 10-90 minutes to obtain a fifth solid product, wherein the reaction temperature is 60-90°C, and the content of alkali in the second alkali-containing solution is 0.45-2 mol / L;

[0043] S5, performing a second ammonium exchange on the fifth solid product to obtain a sixth solid product;

[0044] S6. Mixing the sixth solid product with a fourth solution containing a phosphorus source, and subjecting the obtained second slurry to a third drying and a fifth calcination.

[0045] Optionally, the first organic silicon source is selected from one or more of methyl orthosilicate and ethyl orthosilicate.

[0046] The second inorganic silicon source is selected from one or more of silica sol, water glass and solid silica gel.

[0047] The first template agent and the second template agent are independently selected from one or more of tetrapropylammonium bromide, tetrapropylammonium hydroxide, n-butylamine and hexamethylenediamine.

[0048] The first aluminum source and the second aluminum source are each independently selected from one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum isopropoxide and aluminum sol.

[0049] The first alkali metal hydroxide and the second alkali metal hydroxide are independently selected from one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide.

[0050] The first alkali-containing solution and the third alkali-containing solution are independently selected from one or more of sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution and barium hydroxide solution.

[0051] The phosphorus source is selected from at least one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate.

[0052] Optionally, the molar ratio of the total amount of the first template, the first solvent and the second solvent, the first alkali metal hydroxide and the first organosilicon source is (0.06-0.55):(10-100):(0.02-1.5):1, and the molar ratio of the first organosilicon source to the first aluminum source is (20-500):1; wherein, the first organosilicon source is calculated as SiO2, the first alkali metal hydroxide is calculated as alkali metal oxide, and the first aluminum source is calculated as Al2O3.

[0053] Preferably, in step (2), the molar ratio of the first alkali metal hydroxide calculated as alkali metal oxide, the second solvent and the first aluminum source calculated as Al2O3 is (2-4.5): (80-350):1.

[0054] According to the present invention, in step (3), dynamic crystallization is well known to those skilled in the art, and the conditions for the dynamic crystallization may include: a temperature of 80-200°C and a time of 4-80 hours; preferably, a temperature of 160-180°C and a time of 12-60 hours.

[0055] Preferably, in step (4), the weight ratio of the first solid product to the first alkali-containing solution is 1:(2-10); the ratio of the bulk silicon-aluminum molar ratio to the surface silicon-aluminum molar ratio of the first solid product is 1.2-5.0.

[0056] According to the present invention, in step (5), the second solid product is subjected to a first ammonium exchange. In one embodiment, the method comprises: mixing the second solid product, the first ammonium source and the fifth solvent in a weight ratio of 1: (0.5-2.0): (5-20), and reacting the resulting mixture at 50-100°C, preferably 60-90°C for 0.5-2 hours. The first ammonium source is selected from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate. The ammonium exchange can be performed once or multiple times. The ammonium exchange can also include a roasting step, and the roasting can be performed once or multiple times. For example, the roasting can be carried out after each contact and exchange with ammonium ions, or after multiple contact and exchange with ammonium ions, the roasting can be carried out after drying and roasting. Preferably, roasting is performed after the last ammonium exchange.

[0057] Preferably, in step (6), the weight ratio of the second solution containing the phosphorus source to the third solid product is 1:(0.5-2.0).

[0058] According to the present invention, compared with the first solid product, the mesopore specific surface area of the third solid product increases by 100-500%, the mesopore volume increases by 150-600%, and the total acid content increases by 50-250%.

[0059] The molar ratio of the total amount of the second template, the third solvent and the fourth solvent, the second alkali metal hydroxide and the second inorganic silicon source is (0.06-0.55): (10-100): (0.02-1.5): 1, preferably (0.08-0.50): (15-85): (0.03-1.2): 1, and the molar ratio of the second inorganic silicon source to the second aluminum source is (20-500): 1; wherein, the second inorganic silicon source is calculated as SiO2, the second alkali metal hydroxide is calculated as alkali metal oxide, and the second aluminum source is calculated as Al2O3.

[0060] According to the present invention, the hydrothermal treatment is well known to those skilled in the art and can be performed, for example, in a heat-resistant, sealed container. The present invention does not impose any restrictions on the pressure of the hydrothermal treatment and the hydrothermal treatment can be performed under the autogenous pressure of the reaction system or under an applied pressure, preferably under autogenous pressure.

[0061] In one embodiment, the conditions of the second hydrothermal treatment include: a temperature of 160-180° C. and a time of 12-60 hours.

[0062] Preferably, in step S2, the molar ratio of the second alkali metal hydroxide calculated as alkali metal oxide, the fourth solvent and the second aluminum source calculated as Al2O3 is (2-4.5): (80-350):1.

[0063] Preferably, in step S4, the weight ratio of the fourth solid product to the second alkali-containing solution is 1:(2-10), and the ratio of the bulk silicon-aluminum molar ratio to the surface silicon-aluminum molar ratio of the fourth solid product is 1.2-5.0.

[0064] According to the present invention, in step S5, the second ammonium exchange of the fifth solid product comprises: mixing the fifth solid product, the second ammonium source and the sixth solvent in a weight ratio of 1: (0.5-2): (5-20), and reacting the resulting mixture at 50-100° C., preferably 60-90° C. for 0.5-2 hours. The second ammonium source is selected from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate. The ammonium exchange can be performed once or multiple times. The ammonium exchange can also include a roasting step, and the roasting can be performed once or multiple times. For example, it can be dried and roasted after each contact and exchange with ammonium ions, or it can be dried and roasted after multiple exchanges with ammonium ions. Preferably, roasting is performed after the last ammonium exchange.

[0065] According to the present invention, preferably, in step S6, the weight ratio of the fourth solution containing the phosphorus source to the sixth solid product is 1:(0.5-2.0).

[0066] According to the present invention, preferably, compared with the fourth solid product, the mesopore specific surface area of the sixth solid product increases by 100-500%, the mesopore volume increases by 150-600%, and the total acid content increases by 50-250%.

[0067] According to the present invention, roasting is a technical means conventionally adopted by those skilled in the art. For example, roasting can be carried out in a muffle furnace, a tubular furnace, etc. The conditions of the second roasting, the third roasting, the fourth roasting and the fifth roasting are independently included: a temperature of 400-600°C and a time of 2-6 hours. For other roastings, the roasting temperature is 400-600°C and the roasting time is 2-6 hours. Preferably, the roasting temperature is 450-580°C and the time is 2.5-4.5 hours. The other roastings include, for example, roasting during or after the ammonium exchange process, and roasting of catalyst cracking catalysts.

[0068] Optionally, the conditions for the dynamic crystallization include: a temperature of 160-180° C. and a time of 12-60 hours.

[0069] The conditions of the third hydrothermal treatment include: a temperature of 160-180° C. and a time of 12-60 hours.

[0070] According to the present invention, drying is a conventional technique employed by those skilled in the art. The drying temperature may be 90-120°C, and the drying time may be determined based on the drying method and drying requirements. In one embodiment, the drying time is 1-24 hours. For example, the second drying and the third drying conditions may each independently include: a temperature of 90-120°C and a drying time of 1-24 hours. For example, the drying may be performed in a constant temperature drying oven.

[0071] According to the present invention, the first organic silicon source can be selected from one or more of methyl orthosilicate and ethyl orthosilicate; the second inorganic silicon source can be selected from one or more of silica sol, water glass and solid silica gel; the first template and the second template can be independently selected from one or more of tetrapropylammonium bromide, tetrapropylammonium hydroxide, n-butylamine and hexamethylenediamine; the first aluminum source and the second aluminum source can be independently selected from one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum isopropoxide and aluminum sol; the first alkali metal hydroxide and the second alkali metal hydroxide can be independently selected from one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide; the first alkali solution and the second alkali solution can be independently selected from one or more of sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide and barium hydroxide; the phosphorus source can be selected from at least one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate.

[0072] In a specific embodiment of the present invention, the method for preparing the catalytic cracking catalyst further comprises: mixing the catalyst particles obtained by spray drying and calcining, an ammonium salt, and water in a weight ratio of 1:(0.1-1):(5-15), performing a third ammonium exchange, and optionally washing; the conditions for the third ammonium exchange include: a temperature of 50-100°C and a time of 0.5-2 hours; the solution containing the ammonium salt is calculated as an ammonium salt, and the ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate, and ammonium nitrate. The ammonium exchange can be performed multiple times.

[0073] According to the present invention, the first solvent, the second solvent, the third solvent, the fourth solvent, the fifth solvent and the sixth solvent may each be water.

[0074] The heavy oil catalytic cracking method provided by the present invention is carried out in a fast fluidized bed reactor. The reaction conditions for the heavy oil to contact the catalytic cracking catalyst in the fast bed reactor are preferably: a reaction temperature of 550-600°C, a reaction weight hourly space velocity of 5-20h -1 , the agent-oil ratio is 5-15 by weight. Preferably, the fast fluidized bed reactor has an RTC reactor with quasi-full dense phase fast fluidization characteristics, which has an inverted trapezoidal reactor structure, which can ensure the consistency of the axial gas linear velocity during hydrocarbon cracking and expansion. The reflux of the fast bed reactor ensures the uniformity of the temperature in the reactor. At the same time, the reactor ensures the realization of the full dense phase, which helps to suppress the re-conversion of propylene. Preferably, in the fast fluidized bed reactor, the catalytic cracking catalyst is distributed in a full dense phase. For the reaction in a fast fluidized bed reactor, see WO2020015603A1.

[0075] The present invention further provides a heavy oil catalytic cracking catalyst, which contains the hollow ZSM-5 multi-level pore molecular sieve, the porous oxide material with weak B acid and other carrier materials.

[0076] The heavy oil catalytic cracking method provided by the present invention adopts a fast bed reactor and is combined with the heavy oil catalytic cracking catalyst to achieve a higher yield of light olefins (ethylene, propylene and butene).

[0077] The heavy oil catalytic cracking catalyst provided by the present invention comprises a rationally designed phosphorus-containing enclosed hollow ZSM-5 hierarchical pore molecular sieve, a porous oxide support containing a weak Br acid, and other supports. Its multi-level pore structure effectively increases the yield of light olefins in the heavy oil catalytic cracking process. The catalyst is particularly suitable for rapid bed reactions, significantly improving light olefin yields and propylene selectivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0078] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the following detailed description, they are used to explain the present invention but do not constitute a limitation of the present invention. In the accompanying drawings:

[0079] Figure 1 This is a schematic diagram of the reactor (fast bed reactor) of the RTC process. DETAILED DESCRIPTION

[0080] The following is a detailed description of the specific embodiments of the present invention. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention and are not intended to limit the present invention.

[0081] In the examples and comparative examples, the crystal size of the molecular sieve was measured by SEM, and the sizes of 10 crystals were randomly measured and the average value was taken to obtain the average crystal size of the molecular sieve sample.

[0082] The bulk silicon-to-aluminum ratio and phosphorus-to-aluminum molar ratio of the samples were determined by XRF using a ZSX Primus II (Rigaku) X-ray fluorescence spectrometer. The test conditions were an excitation voltage of 50 kV, an excitation current of 50 mA, and rhodium-palladium. The elemental composition of the molecular sieves was analyzed by measuring the intensity of the spectral peaks of each element using a scintillation counter and a proportional counter.

[0083] The surface Si / Al molar ratios of the samples were determined by XPS using a ThermoFisher ESCALab250 X-ray photoelectron spectrometer. The test conditions were: monochromatized Al Kα X-rays at an excitation energy of 1496.6 eV and a power of 150 W. Electron binding energies were corrected using the C1s peak (284.8 eV) of contaminating carbon.

[0084] The total specific surface area and mesopore specific surface area of the samples were determined using the BET adsorption full analysis method. Instrument: ASAP 2420 adsorption instrument, Micromeritics, USA. Test conditions: The samples were vacuum degassed at 100°C and 300°C for 0.5 h and 6 h, respectively. N adsorption-desorption tests were performed at 77.4 K. The adsorption and desorption amounts of nitrogen on the purified samples were measured under different specific pressures, and N adsorption-desorption isotherms were obtained. The BET specific surface area was calculated using the BET formula, the micropore area was calculated using a t-plot, and the pore size distribution was calculated using the BJH method.

[0085] The relative crystallinity of the samples was determined by X-ray diffraction using an Empyrean instrument. The test conditions were: tube voltage 40 kV, tube current 40 mA, Cu target Kα radiation, 2θ scanning range 5°-35°, and scanning rate 2° / min.

[0086] The strong Br acid content and the total Br acid content of the sample are detected by pyridine infrared adsorption method, and the strong L acid content and the total L acid content are detected by pyridine infrared adsorption method. Instrument: NICOLET 6700 Fourier transform infrared spectrometer of BIQ-RAD Company of the United States. Test method: After the sample is pressed into a tablet, it is placed in the in-situ cell of the infrared spectrometer and sealed. Adsorption and desorption are carried out according to the following test method. The amount of pyridine adsorbed acid is calculated by peak area. Test method: After the sample is pressed into a tablet, it is placed in the in-situ cell of the infrared spectrometer and sealed. Vacuum it to 10 -3 Pa, hold for 1 hour to desorb the gas molecules on the sample surface, and cool to 50 ° C. Introduce pyridine vapor into the in-situ cell, balance for 30 minutes, heat to 200 ° C, vacuum to 10-3 Pa again, hold for 30 minutes, cool to 50 ° C, scan in the wave number range of 1300 cm-1 to 3900 cm-1, and record the infrared absorption spectrum of pyridine adsorption at 200 ° C. Heat to 350 ° C, vacuum to 10 -3 Pa, hold for 30 min, cool to room temperature, and record the infrared spectrum of pyridine adsorption at 350°C. The amount of pyridine adsorbed acid is calculated based on the peak area.

[0087] Examples 1-3 are examples of preparing phosphorus-containing hollow ZSM-5 multi-level pore molecular sieves

[0088] Example 1

[0089] (1) Weighing 91.2 g of ethyl orthosilicate, adding 639.14 g of deionized water, stirring and heating in a water bath at 40° C. for 2 h, then raising the water bath temperature to 70° C. and stirring and heating for 4 h to remove ethanol produced by hydrolysis of the silicon source, intermittently replenishing the system with water evaporated simultaneously with the ethanol during this process, and mixing the resulting mixed liquid with 111.65 g of a tetrapropylammonium hydroxide aqueous solution (mass fraction 25.0%) at 25° C. and stirring for 1 h to obtain a first mixed product;

[0090] (2) Weigh 3.44 g of sodium hydroxide pellets, add 60.8 g of deionized water to completely dissolve the sodium hydroxide, then add 8.16 g of aluminum nitrate nonahydrate, and stir at room temperature for 1.0 h to obtain a second mixed product (i.e., an aluminum source solution);

[0091] (3) The second mixed product was slowly added to the first mixed product, mixed evenly, stirred at room temperature for 4.0 h, and the obtained precursor solution was transferred to a synthesis reactor and dynamically crystallized at 170 ° C for 48 h; after the crystallization, centrifugation was performed, washed, dried, and calcined at 550 ° C for 4 h to obtain the first solid product (denoted as molecular sieve I-M1);

[0092] (4) The first solid product and a sodium hydroxide solution with a concentration of 0.65 mol / L were mixed uniformly, with the mass ratio of the first solid product to the alkaline solution being 1:10, and the mixture was heated to 80°C at a heating rate of 2°C / min, and then stirred at the same temperature for 30 min, filtered, washed, and dried to obtain a second solid product (denoted as molecular sieve I-S1-Na);

[0093] (5) The second solid product: ammonium chloride: deionized water were mixed evenly in a weight ratio of 1:1:10, stirred and heated in a water bath at 80°C for 30 minutes, filtered, washed, and dried. The obtained solid product: ammonium chloride: deionized water were mixed evenly in a weight ratio of 1:0.5:10, subjected to a second ammonium exchange, filtered, washed, dried, and calcined at 550°C for 2 hours to obtain a third solid product (a hydrogen-type hollow ZSM-5 multi-level pore molecular sieve, denoted as I-S1-H).

[0094] (6) Dissolve 2.69 g of H3PO4 solution (concentration of 85 wt%) in 46.25 g of deionized water, stir evenly and fully dissolve to obtain a phosphorus-containing solution; spread 50 g of the third solid product on a watch glass, slowly add the phosphorus-containing solution dropwise, mix thoroughly and evenly to make the molecular sieve into a "viscous paste", dry it in an air atmosphere at 115°C for 4 h, and then calcined it at 550°C for 2 h to obtain the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve of the present invention, which is recorded as SS-1.

[0095] Example 2

[0096] (1) Weighing 60.0 g of methyl orthosilicate, adding 425.0 g of deionized water, and stirring and heating in a water bath at 30° C. for 5 h, then raising the water bath temperature to 70° C. and stirring for 4 h to remove ethanol produced by hydrolysis of the silicon source, intermittently replenishing the system with water evaporated simultaneously with the ethanol during this process, and mixing the resulting mixed liquid with 34.5 g of a 25.0% aqueous solution of tetrapropylammonium bromide at 20° C. and stirring for 0.5 h to obtain a first mixed product;

[0097] (2) Weigh 1.30 g of sodium hydroxide pellets, add 31.0 g of deionized water to completely dissolve the sodium hydroxide, then add 0.85 g of sodium aluminate (alumina content of 62.0%), and stir at 20° C. for 2.0 h to obtain a second mixed product;

[0098] (3) slowly adding the second mixed product to the first mixed product, mixing uniformly, and stirring at room temperature for 4.0 hours; transferring the obtained precursor solution into a synthesis reactor and dynamically crystallizing at 180°C for 24 hours; after the crystallization is completed, centrifugation, filtration, washing, drying, and calcining at 550°C for 4 hours to obtain the first solid product (denoted as molecular sieve I-M2);

[0099] (4) The first solid product and a sodium hydroxide alkaline solution with a concentration of 0.6 mol / L were mixed uniformly, with the mass ratio of the first solid product to the alkaline solution being 1:10, and the temperature was raised to 80°C at a heating rate of 4°C / min, and then heated at 80°C with stirring for 30 min, filtered, washed, and dried to obtain a second solid product (denoted as molecular sieve I-S2-Na);

[0100] (5) The second solid product: ammonium chloride: deionized water were mixed uniformly in a weight ratio of 1:1:10, stirred and heated in a water bath at 80°C for 30 min, filtered, washed, and dried, and the obtained solid product: ammonium chloride: deionized water were mixed uniformly in a weight ratio of 1:0.5:10, subjected to a second ammonium exchange, filtered, washed, dried, and calcined at 550°C for 2 h to obtain a third solid product (hydrogen-type hollow ZSM-5 multi-level pore molecular sieve, denoted as I-S2-H).

[0101] (6) Dissolve 2.68 g of ammonium dihydrogen phosphate in 44.21 g of deionized water, fully dissolve, and stir evenly to obtain a phosphorus-containing solution; spread 50 g of the third solid product on a watch glass, slowly add the prepared phosphorus-containing solution dropwise, and fully mix until the molecular sieve becomes a "viscous paste"; dry at 110° C. in an air atmosphere for 4 h, and calcine at 550° C. for 2 h to obtain the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve of the present invention, which is recorded as SS-2.

[0102] Example 3

[0103] (1) Weighing 65.13 g of a tetrapropylammonium hydroxide aqueous solution (mass fraction 25.0%), adding 476.62 g of deionized water, stirring at room temperature for 10 min, then adding 165.20 g of silica sol (SiO2 content 25%), stirring in a 50°C water bath for 1.0 h, transferring the obtained third mixed product into a reactor, crystallizing at 80°C for 2 h, and then heating to 170°C for crystallization for 12 h to obtain a fourth mixed product;

[0104] (2) Weighing 1.39 g of sodium hydroxide pellets, adding 27.2 g of deionized water to completely dissolve the sodium hydroxide, then adding 4.76 g of aluminum nitrate nonahydrate, and stirring at 25° C. for 1.0 h to obtain a fifth mixed product;

[0105] (3) adding the fourth mixed product to the fifth mixed product, stirring evenly, and continuing to crystallize at 170°C for 36 hours; after the crystallization is completed, centrifugation is performed, washed, dried, and calcined at 550°C for 4 hours to obtain a fourth solid product (denoted as molecular sieve I-M3);

[0106] (4) The fourth solid product and a sodium hydroxide solution with a concentration of 1.0 mol / L were mixed uniformly, with the mass ratio of the fourth solid product to the alkaline solution being 1:10, and the mixture was heated to 80°C at a heating rate of 5°C / min and stirred at the same temperature for 30 min, filtered, washed, and dried to obtain a fifth solid product (denoted as molecular sieve I-S3-Na);

[0107] (5) The fifth solid product: ammonium chloride: deionized water were mixed uniformly in a weight ratio of 1:1:10, stirred and heated in a water bath at 80°C for 30 min, filtered, washed, and dried, and then the obtained solid product: ammonium chloride: deionized water were mixed uniformly in a weight ratio of 1:0.5:10, subjected to a second ammonium exchange, filtered, washed, dried, and calcined at 550°C for 2 h to obtain a sixth solid product (denoted as I-S3-H).

[0108] (6) Dissolve 1.71 g of H3PO4 solution (concentration 85 wt%) in 42.49 g of deionized water, stir evenly and fully dissolve to obtain a phosphorus-containing solution; spread 50 g of the sixth solid product on a watch glass, slowly add the prepared phosphorus-containing solution dropwise, and mix thoroughly to make the molecular sieve into a "viscous paste"; dry in an air atmosphere at 115°C for 4 h, and then calcined at 550°C for 2 h to obtain the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve of the present invention, which is recorded as SS-3.

[0109] Comparative Example 1

[0110] In the comparative example, conventional crystal ZSM-5 molecular sieve DB1 was selected, which was purchased from Sinopec Catalyst Company Qilu Branch and had a silicon-aluminum molar ratio (SiO2 / Al2O3) of 25.

[0111] Table 1 Example sample parameters

[0112]

[0113]

[0114] In Table 1, R represents a template, and the bulk-surface silicon-aluminum molar ratio represents the ratio of the bulk silicon-aluminum molar ratio to the surface silicon-aluminum molar ratio.

[0115] Examples 4-6 and Comparative Examples 2-4 are for preparing catalytic cracking catalysts.

[0116] Unless otherwise specified, the raw materials used in the following examples and comparative examples were commercially available. Among them, kaolin is an industrial product of China Kaolin Corporation, and its solid content is 75% by weight; the pseudo-boehmite used is produced by Shandong Aluminum Plant, and its alumina content is 65% by weight; the aluminum sol is produced by Qilu Branch of Sinopec Catalyst Co., Ltd., and its alumina content is 20% by weight; the silica sol is produced by Qingdao Junqiang New Materials Co., Ltd., and its silicon oxide content is 25% by weight (alkaline silica sol, pH 9.5); and the concentrated hydrochloric acid is chemically pure and produced by Beijing Yinokai.

[0117] Examples 4-6

[0118] Catalytic cracking catalysts were prepared using the phosphorus-containing hollow ZSM-5 hierarchical molecular sieves prepared according to the methods of Examples 1-3. The obtained catalytic cracking catalysts were numbered as A1, A2, and A3, respectively. The preparation method of the catalytic cracking catalyst comprises:

[0119] (1) Pseudoboehmite (abbreviated as diaspore) and water were uniformly mixed, and concentrated hydrochloric acid having a concentration of 36% by weight and an acid-aluminum molar ratio of 0.2 (the weight ratio of HCl to pseudoboehmite calculated as Al2O3) was added under stirring; the resulting mixture was aged at 70°C for 1.5 hours to obtain an aged pseudoboehmite slurry. The aged pseudoboehmite slurry had an alumina content of 12% by weight;

[0120] (2) Preparation of modified silicon-based matrix

[0121] Aluminum nitrate nonahydrate and deionized water are mixed to prepare an aluminum solution in which the Al2O3 concentration is 0.2 g / L; the solution is added to a silica sol to form a silica-alumina gel in which the weight ratio of silicon oxide to aluminum oxide is 3.5:1; an ammonia solution (NH3 content 25 wt%) is added to the silica-alumina gel, the pH value is adjusted to 7.6, and the solution is allowed to stand for 15 minutes; the solution is filtered, dried, and calcined (calcination temperature 550°C, time 2 hours) to obtain a silicon-based matrix containing an additive, wherein the modified silicon-based matrix has a maximum pore size of 8 nm, a total Br2 acid content of 8.0 μmol / g, and a strong Br2 acid content of 2.5 μmol / g.

[0122] (3) uniformly mixing the prepared phosphorus-containing hollow ZSM-5 hierarchical molecular sieve, aluminum sol, modified silicon-based matrix, kaolin, the aged pseudo-boehmite slurry, and deionized water to form a slurry with a solid content of 30% by weight, and spray drying to obtain catalyst microspheres;

[0123] (4) The catalyst microspheres were calcined at 550 °C for 4 h;

[0124] (5) The calcined catalyst microspheres were exchanged at 80° C. for 1 hour, filtered, and the exchange and filtration process was repeated once in a weight ratio of catalyst microspheres: ammonium salt: H O = 1:1:10, followed by drying. The ammonium salt was ammonium chloride, and the resulting catalytic cracking catalyst had a sodium oxide content of less than 0.15% by weight. The composition of the prepared catalyst is shown in Table 2.

[0125] Comparative Example 2

[0126] Comparative Example 2 illustrates the preparation of a catalytic cracking catalyst using the molecular sieve DB1 provided in Comparative Example 1. According to the catalyst preparation method of Example 5, molecular sieve DB1 is mixed with pseudo-boehmite, modified silicon-based matrix, kaolin, water and aluminum sol, and spray-dried to prepare microsphere catalyst DB2.

[0127] Comparative Example 3

[0128] The catalyst was prepared by the method of Reference Example 5, except that the modified silicon-based matrix was not used, but an equal mass amount (on a dry basis) of silica sol (unmodified, with a B acid content of 0) was used instead.

[0129] Comparative Example 4

[0130] Refer to Example 5, except that the modified silicon-based matrix is not used, but an equal mass amount (on a dry basis) of acidified pseudo-boehmite (whose B acid content is 0) is used instead.

[0131] Table 2 Catalyst composition

[0132]

[0133] Performance Testing

[0134] The catalytic cracking catalysts prepared in the Examples and Comparative Examples were aged for 17 hours at 800°C in 100% by volume water vapor, and their catalytic cracking performance was evaluated in a fast bed reactor. The evaluation conditions were a reaction temperature of 600°C and a catalyst-to-oil ratio of 10 by weight. The heavy oil properties are shown in Table 3, and the reaction results are shown in Table 4. The fast bed reactor had dimensions of 350 mm in height, an inverted trapezoidal shape, a top diameter of 100 mm, and a bottom diameter of 16 mm.

[0135] Table 3 Heavy oil properties

[0136]

[0137]

[0138] Table 4 Catalytic performance evaluation results

[0139]

[0140] The yields mentioned herein are calculated based on the raw material feed.

[0141] Conversion rate = (100 - diesel yield - heavy oil yield) × 100%

[0142] Product yield = product yield (weight) / heavy oil feed amount (weight) × 100%

[0143] Propylene selectivity = propylene yield / conversion rate × 100%

[0144] As shown in Table 4, the heavy oil catalytic cracking catalyst provided by the present invention has a higher heavy oil cracking capacity and a higher light olefin yield. It contains a phosphorus-containing, enclosed hollow ZSM-5 hierarchical pore molecular sieve with a microporous-mesoporous-macroporous structure that matches the shell structure of the hollow structure, and a modified matrix macroporous structure. The developed catalyst has excellent diffusion properties and can significantly improve cracking performance. The catalyst is highly stable and maintains excellent performance even after aging for 17 hours.

Claims

1. A heavy oil catalytic cracking method comprising: contacting the heavy oil with a catalytic cracking catalyst in a fast bed reactor, wherein: The catalytic cracking catalyst comprises a phosphorus-containing hollow ZSM-5 hierarchical pore molecular sieve and a carrier comprising a porous oxide having a weak Br acid, wherein, based on the dry weight of the catalytic cracking catalyst, the content of the phosphorus-containing hollow ZSM-5 hierarchical pore molecular sieve is 25-60% by weight on a dry basis, the content of the porous oxide having a weak Br acid is 1-30% by weight on a dry basis, and the total content of the carrier is 40-75% by weight on a dry basis; The porous oxide with weak Br acid has a total Br acid content of 5-15 μmol / g and a strong Br acid content of 0.5-2.5 μmol / g; the porous oxide with weak Br acid is a modified silicon-based matrix, the modified silicon-based matrix contains a modifier and a silicon-based matrix, and the modifier is one or more of boron oxide, aluminum oxide, magnesium oxide, and zirconium oxide; The phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve has a closed hollow structure. The phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve has an average grain size of 0.2-3.0 μm, a ratio of the bulk silicon-aluminum molar ratio to the surface silicon-aluminum molar ratio of 1.0-1.5, a phosphorus-aluminum molar ratio of 0.1-1.5, a strong B acid content in the total B acid content of 65-80%, and a strong L acid content in the total L acid content of 50-75%.

2. The method according to claim 1, wherein The phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve has an N2 adsorption-desorption curve that exhibits an H4-type hysteresis loop.

3. The method according to claim 1 or 2, wherein: The phosphorus-aluminum molar ratio of the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve is 0.2-1.3, and the ratio of the bulk silicon-aluminum molar ratio to the surface silicon-aluminum molar ratio is 1.1-1.

4. The phosphorus-containing hollow ZSM-5 hierarchical pore molecular sieve has an average grain size of 0.4-2.5 μm and a relative crystallinity of 75-90%; The phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve has a mesoporous specific surface area of 40-150 m2 before phosphorus modification. 2 / g, with a total specific surface area of 340-420m 2 / g, and the proportion of mesoporous specific surface area to the total specific surface area is 20-40%.

4. The method according to claim 1, wherein The strong Br acid content of the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve accounts for 70-80% of the total Br acid content, and the strong L acid content accounts for 55-70% of the total L acid content.

5. The method according to claim 1, wherein The carrier includes other carriers, and the other carriers are selected from one or more of natural clay, alumina carrier, and aluminum phosphate carrier; wherein the alumina carrier is one or more of aluminum sol, acidified pseudo-boehmite, hydrated alumina and activated alumina; and the aluminum phosphate carrier is aluminum phosphate gel; Based on the dry weight of the modified silicon-based matrix, the content of the modifier is 5-40% by weight, and the content of silicon oxide is 60-95% by weight, calculated as oxide; based on the dry weight of the catalytic cracking catalyst, the content of the modified silicon-based matrix is 1-20% by weight, calculated as dry weight; the silicon-based matrix is one or more of neutral silica sol, acidic silica sol or alkaline silica sol.

6. The method according to claim 5, wherein: The modified silicon-based matrix is obtained by adding a metal salt solution into the silicon-based matrix for modification; The preparation method of the modified silicon-based matrix comprises: (1) preparing a modifying element salt solution with a concentration of 10-50 wt %, wherein the modifying element is one or more of boron, aluminum, magnesium, and zirconium; (2) adding a modified element salt solution to the silicon-based matrix and adjusting the pH to 6-7 by adding ammonia water; (3) Filter, dry and roast.

7. The method according to claim 1, wherein Based on the dry weight of the catalytic cracking catalyst, the content of the phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve is 30-55 weight percent on a dry basis, and the content of the carrier is 45-70 weight percent on a dry basis; furthermore, the content of the modified silicon-based matrix is 1-20 weight percent on a dry basis, and the content of other carriers is 25-69 weight percent on a dry basis; and the maximum mesopore diameter of the modified silicon-based matrix is 3 nm to 20 nm.

8. The method according to claim 1, wherein The catalytic cracking catalyst is prepared by a preparation method comprising the following steps: obtaining a phosphorus-containing hollow ZSM-5 multi-level porous molecular sieve, forming a slurry with a porous oxide carrier containing weak Br acid, the phosphorus-containing hollow ZSM-5 multi-level porous molecular sieve and water, spray drying, and optionally calcining.

9. The method according to claim 1, wherein The phosphorus-containing hollow ZSM-5 multi-level pore molecular sieve is prepared by a method comprising the following steps: (1) mixing a first organosilicon source and a first solvent at 30-50° C. and stirring for 0.5-5 hours, then heating to 70-100° C. and stirring for 2-10 hours, and mixing the obtained mixed liquid with a first template at 20-30° C. and mixing for 0.5-3.0 hours to obtain a first mixed product; (2) mixing a first alkali metal hydroxide, a second solvent and a first aluminum source, calculated as Al2O3, in a molar ratio of (1.5-5): (60-350): 1 at 20-80°C for 0.5-2.0 hours, Obtaining a second mixed product; (3) mixing the first mixed product and the second mixed product and performing dynamic crystallization, taking out the obtained solid and performing a second roasting to obtain a first solid product; (4) mixing the first solid product with a first solution containing an alkali, heating the mixture to a reaction temperature at a heating rate of 1-5°C / min, and reacting the mixture at the reaction temperature for 10-90 minutes to obtain a second solid product; wherein, The reaction temperature is 60-90° C., and the content of alkali in the first alkali-containing solution is 0.45-2 mol / L; (5) subjecting the second solid product to a first ammonium exchange, and optionally calcining, to obtain a third solid product; (6) mixing the third solid product with the second solution containing a phosphorus source to obtain a first slurry, The obtained first slurry is subjected to a second drying and a third calcination; Alternatively, the phosphorus-containing hollow ZSM-5 hierarchical pore molecular sieve is prepared by a method comprising the following steps: S1, mixing the second template, the second inorganic silicon source and the third solvent at 30-50° C. for 0.5-3.0 hours to obtain a third mixed product, and sequentially performing a first hydrothermal treatment and a second hydrothermal treatment to obtain a fourth mixed product; The conditions of the first hydrothermal treatment include: a temperature of 80-150°C and a time of 1-6 hours; the conditions of the second hydrothermal treatment include: a temperature of 160-180°C and a time of 4-60 hours; S2. Mixing a second alkali metal hydroxide, calculated as alkali metal oxide, a fourth solvent, and a second aluminum source, calculated as Al2O3, in a molar ratio of (1.5-5):(60-350):1 at 20-80°C for 0.5-2.0 hours to obtain a fifth mixed product; S3, mixing the fourth mixed product and the fifth mixed product, subjecting the obtained mixture to a third hydrothermal treatment, taking out the obtained solid and subjecting it to a fourth roasting to obtain a fourth solid product; S4. Mixing the fourth solid product with the second alkali-containing solution, heating the mixture to a reaction temperature at a heating rate of 1-5°C / min, and reacting the mixture at the reaction temperature for 10-90 minutes to obtain a fifth solid product; wherein the reaction temperature is 60-90°C, and the content of alkali in the second alkali-containing solution is 0.45-2 mol / L; S5, subjecting the fifth solid product to a second ammonium exchange, and optionally calcining, to obtain a sixth solid product; S6. Mixing the sixth solid product with a fourth solution containing a phosphorus source, and subjecting the obtained second slurry to a third drying and a fifth calcination.

10. The method according to claim 9, wherein: The first organic silicon source is selected from one or both of methyl orthosilicate and ethyl orthosilicate; the second inorganic silicon source is selected from one or more of silica sol, water glass and solid silica gel; the first template and the second template are each independently selected from one or more of tetrapropylammonium bromide, tetrapropylammonium hydroxide, n-butylamine and hexamethylenediamine; the first aluminum source and the second aluminum source are each independently selected from one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum isopropoxide and aluminum sol; the first alkali metal hydroxide and the second alkali metal hydroxide are each independently selected from one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide; the first alkali solution and the second alkali solution are each independently selected from one or more of sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution and barium hydroxide solution; the phosphorus source is selected from one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate.

11. The method according to claim 9, wherein The molar ratio of the total amount of the first template, the first solvent and the second solvent, the amount of the first alkali metal hydroxide and the amount of the first organic silicon source is (0.06-0.55):(10-100):(0.02-1.5):1, and the molar ratio of the amount of the first organic silicon source to the amount of the first aluminum source is (20-500):1; wherein the first organic silicon source is calculated as SiO2, the first alkali metal hydroxide is calculated as alkali metal oxide, and the first aluminum source is calculated as Al2O3; In step (2), the molar ratio of the first alkali metal hydroxide, calculated as alkali metal oxide, the second solvent, and the first aluminum source, calculated as Al2O3, is (2-4.5): (80-350): 1; In step (4), the weight ratio of the first solid product to the first alkali-containing solution is 1:(2-10); the ratio of the bulk silicon-aluminum molar ratio to the surface silicon-aluminum molar ratio of the first solid product is 1.2-5.0; In step (6), the weight ratio of the second solution containing the phosphorus source to the third solid product is 1:(0.5:2.0); The molar ratio of the total amount of the second template, the third solvent and the fourth solvent, the amount of the second alkali metal hydroxide and the amount of the second inorganic silicon source is (0.06-0.55):(10-100):(0.02-1.5):1, and the molar ratio of the second inorganic silicon source to the second aluminum source is (20-500):1; wherein the second inorganic silicon source is calculated as SiO2, the second alkali metal hydroxide is calculated as alkali metal oxide, and the second aluminum source is calculated as Al2O3; In step S2, the molar ratio of the second alkali metal hydroxide, calculated as alkali metal oxide, the fourth solvent, and the second aluminum source, calculated as Al2O3, is (2-4.5): (80-350): 1; In step S4, the weight ratio of the fourth solid product to the second alkali-containing solution is 1:(2-10), and the ratio of the bulk silicon-aluminum molar ratio to the surface silicon-aluminum molar ratio of the fourth solid product is 1.2-5.0; In step S6, the weight ratio of the fourth solution containing the phosphorus source to the sixth solid product is 1:(0.5:2.0); The conditions of the dynamic crystallization include: temperature of 160-180°C and time of 12-60 hours; The conditions of the third hydrothermal treatment include: temperature of 160-180°C and time of 12-60 hours; The conditions of the second calcination, the third calcination, the fourth calcination and the fifth calcination are independently as follows: a temperature of 400-600° C. and a time of 2-6 hours; The conditions for the second drying and the third drying each independently include: a temperature of 90-120°C.

12. The method according to claim 1 or 9, wherein: The Na2O content of the catalytic cracking catalyst is less than 0.15% by weight.

13. The method according to claim 8, wherein The preparation method of the catalytic cracking catalyst further includes: mixing the catalyst particles obtained by the spray drying, ammonium salt and water in a weight ratio of 1: (0.1-1): (5-15) to perform a third ammonium exchange, and washing; the conditions of the third ammonium exchange include: a temperature of 50-100° C. and a time of 0.5-2 hours; the ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.

14. The method according to claim 1, wherein The fast bed reactor has an inverted trapezoidal reactor structure; the reaction conditions for the heavy oil to contact the catalytic cracking catalyst in the fast bed reactor are: reaction temperature 550-600 ° C, reaction weight hourly space velocity 5-20h -1 , agent-oil ratio 5-15 by weight.

15. The method according to claim 11, wherein The second drying and the third drying are each performed for 1 to 24 hours.

16. A rapid bed heavy oil catalytic cracking catalyst, which is the catalytic cracking catalyst according to any one of claims 1 to 15.

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