WO2021208885A1 - 磷改性mfi结构分子筛、含磷改性mfi结构分子筛的催化裂解助剂和催化裂解催化剂、及其制备方法 - Google Patents

磷改性mfi结构分子筛、含磷改性mfi结构分子筛的催化裂解助剂和催化裂解催化剂、及其制备方法 Download PDF

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WO2021208885A1
WO2021208885A1 PCT/CN2021/086824 CN2021086824W WO2021208885A1 WO 2021208885 A1 WO2021208885 A1 WO 2021208885A1 CN 2021086824 W CN2021086824 W CN 2021086824W WO 2021208885 A1 WO2021208885 A1 WO 2021208885A1
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Prior art keywords
phosphorus
molecular sieve
weight
catalytic cracking
clay
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PCT/CN2021/086824
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English (en)
French (fr)
Inventor
罗一斌
王成强
欧阳颖
邢恩会
舒兴田
Original Assignee
中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
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Priority claimed from CN202010283498.2A external-priority patent/CN113526522B/zh
Priority claimed from CN202011169092.8A external-priority patent/CN114505092B/zh
Priority claimed from CN202011175729.4A external-priority patent/CN114425431B/zh
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司石油化工科学研究院 filed Critical 中国石油化工股份有限公司
Priority to KR1020227039668A priority Critical patent/KR20230002701A/ko
Priority to EP21788715.7A priority patent/EP4137457A1/en
Priority to US17/996,187 priority patent/US20230191380A1/en
Priority to JP2022562487A priority patent/JP2023523558A/ja
Publication of WO2021208885A1 publication Critical patent/WO2021208885A1/zh

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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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Definitions

  • the invention relates to a phosphorus-modified MFI structure molecular sieve, a phosphorus-containing modified MFI structure molecular sieve catalytic cracking aid, and a phosphorus-containing modified MFI structure molecular sieve catalytic cracking catalyst.
  • the invention also relates to phosphorus modification The method for preparing the MFI structure molecular sieve, the catalytic cracking aid of the phosphorus-containing modified MFI structure molecular sieve, and the catalytic cracking catalyst of the phosphorus-containing modified MFI structure molecular sieve; the present invention also relates to the catalytic cracking aid and the catalytic cracking catalyst in the catalytic Application in cracking.
  • ZSM-5 molecular sieve which is a widely used zeolite molecular sieve catalyst material developed by the American Mobil company in 1972.
  • ZSM-5 molecular sieve has a three-dimensional intersecting pore structure.
  • the pores along the a-axis are straight pores, and the cross-sectional size is 0.54 ⁇ 0.56nm, which is approximately circular.
  • the pores along the b-axis are zigzag pores with a cross-sectional size of 0.51. ⁇ 0.56nm, elliptical.
  • ZSM-5 molecular sieve The pores of ZSM-5 molecular sieve are composed of ten-membered rings, and the pore size is between small pore zeolite and large pore zeolite, so it has a unique shape-selective catalysis.
  • ZSM-5 molecular sieve has a unique pore structure, good shape-selective catalysis and isomerization performance, high thermal and hydrothermal stability, high specific surface area, wide range of silicon-to-aluminum ratio, unique surface acidity and low structure.
  • the characteristics of carbon content are widely used as catalysts and catalyst carriers, and successfully used in the production processes of alkylation, isomerization, disproportionation, catalytic cracking, methanol to gasoline, methanol to olefins and other production processes.
  • ZSM-5 molecular sieve is introduced into catalytic cracking and C4 hydrocarbon catalytic cracking, showing excellent catalytic performance, and its molecular shape selectivity can greatly increase the yield of
  • ZSM-5 molecular sieve Since 1983, ZSM-5 molecular sieve has been used in catalytic cracking process as a catalytic cracking octane promoter/catalyst, aiming to improve the octane number of catalytic cracking gasoline and the selectivity of low-carbon olefins.
  • US3758403 first reported the use of ZSM-5 molecular sieve as the active component for increasing the production of propylene. It was used as the active component of FCC catalyst together with REY, or it was prepared together with REY to form FCC catalyst.
  • US5997728 discloses the use of ZSM-5 molecular sieve without any modification as an auxiliary agent for increasing the production of propylene. However, the propylene yield of the above two technologies is not high.
  • HZSM-5 molecular sieve has good shape selection performance and isomerization performance, its shortcomings are poor hydrothermal stability, and it is easy to deactivate under severe high temperature hydrothermal conditions, which reduces the catalytic performance.
  • phosphorus can improve the hydrothermal stability of ZSM-5 molecular sieve, and at the same time, phosphorus modified ZSM-5 molecular sieve to increase the yield of low-carbon olefins.
  • Conventional additives usually contain phosphorus-activated ZSM-5, which enables the selective conversion of primary cracked products (such as gasoline olefins) to C3 and C4 olefins.
  • ZSM-5 molecular sieve is modified by introducing an appropriate amount of inorganic phosphorus compound after synthesis, which can stabilize the framework aluminum under severe hydrothermal conditions.
  • CN106994364A discloses a method for phosphorus-modified ZSM-5 molecular sieve.
  • the method firstly uses one or more phosphorus-containing compounds selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate and high alkali ZSM-5 molecular sieves with metal ion content are mixed to obtain a mixture with a phosphorus content of at least 0.1 wt% based on P2O5.
  • the mixture is dried and roasted, and then subjected to an ammonium cross step and a water washing step to reduce the alkali metal ion content to 0.10wt% or less, and then go through the steps of drying and hydrothermal aging under the conditions of 400-1000°C and 100% water vapor.
  • the phosphorus-containing ZSM-5 molecular sieve obtained by the method has high total acid content, excellent cracking conversion rate and propylene selectivity, and high liquefied gas yield.
  • US5171921 discloses a method for modifying ZSM-5 molecular sieve.
  • the method includes following conventional steps: synthesis ⁇ filtration ⁇ ammonium exchange ⁇ drying ⁇ roasting to obtain ZSM-5 molecular sieve, and then use phosphoric acid to modify the ZSM-5 molecular sieve After modification, drying and roasting, a phosphorus-modified HZSM-5 molecular sieve is obtained, wherein the P2O5 loading is usually in the range of 1-7wt%.
  • phosphoric acid or ammonium phosphate will self-aggregate to form phosphorus species in different aggregate states during the roasting process.
  • the phosphate roots entering the pores interact with the framework aluminum to retain the B acid center and reduce the distribution of phosphorus species.
  • the hierarchical pore ZSM-5 molecular sieve is a ZSM-5 molecular sieve containing both micropores and mesopores. Hard template method, soft template method, acid-base post-treatment method, etc. are commonly used to prepare various types of hierarchical pore ZSM-5 with mesoporous pores. Molecular sieve.
  • the (hierarchical pore) ZSM-5 molecular sieve is modified with an appropriate amount of inorganic phosphorus compounds, it can slow the framework dealumination and improve the hydrothermal stability, and the phosphorus atoms will combine with the twisted four-coordinate framework aluminum to form weak B acid In order to achieve a higher conversion rate of long-chain alkane cracking and higher light olefin selectivity, but excessive inorganic phosphorus compounds used to modify the (multi-pore) ZSM-5 molecular sieve will block the pores of the molecular sieve , So that the pore volume and specific surface area are reduced, and a large number of strong B acid centers are occupied.
  • phosphoric acid or ammonium phosphate will self-aggregate to form phosphorus species in different aggregation states during the roasting process.
  • Phosphorus is not fully coordinated with framework aluminum, and the utilization efficiency of phosphorus is low.
  • Phosphorus modification does not always lead to Satisfactory improved hydrothermal stability results. Therefore, there is an urgent need for new technology to promote the coordination of phosphorus and framework aluminum, improve the hydrothermal stability of phosphorus-modified ZSM-5 molecular sieve, and further improve the cracking activity.
  • An object of the present invention is to provide a phosphorus-modified MFI molecular sieve with a high degree of dispersion of phosphorus species, which is different from the prior art, so that when applied to the catalytic cracking reaction of petroleum hydrocarbons, an excellent cracking conversion rate and The yield of low-carbon olefins, while obtaining a higher yield of liquefied gas.
  • Another object of the present invention is to provide a catalytic cracking aid based on phosphorus-modified ZSM-5 molecular sieve with high dispersion of phosphorus species as the active component, so as to obtain excellent cracking conversion rate and conversion rate in the catalytic cracking reaction of petroleum hydrocarbons.
  • Another object of the present invention is to provide a catalytic cracking catalyst based on a phosphorus-modified MFI structure molecular sieve with a high degree of dispersion of phosphorus species as one of the active components, so that an excellent cracking conversion rate and conversion rate can be obtained in the catalytic cracking reaction of petroleum hydrocarbons.
  • Phosphorus mass content ⁇ 100%, in which the ESCAREB 250 X-ray photoelectron spectrometer from Thermo Fisher-VG is used, the excitation source is a monochromatic AlK ⁇ X-ray with a power of 150W, and the charge displacement is derived from contaminated carbon.
  • C1s peak (284.8eV) correction is used to perform XPS analysis on the surface of the molecular sieve; use JXA-8230 energy spectrometer X-ray detector, counting rate and counting time, generally the cumulative count is greater than 10 5 , the count rate is 10 3 ⁇ 10 4 CPS, count The time is 10-100s to conduct EPMA analysis on the molecular sieve surface.
  • the molar ratio of phosphorus content to alumina in terms of P2O5 is ⁇ 0.01; for example, ⁇ 0.2; further, for example, ⁇ 0.3; and further, for example, 0.4-0.7;
  • the phosphorus-modified MFI molecular sieve can be a microporous ZSM-5 molecular sieve or a hierarchical pore ZSM-5 molecular sieve. Phosphorus is calculated as P2O5 with a loading amount of at least 0.1% by weight.
  • the molar ratio of silica/alumina is 15-1000, for example, 20-200; for the multi-porous ZSM-5 molecular sieve, the ratio of the mesopore volume to the total pore volume is greater than 10%, and the average The pore diameter is 2-20 nm, and its silicon oxide/alumina molar ratio is 15-1000, for example, 20-200.
  • the present invention provides a catalytic cracking aid, based on the dry basis weight of the catalytic cracking aid, the catalytic cracking aid contains 5 to 75% by weight of a phosphorus-modified MFI molecular sieve;
  • the molar ratio of phosphorus content to alumina in terms of P2O5 is ⁇ 0.01; for example, ⁇ 0.2; further, for example, ⁇ 0.3; and further, for example, 0.4-0.7;
  • the phosphorus-modified MFI molecular sieve can be a microporous ZSM-5 molecular sieve or a hierarchical pore ZSM-5 molecular sieve. Phosphorus is calculated as P2O5 with a loading amount of at least 0.1% by weight.
  • the molar ratio of silica/alumina is 15-1000, for example, 20-200;
  • the ratio of the mesopore volume to the total pore volume is greater than 10%, and the average
  • the pore diameter is 2-20nm, and its silicon oxide/alumina molar ratio is 15-1000, for example, 20-200;
  • the catalytic cracking aid of the present invention may also contain 1-40% by weight of the binder and 0-65% by weight of the second clay.
  • the binder contains a phosphor-aluminum inorganic binder.
  • the phosphoaluminum inorganic binder is phosphoalumina gel and/or the phosphoaluminum inorganic binder containing the first clay.
  • the present invention provides a catalytic cracking catalyst containing phosphorus-containing modified MFI structure molecular sieve.
  • the molar ratio of phosphorus content to alumina in terms of P2O5 is ⁇ 0.01; for example, ⁇ 0.2; further, for example, ⁇ 0.3; and further, for example, 0.4-0.7;
  • the phosphorus-modified MFI molecular sieve can be a microporous ZSM-5 molecular sieve or a hierarchical pore ZSM-5 molecular sieve. Phosphorus is calculated as P2O5 with a loading amount of at least 0.1% by weight.
  • the molar ratio of silica/alumina is 15-1000, for example, 20-200;
  • the ratio of the mesopore volume to the total pore volume is greater than 10%, and the average
  • the pore diameter is 2-20nm, and its silicon oxide/alumina molar ratio is 15-1000, for example, 20-200;
  • the Y-type molecular sieve may include at least one of PSRY molecular sieve, PSRY molecular sieve containing rare earth, USY molecular sieve, USY molecular sieve containing rare earth, REY molecular sieve, REHY molecular sieve, and HY molecular sieve;
  • the inorganic binder contains a phosphor-aluminum inorganic binder; further, for example, the phosphor-aluminum inorganic binder is a phosphor-aluminum glue and/or a phosphor-aluminum inorganic binder containing a first clay.
  • the present invention provides a method for preparing a phosphorus-modified MFI molecular sieve, which is characterized by being obtained by an impregnation method, including: setting the temperature to 40-150°C, such as 50-150°C, and further, such as 70-130°C.
  • the aqueous solution of phosphorus-containing compound at °C is mixed and contacted with 40-150°C, for example 50-150°C, further, for example, 70-130°C MFI structure molecular sieve at substantially the same temperature for at least 0.1 hours, and after drying at 200-600°C , Calcination in air or water vapor atmosphere for at least 0.1 hours; or mixing and beating the phosphorus-containing compound, MFI molecular sieve and water, and then adjust the temperature to (for example, the temperature to) 40-150°C, such as 50-150°C, further, For example, it is kept at 70-130°C for at least 0.1 hours, and after drying, it is calcined at 200-600°C in air or water vapor atmosphere for at least 0.1 hours.
  • 40-150°C for example 50-150°C
  • 70-130°C MFI structure molecular sieve at substantially the same temperature for at least 0.1 hours, and after drying at 200-600°C , Calcination in air or
  • the MFI structure molecular sieve can be a hydrogen type microporous ZSM-5 molecular sieve or a hydrogen type multi-porous ZSM-5 molecular sieve. They are obtained by reducing sodium to Na2O ⁇ 0.1wt% through ammonium exchange, and the silicon-to-aluminum ratio (the molar ratio of silicon oxide to aluminum oxide) ranges from ⁇ 10, usually 10-200.
  • the phosphorus-containing compound is calculated as phosphorus (calculated as the oxide), and the MFI molecular sieve (for example, hydrogen type ZSM-5 molecular sieve or hydrogen type
  • the graded pore ZSM-5 molecular sieve is calculated as aluminum (calculated as oxide), and the molar ratio of the two is 0.01-2; for example, the molar ratio of the two is 0.1-1.5; further, for example, the molar ratio of the two is 0.2-1.5.
  • the phosphorus-containing compound is selected from organic phosphorus compounds, such as trimethyl phosphate, triphenylphosphorus, trimethyl phosphite, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphorus hydroxide, trimethylphosphonium Phenylethyl phosphorous bromide, triphenylbutyl phosphorous bromide, triphenylbenzyl phosphorous bromide, hexamethylphosphoric triamide, dibenzyl diethyl phosphorous, 1,3-xylene bis-tris Ethyl phosphorus, etc., inorganic phosphorus compounds, such as phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, boron phosphate, or a mixture thereof.
  • organic phosphorus compounds such as trimethyl phosphate, triphenylphosphorus, trimethyl phosphite,
  • the combination of phosphorus-containing compounds is boron phosphate and selected from Mixtures of trimethyl phosphate, triphenyl phosphate, trimethyl phosphite, phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, and ammonium phosphate.
  • the weight of boron phosphate accounts for 10%-80%, such as 20%-40%, and further, such as 25%-35%.
  • the contact is to make the aqueous solution of the phosphorus-containing compound at a temperature of 30-150°C and the hydrogen-type MFI molecular sieve at a temperature of 30-150°C basically the same
  • the contact temperature is at least 0.1 hours.
  • the contact is carried out in a higher temperature range above 40°C, such as 50-150°C, and further, such as 70-130°C, better effects can be obtained, that is, the phosphorus species is better dispersed and the phosphorus is easier to migrate to
  • the hydrogen type MFI structure molecular sieve is combined with the framework aluminum in the crystal to further improve the coordination degree of phosphorus and the framework aluminum, and finally contribute to the improvement of the hydrothermal stability of the molecular sieve.
  • the basically the same temperature means that the temperature difference between the aqueous solution of the phosphorus compound and the temperature of the hydrogen-type MFI structure molecular sieve is ⁇ 5°C.
  • the temperature of the aqueous solution of the phosphorus compound is 80°C, and the HZSM-5 molecular sieve needs to be heated to 75-85°C.
  • the contact may also be the mixing of the phosphorus-containing compound, the (hydrogen type) MFI structure molecular sieve and water, and then keeping the mixture at 30-150°C for at least 0.1 hours.
  • the phosphorus species is better dispersed, and the phosphorus is easier to migrate into the molecular sieve crystals to combine with the framework aluminum, further improve the coordination degree of phosphorus and the framework aluminum, and ultimately improve the hydrothermal stability of the molecular sieve.
  • the phosphorus-containing compound, hydrogen-type MFI molecular sieve and water are mixed, they are kept in a higher temperature range above 40°C for 0.1 hours, such as a temperature range of 50-150°C, and further, such as a temperature range of 70-130°C.
  • the weight ratio of water to screen is 0.5-1, and the time is 0.5-40 hours.
  • the calcination is, for example, performed at 450-550°C under a water vapor atmosphere.
  • the invention promotes the coordination of phosphorus species with the framework aluminum of the molecular sieve of the MFI structure, thereby improving the hydrothermal stability of the phosphorus-modified molecular sieve.
  • the phosphorus-containing MFI structure molecular sieve of the present invention has excellent cracking conversion rate and low-carbon olefin yield, and at the same time has a higher liquefied gas yield.
  • the present invention provides a method for preparing a catalytic cracking aid.
  • the method includes mixing and beating a phosphorus-modified MFI molecular sieve, a binder, and an optional second clay, and spray drying to obtain the
  • the catalytic cracking aid is characterized in that the phosphorus-modified MFI structure molecular sieve is prepared by the preparation method of the phosphorus-modified MFI structure molecular sieve of the present invention.
  • the binder contains, for example, a phosphor-aluminum inorganic binder.
  • the phosphoaluminum inorganic binder is phosphoalumina gel and/or the first clay-containing phosphoaluminum inorganic binder; based on the dry basis weight of the first clay-containing phosphoaluminum inorganic binder, the
  • the first clay-containing phospho-aluminum inorganic binder contains 10-40% by weight based on Al2O3, for example 15-40% by weight of aluminum component, 45-90% by weight based on P2O5, and 45-80% by weight of phosphorus component.
  • the first clay of greater than 0 and not more than 40% by weight on a dry basis, and the P/Al weight ratio of the first clay-containing phospho-aluminum inorganic binder is 1.0-6.0, the pH is 1-3.5, and the solid content 15-60% by weight;
  • the first clay includes at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, and diatomite;
  • the binder may also include pseudo-thin water At least one other inorganic binder among bauxite, alumina sol, silica alumina sol, and water glass.
  • the second clay is at least one selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, halloysite, hydrotalcite, bentonite, and diatomite.
  • the binder In the preparation method of the catalytic cracking aid, based on the catalytic cracking aid, the binder includes 3-39% by weight of the phosphor-aluminum inorganic binder on a dry basis and a dry basis. Based on 1-30% by weight of the other inorganic binders.
  • the method for preparing the catalytic cracking aid further includes: subjecting the spray-dried product to a first roasting, washing and optional drying treatment to obtain the catalytic cracking aid; wherein the roasting temperature of the first roasting The temperature is 300-650°C, and the roasting time is 0.5-8h; the temperature of the drying treatment is 100-200°C, and the drying time is 0.5-24h.
  • the present invention provides the application of a catalytic cracking aid, that is, a method for the catalytic cracking of hydrocarbon oil.
  • the method includes: contacting and reacting the hydrocarbon oil with the above-mentioned catalytic cracking aid under catalytic cracking conditions.
  • the hydrocarbon oil is contacted and reacted with a catalyst mixture containing the catalytic cracking assistant and a catalytic cracking catalyst; in the catalyst mixture, the content of the catalytic cracking assistant is 0.1-30% by weight.
  • the catalytic cracking conditions include: a reaction temperature of 500-800°C; the hydrocarbon oil is selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric wax oil, vacuum wax oil , DC wax oil, propane light/heavy deoiling, coking wax oil and coal liquefaction products.
  • the catalytic cracking assistant provided by the invention has excellent cracking conversion rate and low-carbon olefin yield in the catalytic cracking reaction of petroleum hydrocarbons, and at the same time has a higher liquefied gas yield.
  • the present invention also provides a method for preparing a catalytic cracking catalyst, which includes mixing and beating Y-type molecular sieve, phosphorus-modified MFI molecular sieve, inorganic binder and optional second clay, and spraying After drying, the catalytic cracking catalyst is obtained, which is characterized in that the phosphorus-modified MFI molecular sieve is prepared by the preparation method of the phosphorus-modified MFI molecular sieve of the present invention.
  • the binder is a phosphor-aluminum inorganic binder.
  • the phosphoaluminum inorganic binder is phosphoalumina gel and/or the first clay-containing phosphoaluminum inorganic binder; based on the dry basis weight of the first clay-containing phosphoaluminum inorganic binder, the
  • the first clay-containing phosphate aluminum inorganic binder contains 10-40% by weight of Al2O3, such as 15-40% by weight of aluminum component, and 45-90% by weight of P2O5, such as 45-80% by weight of phosphorus component.
  • the first clay is more than 0 and not more than 40% by weight on a dry basis, and the first clay-containing phospho-aluminum inorganic binder has a P/Al weight ratio of 1.0-6.0, a pH of 1-3.5, and a solid The content is 15-60% by weight; the first clay includes at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, and diatomite.
  • the second clay is selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, halloysite, hydrotalcite, At least one of bentonite and diatomite.
  • the binder includes 3-39% by weight of the phosphorus-aluminum inorganic binder on a dry basis and 1-30% by weight of other inorganic binders, and the other inorganic binders include at least one of pseudo-boehmite, alumina sol, silica alumina sol, and water glass.
  • the preparation method of the catalytic cracking catalyst of the present invention further includes: subjecting the spray-dried product to the first roasting, washing and optional drying treatments to obtain the catalytic cracking catalyst; wherein the roasting temperature of the first roasting is 300 -650°C, the roasting time is 0.5-8h; the temperature of the drying treatment is 100-200°C, and the drying time is 0.5-24h.
  • the present invention provides the application of a catalytic cracking catalyst, that is, a method for the catalytic cracking of hydrocarbon oil.
  • the method includes: contacting and reacting the hydrocarbon oil with the above catalytic cracking catalyst under catalytic cracking conditions.
  • the catalytic cracking conditions include: a reaction temperature of 500-800°C; the hydrocarbon oil is selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric wax oil, vacuum wax oil, and direct current One or more of wax oil, propane light/heavy deoiling, coking wax oil and coal liquefaction products.
  • the catalytic cracking catalyst provided by the invention has excellent cracking conversion rate and low-carbon olefin yield in the catalytic cracking reaction of petroleum hydrocarbons, and at the same time has a higher liquefied gas yield.
  • pores with a pore diameter of less than 2 nm are called micropores; pores with a pore diameter greater than 50 nm are called macropores; pores with a pore diameter of 2-50 nm are called mesopores.
  • the first clay refers to the clay contained in the phosphorus-aluminum inorganic binder; and the second clay refers to the clay other than the first clay, and "first" and “second” are only to distinguish clay Whether it is in the phosphor-aluminum inorganic binder.
  • the first clay includes, but is not limited to, kaolin, sepiolite, attapulgite, rectorite, montmorillonite, and diatomite.
  • the second clay includes, but is not limited to, kaolin, sepiolite, attapulgite, rectorite, montmorillonite, and diatomite, as well as halloysite, halloysite, hydrotalcite, and bentonite.
  • binder and inorganic binder are synonymous.
  • the binder of the present invention includes phosphor-aluminum inorganic binder and other inorganic binders.
  • other inorganic binders refer to binders that do not contain both phosphorus and aluminum at the same time
  • the phosphoaluminum inorganic binder includes phosphoalumina gel and a phosphoaluminum inorganic binder containing the first clay.
  • examples of other inorganic binders include, but are not limited to, pseudo-boehmite, alumina sol, silica alumina sol, and water glass.
  • Phospho-alumina glue can be used as a binder to prepare a catalyst with excellent strength.
  • the actual ratio of P2O5/Al2O3 in the phosphor-aluminum glue is 3:1 or higher, such as 3:1-10:1, and further, for example, greater than 3:1 and not greater than 5:1.
  • aluminum phosphate glue can be dispersed into a slurry by beating an alumina source with water; adding concentrated phosphoric acid to the slurry under stirring, and reacting the resulting mixed slurry for a period of time (for example, at 50-99°C for 15-90 minutes)
  • the alumina source can be selected from ⁇ -alumina, x-alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, trihydrate
  • the concentration of the concentrated phosphoric acid may be 60-98% by weight, and further, for example, 75 -90% by weight
  • the feed rate of phosphoric acid is, for example, 0.01-0.10 kg phosphoric acid/minute/kg alumina source, and further, for example, 0.03-0.07 kg phosphoric acid/minute/kg alumina source.
  • the first clay-containing phosphoaluminum inorganic binder refers to such a binder, on a dry basis
  • the first clay-containing phosphoaluminum inorganic binder contains 10-40 Al2O3. % By weight, such as 15-40% by weight of aluminum component, 45-90% by weight based on P2O5, such as 45-80% by weight of phosphorus component, and greater than 0 and not more than 40% by weight of the first clay on a dry basis
  • the first clay-containing phosphor-aluminum inorganic binder has a P/Al weight ratio of 1.0-6.0, a pH of 1-3.5, and a solid content of 15-60% by weight.
  • the first clay-containing phospho-aluminum inorganic binder can be prepared by the following method: the alumina source, the first clay and water are beaten and dispersed into a slurry with a solid content of 5-48% by weight
  • the alumina source is aluminum hydroxide and/or alumina that can be peptized by acid, relative to 10-40 parts by weight, for example 15-40 parts by weight of the alumina source as Al2O3, on a dry basis
  • the alumina source may be selected from ⁇ -alumina, x-alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, gibbsite, pyrite At least one of bauxite, gibbsite, diaspore, boehmite, and pseudo-boehmite, the concentration of the concentrated phosphoric acid may be 60-98% by weight, and further, for example, 75-90% by weight %, the feed rate of phosphoric acid is, for example, 0.01-0.10 kg phosphoric acid/minute/kg alumina source, and further, for example, 0.03-0.07 kg phosphoric acid/minute/kg alumina source.
  • the molar ratio of the phosphorus content to the alumina in terms of P2O5 is ⁇ 0.01, for example, the molar ratio is ⁇ 0.2, further, such as ⁇ 0.3, and further, such as 0.4-0.7.
  • the phosphorus-modified MFI molecular sieve is a microporous ZSM-5 molecular sieve or a multi-porous ZSM-5 molecular sieve.
  • the said microporous ZSM-5 molecular sieve has a silica/alumina molar ratio of 15-1000, such as 20-200.
  • the mesopore volume accounts for more than 10% of the total pore volume, the average pore diameter is 2-20 nm, and the silica/alumina molar ratio is 15-1000, such as 20-200.
  • the present invention also provides a method for preparing the above-mentioned phosphorus-modified MFI structure molecular sieve, wherein the phosphorus-modified MFI structure molecular sieve is obtained by an impregnation method, including: setting the temperature to 40-150°C, such as 50-150°C, Further, for example, the aqueous solution of the phosphorus-containing compound at 70-130°C and the molecular sieve of MFI structure at 40-150°C, such as 50-150°C, and further, for example, 70-130°C, are mixed and contacted at substantially the same temperature for at least 0.1 hours.
  • the MFI structure molecular sieve can be a hydrogen type microporous ZSM-5 molecular sieve or a hydrogen type multi-porous ZSM-5 molecular sieve. They are obtained by ammonium exchange and sodium reduction to Na 2 O ⁇ 0.1wt%, and the silicon-to-aluminum ratio (the molar ratio of silicon oxide to aluminum oxide) ranges from ⁇ 10, usually 10-200.
  • the phosphorus-containing compound is calculated as phosphorus (calculated as oxide)
  • hydrogen type ZSM-5 molecular sieve or hydrogen type multi-porous ZSM-5 molecular sieve is calculated as aluminum ( In terms of oxide), the molar ratio of the two is 0.01-2; for example, the molar ratio of the two is 0.1-1.5; further, for example, the molar ratio of the two is 0.2-1.5.
  • the phosphorus-containing compound is selected from organic phosphorus compounds, such as trimethyl phosphate, triphenylphosphorus, trimethyl phosphite, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphorus hydroxide, trimethylphosphonium Phenylethyl phosphorous bromide, triphenylbutyl phosphorous bromide, triphenylbenzyl phosphorous bromide, hexamethylphosphoric triamide, dibenzyl diethyl phosphorous, 1,3-xylene bis-tris Ethyl phosphorus, etc., inorganic phosphorus compounds, such as phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate, boron phosphate, or a mixture thereof.
  • organic phosphorus compounds such as trimethyl phosphate, triphenylphosphorus, trimethyl phosphite,
  • the combination of phosphorus-containing compounds is boron phosphate and selected from Mixtures of trimethyl phosphate, triphenyl phosphate, trimethyl phosphite, phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, and ammonium phosphate.
  • the weight proportion of boron phosphate is 10%-80%, such as 20%-40%, and further, such as 25%-35%.
  • the contact is to make the aqueous solution of the phosphorus compound at a temperature of 30-150°C and the hydrogen-type MFI molecular sieve at a temperature of 30-150°C to be substantially the same by the impregnation method. Contact at temperature for at least 0.1 hours.
  • the contact can be in a higher temperature range above 40°C, such as 50-150°C, and further, for example, at 70-130°C, a better effect can be obtained, that is, the phosphorus species is better dispersed and the phosphorus is easier Migrate into the hydrogen-type MFI structure molecular sieve crystal to combine with the framework aluminum, further improve the coordination degree of phosphorus and framework aluminum, and finally contribute to the improvement of the hydrothermal stability of the molecular sieve.
  • the basically the same temperature means that the temperature difference between the aqueous solution of the phosphorus compound and the temperature of the hydrogen-type MFI structure molecular sieve is ⁇ 5°C.
  • the temperature of the aqueous solution of the phosphorus compound is 80°C, and the HZSM-5 molecular sieve needs to be heated to 75-85°C.
  • the contact can also be the mixing of the phosphorus-containing compound, the hydrogen-type MFI molecular sieve, and water, and then keeping it at 30-150°C for at least 0.1 hours.
  • the phosphorus species is better dispersed, and the phosphorus is more likely to migrate into the molecular sieve crystal to combine with the framework aluminum, further improve the coordination degree of phosphorus and the framework aluminum, and finally improve the hydrothermal stability of the molecular sieve.
  • the weight ratio of water to sieve is 0.5-1, and the time is 0.5-40 hours.
  • the calcination is, for example, performed at 450-550°C under a water vapor atmosphere.
  • the K value in the phosphorus-modified MFI structure molecular sieve satisfies: 75% ⁇ K ⁇ 90%, for example, the K value satisfies: 78% ⁇ K ⁇ 85%.
  • the molar ratio of phosphorus content to alumina in terms of P 2 O 5 is ⁇ 0.01, for example, the molar ratio is ⁇ 0.2, and further, for example, ⁇ 0.3. Further, for example, 0.4-0.7.
  • the phosphorus-modified MFI molecular sieve is a microporous ZSM-5 molecular sieve or a multi-porous ZSM-5 molecular sieve.
  • the said microporous ZSM-5 molecular sieve has a silica/alumina molar ratio of 15-1000, such as 20-200.
  • the mesopore volume accounts for more than 10% of the total pore volume, the average pore diameter is 2-20 nm, and the silica/alumina molar ratio is 15-1000, such as 20-200.
  • the catalytic cracking aid of the present invention based on the dry basis of the catalytic cracking aid, contains 5 to 75% by weight, for example 8 to 60% by weight, of a phosphorus-modified MFI molecular sieve. In addition, it can also contain 1-40% by weight of the binder and 0-65% by weight of the second clay.
  • the binder may be an inorganic oxide binder commonly used in auxiliary or catalyst binder components, such as pseudo-boehmite, alumina sol, silica alumina sol, and water glass, which are well known to those skilled in the art One or more of.
  • the binder contains a phosphorus-aluminum inorganic binder, that is, a phosphorus-aluminum inorganic binder or a mixture of a phosphorus-aluminum inorganic binder and other inorganic binders.
  • a phosphorus-aluminum inorganic binder that is, a phosphorus-aluminum inorganic binder or a mixture of a phosphorus-aluminum inorganic binder and other inorganic binders.
  • the phosphorus-aluminum inorganic binder is, for example, phosphorus-aluminum glue and/or a phosphorus-aluminum inorganic binder containing the first clay.
  • the first clay-containing phospho-aluminum inorganic binder contains 10-40% by weight based on Al 2 O 3 , such as 15-40% by weight %, such as 10-35 wt%, such as 15-35 wt% aluminum component, 45-90 wt% based on P 2 O 5 , such as 45-80 wt%, such as 50-75 wt% phosphorus component, and
  • more than 0 and not more than 40% by weight of the first clay, such as 8 to 35% by weight, and the first clay-containing phospho-aluminum inorganic binder P/Al weight ratio is 1.0-6.0, such as 1.2 -6.0.
  • a dry weight of the inorganic binder is aluminum phosphate as a reference, the inorganic binder comprising aluminum phosphate Al 2 O 3 from 20 -40% by weight of aluminum component to P 2 O 5 and 60-80 wt% of the phosphorus component.
  • the first clay may be at least one selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomite; the other inorganic bonding agent
  • the agent can be selected from one or more of the inorganic oxide binders conventionally used for catalytic cracking aids or catalyst binder components other than the phosphoaluminum glue and the phosphoaluminum inorganic binder, for example, selected from At least one of pseudo-boehmite, aluminum sol, silica-alumina sol, and water glass, and further, for example, at least one selected from pseudo-boehmite and aluminum sol.
  • the second clay is further contained in an amount of 0-65% by weight, for example 5-55 weight%.
  • the second clay is also well known to those skilled in the art, for example, is selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, halloysite, hydrotalcite, bentonite and At least one of diatomaceous earth.
  • the catalytic cracking aid of the present invention based on the dry basis of the catalytic cracking aid, it includes 20-60% by weight of phosphorus-modified MFI molecular sieve and 5-35% by weight of viscosity Binding agent and the second clay at 5-55 wt%.
  • the present invention also provides a method for preparing the catalytic cracking aid, which method comprises mixing and beating the phosphorus-modified MFI molecular sieve of the present invention, a binder, and an optional second clay, and spray drying Then the catalytic cracking aid is obtained.
  • the binder contains a phosphorus-aluminum inorganic binder and other inorganic binders, on a dry basis, the phosphorus-modified MFI molecular sieve, the phosphorus
  • the weight ratio of the aluminum inorganic binder to the other inorganic binder can be (10-75): (3-39): (1-30), for example (10-75): (8-35) : (5-25); wherein the phosphoaluminum inorganic binder can be phosphoalumina gel and/or the phosphoaluminum inorganic binder containing the first clay; the other inorganic binders can include pseudo-boehmite At least one of stone, alumina sol, silica alumina sol, and water glass.
  • the preparation method can be to mix phosphorus-modified MFI molecular sieve, phosphorus-aluminum inorganic binder and other inorganic binders, beating, and the order of its addition has no special requirements, for example, phosphorus-aluminum inorganic binder and other inorganic binders can be used.
  • Mixing agent, phosphorus-modified MFI structure molecular sieve, and second clay (when the second clay is not included, the relevant adding steps can be omitted) beating, for example, the second clay, phosphorus-modified MFI molecular sieve and other inorganic bonding Add the phosphor-aluminum inorganic binder after mixing and beating the agent, which is beneficial to improve the activity and selectivity of the auxiliary agent.
  • the preparation method of the catalytic cracking auxiliary agent further includes the step of spray drying the slurry obtained by beating the slurry.
  • the spray drying method is well known to those skilled in the art, and the present invention has no special requirements.
  • the preparation method may further include: subjecting the spray-dried product to the first roasting, washing and optional drying treatments to obtain the catalytic cracking aid.
  • the roasting temperature of the first roasting may be 300-650°C, for example 400-600°C, for example 450-550°C, and the roasting time may be 0.5-8 hours;
  • the washing may be ammonium sulfate or ammonium chloride.
  • the washing temperature can be 40-70°C;
  • the temperature of the drying treatment can be 100-200°C, for example 100-150°C, and the drying time can be 0.5-24h, for example 1-12h .
  • the binder is mixed with the second clay and water (for example, decationized water and/or deionized water) to prepare a solid content of 10- 50% by weight of the slurry, stir evenly, adjust the pH of the slurry to 1-4 with mineral acids such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, maintain the pH value, and stand for aging at 20-80°C for 0-2 hours (for example, 0.3 -2 hours) and then add an inorganic binder such as aluminum sol and/or silica sol, stir for 0.5-1.5 hours to form a colloid, and then add the phosphorus-modified MFI molecular sieve to form an auxiliary slurry.
  • mineral acids such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid
  • an inorganic binder such as aluminum sol and/or silica sol
  • the solid content of the auxiliary slurry is, for example, 20-45% by weight, continue to be stirred and spray-dried to prepare microsphere additives.
  • water is added to the phosphorus-modified MFI structure molecular sieve, the second clay (for example, kaolin) and the binder (for example, pseudo-boehmite).
  • the second clay for example, kaolin
  • the binder for example, pseudo-boehmite
  • inorganic binders such as aluminum sol and/or silica sol, beating for 0.1-10 hours (such as 120 minutes) to obtain a solid content of 10-50% by weight (such as 30% by weight) ) Slurry, add inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid to adjust the pH of the slurry to 1-4 (for example 3.0), and then continue to beat for 0.1-10 hours (for example, 45 minutes), and then add the phosphor-aluminum inorganic binder, After stirring for 0.1-10 hours (for example, 30 minutes), the obtained slurry is spray-dried to obtain microspheres, and the microspheres are calcined at 350-650°C or 400-600°C (for example, 500°C) for 0.5-6 hours or 0.5-
  • the catalytic cracking aid is prepared in 2 hours (for example, 1 hour).
  • the binder for example, aluminum sol
  • the second clay for example, kaolin
  • water for example, decationized water and/or deionized water
  • the weight of aluminum on a single-mass meter may be selected from ⁇ -alumina, x-alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, gibbsite, pyrite At least one of bauxite, gibbsite, diaspore, boehmite, and pseudo-boehmite, and the aluminum component in the first clay-containing aluminum phosphate inorganic binder is derived from the Alumina source.
  • the first clay can be divided into one or more of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomite, such as rectorite.
  • the concentration of the concentrated phosphoric acid may be 60-98% by weight, further, for example, 75-90% by weight.
  • the feed rate of phosphoric acid is, for example, 0.01-0.10 kg phosphoric acid/minute/kg alumina source, and further, for example, 0.03-0.07 kg phosphoric acid/minute/kg alumina source.
  • the introduction of the first clay-containing phospho-aluminum inorganic binder not only improves the mass and heat transfer between materials during the preparation process, but also avoids The non-uniformity of the material reacts violently and locally, and the adhesive is cured by the super-stable heat release.
  • the adhesive performance of the obtained adhesive is equivalent to that of the phosphor-aluminum adhesive prepared by the method without clay; and the method introduces clay, especially with The layered rectorite improves the heavy oil conversion ability of the catalyst composition, so that the obtained auxiliary agent has better selectivity.
  • the present invention further provides the application of the catalytic cracking aid, that is, a method for the catalytic cracking of hydrocarbon oil, the method comprising: contacting and reacting the hydrocarbon oil with the catalytic cracking aid of the present invention under the conditions of catalytic cracking.
  • the catalytic cracking aid that is, a method for the catalytic cracking of hydrocarbon oil, the method comprising: contacting and reacting the hydrocarbon oil with the catalytic cracking aid of the present invention under the conditions of catalytic cracking.
  • the method for catalytic cracking of hydrocarbon oil of the present invention includes: contacting and reacting the hydrocarbon oil with a catalytic mixture containing the catalytic cracking promoter and a catalytic cracking catalyst under the catalytic cracking conditions; in the catalytic mixture, the The content of the catalytic cracking aid is 0.1-30% by weight.
  • the catalytic cracking conditions include: a reaction temperature of 500-800°C; the hydrocarbon oil is selected from the group consisting of crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric wax oil, and vacuum One or more of wax oil, direct wax oil, propane light/heavy deoiling, coking wax oil and coal liquefaction products.
  • the present invention also provides a catalytic cracking catalyst of phosphorus-containing modified MFI structure molecular sieve. Based on the dry basis of the catalyst, the catalytic cracking catalyst contains 1-25% by weight of Y-type molecular sieve and 5-50% by weight of phosphorus.
  • the excitation source was a monochromatic AlK ⁇ X-ray with a power of 150W.
  • the Y-type molecular sieve includes at least one of PSRY molecular sieve, PSRY molecular sieve containing rare earth, USY molecular sieve, USY molecular sieve containing rare earth, REY molecular sieve, REHY molecular sieve, and HY molecular sieve.
  • the K value in the phosphorus-modified MFI structure molecular sieve satisfies: 75% ⁇ K ⁇ 90%, for example, the K value satisfies: 78% ⁇ K ⁇ 85%.
  • the molar ratio of the phosphorus content to the alumina in terms of P 2 O 5 is ⁇ 0.01, for example, the molar ratio is ⁇ 0.2, and further, for example, ⁇ 0.3 , And further, for example 0.4-0.7.
  • the phosphorus-modified MFI molecular sieve is a microporous ZSM-5 molecular sieve or a multi-porous ZSM-5 molecular sieve.
  • the said microporous ZSM-5 molecular sieve has a silica/alumina molar ratio of 15-1000, such as 20-200.
  • the mesopore volume accounts for more than 10% of the total pore volume, the average pore diameter is 2-20 nm, and the silica/alumina molar ratio is 15-1000, such as 20-200.
  • the catalytic cracking catalyst of the present invention based on the dry basis of the catalytic cracking catalyst, contains 2-20% by weight of Y-type molecular sieve, 10-40% by weight, for example, 20-40% by weight.
  • the phosphorus-modified molecular sieve of MFI structure it can also contain 1-40% by weight of inorganic binder and 0-50% by weight of second clay.
  • the catalyst contains 3-40% by weight of the phosphorus-aluminum inorganic binder or 3-40% by weight of the phosphorus-aluminum inorganic binder and 1-30% by weight of other inorganic binders. Inorganic binder.
  • the phosphorus-aluminum inorganic binder is a phosphorus-aluminum glue and/or a phosphorus-aluminum inorganic binder containing the first clay.
  • the first clay-containing phospho-aluminum inorganic binder contains 10-40% by weight based on Al 2 O 3 , such as 15-40% by weight % Aluminum component, 45-90% by weight based on P 2 O 5 , such as 45-80% by weight of phosphorus component, and greater than 0 and not more than 40% by weight of the first clay on a dry basis, and the content
  • the first clay has a P/Al weight ratio of 1.0-6.0, a pH of 1-3.5, and a solid content of 15-60% by weight.
  • the first clay includes at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, and diatomaceous earth.
  • the phosphorus-aluminum inorganic binder based on the dry basis weight of the phosphorus-aluminum inorganic binder, the phosphorus-aluminum inorganic binder It may include 10-40% by weight based on Al 2 O 3 , such as 15-40% by weight of aluminum component, 45-90% by weight based on P 2 O 5 , such as 45-80% by weight of phosphorus component, and on a dry basis.
  • the phosphorus-aluminum inorganic binder for another specific embodiment of the phosphorus-aluminum inorganic binder, based on the dry basis weight of the phosphorus-aluminum inorganic binder, is The agent includes 20-40% by weight of aluminum component based on Al 2 O 3 and 60-80% by weight of phosphorus component based on P 2 O 5.
  • the other inorganic binder may be selected from inorganic oxides conventionally used for catalytic cracking catalysts or catalyst binder components other than the phosphoalumina gel and phosphoaluminum inorganic binder.
  • One or more of the binders for example, at least one selected from pseudo-boehmite, aluminum sol, silica-alumina sol and water glass, and further, for example, selected from pseudo-boehmite and aluminum sol At least one.
  • the catalytic cracking catalyst of the present invention further contains 0-65% by weight, for example 5%-55% by weight, of the second clay on a dry basis.
  • the second clay is also well known to those skilled in the art, for example, is selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, halloysite, hydrotalcite, bentonite and At least one of diatomaceous earth.
  • the present invention also provides a method for preparing the catalytic cracking catalyst, which comprises mixing and beating Y-type molecular sieve, phosphorus-modified MFI molecular sieve, inorganic binder and optional second clay and spraying
  • the catalytic cracking catalyst is obtained after drying,
  • the method may further include: washing and optionally drying the product obtained by the calcination treatment to obtain the catalytic cracking catalyst; wherein the calcination temperature of the calcination can be The temperature is 300-650°C, such as 400-600°C, such as 450-550°C, and the roasting time can be 0.5-12 hours; the washing can use one of ammonium sulfate, ammonium nitrate, and ammonium chloride, and the washing temperature can be 40-80°C; the temperature of the drying treatment may be 110-200°C, such as 120-150°C, and the drying time may be 0.5-18h, such as 2-12h.
  • the calcination temperature of the calcination can be The temperature is 300-650°C, such as 400-600°C, such as 450-550°C, and the roasting time can be 0.5-12 hours; the washing can use one of ammonium sulfate, ammonium nitrate, and ammonium chloride, and the washing temperature
  • an inorganic binder such as pseudo-boehmite, aluminum sol, silica sol, silica-alumina gel, or two or more of them
  • the mixture is mixed with the second clay (such as kaolin) and water (such as deoxidized ionized water and/or deionized water) to form a slurry with a solid content of 10-50% by weight.
  • the molecular sieves include the phosphorus-modified ZSM-5 molecular sieves and Y-type molecular sieves to form a catalyst slurry.
  • the solid content of the catalyst slurry is, for example, 20-45 wt. ⁇ catalyst.
  • the phosphorus-modified ZSM-5 molecular sieve, Y-type molecular sieve, second clay (such as kaolin) and inorganic binder such as pseudo-thin Mixture of diaspore, aluminum sol, silica sol, silica-alumina gel or a mixture of two or more of them
  • water such as deoxidized ionized water and/or deionized water
  • aluminum sol and/or silica sol and beat 0.1-10 hours (for example, 120 minutes)
  • mineral acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid to adjust the pH of the slurry to 1-4 (for example 3.0)
  • add the phosphor-aluminum inorganic binder stir
  • the spherical catalyst is calcined, for example, at 350-650°C or 400-600°C, such as 450-550°C for 0.5-6 hours or 0.5-2 hours (for example, at 500°C for 1 hour) to prepare a catalytic cracking catalyst.
  • the binder inorganic binder (such as pseudo-boehmite, aluminum sol, silica sol, silica-alumina gel or two or more of them)
  • the mixture of species is mixed with the second clay (for example, kaolin), and the slurry is made into a slurry with a solid content of 10-50% by weight (for example, 30% by weight) with water (for example, deoxidized ionized water and/or deionized water), and stirred Evenly, adjust the pH value of the slurry to 1-4 (for example, 2.8) with inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, and stand and age at 20-80°C (for example 55°C) for 0.1-2 hours (for example, 1 hour) Then, the phosphorus-modified ZSM-5 molecular sieve and Y-type molecular sieve are added to form a catalyst
  • Y-type molecular sieve and phosphorus-modified ZSM-5 molecular sieve, phosphor-aluminum inorganic binder and other inorganic binders can be mixed, with or without Add the second clay, beating and spray drying.
  • the inorganic binder includes the phosphoaluminum inorganic binder and the other inorganic binder, the phosphoaluminum inorganic binder and the other inorganic binder
  • the weight ratio of the material binder can be (3-40): (1-30), for example (5-35): (5-28), further for example (10-30): (5-25); wherein
  • the phosphoaluminum inorganic binder can be phosphoalumina gel and/or the first clay-containing phosphoaluminum inorganic binder; the other inorganic binders can include pseudo-boehmite, alumina sol, silica alumina sol, and At least one of water glass.
  • the phosphorus-containing modified ZSM-5 molecular sieve, the phosphorus-aluminum inorganic binder and other inorganic binders can be mixed and beaten.
  • Phosphate aluminum inorganic binder, other inorganic binders, molecular sieves, and the second clay are mixed (when the second clay is not included, the relevant adding steps can be omitted) beating, for example, the second clay, molecular sieve and other inorganic
  • the phosphor-aluminum inorganic binder is added, which is beneficial to improve the activity and selectivity of the catalyst.
  • the preparation method further includes the step of spray drying the slurry obtained by beating the slurry.
  • the spray drying method is well known to those skilled in the art, and there are no special requirements in this disclosure.
  • the alumina source may be selected from ⁇ -alumina, x-alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, gibbsite, pyrite At least one of bauxite, gibbsite, diaspore, boehmite, and pseudo-boehmite, and the aluminum component in the first clay-containing aluminum phosphate inorganic binder is derived from the Alumina source.
  • the first clay can be divided into one or more of high alumina, sepiolite, attapulgite, rectorite, montmorillonite and diatomite, such as rectorite.
  • the concentration of the concentrated phosphoric acid may be 60-98% by weight, further, for example, 75-90% by weight.
  • the feeding rate of phosphoric acid is, for example, 0.01-0.10 kg phosphoric acid/minute/kg alumina source, and further, for example, 0.03-0.07 kg phosphoric acid/minute/kg alumina source.
  • the first clay-containing phospho-aluminum inorganic binder not only improves the mass transfer and heat transfer between materials during the preparation process, but also avoids materials Inhomogeneous and local instantaneous violent reaction, exothermic and ultra-stable binding of the binding agent, the binding performance of the obtained binding agent is equivalent to that of the phosphor-aluminum binding agent prepared by the method without clay; and the method introduces clay, especially with The layered rectorite improves the heavy oil conversion capacity of the catalyst, so that the resulting catalyst has better selectivity.
  • the present invention also provides a catalytic cracking catalyst obtained by adopting the above preparation method.
  • the present invention further provides the application of the catalytic cracking catalyst, that is, a method for the catalytic cracking of hydrocarbon oil.
  • the method comprises: contacting and reacting the hydrocarbon oil with the catalytic cracking catalyst of the present invention under the conditions of catalytic cracking.
  • the catalytic cracking conditions include: a reaction temperature of 500-800°C; the hydrocarbon oil is selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric wax oil, vacuum wax oil, and direct current One or more of wax oil, propane light/heavy deoiling, coking wax oil and coal liquefaction products.
  • the hydrocarbon oil may contain heavy metal impurities such as nickel and vanadium as well as sulfur and nitrogen impurities.
  • the content of sulfur in the hydrocarbon oil can be as high as 3.0% by weight
  • the content of nitrogen can be as high as 2.0% by weight
  • the content of metal impurities such as vanadium and nickel can be as high as 3000ppm.
  • the catalytic cracking catalyst can be separately added to the catalytic cracking reactor, for example, under the catalytic cracking conditions, the hydrocarbon oil is contacted and reacted with the catalytic cracking catalyst of the present invention;
  • the catalyst can be used in combination with the catalytic cracking catalyst.
  • the hydrocarbon oil can be contacted and reacted with the catalytic mixture containing the catalytic cracking catalyst of the present invention and other catalytic cracking catalysts.
  • the catalyst provided by the present invention may account for no more than 30% by weight of the total amount of the mixture, for example, 1-25% by weight, and further, for example, 3-15% by weight.
  • the combined method of EPMA/XPS is used to carry out surface scanning analysis of the chemical composition of micro-zones and the corresponding depth structure to quantitatively analyze the phosphorus content.
  • the dispersion K value refers to the percentage of the phosphorus mass content on the molecular sieve crystal grain depth interface to the phosphorus content on the surface of the molecular sieve crystal grain.
  • K P2(EPMA)/P1(XPS)%
  • P1(XPS) means the mass content of phosphorus in micro-zones with any crystal plane depth of less than 2nm quantitatively determined by the XPS method
  • P2(EPMA) means the EPMA method Quantitative determination of phosphorus content in deep interface micro-regions with a thickness of 5-10nm using focused ion beam (FIB) cutting.
  • FIB focused ion beam
  • X-ray photoelectron spectroscopy was used to analyze the surface of the molecular sieve, and Thermo Fisher-VG’s ESCAREB 250 X-ray photoelectron spectrometer was used.
  • the excitation source was a monochromatic AlK ⁇ X-ray with a power of 150W, and it was used for charge displacement.
  • the C1s peak (284.8eV) from the polluted carbon was corrected.
  • EPMA uses JXA-8230 energy spectrometer X-ray detector, counting rate and counting time, generally the cumulative count is greater than 10 5 , the counting rate is 10 3 to 10 4 CPS, and the counting time is 10 to 100s.
  • a phosphorus-modified MFI structure molecular sieve is characterized in that the K value of the molecular sieve satisfies: 70% ⁇ K ⁇ 90%; for example, 75% ⁇ K ⁇ 90%; further, for example, 78% ⁇ K ⁇ 85%;
  • P1 represents the mass content of phosphorus in an area of 100 square nanometers within the vertical depth of any crystal plane of the molecular sieve crystal grains measured by the XPS method.
  • P2 represents the phosphorus mass content in the area of 100 square nanometers in the thickness interval of 100 square nanometers in the vertical depth of any crystal plane of the molecular sieve crystal grains of 5-10 nm measured by the EPMA method.
  • the molecular sieve according to any one of the preceding aspects wherein the molar ratio of the phosphorus content to alumina in terms of P2O5 is ⁇ 0.01; for example, ⁇ 0.2; further, for example, ⁇ 0.3; and further, for example, 0.4-0.7.
  • the molecular sieve according to any one of the preceding aspects wherein the phosphorus-modified MFI molecular sieve is a microporous ZSM-5 molecular sieve or a multi-porous ZSM-5 molecular sieve.
  • the microporous ZSM-5 molecular sieve has a silica/alumina molar ratio of 15-1000, for example, 20-200.
  • the molecular sieve according to any one of the preceding aspects the multi-porous ZSM-5 molecular sieve, the mesopore volume of the total pore volume ratio is greater than 10%, the average pore diameter is 2-20nm, silica/oxidation
  • the molar ratio of aluminum is 15-1000, for example, 20-200.
  • a catalytic cracking aid based on the dry basis of the catalytic cracking aid, contains 5 to 75% by weight, for example, 8 to 60% by weight of any of the foregoing aspects
  • the phosphorus-modified MFI structure molecular sieve described in the item 1-40% by weight of the binder and 0-65% by weight, for example, 5-55% by weight of the second clay.
  • a catalytic cracking catalyst containing phosphorous modified MFI structure molecular sieve based on the dry basis of the catalyst, the catalytic cracking catalyst contains 1-25% by weight of Y-type molecular sieve, and 5-50% by weight of the aforementioned The phosphorus-modified MFI structure molecular sieve described in any one of the aspects, 1-60% by weight of the inorganic binder, and optionally added 0-60% by weight of the second clay.
  • the catalytic cracking promoter or catalytic cracking catalyst according to any one of the preceding aspects, wherein the binder or the inorganic binder includes a phosphorus-aluminum inorganic binder and/or other inorganic binders. Binding agent,
  • the phosphoaluminum inorganic binder is phosphoalumina gel and/or the first clay-containing phosphoaluminum inorganic binder, and further, for example, the first clay is selected from kaolin, sepiolite, and bumps.
  • the first clay-containing phosphoaluminum inorganic binder contains 10-40% by weight of Al2O3, for example 15-40% by weight of aluminum group P2O5, 45-90% by weight, for example, 45-80% by weight of the phosphorus component, and more than 0 and not more than 40% by weight of the first clay on a dry basis, and the first clay-containing phosphoaluminum inorganic
  • the weight ratio of the binder P/Al is 1.0-6.0, the pH is 1-3.5, and the solid content is 15-60% by weight;
  • the second clay is selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite, and diatomite, as well as halloysite, halloysite, hydrotalcite, and bentonite;
  • the other inorganic binder is selected from pseudo-boehmite, alumina sol, silica alumina sol and water glass.
  • the catalytic cracking catalyst according to any one of the preceding aspects, wherein the Y-type molecular sieve includes PSRY molecular sieve, PSRY-S molecular sieve, PSRY molecular sieve containing rare earth, PSRY-S molecular sieve containing rare earth, USY molecular sieve , At least one of rare earth-containing USY molecular sieves, REY molecular sieves, REHY molecular sieves and HY molecular sieves.
  • the Y-type molecular sieve includes PSRY molecular sieve, PSRY-S molecular sieve, PSRY molecular sieve containing rare earth, PSRY-S molecular sieve containing rare earth, USY molecular sieve , At least one of rare earth-containing USY molecular sieves, REY molecular sieves, REHY molecular sieves and HY molecular sieves.
  • the method for preparing the phosphorus-modified MFI structure molecular sieve of any one of the foregoing aspects is characterized in that it is obtained by an impregnation method, comprising: setting the temperature to 40-150°C, such as 50-150°C, and further, for example, The aqueous solution of phosphorus-containing compound at 70-130°C is mixed and contacted with a molecular sieve of MFI structure at 40-150°C, for example 50-150°C, and further, for example, 70-130°C, at substantially the same temperature for at least 0.1 hours.
  • the method for preparing a phosphorus-modified MFI structure molecular sieve according to any one of the preceding aspects, wherein the phosphorus-containing compound is selected from an organic phosphorus compound and/or an inorganic phosphorus compound; for example, the organic phosphorus compound Selected from trimethyl phosphate, triphenylphosphorus, trimethyl phosphite, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphorus hydroxide, triphenylethylphosphonium bromide, triphenyl Butyl phosphorus bromide, triphenylbenzyl phosphorus bromide, hexamethylphosphoric triamide, dibenzyl diethyl phosphorus, 1,3-xylene bistriethyl phosphorus, the inorganic phosphorus compounds are selected From phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammoni
  • the twelfth aspect the method for preparing a phosphorus-modified MFI structure molecular sieve according to any one of the preceding aspects, wherein the phosphorus-containing compound is calculated as phosphorus (as oxide), and the MFI structure molecular sieve (such as hydrogen type ZSM-5 Molecular sieve) is calculated as aluminum (calculated as oxide), and the molar ratio of the two is 0.01-2; for example, the molar ratio of the two is 0.1-1.5; further, for example, the molar ratio of the two is 0.2-1.5.
  • the thirteenth aspect the method for preparing a phosphorus-modified MFI molecular sieve according to any one of the preceding aspects, wherein the phosphorus-containing compound is boron phosphate and selected from the group consisting of trimethyl phosphate, triphenylphosphorus, and trimethylmethylene.
  • the phosphorus-containing compound is boron phosphate and selected from the group consisting of trimethyl phosphate, triphenylphosphorus, and trimethylmethylene.
  • the weight proportion of boron phosphate is 10%-80%, for example, the weight proportion of boron phosphate is 20% -40%.
  • the fourteenth aspect the method for preparing a phosphorus-modified MFI molecular sieve according to any one of the preceding aspects, wherein the weight ratio of the water to the sieve is 0.5-1, and the time is 0.5-40 hours.
  • the method for preparing a phosphorus-modified MFI molecular sieve according to any one of the preceding aspects wherein the calcination is performed at 450-550° C. in a water vapor atmosphere.
  • a method for preparing the catalytic cracking aid of any one of the preceding aspects comprising mixing and beating a phosphorus-modified MFI molecular sieve, a binder, and an optional second clay, and spray drying Then the catalytic cracking aid is obtained.
  • Aspect 17 the method for preparing a catalytic cracking aid according to any one of the preceding aspects, wherein the binder includes or is a phosphor-aluminum inorganic binder.
  • the method for preparing a catalytic cracking aid according to any one of the preceding aspects, wherein the phosphoaluminum inorganic binder is phosphoalumina gel and/or a first clay-containing phosphoaluminum inorganic binder; Based on the dry basis weight of the first clay-containing phosphoaluminum inorganic binder, the first clay-containing phosphoaluminum inorganic binder contains 10-40% by weight based on Al2O3, such as 15-40% by weight, Or 10-30% by weight, or 15-35% by weight or 20-40% by weight of aluminum component, 45-90% by weight based on P2O5, for example, 45-80% by weight, or 50-75% by weight or 60-80 Wt% of the phosphorus component and greater than 0 and not more than 40 wt%, for example, 8-35 wt% of the first clay on a dry basis, and the P/Al weight ratio of the first clay-containing phospho-aluminum inorganic binder Is
  • Aspect 19 the method for preparing a catalytic cracking aid according to any one of the preceding aspects, wherein the second clay is selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, etc. At least one of hydrokaolin, halloysite, hydrotalcite, bentonite, and diatomite.
  • the method for preparing a catalytic cracking aid according to any one of the preceding aspects wherein, based on the total weight of the catalytic cracking aid, the binder comprises 3-39 weight on a dry basis. % Of the phosphor-aluminum inorganic binder and 1-30% by weight of other inorganic binders on a dry basis.
  • the method for preparing a catalytic cracking aid further comprises: subjecting the spray-dried product to the first roasting, washing and optional drying treatments to obtain the catalytic cracking Auxiliary; wherein the calcination temperature of the first calcination is 300-650°C, and the calcination time is 0.5-8h; the temperature of the drying treatment is 100-200°C, and the drying time is 0.5-24h.
  • a method for preparing the catalytic cracking catalyst of any one of the foregoing aspects comprising: combining a Y-type molecular sieve, the phosphorus-modified MFI structure molecular sieve of any one of the foregoing aspects, an inorganic binder, and an optional The added second clay is mixed and beaten and spray-dried to obtain the catalytic cracking catalyst.
  • Aspect 25 the method for preparing a catalytic cracking catalyst according to any one of the preceding aspects, wherein the inorganic binder includes or is a phosphor-aluminum inorganic binder.
  • the 26th aspect the method for preparing a catalytic cracking catalyst according to any one of the preceding aspects, wherein the phosphoaluminum inorganic binder is phosphoalumina gel and/or a first clay-containing phosphoaluminum inorganic binder;
  • the first clay-containing phosphoaluminum inorganic binder is based on the dry basis weight, and the first clay-containing phosphoaluminum inorganic binder contains 10-40% by weight of Al2O3, such as 15-40% by weight of aluminum.
  • Components 45-90% by weight based on P2O5, for example 45-80% by weight of phosphorus components, and more than 0 and not more than 40% by weight of the first clay on a dry basis, and the first clay-containing phosphorous aluminum
  • the weight ratio of the inorganic binder P/Al is 1.0-6.0, the pH is 1-3.5, and the solid content is 15-60% by weight;
  • the first clay includes kaolin, sepiolite, attapulgite, rectorite, and smectite. At least one of stone removal and diatomaceous earth.
  • the method for preparing a catalytic cracking catalyst according to any one of the preceding aspects, wherein the second clay is selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, polyhydroxide At least one of kaolin, halloysite, hydrotalcite, bentonite, and diatomite.
  • the second clay is selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, polyhydroxide At least one of kaolin, halloysite, hydrotalcite, bentonite, and diatomite.
  • the method for preparing a catalytic cracking catalyst according to any one of the preceding aspects, wherein, based on the catalytic cracking catalyst, the inorganic binder includes 3-39% by weight of the phosphorus on a dry basis.
  • the method for preparing a catalytic cracking catalyst according to any one of the preceding aspects, wherein the method further comprises: subjecting the spray-dried product to first roasting, washing and optional drying treatments to obtain the catalytic cracking catalyst Cracking catalyst; wherein the calcination temperature of the first calcination is 300-650°C, and the calcination time is 0.5-8h; the temperature of the drying treatment is 100-200°C, and the drying time is 0.5-24h.
  • a catalytic cracking aid obtained by the method for preparing a catalytic cracking aid of any one of the foregoing aspects.
  • a catalytic cracking catalyst obtained by the method for preparing a catalytic cracking catalyst according to any one of the foregoing aspects.
  • Aspect 33 a method for the catalytic cracking of hydrocarbon oil, characterized in that the method comprises: under the conditions of catalytic cracking, the hydrocarbon oil is combined with the catalytic cracking aid of any one of the foregoing aspects or with any one of the foregoing aspects.
  • the method for catalytic cracking of hydrocarbon oil comprises: under the catalytic cracking conditions, combining the hydrocarbon oil with the catalytic cracking aid containing any one of the preceding aspects
  • the catalytic cracking agent is in contact with a catalyst mixture of a catalytic cracking catalyst for reaction; in the catalyst mixture, the content of the catalytic cracking promoter is 0.1-30% by weight.
  • the method for catalytic cracking of hydrocarbon oil according to any one of the preceding aspects, wherein the catalytic cracking conditions include: a reaction temperature of 500-800°C; and the hydrocarbon oil is selected from the group consisting of crude oil, naphtha, gasoline, One or more of atmospheric residue, vacuum residue, atmospheric wax oil, vacuum wax oil, DC wax oil, light/heavy deoiled propane, coking wax oil and coal liquefaction products.
  • the instruments and reagents used in the embodiments of the present invention are the instruments and reagents commonly used by those skilled in the art.
  • a micro-reactor is used to evaluate the effect of the catalytic cracking aid/catalytic cracking catalyst of the present invention on the yield of low-carbon olefins in the catalytic cracking of petroleum hydrocarbons.
  • the prepared catalytic cracking aid sample/catalytic cracking catalyst sample was processed on a fixed bed aging device at 800°C and 100% water vapor for 17 hours, and evaluated on a micro-reactor device.
  • the raw material oil was VGO or naphtha, and the evaluation conditions
  • the reaction temperature is 620°C
  • the regeneration temperature is 620°C
  • the catalyst-oil ratio is 3.2.
  • the micro-reaction activity is determined using the ASTM D5154-2010 standard method.
  • the pseudo-boehmite is an industrial product produced by Shandong Aluminum Company, with a solid content of 60% by weight.
  • the aluminum sol is an industrial product produced by Sinopec Catalyst Qilu Branch, and the content of Al2O3 is 21.5% by weight.
  • Silica sol is an industrial product produced by Sinopec Catalyst Qilu Branch, with a SiO2 content of 28.9% by weight and a Na2O content of 8.9%.
  • Kaolin is a special kaolin for catalytic cracking catalyst produced by Suzhou Kaolin Company, with a solid content of 78% by weight.
  • the rectorite is produced by Hubei Zhongxiang Mingliu Rectorite Development Co., Ltd., the quartz sand content is less than 3.5% by weight, the Al2O3 content is 39.0% by weight, the Na2O content is 0.03% by weight, and the solid content is 77% by weight.
  • ⁇ -alumina produced by Condex, Germany, with an Al2O3 content of 95% by weight.
  • Hydrochloric acid chemically pure, with a concentration of 36-38% by weight, produced by Beijing Chemical Plant.
  • PSRY molecular sieve is an industrial product produced by Sinopec Catalyst Changling Branch.
  • the content of Na2O is less than 1.5% by weight
  • the content of P2O5 is 0.8-1.2% by weight
  • the unit cell constant is less than 2.456nm
  • the crystallinity is ⁇ 64%.
  • the finished molecular sieve of HRY-1 is an industrial product produced by Sinopec Catalyst Changling Branch.
  • the La2O3 content is 11-13% by weight, the unit cell constant is ⁇ 2.464nm, and the crystallinity is ⁇ 40%.
  • the following examples illustrate the phosphorus-modified hierarchical pore ZSM-5 molecular sieve and preparation method of the present invention. These molecular sieves are used in the preparation of the catalytic cracking aid of the present invention and the catalytic cracking catalyst of the present invention.
  • Example 1-1 illustrates the phosphorus-containing hierarchical pore ZSM-5 molecular sieve and the preparation method of the present invention.
  • Example 1-1 Same as Example 1-1, the difference is that the impregnation method is used to impregnate the hydrogen type multi-porous ZSM-5 molecular sieve at 20°C.
  • the obtained comparative sample of phosphorus-containing hierarchical pore ZSM-5 molecular sieve is denoted as D1-1.
  • Example 1-1 Same as Example 1-1, the difference is that after drying, it is treated at 450° C. and 60% steam atmosphere for 0.5 h, and the obtained phosphorus-containing multi-porous ZSM-5 molecular sieve sample is denoted as GPZ1-2.
  • Example 1-2 Same as Example 1-2, the difference is that the impregnation method is used to impregnate the hydrogen type multi-porous ZSM-5 molecular sieve at 20°C.
  • the obtained comparative sample of phosphorus-containing hierarchical pore ZSM-5 molecular sieve is denoted as D1-2.
  • the phosphorus dispersion K of GPZ-1, D1-1, GPZ1-2 and D1-2 are listed in Table 1.
  • Example 2-1 illustrates the phosphorus-containing hierarchical pore ZSM-5 molecular sieve and the preparation method of the present invention.
  • Example 2-1 Same as Example 2-1, the difference is that the impregnation method is adopted to impregnate the hydrogen type multi-porous ZSM-5 molecular sieve at 20°C.
  • the obtained comparative sample of phosphorus-containing hierarchical pore ZSM-5 molecular sieve is denoted as D2-1.
  • Example 2-1 Same as Example 2-1, the difference is that after drying, it is treated at 600° C. under a 50% water vapor atmosphere for 2 hours, and the obtained phosphorus-containing multi-porous ZSM-5 molecular sieve sample is denoted as GPZ2-2.
  • Example 2-2 Same as Example 2-2, the difference is that the impregnation method is adopted to impregnate the hydrogen type multi-porous ZSM-5 molecular sieve at 20°C, which is designated as D2-2.
  • the phosphorus dispersion K of GPZ2-1, D2-1, GPZ2-2 and D2-2 are listed in Table 1.
  • Example 3-1 illustrates the phosphorus-containing hierarchical pore ZSM-5 molecular sieve and the preparation method of the present invention.
  • Example 3-1 Same as Example 3-1, the difference is that the impregnation method is adopted, and the hydrogen type multi-porous ZSM-5 molecular sieve is impregnated with a phosphorus-containing aqueous solution at 20°C.
  • the obtained comparative sample of phosphorus-containing hierarchical pore ZSM-5 molecular sieve is denoted as D3-1.
  • Example 3-1 Same as Example 3-1, the difference is that after drying, it is treated at 430° C. and 100% steam atmosphere for 2 hours, and the obtained phosphorus-containing multi-porous ZSM-5 molecular sieve sample is designated as GPZ3-2.
  • Example 3-2 Same as Example 3-2, the difference is that the impregnation method is adopted, and the hydrogen type multi-porous ZSM-5 molecular sieve is impregnated with a phosphorus-containing aqueous solution at 20°C.
  • the obtained comparative sample of phosphorus-containing hierarchical pore ZSM-5 molecular sieve is denoted as D3-2.
  • the phosphorus dispersion K of GPZ3-1, D3-1, GPZ3-2 and D3-2 are listed in Table 1.
  • Example 4-1 illustrates the phosphorus-containing hierarchical pore ZSM-5 molecular sieve and the preparation method of the present invention.
  • Example 4-1 Same as Example 4-1, the difference is that the impregnation method is used to impregnate the hydrogen type multi-porous ZSM-5 molecular sieve at 20°C.
  • the obtained comparative sample of phosphorus-containing hierarchical pore ZSM-5 molecular sieve is denoted as D4-1.
  • Example 4-1 Same as Example 4-1, the difference is that after drying, it is treated at 350° C. and 100% steam atmosphere for 2 hours, and the obtained phosphorus-containing multi-porous ZSM-5 molecular sieve sample is denoted as GPZ4-2.
  • Example 4 Same as Example 4-2, the difference is that the impregnation method is used to impregnate the hydrogen type multi-porous ZSM-5 molecular sieve at 20°C.
  • the obtained comparative sample of phosphorus-containing hierarchical pore ZSM-5 molecular sieve is denoted as D4-2.
  • the phosphorus dispersion K of GPZ4-1, D4-1, GPZ4-2 and D4-2 are listed in Table 1.
  • Example 5-1 illustrates the phosphorus-containing multi-porous ZSM-5 molecular sieve and the preparation method of the present invention.
  • Example 5-1 Same as Example 5-1, the difference is that the impregnation method is adopted to impregnate the hydrogen type multi-porous ZSM-5 molecular sieve at 20°C.
  • the obtained comparative sample of phosphorus-containing hierarchical pore ZSM-5 molecular sieve is denoted as D5-1.
  • Example 5-1 The same as Example 5-1, the difference is that after drying, it is calcined at 500°C and 40% water vapor atmosphere for 4 hours, and the obtained phosphorus-containing multi-porous ZSM-5 molecular sieve sample is denoted as GPZ5-2.
  • Example 5-2 Same as Example 5-2, the difference is that the impregnation method is adopted to impregnate the hydrogen type multi-porous ZSM-5 molecular sieve at 20°C.
  • the obtained comparative sample of phosphorus-containing hierarchical pore ZSM-5 molecular sieve is denoted as D5-2.
  • the phosphorus dispersion K of GPZ5-1, D5-1, GPZ5-2 and D5-2 are listed in Table 1.
  • Example 6-1 illustrates the phosphorus-containing hierarchical pore ZSM-5 molecular sieve and the preparation method of the present invention.
  • Example 6-1 Same as Example 6-1, the difference is that the impregnation method is used to impregnate the hydrogen type multi-porous ZSM-5 molecular sieve at 20°C.
  • the obtained comparative sample of phosphorus-containing hierarchical pore ZSM-5 molecular sieve is denoted as D6-1.
  • Example 6-1 Same as Example 6-1, the difference is that after drying, it is hydrothermally calcined at 350°C and 60% steam atmosphere for 4 hours to obtain a phosphorus-containing multi-porous ZSM-5 molecular sieve sample, which is recorded as GPZ6-2.
  • Example 6-2 Same as Example 6-2, the difference is that the impregnation method is used to impregnate the hydrogen type multi-porous ZSM-5 molecular sieve at 20°C.
  • the obtained comparative sample of phosphorus-containing hierarchical pore ZSM-5 molecular sieve is denoted as D6-2.
  • the phosphorus dispersion K of GPZ6-1, D6-1, GPZ6-2 and D6-2 are listed in Table 1.
  • Example 7-1 illustrates the phosphorus-containing hierarchical pore ZSM-5 molecular sieve and the preparation method of the present invention.
  • Example 7-1 Same as Example 7-1, the difference is that the impregnation method is adopted, and the hydrogen-type multi-porous ZSM-5 molecular sieve is impregnated with a phosphorus-containing aqueous solution at 20°C.
  • the obtained comparative sample of phosphorus-containing hierarchical pore ZSM-5 molecular sieve is denoted as D7-1.
  • Example 7-1 Same as Example 7-1, the difference is that after drying, it is calcined at 600°C and 50% water vapor atmosphere for 2 hours, and the obtained phosphorus-containing multi-porous ZSM-5 molecular sieve sample is recorded as GPZ7-2.
  • Example 7-2 Same as Example 7-2, the difference is that the impregnation method is adopted, and the hydrogen type multi-porous ZSM-5 molecular sieve is impregnated with a phosphorus-containing aqueous solution at 20°C.
  • the obtained comparative sample of phosphorus-containing hierarchical pore ZSM-5 molecular sieve is denoted as D7-2.
  • the phosphorus dispersion K of GPZ7-1, D7-1, GPZ7-2 and D7-2 are listed in Table 1.
  • Example 4-1 Same as Example 4-1, the difference is that the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the two is 3:1.
  • the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is denoted as GPZ8-1.
  • Example 4-2 Same as Example 4-2, the difference is that the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the two is 3:1.
  • the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is denoted as GPZ8-2.
  • Example 4-1 Same as Example 4-1, the difference is that the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the two is 2:2.
  • the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is denoted as GPZ9-1.
  • Example 4-2 Same as Example 4-2, the difference is that the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the two is 2:2.
  • the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is denoted as GPZ9-2.
  • Example 4-1 Same as Example 4-1, the difference is that the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the two is 1:3.
  • the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is denoted as GPZ10-1.
  • Example 4-2 Same as Example 4-2, the difference is that the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the two is 1:3.
  • the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is denoted as GPZ10-2.
  • the phosphorus dispersion K of GPZ8-1, GPZ8-2, GPZ9-1, GPZ9-2, GPZ10-1, GPZ10-2 are listed in Table 1.
  • Example 8-1 Same as Example 8-1, the difference is that the phosphorus source is phosphoric acid and crystalline boron phosphate, and the weight ratio of the two is 3:1.
  • the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is denoted as GPZ11-2.
  • Example 8-2 Same as Example 8-2, the difference is that the phosphorus source is phosphoric acid and crystalline boron phosphate, and the weight ratio of the two is 3:1.
  • the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is denoted as GPZ11-2.
  • Example 9-1 Same as Example 9-1, the difference is that the phosphorus source is phosphoric acid and crystalline boron phosphate, and the weight ratio of the two is 2:2.
  • the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is denoted as GPZ12-1.
  • Example 9-2 Same as Example 9-2, the difference is that the phosphorus source is phosphoric acid and crystalline boron phosphate, and the weight ratio of the two is 2:2 (the ratio value is the same as or close to that of Example 9-1).
  • the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is denoted as GPZ12-2.
  • Example 10-1 Same as Example 10-1, the difference is that the phosphorus source is phosphoric acid and crystalline boron phosphate, and the weight ratio of the two is 1:3.
  • the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is denoted as GPZ13-2.
  • Example 10-2 Same as Example 10-2, the difference is that the phosphorus source is phosphoric acid and crystalline boron phosphate, and the weight ratio of the two is 1:3.
  • the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is denoted as GPZ13-2.
  • the phosphorus dispersion K of GPZ11-1, GPZ11-2, GPZ12-1, GPZ12-2, GPZ13-1, GPZ13-2 are listed in Table 1.
  • Example 14-1 illustrates the phosphorus-containing microporous ZSM-5 molecular sieve and method of the present invention.
  • Comparative Example 14-1 illustrates the existing industrial conventional method and the obtained phosphorus-modified ZSM-5 comparative sample.
  • Example 14-1 Same as Example 14-1, the difference is that the impregnation method is used to soak the HZSM-5 molecular sieve at 20°C for 2 hours.
  • the obtained comparative sample of phosphorus-modified ZSM-5 molecular sieve is denoted as D14-1.
  • Example 14-2 illustrates the phosphorus-containing microporous ZSM-5 molecular sieve and method of the present invention.
  • Example 14-1 Same as Example 14-1, the difference is that the 550°C air atmosphere is changed to 500°C, 50% water vapor atmosphere for 0.5h.
  • the obtained phosphorus-modified ZSM-5 molecular sieve sample is denoted as GPZ14-2.
  • Example 14-2 Same as Example 14-2, the difference is that the impregnation method is used to impregnate the hydrogen type multi-porous ZSM-5 molecular sieve at 20°C for 2 hours. A comparative sample of phosphorus-modified ZSM-5 molecular sieve was obtained, which was recorded as D14-2.
  • the phosphorus dispersion K of GPZ14-1, D14-1, GPZ14-2 and D14-2 are listed in Table 1.
  • Example 15-1 illustrates the phosphorus-containing microporous ZSM-5 molecular sieve and method of the present invention.
  • Comparative Example 15-1 illustrates the existing industrial conventional method and the obtained phosphorus-modified ZSM-5 comparative sample.
  • Example 15-1 Same as Example 15-1, the difference is that the dipping method is used to immerse the HZSM-5 molecular sieve at 20°C.
  • the obtained comparative sample of phosphorus-modified ZSM-5 molecular sieve is denoted as D15-1.
  • Example 15-2 illustrates the phosphorus-containing microporous ZSM-5 molecular sieve and method of the present invention.
  • Example 15-2 Same as Example 15-1, the difference is that the 550°C air atmosphere is changed to 600°C, 30% water vapor atmosphere for 2h.
  • the obtained phosphorus modified ZSM-5 molecular sieve sample is denoted as GPZ15-2.
  • Example 15-2 Same as Example 15-2, the difference is that the dipping method is used to immerse the HZSM-5 molecular sieve at 20°C. A comparative sample of phosphorus-modified ZSM-5 molecular sieve was obtained, which was recorded as D15-2.
  • the phosphorus dispersion K of GPZ15-1, D15-1, GPZ15-2 and D15-2 are listed in Table 1.
  • Example 16-1 illustrates the phosphorus-containing microporous ZSM-5 molecular sieve and method of the present invention.
  • Comparative Example 16-1 illustrates the existing industrial conventional method and the obtained phosphorus-modified ZSM-5 comparative sample.
  • Example 16-1 Same as Example 16-1, the difference is that the dipping method is adopted, and the HZSM-5 molecular sieve is impregnated with a phosphorus-containing aqueous solution at 20°C.
  • the obtained comparative sample of phosphorus-modified ZSM-5 molecular sieve is denoted as D16-1.
  • Example 16-2 illustrates the phosphorus-containing microporous ZSM-5 molecular sieve and method of the present invention.
  • Example 16-2 Same as Example 16-1, the difference is that the 550°C air atmosphere is changed to 400°C, 100% water vapor atmosphere for 2h.
  • the obtained phosphorus-modified ZSM-5 molecular sieve sample is denoted as GPZ16-2.
  • Example 16-2 Same as Example 16-2, the difference is that the dipping method is adopted, and the HZSM-5 molecular sieve is impregnated with a phosphorus-containing aqueous solution at 20°C. A comparative sample of phosphorus-modified ZSM-5 molecular sieve was obtained, which was recorded as D16-2.
  • the phosphorus dispersion K of GPZ16-1, D16-1, GPZ16-2 and D15-2 are listed in Table 1.
  • Example 17-1 illustrates the phosphorus-containing microporous ZSM-5 molecular sieve and method of the present invention.
  • Comparative Example 17-1 illustrates the existing industrial conventional method and the obtained phosphorus-modified ZSM-5 comparative sample.
  • Example 17-1 Same as Example 17-1, the difference is that the dipping method is used to immerse the HZSM-5 molecular sieve at 20°C.
  • the obtained comparative sample of phosphorus-modified ZSM-5 molecular sieve is denoted as D17-1.
  • Example 17-2 Same as Example 17-1, the difference is that the 550°C air atmosphere is changed to 300°C, 100% water vapor atmosphere for 2h.
  • the obtained phosphorus-modified ZSM-5 molecular sieve sample is denoted as GPZ17-2.
  • Example 17-2 Same as Example 17-2, the difference is that the impregnation method is used to impregnate the HZSM-5 molecular sieve at 20°C. A comparative sample of phosphorus-modified ZSM-5 molecular sieve was obtained, which was recorded as D17-2.
  • the phosphorus dispersion K of GPZ17-1, D17-1, GPZ17-2 and D17-2 are listed in Table 1.
  • Comparative Example 18-1 illustrates the existing industrial conventional method and the obtained phosphorus-modified ZSM-5 comparative sample.
  • Example 18-1 Same as Example 18-1, the difference is that the dipping method is used to immerse the HZSM-5 molecular sieve at 20°C.
  • the obtained comparative sample of phosphorus-modified ZSM-5 molecular sieve is denoted as D18-1.
  • Example 18-2 illustrates the phosphorus-containing microporous ZSM-5 molecular sieve and method of the present invention.
  • Example 18-2 Same as Example 18-1, the difference is that the 550°C air atmosphere is changed to 500°C and 80% water vapor atmosphere for 4 hours.
  • the obtained phosphorus modified ZSM-5 molecular sieve sample is denoted as GPZ18-2.
  • Example 18-2 Same as Example 18-2, the difference is that the dipping method is used to immerse the HZSM-5 molecular sieve at 20°C. A comparative sample of phosphorus-modified ZSM-5 molecular sieve was obtained, which was recorded as D18-2.
  • the phosphorus dispersion K of GPZ18-1, D18-1, GPZ18-2 and D18-2 are listed in Table 1.
  • Example 19-1 illustrates the phosphorus-containing microporous ZSM-5 molecular sieve and method of the present invention.
  • Comparative Example 19-1 illustrates the existing industrial conventional method and the obtained phosphorus-modified ZSM-5 comparative sample.
  • Example 19-1 The same as Example 19-1, the difference is that the dipping method is used to immerse the HZSM-5 molecular sieve at 20°C.
  • the obtained comparative sample of phosphorus-modified ZSM-5 molecular sieve is denoted as D19-1.
  • Example 19-2 illustrates the phosphorus-containing microporous ZSM-5 molecular sieve and method of the present invention.
  • Example 19-1 Same as Example 19-1, the difference is that the air atmosphere at 550°C is changed to 400°C, and the treatment is carried out under a 100% water vapor atmosphere for 4 hours.
  • the obtained phosphorus-modified ZSM-5 molecular sieve sample is denoted as GPZ19-2.
  • Example 19-2 Same as Example 19-2, the difference lies in that the dipping method is used to immerse the HZSM-5 molecular sieve at 20°C. A comparative sample of phosphorus-modified ZSM-5 molecular sieve was obtained, which was recorded as D19-2.
  • the phosphorus dispersion K of GPZ19-1, D19-1, GPZ19-2 and D19-2 are listed in Table 1.
  • Example 20-1 illustrates the phosphorus-containing microporous ZSM-5 molecular sieve and method of the present invention.
  • Comparative Example 20-1 illustrates the existing industrial conventional method and the obtained phosphorus-modified ZSM-5 comparative sample.
  • Example 20-1 Same as Example 20-1, the difference is that the dipping method is adopted, and the HZSM-5 molecular sieve is impregnated with a phosphorus-containing aqueous solution at 20°C.
  • the obtained comparative sample of phosphorus-modified ZSM-5 molecular sieve is denoted as D20-1.
  • Example 20-2 illustrates the phosphorus-containing microporous ZSM-5 molecular sieve and method of the present invention.
  • Example 20-2 Same as Example 20-1, the difference is that the 550°C air atmosphere is changed to 600°C and 30% water vapor atmosphere for 4 hours.
  • the obtained phosphorus-modified ZSM-5 molecular sieve sample is denoted as GPZ20-2.
  • Example 20-2 Same as Example 20-2, the difference is that the impregnation method is adopted, and the HZSM-5 molecular sieve is impregnated with a phosphorus-containing aqueous solution at 20°C. A comparative sample of phosphorus-modified ZSM-5 molecular sieve was obtained, which was recorded as D20-2.
  • the phosphorus dispersion K of GPZ20-1, D20-1, GPZ20-2 and D20-2 are listed in Table 1.
  • Example 17-1 Same as Example 17-1, the difference is that the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the two is 3:1.
  • the obtained phosphorus-containing ZSM-5 molecular sieve sample is designated as GPZ21-1.
  • Example 17-2 Same as Example 17-2, the difference is that the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the two is 3:1.
  • the obtained phosphorus-containing ZSM-5 molecular sieve sample is denoted as GPZ21-2.
  • Example 17-1 Same as Example 17-1, the difference is that, for example, the dual phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the two is 2:2.
  • the obtained phosphorus-containing ZSM-5 molecular sieve sample is designated as GPZ22-1.
  • Example 17-2 Same as Example 17-2, the difference is that the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the two is 2:2.
  • the obtained phosphorus-containing ZSM-5 molecular sieve sample is designated as GPZ23-2.
  • Example 17-1 Same as Example 17-1, the difference is that the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the two is 1:3.
  • the obtained phosphorus-containing ZSM-5 molecular sieve sample is denoted as GPZ23-1.
  • Example 17-2 Same as Example 17-2, the difference is that the phosphorus source is diammonium hydrogen phosphate and crystalline boron phosphate, and the weight ratio of the two is 1:3.
  • the obtained phosphorus-containing ZSM-5 molecular sieve sample is designated as GPZ23-2.
  • the phosphorus dispersion K of GPZ21-1, GPZ21-2, GPZ22-1, GPZ22-2, GPZ23-1, GPZ23-2 are listed in Table 1.
  • Example 21-1 to Example 23-2 the phosphorus sources were replaced with phosphoric acid and crystalline boron phosphate in order, and the ratios of the two were 3:1, 3:1, 2:2, 2:2, respectively. 1:3, 1:3, the obtained samples are GPZ24-1, GPZ24-2, GPZ25-1, GPZ25-2, GPZ26-1, GPZ26-2.
  • the phosphorus dispersion K is listed in Table 1.
  • Micro-reverse evaluation conditions molecular sieve loading is 2g, raw oil is n-tetradecane, oil feed is 1.56g, reaction temperature is 550°C, and regeneration temperature is 600°C (the same below).
  • GPZ13-1, and GPZ13-2; GPZ14-1, D14-1, GPZ14-2 and D14-2; GPZ15-1, D15-1, GPZ15-2 and D15-2; GPZ16-1, D16-1 , GPZ16-2 and D16-2; GPZ17-1, D17-1, GPZ17-2 and D17-2; GPZ18-1, D18-1, GPZ18-2 and D18-2; GPZ19-1, D19-1, GPZ19 -2 and D19-2; GPZ20-1, D20-1, GPZ20-2 and D20-2; GPZ21-1, GPZ21-2, GPZ22-1, GPZ22-2, GPZ23-1, GPZ23-2, GPZ24-1 , GPZ24-2, GPZ25-1, GPZ25-2, GPZ26-1, and GPZ26-2 were subjected to hydrothermal aging treatment at 800°C, 100% steam, 17h, and then subjecte
  • the samples of the examples After being treated with 800°C, 100% steam, and 17h hydrothermal aging, the samples of the examples showed excellent catalytic cracking activity of n-tetradecane, and the conversion rate, liquefied gas yield, and triene yield were all improved. It shows that the phosphorus-modified MFI structure molecular sieve of the present invention has a higher yield of liquefied gas while increasing the yield of low-carbon olefins.
  • Examples 27-30 illustrate the phosphorus-aluminum inorganic binder used in the catalytic cracking promoter/catalyst of the present invention.
  • the phosphor-aluminum inorganic binder was prepared according to the method of Example 27, the material ratio is shown in Table 3, and the sample numbers are Binder 2, Binder 3, and Binder 4.
  • Example Example 27 Example 28 Example 29 Example 30 Binder number Binder 1 Binder 2 Binder 3 Binder 4 Pseudo-boehmite, kg 1.91 To To 1.6 Al2O3, kg 1.19 To To 1 SB aluminum hydroxide powder, kg To 0.94 To To Al2O3, kg To 0.7 To To ⁇ -Alumina, kg To To 0.58 To Al2O3, kg To To 0.58 To Rectorite, kg To 1.28 1.93 To Dry basis, kg To 1 1.5 To Kaolin, kg 0.56 To To To Dry basis, kg 0.5 To To To To Phosphoric acid, kg 5.37 5.36 4.03 6.5 P2O5, kg 3.31 3.3 2.92 4 Decationized water, kg 3.27 6.71 20.18 4.4 Total amount, kg 11.11 14.29 25 12.5 Total dry basis, kg 5 5 5 5 Binder solid content, kg/kg 0.45 0.35 0.2 0.4 P/Al 2.29 3.89 4.19 3.3 Al2O3, wt% 23.82 14 11.53 20 P2O5, wt% 66.
  • Examples 31 to 56 provide the catalytic cracking aid of the present invention, and Comparative Examples 31 to 56 illustrate the catalytic cracking aids for comparison. Among them, Examples 31 to 43 are multi-porous ZSM-5 molecular sieves, and Examples 44 to 56 are microporous ZSM-5 molecular sieves.
  • Example 27 Take the phosphorus-modified molecular sieve GPZ1-1, kaolin and pseudo-boehmite prepared in Example 1-1, add decationized water and aluminum sol to make a slurry for 120 minutes to obtain a slurry with a solid content of 30% by weight, and add hydrochloric acid to adjust the pH of the slurry 3.0, then continue beating for 45 minutes, and then add the phosphor-aluminum inorganic binder Binder1 prepared in Example 27.
  • microspheres After stirring for 30 minutes, the slurry is spray-dried to obtain microspheres, and the microspheres are calcined at 500°C for 1 hour , Prepared a catalytic cracking aid sample, numbered CAZ1-1, the proportion of which is 50% molecular sieve, 23% kaolin, 18% Binder1, pseudo-boehmite (calculated as Al2O3) 5%, aluminum sol (calculated as Al2O3) Count) 4%.
  • CAZ1-1 catalytic cracking aid sample, numbered CAZ1-1, the proportion of which is 50% molecular sieve, 23% kaolin, 18% Binder1, pseudo-boehmite (calculated as Al2O3) 5%, aluminum sol (calculated as Al2O3) Count) 4%.
  • a fixed-bed microreactor is used to evaluate the reaction performance of 100% balancer and the balancer mixed with CAZ1-1 to illustrate the catalytic cracking reaction effect of the catalytic cracking aid provided in the present disclosure.
  • the additive CAZ1-1 was subjected to an aging treatment at 800°C under a 100% water vapor atmosphere for 17 hours. Take the aged CAZ1-1 and industrial FCC equilibrium catalyst (industrial brand DVR-3 FCC equilibrium catalyst, light oil micro-reaction activity is 63) and mix. The mixture of balance agent and auxiliary agent was charged into a fixed-bed micro-reactor, and the feed oil shown in Table 4 was subjected to catalytic cracking.
  • the evaluation conditions were reaction temperature 620°C, regeneration temperature 620°C, and catalyst-oil ratio 3.2. Table 6 shows the results of the reaction, which includes the blank test agent.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ1-2 prepared in Example 1-2.
  • a sample of catalytic cracking aid was prepared, numbered CAZ1-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 12-1 Same as Example 12-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the comparative sample D1-1 of Comparative Example 1-1.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ1-1.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the comparative sample D1-2 of Comparative Example 1-2.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ1-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ2-1 prepared in Example 2-1.
  • a sample of catalytic cracking aid was prepared, numbered CAZ2-1.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 32-1 Same as Example 32-1, the difference is that the phosphorus-modified molecular sieve GPZ2-1 is replaced with the phosphorus-modified molecular sieve GPZ2-2 prepared in Example 2-2.
  • a sample of catalytic cracking aid was prepared, numbered CAZ2-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 32-1 Same as Example 32-1, the difference is that the phosphorus-modified molecular sieve GPZ2-1 is replaced with the comparative sample D2-1 of Comparative Example 2-1.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ2-1.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 32-1 Same as Example 32-1, the difference is that the phosphorus-modified molecular sieve GPZ2-1 is replaced with the comparative sample D2-2 of Comparative Example 2-2.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ2-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ3-1 prepared in Example 3-1.
  • a sample of catalytic cracking aid was prepared, numbered CAZ3-1.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ3-2 prepared in Example 3-2.
  • a sample of catalytic cracking aid was prepared, numbered CAZ3-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the comparative sample D3-1 of Comparative Example 3-1.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ3-1.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the comparative sample D3-2 of Comparative Example 3-2.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ3-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ4-1 prepared in Example 4-1.
  • a sample of catalytic cracking aid was prepared, numbered CAZ4-1.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 34-1 Same as Example 34-1, the difference is that the phosphorus-modified molecular sieve GPZ4-1 is replaced with the phosphorus-modified molecular sieve GPZ4-2 prepared in Example 4-2.
  • a sample of catalytic cracking aid was prepared, numbered CAZ4-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 34-1 Same as Example 34-1, the difference is that the phosphorus-modified molecular sieve GPZ4-1 is replaced with the comparative sample D4-1 of Comparative Example 4-1.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ4-1.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 34-1 Same as Example 34-1, the difference is that the phosphorus-modified molecular sieve GPZ4-1 is replaced with the comparative sample D4-2 of Comparative Example 2-2.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ4-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ5-1 prepared in Example 5-1.
  • a sample of catalytic cracking aid was prepared, numbered CAZ5-1.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 35-1 Same as Example 35-1, the difference is that the phosphorus-modified molecular sieve GPZ5-1 is replaced with the phosphorus-modified molecular sieve GPZ5-2 prepared in Example 5-2.
  • a sample of catalytic cracking aid was prepared, numbered CAZ5-2.
  • the evaluation is the same as in Example 35-1, and the results are shown in Table 6.
  • Example 35-1 Same as Example 35-1, the difference is that the phosphorus-modified molecular sieve GPZ5-1 is replaced with the comparative sample D5-1 of Comparative Example 5-1.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ5-1.
  • the evaluation is the same as in Example 35-1, and the results are shown in Table 6.
  • Example 35-1 Same as Example 35-1, the difference is that the phosphorus-modified molecular sieve GPZ5-1 is replaced with the comparative sample D5-2 of Comparative Example 2-2.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ5-2.
  • the evaluation is the same as in Example 35-1, and the results are shown in Table 6.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ6-1 prepared in Example 6-1.
  • a sample of catalytic cracking aid was prepared, numbered CAZ6-1.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 36-1 Same as Example 36-1, the difference is that the phosphorus-modified molecular sieve GPZ6-1 is replaced with the phosphorus-modified molecular sieve GPZ6-2 prepared in Example 6-2.
  • a sample of catalytic cracking aid was prepared, numbered CAZ6-2.
  • the evaluation is the same as in Example 36-1, and the results are shown in Table 6.
  • Example 36-1 Same as Example 36-1, the difference is that the phosphorus-modified molecular sieve GPZ6-1 is replaced with the comparative sample D6-1 of Comparative Example 6-1.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ6-1.
  • the evaluation is the same as in Example 36-1, and the results are shown in Table 6.
  • Example 36-1 Same as Example 36-1, the difference is that the phosphorus-modified molecular sieve GPZ6-1 is replaced with the comparative sample D6-2 of Comparative Example 6-2.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ6-2.
  • the evaluation is the same as in Example 36-1, and the results are shown in Table 6.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ7-1 prepared in Example 7-1.
  • a sample of catalytic cracking aid was prepared, numbered CAZ7-1.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 37-1 Same as Example 37-1, the difference is that the phosphorus-modified molecular sieve GPZ7-1 is replaced with the phosphorus-modified molecular sieve GPZ7-2 prepared in Example 7-2.
  • a sample of catalytic cracking aid was prepared, numbered CAZ7-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 37-1 Same as Example 37-1, the difference is that the phosphorus-modified molecular sieve GPZ7-1 is replaced with the comparative sample D7-1 of Comparative Example 7-1.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ7-1.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 37-1 Same as Example 37-1, the difference is that the phosphorus-modified molecular sieve GPZ7-1 is replaced with the comparative sample D7-2 of Comparative Example 7-2.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ7-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ8-1 to GPZ13-2 prepared in Example 8-1 to Example 13-2, respectively.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6 respectively.
  • Examples 44 to 56 are additives CAZ14 to CAZ26 containing microporous ZSM-5 (GPZ14 to GPZ26) respectively, and the material ratios correspond to Examples 31 to 43, for example, in Example 44-1, GPZ1-1 was replaced by GPZ14-1, in Example 44-2, GPZ1-2 was replaced by GPZ14-2, and so on, until in Example 56-1, GPZ14-1 was replaced by GPZ26-1, and Example 56-2 In, GPZ14-2 is replaced by GPZ26-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6 respectively.
  • Comparative Example 44 to Comparative Example 50 are the contrast additives DCAZ-14 to DCAZ-20 each containing microporous ZSM-5 (D14 to D20), and the material ratios correspond to Examples 44 to 50, for example, Comparative Example In 44-1, GPZ1-1 was replaced by D14-1, in Comparative Example 44-2, GPZ1-2 was replaced by D14-2, and so on, until in Comparative Example 50-1, GPZ14-1 was replaced by D20-1, In Comparative Example 50-2, GPZ14-2 was replaced with D20-2. The evaluation is the same as in Example 31-1, and the results are shown in Table 6, respectively.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 sequence is replaced by the phosphorus-modified molecular sieve GPZ21-1 to GPZ26-2 prepared in Example 21-1 to Example 26-2, respectively.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6 respectively.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphor-aluminum inorganic binder is replaced with the binder 2 prepared in Example 28.
  • the catalytic cracking aid was prepared, numbered CAZ33-1.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 31-2 Same as Example 31-2, the difference is that the phosphor-aluminum inorganic binder is replaced by the binder 2 prepared in Example 28.
  • the catalytic cracking aid was prepared, numbered CAZ33-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphor-aluminum inorganic binder is replaced with the binder 3 prepared in Example 29.
  • the catalytic cracking aid was prepared, numbered CAZ34-1.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 31-2 The same as Example 31-2, the difference is that the phosphor-aluminum inorganic binder is replaced by the binder 3 prepared in Example 29.
  • the catalytic cracking aid was prepared, numbered CAZ34-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 31-1 Same as Example 31-1, the difference is that the phosphor-aluminum inorganic binder is replaced with the binder 4 prepared in Example 30.
  • the catalytic cracking aid was prepared, numbered CAZ35-1.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 31-2 Same as Example 31-2, the difference is that the phosphor-aluminum inorganic binder is replaced with the binder 4 prepared in Example 30.
  • the catalytic cracking aid was prepared, numbered CAZ35-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 31-1 Same as Example 31-1, the difference lies in the use of phosphorus-modified ZSM-5 molecular sieve sample GPZ1-1 (45% by weight), kaolin (18% by weight), phosphor-aluminum inorganic binder Binder 3 (22% by weight), which is pseudo-thin A catalytic cracking aid was prepared from diaspore (10% by weight) and aluminum sol (5% by weight), numbered CAZ36-1.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 66-1 Same as Example 66-1, the difference is that GPZ1-1 is replaced by GPZ1-2.
  • the catalytic cracking aid was prepared, numbered CAZ36-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 66-1 Same as Example 66-1, the difference is that GPZ1-1 is replaced by D1-1.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ36-1. The evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 66-1 Same as Example 66-1, the difference is that GPZ1-1 is replaced by D1-2.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ36-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 44-1 Same as Example 44-1, the difference lies in the use of phosphorus-modified ZSM-5 molecular sieve sample GPZ14-1 (40% by weight), kaolin (24% by weight), phosphor-aluminum inorganic binder Binder 4 (20% by weight), which is pseudo-thin A catalytic cracking aid was prepared from diaspore (6 wt%) and silica sol (10 wt%), numbered CAZ37-1. The evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 67-1 Same as Example 67-1, the difference is that GPZ14-1 is replaced with GPZ14-2.
  • the catalytic cracking aid was prepared, numbered CAZ37-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 67-1 Same as Example 67-1, the difference is that GPZ14-1 is replaced by D14-1.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ37-1. The evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 67-1 Same as Example 67-1, the difference is that GPZ14-1 is replaced by D14-2.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ37-2.
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 1-1 The phosphorus-modified molecular sieve GPZ1-1 prepared in Example 1-1 was added to form a slurry (with a solid content of 35% by weight), followed by stirring and spray drying to form microspheres.
  • ammonium sulfate:microspheres:water 0.5:1:10)
  • the ionized water is rinsed and filtered, and then dried at 110°C to obtain the additive CAZ38-1.
  • the ratio is 50% molecular sieve, 23% kaolin, and 27% aluminum sol (calculated as Al2O3).
  • the evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 68-1 Same as Example 68-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ1-2 prepared in Example 1-2.
  • a sample of catalytic cracking aid was prepared, numbered CAZ38-2. The evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 68-1 Same as Example 68-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the comparative sample D1-1 of Comparative Example 1-1.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ38-1. The evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 68-1 Same as Example 68-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the comparative sample D1-2 of Comparative Example 1-2.
  • a comparative sample of catalytic cracking aid was prepared, numbered DCAZ38-2. The evaluation is the same as in Example 31-1, and the results are shown in Table 6.
  • Example 69-1 Example 69-2
  • Example 69-1 and Example 69-2 the catalytic cracking aids CAZ1-1 and CAZ1-2 of Example 31-1 and Example 31-2 were used, respectively.
  • the feedstock oil for catalytic cracking is the naphtha shown in Table 5.
  • the evaluation conditions are the reaction temperature of 620°C, the regeneration temperature of 620°C, and the catalyst-to-oil ratio of 3.2.
  • Table 7 shows the weight composition and reaction results of each catalyst mixture containing catalytic cracking promoters.
  • Example 69-1 Same as Example 69-1, except that the catalytic cracking contrast aids DCAZ1-1 and DCAZ1-2 of Comparative Example 31-1 and Comparative Example 31-2 were used respectively.
  • Table 7 shows the weight composition and reaction results of the catalyst mixtures containing the catalytic cracking aid comparative samples.
  • Example 70-1 Example 70-2
  • Example 70-1 and Example 70-2 used the catalytic cracking aids CAZ14-1 and CAZ14-2 of Example 44-1 and Example 44-2, respectively.
  • the feedstock oil for catalytic cracking is the naphtha shown in Table 5.
  • the evaluation conditions are the reaction temperature of 620°C, the regeneration temperature of 620°C, and the catalyst-to-oil ratio of 3.2.
  • Table 7 shows the weight composition and reaction results of each catalyst mixture containing catalytic cracking promoters.
  • Example 70-1 The same as Example 70-1, except that the catalytic cracking contrast aids DCAZ14-1 and DCAZ14-2 of Comparative Example 44-1 and Comparative Example 44-2 were used respectively.
  • Table 7 shows the weight composition and reaction results of the catalyst mixtures containing the catalytic cracking aid comparative samples.
  • Example Y31 to Example Y56 provide the catalytic cracking catalyst of the present invention, and Comparative Example Y31 to Comparative Example Y56 illustrate the catalytic cracking comparative catalyst as a comparison.
  • Examples Y31 to Y43 contain phosphorus-modified multi-porous ZSM-5 molecular sieves, and Examples Y44 to Y56 contain phosphorus-modified microporous ZSM-5 molecular sieves.
  • a fixed-bed micro-reactor was used to evaluate the reaction performance of 100% balancer and balancer mixed with CAZY1-1 to illustrate the effect of catalytic cracking reaction.
  • the catalyst CAZY1-1 was subjected to an aging treatment at 800° C. and a 100% steam atmosphere for 17 hours. Take the aged CAZY1-1 and industrial FCC equilibrium catalyst (industrial brand DVR-3 FCC equilibrium catalyst, light oil micro-reaction activity is 63) and mix. The mixture of balancer and catalyst was charged into a fixed-bed microreactor, and the feedstock oil shown in Table 4 was subjected to catalytic cracking. The evaluation conditions were reaction temperature 620°C, regeneration temperature 620°C, and catalyst-oil ratio 3.2. Table 8 shows the results of the reaction, which includes the blank test agent.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ1-2 prepared in Example 1-2.
  • a sample of catalytic cracking catalyst was prepared, numbered CAZY1-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the comparative sample D1-1 of Comparative Example 1-1.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY1-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the comparative sample D1-2 of Comparative Example 1-2.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY1-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ2-1 prepared in Example 2-1.
  • a sample of catalytic cracking catalyst was prepared, numbered CAZY2-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y32-1 Same as Example Y32-1, the difference is that the phosphorus-modified molecular sieve GPZ2-1 is replaced with the phosphorus-modified molecular sieve GPZ2-2 prepared in Example 2-2.
  • a sample of catalytic cracking catalyst was prepared, numbered CAZY2-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y32-1 Same as Example Y32-1, the difference is that the phosphorus-modified molecular sieve GPZ2-1 is replaced with the comparative sample D2-1 of Comparative Example 2-1.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY2-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y32-1 Same as Example Y32-1, the difference is that the phosphorus-modified molecular sieve GPZ2-1 is replaced with the comparative sample D2-2 of Comparative Example 2-2.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY2-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-1 Same as Example Y31-1, except that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ3-1 prepared in Example 3-1.
  • a sample of catalytic cracking catalyst was prepared, numbered CAZY3-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ3-2 prepared in Example 3-2.
  • a sample of catalytic cracking catalyst was prepared, numbered CAZY3-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the comparative sample D3-1 of Comparative Example 3-1.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY3-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the comparative sample D3-2 of Comparative Example 3-2.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY3-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ4-1 prepared in Example 4-1.
  • a sample of catalytic cracking catalyst was prepared, numbered CAZY4-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y34-1 Same as Example Y34-1, except that the phosphorus-modified molecular sieve GPZ4-1 is replaced by the phosphorus-modified molecular sieve GPZ4-2 prepared in Example 4-2.
  • a sample of catalytic cracking catalyst was prepared, numbered CAZY4-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y34-1 Same as Example Y34-1, the difference is that the phosphorus-modified molecular sieve GPZ4-1 is replaced with the comparative sample D4-1 of Comparative Example 4-1.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY4-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y34-1 Same as Example Y34-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the comparative sample D4-2 of Comparative Example 4-2.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY4-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ5-1 prepared in Example 5-1.
  • a sample of catalytic cracking catalyst was prepared, numbered CAZY5-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y35-1 Same as Example Y35-1, except that the phosphorus-modified molecular sieve GPZ5-1 is replaced by the phosphorus-modified molecular sieve GPZ5-2 prepared in Example 5-2.
  • a sample of catalytic cracking catalyst was prepared, numbered CAZY5-2. The evaluation is the same as that of Example Y35-1, and the results are shown in Table 8.
  • Example Y35-1 Same as Example Y35-1, the difference is that the phosphorus-modified molecular sieve GPZ5-1 is replaced with the comparative sample D5-1 of Comparative Example 5-1.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY5-1. The evaluation is the same as that of Example Y35-1, and the results are shown in Table 8.
  • Example Y35-1 Same as Example Y35-1, the difference is that the phosphorus-modified molecular sieve GPZ5-1 is replaced with the comparative sample D5-2 of Comparative Example 5-2.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY5-2. The evaluation is the same as that of Example Y35-1, and the results are shown in Table 8.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ6-1 prepared in Example 6-1.
  • a sample of catalytic cracking catalyst was prepared, numbered CAZY6-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y36-1 Same as Example Y36-1, the difference is that the phosphorus-modified molecular sieve GPZ6-1 is replaced with the phosphorus-modified molecular sieve GPZ6-2 prepared in Example 6-2.
  • a sample of catalytic cracking catalyst was prepared, numbered CAZY6-2.
  • the evaluation is the same as that of Example Y36-1, and the results are shown in Table 8.
  • Example Y36-1 Same as Example Y36-1, the difference is that the phosphorus-modified molecular sieve GPZ6-1 is replaced with the comparative sample D6-1 of Comparative Example 6-1.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY6-1. The evaluation is the same as that of Example Y36-1, and the results are shown in Table 8.
  • Example Y36-1 Same as Example Y36-1, the difference is that the phosphorus-modified molecular sieve GPZ6-1 is replaced with the comparative sample D6-2 of Comparative Example 6-2.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY6-2. The evaluation is the same as that of Example Y36-1, and the results are shown in Table 8.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ7-1 prepared in Example 7-1.
  • a sample of catalytic cracking catalyst was prepared, numbered CAZY7-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y37-1 Same as Example Y37-1, except that the phosphorus-modified molecular sieve GPZ7-1 is replaced with the phosphorus-modified molecular sieve GPZ7-2 prepared in Example 7-2.
  • a sample of catalytic cracking catalyst was prepared, numbered CAZY7-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y37-1 Same as Example Y37-1, the difference is that the phosphorus-modified molecular sieve GPZ7-1 is replaced with the comparative sample D7-1 of Comparative Example 7-1.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY7-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y37-1 Same as Example Y37-1, the difference is that the phosphorus-modified molecular sieve GPZ7-1 is replaced with the comparative sample D7-2 of Comparative Example 7-2.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY7-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ8-1 to GPZ13-2 prepared in Example 8-1 to Example 13-2, respectively.
  • the catalytic cracking catalyst samples were prepared, serially numbered CAZY8-1 to CAZY13-2.
  • the evaluation is the same as that of Example Y31-1, and the results are shown in Table 8 respectively.
  • Examples Y44 to Y56 are catalysts CAZY14 to CAZY26 containing microporous ZSM-5 (GPZ14 to GPZ26) respectively, and the material ratio corresponds to Example Y31 to Example Y43, for example, in Example Y44-1, GPZ1 -1 is replaced by GPZ14-1, in Example Y44-2, GPZ1-2 is replaced by GPZ14-2, and so on, until in Example Y56-1, GPZ13-1 is replaced by GPZ26-1, and in Example Y56-2 , GPZ13-2 is replaced by GPZ26-2.
  • the evaluation is the same as that of Example Y31-1, and the results are shown in Table 8 respectively.
  • Comparative Example Y44 to Comparative Example Y50 are the comparative catalysts DCAZY-14 to DCAZY-20 containing microporous ZSM-5 (D14 to D20), respectively, and the material ratio corresponds to Example Y44 to Example Y50, for example, Comparative Example Y44 -1, GPZ1-1 was replaced by D14-1, in Comparative Example Y44-2, GPZ1-2 was replaced by D14-2, etc., until Comparative Example Y50-1, GPZ14-1 was replaced by D20-1, In the ratio Y50-2, GPZ14-2 is replaced by D20-2.
  • the evaluation is the same as that of Example Y31-1, and the results are shown in Table 8 respectively.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced by the phosphorus-modified molecular sieve GPZ21-1 to GPZ26-2 prepared in Example 21-1 to Example 26-2, respectively.
  • the catalytic cracking catalyst samples were prepared, serially numbered CAZY27-1 to CAZY32-2.
  • the evaluation is the same as that of Example Y31-1, and the results are shown in Table 8 respectively.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphor-aluminum inorganic binder is replaced by Binder 2 prepared in Example Y28.
  • the catalytic cracking catalyst was prepared, numbered CAZY33-1.
  • the evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-2 Same as Example Y31-2, except that the phosphor-aluminum inorganic binder is replaced by Binder 2 prepared in Example Y28.
  • the catalytic cracking catalyst was prepared, numbered CAZY33-2.
  • the evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphor-aluminum inorganic binder is replaced by Binder 3 prepared in Example Y29.
  • the catalytic cracking catalyst was prepared, numbered CAZY34-1.
  • the evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-2 Same as Example Y31-2, the difference is that the phosphor-aluminum inorganic binder is replaced by Binder 3 prepared in Example Y29.
  • the catalytic cracking catalyst was prepared, numbered CAZY34-2.
  • the evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-1 Same as Example Y31-1, the difference is that the phosphor-aluminum inorganic binder is replaced with Binder 4 prepared in Example Y30.
  • the catalytic cracking catalyst was prepared, numbered CAZY35-1.
  • the evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-2 Same as Example Y31-2, except that the phosphor-aluminum inorganic binder is replaced by Binder 4 prepared in Example Y30.
  • the catalytic cracking catalyst was prepared, numbered CAZY35-2.
  • the evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y31-1 Same as Example Y31-1, the difference lies in the use of phosphorus-modified hierarchical pore ZSM-5 molecular sieve sample GPZ1-1 (35% by weight), PSRY molecular sieve (10% by weight), kaolin (18% by weight), phosphorus-aluminum inorganic bonding Binder 3 (22% by weight), pseudo-boehmite (10% by weight), and aluminum sol (5% by weight).
  • the catalytic cracking catalyst was prepared, numbered CAZY36-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y66-1 Same as Example Y66-1, the difference is that GPZ1-1 is replaced by GPZ1-2.
  • the catalytic cracking catalyst was prepared, numbered CAZY36-2.
  • the evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y66-1 Same as Example Y66-1, the difference is that GPZ1-1 is replaced by D1-1.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY36-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y66-1 Same as Example Y66-1, the difference is that GPZ1-1 is replaced by D1-2.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY36-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y44-1 Same as Example Y44-1, the difference lies in the use of phosphorus-modified microporous ZSM-5 molecular sieve sample GPZ14-1 (30% by weight), PSRY molecular sieve (6% by weight), kaolin (24% by weight), phosphor-aluminum inorganic bonding Catalyst Binder 4 (22% by weight), pseudo-boehmite (8% by weight), and silica sol (10% by weight) were prepared to prepare a catalytic cracking catalyst, numbered CAZY37-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y67-1 Same as Example Y67-1, the difference is that GPZ14-1 is replaced by GPZ14-2.
  • the catalytic cracking catalyst was prepared, numbered CAZY37-2.
  • the evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y67-1 Same as Example Y67-1, the difference is that GPZ14-1 is replaced by D14-1.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY37-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y67-1 Same as Example Y67-1, the difference is that GPZ14-1 is replaced by D14-2.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY37-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • the mixing ratio is 40% for phosphorus-modified ZSM-5 molecular sieve GPZ1-1, 10% for PSRY molecular sieve, 25% for kaolin, and 25% for aluminum sol (calculated as Al2O3).
  • the evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y68-1 Same as Example Y68-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the phosphorus-modified molecular sieve GPZ1-2 prepared in Example 1-2.
  • a sample of catalytic cracking catalyst was prepared, numbered CAZY38-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y68-1 Same as Example Y68-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the comparative sample D1-1 of Comparative Example Y1-1.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY38-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y68-1 Same as Example Y68-1, the difference is that the phosphorus-modified molecular sieve GPZ1-1 is replaced with the comparative sample D1-2 of Comparative Example Y1-2.
  • a comparative sample of catalytic cracking catalyst was prepared, numbered DCAZY38-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 8.
  • Example Y69-1 Example Y69-2
  • Example Y69-1 and Example Y69-2 respectively used the catalytic cracking catalysts CAZY1-1 and CAZY1-2 of Example Y31-1 and Example Y31-2.
  • the feedstock oil for catalytic cracking is the naphtha shown in Table 5.
  • the evaluation conditions are the reaction temperature of 620°C, the regeneration temperature of 620°C, and the catalyst-to-oil ratio of 3.2.
  • Table 9 shows the weight composition and reaction results of each catalyst mixture containing a catalytic cracking catalyst.
  • Example Y69-1 The same as Example Y69-1, except that the catalytic cracking comparison catalysts DCAZY1-1 and DCAZY1-2 of Comparative Example Y31-1 and Comparative Example Y31-2 were used respectively.
  • Table 9 shows the weight composition and reaction results of each catalyst mixture containing catalytic cracking catalyst comparative samples.
  • Example Y70-1 Example Y70-2
  • Example Y70-1 and Example Y70-2 adopt the catalytic cracking catalysts CAZY14-1 and CAZY14-2 of Example Y44-1 and Example Y44-2, respectively.
  • the feedstock oil for catalytic cracking is the naphtha shown in Table 5.
  • the evaluation conditions are the reaction temperature of 620°C, the regeneration temperature of 620°C, and the catalyst-to-oil ratio of 3.2.
  • Table 9 shows the weight composition and reaction results of each catalyst mixture containing a catalytic cracking catalyst.
  • Example Y70-1 Same as Example Y70-1, except that the catalytic cracking comparison catalysts DCAZY14-1 and DCAZY14-2 of Comparative Example Y44-1 and Comparative Example Y44-2 were used respectively.
  • Table 9 shows the weight composition and reaction results of each catalyst mixture containing catalytic cracking catalyst comparative samples.
  • Example Y31-1 Same as Example Y31-1, the difference is that the Y-type molecular sieve (PSRY) is replaced with HRY-1.
  • a catalyst sample was prepared, numbered CAZY39-1.
  • the evaluation is the same as that of Example Y31-1, and the results are shown in Table 10.
  • Example Y31-1 Same as Example Y31-1, except that the Y-type molecular sieve (PSRY) is replaced with HRY-1.
  • a catalyst sample was prepared, numbered CAZY39-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 10.
  • Example Y31-1 Same as Example Y31-1, the difference is that the Y-type molecular sieve (PSRY) is replaced with HRY-1.
  • a comparative sample of catalyst was prepared, numbered DCAZY39-1. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 10.
  • Example Y31-1 Same as Example Y31-1, except that the Y-type molecular sieve (PSRY) is replaced with HRY-1.
  • a comparative sample of catalyst was prepared, numbered DCAZY39-2. The evaluation is the same as that of Example Y31-1, and the results are shown in Table 10.

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Abstract

提供一种磷改性MFI结构分子筛，该分子筛的K值满足：70％≤K≤90％；例如，75％≤K≤90％；进一步地，例如，78％≤K≤85％；其中，K=P1/P2×100%，P1表示采用XPS方法测定的分子筛晶粒的任意晶面垂直深度0-2nm内、100平方纳米区域面积内的磷质量含量，P2表示采用EPMA方法测定的分子筛晶粒的任意晶面垂直深度5-10nm厚度区间100平方纳米区域面积内磷质量含量。还提供了一种包含该磷改性MFI分子筛的裂解助剂或裂解催化剂，以及其制备方法和应用。

Description

磷改性MFI结构分子筛、含磷改性MFI结构分子筛的催化裂解助剂和催化裂解催化剂、及其制备方法
相关申请的交叉引用
本申请要求申请日为2020年04月13日的申请号为202010283498.2的中国专利申请、申请日为2020年10月28日的申请号为202011169092.8的中国专利申请、申请日为2020年10月29日的申请号为202011175729.4的中国专利申请的权利，上述申请的全部内容引入本文中作为参考。
技术领域
本发明涉及一种磷改性的MFI结构分子筛、一种含磷改性MFI结构分子筛的催化裂解助剂、和一种含磷改性MFI结构分子筛的催化裂解催化剂，本发明还涉及磷改性的MFI结构分子筛、含磷改性MFI结构分子筛的催化裂解助剂、和含磷改性MFI结构分子筛的催化裂解催化剂的制备方法；本发明还涉及催化裂解助剂和催化裂解催化剂在烃油催化裂解中的应用。
背景技术
具有MFI骨架结构的分子筛的典型代表为ZSM-5分子筛，它是1972年由美国Mobil公司开发的用途广泛的沸石分子筛催化材料。ZSM-5分子筛具有三维交叉的孔道结构，沿a轴向的孔道为直孔，其截面尺寸为0.54×0.56nm，近似圆形，沿b轴向的孔道是Z字形孔，其截面尺寸为0.51×0.56nm，系椭圆形。ZSM-5分子筛孔口由十元环构成，孔口大小介于小孔沸石和大孔沸石之间，因此具有独特的择形催化作用。ZSM-5分子筛由于具有独特的孔道结构，并有良好的择形催化和异构化性能、高热和水热稳定性、高比表面积、宽硅铝比变化范围、独特的表面酸性和较低结碳量的特点，被广泛用作催化剂和催化剂载体，并成功用于烷基化、异构化、歧化、催化裂解、甲醇制汽油、甲醇制烯烃等生产工艺中。ZSM-5分子筛被引入到催化裂解和碳四烃催化裂解中，表现出优异的催化性能，利用其分子择形性可以大幅度提高低碳烯烃的产率。
自从1983年起，ZSM-5分子筛作为催化裂解辛烷值助剂/催化剂开始应用于催化裂解工艺，旨在提高催化裂解汽油的辛烷值和低碳烯烃的选择性。US3758403最早报道了用ZSM-5分子筛作为增产丙烯的活性组元，它与REY一起作为FCC催化剂的活性组元，或者它与REY一起制备成FCC催化剂。US5997728公开了采用不经任何改性的ZSM-5分子筛作为增产丙烯的助剂。但是，上述两种技术的丙烯收率均不高。
HZSM-5分子筛虽然具有良好的择形性能和异构化性能，但其不足之处是水热稳定性差，在苛刻的高温水热条件下易失活，使催化性能降低。
20世纪80年代，Mobil公司就发现磷能改善ZSM-5分子筛的水热稳定性，同时磷对ZSM-5分子筛进行改性后提高了低碳烯烃收率。常规添加剂通常含有经磷活化的ZSM-5，其使初级裂解产物(例如汽油烯烃)选择性转化成C3和C4烯烃。ZSM-5分子筛在合成后引入适量的无机磷化合物改性，可在苛刻的水热条件下稳定骨架铝。
CN106994364A公开了一种磷改性ZSM-5分子筛的方法，该方法是先以选自磷酸、磷酸氢二铵、磷酸二氢铵和磷酸铵中的一种或多种的含磷化合物与高碱金属离子含量的ZSM-5分子筛混合得到具有磷以P2O5计、至少0.1wt％的载持量的混合物，混合物经干燥、焙烧，再进行铵交步骤和水洗步骤，使得其中碱金 属离子含量降到0.10wt％以下，然后历经干燥和在400-1000℃和100％水蒸气条件下水热老化的步骤。该方法得到的含磷ZSM-5分子筛，总酸量高，具有优异的裂解转化率和丙烯的选择性，同时具有较高的液化气收率。
US5171921公开了一种ZSM-5分子筛进行改性的方法，该方法包括按照常规的步骤：合成→过滤→铵交换→烘干→焙烧，得到ZSM-5分子筛，然后用磷酸对该ZSM-5分子筛进行改性，再烘干、焙烧，从而得到磷改性的HZSM-5分子筛，其中，P2O5载持量通常在1-7wt％范围内。然而，磷酸或磷酸铵盐在焙烧过程中会自聚生成不同聚集态的磷物种，水热处理过程中只有进入孔内的磷酸根与骨架铝相互作用保留B酸中心，降低磷物种的分布。
多级孔ZSM-5分子筛为同时含有微孔和介孔的ZSM-5分子筛，常用硬模板法、软模板法、酸碱后处理法等制备各类具有介孔孔道的多级孔ZSM-5分子筛。
虽然采用适量的无机磷化合物对(多级孔)ZSM-5分子筛进行改性，可减缓骨架脱铝，提高水热稳定性，而且磷原子会与扭曲的四配位骨架铝结合生成弱B酸中心，从而达到较高的长链烷烃裂解的转化率和较高的轻烯烃选择性，但是过量的无机磷化合物用于对(多级孔)ZSM-5分子筛进行改性，会堵塞分子筛的孔道，使孔体积和比表面积降低，并大量占据强B酸中心。而且，现有技术在焙烧过程中磷酸或磷酸铵盐会自聚生成不同聚集态的磷物种，磷与骨架铝配位不充分，磷的利用效率较低，磷改性并不总是得到令人满意的水热稳定性改善结果。因此，急需新的技术促进磷与骨架铝配位，提高磷改性ZSM-5分子筛的水热稳定性，进一步提高裂解活性。
发明内容
本发明的一个目的是提供一种不同于现有技术的磷改性MFI结构分子筛，该分子筛的磷物种的分散度高，从而当应用于石油烃催化裂解反应时能够获得优异的裂解转化率和低碳烯烃的收率，同时获得较高的液化气收率。本发明的又一个目的是提供一种基于磷物种高分散度的磷改性ZSM-5分子筛作为活性组分的催化裂解助剂，从而在石油烃催化裂解反应中能够获得优异的裂解转化率和低碳烯烃的收率，同时获得较高的液化气收率。本发明的另一个目的是提供一种基于磷物种高分散度的磷改性MFI结构分子筛作为活性组分之一的催化裂解催化剂，从而在石油烃催化裂解反应中能够获得优异的裂解转化率和低碳烯烃的收率，同时获得较高的液化气收率。本发明的另一个目的是提供上述磷改性MFI结构分子筛、上述催化裂解助剂和上述催化裂解催化剂的制备方法。本发明的又一个目的是提供上述催化裂解助剂和上述催化裂解催化剂的应用。
为了实现上述目的，本发明提供了一种磷改性MFI结构分子筛，其特征在于，该分子筛的K值满足：70％≤K≤90％，所述的K＝[采用EPMA方法测定的分子筛晶粒的任意晶面垂直深度5-10nm厚度区间100平方纳米区域面积内的磷质量含量]/[采用XPS方法测定的分子筛晶粒的任意晶面垂直深度0-2nm内、100平方纳米区域面积内的磷质量含量]×100％，其中通过使用Thermo Fisher-VG公司的ESCAREB 250型X射线光电子能谱仪，激发源为单色化的功率150W的AlKα X射线，荷电位移用来自污染碳的C1s峰(284.8eV)校正对分子筛表面进行XPS分析；采用JXA-8230能谱仪X射线探测器，计数率及计数时间，一般累计计数大于10 5，计数率为10 3～10 4CPS，计数时间为10～100s对分子筛表面进行EPMA分析。
在上述的磷改性MFI结构分子筛中，磷的含量以P2O5计与氧化铝的摩尔比值≥0.01；例如，≥0.2；进一步地，例如，≥0.3；更进一步地，例如，0.4-0.7；上述的磷改性MFI结构分子筛可以是微孔ZSM-5分子筛或多级孔ZSM-5分子筛，磷以P2O5计、至少0.1wt％的载持量，其中对于所述的微孔ZSM-5分子筛来说，其氧化硅/氧化铝的摩尔比为15-1000、例如，20-200；对于所述的多级孔ZSM-5分子筛来说，介孔体积占总孔体积的比例大于10％，平均孔径为2-20nm，其氧化硅/氧化铝摩尔比为15-1000、例如，20-200。
为了实现上述目的，本发明提供了一种催化裂解助剂，以所述催化裂解助剂的干基重量为基准，所述催化裂解助剂含有5-75重量％的磷改性MFI结构分子筛；其中，所述的磷改性MFI结构分子筛，其K值满足：70％≤K≤90％；例如，75％≤K≤90％；进一步地，例如，78％≤K≤85％，所述的K＝[采用EPMA方法测定的分子筛晶粒的任意晶面垂直深度5-10nm厚度区间100平方纳米区域面积内的磷质量含量]/[采用XPS方法测定的分子筛晶粒的任意晶面垂直深度0-2nm内、100平方纳米区域面积内的磷质量含量]×100％，其中通过使用Thermo Fisher-VG公司的ESCAREB 250型X射线光电子能谱仪，激发源为单色化的功率150W的AlKα X射线，荷电位移用来自污染碳的C1s峰(284.8eV)校正对分子筛表面进行XPS分析；采用JXA-8230能谱仪X射线探测器，计数率及计数时间，一般累计计数大于10 5，计数率为10 3～10 4CPS，计数时间为10～100s对分子筛表面进行EPMA分析。
在上述的磷改性MFI结构分子筛中，磷的含量以P2O5计与氧化铝的摩尔比值≥0.01；例如，≥0.2；进一步地，例如，≥0.3；更进一步地，例如，0.4-0.7；上述的磷改性MFI结构分子筛可以是微孔ZSM-5分子筛或多级孔ZSM-5分子筛，磷以P2O5计、至少0.1wt％的载持量，其中对于所述的微孔ZSM-5分子筛来说，其氧化硅/氧化铝的摩尔比为15-1000、例如，20-200；对于所述的多级孔ZSM-5分子筛来说，介孔体积占总孔体积的比例大于10％，平均孔径为2-20nm，其氧化硅/氧化铝摩尔比为15-1000、例如，20-200；
在本发明的催化裂解助剂中，以所述催化裂解助剂的干基计，催化裂解助剂还可以含有1-40重量％的粘结剂和0-65重量％的第二粘土。所述的粘结剂含有磷铝无机粘结剂。所述的磷铝无机粘结剂为磷铝胶和/或含第一粘土的磷铝无机粘结剂。
为了实现上述目的，本发明提供了一种含磷改性MFI结构分子筛的催化裂解催化剂，以催化剂的干基为基准，所述催化裂解催化剂含有1-25重量％的Y型分子筛、5-50重量％的磷改性MFI结构分子筛、1-60重量％的无机粘结剂和可选加入的0-60重量％的第二粘土，其中，所述无机粘结剂包括磷铝无机粘结剂和/或其他无机粘结剂；所述的磷改性MFI结构分子筛，其K值满足：70％≤K≤90％；例如，75％≤K≤90％；进一步地，例如，78％≤K≤85％，所述的K＝[采用EPMA方法测定的分子筛晶粒的任意晶面垂直深度5-10nm厚度区间100平方纳米区域面积内的磷质量含量]/[采用XPS方法测定的分子筛晶粒的任意晶面垂直深度0-2nm内、100平方纳米区域面积内的磷质量含量]×100％，其中通过使用Thermo Fisher-VG公司的ESCAREB 250型X射线光电子能谱仪，激发源为单色化的功率150W的AlKα X射线，荷电位移用来自污染碳的C1s峰(284.8eV)校正对分子筛表面进行XPS分析；采用JXA-8230能谱仪X射线探测器，计数率及计数时间，一般累计计数大于10 5，计数率为10 3～10 4CPS，计数时间为10～100s对分子筛表面进行EPMA分析。
在上述的磷改性MFI结构分子筛中，磷的含量以P2O5计与氧化铝的摩尔比值≥0.01；例如，≥0.2；进一步地，例如，≥0.3；更进一步地，例如，0.4-0.7；上述的磷改性MFI结构分子筛可以是微孔ZSM-5分子筛或多级孔ZSM-5分子筛，磷以P2O5计、至少0.1wt％的载持量，其中对于所述的微孔ZSM-5分子筛来说，其氧化硅/氧化铝的摩尔比为15-1000、例如，20-200；对于所述的多级孔ZSM-5分子筛来说，介孔体积占总孔体积的比例大于10％，平均孔径为2-20nm，其氧化硅/氧化铝摩尔比为15-1000、例如，20-200；
在上述的催化裂解催化剂中，所述的Y型分子筛可以包括PSRY分子筛、含稀土的PSRY分子筛、USY分子筛、含稀土的USY分子筛、REY分子筛、REHY分子筛和HY分子筛的至少一种；例如，所述的无机粘结剂含有磷铝无机粘结剂；进一步地，例如，所述的磷铝无机粘结剂为磷铝胶和/或含第一粘土的磷铝无机粘结剂。
为了实现上述目的，本发明提供了磷改性MFI结构分子筛的制备方法，特征在于用浸渍法获得的，包括：使温度为40-150℃、例如50-150℃、进一步地，例如70-130℃的含磷化合物的水溶液与40-150℃、例如50-150℃、进一步地，例如70-130℃的MFI结构分子筛在基本相同的温度下混合接触至少0.1小时、干燥后在200-600℃、空气或水蒸气气氛下焙烧至少0.1小时；或者，将含磷化合物、MFI结构分子筛和水混合打浆后调温到(例如，升温到)40-150℃、例如50-150℃、进一步地，例如70-130℃保持至少0.1小时、干燥后在200-600℃、空气或水蒸气气氛下焙烧至少0.1小时。
在所述的磷改性MFI结构分子筛的制备方法中，所述的MFI结构分子筛可以是氢型微孔ZSM-5分子筛，氢型多级孔ZSM-5分子筛。它们是经铵交换降钠至Na2O＜0.1wt％后得到的，硅铝比(氧化硅与氧化铝的摩尔比)范围≥10，通常在10-200。
在所述的磷改性MFI结构分子筛的制备方法中，所述的含磷化合物以磷计(以氧化物计)、所述的MFI结构分子筛(例如，氢型ZSM-5分子筛或氢型多级孔ZSM-5分子筛)以铝计(以氧化物计)，二者的摩尔比值为0.01-2；例如，二者的摩尔比值为0.1-1.5；进一步地，例如，二者的摩尔比值为0.2-1.5。所述的含磷化合物选自有机磷化合物，如磷酸三甲酯、三苯基磷、三甲基亚磷酸酯、四丁基溴化膦、四丁基氯化膦、四丁基氢氧化磷、三苯基乙基溴化磷、三苯基丁基溴化磷、三苯基苄基溴化磷、六甲基磷酰三胺、二苄基二乙基磷、1，3-二甲苯双三乙基磷等，无机磷化合物，如磷酸、磷酸氢铵、磷酸氢二铵、磷酸铵、磷酸硼中之一或其混合物等。发明人发现，当以磷酸硼作为含磷化合物之一并且采用300-500℃水热焙烧时，磷在分子筛中具有更好的分散度，因此，例如含磷化合物的组合为磷酸硼与选自磷酸三甲酯、三苯基磷、三甲基亚磷酸酯、磷酸、磷酸氢铵、磷酸氢二铵、磷酸铵的混合物。所述含磷酸硼的混合物中，磷酸硼重量占比为10％-80％、例如20％-40％、进一步地，例如25％-35％。
在所述的磷改性MFI结构分子筛的制备方法中，所述的接触是用浸渍法使温度为30-150℃的含磷化合物的水溶液与30-150℃的氢型MFI结构分子筛在基本相同的温度下接触至少0.1小时。接触例如是在40℃以上的较高的温度区间，例如50-150℃、进一步地，例如70-130℃下进行，可以获得更好的效果，即磷物种分散更好，磷更容易迁移至氢型MFI结构分子筛晶内与骨架铝结合，进一步提高磷与骨架铝配位程度，最终对分子筛的水热稳定性的提高作出贡献。所述的基本相同的温度，是指含磷化合物的水溶液与氢型MFI结构分子筛各自具有 的温度之间的温度差在±5℃。例如，含磷化合物的水溶液的温度为80℃，HZSM-5分子筛则需加热到75-85℃。
在所述的磷改性MFI结构分子筛的制备方法中，所述的接触还可以是将含磷化合物、(氢型)MFI结构分子筛和水混合后在30-150℃下保持至少0.1小时。例如，为了可以获得更好的效果，即磷物种分散更好，磷更容易迁移至分子筛晶内与骨架铝结合，进一步提高磷与骨架铝配位程度，最终提高分子筛的水热稳定性，所述的含磷化合物、氢型MFI结构分子筛和水混合之后，是在40℃以上的较高的温度区间保持0.1小时，例如50-150℃温度区间、进一步地，例如70-130℃温度区间。所述的接触，水筛重量比为0.5-1，时间为0.5-40小时。所述的焙烧例如是在450-550℃、水蒸汽气氛下进行。
本发明通过促进磷物种与MFI结构分子筛骨架铝配位，从而提高磷改性分子筛的水热稳定性。在正十四烷烃裂解中，本发明的含磷MFI结构分子筛，具有优异的裂解转化率和低碳烯烃的收率，同时具有较高的液化气收率。
为了实现上述目的，本发明提供了催化裂解助剂的制备方法，该方法包括，将磷改性MFI结构分子筛、粘结剂与可选加入的第二粘土混合打浆并经喷雾干燥后得到所述催化裂解助剂，其特征在于，其中所述的磷改性MFI结构分子筛是通过本发明的磷改性MFI结构分子筛的制备方法制备的。
在所述的催化裂解助剂的制备方法中，所述的粘结剂例如含有磷铝无机粘结剂。所述的磷铝无机粘结剂为磷铝胶和/或含第一粘土的磷铝无机粘结剂；以所述含第一粘土的磷铝无机粘结剂干基重量为基准，所述含第一粘土的磷铝无机粘结剂含有以Al2O3计10-40重量％，例如15-40重量％的铝组分、以P2O5计45-90重量％，45-80重量％的磷组分以及以干基计大于0且不超过40重量％的第一粘土，且所述含第一粘土的磷铝无机粘结剂P/Al重量比为1.0-6.0，pH为1-3.5，固含量为15-60重量％；所述第一粘土包括高岭土、海泡石、凹凸棒石、累托石、蒙脱石和硅藻土中的至少一种；所述粘结剂还可以包括拟薄水铝石、铝溶胶、硅铝溶胶和水玻璃中的至少一种其他无机粘结剂。所述的第二粘土为选自高岭土、海泡石、凹凸棒石、累托石、蒙脱石、多水高岭土、埃洛石、水滑石、膨润土以及硅藻土中的至少一种。
在所述的催化裂解助剂的制备方法中，以所述催化裂解助剂为基准，所述粘结剂包括以干基计3-39重量％的所述磷铝无机粘结剂和以干基计1-30重量％的所述其他无机粘结剂。
所述的催化裂解助剂的制备方法还包括：将所述喷雾干燥所得产物进行第一焙烧、洗涤和可选的干燥处理，得到所述催化裂解助剂；其中所述第一焙烧的焙烧温度为300-650℃，焙烧时间为0.5-8h；所述干燥处理的温度为100-200℃，干燥时间为0.5-24h。
所述的催化裂解助剂的制备方法进一步还可包括采用如下步骤制备所述含第一粘土的磷铝无机粘结剂：将氧化铝源、所述第一粘土与水打浆分散成固含量为5-48重量％的浆液；其中所述的氧化铝源为能被酸胶溶的氢氧化铝和/或氧化铝，相对于10-40重量份，例如15-40重量份的以Al2O3计的氧化铝源，以干基重量计的所述第一粘土的用量大于0重量份且不超过40重量份；搅拌下按照P/Al＝1-6的重量比向所述浆液中加入浓磷酸，并使所得混合浆液在50-99℃反应15-90分钟；其中所述的P/Al中P为磷酸中的以单质计的磷的重量，Al为氧化铝源中以单质计的铝的重量。
为了实现上述目的，本发明提供了催化裂解助剂的应用，即一种烃油催化裂解的方法，该方法包括：在催化裂解条件下，使烃油与上述的催化裂解助剂接触反应。例如使所述烃油与含有所述催化裂解助剂和催化裂解催化剂的催化剂混合物接触反应；所述催化剂混合物中，所述催化裂解助剂的含量为0.1-30重量％。其中，所述催化裂解条件包括：反应温度为500-800℃；所述烃油选自原油、石脑油、汽油、常压渣油、减压渣油、常压蜡油、减压蜡油、直流蜡油、丙烷轻/重脱油、焦化蜡油和煤液化产物中的一种或几种。本发明提供的催化裂解助剂在石油烃催化裂解反应中具有优异的裂解转化率和低碳烯烃的收率，同时具有较高的液化气收率。
为了实现上述目的，本发明还提供了催化裂解催化剂的制备方法，该方法包括，将Y型分子筛、磷改性MFI结构分子筛、无机粘结剂与可选加入的第二粘土混合打浆并经喷雾干燥后得到所述催化裂解催化剂，其特征在于，其中所述的磷改性MFI结构分子筛是通过本发明的磷改性MFI结构分子筛的制备方法制备的。
在本发明的催化裂解催化剂的制备方法中，所述的粘结剂为磷铝无机粘结剂。所述的磷铝无机粘结剂为磷铝胶和/或含第一粘土的磷铝无机粘结剂；以所述含第一粘土的磷铝无机粘结剂干基重量为基准，所述含第一粘土的磷铝无机粘结剂含有以Al2O3计10-40重量％，例如15-40重量％的铝组分、以P2O5计45-90重量％，例如45-80重量％的磷组分以及以干基计大于0且不超过40重量％的第一粘土，且所述含第一粘土的磷铝无机粘结剂P/Al重量比为1.0-6.0，pH为1-3.5，固含量为15-60重量％；所述第一粘土包括高岭土、海泡石、凹凸棒石、累托石、蒙脱石和硅藻土中的至少一种。
在本发明的催化裂解催化剂的制备方法中，所述的第二粘土为选自高岭土、海泡石、凹凸棒石、累托石、蒙脱石、多水高岭土、埃洛石、水滑石、膨润土以及硅藻土中的至少一种。
在本发明的催化裂解催化剂的制备方法中，以所述催化裂解催化剂为基准，所述粘结剂包括以干基计3-39重量％的所述磷铝无机粘结剂和以干基计1-30重量％的其他无机粘结剂，所述其他无机粘结剂包括拟薄水铝石、铝溶胶、硅铝溶胶和水玻璃中的至少一种。
本发明的催化裂解催化剂的制备方法还包括：将所述喷雾干燥所得产物进行第一焙烧、洗涤和可选的干燥处理，得到所述催化裂解催化剂；其中所述第一焙烧的焙烧温度为300-650℃，焙烧时间为0.5-8h；所述干燥处理的温度为100-200℃，干燥时间为0.5-24h。
本发明的催化裂解催化剂的制备方法进一步还可包括采用如下步骤制备所述含第一粘土的磷铝无机粘结剂：将氧化铝源、所述第一粘土与水打浆分散成固含量为5-48重量％的浆液；其中所述的氧化铝源为能被酸胶溶的氢氧化铝和/或氧化铝，相对于10-40重量份，例如15-40重量份的以Al2O3计的氧化铝源，以干基重量计的所述第一粘土的用量大于0重量份且不超过40重量份；搅拌下按照P/Al＝1-6的重量比向所述浆液中加入浓磷酸，并使所得混合浆液在50-99℃反应15-90分钟；其中所述的P/Al中P为磷酸中的以单质计的磷的重量，Al为氧化铝源中以单质计的铝的重量。
为了实现上述目的，本发明提供了催化裂解催化剂的应用，即一种烃油催化裂解的方法，该方法包括：在催化裂解条件下，使烃油与上述的催化裂解催化剂接触反应。所述催化裂解条件包括：反应温度为500-800℃；所述烃油选自原 油、石脑油、汽油、常压渣油、减压渣油、常压蜡油、减压蜡油、直流蜡油、丙烷轻/重脱油、焦化蜡油和煤液化产物中的一种或几种。本发明提供的催化裂解催化剂在石油烃催化裂解反应中具有优异的裂解转化率和低碳烯烃的收率，同时具有较高的液化气收率。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
在本发明中，孔径小于2nm的孔称为微孔；孔径大于50nm的孔称为大孔；孔径在2-50nm的孔称为介孔。
在本发明中，第一粘土是指在磷铝无机粘结剂中所含的粘土；而第二粘土是指除第一粘土外的粘土，“第一”和“第二”仅为区分粘土是否在磷铝无机粘结剂中。所述的第一粘土包括但不限于高岭土、海泡石、凹凸棒石、累托石、蒙脱石和硅藻土。所述的第二粘土包括但不限于高岭土、海泡石、凹凸棒石、累托石、蒙脱石、和硅藻土，以及多水高岭土、埃洛石、水滑石、和膨润土。
在本发明中，粘结剂与无机粘结剂是同义词。
本发明的粘结剂包括磷铝无机粘结剂和其他无机粘结剂。
根据本发明，其他无机粘结剂是指不同时含有磷与铝两种元素的粘结剂，而磷铝无机粘结剂包括磷铝胶、和含第一粘土的磷铝无机粘结剂。
根据本发明，其他无机粘结剂的实例包括但不限于拟薄水铝石、铝溶胶、硅铝溶胶和水玻璃。
根据本发明，磷铝胶中的有效成分为磷酸二氢铝，其理论配比为P2O5/Al2O3＝3∶1(摩尔比)。磷铝胶作为粘结剂可以制备出强度优良的催化剂。在本发明中，磷铝胶中的P2O5/Al2O3的实际配比为3∶1或更高，例如3∶1-10∶1，进一步地，例如大于3∶1且不大于5∶1。例如，磷铝胶可以通过将氧化铝源与水打浆分散成浆液；搅拌下向所述浆液中加入浓磷酸，并使所得混合浆液反应一段时间(例如在50-99℃反应15-90分钟)来获得；所述氧化铝源可以为选自ρ-氧化铝、x-氧化铝、η-氧化铝、γ-氧化铝、κ-氧化铝、σ-氧化铝、θ-氧化铝、三水铝石、湃铝石、诺水铝石、硬水铝石、薄水铝石和拟薄水铝石中的至少一种，所述的浓磷酸其浓度可以为60-98重量％，进一步地，例如75-90重量％，磷酸的加料速度例如0.01-0.10kg磷酸/分钟/kg氧化铝源，进一步地，例如0.03-0.07kg磷酸/分钟/kg氧化铝源。
根据本发明，含第一粘土的磷铝无机粘结剂是指这样的粘结剂，以干基重量为基准，所述含第一粘土的磷铝无机粘结剂含有以Al2O3计10-40重量％，例如15-40重量％的铝组分、以P2O5计45-90重量％，例如45-80重量％的磷组分以及以干基计大于0且不超过40重量％的第一粘土，且所述含第一粘土的磷铝无机粘结剂P/Al重量比为1.0-6.0，pH为1-3.5，固含量为15-60重量％。
根据本发明，所述的含第一粘土的磷铝无机粘结剂可以通过下述方法制备：将氧化铝源、所述第一粘土与水打浆分散成固含量为5-48重量％的浆液；其中所述的氧化铝源为能被酸胶溶的氢氧化铝和/或氧化铝，相对于10-40重量份，例如15-40重量份的以Al2O3计的氧化铝源，以干基重量计的所述第一粘土的用量大于0重量份且不超过40重量份；搅拌下按照P/Al＝1-6的重量比向所述浆液中加入浓磷酸，并使所得混合浆液在50-99℃反应15-90分钟；其中所述的P/Al中P为磷酸中的以单质计的磷的重量，Al为氧化铝源中以单质计的铝的重量。 所述氧化铝源可以为选自ρ-氧化铝、x-氧化铝、η-氧化铝、γ-氧化铝、κ-氧化铝、σ-氧化铝、θ-氧化铝、三水铝石、湃铝石、诺水铝石、硬水铝石、薄水铝石和拟薄水铝石中的至少一种，所述的浓磷酸其浓度可以为60-98重量％，进一步地，例如75-90重量％，磷酸的加料速度例如0.01-0.10kg磷酸/分钟/kg氧化铝源，进一步地，例如0.03-0.07kg磷酸/分钟/kg氧化铝源。
本发明提供了一种磷改性MFI结构分子筛，其特征在于，该分子筛的K值满足：70％≤K≤90％；例如，75％≤K≤90％；进一步地，例如，78％≤K≤85％；其中，所述的K＝[采用EPMA方法测定的分子筛晶粒的任意晶面垂直深度5-10nm厚度区间100平方纳米区域面积内的磷质量含量]/[采用XPS方法测定的分子筛晶粒的任意晶面垂直深度0-2nm内、100平方纳米区域面积内的磷质量含量]×100％，其中通过使用Thermo Fisher-VG公司的ESCAREB 250型X射线光电子能谱仪，激发源为单色化的功率150W的AlKα X射线，荷电位移用来自污染碳的C1s峰(284.8eV)校正对分子筛表面进行XPS分析；采用JXA-8230能谱仪X射线探测器，计数率及计数时间，一般累计计数大于10 5，计数率为10 3～10 4CPS，计数时间为10～100s对分子筛表面进行EPMA分析。
所述的磷改性MFI结构分子筛，磷的含量以P2O5计与氧化铝的摩尔比值≥0.01，例如摩尔比值≥0.2、进一步地，例如≥0.3、更进一步地，例如0.4-0.7。例如，所述的磷改性MFI结构分子筛是微孔ZSM-5分子筛或多级孔ZSM-5分子筛。所述的微孔ZSM-5分子筛，其氧化硅/氧化铝的摩尔比为15-1000、例如20-200。所述的多级孔ZSM-5分子筛，介孔体积占总孔体积的比例大于10％，平均孔径为2-20nm，其氧化硅/氧化铝摩尔比为15-1000、例如20-200。
本发明还提供了上述的磷改性MFI结构分子筛的制备方法，其中所述的磷改性MFI结构分子筛是用浸渍法获得的，包括：使温度为40-150℃、例如50-150℃、进一步地，例如70-130℃的含磷化合物的水溶液与40-150℃、例如50-150℃、进一步地，例如70-130℃的MFI结构分子筛在基本相同的温度下混合接触至少0.1小时、干燥后在200-600℃、空气或水蒸气气氛下焙烧至少0.1小时；或者，将含磷化合物、MFI结构分子筛和水混合打浆后调温到(例如，升温到)40-150℃、例如50-150℃、进一步地，例如70-130℃保持至少0.1小时、干燥后在200-600℃、空气或水蒸气气氛下焙烧至少0.1小时。
根据所述的磷改性MFI结构分子筛的制备方法，所述的MFI结构分子筛可以是氢型微孔ZSM-5分子筛，氢型多级孔ZSM-5分子筛。它们是经铵交换降钠至Na 2O＜0.1wt％后得到的，硅铝比(氧化硅与氧化铝的摩尔比)范围≥10，通常在10-200。
根据所述的磷改性MFI结构分子筛的制备方法，所述的含磷化合物以磷计(以氧化物计)、氢型ZSM-5分子筛或氢型多级孔ZSM-5分子筛以铝计(以氧化物计)，二者的摩尔比值为0.01-2；例如，二者的摩尔比值为0.1-1.5；进一步地，例如，二者的摩尔比值为0.2-1.5。所述的含磷化合物选自有机磷化合物，如磷酸三甲酯、三苯基磷、三甲基亚磷酸酯、四丁基溴化膦、四丁基氯化膦、四丁基氢氧化磷、三苯基乙基溴化磷、三苯基丁基溴化磷、三苯基苄基溴化磷、六甲基磷酰三胺、二苄基二乙基磷、1，3-二甲苯双三乙基磷等，无机磷化物，如磷酸、磷酸氢铵、磷酸氢二铵或磷酸铵、磷酸硼中之一或其混合物等。发明人发现，当以磷酸硼作为含磷化合物之一并且采用300-500℃水热焙烧时，磷在分子筛中具有更好的分散度，因此，例如含磷化合物的组合为磷酸硼与选自磷酸三甲酯、三苯基磷、三甲基亚磷酸酯、磷酸、磷酸氢铵、磷酸氢二铵、磷酸铵的混合物。所 述含磷酸硼的混合物中，磷酸硼重量占比为10％-80％、例如20％-40％、进一步地，例如25％-35％。
根据所述的磷改性MFI结构分子筛的制备方法，所述的接触是用浸渍法使温度为30-150℃的含磷化合物的水溶液与30-150℃的氢型MFI结构分子筛在基本相同的温度下接触至少0.1小时。例如接触可以是在40℃以上的较高的温度区间，例如50-150℃、进一步地，例如在70-130℃下进行，可以获得更好的效果，即磷物种分散更好，磷更容易迁移至氢型MFI结构分子筛晶内与骨架铝结合，进一步提高磷与骨架铝配位程度，最终对分子筛的水热稳定性的提高作出贡献。所述的基本相同的温度，是指含磷化合物的水溶液与氢型MFI结构分子筛各自具有的温度之间的温度差在±5℃。例如，含磷化合物的水溶液的温度为80℃，HZSM-5分子筛则需加热到75-85℃。
根据所述的磷改性MFI结构分子筛的制备方法，所述的接触还可以是将含磷化合物、氢型MFI结构分子筛和水混合后在30-150℃下保持至少0.1小时。例如为了可以获得更好的效果，即磷物种分散更好，磷更容易迁移至分子筛晶内与骨架铝结合，进一步提高磷与骨架铝配位程度，最终提高分子筛的水热稳定性，所述的含磷化合物、氢型MFI结构分子筛和水混合之后，是在40℃以上的较高的温度区间保持0.1小时，例如50-150℃温度区间、进一步地，例如70-130℃温度区间。
根据所述的磷改性MFI结构分子筛的制备方法，水筛重量比为0.5-1，时间为0.5-40小时。所述的焙烧例如是在450-550℃、水蒸汽气氛下进行。
本发明还提供了一种催化裂解助剂，以所述催化裂解助剂的干基重量为基准，所述催化裂解助剂含有5-75重量％的磷改性MFI结构分子筛；其中，所述的磷改性MFI结构分子筛，其K值满足：70％≤K≤90％，所述的K＝[采用EPMA方法测定的分子筛晶粒的任意晶面垂直深度5-10nm厚度区间100平方纳米区域面积内的磷质量含量]/[采用XPS方法测定的分子筛晶粒的任意晶面垂直深度0-2nm内、100平方纳米区域面积内的磷质量含量]×100％，其中通过使用Thermo Fisher-VG公司的ESCAREB 250型X射线光电子能谱仪，激发源为单色化的功率150W的AlKα X射线，荷电位移用来自污染碳的C1s峰(284.8eV)校正对分子筛表面进行XPS分析；采用JXA-8230能谱仪X射线探测器，计数率及计数时间，一般累计计数大于10 5，计数率为10 3～10 4CPS，计数时间为10～100s对分子筛表面进行EPMA分析。
在本发明的催化裂解助剂中，所述的磷改性MFI结构分子筛中K值满足：75％≤K≤90％、例如，所述的K值满足：78％≤K≤85％。
在本发明的催化裂解助剂中，对于所述的磷改性MFI结构分子筛，磷的含量以P 2O 5计与氧化铝的摩尔比值≥0.01，例如摩尔比值≥0.2、进一步地，例如≥0.3、更进一步地，例如0.4-0.7。
在本发明的催化裂解助剂中，例如，所述的磷改性MFI结构分子筛是微孔ZSM-5分子筛或多级孔ZSM-5分子筛。所述的微孔ZSM-5分子筛，其氧化硅/氧化铝的摩尔比为15-1000、例如20-200。所述的多级孔ZSM-5分子筛，介孔体积占总孔体积的比例大于10％，平均孔径为2-20nm，其氧化硅/氧化铝摩尔比为15-1000、例如20-200。
在本发明的催化裂解助剂中，以所述催化裂解助剂的干基为基准，所述催化裂解助剂除了含有5-75重量％、例如8-60重量％的磷改性MFI结构分子筛外，还可以含有1-40重量％的粘结剂和0-65重量％的第二粘土。所述粘结剂可以是 本领域技术人员所熟知的惯用于助剂或催化剂粘结剂组分的无机氧化物粘结剂、例如拟薄水铝石、铝溶胶、硅铝溶胶和水玻璃中的一种或多种。例如，所述粘结剂含有磷铝无机粘结剂，即磷铝无机粘结剂或者磷铝无机粘结剂和其他无机粘结剂的混合物。
在本发明的催化裂解助剂中，所述磷铝无机粘结剂例如磷铝胶和/或含第一粘土的磷铝无机粘结剂。以所述含第一粘土的磷铝无机粘结剂干基为基准，所述含第一粘土的磷铝无机粘结剂含有以Al 2O 3计10-40重量％，例如15-40重量％、例如10-35重量％，例如15-35重量％的铝组分、以P 2O 5计45-90重量％，例如45-80重量％、例如50-75重量％的磷组分以及以干基计大于0且不超过40重量％、例如8-35重量％的第一粘土，且所述含第一粘土的磷铝无机粘结剂P/Al重量比为1.0-6.0、例如1.2-6.0、进一步地，例如2.0-5.0，pH为1-3.5、例如2.0-3.0，固含量为15-60重量％。例如，所述磷铝无机粘结剂的一种具体实施方式，以所述磷铝无机粘结剂的干基重量为基准，所述的磷铝无机粘结剂包括以Al 2O 3计20-40重量％铝组分和以P 2O 5计60-80重量％的磷组分。
在本发明的催化裂解助剂中，所述第一粘土可以为选自高岭土、海泡石、凹凸棒石、累托石、蒙脱石和硅藻土的至少一种；所述其他无机粘结剂可以选自除了所述磷铝胶和磷铝无机粘结剂以外的惯用于催化裂解助剂或催化剂粘结剂组分的无机氧化物粘结剂中的一种或多种，例如选自拟薄水铝石、铝溶胶、硅铝溶胶和水玻璃中的至少一种，进一步地，例如选自拟薄水铝石和铝溶胶中的至少一种。
在本发明的催化裂解助剂中，以所述催化裂解助剂的干基计，还含有0-65重量％、例如5-55重量％的第二粘土。所述的第二粘土也是本领域技术人员所熟知的，例如为选自高岭土、海泡石、凹凸棒石、累托石、蒙脱石、多水高岭土、埃洛石、水滑石、膨润土以及硅藻土中的至少一种。
在本发明的催化裂解助剂的一种具体实施方式中，以所述催化裂解助剂的干基为基准，包括20-60重量％的磷改性MFI结构分子筛、5-35重量％的粘结剂和以5-55重量％的第二粘土。
本发明还提供了所述的催化裂解助剂的一种制备方法，该方法包括，将本发明的磷改性MFI结构分子筛、粘结剂与可选加入的第二粘土混合打浆并经喷雾干燥后得到所述催化裂解助剂。
在所述的催化裂解助剂的制备方法中，所述粘结剂含有磷铝无机粘结剂和其他无机物粘结剂，以干基计，所述磷改性MFI结构分子筛、所述磷铝无机粘结剂和所述其他无机物粘结剂的重量用量比可以为(10-75)∶(3-39)∶(1-30)，例如(10-75)∶(8-35)∶(5-25)；其中所述磷铝无机粘结剂可以为磷铝胶和/或含第一粘土的磷铝无机粘结剂；所述其他无机物粘结剂可以包括拟薄水铝石、铝溶胶、硅铝溶胶和水玻璃中的至少一种。制备方法可以是将磷改性MFI结构分子筛、磷铝无机粘结剂和其他无机粘结剂混合，打浆，其加料的顺序没有特殊要求，例如可以将磷铝无机粘结剂、其他无机粘结剂、磷改性MFI结构分子筛、第二粘土混合(当不合第二粘土的时候则可以省略相关的加料步骤)打浆，例如，先将第二粘土、磷改性MFI结构分子筛以及其他无机粘结剂混合打浆后再加入所述磷铝无机粘结剂，这有利于改善助剂的活性和选择性。
在所述的催化裂解助剂的制备方法中，还包括将所述打浆得到的浆液喷雾干燥的步骤。喷雾干燥的方法为本领域技术人员熟知，本发明没有特殊要求。可选地，该制备方法还可包括：将所述喷雾干燥所得产物进行第一焙烧、洗涤和可 选的干燥处理，得到所述催化裂解助剂。其中，所述第一焙烧的焙烧温度可以为300-650℃，例如为400-600℃、例如450-550℃，焙烧时间可以为0.5-8小时；所述洗涤可以采用硫酸铵、氯化铵、硝酸铵中的一种，洗涤温度可以为40-70℃；所述干燥处理的温度可以为100-200℃，例如为100-150℃，干燥时间可以为0.5-24h，例如为1-12h。
在所述的催化裂解助剂的制备方法的一种具体实施方式中，将粘结剂与第二粘土以及水(例如脱阳离子水和/或去离子水)混合，配制成固含量为10-50重量％的浆液，搅拌均匀，用无机酸例如盐酸、硝酸、磷酸或硫酸将浆液pH调至1-4，保持该pH值，于20-80℃下静置老化0-2小时(例如0.3-2小时)后加入铝溶胶和/或硅溶胶等无机粘结剂，搅拌0.5-1.5小时形成胶体，然后加入所述磷改性MFI结构分子筛，形成助剂浆液，助剂浆液固含量例如为20-45重量％，继续搅拌后喷雾干燥制成微球助剂。然后将微球助剂进行第一焙烧，例如在350-650℃或400-600℃例如450-550℃焙烧0.5-6小时或0.5-2小时，再用硫酸铵洗涤(其中，洗涤温度可以在40-70℃，硫酸铵∶微球助剂∶水＝0.2-0.8∶1∶5-15(重量比)至氧化钠含量小于0.25重量％，用水洗涤并过滤，之后干燥。
在所述的催化裂解助剂的制备方法的一种具体实施方式中，向所述磷改性MFI结构分子筛、第二粘土(例如高岭土)和粘结剂(例如拟薄水铝石)加入水(例如脱阳离子水和/或去离子水)以及铝溶胶和/或硅溶胶等无机粘结剂，打浆0.1-10小时(例如120分钟)，得到固含量10-50重量％(例如30重量％)的浆液，加入无机酸例如盐酸、硝酸、磷酸或硫酸调节浆液pH值至1-4(例如3.0)，然后继续打浆0.1-10小时(例如45分钟)，然后加入磷铝无机粘结剂，搅拌0.1-10小时(例如30分钟)后，将得到的浆液喷雾干燥，得到微球，将微球于350-650℃或400-600℃(例如500℃)下焙烧0.5-6小时或0.5-2小时(例如1小时)制得催化裂解助剂。
在所述的催化裂解助剂的制备方法的一种具体实施方式中，将粘结剂(例如铝溶胶)与第二粘土(例如高岭土)混合，并用水(例如脱阳离子水和/或去离子水)将其制成固含量为10-50重量％(例如30重量％)的浆液，搅拌均匀，用无机酸例如盐酸、硝酸、磷酸或硫酸将浆液pH值调至1-4(例如2.8)，于20-80℃(例如55℃)下静置老化0.1-2小时(例如1小时)后加入磷改性MFI结构分子筛，形成固含量10-50重量％(例如35重量％)的浆液，继续搅拌后喷雾干燥制成微球助剂。然后将微球助剂进行第一焙烧，例如在350-650℃或400-600℃例如450-550℃焙烧0.5-6小时或0.5-2小时(例如在500℃下焙烧1小时)，再用硫酸铵洗涤(其中，洗涤温度可以在40-70℃，例如60℃，硫酸铵∶微球助剂∶水＝0.2-0.8∶1∶5-15(重量比，例如0.5∶1∶10)至氧化钠含量小于0.25重量％，用水洗涤并过滤，之后干燥(例如在100-200℃下干燥，如110℃)。
在所述的催化裂解助剂的制备方法中，所述含第一粘土的磷铝无机粘结剂还可以包括采用如下步骤进行制备：将氧化铝源、所述第一粘土与水打浆分散成固含量为5-48重量％的浆液；其中所述的氧化铝源为能被酸胶溶的氢氧化铝和/或氧化铝，相对于10-40重量份，例如15-40重量份的以Al 2O 3计的氧化铝源，以干基重量计的所述第一粘土的用量大于0重量份且不超过40重量份；搅拌下按照P/Al＝1-6的重量比向所述浆液中加入浓磷酸，并使所得混合浆液在50-99℃反应15-90分钟；其中所述的P/Al中P为磷酸中的以单质计的磷的重量，Al为氧化铝源中以单质计的铝的重量。所述氧化铝源可以为选自ρ-氧化铝、x-氧化铝、η-氧化铝、γ-氧化铝、κ-氧化铝、σ-氧化铝、θ-氧化铝、三水铝石、湃铝石、诺 水铝石、硬水铝石、薄水铝石和拟薄水铝石中的至少一种，所述含第一粘土的磷铝无机粘结剂中的铝组分源自所述的氧化铝源。所述的第一粘土可以分为高岭土、海泡石、凹凸棒石、累托石、蒙脱石以及硅藻土中的一种或多种，例如累托石。所述的浓磷酸其浓度可以为60-98重量％，进一步地，例如75-90重量％。磷酸的加料速度例如0.01-0.10kg磷酸/分钟/kg氧化铝源，进一步地，例如0.03-0.07kg磷酸/分钟/kg氧化铝源。
在所述的催化裂解助剂的制备方法中，所述含第一粘土的磷铝无机粘结剂由于粘土的引入，不仅在制备过程中改善了物料之间的传质、传热，避免了物料不均匀局部瞬间剧烈反应放热超稳引起的粘结剂固化，得到的粘结剂的粘结性能与不引入粘土方法制备的磷铝粘结剂相当；而且该方法引入粘土，尤其是具有层状结构的累托石，改善了催化剂组合物的重油转化能力，使得到的助剂具有更佳的选择性。
本发明进一步提供了所述催化裂解助剂的应用，即一种烃油催化裂解的方法，该方法包括：在催化裂解条件下，使烃油与本发明所述的催化裂解助剂接触反应。
本发明的烃油催化裂解的方法包括：在所述催化裂解条件下，使所述烃油与含有所述催化裂解助剂和催化裂解催化剂的催化混合物接触反应；所述催化混合物中，所述催化裂解助剂的含量为0.1-30重量％。
可选地，所述催化裂解条件包括：反应温度为500-800℃；所述烃油选自原油、石脑油、汽油、常压渣油、减压渣油、常压蜡油、减压蜡油、直流蜡油、丙烷轻/重脱油、焦化蜡油和煤液化产物中的一种或几种。
本发明还提供了一种含磷改性MFI结构分子筛的催化裂解催化剂，以催化剂的干基为基准，所述催化裂解催化剂含有1-25重量％的Y型分子筛、5-50重量％的磷改性MFI结构分子筛、1-60重量％的无机粘结剂和可选加入的0-60重量％的第二粘土，其中，所述无机粘结剂包括磷铝无机粘结剂和/或其他无机粘结剂，所述的磷改性MFI结构分子筛，其K值满足：70％≤K≤90％，所述的K＝[采用EPMA方法测定的分子筛晶粒的任意晶面垂直深度5-10nm厚度区间100平方纳米区域面积内的磷质量含量]/[采用XPS方法测定的分子筛晶粒的任意晶面垂直深度0-2nm内、100平方纳米区域面积内的磷质量含量]×100％，其中通过使用Thermo Fisher-VG公司的ESCAREB 250型X射线光电子能谱仪，激发源为单色化的功率150W的AlKα X射线，荷电位移用来自污染碳的C1s峰(284.8eV)校正对分子筛表面进行XPS分析；采用JXA-8230能谱仪X射线探测器，计数率及计数时间，一般累计计数大于10 5，计数率为10 3～10 4CPS，计数时间为10～100s对分子筛表面进行EPMA分析。
在本发明的催化裂解催化剂中，所述Y型分子筛包括PSRY分子筛、含稀土的PSRY分子筛、USY分子筛、含稀土的USY分子筛、REY分子筛、REHY分子筛和HY分子筛的至少一种。
在本发明的催化裂解催化剂中，所述的磷改性MFI结构分子筛中K值满足：75％≤K≤90％、例如，所述的K值满足：78％≤K≤85％。
在本发明的催化裂解催化剂中，对于所述的磷改性MFI结构分子筛，磷的含量以P 2O 5计与氧化铝的摩尔比值≥0.01，例如摩尔比值≥0.2、进一步地，例如≥0.3、更进一步地，例如0.4-0.7。
在本发明的催化裂解催化剂中，例如，所述的磷改性MFI结构分子筛是微孔ZSM-5分子筛或多级孔ZSM-5分子筛。所述的微孔ZSM-5分子筛，其氧化 硅/氧化铝的摩尔比为15-1000、例如20-200。所述的多级孔ZSM-5分子筛，介孔体积占总孔体积的比例大于10％，平均孔径为2-20nm，其氧化硅/氧化铝摩尔比为15-1000、例如20-200。
例如，在本发明的催化裂解催化剂中，以所述催化裂解催化剂的干基为基准，所述催化裂解催化剂除了含有2-20重量％的Y型分子筛、10-40重量％、例如20-40重量％的磷改性MFI结构分子筛外，还可以含有1-40重量％的无机粘结剂和0-50重量％的第二粘土。进一步地，例如，以所述催化剂的干基为基准，含有3-40重量％的磷铝无机粘结剂或者含有3-40重量％的磷铝无机粘结剂和1-30重量％的其他无机粘结剂。
在本发明的催化裂解催化剂中，所述磷铝无机粘结剂为磷铝胶和/或含第一粘土的磷铝无机粘结剂。以所述含第一粘土的磷铝无机粘结剂干基为基准，所述含第一粘土的磷铝无机粘结剂含有以Al 2O 3计10-40重量％，例如15-40重量％的铝组分、以P 2O 5计45-90重量％，例如45-80重量％的磷组分以及以干基计大于0且不超过40重量％的第一粘土，且所述含第一粘土的磷铝无机粘结剂P/Al重量比为1.0-6.0，pH为1-3.5，固含量为15-60重量％。
在本发明的催化裂解催化剂中，所述第一粘土包括高岭土、海泡石、凹凸棒石、累托石、蒙脱石和硅藻土中的至少一种。
在本发明的催化裂解催化剂中，对于所述磷铝无机粘结剂的一种具体实施方式，以所述磷铝无机粘结剂的干基重量为基准，所述的磷铝无机粘结剂可以包括以Al 2O 3计10-40重量％，例如15-40重量％铝组分、以P 2O 5计45-90重量％，例如45-80重量％的磷组分以及以干基重量计0-40重量％的第一粘土，且其P/Al重量比为1.0-6.0，pH值为1-3.5，固含量为15-60重量％；例如含有以Al 2O 3计15-35重量％的铝组分，以P 2O 5计50-75重量％的磷组分以及8-35重量％的第一粘土，且其P/Al重量比例如1.2-6.0，进一步地，例如2.0-5.0，pH值例如2.0-3.0。
在本发明的催化裂解催化剂中，对于所述磷铝无机粘结剂的另一种具体实施方式，以所述磷铝无机粘结剂的干基重量为基准，所述的磷铝无机粘结剂包括以Al 2O 3计20-40重量％铝组分和以P 2O 5计60-80重量％的磷组分。
在本发明的催化裂解催化剂中，所述其他无机粘结剂可以选自除了所述磷铝胶和磷铝无机粘结剂以外的惯用于催化裂解催化剂或催化剂粘结剂组分的无机氧化物粘结剂中的一种或多种，例如选自拟薄水铝石、铝溶胶、硅铝溶胶和水玻璃中的至少一种，进一步地，例如选自拟薄水铝石和铝溶胶中的至少一种。
本发明的催化裂解催化剂中，以干基计，还含有0-65重量％、例如5重量％-55重量％的第二粘土。所述的第二粘土也是本领域技术人员所熟知的，例如为选自高岭土、海泡石、凹凸棒石、累托石、蒙脱石、多水高岭土、埃洛石、水滑石、膨润土以及硅藻土中的至少一种。
本发明还提供了所述的一种催化裂解催化剂的制备方法，该方法包括，将Y型分子筛、磷改性MFI结构分子筛、无机粘结剂与可选加入的第二粘土混合打浆并经喷雾干燥后得到所述催化裂解催化剂，
在本发明的催化裂解催化剂的制备方法中，所述方法还可以包括：将所述焙烧处理所得产物进行洗涤和可选的干燥处理，得到所述催化裂解催化剂；其中所述焙烧的焙烧温度可以为300-650℃，例如为400-600℃例如450-550℃，焙烧时间可以为0.5-12小时；所述洗涤可以采用硫酸铵、硝酸铵、氯化铵中的一种，洗涤温度可以为40-80℃；所述干燥处理的温度可以为110-200℃例如为120-150℃，干燥时间可以为0.5-18h例如为2-12h。
在本发明的催化裂解催化剂的制备方法的一种具体实施方式中，可以将无机粘结剂(例如拟薄水铝石、铝溶胶、硅溶胶、硅铝凝胶或其中两种或多种的混合物)与第二粘土(例如高岭土)以及水(例如脱氧离子水和/或去离子水)混合，配置成固含量为10-50重量％的浆液，搅拌均匀，用无机酸例如盐酸、硝酸、磷酸或硫酸将浆液pH调至1-4，保持该pH值，于20-80℃下静置老化0-2小时后例如0.3-2小时后加入铝溶胶和/或硅溶胶，搅拌0.5-1.5小时形成胶体，然后加入分子筛，所述分子筛包括所述磷改性的ZSM-5分子筛和Y型分子筛，形成催化剂浆液，催化剂浆液固含量例如为20-45重量，继续搅拌后喷雾干燥制成微球催化剂。然后将微球催化剂进行焙烧例如在350-650℃或400-600℃例如450-550℃焙烧0.5-6小时或0.5-2小时，再用硫酸铵洗涤(其中，洗涤温度可以在40-70℃，硫酸铵∶微球催化剂∶水＝0.2-0.8∶1∶5-15重量比)至氧化钠含量小于0.25重量％，用水洗涤并过滤，之后干燥。
在本发明的催化裂解催化剂的制备方法的一种具体实施方式中，将所述磷改性的ZSM-5分子筛、Y型分子筛、第二粘土(例如高岭土)和无机粘结剂(例如拟薄水铝石、铝溶胶、硅溶胶、硅铝凝胶或其中两种或多种的混合物)混合，加入水(例如脱氧离子水和/或去离子水)以及铝溶胶和/或硅溶胶，打浆0.1-10小时(例如120分钟)，得到固含量20-45重量％(例如30重量％)的浆液，加入无机酸例如盐酸、硝酸、磷酸或硫酸调节浆液pH值至1-4(例如3.0)，然后继续打浆0.1-10小时(例如45分钟)，然后加入磷铝无机粘结剂，搅拌0.1-10小时(例如30分钟)后，将得到的浆液喷雾干燥，得到微球催化剂，然后将微球催化剂进行焙烧，例如在350-650℃或400-600℃例如450-550℃焙烧0.5-6小时或0.5-2小时(例如于500℃下焙烧1小时)制得催化裂解催化剂。
在本发明的催化裂解催化剂的制备方法的一种具体实施方式中，将粘结剂无机粘结剂(例如拟薄水铝石、铝溶胶、硅溶胶、硅铝凝胶或其中两种或多种的混合物)与第二粘土(例如高岭土)混合，并用水(例如脱氧离子水和/或去离子水)将其制成固含量为10-50重量％(例如30重量％)的浆液，搅拌均匀，用无机酸例如盐酸、硝酸、磷酸或硫酸将浆液pH值调至1-4(例如2.8)，于20-80℃(例如55℃)下静置老化0.1-2小时(例如1小时)后加入所述磷改性的ZSM-5分子筛和Y型分子筛，形成固含量为20-45重量％(例如35重量％)的催化剂浆液，继续搅拌后喷雾干燥制成微球催化剂。然后将微球催化剂进行焙烧例如在350-650℃或400-600℃例如450-550℃焙烧0.5-6小时或0.5-2小时(例如在500℃下焙烧1小时)，再用硫酸铵洗涤(其中，洗涤温度可以在40-70℃，例如60℃，硫酸铵∶微球催化剂∶水＝0.2-0.8∶1∶5-15重量比，例如0.5∶1∶10重量比)至氧化钠含量小于0.25重量％，用水洗涤并过滤，之后干燥(例如在100-200℃下干燥，如110℃)。
在本发明的催化裂解催化剂的制备方法的另一种具体实施方式中，可以将Y型分子筛和磷改性ZSM-5分子筛、磷铝无机粘结剂和其他无机粘结剂混合，加或不加入第二粘土，打浆，喷雾干燥。
在本发明的催化裂解催化剂的制备方法中，所述无机粘结剂包括所述磷铝无机粘结剂和所述其他无机物粘结剂，所述磷铝无机粘结剂和所述其他无机物粘结剂的重量用量比可以为(3-40)∶(1-30)，例如(5-35)∶(5-28)，进一步例如(10-30)∶(5-25)；其中所述磷铝无机粘结剂可以为磷铝胶和/或含第一粘土的磷铝无机粘结剂；所述其他无机粘结剂可以包括拟薄水铝石、铝溶胶、硅铝溶胶和水玻璃中的至少一种。
在本发明的催化裂解催化剂的制备方法中，可以将含磷改性ZSM-5分子筛、磷铝无机粘结剂和其他无机粘结剂混合，打浆，其加料的顺序没有特殊要求，例如可以将磷铝无机粘结剂、其他无机粘结剂、分子筛、第二粘土混合(当不含第二粘土的时候则可以省略相关的加料步骤)打浆，例如，先将第二粘土、分子筛以及其他无机粘结剂混合打浆后再加入所述磷铝无机粘结剂，这有利于改善催化剂的活性和选择性。
在本发明的催化裂解催化剂的制备方法中，所述制备方法还包括将所述打浆得到的浆液喷雾干燥的步骤。喷雾干燥的方法为本领域技术人员熟知，本公开没有特殊要求。
进一步地，在本发明的催化裂解催化剂的制备方法中，所述制备方法还可以包括采用如下步骤制备所述含第一粘土的磷铝无机粘结剂：将氧化铝源、所述第一粘土与水打浆分散成固含量为5-48重量％的浆液；其中所述的氧化铝源为能被酸胶溶的氢氧化铝和/或氧化铝，相对于10-40重量份，例如15-40重量份的以Al 2O 3计的氧化铝源，以干基重量计的所述第一粘土的用量大于0重量份且不超过40重量份；搅拌下按照P/Al＝1-6的重量比向所述浆液中加入浓磷酸，并使所得混合浆液在50-99℃反应15-90分钟；其中所述的P/Al中P为磷酸中的以单质计的磷的重量，Al为氧化铝源中以单质计的铝的重量。所述氧化铝源可以为选自ρ-氧化铝、x-氧化铝、η-氧化铝、γ-氧化铝、κ-氧化铝、σ-氧化铝、θ-氧化铝、三水铝石、湃铝石、诺水铝石、硬水铝石、薄水铝石和拟薄水铝石中的至少一种，所述含第一粘土的磷铝无机粘结剂中的铝组分源自所述的氧化铝源。所述的第一粘土可以分为高铝土、海泡石、凹凸棒石、累托石、蒙脱石以及硅藻土中的一种或多种，例如累托石。所述的浓磷酸其浓度可以为60-98重量％，进一步地，例如75-90重量％。磷酸的加料速度例如0.01-0.10kg磷酸/分钟/kg氧化铝源，进一步地，例如0.03-0.07kg磷酸/分钟/kg氧化铝源。
在本发明的催化裂解催化剂的制备方法中，所述含第一粘土的磷铝无机粘结剂由于粘土的引入，不仅在制备过程中改善了物料之间的传质、传热，避免了物料不均匀局部瞬间剧烈反应放热超稳引起的粘结剂固话，得到的粘结剂的粘结性能与不引入粘土方法制备的磷铝粘结剂相当；而且该方法引入粘土，尤其是具有层状结构的累托石，改善了催化剂的重油转化能力，使得到的催化剂剂具有更佳的选择性。
本发明还提供采用上述制备方法得到的催化裂解催化剂。
本发明进一步提供了所述催化裂解催化剂的应用，即一种烃油催化裂解的方法，该方法包括：在催化裂解条件下，使烃油与本发明所述的催化裂解催化剂接触反应。所述催化裂解条件包括：反应温度为500-800℃；所述烃油选自原油、石脑油、汽油、常压渣油、减压渣油、常压蜡油、减压蜡油、直流蜡油、丙烷轻/重脱油、焦化蜡油和煤液化产物中的一种或几种。所述烃油可以含有镍、钒等重金属杂质及硫、氮杂质，如烃油中硫的含量可高达3.0重量％，氮的含量可高达2.0重量％，钒、镍等金属杂质的含量可高达3000ppm。
用于催化裂解过程时的一种具体实施方式，催化裂解催化剂可单独往催化裂解反应器里添加，例如在催化裂解条件下，使烃油与本发明所述的催化裂解催化剂接触反应；用于催化裂解过程时的另一种具体实施方式，该催化剂可与催化裂解催化剂混合使用，例如可以使烃油与含有本发明的催化裂解催化剂和其他催化裂解催化剂的催化混合物接触反应。本发明提供的催化剂占上述混合物总量可以不超过30重量％，例如1-25重量％，进一步地，例如3-15重量％。
采用EPMA/XPS联合方法进行面扫描分析微区化学成分与深度结构相对应进行磷含量定量分析，分散度K值指分子筛晶粒深度界面上磷质量含量与分子筛晶粒表面磷含量之百分比，其中，K＝P2(EPMA)/P1(XPS)％，P1(XPS)表示采用XPS方法定量测定的分子筛晶粒的任意晶面深度小于2nm微区的磷质量含量，P2(EPMA)表示采用EPMA方法定量测定的利用聚焦离子束(FIB)切割得到5-10nm厚的深度界面微区磷含量。
采用X射线光电子能谱(XPS)对分子筛表面进行分析，使用Thermo Fisher-VG公司的ESCAREB 250型X射线光电子能谱仪，激发源为单色化的功率150W的AlKα X射线，荷电位移用来自污染碳的C1s峰(284.8eV)校正。
EPMA采用JXA-8230能谱仪X射线探测器，计数率及计数时间，一般累计计数大于10 5，计数率为10 3～10 4CPS，计数时间为10～100s。
本发明还提供了下述方面的技术方案：
第1方面，一种磷改性MFI结构分子筛，其特征在于，该分子筛的K值满足：70％≤K≤90％；例如，75％≤K≤90％；进一步地，例如，78％≤K≤85％；
其中，所述的K＝P2/P1×100％，
P1表示采用XPS方法测定的分子筛晶粒的任意晶面垂直深度0-2nm内、100平方纳米区域面积内的磷质量含量，
P2表示采用EPMA方法测定的分子筛晶粒的任意晶面垂直深度5-10nm厚度区间100平方纳米区域面积内的磷质量含量。
第2方面，根据前述方面中任一项的分子筛，其中，磷的含量以P2O5计与氧化铝的摩尔比值≥0.01；例如，≥0.2；进一步地，例如，≥0.3；更进一步地，例如，0.4-0.7。
第3方面，根据前述方面中任一项的分子筛，其中，所述的磷改性MFI结构分子筛是微孔ZSM-5分子筛或多级孔ZSM-5分子筛。
第4方面，根据前述方面中任一项的分子筛，所述的微孔ZSM-5分子筛，其氧化硅/氧化铝的摩尔比为15-1000、例如，20-200。
第5方面，根据前述方面中任一项的分子筛，所述的多级孔ZSM-5分子筛，其介孔体积占总孔体积的比例大于10％，平均孔径为2-20nm，氧化硅/氧化铝的摩尔比为15-1000、例如，20-200。
第6方面，一种催化裂解助剂，以所述催化裂解助剂的干基为基准，所述催化裂解助剂含有5-75重量％、例如，8-60重量％的前述方面中任一项所述的磷改性MFI结构分子筛、1-40重量％的粘结剂和0-65重量％、例如5-55重量％的第二粘土。
第7方面，一种含磷改性MFI结构分子筛的催化裂解催化剂，以催化剂的干基为基准，所述催化裂解催化剂含有1-25重量％的Y型分子筛、以5-50重量％的前述方面中任一项所述的磷改性MFI结构分子筛、1-60重量％的无机粘结剂和可选加入的0-60重量％的第二粘土。
第8方面，根据前述方面中任一项的催化裂解助剂或催化裂解催化剂，其中，所述的粘结剂或所述的无机粘结剂包括磷铝无机粘结剂和/或其他无机粘结剂，
例如，所述的磷铝无机粘结剂为磷铝胶和/或含第一粘土的磷铝无机粘结剂，进一步地，例如，所述的第一粘土选自高岭土、海泡石、凹凸棒石、累托石、蒙脱石和硅藻土；进一步例如，所述的含第一粘土的磷铝无机粘结剂含有以Al2O3计10-40重量％，例如15-40重量％的铝组分、以P2O5计45-90重量％，例如45-80 重量％的磷组分以及以干基计大于0且不超过40重量％的第一粘土，且所述含第一粘土的磷铝无机粘结剂P/Al重量比为1.0-6.0，pH为1-3.5，固含量为15-60重量％；
例如，所述的第二粘土选自高岭土、海泡石、凹凸棒石、累托石、蒙脱石、和硅藻土，以及多水高岭土、埃洛石、水滑石、和膨润土；
例如，所述的其他无机粘结剂选自拟薄水铝石、铝溶胶、硅铝溶胶和水玻璃。
第9方面，根据前述方面中任一项所述的催化裂解催化剂，其中，所述Y型分子筛包括PSRY分子筛、PSRY-S分子筛、含稀土的PSRY分子筛、含稀土的PSRY-S分子筛、USY分子筛、含稀土的USY分子筛、REY分子筛、REHY分子筛和HY分子筛的至少一种。
第10方面，制备前述方面中任一项的磷改性MFI结构分子筛的方法，其特征在于用浸渍法获得的，包括：使温度为40-150℃、例如50-150℃、进一步地，例如70-130℃的含磷化合物的水溶液与40-150℃、例如50-150℃、进一步地，例如70-130℃的MFI结构分子筛在基本相同的温度下混合接触至少0.1小时、干燥后在200-600℃、空气或水蒸气气氛下焙烧至少0.1小时；或者，将含磷化合物、MFI结构分子筛和水混合打浆后调温到40-150℃、例如50-150℃、进一步地，例如70-130℃保持至少0.1小时、干燥后在200-600℃、空气或水蒸气气氛下焙烧至少0.1小时。
第11方面，根据前述方面中任一项的制备磷改性MFI结构分子筛的方法，其中，所述的含磷化合物选自有机磷化合物和/或无机磷化合物；例如，所述的有机磷化合物选自磷酸三甲酯、三苯基磷、三甲基亚磷酸酯、四丁基溴化膦、四丁基氯化膦、四丁基氢氧化磷、三苯基乙基溴化磷、三苯基丁基溴化磷、三苯基苄基溴化磷、六甲基磷酰三胺、二苄基二乙基磷、1，3-二甲苯双三乙基磷，所述的无机磷化合物选自磷酸、磷酸氢铵、磷酸氢二铵、磷酸铵、磷酸硼。
第12方面，根据前述方面中任一项的制备磷改性MFI结构分子筛的方法，其中，所述的含磷化合物以磷计(以氧化物计)、MFI结构分子筛(例如氢型ZSM-5分子筛)以铝计(以氧化物计)，二者的摩尔比值为0.01-2；例如，二者的摩尔比值为0.1-1.5；进一步地，例如，二者的摩尔比值为0.2-1.5。
第13方面，根据前述方面中任一项的制备磷改性MFI结构分子筛的方法，其中，所述的含磷化合物为磷酸硼与选自磷酸三甲酯、三苯基磷、三甲基亚磷酸酯、磷酸、磷酸氢铵、磷酸氢二铵、磷酸铵之一或多种的混合物，所述混合物中，磷酸硼重量占比为10％-80％，例如磷酸硼重量占比为20％-40％。
第14方面，根据前述方面中任一项的制备磷改性MFI结构分子筛的方法，其中，所述的接触，水筛重量比为0.5-1，时间为0.5-40小时。
第15方面，根据前述方面中任一项的制备磷改性MFI结构分子筛的方法，其中，所述的焙烧是在450-550℃、水蒸汽气氛下进行。
第16方面，一种制备前述方面中任一项的催化裂解助剂的方法，该方法包括，将磷改性MFI结构分子筛、粘结剂与可选加入的第二粘土混合打浆并经喷雾干燥后得到所述催化裂解助剂。
第17方面，根据前述方面中任一项的制备催化裂解助剂的方法，其中，所述的粘结剂包括或者为磷铝无机粘结剂。
第18方面，根据前述方面中任一项的制备催化裂解助剂的方法，其中，所述的磷铝无机粘结剂为磷铝胶和/或含第一粘土的磷铝无机粘结剂；以所述含第 一粘土的磷铝无机粘结剂干基重量为基准，所述含第一粘土的磷铝无机粘结剂含有以Al2O3计10-40重量％，例如15-40重量％、或10-30重量％，或15-35重量％或20-40重量％的铝组分、以P2O5计45-90重量％，例如45-80重量％、或50-75重量％或60-80重量％的磷组分以及以干基计大于0且不超过40重量％、例如8-35重量％的第一粘土，且所述含第一粘土的磷铝无机粘结剂P/Al重量比为1.0-6.0、例如1.2-6.0、进一步地，例如2.0-5.0，pH为1-3.5、例如2.0-3.0，固含量为15-60重量％；所述第一粘土包括高岭土、海泡石、凹凸棒石、累托石、蒙脱石和硅藻土中的至少一种。
第19方面，根据前述方面中任一项的制备催化裂解助剂的方法，其中，所述的第二粘土为选自高岭土、海泡石、凹凸棒石、累托石、蒙脱石、多水高岭土、埃洛石、水滑石、膨润土以及硅藻土中的至少一种。
第20方面，根据前述方面中任一项的制备催化裂解助剂的方法，其中，以所述催化裂解助剂的总重量为基准，所述粘结剂包括以干基重量计3-39重量％的所述磷铝无机粘结剂和以干基重量计1-30重量％的其他无机粘结剂。
第21方面，根据前述方面中任一项的制备催化裂解助剂的方法，其中，所述其他无机粘结剂还可以包括拟薄水铝石、铝溶胶、硅铝溶胶和水玻璃中的至少一种。
第22方面，根据前述方面中任一项的制备催化裂解助剂的方法，该方法还包括：将所述喷雾干燥所得产物进行第一焙烧、洗涤和可选的干燥处理，得到所述催化裂解助剂；其中所述第一焙烧的焙烧温度为300-650℃，焙烧时间为0.5-8h；所述干燥处理的温度为100-200℃，干燥时间为0.5-24h。
第23方面，根据前述方面中任一项的制备催化裂解助剂的方法，该方法还包括：采用如下步骤制备所述含第一粘土的磷铝无机粘结剂：将氧化铝源、所述第一粘土与水打浆分散成固含量为5-48重量％的浆液；其中所述的氧化铝源为能被酸胶溶的氢氧化铝和/或氧化铝，相对于10-40重量份，例如15-40重量份的以Al2O3计的氧化铝源，以干基重量计的所述第一粘土的用量大于0重量份且不超过40重量份；搅拌下按照P/Al＝1-6的重量比向所述浆液中加入浓磷酸，并使所得混合浆液在50-99℃反应15-90分钟；其中所述的P/Al中P为磷酸中的以单质计的磷的重量，Al为氧化铝源中以单质计的铝的重量。
第24方面，一种制备前述方面中任一项的催化裂解催化剂的方法，该方法包括，将Y型分子筛、前述方面中任一项的磷改性MFI结构分子筛、无机粘结剂与可选加入的第二粘土混合打浆并经喷雾干燥后得到所述催化裂解催化剂。
第25方面，根据前述方面中任一项的制备催化裂解催化剂的方法，其中，所述的无机粘结剂包括或者为磷铝无机粘结剂。
第26方面，根据前述方面中任一项的制备催化裂解催化剂的方法，其中，所述的磷铝无机粘结剂为磷铝胶和/或含第一粘土的磷铝无机粘结剂；以所述含第一粘土的磷铝无机粘结剂干基重量为基准，所述含第一粘土的磷铝无机粘结剂含有以Al2O3计10-40重量％，例如15-40重量％的铝组分、以P2O5计45-90重量％，例如45-80重量％的磷组分以及以干基计大于0且不超过40重量％的第一粘土，且所述含第一粘土的磷铝无机粘结剂P/Al重量比为1.0-6.0，pH为1-3.5，固含量为15-60重量％；所述第一粘土包括高岭土、海泡石、凹凸棒石、累托石、蒙脱石和硅藻土中的至少一种。
第27方面，根据前述方面中任一项的制备催化裂解催化剂的方法，其中，所述的第二粘土为选自高岭土、海泡石、凹凸棒石、累托石、蒙脱石、多水高岭 土、埃洛石、水滑石、膨润土以及硅藻土中的至少一种。
第28方面，根据前述方面中任一项的制备催化裂解催化剂的方法，其中，以所述催化裂解催化剂为基准，所述无机粘结剂包括以干基计3-39重量％的所述磷铝无机粘结剂和以干基计1-30重量％的所述其他无机粘结剂，所述的其他无机粘结剂选自拟薄水铝石、铝溶胶、硅铝溶胶和水玻璃中的至少一种。
第29方面，根据前述方面中任一项的制备催化裂解催化剂的方法，其中，该方法还包括：将所述喷雾干燥所得产物进行第一焙烧、洗涤和可选的干燥处理，得到所述催化裂解催化剂；其中所述第一焙烧的焙烧温度为300-650℃，焙烧时间为0.5-8h；所述干燥处理的温度为100-200℃，干燥时间为0.5-24h。
第30方面，根据前述方面中任一项的制备催化裂解催化剂的方法，该方法还包括：采用如下步骤制备所述含第一粘土的磷铝无机粘结剂：将氧化铝源、所述第一粘土与水打浆分散成固含量为5-48重量％的浆液；其中所述的氧化铝源为能被酸胶溶的氢氧化铝和/或氧化铝，相对于10-40重量份，例如15-40重量份的以Al2O3计的氧化铝源，以干基重量计的所述第一粘土的用量大于0重量份且不超过40重量份；搅拌下按照P/Al＝1-6的重量比向所述浆液中加入浓磷酸，并使所得混合浆液在50-99℃反应15-90分钟；其中所述的P/Al中P为磷酸中的以单质计的磷的重量，Al为氧化铝源中以单质计的铝的重量。
第31方面，采用前述方面中任一项的制备催化裂解助剂的方法得到的催化裂解助剂。
第32方面，采用前述方面中任一项的制备催化裂解催化剂的方法得到的催化裂解催化剂。
第33方面，一种烃油催化裂解的方法，其特征在于，该方法包括：在催化裂解条件下，使烃油与前述方面中任一项的催化裂解助剂或者与前述方面中任一项的催化裂解催化剂接触反应。
第34方面，根据前述方面中任一项的烃油催化裂解的方法，其中，该方法包括：在所述催化裂解条件下，使所述烃油与含有前述方面中任一项的催化裂解助剂和一种催化裂解催化剂的催化剂混合物接触反应；所述催化剂混合物中，所述催化裂解助剂的含量为0.1-30重量％。
第35方面，根据前述方面中任一项的烃油催化裂解的方法，其中，所述催化裂解条件包括：反应温度为500-800℃；所述烃油选自原油、石脑油、汽油、常压渣油、减压渣油、常压蜡油、减压蜡油、直流蜡油、丙烷轻/重脱油、焦化蜡油和煤液化产物中的一种或几种。
下面通过实施例对本发明作进一步说明，但并不因此而限制本发明的内容。
本发明实施例所采用的仪器和试剂，如无特别说明，均为本领域技术人员所常用的仪器和试剂。
采用微反装置评价本发明的催化裂解助剂/催化裂解催化剂在石油烃催化裂解中对低碳烯烃产率的影响。
将制备得到的催化裂解助剂样品/催化裂解催化剂样品在固定床老化装置上进行800℃、100％水汽老化17小时处理，微反装置上进行评价，原料油为VGO或石脑油，评价条件为反应温度620℃，再生温度620℃，剂油比3.2。微反活性采用ASTMD5154-2010标准方法进行测定。
本发明所述的RIPP标准方法具体可参见《石油化工分析方法》，杨翠定等编，1990年版。
实施例中所用的部分原料性质如下：
拟薄水铝石为山东铝业公司生产工业产品，固含量60重量％。
铝溶胶为中石化催化剂齐鲁分公司生产的工业产品，Al2O3含量为21.5重量％。
硅溶胶为中石化催化剂齐鲁分公司生产的工业产品，SiO2含量为28.9重量％，Na2O含量8.9％。
高岭土为苏州高岭土公司生产的催化裂解催化剂专用高岭土，固含量78重量％。
累托石为湖北钟祥名流累托石开发有限公司生产，石英砂含量＜3.5重量％，Al2O3含量为39.0重量％，Na2O含量为0.03重量％，固含量77重量％。
SB氢氧化铝粉，德国Condex公司生产，Al2O3含量为75重量％。
γ-氧化铝，德国Condex公司生产，Al2O3含量为95重量％。
盐酸，化学纯，浓度36-38重量％，北京化工厂生产。
PSRY分子筛为中石化催化剂长岭分公司生产的工业产品，Na2O含量＜1.5重量％，P2O5含量为0.8-1.2重量％，晶胞常数＜2.456nm，结晶度≥64％。
HRY-1成品分子筛为中石化催化剂长岭分公司生产的工业产品，La2O3含量为11-13重量％，晶胞常数＜2.464nm，结晶度≥40％。
平衡剂：工业FCC平衡催化剂，其是工业牌号DVR-3的FCC平衡催化剂，轻油微反活性为63，来源于中国石化燕山石化。
下列实施例说明本发明的磷改性多级孔ZSM-5分子筛和制备方法。这些分子筛被用于本发明的催化裂解助剂和本发明的催化裂解催化剂的制备中。
实施例1-1
实施例1-1说明本发明的含磷的多级孔ZSM-5分子筛和制备方法。
取18.5g磷酸氢二铵、108g氢型多级孔ZSM-5分子筛(中国石化催化剂公司齐鲁分公司提供，相对结晶度为88.6％，氧化硅/氧化铝摩尔比为20.8，Na2O含量为0.017重％，比表面积为373m2/g，总孔体积为0.256ml/g，介孔体积0.119ml/g，平均孔径为5.8nm，下同)和60g去离子水混合打成浆液后，加热到100℃并保持2小时，在110℃下烘箱中干燥后，550℃下空气焙烧2h。得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ1-1。
对比例1-1
同实施例1-1，区别在于采用浸渍法，在20℃下浸渍氢型多级孔ZSM-5分子筛。得到的含磷的多级孔ZSM-5分子筛对比样品，记为D1-1。
实施例1-2
同实施例1-1，区别在于干燥后在450℃、60％水蒸气气氛下处理0.5h，得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ1-2。
对比例1-2
同实施例1-2，区别在于采用浸渍法，在20℃下浸渍氢型多级孔ZSM-5分子筛。得到的含磷的多级孔ZSM-5分子筛对比样品，记为D1-2。
GPZ-1、D1-1、GPZ1-2和D1-2的磷分散度K列于表1。
实施例2-1
实施例2-1说明本发明的含磷的多级孔ZSM-5分子筛和制备方法。
将18.5g磷酸氢二铵、108g氢型多级孔ZSM-5分子筛和120g去离子水混合打成浆液后，在70℃下保持2小时，110℃下烘箱中干燥后，550℃下空气焙烧2h，得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ2-1。
对比例2-1
同实施例2-1，区别在于采用浸渍法，在20℃下浸渍氢型多级孔ZSM-5分子筛。得到的含磷的多级孔ZSM-5分子筛对比样品，记为D2-1。
实施例2-2
同实施例2-1，区别在于干燥后在600℃、50％水蒸气气氛下处理2h，得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ2-2。
对比例2-2
同实施例2-2，区别在于采用浸渍法，在20℃下浸渍氢型多级孔ZSM-5分子筛，记为D2-2。
GPZ2-1、D2-1、GPZ2-2和D2-2的磷分散度K列于表1。
实施例3-1
实施例3-1说明本发明的含磷的多级孔ZSM-5分子筛和制备方法。
取11.8g磷酸溶于60g去离子水中，搅拌2h，得到含磷的水溶液；取108g氢型多级孔ZSM-5分子筛；分别将上述的含磷的水溶液和上述的氢型多级孔ZSM-5分子筛加热到80℃后再混合接触4小时，在110℃下烘箱中干燥后，550℃下空气焙烧2h，得到的磷改性多级孔ZSM-5分子筛，记为GPZ3-1。
对比例3-1
同实施例3-1，区别在于采用浸渍法，用含磷的水溶液在20℃下浸渍氢型多级孔ZSM-5分子筛。得到的含磷的多级孔ZSM-5分子筛对比样品，记为D3-1。
实施例3-2
同实施例3-1，区别在于干燥后在430℃、100％水蒸气气氛下处理2h，得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ3-2。
对比例3-2
同实施例3-2，区别在于采用浸渍法，用含磷的水溶液在20℃下浸渍氢型多级孔ZSM-5分子筛。得到的含磷的多级孔ZSM-5分子筛对比样品，记为D3-2。
GPZ3-1、D3-1、GPZ3-2和D3-2的磷分散度K列于表1。
实施例4-1
实施例4-1说明本发明的含磷的多级孔ZSM-5分子筛和制备方法。
9.3g磷酸氢二铵、108g氢型多级孔ZSM-5分子筛和120g去离子水混合打成浆液后，在90℃下保持2小时，在110℃下烘箱中干燥后，550℃下空气焙烧2h，得到的含磷的多级孔ZSM-5分子筛，记为GPZ4-1。
对比例4-1
同实施例4-1，区别在于采用浸渍法，在20℃下浸渍氢型多级孔ZSM-5分子筛。得到的含磷的多级孔ZSM-5分子筛对比样品，记为D4-1。
实施例4-2
同实施例4-1，区别在于干燥后在350℃、100％水蒸气气氛下处理2h，得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ4-2。
对比例4-2
同实施例4-2，区别在于采用浸渍法，在20℃下浸渍氢型多级孔ZSM-5分子筛。得到的含磷的多级孔ZSM-5分子筛对比样品，记为D4-2。
GPZ4-1、D4-1、GPZ4-2和D4-2的磷分散度K列于表1。
实施例5-1
实施例5-1说明本发明的含磷的多级孔ZSM-5分子筛和制备方法。
取9.7g磷酸三甲酯、108g氢型多级孔ZSM-5分子筛和80g去离子水中混合打成浆液后加热到120℃保持8小时，在110℃下烘箱中干燥后，550℃下空气焙烧2h，得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ5-1。
对比例5-1
同实施例5-1，区别在于采用浸渍法，在20℃下浸渍氢型多级孔ZSM-5分子筛。得到的含磷的多级孔ZSM-5分子筛对比样品，记为D5-1。
实施例5-2
同实施例5-1，区别在于干燥后500℃、40％水蒸气气氛下焙烧处理4h，得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ5-2。
对比例5-2
同实施例5-2，区别在于采用浸渍法，在20℃下浸渍氢型多级孔ZSM-5分子筛。得到的含磷的多级孔ZSM-5分子筛对比样品，记为D5-2。
GPZ5-1、D5-1、GPZ5-2和D5-2的磷分散度K列于表1。
实施例6-1
实施例6-1说明本发明的含磷的多级孔ZSM-5分子筛和制备方法。
将13.2g磷酸硼、108g氢型多级孔ZSM-5分子筛和100g去离子水混合打成浆液后，在150℃下保持2小时，110℃下烘箱中干燥后，550℃下空气焙烧2h，得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ6-1。
对比例6-1
同实施例6-1，区别在于采用浸渍法，在20℃下浸渍氢型多级孔ZSM-5分子筛。得到的含磷的多级孔ZSM-5分子筛对比样品，记为D6-1。
实施例6-2
同实施例6-1，区别在于干燥后在350℃、60％水蒸气气氛下水热焙烧处理4h，得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ6-2。
对比例6-2
同实施例6-2，区别在于采用浸渍法，在20℃下浸渍氢型多级孔ZSM-5分子筛。得到的含磷的多级孔ZSM-5分子筛对比样品，记为D6-2。
GPZ6-1、D6-1、GPZ6-2和D6-2的磷分散度K列于表1。
实施例7-1
实施例7-1说明本发明的含磷的多级孔ZSM-5分子筛和制备方法。
取16.3g三苯基磷溶于80g去离子水中，搅拌2h，得到含磷的水溶液；取108g氢型多级孔ZSM-5分子筛；分别将上述的含磷的水溶液和上述的氢型多级孔ZSM-5分子筛加热到80℃后再混合接触4小时，在110℃下烘箱中干燥后，550℃下空气焙烧2h，得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ7-1。
对比例7-1
同实施例7-1，区别在于采用浸渍法，用含磷的水溶液在20℃下浸渍氢型多级孔ZSM-5分子筛。得到的含磷的多级孔ZSM-5分子筛对比样品，记为D7-1。
实施例7-2
同实施例7-1，区别在于干燥后在600℃、50％水蒸气气氛下焙烧处理2h，得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ7-2。
对比例7-2
同实施例7-2，区别在于采用浸渍法，用含磷的水溶液在20℃下浸渍氢型多级孔ZSM-5分子筛。得到的含磷的多级孔ZSM-5分子筛对比样品，记为D7-2。
GPZ7-1、D7-1、GPZ7-2和D7-2的磷分散度K列于表1。
实施例8-1
同实施例4-1，区别在于磷源为磷酸氢二铵和结晶磷酸硼，二者重量比例为3∶1。得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ8-1。
实施例8-2
同实施例4-2，区别在于磷源为磷酸氢二铵和结晶磷酸硼，二者重量比例为3∶1。得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ8-2。
实施例9-1
同实施例4-1，区别在于磷源为磷酸氢二铵和结晶磷酸硼，二者重量比例为2∶2。得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ9-1。
实施例9-2
同实施例4-2，区别在于磷源为磷酸氢二铵和结晶磷酸硼，二者重量比例为2∶2。得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ9-2。
实施例10-1
同实施例4-1，区别在于磷源为磷酸氢二铵和结晶磷酸硼，二者重量比例为1∶3。得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ10-1。
实施例10-2
同实施例4-2，区别在于磷源为磷酸氢二铵和结晶磷酸硼，二者重量比例为1∶3。得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ10-2。
GPZ8-1、GPZ8-2、GPZ9-1、GPZ9-2、GPZ10-1、GPZ10-2的磷分散度K列于表1。
实施例11-1
同实施例8-1，区别在于磷源为磷酸和结晶磷酸硼，二者重量比例为3∶1。得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ11-2。
实施例11-2
同实施例8-2，区别在于磷源为磷酸和结晶磷酸硼，二者重量比例为3∶1。得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ11-2。
实施例12-1
同实施例9-1，区别在于磷源为磷酸和结晶磷酸硼，二者重量比例为2∶2。得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ12-1。
实施例12-2
同实施例9-2，区别在于磷源为磷酸和结晶磷酸硼，二者重量比例为2∶2(与实施例9-1比例值相同或附近)。得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ12-2。
实施例13-1
同实施例10-1，区别在于磷源为磷酸和结晶磷酸硼，二者重量比例为1∶3。得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ13-2。
实施例13-2
同实施例10-2，区别在于磷源为磷酸和结晶磷酸硼，二者重量比例为1∶3。得到的含磷的多级孔ZSM-5分子筛样品，记为GPZ13-2。
GPZ11-1、GPZ11-2、GPZ12-1、GPZ12-2、GPZ13-1、GPZ13-2的磷分散度K列于表1。
从表1的数据可以看出，本发明的磷改性多级孔ZSM-5分子筛中，磷均具有更高的分散度，例如实施例8-2的采用磷酸和结晶磷酸硼的双磷源改性的样品GPZ8-2达到的分散度K值为85％。
下列实施例说明本发明的磷改性的微孔ZSM-5分子筛和制备方法。这些分子筛被用于本发明的催化裂解助剂和本发明的催化裂解催化剂的制备中。
实施例14-1
实施例14-1说明本发明的含磷的微孔ZSM-5分子筛和方法。
取16.2g磷酸氢二铵、113g HZSM-5分子筛(中国石化催化剂公司齐鲁分公司提供，相对结晶度为91.1％，氧化硅/氧化铝摩尔比为24.1，Na2O含量为0.039重％，比表面积为353m2/g，总孔体积为0.177ml/g，下同)和60g去离子水混合打浆加热到100℃后保持2小时，110℃干燥、550℃空气气氛下处理0.5h。得到的磷改性ZSM-5分子筛样品，记为GPZ14-1。
对比例14-1
对比例14-1说明现有工业常规的方法和得到的磷改性ZSM-5对比样品。
同实施例14-1，区别在于采用浸渍法，在20℃下浸渍HZSM-5分子筛2小时。得到的磷改性ZSM-5分子筛对比样品，记为D14-1。
实施例14-2
实施例14-2说明本发明的含磷的微孔ZSM-5分子筛和方法。
同实施例14-1，区别在于550℃空气气氛改为500℃、50％水蒸气气氛下处理0.5h。得到的磷改性ZSM-5分子筛样品，记为GPZ14-2。
对比例14-2
同实施例14-2，区别在于采用浸渍法，在20℃下浸渍氢型多级孔ZSM-5分子筛2小时。得到磷改性ZSM-5分子筛对比样品，记为D14-2。
GPZ14-1、D14-1、GPZ14-2和D14-2的磷分散度K列于表1。
实施例15-1
实施例15-1说明本发明的含磷的微孔ZSM-5分子筛和方法。
将16.2g磷酸氢二铵、113g HZSM-5分子筛和120g去离子水混合打成浆液后，在70℃下保持2小时，110℃干燥、550℃空气气氛下处理2h，得到的磷改性ZSM-5分子筛样品，记为GPZ15-1。
对比例15-1
对比例15-1说明现有工业常规的方法和得到的磷改性ZSM-5对比样品。
同实施例15-1，区别在于采用浸渍法，在20℃下浸渍HZSM-5分子筛。得到的磷改性ZSM-5分子筛对比样品，记为D15-1。
实施例15-2
实施例15-2说明本发明的含磷的微孔ZSM-5分子筛和方法。
同实施例15-1，区别在于550℃空气气氛改为600℃、30％水蒸气气氛下处理2h。得到的磷改性ZSM-5分子筛样品，记为GPZ15-2。
对比例15-2
同实施例15-2，区别在于采用浸渍法，在20℃下浸渍HZSM-5分子筛。得到磷改性ZSM-5分子筛对比样品，记为D15-2。
GPZ15-1、D15-1、GPZ15-2和D15-2的磷分散度K列于表1。
实施例16-1
实施例16-1说明本发明的含磷的微孔ZSM-5分子筛和方法。
取10.4g磷酸溶于60g去离子水中，搅拌2h，得到含磷的水溶液；取113g HZSM-5分子筛；分别将上述的含磷的水溶液和上述的HZSM-5分子筛加热到80℃后再混合接触4小时，110℃干燥、550℃空气气氛下处理2h，得到的磷改性ZSM-5分子筛样品，记为GPZ16-1。
对比例16-1
对比例16-1说明现有工业常规的方法和得到的磷改性ZSM-5对比样品。
同实施例16-1，区别在于采用浸渍法，用含磷的水溶液在20℃下浸渍HZSM-5分子筛。得到的磷改性ZSM-5分子筛对比样品，记为D16-1。
实施例16-2
实施例16-2说明本发明的含磷的微孔ZSM-5分子筛和方法。
同实施例16-1，区别在于550℃空气气氛改为400℃、100％水蒸气气氛下处理2h。得到的磷改性ZSM-5分子筛样品，记为GPZ16-2。
对比例16-2
同实施例16-2，区别在于采用浸渍法，用含磷的水溶液在20℃下浸渍HZSM-5分子筛。得到磷改性ZSM-5分子筛对比样品，记为D16-2。
GPZ16-1、D16-1、GPZ16-2和D15-2的磷分散度K列于表1。
实施例17-1
实施例17-1说明本发明的含磷的微孔ZSM-5分子筛和方法。
将8.1g磷酸氢二铵、113g HZSM-5分子筛和120g去离子水混合打成浆液后，在90℃下保持4小时，110℃干燥、550℃空气气氛下处理2h，得到的磷改性ZSM-5分子筛样品，记为GPZ17-1。
对比例17-1
对比例17-1说明现有工业常规的方法和得到的磷改性ZSM-5对比样品。
同实施例17-1，区别在于采用浸渍法，在20℃下浸渍HZSM-5分子筛。得到的磷改性ZSM-5分子筛对比样品，记为D17-1。
实施例17-2
同实施例17-1，区别在于550℃空气气氛改为300℃、100％水蒸气气氛下处理2h。得到的磷改性ZSM-5分子筛样品，记为GPZ17-2。
对比例17-2
同实施例17-2，区别在于采用浸渍法，在20℃下浸渍HZSM-5分子筛。得到磷改性ZSM-5分子筛对比样品，记为D17-2。
GPZ17-1、D17-1、GPZ17-2和D17-2的磷分散度K列于表1。
实施例18-1
取8.5g磷酸三甲酯、113g HZSM-5分子筛和80g去离子水混合打浆后加热到120℃保持8小时，110℃干燥、550℃空气气氛下处理2h，得到的磷改性ZSM-5分子筛样品，记为GPZ18-1。
对比例18-1
对比例18-1说明现有工业常规的方法和得到的磷改性ZSM-5对比样品。
同实施例18-1，区别在于采用浸渍法，在20℃下浸渍HZSM-5分子筛。得到的磷改性ZSM-5分子筛对比样品，记为D18-1。
实施例18-2
实施例18-2说明本发明的含磷的微孔ZSM-5分子筛和方法。
同实施例18-1，区别在于550℃空气气氛改为500℃、80％水蒸气气氛下处理4h。得到的磷改性ZSM-5分子筛样品，记为GPZ18-2。
对比例18-2
同实施例18-2，区别在于采用浸渍法，在20℃下浸渍HZSM-5分子筛。得到磷改性ZSM-5分子筛对比样品，记为D18-2。
GPZ18-1、D18-1、GPZ18-2和D18-2的磷分散度K列于表1。
实施例19-1
实施例19-1说明本发明的含磷的微孔ZSM-5分子筛和方法。
11.6g磷酸硼、113g HZSM-5分子筛和100g去离子水混合打成浆液后，在150℃下保持2小时，110℃干燥、550℃空气气氛下处理2h，得到的磷改性ZSM-5分子筛样品，记为GPZ19-1。
对比例19-1
对比例19-1说明现有工业常规的方法和得到的磷改性ZSM-5对比样品。
同实施例19-1，区别在于采用浸渍法，在20℃下浸渍HZSM-5分子筛。得到的磷改性ZSM-5分子筛对比样品，记为D19-1。
实施例19-2
实施例19-2说明本发明的含磷的微孔ZSM-5分子筛和方法。
同实施例19-1，区别在于550℃空气气氛改为400℃、100％水蒸气气氛下处理4h。得到的磷改性ZSM-5分子筛样品，记为GPZ19-2。
对比例19-2
同实施例19-2，区别在于采用浸渍法，在20℃下浸渍HZSM-5分子筛。得到磷改性ZSM-5分子筛对比样品，记为D19-2。
GPZ19-1、D19-1、GPZ19-2和D19-2的磷分散度K列于表1。
实施例20-1
实施例20-1说明本发明的含磷的微孔ZSM-5分子筛和方法。
取14.2g三苯基磷溶于80g去离子水中，搅拌2h，得到含磷的水溶液；取113g HZSM-5分子筛；分别将上述的含磷的水溶液和上述的HZSM-5分子筛加热到80℃后再混合接触4小时，110℃干燥、550℃空气气氛下处理2h，得到的磷改性ZSM-5分子筛样品，记为GPZ20-1。
对比例20-1
对比例20-1说明现有工业常规的方法和得到的磷改性ZSM-5对比样品。
同实施例20-1，区别在于采用浸渍法，用含磷的水溶液在20℃下浸渍HZSM-5分子筛。得到的磷改性ZSM-5分子筛对比样品，记为D20-1。
实施例20-2
实施例20-2说明本发明的含磷的微孔ZSM-5分子筛和方法。
同实施例20-1，区别在于550℃空气气氛改为600℃、30％水蒸气气氛下处理4h。得到的磷改性ZSM-5分子筛样品，记为GPZ20-2。
对比例20-2
同实施例20-2，区别在于采用浸渍法，用含磷的水溶液在20℃下浸渍HZSM-5分子筛。得到磷改性ZSM-5分子筛对比样品，记为D20-2。
GPZ20-1、D20-1、GPZ20-2和D20-2的磷分散度K列于表1。
实施例21-1
同实施例17-1，区别在于磷源为磷酸氢二铵和结晶磷酸硼，二者重量比例为3∶1。得到的含磷的ZSM-5分子筛样品，记为GPZ21-1。
实施例21-2
同实施例17-2，区别在于磷源为磷酸氢二铵和结晶磷酸硼，二者重量比例为3∶1。得到的含磷的ZSM-5分子筛样品，记为GPZ21-2。
实施例22-1
同实施例17-1，区别在于例如的双磷源为磷酸氢二铵和结晶磷酸硼，二者重量比例为2∶2。得到的含磷的ZSM-5分子筛样品，记为GPZ22-1。
实施例22-2
同实施例17-2，区别在于磷源为磷酸氢二铵和结晶磷酸硼，二者重量比例为2∶2。得到的含磷的ZSM-5分子筛样品，记为GPZ23-2。
实施例23-1
同实施例17-1，区别在于磷源为磷酸氢二铵和结晶磷酸硼，二者重量比例为1∶3。得到的含磷的ZSM-5分子筛样品，记为GPZ23-1。
实施例23-2
同实施例17-2，区别在于磷源为磷酸氢二铵和结晶磷酸硼，二者重量比例为1∶3。得到的含磷的ZSM-5分子筛样品，记为GPZ23-2。
GPZ21-1、GPZ21-2、GPZ22-1、GPZ22-2、GPZ23-1、GPZ23-2的磷分散度K列于表1。
实施例24-1至实施例26-2
将实施例21-1至实施例23-2按顺序将其中的磷源分别更换为磷酸和结晶磷酸硼，二者的比例分别为3∶1、3∶1、2∶2、2∶2、1∶3、1∶3，得到的样品分别为GPZ24-1、GPZ24-2、GPZ25-1、GPZ25-2、GPZ26-1、GPZ26-2的磷分散度K列于表1。
从表1的数据可以看出，本发明的磷改性ZSM-5分子筛中，磷均具有更高的分散度，尤其实施例24-2的采用磷酸氢二铵和结晶磷酸硼的双磷源改性的样品达到的分散度K值为80％，最高提高18个百分点。
表1
样品   分散度K 样品   分散度K
实施例1-1 GPZ1-1 0.76 对比例1-1 D1-1 0.63
实施例1-2 GPZ1-2 0.78 对比例1-2 D1-2 0.69
实施例2-1 GPZ2-1 0.75 对比例2-1 D2-1 0.62
实施例2-2 GPZ2-2 0.76 对比例2-2 D2-2 0.66
实施例3-1 GPZ3-1 0.78 对比例3-1 D3-1 0.6
实施例3-2 GPZ3-2 0.77 对比例3-2 D3-2 0.64
实施例4-1 GPZ4-1 0.77 对比例4-1 D4-1 0.64
实施例4-2 GPZ4-2 0.8 对比例4-2 D4-2 0.67
实施例5-1 GPZ5-1 0.7 对比例5-1 D5-1 0.63
实施例5-2 GPZ5-2 0.72 对比例5-2 D5-2 0.64
实施例6-1 GPZ6-1 0.76 对比例6-1 D6-1 0.68
实施例6-2 GPZ6-2 0.79 对比例6-2 D6-2 0.69
实施例7-1 GPZ7-1 0.73 对比例7-1 D7-1 0.64
实施例7-2 GPZ7-2 0.75 对比例7-2 D7-2 0.67
实施例8-1 GPZ8-1 0.75      
实施例8-2 GPZ8-2 0.85      
实施例9-1 GPZ9-1 0.73      
实施例9-2 GPZ9-2 0.82      
实施例10-1 GPZ10-1 0.72      
实施例10-2 GPZ10-2 0.81      
实施例11-1 GPZ11-1 0.77      
实施例11-2 GPZ11-2 0.84      
实施例12-1 GPZ12-1 0.74      
实施例12-2 GPZ12-2 0.82      
实施例13-1 GPZ13-1 0.72      
实施例13-2 GPZ13-2 0.8      
样品   分散度K 样品   分散度K
实施例14-1 GPZ14-1 0.71 对比例14-1 D14-1 0.62
实施例14-2 GPZ14-2 0.73 对比例14-2 D14-2 0.65
实施例15-1 GPZ15-1 0.7 对比例15-1 D15-1 0.62
实施例15-2 GPZ15-2 0.71 对比例15-2 D15-2 0.68
实施例16-1 GPZ15-1 0.7 对比例16-1 D16-1 0.63
实施例16-2 GPZ16-2 0.71 对比例16-2 D16-2 0.65
实施例17-1 GPZ17-1 0.72 对比例17-1 D17-1 0.67
实施例17-2 GPZ17-2 0.73 对比例17-2 D17-2 0.68
实施例18-1 GPZ18-1 0.7 对比例18-1 D18-1 0.64
实施例18-2 GPZ18-2 0.72 对比例18-2 D18-2 0.67
实施例19-1 GPZ19-1 0.75 对比例19-1 D19-1 0.69
实施例19-2 GPZ19-2 0.72 对比例19-2 D19-2 0.68
实施例20-1 GPZ20-1 0.74 对比例20-1 D20-1 0.65
实施例20-2 GPZ20-2 0.75 对比例20-2 D20-2 0.67
实施例21-1 GPZ21-1 0.74      
实施例21-2 GPZ21-2 0.8      
实施例22-1 GPZ22-1 0.72      
实施例22-2 GPZ22-2 0.78      
实施例23-1 GPZ23-1 0.7      
实施例23-2 GPZ23-2 0.78      
实施例24-1 GPZ24-1 0.73      
实施例24-2 GPZ24-2 0.8      
实施例25-1 GPZ25-1 0.71      
实施例25-2 GPZ25-2 0.75      
实施例26-1 GPZ26-1 0.7      
实施例26-2 GPZ26-2 0.74      
微反评价
微反评价条件：分子筛装量2g，原料油为正十四烷，进油量为1.56g，反应温度为550℃，再生温度为600℃(下同)。
GPZ-1、D1-1、GPZ1-2和D1-2；GPZ2-1、D2-1、GPZ2-2和D2-2；GPZ3-1、D3-1、GPZ3-2和D3-2；GPZ4-1、D4-1、GPZ4-2和D4-2；GPZ5-1、D5-1、GPZ5-2和D5-2；GPZ6-1、D6-1、GPZ6-2和D6-2；GPZ7-1、D7-1、GPZ7-2和D7-2；GPZ8-1、GPZ8-2、GPZ9-1、GPZ9-2、GPZ10-1、GPZ10-2、GPZ11-1、GPZ11-2、GPZ12-1、GPZ12-2、GPZ13-1、和GPZ13-2；GPZ14-1、D14-1、GPZ14-2和D14-2；GPZ15-1、D15-1、GPZ15-2和D15-2；GPZ16-1、D16-1、GPZ16-2和D16-2；GPZ17-1、D17-1、GPZ17-2和D17-2；GPZ18-1、D18-1、GPZ18-2和D18-2；GPZ19-1、D19-1、GPZ19-2和D19-2；GPZ20-1、D20-1、GPZ20-2和D20-2；GPZ21-1、GPZ21-2、GPZ22-1、GPZ22-2、GPZ23-1、GPZ23-2、GPZ24-1、GPZ24-2、GPZ25-1、GPZ25-2、GPZ26-1、和GPZ26-2经800℃、100％水蒸气、17h水热老化处理后，进行正十四烷烃裂解评价。评价数据见表2。
Figure PCTCN2021086824-appb-000001
Figure PCTCN2021086824-appb-000002
经800℃、100％水蒸气、17h水热老化处理后实施例样品表现出具有较优异的正十四烷催化裂解活性，转化率、液化气收率、三烯收率均有提升。说明本发明的磷改性MFI结构分子筛在增加低碳烯烃收率的同时具有较高的液化气收率。
实施例27-30说明本发明的催化裂解助剂/催化剂中采用的磷铝无机粘结剂。
实施例27
将1.91千克拟薄水铝石(含Al2O3，1.19千克)、0.56千克高岭土(干基0.5千克)与3.27千克脱阳离子水打浆30分钟，搅拌下往浆液中加入5.37千克浓磷酸(质量浓度85％)，磷酸加入速度为0.04千克磷酸/分钟/千克氧化铝源，升温至70℃，然后在此温度下反应45分钟，即制得磷铝无机粘结剂。物料配比见表3，样品编号Binder 1。
实施例28-30
按实施例27的方法制备磷铝无机粘结剂，物料配比见表3，样品编号Binder 2、Binder 3、Binder 4。
表3
实施例 实施例27 实施例28 实施例29 实施例30
粘结剂编号 Binder 1 Binder 2 Binder 3 Binder 4
拟薄水铝石，kg 1.91     1.6
Al2O3，kg 1.19     1
SB氢氧化铝粉，kg   0.94    
Al2O3，kg   0.7    
γ-氧化铝，kg     0.58  
Al2O3，kg     0.58  
累托石，kg   1.28 1.93  
干基，kg   1 1.5  
高岭土，kg 0.56      
干基，kg 0.5      
磷酸，kg 5.37 5.36 4.03 6.5
P2O5，kg 3.31 3.3 2.92 4
脱阳离子水，kg 3.27 6.71 20.18 4.4
总量，kg 11.11 14.29 25 12.5
总干基，kg 5 5 5 5
粘结剂固含量，kg/kg 0.45 0.35 0.2 0.4
P/Al 2.29 3.89 4.19 3.3
Al2O3，重量％ 23.82 14 11.53 20
P2O5，重量％ 66.18 66 58.47 80
第一粘土，重量％ 10 20 30 0
pH 2.2 2.37 1.78 2.46
Figure PCTCN2021086824-appb-000003
实施例31至实施例56提供本发明的催化裂解助剂，对比例31至对比例56说明作为对比的催化裂解助剂。其中，实施例31至实施例43为多级孔ZSM-5分子筛，实施例44至实施例56为微孔ZSM-5分子筛。
实施例31-1
取实施例1-1制备的磷改性分子筛GPZ1-1、高岭土和拟薄水铝石，加入脱阳离子水以及铝溶胶打浆120分钟，得到固含量30重量％的浆液，加入盐酸调节浆液pH值3.0，然后继续打浆45分钟，然后加入实施例27制备的磷铝无机粘结剂Binder 1，搅拌30分钟后，将得到的浆液喷雾干燥，得到微球，将微球于500℃下焙烧1小时，制得催化裂解助剂样品，编号CAZ1-1，其配比为分子筛50％、高岭土23％、Binder 1为18％、拟薄水铝石(以Al2O3计)5％、铝溶胶(以Al2O3计)4％。
采用固定床微反装置对100％平衡剂以及平衡剂掺入CAZ1-1进行反应性能评价，以说明本公开提供的催化裂解助剂的催化裂解反应效果。
将助剂CAZ1-1在800℃下、100％水蒸气气氛条件下进行17小时的老化处理。取经老化处理的CAZ1-1与工业FCC平衡催化剂(工业牌号DVR-3的FCC平衡催化剂，轻油微反活性为63)混合。将平衡剂和助剂的混合物装入固定床微反反应器中，对表4所示原料油进行催化裂解，评价条件为反应温度620℃，再生温度620℃，剂油比3.2。表6给出反应结果，其中包括了空白测试剂。
实施例31-2
同实施例31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例1-2制备的磷改性分子筛GPZ1-2替代。制得催化裂解助剂样品，编号CAZ1-2。评价同实施例31-1，结果见表6。
对比例31-1
同实施例12-1，区别在于其中的磷改性分子筛GPZ1-1用对比例1-1的对比样品D1-1替代。制得催化裂解助剂对比样品，编号DCAZ1-1。评价同实施例31-1，结果见表6。
对比例31-2
同实施例31-1，区别在于其中的磷改性分子筛GPZ1-1用对比例1-2的对比样品D1-2替代。制得催化裂解助剂对比样品，编号DCAZ1-2。评价同实施例31-1，结果见表6。
实施例32-1
同实施例31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例2-1制备的磷改性分子筛GPZ2-1替代。制得催化裂解助剂样品，编号CAZ2-1。评价同实施例31-1，结果见表6。
实施例32-2
同实施例32-1，区别在于其中的磷改性分子筛GPZ2-1用实施例2-2制备的磷改性分子筛GPZ2-2替代。制得催化裂解助剂样品，编号CAZ2-2。评价同实施例31-1，结果见表6。
对比例32-1
同实施例32-1，区别在于其中的磷改性分子筛GPZ2-1用对比例2-1的对比样品D2-1替代。制得催化裂解助剂对比样品，编号DCAZ2-1。评价同实施例31-1，结果见表6。
对比例32-2
同实施例32-1，区别在于其中的磷改性分子筛GPZ2-1用对比例2-2的对比样品D2-2替代。制得催化裂解助剂对比样品，编号DCAZ2-2。评价同实施例31-1，结果见表6。
实施例33-1
同实施例31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例3-1制备的磷改性分子筛GPZ3-1替代。制得催化裂解助剂样品，编号CAZ3-1。评价同实施例31-1，结果见表6。
实施例33-2
同实施例31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例3-2制备的磷改性分子筛GPZ3-2替代。制得催化裂解助剂样品，编号CAZ3-2。评价同实施例31-1，结果见表6。
对比例33-1
同实施例31-1，区别在于其中的磷改性分子筛GPZ1-1用对比例3-1的对比样品D3-1替代。制得催化裂解助剂对比样品，编号DCAZ3-1。评价同实施例31-1，结果见表6。
对比例33-2
同实施例31-1，区别在于其中的磷改性分子筛GPZ1-1用对比例3-2的对比样品D3-2替代。制得催化裂解助剂对比样品，编号DCAZ3-2。评价同实施例31-1，结果见表6。
实施例34-1
同实施例31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例4-1制备的磷改性分子筛GPZ4-1替代。制得催化裂解助剂样品，编号CAZ4-1。评价同实施例31-1，结果见表6。
实施例34-2
同实施例34-1，区别在于其中的磷改性分子筛GPZ4-1用实施例4-2制备的磷改性分子筛GPZ4-2替代。制得催化裂解助剂样品，编号CAZ4-2。评价同实施例31-1，结果见表6。
对比例34-1
同实施例34-1，区别在于其中的磷改性分子筛GPZ4-1用对比例4-1的对比样品D4-1替代。制得催化裂解助剂对比样品，编号DCAZ4-1。评价同实施例31-1，结果见表6。
对比例34-2
同实施例34-1，区别在于其中的磷改性分子筛GPZ4-1用对比例2-2的对比样品D4-2替代。制得催化裂解助剂对比样品，编号DCAZ4-2。评价同实施例31-1，结果见表6。
实施例35-1
同实施例31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例5-1制备的磷改性分子筛GPZ5-1替代。制得催化裂解助剂样品，编号CAZ5-1。评价同实施例31-1，结果见表6。
实施例35-2
同实施例35-1，区别在于其中的磷改性分子筛GPZ5-1用实施例5-2制备的磷改性分子筛GPZ5-2替代。制得催化裂解助剂样品，编号CAZ5-2。评价同实施例35-1，结果见表6。
对比例35-1
同实施例35-1，区别在于其中的磷改性分子筛GPZ5-1用对比例5-1的对比样品D5-1替代。制得催化裂解助剂对比样品，编号DCAZ5-1。评价同实施例35-1，结果见表6。
对比例35-2
同实施例35-1，区别在于其中的磷改性分子筛GPZ5-1用对比例2-2的对比样品D5-2替代。制得催化裂解助剂对比样品，编号DCAZ5-2。评价同实施例35-1，结果见表6。
实施例36-1
同实施例31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例6-1制备的磷改性分子筛GPZ6-1替代。制得催化裂解助剂样品，编号CAZ6-1。评价同实施例31-1，结果见表6。
实施例36-2
同实施例36-1，区别在于其中的磷改性分子筛GPZ6-1用实施例6-2制备的磷改性分子筛GPZ6-2替代。制得催化裂解助剂样品，编号CAZ6-2。评价同实施例36-1，结果见表6。
对比例36-1
同实施例36-1，区别在于其中的磷改性分子筛GPZ6-1用对比例6-1的对比样品D6-1替代。制得催化裂解助剂对比样品，编号DCAZ6-1。评价同实施例36-1，结果见表6。
对比例36-2
同实施例36-1，区别在于其中的磷改性分子筛GPZ6-1用对比例6-2的对比样品D6-2替代。制得催化裂解助剂对比样品，编号DCAZ6-2。评价同实施例36-1，结果见表6。
实施例37-1
同实施例31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例7-1制备的磷改性分子筛GPZ7-1替代。制得催化裂解助剂样品，编号CAZ7-1。评价同实施例31-1，结果见表6。
实施例37-2
同实施例37-1，区别在于其中的磷改性分子筛GPZ7-1用实施例7-2制备的磷改性分子筛GPZ7-2替代。制得催化裂解助剂样品，编号CAZ7-2。评价同实施例31-1，结果见表6。
对比例37-1
同实施例37-1，区别在于其中的磷改性分子筛GPZ7-1用对比例7-1的对比样品D7-1替代。制得催化裂解助剂对比样品，编号DCAZ7-1。评价同实施例31-1，结果见表6。
对比例37-2
同实施例37-1，区别在于其中的磷改性分子筛GPZ7-1用对比例7-2的对比样品D7-2替代。制得催化裂解助剂对比样品，编号DCAZ7-2。评价同实施例31-1，结果见表6。
实施例38至实施例43
同实施例31-1，区别在于其中的磷改性分子筛GPZ1-1分别用实施例8-1至实施例13-2制备的磷改性分子筛GPZ8-1至GPZ13-2替代。制得催化裂解助剂样品，依次编号CAZ8-1至CAZ13-2。评价同实施例31-1，结果分别见表6。
实施例44至实施例56
实施例44至实施例56为依次分别含微孔ZSM-5(GPZ14至GPZ26)的助剂CAZ14至CAZ26，物料配比分别对应实施例31至实施例43，例如，实施例44-1中，GPZ1-1用GPZ14-1替代，实施例44-2中，GPZ1-2用GPZ14-2替代，等等，直至实施例56-1中，GPZ14-1用GPZ26-1替代，实施例56-2中，GPZ14-2用GPZ26-2替代。评价同实施例31-1，结果分别见表6。
对比例44至对比例50
对比例44至对比例50为依次分别含微孔ZSM-5(D14至D20)的对比助剂DCAZ-14至DCAZ-20，物料配比分别对应实施例44至实施例50，例如，对比例44-1中，GPZ1-1用D14-1替代，对比例44-2中，GPZ1-2用D14-2替代，等等，直至对比例50-1中，GPZ14-1用D20-1替代，对比例50-2中，GPZ14-2用D20-2替代。评价同实施例31-1，结果分别见表6。
实施例57至实施例62
同实施例31-1，区别在于其中的磷改性分子筛GPZ1-1顺序分别用实施例21-1至实施例26-2制备的磷改性分子筛GPZ21-1至GPZ26-2替代。制得催化裂解助剂样品，依次编号CAZ27-1至CAZ32-2。评价同实施例31-1，结果分别见表6。
实施例63-1
同实施例31-1，区别在于磷铝无机粘结剂以实施例28制备的Binder 2替代。制得催化裂解助剂，编号CAZ33-1。评价同实施例31-1，结果见表6。
实施例63-2
同实施例31-2，区别在于磷铝无机粘结剂以实施例28制备的Binder 2替代。制得催化裂解助剂，编号CAZ33-2。评价同实施例31-1，结果见表6。
实施例64-1
同实施例31-1，区别在于磷铝无机粘结剂以实施例29制备的Binder 3替代。制得催化裂解助剂，编号CAZ34-1。评价同实施例31-1，结果见表6。
实施例64-2
同实施例31-2，区别在于磷铝无机粘结剂以实施例29制备的Binder 3替代。制得催化裂解助剂，编号CAZ34-2。评价同实施例31-1，结果见表6。
实施例65-1
同实施例31-1，区别在于磷铝无机粘结剂以实施例30制备的Binder 4替代。制得催化裂解助剂，编号CAZ35-1。评价同实施例31-1，结果见表6。
实施例65-2
同实施例31-2，区别在于磷铝无机粘结剂以实施例30制备的Binder 4替代。制得催化裂解助剂，编号CAZ35-2。评价同实施例31-1，结果见表6。
实施例66-1
同实施例31-1，区别在于使用磷改性ZSM-5分子筛样品GPZ1-1(45重量％)、高岭土(18重量％)、磷铝无机粘结剂Binder 3(22重量％)，拟薄水铝石(10重量％)、铝溶胶(5重量％)制得催化裂解助剂，编号CAZ36-1。评价同实施例31-1，结果见表6。
实施例66-2
同实施例66-1，区别在于GPZ1-1用GPZ1-2替代。制得催化裂解助剂，编号CAZ36-2。评价同实施例31-1，结果见表6。
对比例66-1
同实施例66-1，区别在于GPZ1-1用D1-1替代。制得催化裂解助剂对比样品，编号DCAZ36-1。评价同实施例31-1，结果见表6。
对比例66-2
同实施例66-1，区别在于GPZ1-1用D1-2替代。制得催化裂解助剂对比样品，编号DCAZ36-2。评价同实施例31-1，结果见表6。
实施例67-1
同实施例44-1，区别在于使用磷改性ZSM-5分子筛样品GPZ14-1(40重量％)、高岭土(24重量％)、磷铝无机粘结剂Binder 4(20重量％)，拟薄水铝石(6重量％)、硅溶胶(10重量％)制得催化裂解助剂，编号CAZ37-1。评价同实施例31-1，结果见表6。
实施例67-2
同实施例67-1，区别在于GPZ14-1用GPZ14-2替代。制得催化裂解助剂，编号CAZ37-2。评价同实施例31-1，结果见表6。
对比例67-1
同实施例67-1，区别在于GPZ14-1用D14-1替代。制得催化裂解助剂对比样品，编号DCAZ37-1。评价同实施例31-1，结果见表6。
对比例67-2
同实施例67-1，区别在于GPZ14-1用D14-2替代。制得催化裂解助剂对比样品，编号DCAZ37-2。评价同实施例31-1，结果见表6。
实施例68-1
将粘结剂铝溶胶与高岭土混合，并用脱阳离子水将其制成固含量为30重量％的浆液，搅拌均匀，用盐酸将浆液pH值调至2.8，于55℃下静置老化1小时后加入实施例1-1制备的磷改性分子筛GPZ1-1，形成浆液(固含量为35％重量)，继续搅拌后喷雾干燥制成微球。然后将微球在500℃下焙烧1小时，再在60℃下用硫酸铵洗涤(其中，硫酸铵∶微球∶水＝0.5∶1∶10)至氧化钠含量小于0.25重量％，接着用去离子水淋洗并过滤，之后再于110℃下烘干，得到助剂CAZ38-1。其配比为分子筛为50％、高岭土为23％、铝溶胶(以Al2O3计)为27％。评价同实施例31-1，结果见表6。
实施例68-2
同实施例68-1，区别在于其中的磷改性分子筛GPZ1-1用实施例1-2制备的磷改性分子筛GPZ1-2替代。制得催化裂解助剂样品，编号CAZ38-2。评价同实施例31-1，结果见表6。
对比例68-1
同实施例68-1，区别在于其中的磷改性分子筛GPZ1-1用对比例1-1的对比样品D1-1替代。制得催化裂解助剂对比样品，编号DCAZ38-1。评价同实施例31-1，结果见表6。
对比例68-2
同实施例68-1，区别在于其中的磷改性分子筛GPZ1-1用对比例1-2的对比样品D1-2替代。制得催化裂解助剂对比样品，编号DCAZ38-2。评价同实施例31-1，结果见表6。
Figure PCTCN2021086824-appb-000004
Figure PCTCN2021086824-appb-000005
Figure PCTCN2021086824-appb-000006
实施例69-1、实施例69-2
实施例69-1、实施例69-2分别采用实施例31-1和实施例31-2的催化裂解助剂CAZ1-1、CAZ1-2。催化裂解的原料油为表5所示的石脑油。
评价条件为反应温度620℃，再生温度620℃，剂油比3.2。
表7给出了各个含催化裂解助剂的催化剂混合物的重量组成及反应结果。
对比例69-1、对比例69-2
同实施例69-1，区别在于分别采用对比例31-1和对比例31-2的催化裂解对比助剂DCAZ1-1、DCAZ1-2。
各个含催化裂解助剂对比样品的催化剂混合物的重量组成及反应结果表7。
实施例70-1、实施例70-2
实施例70-1、实施例70-2分别采用实施例44-1和实施例44-2的催化裂解助剂CAZ14-1、CAZ14-2。催化裂解的原料油为表5所示的石脑油。
评价条件为反应温度620℃，再生温度620℃，剂油比3.2。
表7给出了各个含催化裂解助剂的催化剂混合物的重量组成及反应结果。
对比例70-1、对比例70-2
同实施例70-1，区别在于分别采用对比例44-1和对比例44-2的催化裂解对比助剂DCAZ14-1、DCAZ14-2。
各个含催化裂解助剂对比样品的催化剂混合物的重量组成及反应结果表7。
表7
Figure PCTCN2021086824-appb-000007
实施例Y31至实施例Y56提供本发明的催化裂解催化剂，对比例Y31至对比例Y56说明作为对比的催化裂解对比催化剂。其中，实施例Y31至实施例Y43中含有磷改性多级孔ZSM-5分子筛，实施例Y44至实施例Y56为含有磷改性微孔ZSM-5分子筛。
实施例Y31-1
取实施例1-1制备的磷改性分子筛GPZ1-1、Y型分子筛(PSRY分子筛)高岭土和拟薄水铝石，加入脱阳离子水以及铝溶胶打浆120分钟，得到固含量30重量％的浆液，加入盐酸调节浆液pH值3.0，然后继续打浆45分钟，然后加入实施例Y27制备的磷铝无机粘结剂Binder 1，搅拌30分钟后，将得到的浆液喷雾干燥，得到微球，将微球于500℃下焙烧1小时，制得催化裂解催化剂样品，编号CAZY1-1，其配比为磷改性ZSM-5分子筛40％、PSRY分子筛10％、高岭土18％、Binder 1为18％、拟薄水铝石(以Al2O3计)5％、铝溶胶(以Al2O3计)9％。
采用固定床微反装置对100％平衡剂以及平衡剂掺入CAZY1-1进行反应性能评价，以说明催化裂解反应效果。
将催化剂CAZY1-1在800℃下、100％水蒸气气氛条件下进行17小时的老化处理。取经老化处理的CAZY1-1与工业FCC平衡催化剂(工业牌号DVR-3的FCC平衡催化剂，轻油微反活性为63)混合。将平衡剂和催化剂的混合物装入固定床微反反应器中，对表4所示原料油进行催化裂解，评价条件为反应温度620℃，再生温度620℃，剂油比3.2。表8给出反应结果，其中包括了空白测试剂。
实施例Y31-2
同实施例Y31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例1-2制备的磷改性分子筛GPZ1-2替代。制得催化裂解催化剂样品，编号CAZY1-2。评价同实施例Y31-1，结果见表8。
对比例Y31-1
同实施例Y31-1，区别在于其中的磷改性分子筛GPZ1-1用对比例1-1的对比样品D1-1替代。制得催化裂解催化剂对比样品，编号DCAZY1-1。评价同实施例Y31-1，结果见表8。
对比例Y31-2
同实施例Y31-1，区别在于其中的磷改性分子筛GPZ1-1用对比例1-2的对比样品D1-2替代。制得催化裂解催化剂对比样品，编号DCAZY1-2。评价同实施例Y31-1，结果见表8。
实施例Y32-1
同实施例Y31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例2-1制备的磷改性分子筛GPZ2-1替代。制得催化裂解催化剂样品，编号CAZY2-1。评价同实施例Y31-1，结果见表8。
实施例Y32-2
同实施例Y32-1，区别在于其中的磷改性分子筛GPZ2-1用实施例2-2制备的磷改性分子筛GPZ2-2替代。制得催化裂解催化剂样品，编号CAZY2-2。评价同实施例Y31-1，结果见表8。
对比例Y32-1
同实施例Y32-1，区别在于其中的磷改性分子筛GPZ2-1用对比例2-1的对比样品D2-1替代。制得催化裂解催化剂对比样品，编号DCAZY2-1。评价同实施例Y31-1，结果见表8。
对比例Y32-2
同实施例Y32-1，区别在于其中的磷改性分子筛GPZ2-1用对比例2-2的对比样品D2-2替代。制得催化裂解催化剂对比样品，编号DCAZY2-2。评价同实施例Y31-1，结果见表8。
实施例Y33-1
同实施例Y31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例3-1制备的磷改性分子筛GPZ3-1替代。制得催化裂解催化剂样品，编号CAZY3-1。评价同实施例Y31-1，结果见表8。
实施例Y33-2
同实施例Y31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例3-2制备的磷改性分子筛GPZ3-2替代。制得催化裂解催化剂样品，编号CAZY3-2。评价同实施例Y31-1，结果见表8。
对比例Y33-1
同实施例Y31-1，区别在于其中的磷改性分子筛GPZ1-1用对比例3-1的对比样品D3-1替代。制得催化裂解催化剂对比样品，编号DCAZY3-1。评价同实施例Y31-1，结果见表8。
对比例Y33-2
同实施例Y31-1，区别在于其中的磷改性分子筛GPZ1-1用对比例3-2的对比样品D3-2替代。制得催化裂解催化剂对比样品，编号DCAZY3-2。评价同实施例Y31-1，结果见表8。
实施例Y34-1
同实施例Y31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例4-1制备的磷改性分子筛GPZ4-1替代。制得催化裂解催化剂样品，编号CAZY4-1。评价同实施例Y31-1，结果见表8。
实施例Y34-2
同实施例Y34-1，区别在于其中的磷改性分子筛GPZ4-1用实施例4-2制备的磷改性分子筛GPZ4-2替代。制得催化裂解催化剂样品，编号CAZY4-2。评价同实施例Y31-1，结果见表8。
对比例Y34-1
同实施例Y34-1，区别在于其中的磷改性分子筛GPZ4-1用对比例4-1的对比样品D4-1替代。制得催化裂解催化剂对比样品，编号DCAZY4-1。评价同实施例Y31-1，结果见表8。
对比例Y34-2
同实施例Y34-1，区别在于其中的磷改性分子筛GPZ1-1用对比例4-2的对比样品D4-2替代。制得催化裂解催化剂对比样品，编号DCAZY4-2。评价同实施例Y31-1，结果见表8。
实施例Y35-1
同实施例Y31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例5-1制备的磷改性分子筛GPZ5-1替代。制得催化裂解催化剂样品，编号CAZY5-1。评价同实施例Y31-1，结果见表8。
实施例Y35-2
同实施例Y35-1，区别在于其中的磷改性分子筛GPZ5-1用实施例5-2制备的磷改性分子筛GPZ5-2替代。制得催化裂解催化剂样品，编号CAZY5-2。评价同实施例Y35-1，结果见表8。
对比例Y35-1
同实施例Y35-1，区别在于其中的磷改性分子筛GPZ5-1用对比例5-1的对比样品D5-1替代。制得催化裂解催化剂对比样品，编号DCAZY5-1。评价同实施例Y35-1，结果见表8。
对比例Y35-2
同实施例Y35-1，区别在于其中的磷改性分子筛GPZ5-1用对比例5-2的对比样品D5-2替代。制得催化裂解催化剂对比样品，编号DCAZY5-2。评价同实施例Y35-1，结果见表8。
实施例Y36-1
同实施例Y31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例6-1制备的磷改性分子筛GPZ6-1替代。制得催化裂解催化剂样品，编号CAZY6-1。评价同实施例Y31-1，结果见表8。
实施例Y36-2
同实施例Y36-1，区别在于其中的磷改性分子筛GPZ6-1用实施例6-2制备的磷改性分子筛GPZ6-2替代。制得催化裂解催化剂样品，编号CAZY6-2。评价同实施例Y36-1，结果见表8。
对比例Y36-1
同实施例Y36-1，区别在于其中的磷改性分子筛GPZ6-1用对比例6-1的对比样品D6-1替代。制得催化裂解催化剂对比样品，编号DCAZY6-1。评价同实施例Y36-1，结果见表8。
对比例Y36-2
同实施例Y36-1，区别在于其中的磷改性分子筛GPZ6-1用对比例6-2的对比样品D6-2替代。制得催化裂解催化剂对比样品，编号DCAZY6-2。评价同实施例Y36-1，结果见表8。
实施例Y37-1
同实施例Y31-1，区别在于其中的磷改性分子筛GPZ1-1用实施例7-1制备的磷改性分子筛GPZ7-1替代。制得催化裂解催化剂样品，编号CAZY7-1。评价同实施例Y31-1，结果见表8。
实施例Y37-2
同实施例Y37-1，区别在于其中的磷改性分子筛GPZ7-1用实施例7-2制备的磷改性分子筛GPZ7-2替代。制得催化裂解催化剂样品，编号CAZY7-2。评价同实施例Y31-1，结果见表8。
对比例Y37-1
同实施例Y37-1，区别在于其中的磷改性分子筛GPZ7-1用对比例7-1的对比样品D7-1替代。制得催化裂解催化剂对比样品，编号DCAZY7-1。评价同实施例Y31-1，结果见表8。
对比例Y37-2
同实施例Y37-1，区别在于其中的磷改性分子筛GPZ7-1用对比例7-2的对比样品D7-2替代。制得催化裂解催化剂对比样品，编号DCAZY7-2。评价同实施例Y31-1，结果见表8。
实施例Y38至实施例Y43
同实施例Y31-1，区别在于其中的磷改性分子筛GPZ1-1分别用实施例8-1至实施例13-2制备的磷改性分子筛GPZ8-1至GPZ13-2替代。制得催化裂解催化剂样品，依次编号CAZY8-1至CAZY13-2。评价同实施例Y31-1，结果分别见表8。
实施例Y44至实施例Y56
实施例Y44至实施例Y56为依次分别含微孔ZSM-5(GPZ14至GPZ26)的催化剂CAZY14至CAZY26，物料配比分别对应实施例Y31至实施例Y43，例如，实施例Y44-1中，GPZ1-1用GPZ14-1替代，实施例Y44-2中，GPZ1-2用GPZ14-2替代，等等，直至实施例Y56-1中、GPZ13-1用GPZ26-1替代，实施例Y56-2中、GPZ13-2用GPZ26-2替代。评价同实施例Y31-1，结果分别见表8。
对比例Y44至对比例Y50
对比例Y44至对比例Y50为依次分别含微孔ZSM-5(D14至D20)的对比催化剂DCAZY-14至DCAZY-20，物料配比分别对应实施例Y44至实施例Y50，例如，对比例Y44-1中，GPZ1-1用D14-1替代，对比例Y44-2中，GPZ1-2用 D14-2替代，等等，直至对比例Y50-1中，GPZ14-1用D20-1替代，对比例Y50-2中，GPZ14-2用D20-2替代。评价同实施例Y31-1，结果分别见表8。
实施例Y57至实施例Y62
同实施例Y31-1，区别在于其中的磷改性分子筛GPZ1-1顺序分别用实施例21-1至实施例26-2制备的磷改性分子筛GPZ21-1至GPZ26-2替代。制得催化裂解催化剂样品，依次编号CAZY27-1至CAZY32-2。评价同实施例Y31-1，结果分别见表8。
实施例Y63-1
同实施例Y31-1，区别在于磷铝无机粘结剂以实施例Y28制备的Binder 2替代。制得催化裂解催化剂，编号CAZY33-1。评价同实施例Y31-1，结果见表8。
实施例Y63-2
同实施例Y31-2，区别在于磷铝无机粘结剂以实施例Y28制备的Binder 2替代。制得催化裂解催化剂，编号CAZY33-2。评价同实施例Y31-1，结果见表8。
实施例Y64-1
同实施例Y31-1，区别在于磷铝无机粘结剂以实施例Y29制备的Binder 3替代。制得催化裂解催化剂，编号CAZY34-1。评价同实施例Y31-1，结果见表8。
实施例Y64-2
同实施例Y31-2，区别在于磷铝无机粘结剂以实施例Y29制备的Binder 3替代。制得催化裂解催化剂，编号CAZY34-2。评价同实施例Y31-1，结果见表8。
实施例Y65-1
同实施例Y31-1，区别在于磷铝无机粘结剂以实施例Y30制备的Binder 4替代。制得催化裂解催化剂，编号CAZY35-1。评价同实施例Y31-1，结果见表8。
实施例Y65-2
同实施例Y31-2，区别在于磷铝无机粘结剂以实施例Y30制备的Binder 4替代。制得催化裂解催化剂，编号CAZY35-2。评价同实施例Y31-1，结果见表8。
实施例Y66-1
同实施例Y31-1，区别在于使用磷改性多级孔ZSM-5分子筛样品GPZ1-1(35重量％)、PSRY分子筛(10重量％)、高岭土(18重量％)、磷铝无机粘结剂Binder 3(22重量％)，拟薄水铝石(10重量％)、铝溶胶(5重量％)。制得催化裂解催化剂，编号CAZY36-1。评价同实施例Y31-1，结果见表8。
实施例Y66-2
同实施例Y66-1，区别在于GPZ1-1用GPZ1-2替代。制得催化裂解催化剂，编号CAZY36-2。评价同实施例Y31-1，结果见表8。
对比例Y66-1
同实施例Y66-1，区别在于GPZ1-1用D1-1替代。制得催化裂解催化剂对比样品，编号DCAZY36-1。评价同实施例Y31-1，结果见表8。
对比例Y66-2
同实施例Y66-1，区别在于GPZ1-1用D1-2替代。制得催化裂解催化剂对比样品，编号DCAZY36-2。评价同实施例Y31-1，结果见表8。
实施例Y67-1
同实施例Y44-1，区别在于使用磷改性的微孔ZSM-5分子筛样品GPZ14-1(30重量％)、PSRY分子筛(6重量％)、高岭土(24重量％)、磷铝无机粘结剂Binder 4(22重量％)，拟薄水铝石(8重量％)、硅溶胶(10重量％)制得催化裂解催化剂，编号CAZY37-1。评价同实施例Y31-1，结果见表8。
实施例Y67-2
同实施例Y67-1，区别在于GPZ14-1用GPZ14-2替代。制得催化裂解催化剂，编号CAZY37-2。评价同实施例Y31-1，结果见表8。
对比例Y67-1
同实施例Y67-1，区别在于GPZ14-1用D14-1替代。制得催化裂解催化剂对比样品，编号DCAZY37-1。评价同实施例Y31-1，结果见表8。
对比例Y67-2
同实施例Y67-1，区别在于GPZ14-1用D14-2替代。制得催化裂解催化剂对比样品，编号DCAZY37-2。评价同实施例Y31-1，结果见表8。
实施例Y68-1
将粘结剂铝溶胶与高岭土混合，并用脱阳离子水将其制成固含量为30重量％的浆液，搅拌均匀，用盐酸将浆液pH值调至2.8，于55℃下静置老化1小时后加入实施例1-1制备的磷改性分子筛GPZ1-1和Y型分子筛(PSRY分子筛)，形成催化剂浆液(固含量为35％重量)，继续搅拌后喷雾干燥制成微球催化剂。然后将微球催化剂在500℃下焙烧1小时，再在60℃下用硫酸铵洗涤(其中，硫酸铵∶微球催化剂∶水＝0.5∶1∶10)至氧化钠含量小于0.25重量％，接着用去离子水淋洗并过滤，之后再于110℃下烘干，得到催化剂CAZY38-1。其配比为磷改性ZSM-5分子筛GPZ1-1为40％、PSRY分子筛为10％、高岭土为25％、铝溶胶(以Al2O3计)为25％。评价同实施例Y31-1，结果见表8。
实施例Y68-2
同实施例Y68-1，区别在于其中的磷改性分子筛GPZ1-1用实施例1-2制备的磷改性分子筛GPZ1-2替代。制得催化裂解催化剂样品，编号CAZY38-2。评价同实施例Y31-1，结果见表8。
对比例Y68-1
同实施例Y68-1，区别在于其中的磷改性分子筛GPZ1-1用对比例Y1-1的对比样品D1-1替代。制得催化裂解催化剂对比样品，编号DCAZY38-1。评价同实施例Y31-1，结果见表8。
对比例Y68-2
同实施例Y68-1，区别在于其中的磷改性分子筛GPZ1-1用对比例Y1-2的对比样品D1-2替代。制得催化裂解催化剂对比样品，编号DCAZY38-2。评价同实施例Y31-1，结果见表8。
实施例Y69-1、实施例Y69-2
实施例Y69-1、实施例Y69-2分别采用实施例Y31-1和实施例Y31-2的催化裂解催化剂CAZY1-1、CAZY1-2。催化裂解的原料油为表5所示的石脑油。
评价条件为反应温度620℃，再生温度620℃，剂油比3.2。
表9给出了各个含催化裂解催化剂的催化剂混合物的重量组成及反应结果。
对比例Y69-1、对比例Y69-2
Figure PCTCN2021086824-appb-000008
Figure PCTCN2021086824-appb-000009
Figure PCTCN2021086824-appb-000010
同实施例Y69-1，区别在于分别采用对比例Y31-1和对比例Y31-2的催化裂解对比催化剂DCAZY1-1、DCAZY1-2。
各个含催化裂解催化剂对比样品的催化剂混合物的重量组成及反应结果表9。
实施例Y70-1、实施例Y70-2
实施例Y70-1、实施例Y70-2分别采用实施例Y44-1和实施例Y44-2的催化裂解催化剂CAZY14-1、CAZY14-2。催化裂解的原料油为表5所示的石脑油。
评价条件为反应温度620℃，再生温度620℃，剂油比3.2。
表9给出了各个含催化裂解催化剂的催化剂混合物的重量组成及反应结果。
对比例Y70-1、对比例Y70-2
同实施例Y70-1，区别在于分别采用对比例Y44-1和对比例Y44-2的催化裂解对比催化剂DCAZY14-1、DCAZY14-2。
各个含催化裂解催化剂对比样品的催化剂混合物的重量组成及反应结果表9。
表9
Figure PCTCN2021086824-appb-000011
实施例Y71-1
同实施例Y31-1，区别在于其中的Y型分子筛(PSRY)以HRY-1替换。制得催化剂样品，编号CAZY39-1。评价同实施例Y31-1，结果见表10。
实施例Y71-2
同实施例Y31-1，区别在于其中的Y型分子筛(PSRY)以HRY-1替换。制得催化剂样品，编号CAZY39-2。评价同实施例Y31-1，结果见表10。
对比例Y71-1
同实施例Y31-1，区别在于其中的Y型分子筛(PSRY)以HRY-1替换。制得催化剂对比样品，编号DCAZY39-1。评价同实施例Y31-1，结果见表10。
对比例Y71-2
同实施例Y31-1，区别在于其中的Y型分子筛(PSRY)以HRY-1替换。制得催化剂对比样品，编号DCAZY39-2。评价同实施例Y31-1，结果见表10。
表10
Figure PCTCN2021086824-appb-000012

Claims (35)

  1. 一种磷改性MFI结构分子筛，其特征在于，该分子筛的K值满足：70％≤K≤90％；例如，75％≤K≤90％；进一步地，例如，78％≤K≤85％；
    其中，所述的K＝P1/P2×100％，
    P1表示采用XPS方法测定的分子筛晶粒的任意晶面垂直深度0-2nm内、100平方纳米区域面积内的磷质量含量，
    P2表示采用EPMA方法测定的分子筛晶粒的任意晶面垂直深度5-10nm厚度区间100平方纳米区域面积内的磷质量含量。
  2. 根据前述权利要求中任一项的分子筛，其中，磷的含量以P2O5计与氧化铝的摩尔比值≥0.01；例如，≥0.2；进一步地，例如，≥0.3；更进一步地，例如，0.4-0.7。
  3. 根据前述权利要求中任一项的分子筛，其中，所述的磷改性MFI结构分子筛是微孔ZSM-5分子筛或多级孔ZSM-5分子筛。
  4. 根据前述权利要求中任一项的分子筛，所述的微孔ZSM-5分子筛，其氧化硅/氧化铝的摩尔比为15-1000、例如，20-200。
  5. 根据前述权利要求中任一项的分子筛，所述的多级孔ZSM-5分子筛，其介孔体积占总孔体积的比例大于10％，平均孔径为2-20nm，氧化硅/氧化铝的摩尔比为15-1000、例如，20-200。
  6. 一种催化裂解助剂，以所述催化裂解助剂的干基为基准，所述催化裂解助剂含有5-75重量％、例如，8-60重量％的前述权利要求中任一项所述的磷改性MFI结构分子筛、1-40重量％的粘结剂和0-65重量％、例如5-55重量％的第二粘土。
  7. 一种含磷改性MFI结构分子筛的催化裂解催化剂，以催化剂的干基为基准，所述催化裂解催化剂含有1-25重量％的Y型分子筛、以5-50重量％的前述权利要求中任一项所述的磷改性MFI结构分子筛、1-60重量％的无机粘结剂和可选加入的0-60重量％的第二粘土。
  8. 根据前述权利要求中任一项的催化裂解助剂或催化裂解催化剂，其中，所述的粘结剂或所述的无机粘结剂包括磷铝无机粘结剂和/或其他无机粘结剂，
    例如，所述的磷铝无机粘结剂为磷铝胶和/或含第一粘土的磷铝无机粘结剂，进一步地，例如，所述的第一粘土选自高岭土、海泡石、凹凸棒石、累托石、蒙脱石和硅藻土；进一步例如，所述的含第一粘土的磷铝无机粘结剂含有以Al2O3计10-40重量％，例如15-40重量％的铝组分、以P2O5计45-90重量％，例如45-80重量％的磷组分以及以干基计大于0且不超过40重量％的第一粘土，且所述含第一粘土的磷铝无机粘结剂P/Al重量比为1.0-6.0，pH为1-3.5，固含量为15-60重量％；
    例如，所述的第二粘土选自高岭土、海泡石、凹凸棒石、累托石、蒙脱石、和硅藻土，以及多水高岭土、埃洛石、水滑石、和膨润土；
    例如，所述的其他无机粘结剂选自拟薄水铝石、铝溶胶、硅铝溶胶和水玻璃；
  9. 根据前述权利要求中任一项所述的催化裂解催化剂，其中，所述Y型分子筛包括PSRY分子筛、PSRY-S分子筛、含稀土的PSRY分子筛、含稀土的PSRY-S分子筛、USY分子筛、含稀土的USY分子筛、REY分子筛、REHY分子筛和HY分子筛的至少一种。
  10. 制备前述权利要求中任一项的磷改性MFI结构分子筛的方法，其特征在于用浸渍法获得的，包括：使温度为40-150℃、例如50-150℃、进一步地，例如70-130℃的含磷化合物的水溶液与40-150℃、例如50-150℃、进一步地，例如70-130℃的MFI结构分子筛在基本相同的温度下混合接触至少0.1小时、干燥后在200-600℃、空气或水蒸气气氛下焙烧至少0.1小时；或者，将含磷化合物、MFI结构分子筛和水混合打浆后调温到40-150℃、例如50-150℃、进一步地，例如70-130℃保持至少0.1小时、干燥后在200-600℃、空气或水蒸气气氛下焙烧至少0.1小时。
  11. 根据前述权利要求中任一项的制备磷改性MFI结构分子筛的方法，其中，所述的含磷化合物选自有机磷化合物和/或无机磷化合物；例如，所述的有机磷化合物选自磷酸三甲酯、三苯基磷、三甲基亚磷酸酯、四丁基溴化膦、四丁基氯化膦、四丁基氢氧化磷、三苯基乙基溴化磷、三苯基丁基溴化磷、三苯基苄基溴化磷、六甲基磷酰三胺、二苄基二乙基磷、1，3-二甲苯双三乙基磷，所述的无机磷化合物选自磷酸、磷酸氢铵、磷酸氢二铵、磷酸铵、磷酸硼。
  12. 根据前述权利要求中任一项的制备磷改性MFI结构分子筛的方法，其中，所述的含磷化合物以磷计(以氧化物计)、MFI结构分子筛(例如氢型ZSM-5分子筛)以铝计(以氧化物计)，二者的摩尔比值为0.01-2；例如，二者的摩尔比值为0.1-1.5；进一步地，例如，二者的摩尔比值为0.2-1.5。
  13. 根据前述权利要求中任一项的制备磷改性MFI结构分子筛的方法，其中，所述的含磷化合物为磷酸硼与选自磷酸三甲酯、三苯基磷、三甲基亚磷酸酯、磷酸、磷酸氢铵、磷酸氢二铵、磷酸铵之一或多种的混合物，所述混合物中，磷酸硼重量占比为10％-80％，例如磷酸硼重量占比为20％-40％。
  14. 根据前述权利要求中任一项的制备磷改性MFI结构分子筛的方法，其中，所述的接触，水筛重量比为0.5-1，时间为0.5-40小时。
  15. 根据前述权利要求中任一项的制备磷改性MFI结构分子筛的方法，其中，所述的焙烧是在450-550℃、水蒸汽气氛下进行。
  16. 一种制备前述权利要求中任一项的催化裂解助剂的方法，该方法包括，将磷改性MFI结构分子筛、粘结剂与可选加入的第二粘土混合打浆并经喷雾干燥后得到所述催化裂解助剂。
  17. 根据前述权利要求中任一项的制备催化裂解助剂的方法，其中，所述的粘结剂包括或者为磷铝无机粘结剂。
  18. 根据前述权利要求中任一项的制备催化裂解助剂的方法，其中，所述的磷铝无机粘结剂为磷铝胶和/或含第一粘土的磷铝无机粘结剂；以所述含第一粘土 的磷铝无机粘结剂干基重量为基准，所述含第一粘土的磷铝无机粘结剂含有以Al2O3计10-40重量％，例如15-40重量％、或10-30重量％，或15-35重量％或20-40重量％的铝组分、以P2O5计45-90重量％，例如45-80重量％、或50-75重量％或60-80重量％的磷组分以及以干基计大于0且不超过40重量％、例如8-35重量％的第一粘土，且所述含第一粘土的磷铝无机粘结剂P/Al重量比为1.0-6.0、例如1.2-6.0、进一步地，例如2.0-5.0，pH为1-3.5、例如2.0-3.0，固含量为15-60重量％；所述第一粘土包括高岭土、海泡石、凹凸棒石、累托石、蒙脱石和硅藻土中的至少一种。
  19. 根据前述权利要求中任一项的制备催化裂解助剂的方法，其中，所述的第二粘土为选自高岭土、海泡石、凹凸棒石、累托石、蒙脱石、多水高岭土、埃洛石、水滑石、膨润土以及硅藻土中的至少一种。
  20. 根据前述权利要求中任一项的制备催化裂解助剂的方法，其中，以所述催化裂解助剂的总重量为基准，所述粘结剂包括以干基重量计3-39重量％的所述磷铝无机粘结剂和以干基重量计1-30重量％的其他无机粘结剂。
  21. 根据前述权利要求中任一项的制备催化裂解助剂的方法，其中，所述其他无机粘结剂还可以包括拟薄水铝石、铝溶胶、硅铝溶胶和水玻璃中的至少一种。
  22. 根据前述权利要求中任一项的制备催化裂解助剂的方法，该方法还包括：将所述喷雾干燥所得产物进行第一焙烧、洗涤和可选的干燥处理，得到所述催化裂解助剂；其中所述第一焙烧的焙烧温度为300-650℃，焙烧时间为0.5-8h；所述干燥处理的温度为100-200℃，干燥时间为0.5-24h。
  23. 根据前述权利要求中任一项的制备催化裂解助剂的方法，该方法还包括：采用如下步骤制备所述含第一粘土的磷铝无机粘结剂：将氧化铝源、所述第一粘土与水打浆分散成固含量为5-48重量％的浆液；其中所述的氧化铝源为能被酸胶溶的氢氧化铝和/或氧化铝，相对于10-40重量份，例如15-40重量份的以Al2O3计的氧化铝源，以干基重量计的所述第一粘土的用量大于0重量份且不超过40重量份；搅拌下按照P/Al＝1-6的重量比向所述浆液中加入浓磷酸，并使所得混合浆液在50-99℃反应15-90分钟；其中所述的P/Al中P为磷酸中的以单质计的磷的重量，Al为氧化铝源中以单质计的铝的重量。
  24. 一种制备前述权利要求中任一项的催化裂解催化剂的方法，该方法包括，将Y型分子筛、前述权利要求中任一项的磷改性MFI结构分子筛、无机粘结剂与可选加入的第二粘土混合打浆并经喷雾干燥后得到所述催化裂解催化剂。
  25. 根据前述权利要求中任一项的制备催化裂解催化剂的方法，其中，所述的无机粘结剂包括或者为磷铝无机粘结剂。
  26. 根据前述权利要求中任一项的制备催化裂解催化剂的方法，其中，所述的磷铝无机粘结剂为磷铝胶和/或含第一粘土的磷铝无机粘结剂；以所述含第一粘土的磷铝无机粘结剂干基重量为基准，所述含第一粘土的磷铝无机粘结剂含有以Al2O3计10-40重量％，例如15-40重量％的铝组分、以P2O5计45-90重量％，例如45-80重量％的磷组分以及以干基计大于0且不超过40重量％的第一粘土， 且所述含第一粘土的磷铝无机粘结剂P/Al重量比为1.0-6.0，pH为1-3.5，固含量为15-60重量％；所述第一粘土包括高岭土、海泡石、凹凸棒石、累托石、蒙脱石和硅藻土中的至少一种。
  27. 根据前述权利要求中任一项的制备催化裂解催化剂的方法，其中，所述的第二粘土为选自高岭土、海泡石、凹凸棒石、累托石、蒙脱石、多水高岭土、埃洛石、水滑石、膨润土以及硅藻土中的至少一种。
  28. 根据前述权利要求中任一项的制备催化裂解催化剂的方法，其中，以所述催化裂解催化剂为基准，所述无机粘结剂包括以干基计3-39重量％的所述磷铝无机粘结剂和以干基计1-30重量％的所述其他无机粘结剂，所述的其他无机粘结剂选自拟薄水铝石、铝溶胶、硅铝溶胶和水玻璃中的至少一种。
  29. 根据前述权利要求中任一项的制备催化裂解催化剂的方法，其中，该方法还包括：将所述喷雾干燥所得产物进行第一焙烧、洗涤和可选的干燥处理，得到所述催化裂解催化剂；其中所述第一焙烧的焙烧温度为300-650℃，焙烧时间为0.5-8h；所述干燥处理的温度为100-200℃，干燥时间为0.5-24h。
  30. 根据前述权利要求中任一项的制备催化裂解催化剂的方法，该方法还包括：采用如下步骤制备所述含第一粘土的磷铝无机粘结剂：将氧化铝源、所述第一粘土与水打浆分散成固含量为5-48重量％的浆液；其中所述的氧化铝源为能被酸胶溶的氢氧化铝和/或氧化铝，相对于10-40重量份，例如15-40重量份的以Al2O3计的氧化铝源，以干基重量计的所述第一粘土的用量大于0重量份且不超过40重量份；搅拌下按照P/Al＝1-6的重量比向所述浆液中加入浓磷酸，并使所得混合浆液在50-99℃反应15-90分钟；其中所述的P/Al中P为磷酸中的以单质计的磷的重量，Al为氧化铝源中以单质计的铝的重量。
  31. 采用前述权利要求中任一项的制备催化裂解助剂的方法得到的催化裂解助剂。
  32. 采用前述权利要求中任一项的制备催化裂解催化剂的方法得到的催化裂解催化剂。
  33. 一种烃油催化裂解的方法，其特征在于，该方法包括：在催化裂解条件下，使烃油与前述权利要求中任一项的催化裂解助剂或者与前述权利要求中任一项的催化裂解催化剂接触反应。
  34. 根据前述权利要求中任一项的烃油催化裂解的方法，其中，该方法包括：在所述催化裂解条件下，使所述烃油与含有前述权利要求中任一项的催化裂解助剂和一种催化裂解催化剂的催化剂混合物接触反应；所述催化剂混合物中，所述催化裂解助剂的含量为0.1-30重量％。
  35. 根据前述权利要求中任一项的烃油催化裂解的方法，其中，所述催化裂解条件包括：反应温度为500-800℃；所述烃油选自原油、石脑油、汽油、常压渣油、减压渣油、常压蜡油、减压蜡油、直流蜡油、丙烷轻/重脱油、焦化蜡油和煤液化产物中的一种或几种。
PCT/CN2021/086824 2020-04-13 2021-04-13 磷改性mfi结构分子筛、含磷改性mfi结构分子筛的催化裂解助剂和催化裂解催化剂、及其制备方法 WO2021208885A1 (zh)

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