RU2807083C1 - Phosphorus modified molecular sieve with mfi structure, catalytic cracking auxiliary and catalytic cracking catalyst containing phosphorus modified molecular sieve with mfi structure, and also processes for their preparation - Google Patents

Abstract

FIELD: molecular sieve.

SUBSTANCE: present invention relates to a phosphorus modified molecular sieve with an MFI structure. A phosphorus modified molecular sieve with an MFI structure having a K value satisfying the condition 70%≤K≤90% is described, where K=P1/P2×100%, P1 is the XPS measured mass content of phosphorus in a region with an area of 100 sq. nm and a vertical depth of 0 to 2 nm on any surface of the molecular sieve crystal grain, P2 is the measured EPMA mass content of phosphorus in a region with an area of 100 sq.nm and a vertical depth of 5 to 10 nm on any surface of the crystalline grain of the molecular sieve, and a method for its preparation. A catalytic cracking aid which, based on the dry weight of the catalytic cracking aid, contains 5-75 wt.% of said phosphorus-modified molecular sieve with an MFI structure, 1-40 wt.% binder and 0-65 wt.% of the second clay, method of obtaining the specified auxiliary agent; catalytic cracking catalyst containing a phosphorus-modified molecular sieve with an MFI structure, which, based on the dry weight of the catalytic cracking catalyst, contains 1-25 wt.% zeolite Y, 5-50 wt.% phosphorus-modified molecular sieve with an MFI structure, 1-60 wt.% inorganic binder and optionally 0-60 wt.% second clay, and a method for producing said catalyst are described. The method for catalytic cracking of liquid petroleum products includes: reacting liquid petroleum products by contact with the specified auxiliary agent for catalytic cracking or with the specified catalytic cracking catalyst under catalytic cracking conditions.

EFFECT: proposition of new technologies to improve the coordination of phosphorus and aluminium frame, improve the hydrothermal stability of the phosphorus-modified molecular sieve ZSM-5 and further increase the cracking activity.

41 cl, 239 ex, 10 tbl

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This patent application claims priority to Chinese Patent Application No. 202010283498.2 filed on April 13, 2020, Chinese Patent Application No. 202011169092.8 filed on October 28, 2020, and Chinese Patent Application No. 202011175729.4 filed on October 29, 2020 d. All of the above applications are included herein document by reference in their entirety for all purposes.

FIELD OF TECHNOLOGY TO WHICH THE INVENTION RELATES

The present invention relates to a phosphorus-modified molecular sieve with an MFI structure, a catalytic cracking aid containing phosphorus-modified molecular sieve(s) with an MFI structure, and a catalytic cracking catalyst containing phosphorus-modified molecular sieve(s) with an MFI structure, the present The invention also relates to processes for preparing a phosphorus-modified molecular sieve with an MFI structure, a catalytic cracking aid containing phosphorus-modified molecular sieve(s) with an MFI structure, and a catalytic cracking catalyst containing phosphorus-modified molecular sieve(s) with an MFI structure; and the present invention relates to the use of a catalytic cracking aid and a catalytic cracking catalyst in the catalytic cracking of liquid petroleum products.

BACKGROUND OF THE ART

A representative molecular sieve having an MFI structure is the ZSM-5 molecular sieve, which is a widely used zeolite molecular catalyst material developed by Mobil Corporation, USA, in 1972. The ZSM-5 molecular sieve has a three-dimensional intersecting channel structure. The channels along the A-axis are straight channels having a cross-sectional size of 0.54 × 0.56 nm, which is approximately circular. The channels along the B axis are zigzag channels having a cross-sectional size of 0.51×0.56 nm, which is elliptical. ZSM-5 molecular sieve has holes composed of ten-membered rings, and the hole size is between small pore zeolite and large pore zeolite, so it has a unique selective catalytic effect. ZSM-5 molecular sieve has unique pore structure, good configuration-selective catalysis and isomerization efficiency, high thermal and hydrothermal stability, high specific surface area, wide variation range of alumina-silica ratio, unique surface acidity and relatively low carbon formation, so it is widely used is used as a catalyst and catalyst support and has been successfully used in production processes such as alkylation, isomerization, disproportionation, catalytic cracking, methanol to gasoline refining and methanol to olefins refining. ZSM-5 molecular sieve is used in catalytic cracking and catalytic cracking of C4 hydrocarbons, and shows excellent catalytic efficiency, and exploiting its molecular shape selectivity can greatly improve the yield of lower olefins.

Since 1983, ZSM-5 molecular sieve has been used as a catalytic cracking aid/catalyst for octane improvement in the catalytic cracking process to improve catalytic cracked gasoline octane number and selectivity for light olefins. Patent document US3758403 was the first to report the use of ZSM-5 molecular sieve as an active component to enhance propylene production, and it was used together with REY as an active component of an FCC catalyst, or it was prepared together with REY to form an FCC catalyst. Patent document US5997728 disclosed the use of ZSM-5 molecular sieve without any modification as an auxiliary for increasing propylene production. However, the propylene yield for the two above-mentioned technologies is low.

Although HZSM-5 molecular sieve has good configuration selectivity efficiency and isomerization efficiency, it has the disadvantage of poor hydrothermal stability, and it is easily deactivated under harsh high-temperature hydrothermal conditions, which reduces the catalytic efficiency.

In the 1980s, Mobil Corporation discovered that phosphorus could improve the hydrothermal stability of ZSM-5 molecular sieves, and at the same time, modification of ZSM-5 molecular sieves with phosphorus increased the yield of low-carbon olefins. Traditional additives typically contain phosphorus-activated ZSM-5, which selectively converts primary cracking products (such as gasoline olefins) into C3 and C4 olefins. The ZSM-5 molecular sieve is modified by introducing an appropriate amount of inorganic phosphorus compounds after synthesis, which can stabilize the aluminum framework under harsh hydrothermal conditions.

Patent document CN106994364A discloses a method for producing phosphorus-modified molecular sieve ZSM-5. This method involves first mixing one or more phosphorus-containing compounds selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate with a ZSM-5 molecular sieve having a high alkali metal ion content to obtain a mixture containing phosphorus (for example P ₂ O ₅ ) at least 0.1 mass%, drying and calcining this mixture, then performing an ammonium exchange step and a water washing step so that the alkali metal ion content is reduced to 0.10 mass% or less, and then performing the step drying and hydrothermal aging at 400-1000°C in 100% water vapor. The phosphorus-containing ZSM-5 molecular sieve produced by this process has high total acid content, excellent cracking conversion ratio and propylene selectivity, and relatively high liquefied gas yield.

Patent document US5171921 discloses a method for modifying a ZSM-5 molecular sieve. This method involves producing HZSM-5 molecular sieve according to the usual steps: synthesis→filtration→ammonium exchange→drying→calcination, and then modification of ZSM-5 molecular sieve with phosphoric acid, drying and calcination, to obtain phosphorus modified molecular sieve HZSM-5 , in which the P ₂ O ₅ content is usually in the range of 1-7 wt.%. However, phosphoric acid or ammonium salts of phosphoric acid will undergo spontaneous aggregation, forming phosphorus species in different states of aggregation during the calcination process. During the hydrothermal treatment process, only the phosphate groups entering the pores interact with the aluminum framework, maintaining the B acid site and reducing the distribution of phosphorus species.

ZSM-5 Hierarchical Molecular Sieve is a ZSM-5 molecular sieve containing both micropores and mesopores. Various types of ZSM-5 hierarchical molecular sieves with mesoporous channels are usually prepared by hard template method, soft template method, acid-base post-processing method, etc.

Although modification of the (hierarchical) ZSM-5 molecular sieve with a suitable amount of inorganic phosphorus-containing compound can slow down the dealumination of the framework and improve the hydrothermal stability, and the phosphorus atoms will combine with the deformed aluminum of the four-coordination bond framework to form weak B acid sites to achieve higher cracking conversion long-chain alkanes and higher selectivity for light olefins, modification of the (hierarchical) ZSM-5 molecular sieve with excessive amounts of inorganic phosphorus-containing compound will block the molecular sieve channels, reduce the pore space volume and specific surface area, and occupy a large number of strong acidic B sites. Additionally In the prior art, phosphoric acid or ammonium salts of phosphoric acid self-polymerize to form phosphorus species in different states of aggregation during the calcination process, the coordination of phosphorus and aluminum framework is insufficient, the utilization efficiency of phosphorus is low, and modification with phosphorus does not always achieve satisfactory improvement results hydrothermal stability. Therefore, new technologies are urgently needed to improve the phosphorus-aluminum coordination of the framework, improve the hydrothermal stability of the phosphorus-modified (hierarchical) ZSM-5 molecular sieve, and further increase the cracking activity.

SUMMARY OF THE INVENTION

One of the objects of the present invention is to provide a phosphorus modified molecular sieve with an MFI structure, which differs from the prior art in that it has a high dispersion of phosphorus species, so that when used in a catalytic cracking reaction of liquid petroleum products, excellent cracking conversion can be obtained and excellent yield of lower olefins, and at the same time higher yield of liquefied gas can be obtained. Another object of the present invention is to provide a catalytic cracking auxiliary based on using phosphorus-modified molecular sieve ZSM-5 having a high dispersion of phosphorus species as an active component, so that excellent performance can be obtained in the catalytic cracking reaction of petroleum hydrocarbons. cracking conversion and excellent yield of lower olefins, and at the same time higher yield of liquefied gas could be obtained. Another object of the present invention is to provide a catalytic cracking catalyst based on the use as one of the active components of a phosphorus-modified molecular sieve with an MFI structure having a high dispersion of phosphorus species, so that petroleum hydrocarbons can be produced in the catalytic cracking reaction excellent cracking conversion and excellent yield of lower olefins, and at the same time a higher yield of liquefied gas could be obtained. Another object of the present invention is to provide processes for producing the above-mentioned phosphorus-modified molecular sieve with MFI structure, the above-mentioned catalytic cracking aid and the above-mentioned catalytic cracking catalyst. Another object of the present invention is to provide the use of the above-mentioned catalytic cracking aid and the above-mentioned catalytic cracking catalyst.

To solve the above problems, the present invention provides a phosphorus modified molecular sieve with an MFI structure, which is characterized in that the K value of the molecular sieve satisfies the condition: 70%≤K≤90%, K=[mass content of phosphorus within a region having an area of 100 square meters. nm and a vertical depth of 5 to 10 nm on any surface of the crystal grain of the molecular sieve, measured by the EPMA method] / [mass phosphorus content within a region having an area of 100 sq. nm and a vertical depth of 0 to 2 nm on any molecular sieve crystal grain surface measured by XPS]×100%, wherein XPS analysis of the molecular sieve surface is performed using an ESCAREB 250 Type X-ray photoelectron spectrometer manufactured by Thermo Fisher-VG Company, excitation source is a monochromatic AlKα X-ray source with a power of 150 W, and the charge shift is calibrated to the C1s peak (284.8 eV) of the contaminated carbon; EPMA analysis of molecular sieve surface is performed using energy spectrometer with X-ray detector JXA-8230, and for the counting rate and counting time, the total counting number is usually greater than 10 ⁵ , the counting rate is 10 ³ -10 ⁴ 1/s, and the counting time is 10- 100 s.

In the above phosphorus modified molecular sieve with MFI structure, the molar ratio of phosphorus content as P ₂ O ₅ to alumina content is ≥0.01; for example≥0.2; or≥0.3; or for example 0.4-0.7; the aforementioned phosphorus-modified molecular sieve with an MFI structure may be a microporous molecular sieve ZSM-5 or a hierarchical molecular sieve ZSM-5 with a phosphorus content (as P ₂ O ₅ ) of at least 0.1 wt.%, wherein the microporous molecular sieve ZSM -5 has a silica/alumina molar ratio of 15-1000, for example 20-200; The ZSM-5 hierarchical molecular sieve has a mesopore volume fraction relative to the total pore space volume of more than 10%, an average pore diameter of 2-20 nm, and a silica/alumina molar ratio of 15-1000, such as 20-200.

To solve the above objects, the present invention provides a catalytic cracking aid containing 5-75 wt.% of a phosphorus-modified molecular sieve with an MFI structure based on the dry weight of the catalytic cracking aid; wherein the phosphorus-modified molecular sieve with an MFI structure has a K value satisfying the condition: 70%≤K≤90%, for example 75%≤K≤90%; or 78%≤K≤85%, where K=[mass content of phosphorus within an area having an area of 100 square meters. nm and a vertical depth of 5 to 10 nm on any surface of the crystal grain of the molecular sieve, measured by the EPMA method] / [mass phosphorus content within a region having an area of 100 sq. nm and a vertical depth of 0 to 2 nm on any molecular sieve crystal grain surface measured by XPS]×100%, wherein XPS analysis of the molecular sieve surface is performed using an ESCAREB 250 Type X-ray photoelectron spectrometer manufactured by Thermo Fisher-VG Company, excitation source is a monochromatic AlKα X-ray source with a power of 150 W, and the charge shift is calibrated to the C1s peak (284.8 eV) of the contaminated carbon; EPMA analysis of molecular sieve surface is performed using energy spectrometer with X-ray detector JXA-8230, and for the counting rate and counting time, the total counting number is usually greater than 10 ⁵ , the counting rate is 10 ³ -10 ⁴ 1/s, and the counting time is 10- 100 s.

In the above phosphorus modified molecular sieve with MFI structure, the molar ratio of phosphorus content as P ₂ O ₅ to alumina content is ≥0.01; for example≥0.2; or≥0.3; or for example 0.4-0.7; the aforementioned phosphorus-modified molecular sieve with an MFI structure may be a microporous molecular sieve ZSM-5 or a hierarchical molecular sieve ZSM-5 with a phosphorus content (as P ₂ O ₅ ) of at least 0.1 wt.%, wherein the microporous molecular sieve ZSM -5 has a silica/alumina molar ratio of 15-1000, for example 20-200; The ZSM-5 hierarchical molecular sieve has a mesopore volume fraction relative to the total pore space volume of more than 10%, an average pore diameter of 2-20 nm, and a silica/alumina molar ratio of 15-1000, such as 20-200.

The catalytic cracking aid of the present invention may also contain 1-40 mass% of a binder and 0-65 mass% of a second clay based on the dry weight of the catalytic cracking aid. The binder contains a phosphorus-aluminum inorganic binder. The inorganic phosphorus-aluminum binder is an aluminum phosphorus adhesive and/or a first clay-containing inorganic phosphorus-aluminum binder.

To solve the above objects, the present invention provides a catalytic cracking catalyst containing a phosphorus-modified molecular sieve with an MFI structure, the catalytic cracking catalyst containing 1-25 wt.% zeolite Y, 5-50 wt.% phosphorus-modified molecular sieve with an MFI structure, 1- 60 wt.% inorganic binder and optionally 0-60 wt.% of the second clay by dry weight of the catalyst, where the inorganic binder contains phosphorus-aluminum inorganic binder and/or other inorganic binder(s); wherein the phosphorus-modified molecular sieve with an MFI structure has a K value satisfying the condition: 70%≤K≤90%, for example 75%≤K≤90%; or 78%≤K≤85%, where K=[mass content of phosphorus within an area having an area of 100 square meters. nm and a vertical depth of 5 to 10 nm on any surface of the crystal grain of the molecular sieve, measured by the EPMA method] / [mass phosphorus content within a region having an area of 100 sq. nm and a vertical depth of 0 to 2 nm on any molecular sieve crystal grain surface measured by XPS]×100%, wherein XPS analysis of the molecular sieve surface is performed using an ESCAREB 250 Type X-ray photoelectron spectrometer manufactured by Thermo Fisher-VG Company, excitation source is a monochromatic AlKα X-ray source with a power of 150 W, and the charge shift is calibrated to the C1s peak (284.8 eV) of the contaminated carbon; EPMA analysis of molecular sieve surface is performed using energy spectrometer with X-ray detector JXA-8230, and for the counting rate and counting time, the total counting number is usually greater than 10 ⁵ , the counting rate is 10 ³ -10 ⁴ 1/s, and the counting time is 10- 100 s.

In the above phosphorus modified molecular sieve with MFI structure, the molar ratio of phosphorus content as P ₂ O ₅ to alumina content is ≥0.01; for example≥0.2; or≥0.3; or for example 0.4-0.7; the aforementioned phosphorus-modified molecular sieve with an MFI structure may be a microporous molecular sieve ZSM-5 or a hierarchical molecular sieve ZSM-5 with a phosphorus content (as P ₂ O ₅ ) of at least 0.1 wt.%, wherein the microporous molecular sieve ZSM -5 has a silica/alumina molar ratio of 15-1000, for example 20-200; The ZSM-5 hierarchical molecular sieve has a mesopore volume fraction relative to the total pore space volume of more than 10%, an average pore diameter of 2-20 nm, and a silica/alumina molar ratio of 15-1000, such as 20-200.

In the above catalytic cracking catalyst, the Y zeolite may contain at least one of a PSRY zeolite, a rare earth element containing PSRY zeolite, a USY zeolite, a rare earth element containing USY zeolite, a REY zeolite, a REHY zeolite and an HY zeolite; for example, the inorganic binder comprises a phosphorus-aluminum inorganic binder; or, for example, the phosphorus-aluminum inorganic binder is a phosphorus-aluminum adhesive and/or a first clay-containing phosphorus-aluminum inorganic binder.

To solve the above problems, the present invention proposes a process for preparing a phosphorus-modified molecular sieve with an MFI structure, characterized in that it is obtained by an immersion method, which contains: contact by mixing an aqueous solution of a phosphorus-containing compound at a temperature of 40-150°C, for example 50-150°C , or for example 70-130°C, and a molecular sieve with an MFI structure at 40-150°C, for example 50-150°C, or for example 70-130°C at essentially the same temperature for at least 0. 1 hour, then drying and calcining at 200-600°C in air or steam for at least 0.1 hour; or vigorously mixing and agitating the phosphorus-containing compound, the MFI molecular sieve, and water, raising (e.g., increasing) the temperature to 40-150°C, e.g., 50-150°C, or e.g., 70-130°C, holding for about at least 0.1 hour, then drying and calcining at 200-600°C in air or steam for at least 0.1 hour.

In the process of preparing the phosphorus-modified molecular sieve with an MFI structure, the molecular sieve with an MFI structure may be a microporous hydrogen-type molecular sieve ZSM-5 or a hierarchical molecular sieve ZSM-5 hydrogen type. They are produced by ammonium exchange to reduce the sodium content to Na ₂ O<0.1 wt.% and bringing the silica-to-alumina ratio (molar ratio of silicon oxide to alumina) to the range of ≥10, typically 10-200.

In the process of preparing a phosphorus-modified molecular sieve with an MFI structure, the molar ratio of the phosphorus-containing compound (in terms of phosphorus) (as oxide) to the molecular sieve with an MFI structure (for example, ZSM-5 hydrogen-type molecular sieve or ZSM-5 hydrogen-type hierarchical molecular sieve type) (in terms of aluminum) (in the form of oxide) is 0.01-2; for example 0.1-1.5 or 0.2-1.5. The phosphorus-containing compound is selected from organic phosphorus compounds such as trimethylphosphate, triphenylphosphine, trimethylphosphite, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium hydroxide, triphenylethylphosphonium bromide, triphenylbutylphosphonium bromide, triphenylbenzylphosphonium bromide, hexamethylphosphoric acid triamide, dibenzyldiethylphosphoramidite, 1,3-bis((triethylphosphanyl) methyl)benzene and the like, inorganic phosphorus compounds such as phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate or a mixture thereof, etc. The present inventors have found that when boron phosphate is used as one of the phosphorus-containing compounds and hydrothermal calcination is carried out at 300-500°C, the phosphorus has better dispersion in the molecular sieve. Therefore, for example, the combination of phosphorus-containing compounds is a mixture of boron phosphate and one or more of trimethylphosphate, triphenylphosphine, trimethylphosphite, phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate. In the mixture containing boron phosphate, boron phosphate constitutes 10-80% by weight, for example 20-40% by weight or 25-35% by weight.

In the process of preparing a phosphorus-modified molecular sieve with an MFI structure, contacting consists of preparing an aqueous solution of a phosphorus-containing compound at a temperature of 30-150°C and a hydrogen-type molecular sieve with an MFI structure at a temperature of 30-150°C and their contact at almost the same temperature for at least 0.1 hour by immersion method. The contact is carried out, for example, in a higher temperature range, above 40°C, for example 50-150°C or 70-130°C, which can lead to a better result, that is, a better dispersion of the phosphorus species, and to an easier movement of phosphorus inward molecular sieve crystal with a hydrogen-type MFI structure to bond with the framework aluminum, which further improves the degree of coordination of phosphorus and framework aluminum, and finally helps to improve the hydrothermal stability of the molecular sieve. Substantially the same temperature means that the temperature difference between the temperature of the aqueous solution of the phosphorus-containing compound and the temperature of the hydrogen-type MFI molecular sieve does not exceed ±5°C. For example, if the temperature of an aqueous solution of a phosphorus-containing compound is 80°C, then the HZSM-5 molecular sieve should be heated to 75-85°C.

In the process of preparing phosphorus-modified molecular sieve with MFI structure, contacting may also involve mixing a phosphorus-containing compound, molecular sieve (hydrogen type) with MFI structure and water, and holding at 30-150°C for at least 0.1 hour. For example, to obtain a better result, i.e., better dispersion of phosphorus particles and easier migration of phosphorus into the molecular sieve crystal to combine with the aluminum framework, to further improve the degree of coordination of phosphorus and aluminum framework, and finally to improve the hydrothermal stability of the molecular sieve, phosphorus-containing compound, hydrogen type MFI molecular sieve and water are mixed and then maintained at a higher temperature range, above 40°C, for 0.1 hour, for example in a temperature range of 50-150°C or 70-130°C. Regarding contacting, the mass ratio of water/molecular sieve is 0.5-1, and the time is 0.5-40 hours. For example, calcination is performed at 450-550°C in an atmosphere of water vapor.

The present invention improves the hydrothermal stability of a phosphorus-modified molecular sieve by maintaining the coordination of phosphorus compounds with the aluminum framework of the MFI-structured molecular sieve. In cracking n-tetradecane, the phosphorus-containing molecular sieve with the MFI structure of the present invention can provide excellent cracking conversion and excellent yield of lower olefins, and at the same time can provide higher liquefied gas yield.

To achieve the above objects, the present invention provides a method for preparing a catalytic cracking aid comprising vigorously mixing and kneading a phosphorus modified molecular sieve with an MFI structure, a binder and optionally a second clay with water, and spray drying to produce a catalytic cracking aid. which is characterized in that the phosphorus-modified molecular sieve with an MFI structure is prepared by the phosphorus-modified molecular sieve with an MFI structure preparation process of the present invention.

In the process of preparing the catalytic cracking aid, the binder, for example, contains a phosphorus-aluminum inorganic binder. The phosphorus-aluminum inorganic binder is a phosphorus-aluminum adhesive and/or a first clay-containing phosphorus-aluminum inorganic binder; based on the dry weight of the phosphorus-aluminum inorganic binder containing the first clay, the phosphorus-aluminum inorganic binder containing the first clay contains 10-40 wt.%, for example 15-40 wt.% of the aluminum component (in terms of Al ₂ O ₃ ), 45-90 wt.% or 45-80 wt.% of the phosphorus component (in terms of P ₂ O ₅ ) and more than 0 and not more than 40 wt.% of the first clay in terms of dry matter, and inorganic phosphorus-aluminum containing the first clay the binder has a P/Al mass ratio of 1.0-6.0, a pH value of 1-3.5 and a solid content of 15-60 wt.%; the first clay contains at least one of kaolin, sepiolite, attapulgite, rectorite, smectite and diatomite; the binder may also include at least one other inorganic binder of pseudoboehmite, alumina sol, silica-alumina sol and water glass; the second clay is at least one substance selected from kaolin, sepiolite, attapulgite, rectorite, smectite, giagerite, halloysite, hydrotalcite, bentonite and diatomite.

In the process of preparing the catalytic cracking aid, the binder contains, based on the dry weight of the catalytic cracking aid, 3-39 wt.% phosphorus-aluminum inorganic binder and 1-30 wt.% other inorganic binder.

The process for preparing the catalytic cracking aid further comprises: subjecting the spray-dried product to first calcination and then washing and optionally drying to produce the catalytic cracking aid; moreover, for the first calcination, the calcination temperature is 300-650°C, the calcination time is 0.5-8 hours; The drying temperature is 100-200°C, and the drying time is 0.5-24 hours.

The process of preparing the catalytic cracking aid may further comprise: preparing a first clay-containing phosphorus-aluminum inorganic binder by the following steps: the alumina source, the first clay and water are vigorously mixed and mixed to obtain a thick slurry having a solids content of 5-48 wt. %; wherein the source of alumina is aluminum hydroxide and/or alumina, which can be peptized with acid, in an amount of 10-40 parts by weight, for example 15-40 parts by weight. source of alumina (in terms of Al ₂ O ₃ ), the amount of first clay used by dry weight is more than 0 ppm. and no more than 40 m.h.; concentrated phosphoric acid is added to the thick suspension with stirring according to the mass ratio of P/Al=1-6, and the resulting mixed thick suspension is reacted at 50-99°C for 15-90 minutes; wherein P in P/Al represents the mass of phosphorus as a base element in phosphoric acid, and Al represents the mass of aluminum as a base element in the alumina source.

To achieve the above objects, the present invention provides the use of a catalytic cracking aid, that is, a process for catalytic cracking of petroleum liquids, comprising: reacting the liquid petroleum by contacting with the above-mentioned catalytic cracking aid under catalytic cracking conditions. For example, liquid petroleum products are reacted by contacting with a catalyst mixture containing a catalytic cracking aid and a catalytic cracking catalyst; wherein in the catalyst mixture the content of the catalytic cracking auxiliary agent is 0.1-30 wt.%. Catalytic cracking conditions include: reaction temperature 500-800°C; The liquid petroleum products are one or more selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric gas oil, vacuum gas oil, straight run gas oil, propane light/heavy deasphalting oil, coker gas oil, and coal liquefaction product. In the catalytic cracking reaction of liquid petroleum products, the catalytic cracking aid of the present invention can provide excellent cracking conversion and excellent yield of lower olefins, and at the same time can provide higher liquefied gas yield.

To achieve the above objects, the present invention also provides a process for preparing a catalytic cracking catalyst comprising vigorously mixing and kneading a Y zeolite, a phosphorus modified MFI molecular sieve, an inorganic binder, and optionally a second clay with water, and spray drying to produce a catalytic cracking catalyst. cracking, characterized in that the phosphorus-modified molecular sieve with an MFI structure is prepared by the phosphorus-modified molecular sieve with an MFI structure preparation process of the present invention.

In the process of preparing the catalytic cracking catalyst of the present invention, the binder is a phosphorus-aluminum inorganic binder. The phosphorus-aluminum inorganic binder is a phosphorus-aluminum adhesive and/or a first clay-containing phosphorus-aluminum inorganic binder; The phosphorus-aluminum inorganic binder containing the first clay contains 10-40 wt.%, for example 15-40 wt.% of the aluminum component (in terms of Al ₂ O ₃ ), 45-90 wt.%, for example 45- 80 wt.% phosphorus component (in terms of P ₂ O ₅ ), and in terms of dry matter, more than 0 and not more than 40 wt.% of the first clay, and the phosphorus-aluminum inorganic binder containing the first clay has a mass ratio of P/Al , equal to 1.0-6.0, pH value 1-3.5, and solids content 15-60 wt.%; and the first clay contains at least one of kaolin, sepiolite, attapulgite, rectorite, smectite and diatomite.

In the process of preparing the catalytic cracking catalyst of the present invention, the second clay is at least one selected from kaolin, sepiolite, attapulgite, rectorite, smectite, giagerite, halloysite, hydrotalcite, bentonite and diatomite.

In the process of preparing the catalytic cracking catalyst of the present invention, the binder contains, on a dry weight basis based on the total weight of the catalytic cracking catalyst, 3-39 wt.% of phosphorus-aluminum inorganic binder and 1-30 wt.% of other inorganic binder(s), wherein the other inorganic binder comprises at least one of pseudoboehmite, alumina sol, silica-alumina sol and liquid glass.

The process for preparing a catalytic cracking catalyst further comprises: subjecting the spray-dried product to first calcination and then washing and optionally drying to produce a catalytic cracking catalyst; moreover, for the first calcination, the calcination temperature is 300-650°C, the calcination time is 0.5-8 hours; The drying temperature is 100-200°C, and the drying time is 0.5-24 hours.

The process of preparing a catalytic cracking catalyst of the present invention may further comprise: preparing a first clay-containing phosphorus-aluminum inorganic binder by the following steps: the alumina source, the first clay and water are vigorously mixed and mixed to obtain a thick slurry having a solids content of 5-48 wt. .%; wherein the source of alumina is aluminum hydroxide and/or alumina, which can be peptized with acid, in an amount of 10-40 parts by weight, for example 15-40 parts by weight. source of alumina (in terms of Al ₂ O ₃ ), the amount of first clay used by dry weight is more than 0 ppm. and no more than 40 m.h.; concentrated phosphoric acid is added to the thick suspension with stirring according to the mass ratio of P/Al=1-6, and the resulting mixed thick suspension is reacted at 50-99°C for 15-90 minutes; wherein P in P/Al represents the mass of phosphorus as a base element in phosphoric acid, and Al represents the mass of aluminum as a base element in the alumina source.

To achieve the above objects, the present invention provides the use of a catalytic cracking catalyst according to the present catalytic cracking invention, that is, a process for catalytic cracking of liquid petroleum products, comprising: reacting liquid petroleum products by contacting with the above-mentioned catalytic cracking catalyst under catalytic cracking conditions. Catalytic cracking conditions include: reaction temperature 500-800°C; The liquid petroleum products are one or more selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric gas oil, vacuum gas oil, straight run gas oil, propane light/heavy deasphalting oil, coker gas oil, and coal liquefaction product. In the catalytic cracking reaction of liquid petroleum products, the catalytic cracking catalyst proposed by the present invention can provide excellent cracking conversion and excellent yield of lower olefins, and at the same time can provide a higher yield of liquefied gas.

DETAILED DESCRIPTION

Next, specific embodiments of the present invention will be described in detail. It should be understood that the specific embodiments described herein are used only to illustrate and explain the present invention and are not intended to limit it.

In the present invention, pores with a size less than 2 nm are called micropores; pores with a size greater than 50 nm are called macropores, and pores with a size of 2-50 nm are called mesopores.

In the present invention, the first clay refers to a clay contained in a phosphorus-aluminum inorganic binder; and the second clay refers to a clay different from the first clay, and "first" and "second" are only intended to distinguish whether the clay is in the phosphorus-aluminum inorganic binder or not. The first clay includes, but is not limited to, kaolin, sepiolite, attapulgite, rectorite, smectite and diatomite. The second clay includes, but is not limited to, kaolin, sepiolite, attapulgite, rectorite, smectite, diatomite, giagerite, halloysite, hydrotalcite and bentonite.

In the present invention, binder and inorganic binder are synonymous.

The binder of the present invention contains a phosphorus-aluminum inorganic binder and other inorganic binder(s).

According to the present invention, the other inorganic binder(s) refers to a binder that does not contain phosphorus and aluminum elements, and the phosphorus-aluminum inorganic binder includes a phosphorus-aluminum adhesive and a first clay-containing phosphorus-aluminum inorganic binder.

In accordance with the present invention, examples of other inorganic binder(s) include, but are not limited to, pseudoboehmite, alumina sol, silica-alumina sol and water glass.

According to the present invention, the active component of the aluminum phosphorus adhesive is aluminum dihydrogen phosphate, and its theoretical ratio is P ₂ O ₅ /Al ₂ O ₃ =3:1 (molar ratio). Phosphorus-aluminum glue can be used as a binder to prepare a catalyst with excellent strength. In the present invention, the actual ratio of P ₂ O ₅ /Al ₂ O ₃ in the aluminum phosphorus adhesive is 3:1 or higher, for example 3:1 to 10:1 or greater than 3:1 and not greater than 5:1. For example, aluminum phosphorus adhesive can be prepared by vigorously mixing and stirring an alumina source with water to produce a thick slurry; adding concentrated phosphoric acid to this thick slurry while stirring and allowing the resulting mixed thick slurry to react for a certain period of time (eg 15-90 minutes at 50-99°C); the alumina source may be at least one selected from ρ-alumina, x-alumina, ƞ-alumina, γ-alumina, κ-alumina, Ʃ-alumina, Θ-alumina, gibbsite, bayerite, Nordstrandite, diaspore, boehmite and pseudoboehmite , the concentration of concentrated phosphoric acid may be 60-98 wt.%, for example 75-90 wt.%, and the phosphoric acid feed rate is, for example, 0.01-0.10 kg phosphoric acid/min/kg alumina source, or 0 .03-0.07 kg phosphoric acid/min/kg alumina source.

In accordance with the present invention, the first clay-containing phosphorus-aluminum inorganic binder refers to a binder that, on a dry weight basis, contains 10-40 wt.%, for example, 15-40 wt.% aluminum component (calculated as Al ₂ O ₃ ), 45-90 wt.%, for example 45-80 wt.% of the phosphorus component (in terms of P ₂ O ₅ ) and more than 0 and not more than 40 wt.% of the first clay in terms of dry matter, and containing the first The phosphorus-aluminum clay inorganic binder has a P/Al mass ratio of 1.0-6.0, a pH value of 1-3.5 and a solids content of 15-60 wt%.

In accordance with the present invention, the first clay-containing phosphorus-aluminum inorganic binder can be prepared by the following method: the alumina source, the first clay and water are vigorously mixed and stirred to obtain a thick slurry having a solids content of 5-48 wt.%; wherein the source of alumina is aluminum hydroxide and/or alumina, which can be peptized with acid, in an amount of 10-40 parts by weight, for example 15-40 parts by weight. source of alumina (in terms of Al ₂ O ₃ ), the amount of first clay used by dry weight is more than 0 ppm. and no more than 40 m.h.; concentrated phosphoric acid is added to the thick suspension with stirring according to the mass ratio of P/Al=1-6, and the resulting mixed thick suspension is reacted at 50-99°C for 15-90 minutes; wherein P in P/Al represents the mass of phosphorus as a base element in phosphoric acid, and Al represents the mass of aluminum as a base element in the alumina source. The alumina source may be at least one selected from ρ-alumina, x-alumina, ƞ-alumina, γ-alumina, κ-alumina, Ʃ-alumina, Θ-alumina, gibbsite, bayerite, Nordstrandite, diaspore, boehmite and pseudoboehmite , the concentration of concentrated phosphoric acid may be 60-98 wt.%, for example 75-90 wt.%, and the phosphoric acid feed rate is, for example, 0.01-0.10 kg phosphoric acid/min/kg alumina source, or 0 .03-0.07 kg phosphoric acid/min/kg alumina source.

The present invention provides a phosphorus-modified molecular sieve with an MFI structure, characterized in that it has a K value satisfying the condition: 70%≤K≤90%, for example 75%≤K≤90%; or 78%≤K≤85%, where K=[mass content of phosphorus within an area having an area of 100 square meters. nm and a vertical depth of 5 to 10 nm on any surface of the crystal grain of the molecular sieve, measured by the EPMA method] / [mass phosphorus content within a region having an area of 100 sq. nm and a vertical depth of 0 to 2 nm on any molecular sieve crystal grain surface measured by XPS]×100%, wherein XPS analysis of the molecular sieve surface is performed using an ESCAREB 250 Type X-ray photoelectron spectrometer manufactured by Thermo Fisher-VG Company, excitation source is a monochromatic AlKα X-ray source with a power of 150 W, and the charge shift is calibrated to the C1s peak (284.8 eV) of the contaminated carbon; EPMA analysis of molecular sieve surface is performed using energy spectrometer with X-ray detector JXA-8230, and for the counting rate and counting time, the total counting number is usually greater than 10 ⁵ , the counting rate is 10 ³ -10 ⁴ 1/s, and the counting time is 10- 100 s.

The phosphorus-modified molecular sieve with the MFI structure has a molar ratio of phosphorus content in terms of P ₂ O ₅ to alumina content of ≥0.01; for example≥0.2;≥0.3; or 0.4-0.7. For example, a phosphorus-modified molecular sieve with an MFI structure is a microporous molecular sieve ZSM-5 or a hierarchical molecular sieve ZSM-5. Microporous molecular sieve ZSM-5 has a silica/alumina molar ratio of 15-1000, for example 20-200. The ZSM-5 hierarchical molecular sieve has a mesopore volume fraction relative to the total pore space volume of more than 10%, an average pore diameter of 2-20 nm, and a silica/alumina molar ratio of 15-1000, for example 20-200.

The present invention also provides a process for preparing the above-mentioned phosphorus-modified molecular sieve with an MFI structure, which is obtained by an immersion method comprising: contact by mixing an aqueous solution of a phosphorus-containing compound at a temperature of 40-150°C, for example 50-150°C, or for example 70-130°C C, and a molecular sieve with an MFI structure at 40-150°C, for example 50-150°C, or for example 70-130°C at essentially the same temperature for at least 0.1 hour, then drying and calcining at 200-600°C in air or water vapor for at least 0.1 hour; or vigorously mixing and stirring the phosphorus-containing compound, the MFI molecular sieve and water, raising (for example, increasing) the temperature to 40-150°C, for example 50-150°C, or for example 70-130°C, holding for about at least 0.1 hour, then drying and calcining at 200-600°C in air or steam for at least 0.1 hour.

According to the preparation process of the phosphorus-modified molecular sieve with an MFI structure, the molecular sieve with an MFI structure may be a microporous hydrogen-type molecular sieve ZSM-5 or a hierarchical molecular sieve ZSM-5 hydrogen type. They are produced by ammonium exchange to reduce the sodium content to Na ₂ O<0.1 wt.% and bringing the silica-to-alumina ratio (molar ratio of silicon oxide to alumina) to the range of ≥10, typically 10-200.

According to the preparation process of phosphorus-modified molecular sieve with MFI structure, the molar ratio of phosphorus-containing compound (as phosphorus) (as oxide) to ZSM-5 hydrogen-type molecular sieve or ZSM-5 hydrogen-type hierarchical molecular sieve (as oxide) aluminum) is 0.01-2; for example 0.1-1.5 or 0.2-1.5. The phosphorus-containing compound is selected from organic phosphorus compounds such as trimethylphosphate, triphenylphosphine, trimethylphosphite, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium hydroxide, triphenylethylphosphonium bromide, triphenylbutylphosphonium bromide, triphenylbenzylphosphonium bromide, hexamethylphosphoric acid triamide, dibenzyldiethylphosphoramidite, 1,3-bis((triethylphosphanyl) methyl)benzene and the like, inorganic phosphorus compounds such as phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate or a mixture thereof, etc. The present inventors have found that by using boron phosphate as one of the phosphorus-containing compounds and carrying out hydrothermal calcination at 300-500°C, phosphorus has better dispersion in the molecular sieve. Therefore, for example, the combination of phosphorus-containing compounds is a mixture of boron phosphate and one or more of trimethylphosphate, triphenylphosphine, trimethylphosphite, phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate. In the mixture containing boron phosphate, boron phosphate constitutes 10-80 wt.%, for example 20-40 wt.% or 25-35 wt.%.

In accordance with the process of preparing a phosphorus-modified molecular sieve with an MFI structure, contacting consists of preparing an aqueous solution of a phosphorus-containing compound at a temperature of 30-150°C and a hydrogen-type molecular sieve with an MFI structure at a temperature of 30-150°C and contacting them at almost the same temperature for at least 0.1 hour by immersion method. The contact is carried out, for example, in a higher temperature range, above 40°C, for example 50-150°C or 70-130°C, which can lead to a better result, that is, a better dispersion of the phosphorus species, and to an easier movement of phosphorus inward molecular sieve crystal with a hydrogen-type MFI structure to bond with the framework aluminum, which further improves the degree of coordination of phosphorus and framework aluminum, and finally helps to improve the hydrothermal stability of the molecular sieve. Substantially the same temperature means that the temperature difference between the temperature of the aqueous solution of the phosphorus-containing compound and the temperature of the hydrogen-type MFI molecular sieve does not exceed ±5°C. For example, if the temperature of an aqueous solution of a phosphorus-containing compound is 80°C, then the HZSM-5 molecular sieve should be heated to 75-85°C.

According to the process of preparing phosphorus-modified molecular sieve with MFI structure, contacting may also consist of mixing a phosphorus-containing compound, hydrogen-type molecular sieve with MFI structure and water, and holding at 30-150°C for at least 0.1 hour. For example, to get a better result, i.e. better dispersion of phosphorus particles and easier migration of phosphorus into the molecular sieve crystal to combine with the aluminum framework, to further improve the degree of coordination of phosphorus and aluminum framework, and finally to improve the hydrothermal stability of the molecular sieve phosphorus-containing compound, hydrogen-type MFI molecular sieve and water mixed and then kept at a higher temperature range, above 40°C, for 0.1 hour, for example in the temperature range 50-150°C or 70-130°C.

According to the preparation process of phosphorus modified molecular sieve with MFI structure, the mass ratio of water/molecular sieve is 0.5-1, and the time is 0.5-40 hours. For example, calcination is performed at 450-550°C in an atmosphere of water vapor.

The present invention also provides a catalytic cracking aid containing 5-75 wt.% of a phosphorus-modified molecular sieve with an MFI structure based on the dry weight of the catalytic cracking aid; wherein the phosphorus-modified molecular sieve with the MFI structure has a K value satisfying the condition: 70%≤K≤90%, K=[mass content of phosphorus within a region having an area of 100 square meters. nm and a vertical depth of 5 to 10 nm on any surface of the crystal grain of the molecular sieve, measured by the EPMA method] / [mass phosphorus content within a region having an area of 100 sq. nm and a vertical depth of 0 to 2 nm on any molecular sieve crystal grain surface measured by XPS]×100%, wherein XPS analysis of the molecular sieve surface is performed using an ESCAREB 250 Type X-ray photoelectron spectrometer manufactured by Thermo Fisher-VG Company, excitation source is a monochromatic AlKα X-ray source with a power of 150 W, and the charge shift is calibrated to the C1s peak (284.8 eV) of the contaminated carbon; EPMA analysis of molecular sieve surface is performed using energy spectrometer with X-ray detector JXA-8230, and for the counting rate and counting time, the total counting number is usually greater than 10 ⁵ , the counting rate is 10 ³ -10 ⁴ 1/s, and the counting time is 10- 100 s.

In the catalytic cracking aid of the present invention, the K value of the phosphorus modified molecular sieve with MFI structure satisfies the condition of 75%≤K≤90%, for example 78%≤K≤85%.

In the catalytic cracking aid of the present invention for the phosphorus modified molecular sieve with MFI structure, the molar ratio of phosphorus content in terms of P ₂ O ₅ to alumina content is ≥0.01; for example≥0.2;≥0.3; or 0.4-0.7.

In the catalytic cracking aid of the present invention, for example, the phosphorus modified molecular sieve with an MFI structure is a ZSM-5 microporous molecular sieve or a ZSM-5 hierarchical molecular sieve. Microporous molecular sieve ZSM-5 has a silica/alumina molar ratio of 15-1000, for example 20-200. The ZSM-5 hierarchical molecular sieve has a mesopore volume fraction relative to the total pore space volume of more than 10%, an average pore diameter of 2-20 nm, and a silica/alumina molar ratio of 15-1000, for example 20-200.

The catalytic cracking aid of the present invention contains 5-75 wt.%, for example 8-60 wt.% phosphorus modified molecular sieve with MFI structure, and may also contain 1-40 wt.% binder and 0-65 wt. .% second clay by dry weight of catalytic cracking aid. The binder may be an inorganic oxide binder known to those skilled in the art and conventionally used as a binder component of an adjuvant or catalyst, for example may be one or more of pseudoboehmite, alumina sol, silica-alumina sol and water glass. For example, the binder comprises a phosphorus-aluminum inorganic binder, that is, it is a phosphorus-aluminum inorganic binder or a mixture of a phosphorus-aluminum inorganic binder and other inorganic binder(s).

In the catalytic cracking aid of the present invention, the phosphorus-aluminum inorganic binder is, for example, a phosphorus-aluminum adhesive and/or a first clay-containing phosphorus-aluminum inorganic binder. The phosphorus-aluminum inorganic binder containing the first clay contains, by its dry weight, 10-40 wt.%, for example, 15-40 wt.%, or 10-35 wt.%, or 15-35 wt.% of the aluminum component (in terms of on Al ₂ O ₃ ), 45-90 wt.%, for example 45-80 wt.%, or 50-75 wt.% of the phosphorus component (in terms of P ₂ O ₅ ), and in terms of dry matter more than 0 and not more than 40 wt.%, for example 8-35 wt.% of the first clay, and the phosphorus-aluminum inorganic binder containing the first clay has a P/Al mass ratio of 1.0-6.0, for example 1.2-6, 0 or 2.0-5.0, pH value 1-3.5, for example 2.0-3.0, and solids content 15-60 wt%. For example, in one embodiment of the phosphorus-aluminum inorganic binder, the phosphorus-aluminum inorganic binder contains, by dry weight, 20-40 wt.% aluminum component (calculated as Al ₂ O ₃ ) and 60-80 wt.% phosphorus component ( in terms of P ₂ O ₅ ).

In the catalytic cracking aid of the present invention, the first clay may be at least one of kaolin, sepiolite, attapulgite, rectorite, smectite and diatomite; the other inorganic binder may be selected from one or more inorganic oxide binders conventionally used in the binder component of a catalytic cracking aid or catalyst other than the aluminum phosphorus glue and the aluminum phosphorus inorganic binder, for example it may be at least one of pseudoboehmite, alumina sol, silica-alumina sol and liquid glass, or, for example, at least one of pseudoboehmite and alumina sol.

The catalytic cracking aid of the present invention further contains 0-65% by weight, for example 5-55% by weight, of a second clay by dry weight. The second clay is also known to those skilled in the art and, for example, is at least one of kaolin, sepiolite, attapulgite, rectorite, smectite, giagerite, halloysite, hydrotalcite, bentonite and diatomite.

In one embodiment, the catalytic cracking aid of the present invention contains, on a dry weight basis, 20-60 wt% phosphorus-modified molecular sieve with an MFI structure, 5-35 wt% binder, and 5-55 wt% second clay.

The present invention also provides a process for preparing a catalytic cracking aid comprising vigorously mixing and kneading the phosphorus modified molecular sieve with an MFI structure of the present invention, a binder and optionally a second clay with water, and then spray drying to produce a catalytic cracking aid. cracking.

In the process of preparing the catalytic cracking aid, the binder contains a phosphorus-aluminum inorganic binder and other inorganic binders, and on a dry weight basis, the mass ratio of phosphorus-modified molecular sieve with MFI structure:phosphorus-aluminum inorganic binder:other inorganic binder may be (10-75):(3-39):(1-30), for example (10-75):(8-35):(5-25); wherein the phosphorus-aluminum inorganic binder may be a phosphorus-aluminum adhesive and/or a phosphorus-aluminum inorganic binder containing the first clay; and the other inorganic binder may comprise at least one of pseudoboehmite, alumina sol, silica-alumina sol and liquid glass. The preparation process may comprise "mixing" or "vigorously mixing and agitating (with water)" the phosphorus-modified MFI molecular sieve, the phosphorus-aluminum inorganic binder, and other inorganic binder(s). There are no special loading order requirements. For example, a phosphorus-aluminum inorganic binder, other inorganic binder(s), a phosphorus-modified molecular sieve with an MFI structure, and a second clay (in case the second clay is not used, the corresponding loading step can be omitted) can be mixed, and can be vigorously mixed and mixed with water. Alternatively, the second clay, phosphorus-modified molecular sieve with MFI structure and other inorganic binder(s) can be vigorously mixed and mixed with water, and then the phosphorus-aluminum inorganic binder is added, which can help improve the activity and selectivity of the adjuvant.

The catalytic cracking aid preparation process further comprises a step of spray drying the thick slurry resulting from "vigorous mixing and agitation with water." The spray drying method is known to those skilled in the art, and the present invention does not place any special requirements on it. Optionally, the preparation process may further comprise subjecting the spray-dried product to first calcination and then washing and optionally drying to produce a catalytic cracking aid. Herein, the first calcination temperature may be 300-650°C, such as 400-600°C or 450-550°C, and the calcination time may be 0.5-8 hours; For washing, one of ammonium sulfate, ammonium chloride and ammonium nitrate can be used, the washing temperature can be 40-70°C; the drying temperature may be 100-200°C, such as 100-150°C, and the drying time may be 0.5-24 hours, such as 1-12 hours.

In one embodiment of the catalytic cracking aid preparation process, the binder, the second clay, and water (eg, decationized and/or demineralized water) are mixed to form a thick slurry having a solids content of 10-50% by weight. The thick suspension is well mixed, adjusted with an inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid to a pH value of 1-4, maintained at this pH value, and aged at 20-80°C for 0- 2 hours (for example 0.3-2 hours). An inorganic binder such as alumina sol and/or silica sol is then added and the mixture is stirred for 0.5-1.5 hour to form a gel. A phosphorus modified MFI molecular sieve is then added to form an auxiliary thick slurry with a solids content of, for example, 20-45 wt%. This auxiliary thick suspension is mixed and spray dried to form auxiliary microspheres. Then the auxiliary microspheres undergo a first calcination, for example at 350-650°C or 400-600°C, for example 450-550°C for 0.5-6 hours or 0.5-2 hours, and then washed with ammonium sulfate (and the washing temperature can be 40-70°C with a mass ratio of ammonium sulfate: auxiliary microspheres: water = 0.2-0.8: 1: 5-15) until the sodium oxide content is less than 0.25 wt.%, washed with water and filtered and then dried.

In one embodiment of the catalytic cracking aid preparation process, water (e.g., decationized and/or deionized water) and inorganic a binder such as an alumina sol and/or a silica sol are all vigorously mixed and stirred for 0.1-10 hours (eg 120 minutes) to produce a thick slurry containing 10-50 wt% solids (eg 30 wt.%); then a mineral acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid is added to adjust the pH to 1-4 (eg 3.0); then vigorous mixing and stirring is continued for 0.1-10 hours (eg 45 minutes), then the phosphorus-aluminum inorganic binder is added and the mixture is stirred for 0.1-10 hours (eg 30 minutes); the resulting thick suspension is spray dried to obtain microspheres, and these microspheres are calcined at 350-650°C or 400-600°C (eg 500°C) for 0.5-6 hours or 0.5-2 hours (eg 1 hour ) to produce a catalytic cracking aid.

In one embodiment of the catalytic cracking aid preparation process, a binder (eg, alumina sol) and a second clay (eg, kaolin) are mixed and water (eg, decationized and/or deionized water) is added to form a thick slurry with a solids content of 10 -50 wt.% (for example 30 wt.%); this thick suspension is well mixed and adjusted to a pH of 1-4 (eg 2.8) with an inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid; aged for aging at 20-80°C (eg 55°C) for 0.1-2 hours (eg 1 hour); then a phosphorus modified molecular sieve with an MFI structure is added to form a thick slurry with a solids content of 10-50 wt.% (eg 35 wt.%); and this thick suspension is continuously stirred and then spray dried to produce supporting microspheres. Then the auxiliary microspheres are subjected to a first calcination, for example at 350-650°C or 400-600°C, for example 450-550°C for 0.5-6 hours or 0.5-2 hours (for example at 500°C for 1 hour), and then washed with ammonium sulfate (and the washing temperature can be 40-70°C, for example 60°C, with a mass ratio of ammonium sulfate: auxiliary microspheres: water = 0.2-0.8: 1: 5-15 (for example 0.5:1:10)) to a sodium oxide content of less than 0.25 wt.%, washed with water and filtered, and then dried (for example at 100-200°C or 110°C).

In the process of preparing the catalytic cracking aid, the first clay-containing phosphorus-aluminum inorganic binder can be prepared by the following steps: the alumina source, the first clay and water are vigorously mixed and stirred to obtain a thick slurry having a solids content of 5-48 wt.% ; wherein the source of alumina is aluminum hydroxide and/or alumina, which can be peptized with acid, in an amount of 10-40 parts by weight, for example 15-40 parts by weight. source of alumina (in terms of Al ₂ O ₃ ), the amount of first clay used by dry weight is more than 0 ppm. and no more than 40 m.h.; concentrated phosphoric acid is added to the thick suspension with stirring according to the mass ratio of P/Al=1-6, and the resulting mixed thick suspension is reacted at 50-99°C for 15-90 minutes; wherein P in P/Al represents the mass of phosphorus as a base element in phosphoric acid, and Al represents the mass of aluminum as a base element in the alumina source. The alumina source may be at least one selected from ρ-alumina, x-alumina, ƞ-alumina, γ-alumina, κ-alumina, Ʃ-alumina, Θ-alumina, gibbsite, bayerite, Nordstrandite, diaspore, boehmite and pseudoboehmite , and the aluminum component in the first clay-containing phosphorus-aluminum inorganic binder is obtained from this alumina source. The first clay may contain one or more of kaolin, sepiolite, attapulgite, rectorite, smectite and diatomite, such as rectorite. The concentration of concentrated phosphoric acid may be 60-98 wt.%, for example 75-90 wt.%, and the phosphoric acid feed rate is, for example, 0.01-0.10 kg phosphoric acid/min/kg alumina source, or 0. 03-0.07 kg phosphoric acid/min/kg alumina source.

In the process of preparing the catalytic cracking aid, the incorporation of clay into the first clay-containing phosphorus-aluminum inorganic binder not only improves the mass and heat transfer between the materials during the preparation process, but also avoids the cure of the binder due to the temperature increase caused by heat generation due to the instantaneous strong local reaction of uneven materials; and the binding efficiency of the resulting binder is comparable to that of a phosphorus-aluminum binder prepared by a method without introducing clay. In addition, the addition of clay, especially rectorite with a layered structure, to the process improves the heavy oil conversion ability of the catalyst composition so that the resulting adjuvant has better selectivity.

The present invention further provides the use of a catalytic cracking aid, that is, a process for catalytic cracking of petroleum liquids comprising: reacting the liquid petroleum by contacting with the catalytic cracking aid according to the present invention under catalytic cracking conditions.

The process for catalytic cracking of petroleum liquids of the present invention comprises: reacting the liquid petroleum by contacting with a catalyst mixture containing a catalytic cracking aid and a catalytic cracking catalyst under catalytic cracking conditions; wherein in the catalyst mixture the content of the catalytic cracking auxiliary agent is 0.1-30 wt.%.

Optionally, catalytic cracking conditions include: reaction temperature 500-800°C; The liquid petroleum products are one or more selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric gas oil, vacuum gas oil, straight run gas oil, propane light/heavy deasphalting oil, coker gas oil, and coal liquefaction product.

The present invention also provides a catalytic cracking catalyst containing a phosphorus-modified molecular sieve with an MFI structure, the catalytic cracking catalyst containing 1-25 wt.% zeolite Y, 5-50 wt.% phosphorus-modified molecular sieve with an MFI structure, 1-60 wt.% % inorganic binder and optionally 0-60 wt.% of the second clay by dry weight of the catalyst, where the inorganic binder contains phosphorus-aluminum inorganic binder and/or other inorganic binder(s); wherein the phosphorus-modified molecular sieve with the MFI structure has a K value satisfying the condition: 70%≤K≤90%, K=[mass content of phosphorus within a region having an area of 100 square meters. nm and a vertical depth of 5 to 10 nm on any surface of the crystal grain of the molecular sieve, measured by the EPMA method] / [mass phosphorus content within a region having an area of 100 sq. nm and a vertical depth of 0 to 2 nm on any molecular sieve crystal grain surface measured by XPS]×100%, wherein XPS analysis of the molecular sieve surface is performed using an ESCAREB 250 Type X-ray photoelectron spectrometer manufactured by Thermo Fisher-VG Company, excitation source is a monochromatic AlKα X-ray source with a power of 150 W, and the charge shift is calibrated to the C1s peak (284.8 eV) of the contaminated carbon; EPMA analysis of molecular sieve surface is performed using energy spectrometer with X-ray detector JXA-8230, and for the counting rate and counting time, the total counting number is usually greater than 10 ⁵ , the counting rate is 10 ³ -10 ⁴ 1/s, and the counting time is 10- 100 s.

In the catalytic cracking catalyst of the present invention, zeolite Y contains at least one of PSRY zeolite, rare earth element containing PSRY zeolite, USY zeolite, rare earth element containing USY zeolite, REY zeolite, REHY zeolite and HY zeolite.

In the catalytic cracking catalyst of the present invention, the K value of the phosphorus-modified molecular sieve with an MFI structure satisfies the condition of 75%≤K≤90%, such as 78%≤K≤85%.

In the catalytic cracking catalyst of the present invention, for the phosphorus-modified molecular sieve with MFI structure, the molar ratio of phosphorus content in terms of P ₂ O ₅ to alumina content is ≥0.01; for example≥0.2;≥0.3; or 0.4-0.7.

In the catalytic cracking catalyst of the present invention, for example, the phosphorus modified molecular sieve with an MFI structure is a ZSM-5 microporous molecular sieve or a ZSM-5 hierarchical molecular sieve. Microporous molecular sieve ZSM-5 has a silica/alumina molar ratio of 15-1000, for example 20-200. The ZSM-5 hierarchical molecular sieve has a mesopore volume fraction relative to the total pore space volume of more than 10%, an average pore diameter of 2-20 nm, and a silica/alumina molar ratio of 15-1000, for example 20-200.

For example, in the catalytic cracking catalyst of the present invention, the catalytic cracking catalyst may contain, by dry weight, 2-20 wt% Y zeolite, 10-40 wt%, for example 20-40 wt% phosphorus-modified molecular sieve with MFI structure, and may also contain 1-40 wt.% inorganic binder and 0-50 wt.% second clay. Additionally, the catalyst, by its dry weight, may contain 3-40 wt.% phosphorus-aluminum inorganic binder, or 3-40 wt.% phosphorus-aluminum inorganic binder and 1-30 wt.% other inorganic binder(s).

In the catalytic cracking catalyst of the present invention, the phosphorus-aluminum inorganic binder is a phosphorus-aluminum adhesive and/or a first clay-containing phosphorus-aluminum inorganic binder. The phosphorus-aluminum inorganic binder containing the first clay, calculated on a dry weight basis, contains 10-40 wt.%, for example, 15-40 wt.% of the aluminum component (in terms of Al ₂ O ₃ ), 45-90 wt.%, for example 45-80 wt.% of the phosphorus component (in terms of P ₂ O ₅ ) and more than 0 and not more than 40 wt.% of the first clay in terms of dry matter, and the phosphorus-aluminum inorganic binder containing the first clay has a mass ratio of P/ Al 1.0-6.0, pH value 1-3.5 and solids content 15-60 wt.%.

In the catalytic cracking catalyst of the present invention, the first clay contains at least one of kaolin, sepiolite, attapulgite, rectorite, smectite and diatomite.

In the catalytic cracking catalyst of the present invention, in one embodiment, the phosphorus-aluminum inorganic binder may contain, by dry weight, 10-40 wt.%, for example 15-40 wt.% aluminum components (calculated as Al ₂ O ₃ ), 45-90 wt.%, for example 45-80 wt.% phosphorus component (in terms of P ₂ O ₅ ) and 0-40 wt.% dry first clay, and may have a P/Al mass ratio of 1.0- 6.0, pH value 1-3.5 and solids content 15-60 wt.%; for example, it may contain 15-35 wt.% aluminum component (in terms of Al ₂ O ₃ ), 50-75 wt.% phosphorus component (in terms of P ₂ O ₅ ) and 8-35 wt.% first clay, and may have a P/Al mass ratio, for example, 1.2-6.0 or 2.0-5.0, and a pH value, for example, 2.0-3.0.

In the catalytic cracking catalyst of the present invention, in another embodiment of the phosphorus-aluminum inorganic binder, the phosphorus-aluminum inorganic binder contains, by dry weight, 20-40 wt.% aluminum component (in terms of Al ₂ O ₃ ) and 60-80 wt. .% phosphorus component (in terms of P ₂ O ₅ ).

In the catalytic cracking catalyst of the present invention, the other inorganic binder may be selected from one or more inorganic oxide binders conventionally used in the binder component of the catalytic cracking aid or catalyst other than aluminum phosphorus glue and aluminum phosphorus inorganic binder, for example it may be at least one of pseudoboehmite, alumina sol, silica-alumina sol and liquid glass, or, for example, at least one of pseudoboehmite and alumina sol.

The catalytic cracking catalyst of the present invention, based on dry matter, further contains 0-65 wt.%, for example 5-55 wt.% of the second clay. The second clay is also known to those skilled in the art and, for example, is at least one of kaolin, sepiolite, attapulgite, rectorite, smectite, giagerite, halloysite, hydrotalcite, bentonite and diatomite.

The present invention also provides a process for preparing a catalytic cracking catalyst comprising vigorously mixing and kneading a Y zeolite, a phosphorus modified MFI molecular sieve, an inorganic binder, and optionally a second clay with water, and then spray drying to produce a catalytic cracking catalyst.

In the process of preparing the catalytic cracking catalyst of the present invention, the process may also include: washing and optionally drying the calcined product to obtain the catalytic cracking catalyst; herein, the calcination temperature may be 300-650°C, such as 400-600°C, preferably 450-550°C, and the calcination time may be 0.5-12 hours; For washing, one of ammonium sulfate, ammonium chloride and ammonium nitrate can be used, the washing temperature can be 40-80°C; the drying temperature may be 110-200°C, such as 120-150°C, and the drying time may be 0.5-18 hours, such as 2-12 hours.

In one embodiment of the catalytic cracking catalyst preparation process of the present invention, an inorganic binder (e.g., pseudoboehmite, alumina sol, silica sol, silica-alumina gel, or a mixture of two or more thereof) and a second clay (e.g., kaolin) and water (e.g., deionized and/or deionized water) may be mixed to form a thick slurry having a solids content of 10-50 wt%. This thick suspension is well mixed, adjusted with an inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid to a pH value of 1-4, maintained at this pH value, and aged at 20-80°C for 0 -2 hour (for example 0.3-2 hour). Then, alumina sol and/or silica sol is added and the mixture is stirred for 0.5-1.5 hour to form a gel. A molecular sieve (including phosphorus modified ZSM-5 molecular sieve and zeolite Y) is then added to form a thick catalyst slurry with a solids content of, for example, 20-45 wt%. This thick catalyst slurry is mixed and spray dried to form catalyst microspheres. Then the catalyst microspheres are calcined, for example at 350-650°C or 400-600°C, for example 450-550°C for 0.5-6 hours or 0.5-2 hours, and then washed with ammonium sulfate (and the washing temperature can be 40-70°C with a mass ratio of ammonium sulfate: catalyst microspheres: water = 0.2-0.8: 1: 5-15) to a sodium oxide content of less than 0.25 wt.%, washed with water and filtered, and then dried.

In one embodiment of the catalytic cracking catalyst preparation process of the present invention, a phosphorus modified ZSM-5 molecular sieve, a Y zeolite, a second clay (e.g., kaolin), and an inorganic binder (e.g., pseudoboehmite, alumina sol, silica sol, silica-alumina gel, or a mixture of two or more of them), to this mixture are added water (for example, deionized and/or deionized water) and an alumina sol and/or a silica sol, the resulting mixture is vigorously mixed and stirred for 0.1-10 hours (for example 120 min) to form a thick suspension having a solids content of 20-45 wt.% (eg 30 wt.%). This thick suspension is adjusted to a pH of 1-4 (eg 3.0) by adding an inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, after which vigorous mixing and agitation is continued for 0.1-10 hours ( for example 45 min). The phosphorus-aluminum inorganic binder is then added and the mixture is stirred for 0.1-10 hours (eg 30 minutes) to produce a thick slurry. The resulting thick slurry is spray dried to form catalyst microspheres. Then the catalyst microspheres are calcined, for example at 350-650°C or 400-600°C, for example 450-550°C for 0.5-6 hours or 0.5-2 hours (for example at 500°C for 1 hour ) to produce a catalytic cracking catalyst.

In one embodiment of the catalytic cracking catalyst preparation process of the present invention, an inorganic binder (e.g., pseudoboehmite, alumina sol, silica sol, silica-alumina gel, or a mixture of two or more of these) and a second clay (e.g., kaolin) are mixed and added to the mixture. water (eg, deionized and/or deionized water) to form a thick slurry having a solids content of 10-50% by weight (eg, 30% by weight); this thick suspension is well mixed and adjusted to a pH of 1-4 (eg 2.8) by adding an inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid; aged for aging at 20-80°C (eg 55°C) for 0.1-2 hours (eg 1 hour); phosphorus modified molecular sieve ZSM-5 and zeolite Y are then added to form a thick catalyst slurry having a solids content of 20-45 wt% (eg 35 wt%); this thick slurry of catalyst is continuously stirred and then spray dried to form catalyst microspheres. Then the catalyst microspheres are calcined, for example at 350-650°C or 400-600°C, for example 450-550°C for 0.5-6 hours or 0.5-2 hours (for example at 500°C for 1 hour ), and then washed with ammonium sulfate (and the washing temperature can be 40-70°C, for example 60°C, with a mass ratio of ammonium sulfate: catalyst microspheres: water = 0.2-0.8: 1: 5-15 (for example 0.5:1:10)) until the sodium oxide content is less than 0.25 wt.%, washed with water and filtered, and then dried (for example at 100-200°C or 110°C).

In another embodiment of the catalytic cracking catalyst preparation process of the present invention, the zeolite Y, phosphorus modified molecular sieve ZSM-5, phosphorus-aluminum inorganic binder and other inorganic binder(s), and optionally the second clay may be vigorously mixed and mixed with water and Spray dry.

In the process of preparing the catalytic cracking catalyst of the present invention, the inorganic binder contains a phosphorus-aluminum inorganic binder and another inorganic binder, and the mass ratio of the phosphorus-aluminum inorganic binder to the other inorganic binder may be (3-40): (1- 30), for example (5-35): (5-28) or (10-30): (5-25); wherein the phosphorus-aluminum inorganic binder may be a phosphorus-aluminum adhesive and/or a phosphorus-aluminum inorganic binder containing the first clay; and the other inorganic binder may comprise at least one of pseudoboehmite, alumina sol, silica-alumina sol and liquid glass.

The process for preparing the catalytic cracking catalyst of the present invention may comprise "mixing" or "vigorously mixing and stirring (with water)" of the phosphorus-modified molecular sieve, the phosphorus-aluminum inorganic binder, and other inorganic binder(s). There are no special loading order requirements. For example, a phosphorus-aluminum inorganic binder, other inorganic binder(s), a molecular sieve, and a second clay (in case the second clay is not used, the corresponding loading step may be omitted) can be mixed, and can be vigorously mixed and mixed with water. Alternatively, the second clay, molecular sieve and other inorganic binder(s) can be vigorously mixed and mixed with water, and then a phosphorus-aluminum inorganic binder is added, which can help improve the activity and selectivity of the catalyst.

In the process of preparing the catalytic cracking catalyst of the present invention, the preparation process further comprises a spray drying step of the thick slurry obtained by "vigorously mixing and agitating with water." The spray drying method is known to those skilled in the art, and the present invention does not place any special requirements on it.

In addition, the process of preparing the catalytic cracking catalyst of the present invention may also include: preparing a first clay-containing phosphorus-aluminum inorganic binder through the following steps: the alumina source, the first clay and water are vigorously mixed and mixed to obtain a thick solids-containing slurry substances 5-48 wt.%; wherein the source of alumina is aluminum hydroxide and/or alumina, which can be peptized with acid, in an amount of 10-40 parts by weight, for example 15-40 parts by weight. source of alumina (in terms of Al ₂ O ₃ ), the amount of first clay used by dry weight is more than 0 ppm. and no more than 40 m.h.; concentrated phosphoric acid is added to the thick suspension with stirring according to the mass ratio of P/Al=1-6, and the resulting mixed thick suspension is reacted at 50-99°C for 15-90 minutes; wherein P in P/Al represents the mass of phosphorus as a base element in phosphoric acid, and Al represents the mass of aluminum as a base element in the alumina source. The alumina source may be at least one selected from ρ-alumina, x-alumina, ƞ-alumina, γ-alumina, κ-alumina, Ʃ-alumina, Θ-alumina, gibbsite, bayerite, Nordstrandite, diaspore, boehmite and pseudoboehmite , and the aluminum component in the first clay-containing phosphorus-aluminum inorganic binder is obtained from this alumina source. The first clay may contain one or more of kaolin, sepiolite, attapulgite, rectorite, smectite and diatomite, such as rectorite. The concentration of concentrated phosphoric acid may be 60-98 wt.%, for example 75-90 wt.%, and the phosphoric acid feed rate is, for example, 0.01-0.10 kg phosphoric acid/min/kg alumina source, or 0. 03-0.07 kg phosphoric acid/min/kg alumina source.

In the process of preparing the catalytic cracking catalyst of the present invention, incorporating clay into the first clay-containing phosphorus-aluminum inorganic binder not only improves the mass and heat transfer between the materials during the preparation process, but also avoids hardening of the binder due to the temperature increase caused by the release heat due to an instant strong local reaction of uneven materials; and the binding efficiency of the resulting binder is comparable to that of a phosphorus-aluminum binder prepared by a method without introducing clay. In addition, the introduction of clay, especially rectorite with a layered structure, into the process improves the catalyst's ability to convert heavy oil so that the resulting catalyst has better selectivity.

The present invention also provides a catalytic cracking catalyst prepared by the above process.

The present invention further provides the use of a catalytic cracking catalyst, that is, a process for catalytic cracking of petroleum liquids, comprising: reacting the liquid petroleum by contacting the catalytic cracking catalyst in accordance with the present invention under catalytic cracking conditions. Catalytic cracking conditions include: reaction temperature 500-800°C; The liquid petroleum products are one or more selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric gas oil, vacuum gas oil, straight run gas oil, propane light/heavy deasphalting oil, coker gas oil, and coal liquefaction product. Liquid petroleum products may contain impurities of heavy metals such as nickel and vanadium, as well as impurities of sulfur and nitrogen. For example, the sulfur content of petroleum liquids can be up to 3.0 wt.%, the nitrogen content can be up to 2.0 wt.%, and the content of metallic impurities such as vanadium and nickel can be up to 3000 ppm.

One embodiment when used in a catalytic cracking process is that the catalytic cracking catalyst can be added separately to the catalytic cracking reactor, for example, under catalytic cracking conditions, liquid petroleum products are reacted by contacting the catalytic cracking catalyst of the present invention; Another embodiment is that the catalyst can be mixed with other catalytic cracking catalyst(s), for example, liquid petroleum products can be reacted by contacting a catalyst mixture containing the catalytic cracking catalyst of the present invention and other catalytic cracking catalyst(s). The catalyst proposed by the present invention may constitute no more than 30 wt.% of the entire above mixture, for example 1-25 wt.% or 3-15 wt.%.

The combined EPMA/XPS method is used to carry out quantitative analysis of phosphorus content by scanning the surface and analyzing the chemical composition in micro-zones and the corresponding deep structure, and the dispersity value K refers to the ratio in percentage of the mass content of phosphorus at the depth boundary of the molecular sieve crystal grain to the phosphorus content at the surface molecular sieve crystal grain, where K=P2(EPMA)/P1(XPS)%, P1(XPS) is the mass content of phosphorus in microzones less than 2 nm deep on any surface of the molecular sieve crystal grain, quantified by XPS, and P2 ( EPMA) is the mass content of phosphorus in microzones 5 to 10 nm deep, obtained by focused ion beam (FIB) cutting and quantified by the EPMA method.

Molecular sieve surface analysis is performed by X-ray photoelectron spectroscopy (XPS) using an ESCAREB 250 Type X-ray photoelectron spectrometer from Thermo Fisher-VG Company, in which the excitation source is a 150 W monochromatic AlKα X-ray source and the charge shift is calibrated to the C1s peak (284 .8 eV) from contaminated carbon.

EPMA: When using the X-ray detector of JXA-8230 energy spectrometer, the counting speed and counting time, the total number of counts usually exceeds 10 ⁵ , the counting rate is 10 ³ -10 ⁴ CPS, and the counting time is 10-100 s.

The present invention also offers the following technical solutions:

Aspect 1. Phosphorus modified molecular sieve with MFI structure, characterized in that it has a K value satisfying the condition of 70%≤K≤90%; for example 75%≤K≤90% or 78%≤K≤85%;

where K=P1/P2×100%,

P1 is the mass content of phosphorus measured by XPS in a region with an area of 100 sq.nm and a vertical depth of 0 to 2 nm on any surface of the molecular sieve crystal grain,

P2 is the EPMA-measured mass content of phosphorus in a region with an area of 100 nm2 and a vertical depth of 5 to 10 nm on any surface of the molecular sieve crystalline grain.

Aspect 2. The molecular sieve according to any of the preceding aspects, wherein the molar ratio of phosphorus content in terms of P ₂ O ₅ to alumina content is ≥0.01; for example≥0.2;≥0.3; or 0.4-0.7.

Aspect 3. The molecular sieve of any one of the preceding aspects, wherein the phosphorus modified molecular sieve with an MFI structure is a ZSM-5 microporous molecular sieve or a ZSM-5 hierarchical molecular sieve.

Aspect 4. The molecular sieve of any one of the preceding aspects, wherein the ZSM-5 microporous molecular sieve has a silica/alumina molar ratio of 15-1000, such as 20-200.

Aspect 5. The molecular sieve of any one of the preceding aspects, wherein the ZSM-5 hierarchical molecular sieve has a mesopore volume fraction relative to the total pore volume of more than 10%, an average pore diameter of 2-20 nm, and a silica/alumina molar ratio of 15-1000, for example 20-200.

Aspect 6. A catalytic cracking aid which, by dry weight of the catalytic cracking aid, contains 5-75 wt.%, for example 8-60 wt.% phosphorus modified molecular sieve with an MFI structure according to any of the preceding aspects, 1-40 wt. .% binder and 0-65 wt.%, for example 5-55 wt.% second clay.

Aspect 7. A catalytic cracking catalyst containing phosphorus modified molecular sieve(s) with an MFI structure, which by dry weight of the catalytic cracking catalyst contains 1-25 wt.% zeolite Y, 5-50 wt.% phosphorus modified molecular sieve with an MFI structure any of the preceding aspects, 1-60 wt.% inorganic binder and optionally 0-60 wt.% second clay.

Aspect 8. The catalytic cracking aid or catalytic cracking catalyst according to any of the preceding aspects, wherein the binder or inorganic binder comprises a phosphorus-aluminum inorganic binder and/or other inorganic binder(s),

for example, the phosphorus-aluminum inorganic binder is a phosphorus-aluminum glue and/or a first clay-containing phosphorus-aluminum inorganic binder, or, for example, the first clay is selected from kaolin, sepiolite, attapulgite, rectorite, smectite and diatomite; in addition, for example, the phosphorus-aluminum inorganic binder containing the first clay contains 10-40 wt.%, for example 15-40 wt.% of the aluminum component (in terms of Al ₂ O ₃ ), 45-90 wt.%, for example 45 -80 wt.% phosphorus component (in terms of P ₂ O ₅ ) and more than 0 and not more than 40 wt.% of the first clay in terms of dry matter, and the phosphorus-aluminum inorganic binder containing the first clay has a mass ratio of P/Al 1.0-6.0, pH value 1-3.5 and solids content 15-60 wt.%;

for example, the second clay is selected from kaolin, sepiolite, attapulgite, rectorite, smectite, diatomite, giagerite, halloysite, hydrotalcite and bentonite;

for example, the other inorganic binder(s) is selected from pseudoboehmite, alumina sol, silica-alumina sol and water glass.

Aspect 9. The catalytic cracking catalyst according to any one of the preceding aspects, wherein the Y zeolite contains at least one of a PSRY zeolite, a PSRY-S zeolite containing rare earth elements, a PSRY zeolite containing rare earth elements, a PSRY-S zeolite, a USY zeolite containing rare earth elements USY zeolite, REY zeolite, REHY zeolite and HY zeolite.

Aspect 10. A process for preparing a phosphorus-modified molecular sieve with an MFI structure according to any one of the preceding aspects, characterized in that the phosphorus-modified molecular sieve with an MFI structure is prepared by an immersion method comprising: contact by mixing an aqueous solution of a phosphorus-containing compound at a temperature of 40-150°C, for example 50-150°C, or for example 70-130°C, and a molecular sieve with an MFI structure at 40-150°C, for example 50-150°C, or for example 70-130°C at essentially the same temperature in for at least 0.1 hour, then drying and calcining at 200-600°C in air or steam for at least 0.1 hour; or vigorously mixing and stirring the phosphorus-containing compound, the MFI molecular sieve and water, raising (for example, increasing) the temperature to 40-150°C, for example 50-150°C, or for example 70-130°C, holding for about at least 0.1 hour, then drying and calcining at 200-600°C in air or steam for at least 0.1 hour.

Aspect 11. A process for preparing a phosphorus-modified molecular sieve with an MFI structure according to any one of the preceding aspects, wherein the phosphorus-containing compound is selected from organic phosphorus compounds and/or inorganic phosphorus compounds; for example, the organic phosphorus compound is selected from trimethylphosphate, triphenylphosphine, trimethylphosphite, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium hydroxide, triphenylethylphosphonium bromide, triphenylbutylphosphonium bromide, triphenylbenzylphosphonium bromide, hexamethylphosphoric acid triamide, dibenzyldiethylphosphoramidite, 1,3-bi c((triethylphosphanyl)methyl)benzene, and the inorganic phosphorus compound is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.

Aspect 12. A process for preparing a phosphorus-modified molecular sieve with an MFI structure according to any one of the preceding aspects, wherein the molar ratio of a phosphorus-containing compound (in terms of phosphorus oxide) to a molecular sieve with an MFI structure (for example, a ZSM-5 hydrogen-type molecular sieve) ( in terms of aluminum oxide) is 0.01-2; for example 0.1-1.5 or 0.2-1.5.

Aspect 13. A process for preparing a phosphorus-modified molecular sieve with an MFI structure according to any one of the preceding aspects, wherein the phosphorus-containing compound is a mixture of boron phosphate and one or more substances selected from trimethylphosphate, triphenylphosphine, trimethylphosphite, phosphoric acid, hydrogen ammonium phosphate, diammonium hydrogen phosphate and ammonium phosphate, and in this mixture boron phosphate constitutes 10-80 wt.%, for example 20-40 wt.%.

Aspect 14. A process for preparing a phosphorus-modified molecular sieve with an MFI structure according to any one of the preceding aspects, wherein the water/molecular sieve contact mass ratio is 0.5-1 and the contact time is 0.5-40 hours.

Aspect 15: A process for preparing a phosphorus-modified molecular sieve with an MFI structure according to any one of the preceding aspects, wherein calcination is performed at 450-550° C. under a steam atmosphere.

Aspect 16. The process of preparing a catalytic cracking aid according to any of the preceding aspects, comprising vigorously mixing and kneading a phosphorus modified molecular sieve with an MFI structure, a binder, and optionally a second clay with water, and then spray drying to produce a catalytic cracking aid. catalytic cracking.

Aspect 17. A process for preparing a catalytic cracking aid according to any of the preceding aspects, wherein the binder includes or is a phosphorus-aluminum inorganic binder.

Aspect 18. The catalytic cracking aid preparation process of any one of the preceding aspects, wherein the phosphorus-aluminum inorganic binder is a phosphorus-aluminum adhesive and/or a first clay-containing phosphorus-aluminum inorganic binder; The phosphorus-aluminum inorganic binder containing the first clay contains 10-40 wt.% in its dry weight, for example, 15-40 wt.%, or 10-30 wt.%, or 15-35 wt.% or 20-40 wt. .% aluminum component (in terms of Al ₂ O ₃ ), 45-90 wt.%, for example 45-80 wt.%, or 50-75 wt.%, or 60-80 wt.% phosphorus component (in terms of P ₂ O ₅ ), and in terms of dry matter more than 0 and not more than 40 wt.%, for example 8-35 wt.% of the first clay, and the phosphorus-aluminum inorganic binder containing the first clay has a P/Al mass ratio equal to 1.0-6.0, for example 1.2-6.0 or 2.0-5.0, pH value 1-3.5, for example 2.0-3.0, and solids content 15-60 wt. .%; and the first clay contains at least one of kaolin, sepiolite, attapulgite, rectorite, smectite and diatomite.

Aspect 19. A process for preparing a catalytic cracking aid according to any of the preceding aspects, wherein the second clay is at least one selected from kaolin, sepiolite, attapulgite, rectorite, smectite, giagerite, halloysite, hydrotalcite, bentonite and diatomite.

Aspect 20. A process 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 contains, on a dry weight basis, 3-39 wt.% phosphorus-aluminum inorganic binder and 1-30 wt.% other inorganic binders.

Aspect 21. The process for preparing a catalytic cracking aid according to any of the preceding aspects, wherein the other inorganic binder(s) may also include at least one of pseudoboehmite, alumina sol, silica-alumina sol, and water glass.

Aspect 22. The process for preparing a catalytic cracking aid according to any of the preceding aspects, further comprising: subjecting the spray-dried product to first calcination and then washing and optionally drying in order to produce a catalytic cracking aid; moreover, for the first calcination, the calcination temperature is 300-650°C, the calcination time is 0.5-8 hours; The drying temperature is 100-200°C, and the drying time is 0.5-24 hours.

Aspect 23. The process of preparing a catalytic cracking aid according to any of the preceding aspects, further comprising: preparing a first clay-containing phosphorus-aluminum inorganic binder by the following steps: the alumina source, the first clay and water are vigorously mixed and mixed to obtain a thick slurry with solids content 5-48 wt.%; wherein the source of alumina is aluminum hydroxide and/or alumina, which can be peptized with acid, in an amount of 10-40 parts by weight, for example 15-40 parts by weight. source of alumina (in terms of Al ₂ O ₃ ), the amount of first clay used by dry weight is more than 0 ppm. and no more than 40 m.h.; concentrated phosphoric acid is added to the thick suspension with stirring according to the mass ratio of P/Al=1-6, and the resulting mixed thick suspension is reacted at 50-99°C for 15-90 minutes; wherein P in P/Al represents the mass of phosphorus as a base element in phosphoric acid, and Al represents the mass of aluminum as a base element in the alumina source.

Aspect 24. A process for preparing a catalytic cracking catalyst according to any one of the preceding aspects, wherein the process comprises vigorously mixing and agitating a Y zeolite, a phosphorus modified molecular sieve with an MFI structure according to any one of the preceding aspects, an inorganic binder, and optionally a second clay with water, and then spray drying to produce a catalytic cracking catalyst.

Aspect 25. A process for preparing a catalytic cracking catalyst according to any of the preceding aspects, wherein the inorganic binder includes or is a phosphorus-aluminum inorganic binder.

Aspect 26. A process for preparing a catalytic cracking catalyst according to any of the preceding aspects, wherein the phosphorus-aluminum inorganic binder is a phosphorus-aluminum adhesive and/or a first clay-containing phosphorus-aluminum inorganic binder; The phosphorus-aluminum inorganic binder containing the first clay contains 10-40 wt.%, for example 15-40 wt.% of the aluminum component (in terms of Al ₂ O ₃ ), 45-90 wt.%, for example 45- 80 wt.% phosphorus component (in terms of P ₂ O ₅ ), and in terms of dry matter, more than 0 and not more than 40 wt.% of the first clay, and the phosphorus-aluminum inorganic binder containing the first clay has a mass ratio of P/Al , equal to 1.0-6.0, pH value 1-3.5, and solids content 15-60 wt.%; and the first clay contains at least one of kaolin, sepiolite, attapulgite, rectorite, smectite and diatomite.

Aspect 27. The process of preparing a catalytic cracking catalyst according to any of the preceding aspects, wherein the second clay is at least one selected from kaolin, sepiolite, attapulgite, rectorite, smectite, giagerite, halloysite, hydrotalcite, bentonite and diatomite.

Aspect 28. The process for preparing a catalytic cracking catalyst according to any one of the preceding aspects, wherein, based on the total weight of the catalytic cracking catalyst, the inorganic binder contains, on a dry weight basis, 3-39 wt.% phosphorus-aluminum inorganic binder and 1-30 wt.% another inorganic binder, where the other inorganic binder(s) is at least one selected from pseudoboehmite, alumina sol, silica-alumina sol and liquid glass.

Aspect 29. The process of preparing a catalytic cracking catalyst according to any of the preceding aspects, further comprising: subjecting the spray-dried product to first calcination and then washing and optionally drying to produce a catalytic cracking catalyst; moreover, for the first calcination, the calcination temperature is 300-650°C, the calcination time is 0.5-8 hours; The drying temperature is 100-200°C, and the drying time is 0.5-24 hours.

Aspect 30. The process of preparing a catalytic cracking catalyst according to any of the preceding aspects, further comprising: preparing a first clay-containing phosphorus-aluminum inorganic binder by the following steps: the alumina source, the first clay and water are vigorously mixed and mixed to obtain a thick solids-containing slurry substances 5-48 wt.%; wherein the source of alumina is aluminum hydroxide and/or alumina, which can be peptized with acid, in an amount of 10-40 parts by weight, for example 15-40 parts by weight. source of alumina (in terms of Al ₂ O ₃ ), the amount of first clay used by dry weight is more than 0 ppm. and no more than 40 m.h.; concentrated phosphoric acid is added to the thick suspension with stirring according to the mass ratio of P/Al=1-6, and the resulting mixed thick suspension is reacted at 50-99°C for 15-90 minutes; wherein P in P/Al represents the mass of phosphorus as a base element in phosphoric acid, and Al represents the mass of aluminum as a base element in the alumina source.

Aspect 31: A catalytic cracking aid produced by the catalytic cracking aid preparation process of any one of the preceding aspects.

Aspect 32. A catalytic cracking catalyst produced by the catalytic cracking catalyst preparation process of any of the preceding aspects.

Aspect 33. A process for the catalytic cracking of petroleum liquids, characterized in that it comprises: reacting the liquid petroleum by contacting with a catalytic cracking aid according to any of the preceding aspects or with a catalytic cracking catalyst according to any one of the preceding aspects under catalytic cracking conditions.

Aspect 34. A process for catalytic cracking of petroleum liquids according to any one of the preceding aspects, comprising: reacting the liquid petroleum by contact with a catalyst mixture containing a catalytic cracking aid according to any one of the preceding aspects and a catalytic cracking catalyst, under catalytic cracking conditions; wherein in the catalyst mixture the content of the catalytic cracking auxiliary agent is 0.1-30 wt.%.

Aspect 35. A process for catalytic cracking of petroleum liquids according to any of the preceding aspects, wherein the catalytic cracking conditions include: a reaction temperature of 500-800° C.; The liquid petroleum products are one or more selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric gas oil, vacuum gas oil, straight run gas oil, propane light/heavy deasphalting oil, coker gas oil, and coal liquefaction product.

The present invention will be further described below with reference to specific examples, but the present invention is not limited to these examples.

The tools and reagents used in the examples of the present invention are those commonly used by those skilled in the art unless otherwise specifically stated.

A microreaction apparatus was used to evaluate the effect of the catalytic cracking aid/catalyst of the present invention on the yield of lower olefins in the catalytic cracking of petroleum hydrocarbons.

The prepared catalytic cracking aid/catalyst sample was aged at 800°C with 100% steam for 17 hours in a fixed bed aging apparatus and then evaluated in a microreaction apparatus. The feedstock petroleum products are VGO (vacuum gas oil) or naphtha. Evaluation conditions included a reaction temperature of 620°C, a regeneration temperature of 620°C, and a catalyst-to-oil ratio of 3.2. Microreactivity was measured using the standard ASTM D5154-2010 method.

The standard RIPP method mentioned in the present invention is described in the publication "Analysis Method of Petrochemical Industry", edited by Yang Cuiding et al., 1990 edition.

The properties of some of the raw materials used in the Example were as follows:

Pseudoboehmite was an industrial product produced by Shandong Aluminum Company, with a solid content of 60 wt%.

The alumina sol was a commercial product produced by Sinopec Catalyst Qilu Branch and had an Al ₂ O ₃ content of 21.5 wt%.

The silica sol was an industrial product produced by Sinopec Catalyst Qilu Branch, with a SiO ₂ content of 28.9 wt% and a Na ₂ O content of 8.9%.

The kaolin was a special kaolin for catalytic cracking catalyst produced by Suzhou Kaolin Company, with a solid content of 78 wt%.

Rectorite was produced by Hubei Zhongxiang Mingliu Rectorite Development Co., Ltd., with a quartz sand content of <3.5 wt%, an _Al2O3 content of _39.0 wt%, a _Na2O content of 0.03 wt%, and solids content 77 wt.%.

SB: Aluminum hydroxide powder produced by Condex Corporation, Germany, containing Al ₂ O ₃ 75 wt.%.

Gamma alumina produced by Condex Corporation, Germany, with an Al ₂ O ₃ content of 95 wt.%.

Hydrochloric acid, chemically pure, with a concentration of 36-38 wt.%, produced by the Beijing Chemical Plant.

The PSRY molecular sieve was an industrial product manufactured by Sinopec Catalyst Changling Branch, with _Na2O content <1.5 wt%, _P2O5 content _0.8-1.2 wt%, unit cell constant <2.456 nm, and crystallinity≥64%.

The commercial molecular sieve HRY-1 was a commercial product produced by Sinopec Catalyst Changling Branch, with a La ₂ O ₃ content of 11-13 wt%, a unit cell constant of <2.464 nm, and a crystallinity of ≥40%.

The equilibrium catalyst was an industrial equilibrium catalyst FCC manufactured by Sinopec Yanshan Petrochemical, commercial grade DVR-3 with a light oil microactivity of 63.

The following examples illustrate the phosphorus-modified ZSM-5 hierarchical molecular sieves of the present invention and processes for their preparation. These molecular sieves can be 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

Example 1-1 illustrates the phosphorus-containing ZSM-5 hierarchical molecular sieve of the present invention and its preparation process.

18.5 g diammonium hydrogen phosphate, 108 g hydrogen-type hierarchical molecular sieve ZSM-5 (provided by Qilu Division of Sinopec Catalyst Company, relative crystallinity 88.6%, silica/alumina molar ratio 20.8, Na ₂ O content 0.017 wt.% , specific surface area 373 m ² /g, total pore volume 0.256 ml/g, mesopore volume 0.119 ml/g and average pore diameter 5.8 nm, the same holds true hereafter) and 60 g of deionized water were vigorously mixed and stirred to form a thick suspension. This thick slurry was heated to 100°C for 2 hours, dried at 110°C in an oven, and air calcined at 550°C for 2 hours to produce a sample of phosphorus-containing hierarchical molecular sieve ZSM-5, which was designated like GPZ1-1.

Comparative Example 1-1

Identical to Example 1-1 except that a ZSM-5 hydrogen hierarchical molecular sieve immersion method at 20° C. was used to prepare a comparative ZSM-5 phosphorus hierarchical molecular sieve sample, which was designated D1-1.

Example 1-2

Identical to Example 1-1 except that drying was followed by treatment at 450°C with 60% steam for 0.5 hour to obtain a ZSM-5 phosphorus-containing hierarchical molecular sieve sample designated GPZ1-2.

Comparative example 1-2

Identical to Example 1-2 except that a ZSM-5 hydrogen hierarchical molecular sieve immersion method was used at 20°C to produce a ZSM-5 phosphorus-containing hierarchical molecular sieve comparative sample, designated D1-2.

Phosphorus dispersity data K for GPZ1-1, D1-1, GPZ1-2 and D1-2 are shown in Table 1.

Example 2-1

Example 2-1 illustrates the phosphorus-containing ZSM-5 hierarchical molecular sieve of the present invention and its preparation process.

18.5 g of diammonium hydrogen phosphate, 108 g of ZSM-5 hierarchical hydrogen molecular sieve and 120 g of deionized water were vigorously mixed and stirred to form a thick slurry. This thick slurry was kept at 70°C for 2 hours, dried at 110°C in an oven and air calcined at 550°C for 2 hours to produce a sample of phosphorus-containing hierarchical molecular sieve ZSM-5, which was designated GPZ2 -1.

Comparative Example 2-1

Identical to Example 2-1 except that a ZSM-5 hydrogen hierarchical molecular sieve immersion method at 20° C. was used to produce a comparative ZSM-5 phosphorus hierarchical molecular sieve sample, designated D2-1.

Example 2-2

Identical to Example 2-1 except that drying was followed by treatment at 600° C. with 50% steam for 2 hours to obtain a sample of phosphorus-containing hierarchical molecular sieve ZSM-5, which was designated GPZ2-2.

Comparative Example 2-2

Identical to Example 2-2 except that the ZSM-5 hierarchical hydrogen molecular sieve immersion method was used at 20° C. to obtain a comparative sample, which was designated D2-2.

Phosphorus K dispersity data for GPZ2-1, D2-1, GPZ2-2 and D2-2 are shown in Table 1.

Example 3-1

Example 3-1 illustrates the phosphorus-containing ZSM-5 hierarchical molecular sieve of the present invention and its preparation process.

11.8 g of phosphoric acid were dissolved in 60 g of deionized water and stirred for 2 hours to obtain an aqueous solution containing phosphorus; 108 g of hierarchical molecular sieve of the hydrogen type ZSM-5 was taken; the above-mentioned phosphorus-containing aqueous solution and the above-mentioned ZSM-5 hierarchical hydrogen molecular sieve were respectively heated to 80°C, then mixed for 4 hours, dried in an oven at 110°C, and calcined in air at 550°C for 2 hours to produce a sample of phosphorus modified hierarchical molecular sieve ZSM-5, which was designated GPZ3-1.

Comparative Example 3-1

Identical to Example 3-1 except that the method of immersing a ZSM-5 hydrogen hierarchical molecular sieve at 20°C in an aqueous solution containing phosphorus was used to obtain a comparative sample of a ZSM-5 phosphorus hierarchical molecular sieve, which was designated D3- 1.

Example 3-2

Identical to Example 3-1 except that drying was followed by treatment at 430°C with 100% steam for 2 hours to obtain a ZSM-5 phosphorus-containing hierarchical molecular sieve sample designated GPZ3-2.

Comparative Example 3-2

Identical to Example 3-2 except that the method of immersing a ZSM-5 hydrogen hierarchical molecular sieve at 20°C in an aqueous solution containing phosphorus was used to obtain a comparative sample of the ZSM-5 phosphorus hierarchical molecular sieve, which was designated D3- 2.

Phosphorus dispersity data K for GPZ3-1, D3-1, GPZ3-2 and D3-2 are shown in Table 1.

Example 4-1

Example 4-1 illustrates the phosphorus-containing ZSM-5 hierarchical molecular sieve of the present invention and its preparation process.

9.3 g of diammonium hydrogen phosphate, 108 g of ZSM-5 hierarchical hydrogen molecular sieve and 120 g of deionized water were vigorously mixed and stirred to form a thick slurry. This thick slurry was kept at 90°C for 2 hours, dried at 110°C in an oven and air calcined at 550°C for 2 hours to produce a sample of phosphorus-containing hierarchical molecular sieve ZSM-5, which was designated GPZ4 -1.

Comparative Example 4-1

Identical to Example 4-1 except that a ZSM-5 hydrogen hierarchical molecular sieve immersion method at 20°C was used to produce a ZSM-5 phosphorus hierarchical molecular sieve comparative sample, designated D4-1.

Example 4-2

Identical to Example 4-1 except that drying was followed by treatment at 350°C with 100% steam for 2 hours to obtain a ZSM-5 phosphorus-containing hierarchical molecular sieve sample designated GPZ4-2.

Comparative Example 4-2

Identical to Example 4-2 except that a ZSM-5 hydrogen hierarchical molecular sieve immersion method at 20°C was used to produce a ZSM-5 phosphorus hierarchical molecular sieve comparative sample, designated D4-2.

Phosphorus K dispersity data for GPZ4-1, D4-1, GPZ4-2 and D4-2 are shown in Table 1.

Example 5-1

Example 5-1 illustrates the phosphorus-containing ZSM-5 hierarchical molecular sieve of the present invention and its preparation process.

9.7 g of trimethylphosphate, 108 g of ZSM-5 hierarchical hydrogen molecular sieve and 80 g of deionized water were vigorously mixed and stirred to form a thick slurry. This thick slurry was kept at 120°C for 8 hours, dried at 110°C in an oven and air calcined at 550°C for 2 hours to produce a sample of phosphorus-containing hierarchical molecular sieve ZSM-5, which was designated GPZ5 -1.

Comparative Example 5-1

Identical to Example 5-1 except that the ZSM-5 Hierarchical Molecular Sieve ZSM-5 Hydrogen Hierarchical Molecular Sieve Immersion Method at 20° C. was used to produce a ZSM-5 Phosphorus Hierarchical Molecular Sieve Comparative Sample which was designated D5-1.

Example 5-2

Identical to Example 5-1 except that drying was followed by calcination treatment at 500° C. with 40% steam for 4 hours to obtain a sample of phosphorus-containing hierarchical molecular sieve ZSM-5, which was designated GPZ5-2.

Comparative Example 5-2

Identical to Example 5-2 except that a ZSM-5 hydrogen hierarchical molecular sieve immersion method was used at 20° C. to produce a ZSM-5 phosphorus hierarchical molecular sieve comparative sample, designated D5-2.

Phosphorus K dispersity data for GPZ5-1, D5-1, GPZ5-2 and D5-2 are shown in Table 1.

Example 6-1

Example 6-1 illustrates the phosphorus-containing ZSM-5 hierarchical molecular sieve of the present invention and its preparation process.

13.2 g of boron phosphate, 108 g of ZSM-5 hierarchical hydrogen molecular sieve and 100 g of deionized water were vigorously mixed and stirred to form a thick slurry. This thick slurry was held at 150°C for 2 hours, dried at 110°C in an oven and air calcined at 550°C for 2 hours to produce a sample of phosphorus-containing hierarchical molecular sieve ZSM-5, which was designated GPZ6 -1.

Comparative Example 6-1

Identical to Example 6-1 except that a ZSM-5 hydrogen hierarchical molecular sieve immersion method at 20° C. was used to produce a comparative ZSM-5 phosphorus hierarchical molecular sieve sample, designated D6-1.

Example 6-2

Identical to Example 6-1 except that drying was followed by hydrothermal calcination treatment at 350° C. with 60% steam for 4 hours to obtain a sample of phosphorus-containing hierarchical molecular sieve ZSM-5, which was designated GPZ6-2.

Comparative Example 6-2

Identical to Example 6-2 except that the ZSM-5 Hierarchical Molecular Sieve ZSM-5 immersion method was used at 20° C. to produce a comparative sample of the phosphorus-containing ZSM-5 Hierarchical Molecular Sieve, which was designated D6-2.

Phosphorus K dispersity data for GPZ6-1, D6-1, GPZ6-2 and D6-2 are shown in Table 1.

Example 7-1

Example 7-1 illustrates the phosphorus-containing ZSM-5 hierarchical molecular sieve of the present invention and its preparation process.

16.3 g of triphenylphosphine were dissolved in 80 g of deionized water and stirred for 2 hours to obtain an aqueous solution containing phosphorus; 108 g of hierarchical molecular sieve of the hydrogen type ZSM-5 was taken; the above-mentioned phosphorus-containing aqueous solution and the above-mentioned ZSM-5 hierarchical hydrogen molecular sieve were respectively heated to 80°C, then mixed for 4 hours, dried in an oven at 110°C, and calcined in air at 550°C for 2 hours to produce a sample of phosphorus-containing hierarchical molecular sieve ZSM-5, which was designated GPZ7-1.

Comparative Example 7-1

Identical to Example 7-1 except that the method of immersing a ZSM-5 hydrogen hierarchical molecular sieve at 20°C in an aqueous solution containing phosphorus was used to obtain a comparative sample of a ZSM-5 phosphorus hierarchical molecular sieve, which was designated D7- 1.

Example 7-2

Identical to Example 7-1 except that drying was followed by calcination treatment at 600° C. with 50% steam for 2 hours to obtain a sample of phosphorus-containing hierarchical molecular sieve ZSM-5, which was designated GPZ7-2.

Comparative Example 7-2

Identical to Example 7-2 except that the method of immersing a ZSM-5 hydrogen hierarchical molecular sieve at 20°C in an aqueous solution containing phosphorus was used to produce a comparative sample of a ZSM-5 phosphorus hierarchical molecular sieve, designated D7- 2.

Phosphorus K dispersity data for GPZ7-1, D7-1, GPZ7-2 and D7-2 are shown in Table 1.

Example 8-1

Identical to Example 4-1 except that the phosphorus source was diammonium hydrogen phosphate and crystallized boron phosphate, and their mass ratio was 3:1 to obtain a phosphorus-containing hierarchical molecular sieve sample ZSM-5, which was designated GPZ8-1.

Example 8-2

Identical to Example 4-2 except that the phosphorus source was diammonium hydrogen phosphate and crystallized boron phosphate in a 3:1 weight ratio to produce a ZSM-5 hierarchical molecular sieve phosphorus sample designated GPZ8-2.

Example 9-1

Identical to Example 4-1 except that the phosphorus source was diammonium hydrogen phosphate and crystallized boron phosphate, and their mass ratio was 2:2 to obtain a phosphorus-containing hierarchical molecular sieve sample ZSM-5, which was designated GPZ9-1.

Example 9-2

Identical to Example 4-2 except that the phosphorus source was diammonium hydrogen phosphate and crystallized boron phosphate in a 2:2 weight ratio to produce a phosphorus-containing hierarchical molecular sieve sample ZSM-5 designated GPZ9-2.

Example 10-1

Identical to Example 4-1 except that the phosphorus source was diammonium hydrogen phosphate and crystallized boron phosphate, and their mass ratio was 1:3 to obtain a phosphorus-containing hierarchical molecular sieve sample ZSM-5, which was designated GPZ10-1.

Example 10-2

Identical to Example 4-2 except that the phosphorus source was diammonium hydrogen phosphate and crystallized boron phosphate, and their mass ratio was 1:3 to obtain a phosphorus-containing hierarchical molecular sieve sample ZSM-5, which was designated GPZ10-2.

Phosphorus K dispersity data for GPZ8-1, GPZ8-2, GPZ9-1, GPZ9-2, GPZ10-1 and GPZ10-2 are shown in Table 1.

Example 11-1

Identical to Example 8-1 except that the phosphorus source was phosphoric acid and crystallized boron phosphate in a 3:1 weight ratio to produce a phosphorus-containing hierarchical molecular sieve sample ZSM-5 designated GPZ11-2.

Example 11-2

Identical to Example 8-2 except that the phosphorus source was phosphoric acid and crystallized boron phosphate in a 3:1 weight ratio to produce a phosphorus-containing hierarchical molecular sieve sample ZSM-5 designated GPZ11-2.

Example 12-1

Identical to Example 9-1 except that the phosphorus source was phosphoric acid and crystallized boron phosphate in a 2:2 weight ratio to produce a phosphorus-containing hierarchical molecular sieve sample ZSM-5 designated GPZ12-1.

Example 12-2

Identical to Example 9-2 except that the phosphorus source was phosphoric acid and crystallized boron phosphate and their mass ratio was 2:2 (identical to or similar to the ratio of Example 9-1) to obtain a sample of phosphorus-containing hierarchical molecular sieve ZSM-5 , which was designated GPZ12-2.

Example 13-1

Identical to Example 10-1 except that the phosphorus source was phosphoric acid and crystallized boron phosphate, and their mass ratio was 1:3 to obtain a phosphorus-containing hierarchical molecular sieve sample ZSM-5, which was designated GPZ13-2.

Example 13-2

Identical to Example 10-2 except that the phosphorus source was phosphoric acid and crystallized boron phosphate in a 1:3 weight ratio to produce a phosphorus-containing hierarchical molecular sieve sample ZSM-5 designated GPZ13-2.

Phosphorus K dispersity data for GPZ11-1, GPZ11-2, GPZ12-1, GPZ12-2, GPZ13-1 and GPZ13-2 are shown in Table 1.

From the data in Table 1, it can be seen that the phosphorus-modified ZSM-5 hierarchical molecular sieves of the present invention have higher phosphorus dispersion, for example, sample GPZ8-2 in Example 8-2, which was modified with a dual phosphorus source, that is, phosphoric acid and crystallized phosphate boron, reached a dispersity value K of 85%.

The following examples illustrate the phosphorus-modified ZSM-5 microporous molecular sieves of the present invention and methods for their preparation. These molecular sieves can be used in the preparation of the catalytic cracking aid of the present invention and the catalytic cracking catalyst of the present invention.

Example 14-1

Example 14-1 illustrates the ZSM-5 phosphorus-containing microporous molecular sieve of the present invention and its preparation process.

16.2 g diammonium hydrogen phosphate, 113 g HZSM-5 molecular sieve (provided by Qilu Division of Sinopec Catalyst Company, relative crystallinity was 91.1%, silica/alumina molar ratio was 24.1, Na ₂ O content was 0.039 wt.% , the specific surface area was 353 m ² /g, the total pore volume was 0.177 ml/g, the same is true) and 60 g of deionized water were vigorously mixed and stirred to form a thick suspension. This thick slurry was heated to 100°C, held for 2 hours, dried at 110°C and treated at 550°C in air for 0.5 hour to obtain a sample of phosphorus modified molecular sieve ZSM-5, which was designated as GPZ14-1.

Comparative Example 14-1

Comparative Example 14-1 illustrates a current conventional industrial process and a comparative sample of phosphorus modified ZSM-5 obtained therefrom.

It is identical to Example 14-1 except that the method of immersing the HZSM-5 molecular sieve at 20° C. for 2 hours was used to obtain a comparative sample of phosphorus-modified molecular sieve ZSM-5, which was designated D14-1.

Example 14-2

Example 14-2 illustrates the ZSM-5 phosphorus-containing microporous molecular sieve of the present invention and its preparation process.

It is identical to Example 14-1 except that the 550°C air treatment was replaced by a 500°C 50% steam treatment for 0.5 hour to obtain a ZSM-5 phosphorus modified molecular sieve sample. which was designated GPZ14-2.

Comparative Example 14-2

Identical to Example 14-2 except that the method of immersing the ZSM-5 Hierarchical Hydrogen Type Molecular Sieve at 20°C for 2 hours was used to produce a comparative sample of the ZSM-5 Phosphorus Modified Molecular Sieve, which was designated D14-2.

Phosphorus K dispersity data for GPZ14-1, D14-1, GPZ14-2 and D14-2 are shown in Table 1.

Example 15-1

Example 15-1 illustrates the ZSM-5 phosphorus-containing microporous molecular sieve of the present invention and its preparation process.

16.2 g diammonium hydrogen phosphate, 113 g HZSM-5 molecular sieve and 120 g deionized water were vigorously mixed and stirred to form a thick slurry. This thick slurry was kept at 70°C for 2 hours, dried at 110°C and processed at 550°C in air for 2 hours to obtain a sample of phosphorus modified molecular sieve ZSM-5, which was designated GPZ15-1.

Comparative Example 15-1

Comparative Example 15-1 illustrates a current conventional industrial process and a comparative sample of phosphorus modified ZSM-5 obtained therefrom.

It is identical to Example 15-1 except that the HZSM-5 molecular sieve immersion method at 20° C. was used to produce a comparative sample of phosphorus modified ZSM-5 molecular sieve, which was designated D15-1.

Example 15-2

Example 15-2 illustrates the ZSM-5 phosphorus-containing microporous molecular sieve of the present invention and its preparation process.

It is identical to Example 15-1 except that the 550°C air treatment was replaced by a 600°C 30% steam treatment for 2 hours to obtain a ZSM-5 phosphorus modified molecular sieve sample that was designated as GPZ15-2.

Comparative Example 15-2

Identical to Example 15-2 except that the HZSM-5 molecular sieve immersion process at 20° C. was used to produce a comparative sample of phosphorus modified ZSM-5 molecular sieve, designated D15-2.

Phosphorus K dispersity data for GPZ15-1, D15-1, GPZ15-2 and D15-2 are shown in Table 1.

Example 16-1

Example 16-1 illustrates the ZSM-5 phosphorus-containing microporous molecular sieve of the present invention and its preparation process.

10.4 g of phosphoric acid were dissolved in 60 g of deionized water and stirred for 2 hours to obtain an aqueous solution containing phosphorus; 113 g of molecular sieve HZSM-5 was taken; the above-mentioned phosphorus-containing aqueous solution and the above-mentioned HZSM-5 molecular sieve were respectively heated to 80°C, then mixed for 4 hours, dried at 110°C and processed at 550°C in an air atmosphere for 2 hours to produce a sample phosphorus modified molecular sieve ZSM-5, which was designated GPZ16-1.

Comparative Example 16-1

Comparative Example 16-1 illustrates a current conventional industrial process and a comparative sample of phosphorus modified ZSM-5 obtained therefrom.

It is identical to Example 16-1 except that the method of immersing an HZSM-5 molecular sieve at 20° C. in an aqueous solution containing phosphorus was used to produce a comparative sample of phosphorus-modified ZSM-5 molecular sieve, which was designated D16-1.

Example 16-2

Example 16-2 illustrates the ZSM-5 phosphorus-containing microporous molecular sieve of the present invention and its preparation process.

It is identical to Example 16-1 except that the 550°C air treatment was replaced by a 400°C 100% steam treatment for 2 hours to obtain a ZSM-5 phosphorus modified molecular sieve sample that was designated as GPZ16-2.

Comparative Example 16-2

Identical to Example 16-2 except that the method of immersing an HZSM-5 molecular sieve at 20° C. in an aqueous solution containing phosphorus was used to produce a comparative sample of phosphorus-modified ZSM-5 molecular sieve, designated D16-2.

Phosphorus K dispersity data for GPZ16-1, D16-1, GPZ16-2 and D16-2 are shown in Table 1.

Example 17-1

Example 17-1 illustrates the ZSM-5 phosphorus-containing microporous molecular sieve of the present invention and its preparation process.

8.1 g diammonium hydrogen phosphate, 113 g HZSM-5 molecular sieve and 120 g deionized water were vigorously mixed and stirred to form a thick slurry. This thick slurry was kept at 90°C for 4 hours, dried at 110°C and processed at 550°C in air for 2 hours to obtain a sample of phosphorus modified molecular sieve ZSM-5, which was designated GPZ17-1.

Comparative Example 17-1

Comparative Example 17-1 illustrates a current conventional industrial process and a comparative sample of phosphorus modified ZSM-5 obtained therefrom.

It is identical to Example 17-1 except that the HZSM-5 molecular sieve immersion method at 20° C. was used to produce a comparative sample of phosphorus modified ZSM-5 molecular sieve, which was designated D17-1.

Example 17-2

Identical to Example 17-1 except that the 550°C air treatment was replaced by a 300°C 100% steam treatment for 2 hours to produce the ZSM-5 phosphorus modified molecular sieve sample designated like GPZ17-2.

Comparative Example 17-2

Identical to Example 17-2 except that the HZSM-5 molecular sieve immersion method at 20° C. was used to produce a comparative sample of phosphorus modified ZSM-5 molecular sieve, designated D17-2.

Phosphorus K dispersity data for GPZ17-1, D17-1, GPZ17-2 and D17-2 are shown in Table 1.

Example 18-1

8.5 g trimethylphosphate, 113 g HZSM-5 molecular sieve and 80 g deionized water were vigorously mixed and stirred to form a thick slurry. This thick slurry was heated to 120°C, held for 8 hours, dried at 110°C and treated at 550°C in air for 2 hours to obtain a sample of phosphorus modified molecular sieve ZSM-5, which was designated GPZ18- 1.

Comparative Example 18-1

Comparative Example 18-1 illustrates a current conventional industrial process and a comparative sample of phosphorus modified ZSM-5 obtained therefrom.

It is identical to Example 18-1 except that the HZSM-5 molecular sieve immersion method at 20° C. was used to produce a comparative sample of phosphorus modified ZSM-5 molecular sieve, which was designated D18-1.

Example 18-2

Example 18-2 illustrates the ZSM-5 phosphorus-containing microporous molecular sieve of the present invention and its preparation process.

It is identical to Example 18-1 except that the 550°C air treatment was replaced by a 500°C 80% steam treatment for 4 hours to obtain a ZSM-5 phosphorus modified molecular sieve sample that was designated as GPZ18-2.

Comparative Example 18-2

Identical to Example 18-2 except that the HZSM-5 molecular sieve immersion process at 20° C. was used to produce a comparative sample of phosphorus modified ZSM-5 molecular sieve, designated D18-2.

Phosphorus K dispersity data for GPZ18-1, D18-1, GPZ18-2 and D18-2 are shown in Table 1.

Example 19-1

Example 19-1 illustrates the ZSM-5 phosphorus-containing microporous molecular sieve of the present invention and its preparation process.

11.6 g boron phosphate, 113 g HZSM-5 molecular sieve and 100 g deionized water were vigorously mixed and stirred to form a thick slurry. This thick slurry was kept at 150°C for 2 hours, dried at 110°C and processed at 550°C in air for 2 hours to obtain a sample of phosphorus modified molecular sieve ZSM-5, which was designated GPZ19-1.

Comparative Example 19-1

Comparative Example 19-1 illustrates a current conventional industrial process and a comparative sample of phosphorus modified ZSM-5 obtained therefrom.

It is identical to Example 19-1 except that the HZSM-5 molecular sieve immersion method at 20° C. was used to produce a comparative sample of phosphorus modified ZSM-5 molecular sieve, which was designated D19-1.

Example 19-2

Example 19-2 illustrates the ZSM-5 phosphorus-containing microporous molecular sieve of the present invention and its preparation process.

It is identical to Example 19-1 except that the 550°C air treatment was replaced by a 400°C 100% steam treatment for 4 hours to obtain a ZSM-5 phosphorus modified molecular sieve sample that was designated as GPZ19-2.

Comparative Example 19-2

Identical to Example 19-2 except that the HZSM-5 molecular sieve immersion process at 20° C. was used to produce a comparative sample of phosphorus modified ZSM-5 molecular sieve, designated D19-2.

Phosphorus K dispersity data for GPZ19-1, D19-1, GPZ19-2 and D19-2 are shown in Table 1.

Example 20-1

Example 20-1 illustrates the ZSM-5 phosphorus-containing microporous molecular sieve of the present invention and its preparation process.

14.2 g of triphenylphosphine were dissolved in 80 g of deionized water and stirred for 2 hours to obtain an aqueous solution containing phosphorus; 113 g of molecular sieve HZSM-5 was taken; the above-mentioned phosphorus-containing aqueous solution and the above-mentioned HZSM-5 molecular sieve were respectively heated to 80°C, then mixed for 4 hours, dried at 110°C and processed at 550°C in an air atmosphere for 2 hours to produce a sample phosphorus modified molecular sieve ZSM-5, which was designated GPZ20-1.

Comparative Example 20-1

Comparative Example 20-1 illustrates a current conventional industrial process and a comparative sample of phosphorus modified ZSM-5 obtained therefrom.

It is identical to Example 20-1 except that the method of immersing an HZSM-5 molecular sieve at 20° C. in an aqueous solution containing phosphorus was used to produce a comparative sample of phosphorus-modified molecular sieve ZSM-5, which was designated D20-1.

Example 20-2

Example 20-2 illustrates the ZSM-5 phosphorus-containing microporous molecular sieve of the present invention and its preparation process.

It is identical to Example 20-1 except that the 550°C air treatment was replaced by a 600°C 30% steam treatment for 4 hours to obtain a ZSM-5 phosphorus modified molecular sieve sample that was designated as GPZ20-2.

Comparative Example 20-2

Identical to Example 20-2 except that the method of immersing an HZSM-5 molecular sieve at 20° C. in an aqueous solution containing phosphorus was used to produce a comparative sample of phosphorus-modified ZSM-5 molecular sieve, designated D20-2.

Phosphorus dispersity data K for GPZ20-1, D20-1, GPZ20-2 and D20-2 are shown in Table 1.

Example 21-1

Identical to Example 17-1 except that the phosphorus source was diammonium hydrogen phosphate and crystallized boron phosphate in a 3:1 weight ratio to produce a ZSM-5 phosphorus-containing molecular sieve sample designated GPZ21-1.

Example 21-2

Identical to Example 17-2 except that the phosphorus source was diammonium hydrogen phosphate and crystallized boron phosphate in a 3:1 weight ratio to produce a ZSM-5 phosphorus-containing molecular sieve sample designated GPZ21-2.

Example 22-1

Identical to Example 17-1 except that the dual phosphorus source was diammonium hydrogen phosphate and crystallized boron phosphate in a 2:2 weight ratio to produce a ZSM-5 phosphorus-containing molecular sieve sample designated GPZ22-1.

Example 22-2

Identical to Example 17-2 except that the phosphorus source was diammonium hydrogen phosphate and crystallized boron phosphate in a 2:2 weight ratio to produce a ZSM-5 phosphorus-containing molecular sieve sample designated GPZ23-2.

Example 23-1

Identical to Example 17-1 except that the phosphorus source was diammonium hydrogen phosphate and crystallized boron phosphate in a 1:3 weight ratio to produce a ZSM-5 phosphorus-containing molecular sieve sample designated GPZ23-1.

Example 23-2

Identical to Example 17-2 except that the phosphorus source was diammonium hydrogen phosphate and crystallized boron phosphate in a 1:3 weight ratio to produce a ZSM-5 phosphorus-containing molecular sieve sample designated GPZ23-2.

Phosphorus dispersity data K for GPZ21-1, GPZ21-2, GPZ22-1, GPZ22-2, GPZ23-1 and GPZ23-2 are shown in Table 1.

Examples 24-1-26-2

The phosphorus sources in Examples 21-1 to 23-2 were respectively replaced with phosphoric acid and crystallized boron phosphate at their ratios of 3:1, 3:1, 2:2, 2:2, 1:3 and 1:3, respectively, to produce samples that were designated as GPZ24-1, GPZ24-2, GPZ25-1, GPZ25-2, GPZ26-1 and GPZ26-2, the K phosphorus dispersity data for which are shown in Table 1.

From the data in Table 1, it can be seen that the phosphorus modified ZSM-5 molecular sieves of the present invention have higher phosphorus dispersion, in particular, the sample in Example 24-2, which was modified with a dual source of phosphorus, that is, diammonium hydrogen phosphate and crystallized boron phosphate, achieved dispersity values K 80%, with a maximum increase of 18%.

Table 1

Sample Dispersity K Sample Dispersity K Example 1-1 GPZ1-1 0.76 Comparative Example 1-1 D1-1 0.63 Example 1-2 GPZ1-2 0.78 Comparative example 1-2 D1-2 0.69 Example 2-1 GPZ2-1 0.75 Comparative Example 2-1 D2-1 0.62 Example 2-2 GPZ2-2 0.76 Comparative Example 2-2 D2-2 0.66 Example 3-1 GPZ3-1 0.78 Comparative Example 3-1 D3-1 0.6 Example 3-2 GPZ3-2 0.77 Comparative Example 3-2 D3-2 0.64 Example 4-1 GPZ4-1 0.77 Comparative Example 4-1 D4-1 0.64 Example 4-2 GPZ4-2 0.8 Comparative Example 4-2 D4-2 0.67 Example 5-1 GPZ5-1 0.7 Comparative Example 5-1 D5-1 0.63 Example 5-2 GPZ5-2 0.72 Comparative Example 5-2 D5-2 0.64 Example 6-1 GPZ6-1 0.76 Comparative Example 6-1 D6-1 0.68 Example 6-2 GPZ6-2 0.79 Comparative Example 6-2 D6-2 0.69 Example 7-1 GPZ7-1 0.73 Comparative Example 7-1 D7-1 0.64 Example 7-2 GPZ7-2 0.75 Comparative Example 7-2 D7-2 0.67 Example 8-1 GPZ8-1 0.75 Example 8-2 GPZ8-2 0.85 Example 9-1 GPZ9-1 0.73 Example 9-2 GPZ9-2 0.82 Example 10-1 GPZ10-1 0.72 Example 10-2 GPZ10-2 0.81 Example 11-1 GPZ11-1 0.77 Example 11-2 GPZ11-2 0.84 Example 12-1 GPZ12-1 0.74 Example 12-2 GPZ12-2 0.82 Example 13-1 GPZ13-1 0.72 Example 13-2 GPZ13-2 0.8 Example 14-1 GPZ14-1 0.71 Comparative Example 14-1 D14-1 0.62 Example 14-2 GPZ14-2 0.73 Comparative Example 14-2 D14-2 0.65 Example 15-1 GPZ15-1 0.7 Comparative Example 15-1 D15-1 0.62 Example 15-2 GPZ15-2 0.71 Comparative Example 15-2 D15-2 0.68 Example 16-1 GPZ15-1 0.7 Comparative Example 16-1 D16-1 0.63 Example 16-2 GPZ16-2 0.71 Comparative Example 16-2 D16-2 0.65 Example 17-1 GPZ17-1 0.72 Comparative Example 17-1 D17-1 0.67 Example 17-2 GPZ17-2 0.73 Comparative Example 17-2 D17-2 0.68 Example 18-1 GPZ18-1 0.7 Comparative Example 18-1 D18-1 0.64 Example 18-2 GPZ18-2 0.72 Comparative Example 18-2 D18-2 0.67 Example 19-1 GPZ19-1 0.75 Comparative Example 19-1 D19-1 0.69 Example 19-2 GPZ19-2 0.72 Comparative Example 19-2 D19-2 0.68 Example 20-1 GPZ20-1 0.74 Comparative Example 20-1 D20-1 0.65 Example 20-2 GPZ20-2 0.75 Comparative Example 20-2 D20-2 0.67 Example 21-1 GPZ21-1 0.74 Example 21-2 GPZ21-2 0.8 Example 22-1 GPZ22-1 0.72 Example 22-2 GPZ22-2 0.78 Example 23-1 GPZ23-1 0.7 Example 23-2 GPZ23-2 0.78 Example 24-1 GPZ24-1 0.73 Example 24-2 GPZ24-2 0.8 Example 25-1 GPZ25-1 0.71 Example 25-2 GPZ25-2 0.75 Example 26-1 GPZ26-1 0.7 Example 26-2 GPZ26-2 0.74

Microreaction assessment

Microreaction evaluation conditions: molecular sieve loading amount 2 g, n-tetradecane feedstock, feedstock amount 1.56 g, reaction temperature 550°C and regeneration temperature 600°C (the same hereafter).

Samples GPZ-1, D1-1, GPZ1-2 and D1-2; GPZ2-1, D2-1, GPZ2-2 and D2-2; GPZ3-1, D3-1, GPZ3-2 and D3-2; GPZ4-1, D4-1, GPZ4-2 and D4-2; GPZ5-1, D5-1, GPZ5-2 and D5-2; GPZ6-1, D6-1, GPZ6-2 and D6-2; GPZ7-1, D7-1, GPZ7-2 and D7-2; GPZ8-1, GPZ8-2, GPZ9-1, GPZ9-2, GPZ10-1, GPZ10-2, GPZ11-1, GPZ11-2, GPZ12-1, GPZ12-2, 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 processed hydrothermal aging at 800°C in 100% steam for 17 hours and then assessed for n-tetradecane cracking.

The estimated data are shown in Table 2.

table 2

Sample N-C14
Conversion
wt.% Material balance, wt.% Target products in cracked gas, wt.% Sample N-C14
Conversion
wt.% Material balance, wt.% Target products in cracked gas, wt.% Example Dry gas Liquefied
gas Petrol Diesel Ethylene Propylene Total
butylene Comparative example Dry gas Liquefied
gas Petrol Diesel Ethylene Propylene Total
butylene 1-1 GPZ1-1 70.4 4.6 37.6 36.9 20.4 3.7 14.8 8.2 1-1 D1-1 64.3 5.1 32.1 31.8 28 3.2 12 5.6 1-2 GPZ1-2 71.8 5 43.7 22 22 4 14.5 10.2 1-2 D1-2 66.2 3.6 32 34.9 23.7 3 13.4 6.6 2-1 GPZ2-1 69.4 3.8 32.9 35.1 25.8 2.9 12.2 6.5 2-1 D2-1 65 5 31.6 32.8 28.9 3.1 11.5 5.8 2-2 GPZ2-2 70.6 4.8 38.3 35.1 20 3.9 15.3 8.3 2-2 D2-2 66.4 3.6 32.5 23.2 34.5 2.7 13.8 7.6 3-1 GPZ3-1 71.9 4.4 35.1 33.6 25 3.4 13.8 7.4 3-1 D3-1 65.9 3.6 30.4 35.9 26.6 2.8 13 6.2 3-2 GPZ3-2 72.1 4.2 39.2 34.3 19.3 3.6 14.2 8.4 3-2 D3-2 66.8 4.8 31.6 33.2 27.6 3.3 12.5 6.5 4-1 GPZ4-1 75.7 4.4 41 33.7 18.9 3.9 15.8 9.8 4-1 D4-1 73.1 4.9 31.9 40.8 16.3 3.9 13.5 5.4 4-2 GPZ4-2 77.9 4.2 38 37.3 15.9 4 17 9.7 4-2 D4-2 74 4.9 34 31.7 25.4 3.4 13 6.7 5-1 GPZ5-1 73.8 4.3 37.6 34.9 21.2 3.7 15.4 9.5 5-1 D5-1 71.9 4.9 32.1 31 thirty 3 11.6 5 5-2 GPZ5-2 75.9 4.7 42.8 23.4 23.2 3.8 16.7 10.4 5-2 D5-2 73.5 5.3 39.1 28.7 25 3.9 14.4 9.1 6-1 GPZ6-1 75.2 4.8 39.7 29.4 19.2 3.8 16 7.6 6-1 D6-1 73.3 4.7 35.4 27.3 27.9 3.6 15.1 7 6-2 GPZ6-2 76 5.6 41 28.6 18.3 4 16.3 8 6-2 D6-2 74.1 4.1 36.2 27 29 3.5 14.2 11.5 7-1 GPZ7-1 73.9 4.9 40.2 31.6 20.8 3.8 15.3 10.7 7-1 D7-1 70.4 4.4 38.3 29.7 21.9 3.2 13.1 9.2 7-2 GPZ7-2 75.1 4.1 41.8 33.2 19.2 3.5 15.6 12.4 7-2 D7-2 71.3 6.3 39.6 31.9 20.3 4.3 13.5 8.8 8-1 GPZ8-1 69.4 5.1 32 32.1 28.8 3 12.1 6.5 8-2 GPZ8-2 80.8 4.2 42.5 36 15.3 4.2 16.5 10.1 9-1 GPZ9-1 70.3 5.2 34.1 31.9 26.8 3.2 11.5 6.6 9-2 GPZ9-2 81.6 4.5 40.3 35.4 17.8 3.9 15.9 9.7 10-1 GPZ10-1 64.2 5.6 30.8 30.7 30.9 3.1 10.7 5.8 10-2 GPZ10-2 76.9 4.8 37.9 33.9 21.4 3.7 15.6 9.3 11-1 GPZ11-1 73.9 4.8 34.7 33.6 26.3 3.6 12.8 6.8 11-2 GPZ11-2 82.9 4 41.2 35.1 15 3.8 16.2 9.4 12-1 GPZ12-1 72.8 5 35.7 31 24.3 3 10.4 6.4 12-2 GPZ12-2 80.5 4.3 39.6 34.1 16.3 3.7 15.2 9 13-1 GPZ13-1 68.8 5.1 31.3 29.5 25.7 2.9 11.5 6 13-2 GPZ13-2 78.6 4.5 37 32.6 20.5 3.3 15.2 8.7 14-1 GPZ14-2 67.5 3.9 32.4 33.8 26.9 2.7 11.9 6.2 14-1 D14-2 66.8 4.2 31.5 34.1 27.8 2.6 11.2 5.6 14-2 GPZ14-1 69.2 3.7 33 34.7 25.9 2.9 12.4 6.6 14-2 D14-1 68.9 3.8 32.9 35.1 25.8 2.9 12.2 6.5 15-1 GPZ15-1 66.4 4.1 31.2 35.6 26.9 2.5 11.4 6 15-1 D15-1 65.2 4.3 thirty 34.8 27.5 2.3 10.2 5.2 15-2 GPZ15-2 67.5 3.8 33.2 34.9 25.7 2.8 12.1 6.6 15-2 D15-2 66 3.8 33 35.4 25.9 2.7 12 6.4 16-1 GPZ15-1 65.2 3.6 32.2 33 27.5 3.2 12.1 6.8 16-1 D16-1 64.8 3.9 31.8 32.8 27.9 2.7 11.4 6.1 16-2 GPZ16-2 66.5 3.9 35 33.6 25.1 3 13.2 7.9 16-2 D16-2 65.9 3.7 34.1 33.2 25.6 2.9 12.8 7.7 17-1 GPZ17-1 66.9 4.1 26.4 35.6 28.1 2.8 9.7 5.7 17-1 D17-1 65.7 3.5 26.8 34.3 25.4 2.5 10.2 6.3 17-2 GPZ17-2 67.6 3.7 28.2 38.6 27.4 2.9 10.8 5.5 17-2 D17-2 65 4.3 25.7 34.8 29.3 3.1 9.5 5.2 18-1 GPZ18-1 64.1 3.9 24.9 34.1 27.8 3.1 9.7 6.5 18-1 D18-1 63.2 4.3 23.8 34.2 28.5 3.3 9 5.8 18-2 GPZ18-2 65.6 3.7 26.5 32.7 26.6 2.7 10.6 6.9 18-2 D18-2 65.1 3.5 25.3 33.2 26.1 2.5 10 6.1 19-1 GPZ19-1 61.1 3 28.7 29.1 35.2 2.7 12.3 7 19-1 D19-1 59.3 2.8 27.8 29.7 36.6 2 11.7 6.7 19-2 GPZ19-2 64.5 3.7 31.2 29.8 33.6 2.6 13.4 7.5 19-2 D19-2 60.1 3.9 29.8 28.9 34.2 3.2 12.8 6.5 20-1 GPZ20-1 62.7 3.5 29.9 30.2 32.2 3 12.3 6.8 20-1 D20-1 61.3 3.4 28.7 31.3 33.9 2.7 12 6.3 20-2 GPZ20-2 64.1 3.8 32.5 31.6 30.6 3.6 13.4 7.8 20-2 D20-2 62.5 4.2 31.7 30.9 31.4 4.2 13 7.1 21-1 GPZ21-1 65.8 5.3 31 34.2 29.5 3.1 11.8 6.3 21-2 GPZ21-2 79.6 4 41.5 37 17.5 4 15.1 10 22-1 GPZ22-1 68.7 5 33.4 30.6 31 3 11.1 6.1 22-2 GPZ22-2 79.5 4.1 38.5 36.8 20.6 3.1 15.2 9 23-1 GPZ23-1 62.1 5.1 28.9 32.3 33.7 3 10.2 5.2 23-2 GPZ23-2 73.2 4.2 35.3 35.4 25.1 3.4 15 9 24-1 GPZ24-1 70.5 3.8 32.9 33.8 29.5 3.7 12.8 6.9 24-2 GPZ24-2 74.6 3.5 38.5 31.4 26.6 3.9 13.9 7.4 25-1 GPZ25-1 70.1 4 32.2 33.9 29.9 4 12.8 6.3 25-2 GPZ25-2 73.1 4 36.2 29.9 29.9 4 12.8 6.3 26-1 GPZ26-1 68.3 3.8 31 34.2 31 3.7 11.3 5.7 26-2 GPZ26-2 72.8 3.8 36.4 31.1 28.7 3.8 12.7 6.9

After hydrothermal aging treatment at 800°C with 100% steam for 17 hours, the example samples showed excellent activity and conversion for catalytic cracking of n-tetradecane, and the liquefied gas yield and the yields of three olefins were improved. This showed that the phosphorus modified molecular sieves with the MFI structure of the present invention provide higher liquefied gas yield while increasing the yield of lower olefins.

Examples 27-30 illustrate the phosphorus-aluminum inorganic binder used in the catalytic cracking aid/catalyst of the present invention.

Example 27

1.91 kg pseudoboehmite (containing 1.19 kg Al ₂ O ₃ ), 0.56 kg kaolin (0.5 kg dry matter basis) and 3.27 kg decationized water were vigorously mixed and stirred for 30 minutes in order to form a thick slurry, and 5.37 kg of concentrated phosphoric acid (85 wt.%) was added to this thick slurry with stirring, and the phosphoric acid addition rate was 0.04 kg phosphoric acid/min/kg alumina source. This mixture was heated to 70°C and then reacted at this temperature for 45 minutes to obtain a phosphorus-aluminum inorganic binder. The material composition is shown in Table 3, and this sample was designated as Binder 1.

Examples 28-30

Phosphorus-aluminum inorganic binders were prepared in accordance with the method of Example 27, the material compositions are shown in Table 3, and these samples were designated as Binder 2, Binder 3 and Binder 4.

Table 3

Example Example 27 Example 28 Example 29 Example 30 Binder No. Binder 1 Binder 2 Binder 3 Binder 4 Pseudoboehmite, kg 1.91 1.6 Al ₂ O ₃ , kg 1.19 1 Aluminum hydroxide powder SB, kg 0.94 Al ₂ O ₃ , kg 0.7 γ-alumina, kg 0.58 Al ₂ O ₃ , kg 0.58 Rectorit, kg 1.28 1.93 Dry base, kg 1 1.5 Kaolin, kg 0.56 Dry base, kg 0.5 phosphoric acid, kg 5.37 5.36 4.03 6.5 P ₂ O ₅ , kg 3.31 3.3 2.92 4 Water purified from cations, kg 3.27 6.71 20.18 4.4 Total quantity, kg 11.11 14.29 25 12.5 Total dry base, kg 5 5 5 5 Solid binder content, kg/kg 0.45 0.35 0.2 0.4 P/Al 2.29 3.89 4.19 3.3 Al ₂ O ₃ , wt.% 23.82 14 11.53 20 P ₂ O ₅ , wt.% 66.18 66 58.47 80 First clay, wt.% 10 20 thirty 0 pH 2.2 2.37 1.78 2.46

Table 4 Table 5 Index Source oil Material Naphtha Density (20°C), g/cm ³ 0.9334 Density (20°C), g/m ³ 735.8 Refraction (70°C) 1.5061 Steam pressure, kPa 32 SARA, wt.% Group component, wt.% Saturated 55.6 Paraffins 51.01 Aromatic compounds thirty Normal paraffins 29.4 Resin 14.4 Naphthene 38.24 Asphaltene <0.1 Olefins 0.12 Freezing temperature, °C 34 Aromatic compounds 10.52 Metal content, parts per million Boiling range, °C Ca 3.9 Initial 45.5 Fe 1.1 0.05 72.5 Mg <0.1 0.1 86.7 Na 0.9 0.3 106.5 Ni 3.1 0.5 120 Pb <0.1 0.7 132.7 V 0.5 0.9 148.5 cm% 86.88 0.95 155.2 Hm% 11.94 End point 166.5 Sm% 0.7 Carbon residue, wt.% 1.77

Examples 31-56 are catalytic cracking aids of the present invention, and Comparative Examples 31-56 illustrate comparative catalytic cracking aids, with Examples 31-43 being ZSM-5 hierarchical molecular sieves and Examples 44-56 being microporous molecular sieves ZSM-5.

Example 31-1

The phosphorus modified molecular sieve GPZ1-1 prepared in Example 1-1, kaolin and pseudoboehmite were taken, and cation-free water and alumina sol were added thereto. This mixture was vigorously mixed and stirred for 120 minutes to obtain a thick suspension having a solids content of 30 wt.%. Hydrochloric acid was added to adjust the pH of the thick slurry to 3.0, and then vigorous mixing and mixing continued for another 45 minutes. The phosphorus-aluminum inorganic binder, Binder 1 prepared in Example 27, was then added and the mixture was stirred for 30 minutes. The resulting thick suspension was spray dried to obtain microspheres. These microspheres were calcined at 500°C for 1 hour to produce a sample of catalytic cracking aid, which was designated CAZ1-1 and had the following composition: molecular sieve: 50%, kaolin: 23%, Binder 1: 18% , pseudoboehmite (in terms of Al ₂ O ₃ ): 5%, and alumina sol (in terms of Al ₂ O ₃ ): 4%.

A fixed bed microreactor was used to evaluate the reaction characteristics of a 100% equilibrium catalyst and an equilibrium catalyst in which CAZ1-1 was included to illustrate the effect on the catalytic cracking reaction of the catalytic cracking aid proposed in the present invention.

The CAZ1-1 auxiliary was subjected to aging treatment at 800°C in an atmosphere of 100% steam for 17 hours. Aging-treated CAZ1-1 was mixed with commercial equilibrium catalyst FCC (grade: DVR-3, light oil microactivity 63). The mixture of equilibrium catalyst and auxiliary was charged into a fixed bed microreactor, and the petroleum feedstock shown in Table 4 was subjected to catalytic cracking. Evaluation conditions included a reaction temperature of 620°C, a regeneration temperature of 620°C, and a catalyst-to-oil ratio of 3.2. Table 6 shows the reaction results including the blank test.

Example 31-2

Identical to Example 31-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by the phosphorus modified molecular sieve GPZ1-2 prepared in Example 1-2 to produce a catalytic cracking aid sample which was designated CAZ1-2 . His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 31-1

Identical to Example 12-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced by Comparative Sample D1-1 of Comparative Example 1-1 to produce a catalytic cracking aid sample designated as DCAZ1-1. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 31-2

Identical to Example 31-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by Comparative Sample D1-2 of Comparative Example 1-2 to produce catalytic cracking aid sample which was designated DCAZ1-2. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 32-1

Identical to Example 31-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by the phosphorus modified molecular sieve GPZ2-1 prepared in Example 2-1 to produce a catalytic cracking aid sample which was designated CAZ2-1 . His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 32-2

Identical to Example 32-1 except that the phosphorus modified molecular sieve GPZ2-1 was replaced by the phosphorus modified molecular sieve GPZ2-2 prepared in Example 2-2 to produce a catalytic cracking aid sample which was designated CAZ2-2 . His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 32-1

Identical to Example 32-1 except that the phosphorus modified molecular sieve GPZ2-1 was replaced by Comparative Sample D2-1 of Comparative Example 2-1 to produce a catalytic cracking aid sample designated DCAZ2-1. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 32-2

Identical to Example 32-1 except that the phosphorus-modified molecular sieve GPZ2-1 was replaced by Comparative Sample D2-2 of Comparative Example 2-2 to produce a catalytic cracking aid sample designated DCAZ2-2. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 33-1

Identical to Example 31-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by the phosphorus modified molecular sieve GPZ3-1 prepared in Example 3-1 to produce a catalytic cracking aid sample which was designated CAZ3-1 . His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 33-2

Identical to Example 31-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by the phosphorus modified molecular sieve GPZ3-3 prepared in Example 3-2 to produce a catalytic cracking aid sample which was designated CAZ3-2 . His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 33-1

Identical to Example 31-1 except that phosphorus modified molecular sieve GPZ1-1 was replaced by Comparative Example 3-1 D3-1 to produce catalytic cracking aid sample designated DCAZ3-1. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 33-2

Identical to Example 31-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by Comparative Sample D3-2 of Comparative Example 3-2 to produce catalytic cracking aid sample which was designated DCAZ3-2. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 34-1

Identical to Example 31-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by the phosphorus modified molecular sieve GPZ4-1 prepared in Example 4-1 to produce a catalytic cracking aid sample which was designated CAZ4-1 . His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 34-2

Identical to Example 34-1 except that the phosphorus modified molecular sieve GPZ4-1 was replaced by the phosphorus modified molecular sieve GPZ4-2 prepared in Example 4-2 to produce a catalytic cracking aid sample which was designated CAZ4-2 . His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 34-1

Identical to Example 34-1 except that the phosphorus modified molecular sieve GPZ4-1 was replaced by Comparative Sample D4-1 of Comparative Example 4-1 to produce catalytic cracking aid sample which was designated DCAZ4-1. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 34-2

Identical to Example 34-1 except that the phosphorus modified molecular sieve GPZ4-1 was replaced by Comparative Sample D4-2 of Comparative Example 2-2 to produce a catalytic cracking aid sample designated DCAZ4-2. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 35-1

Identical to Example 31-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by the phosphorus modified molecular sieve GPZ5-1 prepared in Example 5-1 to produce a catalytic cracking aid sample which was designated CAZ5-1 . His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 35-2

Identical to Example 35-1 except that the phosphorus modified molecular sieve GPZ5-1 was replaced by the phosphorus modified molecular sieve GPZ5-2 prepared in Example 5-2 to produce a catalytic cracking aid sample which was designated CAZ5-2 . His evaluation was identical to Example 35-1, and the result is shown in Table 6.

Comparative Example 35-1

Identical to Example 35-1 except that the phosphorus modified molecular sieve GPZ5-1 was replaced by Comparative Sample D5-1 of Comparative Example 5-1 to produce catalytic cracking aid sample which was designated DCAZ5-1. His evaluation was identical to Example 35-1, and the result is shown in Table 6.

Comparative Example 35-2

Identical to Example 35-1 except that the phosphorus-modified molecular sieve GPZ5-1 was replaced by Comparative Sample D5-2 of Comparative Example 2-2 to produce a catalytic cracking aid sample designated DCAZ5-2. His evaluation was identical to Example 35-1, and the result is shown in Table 6.

Example 36-1

Identical to Example 31-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by the phosphorus modified molecular sieve GPZ6-1 prepared in Example 6-1 to produce a catalytic cracking aid sample which was designated CAZ6-1 . His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 36-2

Identical to Example 36-1 except that the phosphorus modified molecular sieve GPZ6-1 was replaced by the phosphorus modified molecular sieve GPZ6-2 prepared in Example 6-2 to produce a catalytic cracking aid sample which was designated CAZ6-2 . His evaluation was identical to Example 36-1, and the result is shown in Table 6.

Comparative Example 36-1

Identical to Example 36-1 except that the phosphorus modified molecular sieve GPZ6-1 was replaced by Comparative Example 6-1 D6-1 to produce catalytic cracking aid sample which was designated DCAZ6-1. His evaluation was identical to Example 36-1, and the result is shown in Table 6.

Comparative Example 36-2

Identical to Example 36-1 except that the phosphorus modified molecular sieve GPZ6-1 was replaced by Comparative Sample D6-2 of Comparative Example 6-2 to produce catalytic cracking aid sample which was designated DCAZ6-2. His evaluation was identical to Example 36-1, and the result is shown in Table 6.

Example 37-1

Identical to Example 31-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by the phosphorus modified molecular sieve GPZ7-1 prepared in Example 7-1 to produce a catalytic cracking aid sample which was designated CAZ7-1 . His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 37-2

Identical to Example 37-1 except that the phosphorus modified molecular sieve GPZ7-1 was replaced by the phosphorus modified molecular sieve GPZ7-2 prepared in Example 7-2 to produce a catalytic cracking aid sample which was designated CAZ7-2 . His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 37-1

Identical to Example 37-1 except that the phosphorus modified molecular sieve GPZ7-1 was replaced by Comparative Example 7-1 D7-1 to produce a catalytic cracking aid sample designated DCAZ7-1. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 37-2

Identical to Example 37-1 except that phosphorus modified molecular sieve GPZ7-1 was replaced by Comparative Example 7-2 D7-2 to produce catalytic cracking aid sample which was designated DCAZ7-2. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Examples 38-43

Identical to Example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced by the phosphorus-modified molecular sieves GPZ8-1 to GPZ13-2 prepared in Examples 8-1 to 13-2, respectively, to produce catalyst aid samples cracking, which were successively designated as CAZ8-1 - CAZ13-2. Their estimates were identical to Example 31-1, and the results are shown in Table 6 accordingly.

Examples 44-56

Examples 44-56 are auxiliaries CAZ14 - CAZ26 containing microporous ZSM-5 (GPZ14 - GPZ26), respectively, and their material compositions corresponded to the compositions of Examples 31-43, respectively, for example in Example 44-1 GPZ1-1 was replaced by GPZ14- 1, in Example 44-2 GPZ1-2 was replaced by GPZ14-2, etc., and in Example 56-1 GPZ14-1 was replaced by GPZ26-1, and in Example 56-2 GPZ14-2 was replaced by GPZ26-2. Their estimates were identical to Example 31-1, and the results are shown in Table 6 accordingly.

Comparative examples 44-50

Comparative Examples 44-50 are comparative adjuvants DCAZ-14 to DCAZ-20 containing microporous ZSM-5 (D14 to D20), respectively, and their material compositions corresponded to those of Examples 44-50, respectively, such as Comparative Example 44-1 GPZ1 -1 was replaced by D14-1, in Comparative Example 44-2 GPZ1-2 was replaced by D14-2, etc., and in Comparative Example 50-1 GPZ14-1 was replaced by D20-1, and in Comparative Example example 50-2 GPZ14-2 was replaced by D20-2. Their estimates were identical to Example 31-1, and the results are shown in Table 6 accordingly.

Examples 57-62

Identical to Example 31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced by the phosphorus-modified molecular sieves GPZ21-1 to GPZ26-2 prepared in Examples 21-1 to 26-2, respectively, to produce catalyst aid samples cracking, which were successively designated as CAZ27-1 - CAZ32-2. Their estimates were identical to Example 31-1, and the results are shown in Table 6 accordingly.

Example 63-1

Identical to Example 31-1 except that the phosphorus-aluminum inorganic binder was replaced by Binder 2 prepared in Example 28 to produce a catalytic cracking aid, which was designated CAZ33-1. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 63-2

Identical to Example 31-2 except that the phosphorus-aluminum inorganic binder was replaced by Binder 2 prepared in Example 28 to produce a catalytic cracking aid, which was designated CAZ33-2. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 64-1

Identical to Example 31-1 except that the phosphorus-aluminum inorganic binder was replaced by Binder 3 prepared in Example 29 to produce a catalytic cracking aid, which was designated CAZ34-1. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 64-2

Identical to Example 31-2 except that the phosphorus-aluminum inorganic binder was replaced by Binder 3 prepared in Example 29 to produce a catalytic cracking aid which was designated CAZ34-2. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 65-1

Identical to Example 31-1 except that the phosphorus-aluminum inorganic binder was replaced by Binder 4 prepared in Example 30 to produce a catalytic cracking aid, which was designated CAZ35-1. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 65-2

Identical to Example 31-2 except that the phosphorus-aluminum inorganic binder was replaced by Binder 4 prepared in Example 30 to produce a catalytic cracking aid which was designated CAZ35-2. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 66-1

Identical to Example 31-1 except that phosphorus-modified sample GPZ1-1 molecular sieve ZSM-5 (45 wt%), kaolin (18 wt%), phosphorus-aluminum inorganic Binder 3 (22 wt%), pseudoboehmite (10 wt%) and alumina sol (5 wt%) were used to produce a catalytic cracking aid, which was designated CAZ36-1. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 66-2

Identical to Example 66-1 except that GPZ1-1 was replaced by GPZ1-2 to produce a catalytic cracking aid which was designated CAZ36-2. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 66-1

Identical to Example 66-1 except that GPZ1-1 was replaced by D1-1 in order to produce a reference catalytic cracking aid which was designated DCAZ36-1. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 66-2

Identical to Example 66-1 except that GPZ1-1 was replaced by D1-2 to produce a comparative catalytic cracking aid sample which was designated DCAZ36-2. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 67-1

Identical to Example 44-1 except that phosphorus-modified sample GPZ14-1 molecular sieve ZSM-5 (40 wt%), kaolin (24 wt%), phosphorus-aluminum inorganic Binder 4 (20 wt%), pseudoboehmite (6 wt%) and silica sol (10 wt%) were used to produce a catalytic cracking aid, which was designated CAZ37-1. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 67-2

Identical to Example 67-1 except that GPZ14-1 was replaced by GPZ14-2 to produce a catalytic cracking aid, which was designated CAZ37-2. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 67-1

Identical to Example 67-1 except that GPZ14-1 was replaced by D14-1 to produce a reference catalytic cracking aid which was designated DCAZ37-1. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 67-2

Identical to Example 67-1 except that GPZ14-1 was replaced by D14-2 to produce a reference catalytic cracking aid which was designated DCAZ37-2. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 68-1

The alumina sol binder was mixed with kaolin and de-cationized water was added to form a thick slurry containing 30 wt.% solids. This thick suspension was well mixed and adjusted with hydrochloric acid to a pH of 2.8. The thick suspension was aged at 55°C for 1 hour. The phosphorus modified molecular sieve GPZ1-1 prepared in Example 1-1 was then added to form a thick slurry with a solids content of 35 wt%. This thick suspension was continuously stirred and spray dried to obtain microspheres. These microspheres were then calcined at 500°C for 1 hour, washed with ammonium sulfate at 60°C (at a ratio of ammonium sulfate:microspheres:water=0.5:1:10) until the sodium oxide content was less than 0.25 wt.%, then washed with deionized water and filtered, and then dried at 110°C to obtain the adjuvant CAZ38-1. Its composition contained: molecular sieve, 50%; kaolin, 23%; and alumina sol (in terms of Al ₂ O ₃ ), 27%. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Example 68-2

Identical to Example 68-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by the phosphorus modified molecular sieve GPZ1-2 prepared in Example 1-2 to produce a catalytic cracking aid sample which was designated CAZ38-2 . His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 68-1

Identical to Example 68-1 except that phosphorus modified molecular sieve GPZ1-1 was replaced by Comparative Example 1-1 D1-1 to produce catalytic cracking aid sample which was designated DCAZ38-1. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Comparative Example 68-2

Identical to Example 68-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by Comparative Sample D1-2 of Comparative Example 1-2 to produce catalytic cracking aid sample which was designated DCAZ38-2. His evaluation was identical to Example 31-1, and the result is shown in Table 6.

Table 6

Index Catalyst mixture Material balance, wt.% Index Catalyst mixture Material balance, wt.% Liquefied gas Ethylene yield Propylene yield Liquefied gas Ethylene yield Propylene yield Blank test example / 100% equilibrium catalyst 18.54 1.39 8.05 Example 31-1 10% CAZ1-1 90% equilibrium catalyst 32.39 3.69 15.58 Comparative Example 31-1 10% DCAZ1-1 90% equilibrium catalyst 26.17 2.74 11.17 Example 31-2 10% CAZ1-2 90% equilibrium catalyst 38.69 4.5 17.32 Comparative Example 31-2 10% DCAZ--2 90% equilibrium catalyst 27.29 2.9 12.02 Example 32-1 10% CAZ2-1 90% equilibrium catalyst 39.22 4.31 16.3 Comparative Example 32-1 10% DCAZ2-1 90% equilibrium catalyst 27.72 2.89 12.07 Example 32-2 10% CAZ2-2 90% equilibrium catalyst 43.2 4.8 16.99 Comparative Example 32-2 10% DCAZ2-2 90% equilibrium catalyst 31 3.3 12.75 Example 33-1 10% CAZ3-1 90% equilibrium catalyst 36.47 4.1 14.68 Comparative Example 33-1 10% DCAZ3-1 90% equilibrium catalyst 26.28 2.86 11.44 Example 33-2 10% CAZ3-2 90% equilibrium catalyst 39.71 4.5 15.83 Comparative Example 33-2 10% DCAZ3-2 90% equilibrium catalyst 30.68 3.15 12.19 Example 34-1 10% CAZ4-1 90% equilibrium catalyst 38.3 4.15 15.25 Comparative Example 34-1 10% DCAZ4-1 90% equilibrium catalyst 28.08 3 12.43 Example 34-2 10% CAZ4-2 90% equilibrium catalyst 41.7 4.61 16.06 Comparative Example 34-2 10% DCAZ4-2 90% equilibrium catalyst 31.84 3.2 12.98 Example 35-1 10% CAZ5-1 90% equilibrium catalyst 33.41 3.69 13.22 Comparative Example 35-1 10% DCAZ5-1 90% equilibrium catalyst 22.88 3.15 9.62 Example 35-2 10% CAZ5-2 90% equilibrium catalyst 36.48 4.02 14.68 Comparative Example 35-2 10% DCAZ5-2 90% equilibrium catalyst 24.72 3.35 10.77 Example 36-1 10% CAZ6-1 90% equilibrium catalyst 37.71 3.91 14.95 Comparative Example 36-1 10% DCAZ6-1 90% equilibrium catalyst 28.2 3 12.91 Example 36-2 10% CAZ6-2 90% equilibrium catalyst 41.64 4.61 15.86 Comparative Example 36-2 10% DCAZ6-2 90% equilibrium catalyst 29.85 3.35 13.64 Example 37-1 10% CAZ7-1 90% equilibrium catalyst 27.49 2.96 10.87 Comparative Example 37-1 10% DCAZ7-1 90% equilibrium catalyst 18.76 3.09 8.82 Example 37-2 10% CAZ7-2 90% equilibrium catalyst 31.92 3.69 13.18 Comparative Example 37-2 10% DCAZ7-2 90% equilibrium catalyst 20.32 3.23 9.98 Example 38-1 10% CAZ8-1 90% equilibrium catalyst 29.44 3.31 14.87 Example 38-2 10% CAZ8-2 90% equilibrium catalyst 36.6 3.65 15.8 Example 39-1 10% CAZ9-1 90% equilibrium catalyst 29.03 3.26 14.84 Example 39-2 10% CAZ9-2 90% equilibrium catalyst 35.92 3.46 15.38 Example 40-1 10% CAZ10-1 90% equilibrium catalyst 29.12 3.17 14.53 Example 40-2 10% CAZ10-2 90% equilibrium catalyst 36.06 3.47 15.37 Example 41-1 10% CAZ11-1 90% equilibrium catalyst 32.86 3.56 13.7 Example 41-2 10% CAZ11-2 90% equilibrium catalyst 38.02 4.34 16.34 Example 42-1 10% CAZ12-1 90% equilibrium catalyst 32.09 3.62 13.9 Example 42-2 10% CAZ12-2 90% equilibrium catalyst 39.01 4.56 16.02 Example 43-1 10% CAZ13-1 90% equilibrium catalyst 31.89 3.38 13.09 Example 43-2 10% CAZ13-2 90% equilibrium catalyst 38.78 4.31 16.81 Example 44-1 10% CAZ14-1 90% equilibrium catalyst 30.09 3.5 14.52 Comparative Example 44-1 10% DCAZ14-1 90% equilibrium catalyst 24.31 2.6 10.41 Example 44-2 10% CAZ14-2 90% equilibrium catalyst 35.94 4.27 16.14 Comparative Example 44-2 10% DCAZ14-2 90% equilibrium catalyst 25.35 2.75 11.2 Example 45-1 10% CAZ15-1 90% equilibrium catalyst 36.44 4.09 15.19 Comparative Example 45-1 10% DCAZ15-1 90% equilibrium catalyst 25.75 2.74 11.25 Example 45-2 10% CAZ15-2 90% equilibrium catalyst 40.13 4.55 15.83 Comparative Example 45-2 10% DCAZ15-2 90% equilibrium catalyst 28.8 3.13 11.88 Example 46-1 10% CAZ16-1 90% equilibrium catalyst 33.88 3.89 13.68 Comparative Example 46-1 10% DCAZ16-1 90% equilibrium catalyst 24.41 2.71 10.66 Example 46-2 10% CAZ16-2 90% equilibrium catalyst 36.89 4.27 14.75 Comparative Example 46-2 10% DCAZ16-2 90% equilibrium catalyst 28.5 2.99 11.36 Example 47-1 10% CAZ17-1 90% equilibrium catalyst 35.58 3.93 14.21 Comparative Example 47-1 10% DCAZ17-1 90% equilibrium catalyst 26.09 2.84 11.58 Example 47-2 10% CAZ17-2 90% equilibrium catalyst 38.74 4.37 14.97 Comparative Example 47-2 10% DCAZ17-2 90% equilibrium catalyst 29.58 3.03 12.1 Example 48-1 10% CAZ18-1 90% equilibrium catalyst 31.04 3.5 12.32 Comparative Example 48-1 10% DCAZ18-1 90% equilibrium catalyst 21.26 2.99 8.97 Example 48-2 10% CAZ18-2 90% equilibrium catalyst 33.89 3.81 13.68 Comparative Example 48-2 10% DCAZ18-2 90% equilibrium catalyst 22.96 3.18 10.04 Example 49-1 10% CAZ19-1 90% equilibrium catalyst 35.03 3.71 13.93 Comparative Example 49-1 10% DCAZ19-1 90% equilibrium catalyst 26.2 2.84 12.03 Example 49-2 10% CAZ19-2 90% equilibrium catalyst 38.68 4.37 14.78 Comparative Example 49-2 10% DCAZ19-2 90% equilibrium catalyst 27.73 3.18 12.71 Example 50-1 10% CAZ20-1 90% equilibrium catalyst 25.54 2.81 10.13 Comparative Example 50-1 10% DCAZ20-1 90% equilibrium catalyst 17.43 2.93 8.22 Example 50-2 10% CAZ20-2 90% equilibrium catalyst 29.65 3.5 12.28 Comparative Example 50-2 10% DCAZ20-2 90% equilibrium catalyst 18.88 3.06 9.3 Example 51-1 10% CAZ21-1 90% equilibrium catalyst 31.41 3.79 15.32 Example 51-2 10% CAZ21-2 90% equilibrium catalyst 40.75 4.7 17.49 Example 52-1 10% CAZ22-1 90% equilibrium catalyst 28.55 3.49 13.36 Example 52-2 10% CAZ22-2 90% equilibrium catalyst 37.04 4.33 15.25 Example 53-1 10% CAZ23-1 90% equilibrium catalyst 28.49 3.01 11.46 Example 53-2 10% CAZ23-2 90% equilibrium catalyst 33.08 3.77 13.91 Example 54-1 10% CAZ24-1 90% equilibrium catalyst 31.77 3.49 12.32 Example 54-2 10% CAZ24-2 90% equilibrium catalyst 34.69 3.8 13.68 Example 55-1 10% CAZ25-1 90% equilibrium catalyst 35.86 3.7 13.93 Example 55-2 10% CAZ25-2 90% equilibrium catalyst 39.6 4.36 14.78 Example 56-1 10% CAZ26-1 90% equilibrium catalyst 26.14 2.8 10.13 Example 56-2 10% CAZ26-2 90% equilibrium catalyst 30.36 3.49 12.28 Example 57-1 10% CAZ27-1 90% equilibrium catalyst 26.79 2.99 13.22 Example 57-2 10% CAZ27-2 90% equilibrium catalyst 33.31 3.3 14.05 Example 58-1 10% CAZ28-1 90% equilibrium catalyst 26.42 2.95 13.19 Example 58-2 10% CAZ28-2 90% equilibrium catalyst 32.69 3.13 13.67 Example 59-1 10% CAZ29-1 90% equilibrium catalyst 26.5 2.87 12.92 Example 59-2 10% CAZ29-2 90% equilibrium catalyst 32.81 3.14 13.66 Example 60-1 10% CAZ30-1 90% equilibrium catalyst 26.11 3.02 12.89 Example 60-2 10% CAZ30-2 90% equilibrium catalyst 32.46 3.33 13.7 Example 61-1 10% CAZ31-1 90% equilibrium catalyst 25.75 2.97 12.87 Example 61-2 10% CAZ31-2 90% equilibrium catalyst 31.86 3.16 13.33 Example 62-1 10% CAZ32-1 90% equilibrium catalyst 25.83 2.89 12.6 Example 62-2 10% CAZ32-2 90% equilibrium catalyst 31.99 3.16 13.33 Example 63-1 10% CAZ33-1 90% equilibrium catalyst 29.81 3.5 15.18 Example 63-2 10% CAZ33-2 90% equilibrium catalyst 37.06 3.87 16.13 Example 64-1 10% CAZ34-1 90% equilibrium catalyst 29.4 3.45 15.16 Example 64-2 10% CAZ34-2 90% equilibrium catalyst 36.38 3.66 15.71 Example 65-1 10% CAZ35-1 90% equilibrium catalyst 29.48 3.36 14.84 Example 65-2 10% CAZ35-2 90% equilibrium catalyst 36.51 3.68 15.69 Example 66-1 10% CAZ36-1 90% equilibrium catalyst 30.17 3.16 14.44 Comparative Example 66-1 10% DCAZ36-1 90% equilibrium catalyst 22.03 2.15 9.96 Example 66-2 10% CAZ36-2 90% equilibrium catalyst 35.04 3.68 16.24 Comparative Example 66-2 10% DCAZ36-2 90% equilibrium catalyst 24.37 2.76 11.16 Example 67-1 10% CAZ37-1 90% equilibrium catalyst 36.68 3.88 15.33 Comparative Example 67-1 10% DCAZ37-1 90% equilibrium catalyst 25.93 2.61 11.35 Example 67-2 10% CAZ37-2 90% equilibrium catalyst 40.39 4.32 15.97 Comparative Example 67-2 10% DCAZ37-2 90% equilibrium catalyst 28.99 2.97 11.99 Example 68-1 10% CAZ38-1 90% equilibrium catalyst 33.85 3.73 16.44 Comparative Example 68-1 10% DCAZ38-1 90% equilibrium catalyst 27.35 2.77 11.79 Example 68-2 10% CAZ38-2 90% equilibrium catalyst 40.43 4.55 18.27 Comparative Example 68-2 10% DCAZ38-2 90% equilibrium catalyst 28.52 2.93 12.68

Example 69-1 and Example 69-2

In Example 69-1 and Example 69-2, respectively, the catalytic cracking auxiliaries CAZ1-1 and CAZ1-2 of Example 31-1 and Example 31-2 were used. The catalytic cracking feedstock was naphtha shown in Table 5.

Evaluation conditions included a reaction temperature of 620°C, a regeneration temperature of 620°C, and a catalyst-to-oil ratio of 3.2.

Table 7 shows the mass composition and reaction result of each catalyst mixture containing the catalytic cracking aid.

Comparative Example 69-1 and Comparative Example 69-2

Identical to Example 69-1 except that comparative catalytic cracking aids DCAZ1-1 and DCAZ1-2 of Comparative Example 31-1 and Comparative Example 31-2 were used, respectively.

The mass composition and reaction result of each catalyst mixture containing a comparative sample of the catalytic cracking aid are shown in Table 7.

Example 70-1 and Example 70-2

Example 70-1 and Example 70-2 respectively used catalytic cracking auxiliaries CAZ14-1 and CAZ14-2 of Example 44-1 and Example 44-2. The catalytic cracking feedstock was naphtha shown in Table 5.

Evaluation conditions included a reaction temperature of 620°C, a regeneration temperature of 620°C, and a catalyst-to-oil ratio of 3.2.

Table 7 shows the mass composition and reaction result of each catalyst mixture containing the catalytic cracking aid.

Comparative Example 70-1 and Comparative Example 70-2

Identical to Example 70-1 except that comparative catalytic cracking aids DCAZ14-1 and DCAZ14-2 of Comparative Example 44-1 and Comparative Example 44-2 were used, respectively.

The mass composition and reaction result of each catalyst mixture containing a comparative sample of the catalytic cracking aid are shown in Table 7.

Table 7

Catalyst mixture Yield of product cracking gas, wt.% Liquefied gas Propylene yield Blank test example / 100% equilibrium catalyst 69.13 8.42 Example 69-1 10% CAZ1-1 90% equilibrium catalyst 80.32 14.1 Example 69-2 10% CAZ1-2 90% equilibrium catalyst 85.42 15.36 Comparative Example 69-1 10% DCAZ1-1 90% equilibrium catalyst 73.16 9.98 Comparative Example 69-2 10% DCAZ1-2 90% equilibrium catalyst 75.46 10.68 Example 70-1 10% CAZ14-1 90% equilibrium catalyst 73.17 12.92 Example 70-2 10% CAZ14-2 90% equilibrium catalyst 77.82 14.07 Comparative Example 70-1 10% DCAZ14-1 90% equilibrium catalyst 66.65 9.14 Comparative Example 70-2 10% DCAZ14-2 90% equilibrium catalyst 68.74 9.78

Examples Y31 - Y56 represent the catalytic cracking catalysts of the present invention, and Comparative Examples Y31 - Y56 illustrate comparative catalytic cracking catalysts, with Examples Y31 - Y43 containing phosphorus-modified ZSM-5 hierarchical molecular sieves and Examples Y44 - Y56 containing phosphorus-modified microporous molecular sieves sieves ZSM-5.

Example Y31-1

The phosphorus-modified molecular sieve GPZ1-1 prepared in Example 1-1, zeolite Y (PSRY zeolite), kaolin, and pseudoboehmite were taken, and deionized water and alumina sol were added thereto. This mixture was vigorously mixed and stirred for 120 minutes to obtain a thick suspension having a solids content of 30 wt.%. Hydrochloric acid was added to adjust the pH of the thick slurry to 3.0, and then vigorous mixing and mixing continued for another 45 minutes. The phosphorus-aluminum inorganic binder, Binder 1 prepared in Example 27, was then added and the mixture was stirred for 30 minutes. The resulting thick suspension was spray dried to obtain microspheres. These microspheres were calcined at 500°C for 1 hour to produce a sample of catalytic cracking catalyst, which was designated CAZY1-1 and had the following composition: ZSM-5 phosphorus modified molecular sieve: 40%, PSRY zeolite: 10%, kaolin: 18%, Binder 1: 18%, pseudoboehmite (in terms of Al ₂ O ₃ ): 5%, and alumina sol (in terms of Al ₂ O ₃ ): 9%.

A fixed-bed microreactor was used to evaluate the reaction characteristics of the 100% equilibrium catalyst and the equilibrium catalyst in which CAZY1-1 was incorporated to illustrate the effect on the catalytic cracking reaction.

The CAZY1-1 catalyst was subjected to aging treatment at 800°C in an atmosphere of 100% steam for 17 hours. Aging-treated CAZY1-1 was mixed with commercial equilibrium catalyst FCC (grade: DVR-3, light oil microactivity 63). The mixture of equilibrium catalyst and catalyst was loaded into a fixed bed microreactor, and the petroleum feedstock shown in Table 4 was subjected to catalytic cracking. Evaluation conditions included a reaction temperature of 620°C, a regeneration temperature of 620°C, and a catalyst-to-oil ratio of 3.2. Table 8 shows the reaction results including the blank test.

Example Y31-2

Identical to Example Y31-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by the phosphorus modified molecular sieve GPZ1-2 prepared in Example 1-2 to produce a catalytic cracking catalyst sample which was designated CAZY1-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative Example Y31-1

Identical to Example Y31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced by Comparative Example 1-1 D1-1 to produce a catalytic cracking catalyst sample designated DCAZY1-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative Example Y31-2

Identical to Example Y31-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by Comparative Example 1-2 D1-2 to produce a catalytic cracking catalyst sample designated DCAZY1-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y32-1

Identical to Example Y31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced by the phosphorus-modified molecular sieve GPZ2-1 prepared in Example 2-1 to produce a catalytic cracking catalyst sample that was designated CAZY2-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y32-2

Identical to Example Y32-1 except that the phosphorus-modified molecular sieve GPZ2-1 was replaced by the phosphorus-modified molecular sieve GPZ2-2 prepared in Example 2-2 to produce a catalytic cracking catalyst sample that was designated CAZY2-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative Example Y32-1

Identical to Example Y32-1 except that the phosphorus modified molecular sieve GPZ2-1 was replaced by Comparative Example 2-1 D2-1 to produce a catalytic cracking catalyst sample designated DCAZY2-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative example Y32-2

Identical to Example Y32-1 except that the phosphorus modified molecular sieve GPZ2-1 was replaced by Comparative Example 2-2 D2-2 to produce a catalytic cracking catalyst sample designated DCAZY2-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y33-1

Identical to Example Y31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced by the phosphorus-modified molecular sieve GPZ3-1 prepared in Example 3-1 to produce a catalytic cracking catalyst sample that was designated CAZY3-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y33-2

Identical to Example Y31-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by the phosphorus modified molecular sieve GPZ3-2 prepared in Example 3-2 to produce a sample catalytic cracking catalyst which was designated CAZY3-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative Example Y33-1

Identical to Example Y31-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by Comparative Sample D3-1 of Comparative Example 3-1 to produce a catalytic cracking catalyst sample designated as DCAZY3-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative example Y33-2

Identical to Example Y31-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by Comparative Sample D3-2 of Comparative Example 3-2 to produce a catalytic cracking catalyst sample designated DCAZY3-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y34-1

Identical to Example Y31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced by the phosphorus-modified molecular sieve GPZ4-1 prepared in Example 4-1 to produce a catalytic cracking catalyst sample that was designated CAZY4-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y34-2

Identical to Example Y34-1 except that the phosphorus modified molecular sieve GPZ4-1 was replaced by the phosphorus modified molecular sieve GPZ4-2 prepared in Example 4-2 to produce a catalytic cracking catalyst sample which was designated CAZY4-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative Example Y34-1

Identical to Example Y34-1 except that the phosphorus modified molecular sieve GPZ4-1 was replaced by Comparative Sample D4-1 of Comparative Example 4-1 to produce a catalytic cracking catalyst sample designated DCAZY4-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative example Y34-2

Identical to Example Y34-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by Comparative Sample D4-2 of Comparative Example 4-2 to produce a catalytic cracking catalyst sample designated DCAZY4-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y35-1

Identical to Example Y31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced by the phosphorus-modified molecular sieve GPZ5-1 prepared in Example 5-1 to produce a catalytic cracking catalyst sample that was designated CAZY5-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y35-2

Identical to Example Y35-1 except that the phosphorus modified molecular sieve GPZ5-1 was replaced by the phosphorus modified molecular sieve GPZ5-2 prepared in Example 5-2 to produce a catalytic cracking catalyst sample which was designated CAZY5-2. Its evaluation was identical to Example Y35-1, and the result is shown in Table 8.

Comparative example Y35-1

Identical to Example Y35-1 except that the phosphorus modified molecular sieve GPZ5-1 was replaced by Comparative Sample D5-1 of Comparative Example 5-1 to produce a catalytic cracking catalyst sample designated DCAZY5-1. Its evaluation was identical to Example Y35-1, and the result is shown in Table 8.

Comparative example Y35-2

Identical to Example Y35-1 except that the phosphorus modified molecular sieve GPZ5-1 was replaced by Comparative Sample D5-2 of Comparative Example 5-2 to produce a catalytic cracking catalyst sample designated DCAZY5-2. Its evaluation was identical to Example Y35-1, and the result is shown in Table 8.

Example Y36-1

Identical to Example Y31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced by the phosphorus-modified molecular sieve GPZ6-1 prepared in Example 6-1 to produce a catalytic cracking catalyst sample that was designated CAZY6-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y36-2

Identical to Example Y36-1 except that the phosphorus-modified molecular sieve GPZ6-1 was replaced by the phosphorus-modified molecular sieve GPZ6-2 prepared in Example 6-2 to produce a catalytic cracking catalyst sample that was designated CAZY6-2. Its evaluation was identical to Example Y36-1, and the result is shown in Table 8.

Comparative example Y36-1

Identical to Example Y36-1 except that the phosphorus modified molecular sieve GPZ6-1 was replaced by Comparative Example 6-1 D6-1 to produce a catalytic cracking catalyst sample designated DCAZY6-1. Its evaluation was identical to Example Y36-1, and the result is shown in Table 8.

Comparative example Y36-2

Identical to Example Y36-1 except that the phosphorus modified molecular sieve GPZ6-1 was replaced by Comparative Sample D6-2 of Comparative Example 6-2 to produce a catalytic cracking catalyst sample designated DCAZY6-2. Its evaluation was identical to Example Y36-1, and the result is shown in Table 8.

Example Y37-1

Identical to Example Y31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced by the phosphorus-modified molecular sieve GPZ7-1 prepared in Example 7-1 to produce a catalytic cracking catalyst sample that was designated CAZY7-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y37-2

Identical to Example Y37-1 except that the phosphorus modified molecular sieve GPZ7-1 was replaced by the phosphorus modified molecular sieve GPZ7-2 prepared in Example 7-2 to produce a catalytic cracking catalyst sample which was designated CAZY7-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative example Y37-1

Identical to Example Y37-1 except that the phosphorus modified molecular sieve GPZ7-1 was replaced by Comparative Example 7-1 D7-1 to produce a catalytic cracking catalyst sample designated DCAZY7-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative example Y37-2

Identical to Example Y37-1 except that the phosphorus modified molecular sieve GPZ7-1 was replaced by Comparative Sample D7-2 of Comparative Example 7-2 to produce a catalytic cracking catalyst sample designated DCAZY7-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Examples Y38 - Y43

Identical to Example Y31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced by the phosphorus-modified molecular sieves GPZ8-1 to GPZ13-2 prepared in Examples 8-1 to 13-2, respectively, to produce catalytic cracking catalyst samples, which were sequentially designated CAZY8-1 - CAZY13-2. Their evaluations were identical to Example Y31-1, and the results are shown in Table 8 accordingly.

Examples Y44 - Y56

Examples Y44 - Y56 are catalysts CAZY14 - CAZY26 containing microporous ZSM-5 (GPZ14 - GPZ26), respectively, and their material compositions correspond to the compositions of Examples Y31 - Y43, respectively, for example in Example Y44-1 GPZ1-1 was replaced by GPZ14-1 , in Example Y44-2 GPZ1-2 was replaced by GPZ14-2 etc., and in Example Y56-1 GPZ13-1 was replaced by GPZ26-1, and in Example Y56-2 GPZ13-2 was replaced by GPZ26 -2. Their evaluations were identical to Example Y31-1, and the results are shown in Table 8 accordingly.

Comparative examples Y44 - Y50

Comparative Examples Y44 to Y50 are comparative catalysts DCAZY-14 to DCAZY-20 containing microporous ZSM-5 (D14 to D20), respectively, and their material compositions correspond to those of Examples Y44 to Y50, respectively, such as Comparative Example Y44-1 GPZ1- 1 was replaced by D14-1, in Comparative Example Y44-2 GPZ1-2 was replaced by D14-2, etc., and in Comparative Example Y50-1 GPZ14-1 was replaced by D20-1, and in Comparative Example Y50-2 GPZ14-2 was replaced by D20-2. Their evaluations were identical to Example Y31-1, and the results are shown in Table 8 accordingly.

Examples Y57 - Y62

Identical to Example Y31-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced by the phosphorus-modified molecular sieves GPZ21-1 to GPZ26-2 prepared in Examples 21-1 to 26-2, respectively, to produce catalytic cracking catalyst samples, which were sequentially designated CAZY27-1 - CAZY32-2. Their evaluations were identical to Example Y31-1, and the results are shown in Table 8 accordingly.

Example Y63-1

Identical to Example Y31-1 except that the phosphorus-aluminum inorganic binder was replaced by Binder 2 prepared in Example Y28 to produce a catalytic cracking catalyst, which was designated CAZY33-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y63-2

Identical to Example Y31-2 except that the phosphorus-aluminum inorganic binder was replaced by Binder 2 prepared in Example Y28 to produce a catalytic cracking catalyst, which was designated CAZY33-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y64-1

Identical to Example Y31-1 except that the phosphorus-aluminum inorganic binder was replaced by Binder 3 prepared in Example Y29 to produce a catalytic cracking catalyst, which was designated CAZY34-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y64-2

Identical to Example Y31-2 except that the phosphorus-aluminum inorganic binder was replaced by Binder 3 prepared in Example Y29 to produce a catalytic cracking catalyst, which was designated CAZY34-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y65-1

Identical to Example Y31-1 except that the phosphorus-aluminum inorganic binder was replaced by Binder 4 prepared in Example Y30 to produce a catalytic cracking catalyst, which was designated CAZY35-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y65-2

Identical to Example Y31-2 except that the phosphorus-aluminum inorganic binder was replaced by Binder 4 prepared in Example Y30 to produce a catalytic cracking catalyst, which was designated CAZY35-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y66-1

Identical to Example Y31-1 except that sample GPZ1-1 is phosphorus-modified hierarchical molecular sieve ZSM-5 (35 wt%), PSRY zeolite (10 wt%), kaolin (18 wt%), phosphorus-aluminum inorganic Binder 3 (22 wt%), pseudoboehmite (10 wt%) and alumina sol (5 wt%) were used to produce a catalytic cracking catalyst, which was designated as CAZY36-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y66-2

Identical to Example Y66-1 except that GPZ1-1 was replaced by GPZ1-2 to produce a catalytic cracking catalyst, which was designated CAZY36-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative Example Y66-1

Identical to Example Y66-1 except that GPZ1-1 was replaced by D1-1 in order to produce a catalytic cracking catalyst, which was designated DCAZY36-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative Example Y66-2

Identical to Example Y66-1 except that GPZ1-1 was replaced by D1-2 in order to produce a catalytic cracking catalyst, which was designated DCAZY36-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y67-1

Identical to Example Y44-1 except that sample GPZ14-1 phosphorus modified microporous molecular sieve ZSM-5 (30 wt%), PSRY zeolite (6 wt%), kaolin (24 wt%), phosphorus-aluminum inorganic Binder 4 (22 wt%), pseudoboehmite (8 wt%) and silica sol (10 wt%) were used to produce a catalytic cracking catalyst, which was designated CAZY37-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y67-2

Identical to Example Y67-1 except that GPZ14-1 was replaced by GPZ14-2 in order to produce a catalytic cracking catalyst, which was designated CAZY37-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative Example Y67-1

Identical to Example Y67-1 except that GPZ14-1 was replaced by D14-1 to produce a catalytic cracking catalyst, which was designated DCAZY37-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative Example Y67-2

Identical to Example Y67-1 except that GPZ14-1 was replaced by D14-2 in order to produce a catalytic cracking catalyst, which was designated DCAZY37-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y68-1

The alumina sol binder was mixed with kaolin and de-cationized water was added to form a thick slurry containing 30 wt.% solids. This thick suspension was well mixed and adjusted with hydrochloric acid to a pH of 2.8. The thick suspension was aged at 55°C for 1 hour. The phosphorus modified molecular sieve GPZ1-1 prepared in Example 1-1 and zeolite Y (PSRY zeolite) were then added to form a thick catalyst slurry with a solids content of 35 wt%. This thick suspension was continuously stirred and spray dried to produce catalyst microspheres. These catalyst microspheres were then calcined at 500°C for 1 hour, washed with ammonium sulfate at 60°C (at a ratio of ammonium sulfate:catalyst microspheres:water=0.5:1:10) until the sodium oxide content was less than 0.25 wt. %, after which they were washed with deionized water and filtered, and then dried at 110°C to obtain the CAZY38-1 catalyst. Its composition contained: phosphorus-modified molecular sieve ZSM-5 GPZ1-1, 40%; PSRY zeolite, 10%; kaolin, 25%; and alumina sol (in terms of Al ₂ O ₃ ), 25%. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y68-2

Identical to Example Y68-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by the phosphorus modified molecular sieve GPZ1-2 prepared in Example 1-2 to produce a catalytic cracking catalyst sample which was designated CAZY38-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative Example Y68-1

Identical to Example Y68-1 except that the phosphorus modified molecular sieve GPZ1-1 was replaced by Comparative Example Y1-1 Comparative Sample D1-1 to produce a catalytic cracking catalyst sample which was designated DCAZY38-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Comparative Example Y68-2

Identical to Example Y68-1 except that the phosphorus-modified molecular sieve GPZ1-1 was replaced by Comparative Example Y1-2 Comparative Sample D1-2 to produce a catalytic cracking catalyst sample designated DCAZY38-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 8.

Example Y69-1 and Example Y69-2

Example Y69-1 and Example Y69-2 respectively used catalytic cracking catalysts CAZY1-1 and CAZY1-2 of Example Y31-1 and Example Y31-2. The catalytic cracking feedstock was naphtha shown in Table 5.

Evaluation conditions included a reaction temperature of 620°C, a regeneration temperature of 620°C, and a catalyst-to-oil ratio of 3.2.

Table 9 shows the mass composition and reaction result of each catalyst mixture containing the catalytic cracking catalyst.

Table 8

Catalyst Material balance, wt.% Catalyst Material balance, wt.% Liquefied gas Ethylene yield Propylene yield Liquefied gas Ethylene yield Propylene yield Blank test example / 100% equilibrium catalyst 18.54 1.39 8.05 Example Y31-1 10% CAZY1-1 90% equilibrium catalyst 35.63 4.01 17.87 Comparative Example Y31-1 10% DCAZY1-1 90% equilibrium catalyst 25.12 2.56 11.35 Example Y31-2 10% CAZY1-2 90% equilibrium catalyst 38.91 4.15 18.53 Comparative Example Y31-2 10% DCAZY-2 90% equilibrium catalyst 28.9 2.9 11.87 Example Y32-1 10% CAZY2-1 90% equilibrium catalyst 33.63 3.68 16.67 Comparative Example Y32-1 10% DCAZY2-1 90% equilibrium catalyst 24.68 2.45 11.01 Example Y32-2 10% CAZY2-2 90% equilibrium catalyst 36.71 4.01 17.78 Comparative example Y32-2 10% DCAZY2-2 90% equilibrium catalyst 27.39 2.68 11.13 Example Y33-1 10% CAZY3-1 90% equilibrium catalyst 35.34 3.81 16.98 Comparative Example Y33-1 10% DCAZY3-1 90% equilibrium catalyst 22.76 2.31 11.03 Example Y33-2 10% CAZY3-2 90% equilibrium catalyst 37.72 4.12 17.98 Comparative example Y33-2 10% DCAZY3-2 90% equilibrium catalyst 24.82 2.54 11.09 Example Y34-1 10% CAZY4-1 90% equilibrium catalyst 35.01 3.68 17.13 Comparative Example Y34-1 10% DCAZY4-1 90% equilibrium catalyst 24.79 2.67 11.37 Example Y34-2 10% CAZY4-2 90% equilibrium catalyst 37.98 4.23 18.54 Comparative example Y34-2 10% DCAZY4-2 90% equilibrium catalyst 26.86 2.81 11.8 Example Y35-1 10% CAZY5-1 90% equilibrium catalyst 31.56 3.31 15.61 Comparative example Y35-1 10% DCAZY5-1 90% equilibrium catalyst 23.09 2.42 11.12 Example Y35-2 10% CAZY5-2 90% equilibrium catalyst 34.29 3.8 16.59 Comparative example Y35-2 10% DCAZY5-2 90% equilibrium catalyst 23.34 2.5 11.21 Example Y36-1 10% CAZY6-1 90% equilibrium catalyst 35.89 3.9 17.67 Comparative example Y36-1 10% DCAZY6-1 90% equilibrium catalyst 25.78 2.79 13.74 Example Y36-2 10% CAZY6-2 90% equilibrium catalyst 38.45 4.34 18.23 Comparative example Y36-2 10% DCAZY6-2 90% equilibrium catalyst 27.8 2.98 14.12 Example Y37-1 10% CAZY7-1 90% equilibrium catalyst 32.67 3.56 16.03 Comparative example Y37-1 10% DCAZY7-1 90% equilibrium catalyst 23.69 2.62 11.82 Example Y37-2 10% CAZY7-2 90% equilibrium catalyst 35.02 4.01 16.69 Comparative example Y37-2 10% DCAZY7-2 90% equilibrium catalyst 25.52 2.81 11.99 Example Y38-1 10% CAZY8-1 90% equilibrium catalyst 30.35 3.21 16.12 Example Y38-2 10% CAZY8-2 90% equilibrium catalyst 38.85 4.46 18.62 Example Y39-1 10% CAZY9-1 90% equilibrium catalyst 28.58 2.96 14.27 Example Y39-2 10% CAZY9-2 90% equilibrium catalyst 36.51 4.21 17.31 Example Y40-1 10% CAZY10-1 90% equilibrium catalyst 27.51 2.89 13.12 Example Y40-2 10% CAZY10-2 90% equilibrium catalyst 35.68 4.02 17.15 Example Y41-1 10% CAZY11-1 90% equilibrium catalyst 30.69 3.46 16.98 Example Y41-2 10% CAZY11-2 90% equilibrium catalyst 38.61 4.31 18.02 Example Y42-1 10% CAZY12-1 90% equilibrium catalyst 28.13 2.81 14.02 Example Y42-2 10% CAZY12-2 90% equilibrium catalyst 35.84 4.16 17.12 Example Y43-1 10% CAZY13-1 90% equilibrium catalyst 27.03 2.8 13.02 Example Y43-2 10% CAZY13-2 90% equilibrium catalyst 34.79 3.87 17 Example Y44-1 10% CAZY14-1 90% equilibrium catalyst 34.14 3.67 16.89 Comparative Example Y44-1 10% DCAZY14-1 90% equilibrium catalyst 23.65 2.74 10.86 Example Y44-2 10% CAZY14-2 90% equilibrium catalyst 36.37 4.01 17.92 Comparative example Y44-2 10% DCAZY14-2 90% equilibrium catalyst 27.02 2.8 11.23 Example Y45-1 10% CAZY15-1 90% equilibrium catalyst 31.54 3.34 16.09 Comparative example Y45-1 10% DCAZY15-1 90% equilibrium catalyst 23.62 2.34 10.68 Example Y45-2 10% CAZY15-2 90% equilibrium catalyst 35.43 3.87 17.1 Comparative example Y45-2 10% DCAZY15-2 90% equilibrium catalyst 25.6 2.45 11.03 Example Y46-1 10% CAZY16-1 90% equilibrium catalyst 33.65 3.45 16.68 Comparative Example Y46-1 10% DCAZY16-1 90% equilibrium catalyst 23.95 2.48 11.02 Example Y46-2 10% CAZY16-2 90% equilibrium catalyst 36.56 4.16 17.76 Comparative example Y46-2 10% DCAZY16-2 90% equilibrium catalyst 25.84 2.67 11.43 Example Y47-1 10% CAZY17-1 90% equilibrium catalyst 30.45 3.23 15.03 Comparative Example Y47-1 10% DCAZY17-1 90% equilibrium catalyst 22.68 2.28 11.03 Example Y47-2 10% CAZY17-2 90% equilibrium catalyst 33.13 3.31 16.05 Comparative example Y47-2 10% DCAZY17-2 90% equilibrium catalyst 23.12 2.34 11.11 Example Y48-1 10% CAZY18-1 90% equilibrium catalyst 34.16 3.65 16.69 Comparative example Y48-1 10% DCAZY18-1 90% equilibrium catalyst 23.46 2.56 12.83 Example Y48-2 10% CAZY18-2 90% equilibrium catalyst 37.57 4.16 17.53 Comparative example Y48-2 10% DCAZY18-2 90% equilibrium catalyst 26.12 2.84 13.69 Example Y49-1 10% CAZY19-1 90% equilibrium catalyst 31.34 3.23 15.13 Comparative Example Y49-1 10% DCAZY19-1 90% equilibrium catalyst 22.17 2.53 11.23 Example Y49-2 10% CAZY19-2 90% equilibrium catalyst 33.74 3.87 16.12 Comparative Example Y49-2 10% DCAZY19-2 90% equilibrium catalyst 24.79 2.67 11.79 Example Y50-1 10% CAZY20-1 90% equilibrium catalyst 32.07 3.36 15.78 Comparative Example Y50-1 10% DCAZY20-1 90% equilibrium catalyst 22.73 2.87 11.63 Example Y50-2 10% CAZY20-2 90% equilibrium catalyst 34.46 3.89 16.54 Comparative example Y50-2 10% DCAZY20-2 90% equilibrium catalyst 24.56 2.69 11.98 Example Y51-1 10% CAZY21-1 90% equilibrium catalyst 28.67 3.12 15.68 Example Y51-2 10% CAZY21-2 90% equilibrium catalyst 36.13 4.13 17.58 Example Y52-1 10% CAZY22-1 90% equilibrium catalyst 26.89 2.78 13.95 Example Y52-2 10% CAZY22-2 90% equilibrium catalyst 34.68 4.01 16.35 Example Y53-1 10% CAZY23-1 90% equilibrium catalyst 26.56 2.59 12.69 Example Y53-2 10% CAZY23-2 90% equilibrium catalyst 34.12 3.87 16.02 Example Y54-1 10% CAZY24-1 90% equilibrium catalyst 28.95 3.24 16.12 Example Y54-2 10% CAZY24-2 90% equilibrium catalyst 36.59 4.14 17.28 Example Y55-1 10% CAZY25-1 90% equilibrium catalyst 27.02 2.65 13.61 Example Y55-2 10% CAZY25-2 90% equilibrium catalyst 33.72 4.01 16.47 Example Y56-1 10% CAZY26-1 90% equilibrium catalyst 26.23 2.67 12.71 Example Y56-2 10% CAZY26-2 90% equilibrium catalyst 33.61 3.78 16.13 Example Y57-1 10% CAZY27-1 90% equilibrium catalyst 28.68 3.12 15.45 Example Y57-2 10% CAZY27-2 90% equilibrium catalyst 36.23 4.34 18.01 Example Y58-1 10% CAZY28-1 90% equilibrium catalyst 26.46 2.46 13.43 Example Y58-2 10% CAZY28-2 90% equilibrium catalyst 34.87 4.13 16.73 Example Y59-1 10% CAZY29-1 90% equilibrium catalyst 26.24 2.46 13.01 Example Y59-2 10% CAZY29-2 90% equilibrium catalyst 33.62 3.74 16.35 Example Y60-1 10% CAZY30-1 90% equilibrium catalyst 28.89 3.17 15.78 Example Y60-2 10% CAZY30-2 90% equilibrium catalyst 36.9 4.12 16.92 Example Y61-1 10% CAZY31-1 90% equilibrium catalyst 26.46 2.23 13.13 Example Y61-2 10% CAZY31-2 90% equilibrium catalyst 34.82 4.01 16.34 Example Y62-1 10% CAZY32-1 90% equilibrium catalyst 26.02 2.34 12.64 Example Y62-2 10% CAZY32-2 90% equilibrium catalyst 33.23 3.46 16.03 Example Y63-1 10% CAZY33-1 90% equilibrium catalyst 33.61 3.84 17.51 Example Y63-2 10% CAZY33-2 90% equilibrium catalyst 41.78 4.24 18.61 Example Y64-1 10% CAZY34-1 90% equilibrium catalyst 33.14 3.78 17.48 Example Y64-2 10% CAZY34-2 90% equilibrium catalyst 41.01 4.01 18.12 Example Y65-1 10% CAZY35-1 90% equilibrium catalyst 33.24 3.68 17.12 Example Y65-2 10% CAZY35-2 90% equilibrium catalyst 41.16 4.03 18.1 Example Y66-1 10% CAZY36-1 90% equilibrium catalyst 33.12 3.45 16.12 Comparative Example Y66-1 10% DCAZY36-1 90% equilibrium catalyst 22.76 2.35 11.17 Example Y66-2 10% CAZY36-2 90% equilibrium catalyst 36.63 3.78 16.96 Comparative Example Y66-2 10% DCAZY36-2 90% equilibrium catalyst 25.56 3.02 12.23 Example Y67-1 10% CAZY37-1 90% equilibrium catalyst 36.68 3.88 15.33 Comparative Example Y67-1 10% DCAZY37-1 90% equilibrium catalyst 25.93 2.61 11.35 Example Y67-2 10% CAZY37-2 90% equilibrium catalyst 40.39 4.32 15.97 Comparative Example Y67-2 10% DCAZY37-2 90% equilibrium catalyst 28.99 2.97 11.99 Example Y68-1 10% CAZY38-1 90% equilibrium catalyst 33.85 3.73 16.44 Comparative Example Y68-1 10% DCAZY38-1 90% equilibrium catalyst 27.35 2.77 11.79 Example Y68-2 10% CAZY38-2 90% equilibrium catalyst 40.43 4.55 18.27 Comparative Example Y68-2 10% DCAZY38-2 90% equilibrium catalyst 28.52 2.93 12.68

Comparative Example Y69-1 and Comparative Example Y69-2

Identical to Example Y69-1 except that comparative catalytic cracking catalysts DCAZY1-1 and DCAZY1-2 of Comparative Example Y31-1 and Comparative Example Y31-2 were used, respectively.

The mass composition and reaction result of each catalyst mixture containing a comparative sample of the catalytic cracking catalyst are shown in Table 9.

Example Y70-1 and Example Y70-2

Example Y70-1 and Example Y70-2 respectively used catalytic cracking catalysts CAZY14-1 and CAZY14-2 of Example Y44-1 and Example Y44-2. The catalytic cracking feedstock was naphtha shown in Table 5.

Evaluation conditions included a reaction temperature of 620°C, a regeneration temperature of 620°C, and a catalyst-to-oil ratio of 3.2.

Table 9 shows the mass composition and reaction result of each catalyst mixture containing the catalytic cracking catalyst.

Comparative Example Y70-1 and Comparative Example Y70-2

Identical to Example Y70-1 except that comparative catalytic cracking catalysts DCAZY14-1 and DCAZY14-2 of Comparative Example Y44-1 and Comparative Example Y44-2 were used, respectively.

The mass composition and reaction result of each catalyst mixture containing a comparative sample of the catalytic cracking catalyst are shown in Table 9.

Table 9

Catalyst Yield of product cracking gas, wt.% Liquefied gas Propylene yield Blank test example / 100% equilibrium catalyst 69.13 8.42 Example Y69-1 10% CAZY1-1 90% equilibrium catalyst 78.82 13.56 Example Y69-2 10% CAZY1-2 90% equilibrium catalyst 82.56 15.12 Comparative Example Y69-1 10% DCAZY1-1 90% equilibrium catalyst 70.59 9.5 Comparative Example Y69-2 10% DCAZY1-2 90% equilibrium catalyst 73.49 10.12 Example Y70-1 10% CAZY14-1 90% equilibrium catalyst 77.83 14.01 Example Y70-2 10% CAZY14-2 90% equilibrium catalyst 83.12 15.18 Comparative Example Y70-1 10% DCAZY14-1 90% equilibrium catalyst 71.72 9.56 Comparative Example Y70-2 10% DCAZY14-2 90% equilibrium catalyst 73.05 10.12

Example Y71-1

Identical to Example Y31-1 except that zeolite Y (PSRY) was replaced by HRY-1 to produce a catalyst sample which was designated CAZY39-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 10.

Example Y71-2

Identical to Example Y31-1 except that zeolite Y (PSRY) was replaced by HRY-1 to produce a catalyst sample which was designated CAZY39-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 10.

Comparative Example Y71-1

Identical to Example Y31-1 except that zeolite Y (PSRY) was replaced by HRY-1 to produce a reference catalyst which was designated DCAZY39-1. Its evaluation was identical to Example Y31-1, and the result is shown in Table 10.

Comparative Example Y71-2

Identical to Example Y31-1 except that zeolite Y (PSRY) was replaced by HRY-1 to produce a reference catalyst which was designated DCAZY39-2. Its evaluation was identical to Example Y31-1, and the result is shown in Table 10.

Table 10

Material balance, wt.% Index Liquefied gas Ethylene yield Propylene yield Blank test example 18.54 1.39 8.05 Example Y71-1 36.75 3.98 16.87 Example Y71-2 39.43 4.45 17.95 Comparative Example Y71-1 25.58 2.89 11.96 Comparative Example Y71-2 26.84 2.98 12.23

Claims (53)

1. Phosphorus modified molecular sieve with MFI structure, characterized in that it has a K value satisfying the condition of 70%≤K≤90%; where K=P1/P2×100%, P1 is the mass content of phosphorus measured by XPS in a region with an area of 100 sq.nm and a vertical depth of 0 to 2 nm on any surface of the molecular sieve crystal grain, P2 is the EPMA-measured mass content of phosphorus in a region with an area of 100 nm2 and a vertical depth of 5 to 10 nm on any surface of the molecular sieve crystal grain. 2. The molecular sieve according to claim 1, wherein the K value satisfies the condition of 75%≤K≤90%. 3. The molecular sieve according to claim 1, wherein the K value satisfies the condition of 78%≤K≤85%. 4. Molecular sieve according to any one of claims 1-3, in which the molar ratio of phosphorus content in terms of P ₂ O ₅ to alumina content is ≥0.01; for example ≥0.2; ≥0.3; or 0.4-0.7. 5. Molecular sieve according to any one of paragraphs. 1-4, in which the phosphorus modified molecular sieve with the MFI structure is a microporous molecular sieve ZSM-5 or a hierarchical molecular sieve ZSM-5. 6. Molecular sieve according to any one of paragraphs. 1-5, in which the microporous molecular sieve ZSM-5 has a silica/alumina molar ratio of 15-1000, for example 20-200. 7. Molecular sieve according to any one of paragraphs. 1-6, in which the hierarchical molecular sieve ZSM-5 has a mesopore volume fraction relative to the total pore space volume of more than 10%, an average pore diameter of 2-20 nm, and a silica/alumina molar ratio of 15-1000, for example 20-200. 8. A catalytic cracking aid, which, based on the dry weight of the catalytic cracking aid, contains 5-75 wt.% phosphorus modified molecular sieve with an MFI structure according to any one of paragraphs. 1-7, 1-40 wt.% binder and 0-65 wt.% second clay. 9. The catalytic cracking aid according to claim 8, which, based on the dry weight of the catalytic cracking aid, contains: 8-60 wt.% phosphorus-modified molecular sieve with MFI structure according to any one of paragraphs. 1-7, 1-40 wt.% binder, and 5-55 wt.% second clay. 10. Auxiliary agent for catalytic cracking according to any one of paragraphs. 8-9, in which the binder or inorganic binder contains a phosphorus-aluminum inorganic binder and/or other inorganic binders, for example, the phosphorus-aluminum inorganic binder is a phosphorus-aluminum adhesive and/or a first clay-containing phosphorus-aluminum inorganic binder, or, for example, the first clay is selected from kaolin, sepiolite, attapulgite, rectorite, smectite and diatomite; in addition, for example, the phosphorus-aluminum inorganic binder containing the first clay contains 10-40 wt.%, for example 15-40 wt.% of the aluminum component in terms of Al ₂ O ₃ , 45-90 wt.%, for example 45-80 wt.% of the phosphorus component in terms of P ₂ O ₅ and more than 0 and not more than 40 wt.% of the first clay in terms of dry matter, and the phosphorus-aluminum inorganic binder containing the first clay has a mass ratio P/Al of 1.0- 6.0, pH value 1-3.5 and solids content 15-60 wt.%; for example, the second clay is selected from kaolin, sepiolite, attapulgite, rectorite, smectite, diatomite, giagerite, halloysite, hydrotalcite and bentonite; for example, other inorganic binders are selected from pseudoboehmite, alumina sol, silica-alumina sol and water glass. 11. A catalytic cracking catalyst containing a phosphorus-modified molecular sieve with an MFI structure, which, based on the dry weight of the catalytic cracking catalyst, contains 1-25 wt.% zeolite Y, 5-50 wt.% phosphorus-modified molecular sieve with an MFI structure according to any one of pp. 1-7, 1-60 wt.% inorganic binder and optionally 0-60 wt.% second clay. 12. The catalytic cracking catalyst according to claim 11, wherein the binder or inorganic binder contains a phosphorus-aluminum inorganic binder and/or other inorganic binders, for example, the phosphorus-aluminum inorganic binder is a phosphorus-aluminum adhesive and/or a first clay-containing phosphorus-aluminum inorganic binder, or, for example, the first clay is selected from kaolin, sepiolite, attapulgite, rectorite, smectite and diatomite; in addition, for example, the phosphorus-aluminum inorganic binder containing the first clay contains 10-40 wt.%, for example 15-40 wt.% of the aluminum component in terms of Al ₂ O ₃ , 45-90 wt.%, for example 45-80 wt.% of the phosphorus component in terms of P ₂ O ₅ and more than 0 and not more than 40 wt.% of the first clay in terms of dry matter, and the phosphorus-aluminum inorganic binder containing the first clay has a mass ratio P/Al of 1.0- 6.0, pH value 1-3.5 and solids content 15-60 wt.%; for example, the second clay is selected from kaolin, sepiolite, attapulgite, rectorite, smectite, diatomite, giagerite, halloysite, hydrotalcite and bentonite; for example, other inorganic binders are selected from pseudoboehmite, alumina sol, silica-alumina sol and water glass. 13. Catalytic cracking catalyst according to any one of paragraphs. 11-12, in which the zeolite Y contains at least one zeolite of PSRY zeolite, PSRY-S zeolite, containing rare earth elements, PSRY zeolite, containing rare earth elements, PSRY-S zeolite, USY zeolite, containing rare earth elements, USY zeolite, REY zeolite, zeolite REHY and zeolite HY. 14. A method for producing a phosphorus-modified molecular sieve with an MFI structure according to any one of claims. 1-7, characterized in that a phosphorus-modified molecular sieve with an MFI structure is produced by an immersion method, including: contact by mixing an aqueous solution of a phosphorus-containing compound at a temperature of 40-150°C and a molecular sieve with an MFI structure at a temperature of 40-150°C, according to essentially at the same temperature for at least 0.1 hour, then drying and calcining at 200-600°C in air or steam for at least 0.1 hour; or vigorously mixing and stirring the phosphorus-containing compound, MFI molecular sieve and water, raising the temperature to 40-150°C, holding for at least 0.1 hour, then drying and calcining at 200-600°C in air or water vapor for at least 0.1 hour. 15. The method according to claim 14, characterized in that a phosphorus-modified molecular sieve with an MFI structure is obtained by an immersion method, including: contact by mixing an aqueous solution of a phosphorus-containing compound at a temperature of 50-150°C and a molecular sieve with an MFI structure at a temperature of 50-150 °C at substantially the same temperature for at least 0.1 hour, then drying and calcining at 200-600°C in air or steam for at least 0.1 hour; or vigorously mixing and stirring the phosphorus-containing compound, MFI molecular sieve and water, raising the temperature to 50-150°C for at least 0.1 hour, then drying and calcining at 200-600°C in air or steam for at least 0.1 hour. 16. The method according to claim 14, characterized in that a phosphorus-modified molecular sieve with an MFI structure is obtained by an immersion method, including: contact by mixing an aqueous solution of a phosphorus-containing compound at a temperature of 70-130°C and a molecular sieve with an MFI structure at a temperature of 70-130 °C at substantially the same temperature for at least 0.1 hour, then drying and calcining at 200-600°C in air or steam for at least 0.1 hour; or vigorously mixing and stirring the phosphorus-containing compound, MFI molecular sieve and water, raising the temperature to 70-130°C, holding for at least 0.1 hour, then drying and calcining at 200-600°C in air or water vapor for at least 0.1 hour. 17. Method according to any one of paragraphs. 14-16, wherein the phosphorus-containing compound is selected from organic phosphorus compounds and/or inorganic phosphorus compounds; for example, the organic phosphorus compound is selected from trimethylphosphate, triphenylphosphine, trimethylphosphite, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium hydroxide, triphenylethylphosphonium bromide, triphenylbutylphosphonium bromide, triphenylbenzylphosphonium bromide, hexamethylphosphoric acid triamide, dibenzyldiethylphosphoramidite, 1,3-bis ((triethylphosphanyl)methyl)benzene, and the inorganic phosphorus compound is selected from phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate. 18. Method according to any one of paragraphs. 14-17, in which the molar ratio of the phosphorus-containing compound in terms of phosphorus oxide to a molecular sieve with an MFI structure, such as the ZSM-5 hydrogen type molecular sieve, in terms of alumina is 0.01-2; for example 0.1-1.5 or 0.2-1.5. 19. Method according to any one of paragraphs. 14-18, in which the phosphorus-containing compound is a mixture of boron phosphate and one or more substances selected from trimethylphosphate, triphenylphosphine, trimethylphosphite, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate, and in this mixture boron phosphate makes up 10-80 wt.%, for example 20-40 wt.%. 20. Method according to any one of paragraphs. 14-19, in which the mass ratio of water/molecular sieve upon contact is 0.5-1, and the contact time is 0.5-40 hours. 21. Method according to any one of paragraphs. 14-20, in which calcination is performed at 450-550°C in an atmosphere of water vapor. 22. A method for producing an auxiliary agent for catalytic cracking according to any one of paragraphs. 8-10, including vigorous mixing and agitation of the phosphorus-modified molecular sieve with an MFI structure according to any one of paragraphs. 1-7, a binder and optionally a second clay with water, and then spray-dried to obtain a catalytic cracking aid. 23. The method of claim 22, wherein the binder includes or is a phosphorus-aluminum inorganic binder. 24. Method according to any one of paragraphs. 22-23, in which the phosphorus-aluminum inorganic binder is a phosphorus-aluminum adhesive and/or a first clay-containing phosphorus-aluminum inorganic binder; wherein the phosphorus-aluminum inorganic binder containing the first clay, calculated on a dry weight basis, contains 10-40 wt.%, for example, 15-40 wt.%, or 10-30 wt.%, or 15-35 wt.% or 20 -40 wt.% aluminum component in terms of Al ₂ O ₃ , 45-90 wt.%, for example 45-80 wt.%, or 50-75 wt.%, or 60-80 wt.% phosphorus component in terms of P ₂ O ₅ , and on a dry matter basis, greater than 0 and not more than 40 wt.%, for example 8-35 wt.% of the first clay, and the phosphorus-aluminum inorganic binder containing the first clay has a P/Al mass ratio of 1 .0-6.0, for example 1.2-6.0 or 2.0-5.0, pH value 1-3.5, for example 2.0-3.0, and solids content 15-60 wt. %; and the first clay contains at least one of kaolin, sepiolite, attapulgite, rectorite, smectite and diatomite. 25. Method according to any one of paragraphs. 22-24, wherein the second clay is at least one substance selected from kaolin, sepiolite, attapulgite, rectorite, smectite, giagerite, halloysite, hydrotalcite, bentonite and diatomite. 26. Method according to any one of paragraphs. 22-25, in which, based on the total weight of the catalytic cracking aid, the binder contains, on a dry weight basis, 3-39 wt.% phosphorus-aluminum inorganic binder and 1-30 wt.% other inorganic binder. 27. Method according to any one of paragraphs. 22-26, wherein the other inorganic binder may also include at least one of pseudoboehmite, alumina sol, silica-alumina sol and water glass. 28. Method according to any one of paragraphs. 22-27, further comprising: subjecting the spray-dried product to first calcination, and then washing and optionally drying to obtain a catalytic cracking aid; moreover, for the first calcination, the calcination temperature is 300-650°C, the calcination time is 0.5-8 hours; The drying temperature is 100-200°C, and the drying time is 0.5-24 hours. 29. Method according to any one of paragraphs. 22-28, further comprising: preparing a first clay-containing phosphorus-aluminum inorganic binder by the following steps: the alumina source, the first clay and water are vigorously mixed and stirred to obtain a slurry having a solids content of 5-48 wt.%; wherein the source of alumina is aluminum hydroxide and/or alumina, which can be peptized with acid, in an amount of 10-40 parts by weight, for example 15-40 parts by weight. source of alumina in terms of Al ₂ O ₃ , the amount of first clay used by dry weight is more than 0 parts by weight. and no more than 40 parts by mass; concentrated phosphoric acid is added to the thick suspension with stirring according to the mass ratio of P/Al=1-6, and the resulting mixed suspension is reacted at 50-99°C for 15-90 minutes; wherein P in P/Al represents the mass of phosphorus as a base element in phosphoric acid, and Al represents the mass of aluminum as a base element in the alumina source. 30. A method for producing a catalytic cracking catalyst according to any one of claims. 11-13, comprising vigorously mixing and kneading the Y zeolite, the phosphorus modified MFI molecular sieve of any one of claims 1-7, the inorganic binder, and optionally the second clay with water, and then spray drying to obtain a catalytic cracking catalyst. 31. The production method of claim 30, wherein the inorganic binder includes or is a phosphorus-aluminum inorganic binder. 32. Method according to any one of paragraphs. 30-31, in which the phosphorus-aluminum inorganic binder is a phosphorus-aluminum adhesive and/or a first clay-containing phosphorus-aluminum inorganic binder; The phosphorus-aluminum inorganic binder containing the first clay contains 10-40 wt.%, for example 15-40 wt.% of the aluminum component in terms of Al ₂ O ₃ , 45-90 wt.%, for example 45-80 wt. .% phosphorus component in terms of P ₂ O ₅ , and in terms of dry matter is more than 0 and not more than 40 wt.% of the first clay, and the phosphorus-aluminum inorganic binder containing the first clay has a P/Al mass ratio equal to 1, 0-6.0, pH value 1-3.5, and solids content 15-60 wt.%; and the first clay contains at least one of kaolin, sepiolite, attapulgite, rectorite, smectite and diatomite. 33. Method according to any one of paragraphs. 30-32, wherein the second clay is at least one substance selected from kaolin, sepiolite, attapulgite, rectorite, smectite, giagerite, halloysite, hydrotalcite, bentonite and diatomite. 34. Method according to any one of paragraphs. 30-33, in which, based on the total weight of the catalytic cracking catalyst, the inorganic binder contains, on a dry weight basis, 3-39 wt.% of a phosphorus-aluminum inorganic binder and 1-30 wt.% of another inorganic binder, where the other inorganic binder is at least one substance selected from pseudoboehmite, alumina sol, silica-alumina sol and liquid glass. 35. Method according to any one of paragraphs. 30-34, further comprising: subjecting the spray-dried product to first calcination, and then washing and optionally drying to obtain a catalytic cracking catalyst; moreover, for the first calcination, the calcination temperature is 300-650°C, the calcination time is 0.5-8 hours; The drying temperature is 100-200°C, and the drying time is 0.5-24 hours. 36. Method according to any one of paragraphs. 30-35, further comprising: preparing a first clay-containing phosphorus-aluminum inorganic binder by the following steps: the alumina source, the first clay and water are vigorously mixed and stirred to obtain a slurry having a solids content of 5-48 wt.%; wherein the source of alumina is aluminum hydroxide and/or alumina, which can be peptized with acid, in an amount of 10-40 parts by weight, for example 15-40 parts by weight. source of alumina in terms of Al ₂ O ₃ , the amount of first clay used per dry weight is more than 0 parts by weight. and no more than 40 parts by mass; concentrated phosphoric acid is added to the suspension with stirring according to the mass ratio of P/Al=1-6, and the resulting mixed suspension is reacted at 50-99°C for 15-90 minutes; wherein P in P/Al represents the mass of phosphorus as a base element in phosphoric acid, and Al represents the mass of aluminum as a base element in the alumina source. 37. A catalytic cracking aid obtained by the method for producing a catalytic cracking aid according to any one of claims. 22-29 38. A catalytic cracking catalyst obtained by the method for producing a catalytic cracking catalyst according to any one of claims 30 to 36 39. A method for catalytic cracking of liquid petroleum products, characterized in that it includes: reaction of liquid petroleum products by contact with an auxiliary agent for catalytic cracking according to any one of paragraphs. 8-10 and 37 or with a catalytic cracking catalyst according to any one of paragraphs. 11-13 and 38 under catalytic cracking conditions. 40. The method according to claim 39, including: reacting liquid petroleum products by contact with a catalyst mixture containing an auxiliary agent for catalytic cracking according to any one of claims. 8-10 and 37 and a catalytic cracking catalyst according to any one of paragraphs. 11-13 and 38, under catalytic cracking conditions; wherein in the catalyst mixture the content of the catalytic cracking auxiliary agent is 0.1-30 wt.%. 41. Method for catalytic cracking of liquid petroleum products according to any one of paragraphs. 39 and 40, in which the catalytic cracking conditions include: reaction temperature 500-800°C; The liquid petroleum products are one or more types selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric gas oil, vacuum gas oil, straight run gas oil, propane light/heavy deasphalting oil, coker gas oil, and coal liquefaction product.