CN114425430A

CN114425430A - Catalytic cracking catalyst

Info

Publication number: CN114425430A
Application number: CN202011175727.5A
Authority: CN
Inventors: 王成强; 罗一斌; 欧阳颖; 邢恩会; 舒兴田
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2020-10-29
Filing date: 2020-10-29
Publication date: 2022-05-03
Anticipated expiration: 2040-10-29
Also published as: CN114425430B

Abstract

A catalytic cracking catalyst is characterized by containing a Y-type molecular sieve and a phosphorus modified ZSM-5 molecular sieve, wherein the phosphorus modified ZSM-5 molecular sieve,²⁷in Al MAS-NMR, the ratio of the peak area of the resonance signal with a chemical shift of 39. + -.3 ppm to the peak area of the resonance signal with a chemical shift of 54 ppm. + -.3 ppm is not less than 1.

Description

Catalytic cracking catalyst

Technical Field

The invention relates to a catalytic cracking catalyst, in particular to a catalytic cracking catalyst containing a Y-type molecular sieve and a ZSM-5 molecular sieve.

Background

MFI structure molecular sieves, including ZSM-5 molecular sieves, were a widely used class of zeolitic molecular sieve catalytic materials developed in 1972 by Mobil corporation of america. The molecular sieve has a three-dimensional crossed pore channel structure, wherein the pore channel along the axial direction a is a straight pore, the cross section dimension of the pore channel is 0.54 multiplied by 0.56nm and is approximately circular, and the pore channel along the axial direction b is a Z-shaped pore, the cross section dimension of the pore channel is 0.51 multiplied by 0.56nm and is oval. The pore opening is composed of ten-membered rings, and the size of the molecular sieve is between that of the small-pore zeolite and that of the large-pore zeolite, so that the molecular sieve has a unique shape-selective catalytic action. It has the characteristics of unique pore channel structure, good shape-selective catalysis and isomerization performance, high thermal and hydrothermal stability, high specific surface area, wide silicon-aluminum ratio variation range, unique surface acidity and lower carbon content, is widely used as a catalyst and a catalyst carrier, and is successfully used in production processes of alkylation, isomerization, disproportionation, catalytic cracking, gasoline preparation from methanol, olefin preparation from methanol and the like. The molecular sieve is introduced into catalytic cracking and carbon four-hydrocarbon catalytic cracking, shows excellent catalytic performance, and can greatly improve the yield of low-carbon olefin by utilizing the shape selectivity of the molecules.

Since 1983, ZSM-5 molecular sieve was applied to catalytic cracking process as an octane number promoter for catalytic cracking, aiming at improving the octane number of catalytic cracking gasoline and the selectivity of low-carbon olefin. In US3758403, ZSM-5 was first reported as an active component for propylene production increase, i.e. ZSM-5 was prepared with REY as an active component to make FCC catalyst. US5997728 discloses the use of a ZSM-5 molecular sieve as an aid to propylene production without any modification of the molecular sieve. The two technologies have low propylene yield. The ZSM-5 molecular sieve has good shape-selective performance and isomerization performance, but has the defects of poor hydrothermal stability and easy inactivation under severe high-temperature hydrothermal conditions, so that the catalytic performance is reduced.

In the 80 s of the 20 th century, Mobil company found that phosphorus can improve the hydrothermal stability of the ZSM-5 molecular sieve, and meanwhile, phosphorus modifies the ZSM-5 molecular sieve to improve the yield of low-carbon olefin. Conventional additives typically contain phosphorus activated ZSM-5, which selectively converts primary cracked products (e.g., gasoline olefins) to C3 and C4 olefins. After being synthesized, the ZSM-5 molecular sieve is modified by introducing a proper amount of inorganic phosphorus compound, and can stabilize framework aluminum under severe hydrothermal conditions.

CN 106994364A discloses a method for modifying ZSM-5 molecular sieve by phosphorusMixing a phosphorus-containing compound selected from one or more of 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 and P₂O₅At least 0.1 wt% of the mixture, drying, roasting, further carrying out an ammonium exchange step and a water washing step so that the content of alkali metal ions therein is reduced to less than 0.10 wt%, and then carrying out a drying and hydrothermal aging step at 400-1000 ℃ and 100% steam. The phosphorus-containing ZSM-5 molecular sieve obtained by the method has high total acid content, excellent cracking conversion rate and propylene selectivity and higher liquefied gas yield.

In CN1506161A, a method for modifying a hierarchical pore ZSM-5 molecular sieve is disclosed, which comprises the following conventional steps: synthesizing → filtering → ammonium exchanging → drying → roasting to obtain the hierarchical pore ZSM-5 molecular sieve, then modifying the hierarchical pore ZSM-5 molecular sieve with phosphoric acid, and then drying and roasting to obtain the phosphorus modified hierarchical pore ZSM-5 molecular sieve. Wherein, P₂O₅The loading is usually in the range of 1 to 7 wt%. However, phosphoric acid or ammonium phosphate can generate phosphorus species in different aggregation states by self-polymerization in the roasting process, and only phosphate radical entering pores is interacted with framework aluminum in the hydrothermal treatment process to keep B acid centers and reduce the distribution of the phosphorus species.

Although the ZSM-5 molecular sieve is modified by adopting a proper amount of inorganic phosphide, the framework dealumination can be slowed down, the hydrothermal stability is improved, and phosphorus atoms can be combined with distorted four-coordination framework aluminum to generate weak B acid centers, so that the higher conversion rate of long paraffin cracking and the higher selectivity of light olefins are achieved, the excessive inorganic phosphide is used for modifying the ZSM-5 molecular sieve, so that the pore channels of the molecular sieve are blocked, the pore volume and the specific surface area are reduced, and a large amount of strong B acid centers are occupied. In addition, in the prior art, phosphoric acid or ammonium phosphate salts can generate phosphorus species in different aggregation states by self-polymerization in the roasting process, phosphorus is insufficiently coordinated with framework aluminum, the utilization efficiency of phosphorus is low, and phosphorus modification does not always obtain a satisfactory hydrothermal stability improvement result. Therefore, a new technology is urgently needed to promote the coordination of phosphorus and framework aluminum, improve the hydrothermal stability of the phosphorus modified ZSM-5 molecular sieve and further improve the cracking activity.

Disclosure of Invention

One of the objects of the present invention is to provide a catalytic cracking catalyst based on a phosphorus-modified ZSM-5 molecular sieve with better hydrothermal stability as one of the active components; the other purpose is to provide a preparation method of the catalytic cracking catalyst; the application of the catalytic cracking catalyst in the catalytic cracking reaction of petroleum hydrocarbon is provided, the excellent cracking conversion rate and the yield of low-carbon olefin can be obtained, and the yield of liquefied gas is higher.

In order to achieve one of the above objects, the first aspect of the present invention provides a catalytic cracking catalyst comprising, on a dry basis of the catalytic cracking catalyst, 1 to 25 wt% of a Y-type molecular sieve, on a dry basis, 5 to 50 wt% of a phosphorus-modified ZSM-5 molecular sieve, on a dry basis, 1 to 60 wt% of an inorganic binder, and optionally 0 to 60 wt% of a second clay, on a dry basis, wherein the phosphorus-modified ZSM-5 molecular sieve,²⁷in Al MAS-NMR, the ratio of the peak area of resonance signal with chemical shift of 39 +/-3 ppm to the peak area of resonance signal with chemical shift of 54ppm +/-3 ppm is more than or equal to 1, and the inorganic binder comprises phosphor-aluminum inorganic binder and/or other inorganic binders.

Preferably, the Y-type molecular sieve comprises at least one of a PSRY molecular sieve, a PSRY-S molecular sieve, a PSRY molecular sieve containing rare earth, a PSRY-S molecular sieve containing rare earth, a USY molecular sieve containing rare earth, a REY molecular sieve, a REHY molecular sieve and an HY molecular sieve.

Preferably, the phosphorus modified ZSM-5 molecular sieve²⁷In the Al MAS-NMR, the ratio of the peak area of the resonance signal with the chemical shift of 39 +/-3 ppm to the peak area of the resonance signal with the chemical shift of 54ppm +/-3 ppm is not less than 1, the preferred ratio is not less than 10, and the more preferred ratio is 12-25.

In surface XPS elemental analysis of the phosphorus modified ZSM-5 molecular sieve, n1/n2 is not more than 0.1, preferably n1/n2 is not more than 0.09, more preferably n1/n2 is not more than 0.08, most preferably n1/n2 is 0.04-0.07, n1 represents the mole number of phosphorus, and n2 represents the total mole number of silicon and aluminum.

After the molecular sieve is subjected to hydrothermal aging at 800 ℃ and 100% steam for 17 hours, in an NH3-TPD (nitric oxide synthase-phosphorus dehydrogenase) map, the proportion of the central peak area of strong acid accounting for the central peak area of total acid at the desorption temperature of more than 200 ℃ is more than or equal to 40%, preferably more than or equal to 42%, more preferably more than or equal to 45%, and most preferably 48-85%.

When the phosphorus and the aluminum are counted by mol, the ratio of the phosphorus to the aluminum is 0.01-2, the preferable ratio is 0.1-1.5, and the more preferable ratio is 0.2-1.5.

In order to achieve the second object, the present invention provides a method for preparing a catalytic cracking catalyst, comprising: mixing and pulping the Y-type molecular sieve, the phosphorus modified ZSM-5 molecular sieve and the inorganic binder, spray-drying, and optionally roasting to obtain the catalytic cracking catalyst; wherein a second clay is added or not added to the mixing; the weight ratio of the Y-type molecular sieve, the phosphorus-containing modified ZSM-5 molecular sieve, the inorganic binder and the second clay is (1-25): (5-50): (1-60): (0-60); the inorganic binder comprises a phosphor-aluminum inorganic binder and/or other inorganic binders; the phosphorus-modified ZSM-5 molecular sieve is obtained by contacting a phosphorus-containing compound solution with an HZSM-5 molecular sieve, drying, performing hydrothermal roasting treatment under the atmosphere environment of externally applied pressure and externally added water, and recovering a product; the contact is that an impregnation method is adopted to mix and contact a water solution of a phosphorus-containing compound with the temperature of 0-150 ℃ and an HZSM-5 molecular sieve with the temperature of 0-150 ℃ for at least 0.1 hour at the basically same temperature, or the contact is that the phosphorus-containing compound, the HZSM-5 molecular sieve and water are mixed and pulped and then are kept for at least 0.1 hour at the temperature of 0-150 ℃; the atmosphere environment has an apparent pressure of 0.01 to 1.0MPa and contains 1 to 100 percent of water vapor.

The phosphorus-containing compound is selected from organic phosphide and/or inorganic phosphide. The organic phosphide is selected from trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium hydroxide, triphenyl ethyl phosphonium bromide, triphenyl butyl phosphonium bromide, triphenyl benzyl phosphonium bromide, hexamethyl phosphoric triamide, dibenzyl diethyl phosphonium and 1, 3-xylene bis triethyl phosphonium; the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.

In the HZSM-5 molecular sieve, Na₂O<0.1wt％。

The phosphorus-containing compound is calculated by phosphorus, the HZSM-5 molecular sieve is calculated by aluminum, and the molar ratio of the phosphorus-containing compound to the HZSM-5 molecular sieve is 0.01-2; preferably, the molar ratio of the two is 0.1-1.5; more preferably, the molar ratio of the two is 0.2 to 1.5.

The weight ratio of the water sieve is 0.5-1, and the contact is carried out for 0.5-40 hours at 50-150 ℃, preferably 70-130 ℃.

The apparent pressure of the atmosphere environment is 0.1-0.8 Mpa, preferably 0.3-0.6 Mpa, and the atmosphere environment contains 30-100% of water vapor, preferably 60-100% of water vapor; the hydrothermal roasting treatment is carried out at 200-800 ℃, preferably 300-500 ℃.

The binder is a phosphor-aluminum inorganic binder and/or other inorganic binders. Preferably, the binder is preferably a phosphor-aluminum inorganic binder, more preferably phosphor-aluminum glue and/or a phosphor-aluminum inorganic binder containing first clay; the phosphorus-aluminum inorganic binder containing the first clay contains Al based on the dry weight of the phosphorus-aluminum inorganic binder containing the first clay₂O₃15-40% by weight, calculated as P, of an aluminium component₂O₅45-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay calculated on dry basis, and the P/Al weight ratio of the phosphorus-aluminum inorganic binder containing first clay is 1.0-6.0, pH is 1-3.5, and solid content is 15-60 wt%; the first clay comprises at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomaceous earth. The other inorganic binder includes at least one of pseudo-boehmite, alumina sol, silica-alumina sol and water glass. The second clay is at least one selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, hydrotalcite, bentonite and diatomite.

Preferably, the catalyst contains 3-40 wt% of phosphorus-aluminum inorganic binder or contains 3-40 wt% of phosphorus-aluminum inorganic binder and 1-30 wt% of other inorganic binder based on the dry weight of the catalyst.

The Y-type molecular sieve comprises at least one of a PSRY molecular sieve, a PSRY-S molecular sieve, a PSRY molecular sieve containing rare earth, a PSRY-S molecular sieve containing rare earth, a USY molecular sieve containing rare earth, a REY molecular sieve, a REHY molecular sieve and an HY molecular sieve.

The preparation method provided by the invention also comprises the following steps: washing and optionally drying the product obtained by roasting to obtain the catalytic cracking catalyst; wherein the roasting temperature of the first roasting treatment is 300-650 ℃, and the roasting time is 0.5-12 h.

Preferably, the preparation method of the invention further comprises preparing the first clay-containing phosphorus-aluminum inorganic binder by the following steps: pulping an alumina source, the first clay and water to disperse into slurry with solid content of 5-48 wt%; wherein the alumina source is aluminum hydroxide and/or aluminum oxide which can be peptized by acid, and the aluminum oxide source is 15-40 parts by weight of Al₂O₃(ii) an alumina source in an amount greater than 0 parts by weight and not greater than 40 parts by weight of the first clay on a dry basis; adding concentrated phosphoric acid to the slurry in a weight ratio of P/Al to 1-6 with stirring, and reacting the resulting mixed slurry at 50-99 ℃ for 15-90 minutes; in the P/Al, P is the weight of phosphorus in the phosphoric acid in terms of simple substance, and Al is the weight of aluminum in the alumina source in terms of simple substance.

In order to achieve the third object, the present invention provides an application method of a catalytic cracking catalyst, comprising the step of contacting and reacting a hydrocarbon oil with the catalytic cracking catalyst under catalytic cracking reaction conditions, wherein the catalytic cracking reaction conditions comprise: the reaction temperature is 500-800 ℃. The hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residue oil, vacuum residue oil, atmospheric wax oil, vacuum wax oil, direct current wax oil, propane light/heavy deoiling, coker wax oil and coal liquefaction products.

The catalytic cracking catalyst provided by the invention contains a phosphorus modified ZSM-5 molecular sieve with special physical and chemical parameters, and the molecular sieve and the Y-type molecular sieve are jointly used as active components of the catalyst, so that the catalytic cracking catalyst has the characteristics of high cracking conversion rate, high yield of low-carbon olefin and high yield of liquefied gas in the catalytic cracking reaction of hydrocarbon oil.

Drawings

FIG. 1 shows a sample of a phosphorus-modified ZSM-5 molecular sieve PSZ1-1 in a catalytic cracking catalyst of the invention²⁷Al MAS-NMR spectrum.

FIG. 2 shows NH of a phosphorus-modified ZSM-5 molecular sieve sample PSZ1-1 subjected to hydrothermal aging at 800 deg.C under 100% steam for 17h in a catalytic cracking catalyst of the present invention₃-TPD spectrum.

FIG. 3 is a graph of comparative sample DBZ1-1 of phosphorus modified ZSM-5 molecular sieve²⁷Al MAS-NMR spectrum.

FIG. 4 shows NH of a comparative sample DBZ1-1 of phosphorus-modified ZSM-5 molecular sieve after hydrothermal aging at 800 deg.C under 100% water vapor for 17h₃-TPD spectrum.

Detailed Description

The catalytic cracking catalyst of the invention is characterized in that the catalytic cracking catalyst contains 1-25 wt% of Y-type molecular sieve based on dry basis, 5-50 wt% of phosphorus modified ZSM-5 molecular sieve based on dry basis, 1-60 wt% of inorganic binder based on dry basis and 0-60 wt% of second clay optionally added based on dry basis, wherein the phosphorus modified ZSM-5 molecular sieve,²⁷in Al MAS-NMR, the ratio of the peak area of resonance signal with chemical shift of 39 +/-3 ppm to the peak area of resonance signal with chemical shift of 54ppm +/-3 ppm is more than or equal to 1, and the inorganic binder comprises phosphor-aluminum inorganic binder and/or other inorganic binders.

The Y-type molecular sieve preferably comprises at least one of a PSRY molecular sieve, a PSRY molecular sieve containing rare earth, a USY molecular sieve containing rare earth, a REY molecular sieve, a REHY molecular sieve and an HY molecular sieve.

The invention provides a catalyst, wherein the phosphorus modified ZSM-5 molecular sieve,²⁷in the Al MAS-NMR, the ratio of the peak area of the resonance signal with the chemical shift of 39 +/-3 ppm to the peak area of the resonance signal with the chemical shift of 54ppm +/-3 ppm is more than or equal to 1, preferably more than or equal to 5, more preferably more than or equal to 10, and the most preferred ratio is 12-25.

Further, in the phosphorus modified ZSM-5 molecular sieve, in surface XPS elemental analysis, n1/n2 is not more than 0.1, wherein n1 represents the mole number of phosphorus, n2 represents the total mole number of silicon and aluminum, preferably, n1/n2 is not more than 0.09, more preferably, n1/n2 is not more than 0.08, and most preferably, n1/n2 is 0.04-0.07; the characterization parameter shows that the content of surface phosphorus species in the molecular sieve is reduced, and also shows that the surface phosphorus species are more migrated to the molecular sieve body phase, namely the value of n1/n2 shows that the dispersion effect of the phosphorus species on the surface of the molecular sieve and the migration degree from the surface of the ZSM-5 molecular sieve to the inside of the crystal are shown, the smaller the value is, the content of the surface phosphorus species is reduced, the phosphorus species are well dispersed and the migration degree to the inside is high, and therefore the hydrothermal stability of the molecular sieve is better.

Furthermore, the catalyst of the invention, wherein the phosphorus modified ZSM-5 molecular sieve is subjected to hydrothermal aging at 800 ℃ for 17 hours under the condition of 100% water vapor, and then NH of the molecular sieve₃In a TPD (thermoplastic polymer-bound-silica) map, the proportion of the area of the strong acid center peak occupying the total acid center peak area at the desorption temperature of more than 200 ℃ is more than or equal to 40 percent, which shows that the molecular sieve has higher strong acid center retention after 17 hours of hydrothermal aging under the conditions of 800 ℃ and 100 percent of water vapor, so that the molecular sieve has higher cracking activity. Preferably, the specific gravity is 42% or more, more preferably 45% or more, and most preferably 48% to 85%.

According to the catalyst, when the phosphorus content in the phosphorus modified ZSM-5 molecular sieve is calculated by mol, the ratio of phosphorus to aluminum is 0.01-2; preferably, the ratio of the two is 0.1-1.5; more preferably, the ratio of the two is 0.2 to 1.5.

In the catalytic cracking catalyst of the present invention, the clay is well known to those skilled in the art, and the second clay may be at least one selected from the group consisting of kaolin, metakaolin, diatomaceous earth, sepiolite, attapulgite, montmorillonite and rectorite, and is preferably one selected from the group consisting of kaolin, metakaolin and rectorite. The catalyst of the present invention preferably contains 10 to 50 wt% of the second clay, for example 12 to 28 wt% or 15 to 40 wt% of the second clay, based on the total weight of the catalyst.

In one embodiment of the catalyst of the invention, the catalyst comprises, on a dry basis, 5 to 35 wt% of a aluminophosphate inorganic binder, 1.5 to 20 wt% of a Y-type molecular sieve, 10 to 45 wt% of a phosphorus modified ZSM-5 molecular sieve, 10 to 50 wt% of a second clay, and 5 to 28 wt% of other inorganic binders.

The invention also provides a preparation method of the catalyst, which comprises the following steps: mixing and pulping the Y-type molecular sieve, the phosphorus modified ZSM-5 molecular sieve and the inorganic binder, spray-drying, and optionally roasting to obtain the catalytic cracking catalyst; wherein a second clay is added or not added to the mixing; the weight ratio of the Y-type molecular sieve, the phosphorus modified ZSM-5 molecular sieve, the inorganic binder and the second clay is (1-25): (5-50): (1-60): (0-60); the inorganic binder comprises a phosphor-aluminum inorganic binder and/or other inorganic binders; wherein the phosphorus modified ZSM-5 molecular sieve is prepared by the following steps: contacting a phosphorus-containing compound solution with an HZSM-5 molecular sieve, drying, performing hydrothermal roasting treatment under the atmosphere environment of externally applied pressure and externally added water, and recovering a product to obtain the catalyst; the contact is that an impregnation method is adopted to mix and contact a water solution of a phosphorus-containing compound with the temperature of 0-150 ℃ and an HZSM-5 molecular sieve with the temperature of 0-150 ℃ for at least 0.1 hour at the basically same temperature, or the contact is that the phosphorus-containing compound, the HZSM-5 molecular sieve and water are mixed and pulped and then are kept for at least 0.1 hour at the temperature of 0-150 ℃; the atmosphere environment has an apparent pressure of 0.01 to 1.0MPa and contains 1 to 100 percent of water vapor.

The preparation steps adopted by the phosphorus modified ZSM-5 molecular sieve promote the migration of surface phosphorus species to a ZSM-5 molecular sieve bulk phase; the coordination of phosphorus and the framework aluminum is sufficient, the framework aluminum is fully protected, and the molecular sieve has excellent hydrothermal stability.

The preparation steps adopted by the phosphorus modified ZSM-5 molecular sieve are as followsThe HZSM-5 molecular sieve is a microporous ZSM-5 molecular sieve for reducing sodium to Na by ammonium exchange₂O<0.1 wt% is obtained, and the silicon-aluminum ratio (the molar ratio of silicon oxide to aluminum oxide, the same applies hereinafter) is more than or equal to 10, and is usually 10-200.

In the preparation steps of the phosphorus modified ZSM-5 molecular sieve, a phosphorus-containing compound is selected from organic phosphide and/or inorganic phosphide. The organic phosphide is selected from trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium hydroxide, triphenyl ethyl phosphonium bromide, triphenyl butyl phosphonium bromide, triphenyl benzyl phosphonium bromide, hexamethyl phosphoric triamide, dibenzyl diethyl phosphonium and 1, 3-xylene bis triethyl phosphorus, and the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.

In the preparation steps of the phosphorus modified ZSM-5 molecular sieve, the first contact mode is to contact an aqueous solution of a phosphorus-containing compound with the temperature of 0-150 ℃ with the HZSM-5 molecular sieve with the temperature of 0-150 ℃ for at least 0.1 hour at the basically same temperature by an impregnation method. For example, the contacting may be performed at a normal temperature range of 0 to 30 ℃, preferably, at a higher temperature range of 40 ℃ or higher, for example, 50 to 150 ℃, more preferably 70 to 130 ℃, so as to obtain a better effect, that is, the phosphorus species are better dispersed, the phosphorus is more easily migrated into the HZSM-5 molecular sieve crystals to be combined with the framework aluminum, the coordination degree of the phosphorus and the framework aluminum is further improved, and finally, the improvement of the hydrothermal stability of the molecular sieve is contributed. The substantially same temperature means that the temperature difference between the aqueous solution of the phosphorus-containing compound and the HZSM-5 molecular sieve is within + -5 ℃. For example, the temperature of the aqueous solution of the phosphorus-containing compound is 80 ℃ and the HZSM-5 molecular sieve is heated to 75-85 ℃.

In the preparation steps of the phosphorus modified ZSM-5 molecular sieve, the second contact mode is to mix a phosphorus compound, the HZSM-5 molecular sieve and water and then keep the mixture at 0-150 ℃ for at least 0.1 hour. For example, after mixing, the mixture is kept at a normal temperature range of 0 to 30 ℃ for at least 0.1 hour, preferably, in order to obtain a better effect, that is, in order to achieve better dispersion of phosphorus species, easier migration of phosphorus into molecular sieve crystals to combine with framework aluminum, further improve the coordination degree of phosphorus and framework aluminum, and finally improve the hydrothermal stability of the molecular sieve, the phosphorus-containing compound, the HZSM-5 molecular sieve and water are mixed and then kept at a higher temperature range of more than 40 ℃ for 0.1 hour, for example, a temperature range of 50 to 150 ℃, more preferably a temperature range of 70 to 130 ℃.

In the preparation steps of the phosphorus modified ZSM-5 molecular sieve, when a phosphorus-containing compound is counted by phosphorus and an HZSM-5 molecular sieve is counted by aluminum, the molar ratio of the phosphorus-containing compound to the HZSM-5 molecular sieve is 0.01-2; preferably, the molar ratio of the two is 0.1-1.5; more preferably, the molar ratio of the two is 0.2 to 1.5. The weight ratio of the water sieve to the contact is 0.5-1, and the preferable contact time is 0.5-40 hours.

In the preparation steps of the phosphorus modified ZSM-5 molecular sieve, the hydrothermal roasting treatment is carried out under the atmosphere environment of externally applied pressure and externally added water. The atmosphere is obtained by externally applying pressure and water, preferably apparent pressure is 0.1-0.8 MPa, more preferably apparent pressure is 0.3-0.6 MPa, preferably 30-100% water vapor, more preferably 60-100% water vapor. The external pressure is applied to the hydrothermal roasting treatment of the prepared material from the outside, and for example, the external pressure may be applied by introducing an inert gas from the outside to maintain a certain back pressure. The amount of the externally added water is determined to satisfy the requirement that the atmosphere contains 1-100% of water vapor. The step of hydrothermal roasting treatment is carried out at 200-800 ℃, preferably 300-500 ℃.

In the catalyst of the present invention, it is preferable that the catalyst contains 3 to 40 wt% of the phosphor-aluminum inorganic binder or 3 to 40 wt% of the phosphor-aluminum inorganic binder and 1 to 30 wt% of other inorganic binders, based on the dry basis of the catalyst.

The phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or a phosphorus-aluminum inorganic binder containing first clay; the phosphorus-aluminum inorganic binder containing the first clay contains Al based on the dry weight of the phosphorus-aluminum inorganic binder containing the first clay₂O₃15-40% by weight, calculated as P, of an aluminium component₂O₅45-80 wt% of phosphorus component and more than 0 and not more than 40 wt% of first clay calculated on dry basis, and the P/Al weight ratio of the phosphorus-aluminum inorganic binder containing first clay is 1.0-6.0, pH is 1-3.5, and solid content is 15-60 wt%; the first clay comprises at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomaceous earth. The other inorganic binder includes at least one of pseudo-boehmite, alumina sol, silica-alumina sol and water glass. The second clay is at least one selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, hydrotalcite, bentonite and diatomite.

The Y-type molecular sieve comprises at least one of a PSRY molecular sieve, a PSRY molecular sieve containing rare earth, a USY molecular sieve containing rare earth, a REY molecular sieve, a REHY molecular sieve and an HY molecular sieve.

The preparation method of the catalytic cracking catalyst further comprises the following steps: carrying out first roasting, washing and optional drying treatment on the product obtained by spray drying to obtain the catalyst; wherein the roasting temperature of the first roasting is 300-650 ℃, and the roasting time is 0.5-8 h; the drying temperature is 100-200 deg.C, and the drying time is 0.5-24 h.

The preparation method of the catalytic cracking catalyst further comprises the following steps of preparing the first clay-containing phosphorus-aluminum inorganic binder: pulping an alumina source, the first clay and water to disperse into slurry with solid content of 5-48 wt%; wherein the alumina source is aluminum hydroxide and/or aluminum oxide which can be peptized by acid, and the aluminum oxide source is 15-40 parts by weight of Al₂O₃(ii) an alumina source in an amount greater than 0 parts by weight and not greater than 40 parts by weight of the first clay on a dry basis; adding concentrated phosphoric acid to the slurry in a weight ratio of P/Al to 1-6 with stirring, and reacting the resulting mixed slurry at 50-99 ℃ for 15-90 minutes; in the P/Al, P is the weight of phosphorus in the phosphoric acid in terms of simple substance, and Al is the weight of aluminum in the alumina source in terms of simple substance.

The invention relates to a phosphorus-aluminum inorganic binderIn one embodiment, the phosphorus-aluminum inorganic binder preferably contains Al based on the dry weight of the binder₂O₃15-35% by weight, calculated as P, of an aluminium component₂O₅50-75 wt% of a phosphorus component and 8-35 wt% of a first clay, calculated on a dry basis, and preferably having a P/Al weight ratio of 1.2-6.0, more preferably 2.0-5.0, and a pH value of preferably 2.0-3.0. In another embodiment of the phosphor-aluminum inorganic binder of the present invention, the phosphor-aluminum inorganic binder comprises Al based on the dry weight of the phosphor-aluminum inorganic binder₂O₃20-40% by weight, calculated as P, of an aluminium component₂O₅60-80% by weight of a phosphorus component.

The preparation method of the catalytic cracking catalyst can also comprise the following steps: washing and optionally drying the product obtained by roasting treatment to obtain the catalytic cracking catalyst; wherein the roasting temperature can be 300-650 ℃, for example 400-600 ℃, preferably 450-550 ℃, and the roasting time can be 0.5-12 hours; the washing can be one of ammonium sulfate, ammonium nitrate and ammonium chloride, and the washing temperature can be 40-80 ℃; the temperature of the drying treatment can be 110-200 ℃, for example 120-150 ℃, and the drying time can be 0.5-18 h, for example 2-12 h.

In one embodiment of the preparation method provided by the present invention, an inorganic binder (e.g., pseudo-boehmite, alumina sol, silica-alumina gel, or a mixture of two or more thereof) may be mixed with a second clay (e.g., kaolin) and water (e.g., deionized water and/or deionized water) to prepare a slurry with a solid content of 10 to 50 wt%, the slurry is uniformly stirred, the pH of the slurry is adjusted to 1 to 4 with an inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid, or sulfuric acid, the pH is maintained, after standing and aging at 20 to 80 ℃ for 0 to 2 hours, for example, 0.3 to 2 hours, alumina sol and/or silica sol is added, the slurry is stirred for 0.5 to 1.5 hours to form a colloid, and then a molecular sieve is added, wherein the molecular sieve includes the phosphorus-modified ZSM-5 molecular sieve and Y-type molecular sieve, to form a catalyst slurry with a solid content of 20 to 45 wt%, for example, continuously stirring and then spray-drying to prepare the microsphere catalyst. Then, the microspherical catalyst is roasted, for example, at 350 to 650 ℃ or 400 to 600 ℃, preferably 450 to 550 ℃, for 0.5 to 6 hours or 0.5 to 2 hours, washed with ammonium sulfate (wherein, the washing temperature can be 40 to 70 ℃, the ammonium sulfate: the microspherical catalyst: water is 0.2 to 0.8:1:5 to 15 weight ratio) until the content of sodium oxide is less than 0.25 weight percent, washed with water, filtered, and then dried.

In another embodiment of the preparation method provided by the invention, the Y-type molecular sieve, the phosphorus modified ZSM-5 molecular sieve, the phosphorus-aluminum inorganic binder and other inorganic binders can be mixed, the second clay is added or not added, and the mixture is pulped and spray-dried.

The inorganic binder comprises the phosphor-aluminum inorganic binder and the other inorganic binders, and the weight and dosage ratio of the phosphor-aluminum inorganic binder to the other inorganic binders can be (3-40): (1-30), preferably (5-35): (5-28), more preferably (10-30): (5-25); wherein the aluminophosphate inorganic binder can be an aluminophosphate glue and/or a aluminophosphate inorganic binder comprising a first clay; the other inorganic binder may include at least one of pseudoboehmite, alumina sol, silica alumina sol, and water glass.

The preparation method of the catalytic cracking catalyst of the invention can mix and pulp the phosphorus-containing modified ZSM-5 molecular sieve, the phosphorus-aluminum inorganic binder and other inorganic binders, and the order of feeding does not have special requirements, for example, the phosphorus-aluminum inorganic binder, other inorganic binders, the molecular sieve and the second clay can be mixed and beaten (when the second clay is not contained, the relevant feeding step can be omitted), preferably, the phosphorus-aluminum inorganic binder is added after the second clay, the molecular sieve and other inorganic binders are mixed and beaten, which is beneficial to improving the activity and selectivity of the catalyst.

The preparation method of the catalytic cracking catalyst further comprises the step of spray drying the slurry obtained by pulping. Methods of spray drying are well known to those skilled in the art and no particular requirement of the present disclosure exists.

Further, the method of the present invention may further comprise preparing the first clay-containing aluminophosphate inorganic binder by:pulping an alumina source, the first clay and water to disperse into slurry with solid content of 5-48 wt%; wherein the alumina source is aluminum hydroxide and/or aluminum oxide which can be peptized by acid, and the aluminum oxide source is 15-40 parts by weight of Al₂O₃(ii) an alumina source in an amount greater than 0 parts by weight and not greater than 40 parts by weight of the first clay on a dry basis; adding concentrated phosphoric acid to the slurry in a weight ratio of P/Al to 1-6 with stirring, and reacting the resulting mixed slurry at 50-99 ℃ for 15-90 minutes; in the P/Al, P is the weight of phosphorus in the phosphoric acid in terms of simple substance, and Al is the weight of aluminum in the alumina source in terms of simple substance. The alumina source may be at least one selected from the group consisting of rho-alumina, x-alumina, η -alumina, γ -alumina, κ -alumina, σ -alumina, θ -alumina, gibbsite, surge, nordstrandite, diaspore, boehmite, and pseudo-boehmite from which the aluminum component of the first clay-containing aluminophosphate inorganic binder is derived. The first clay can be one or more of high alumina, sepiolite, attapulgite, rectorite, montmorillonite and diatomite, and preferably rectorite. The concentrated phosphoric acid may be present in a concentration of 60 to 98 wt.%, more preferably 75 to 90 wt.%. The feed rate of phosphoric acid is preferably 0.01 to 0.10kg of phosphoric acid per minute per kg of alumina source, more preferably 0.03 to 0.07kg of phosphoric acid per minute per kg of alumina source.

In the embodiment, due to the introduction of the clay, the phosphorus-aluminum inorganic binder containing the first clay not only improves mass transfer and heat transfer among materials in the preparation process, avoids the binder fixed line caused by nonuniform, local, instantaneous, violent reaction and heat release and superstability of the materials, but also obtains the binder with the bonding performance equivalent to that of the phosphorus-aluminum binder prepared by a method without introducing the clay; in addition, the method introduces clay, especially rectorite with a layered structure, improves the heavy oil conversion capability of the catalyst, and enables the obtained catalyst to have better selectivity.

The invention also provides the catalytic cracking catalyst prepared by the method.

The invention further provides a method for catalytic cracking of hydrocarbon oil. When used in a catalytic cracking process, in one embodiment, the catalytic cracking catalyst may be added separately to the catalytic cracking reactor, for example, under catalytic cracking conditions, the hydrocarbon oil is contacted with the catalytic cracking catalyst of the present invention for reaction; in another embodiment for use in a catalytic cracking process, the catalyst may be used in combination with a catalytic cracking catalyst, for example, a hydrocarbon oil may be contacted with a catalytic mixture containing the catalytic cracking catalyst of the present invention and other catalytic cracking catalysts. The catalyst provided by the invention can account for no more than 30 wt% of the total mixture, preferably 1-25 wt%, and more preferably 3-15 wt%. The hydrocarbon oil may be selected from one or more of various petroleum fractions such as crude oil, naphtha, catalytic gasoline, atmospheric residue, vacuum residue, atmospheric wax oil, vacuum wax oil, straight-run wax oil, propane light/heavy deoiled, coker wax oil, and coal liquefaction product. The hydrocarbon oil may contain heavy metal impurities such as nickel and vanadium, and sulfur and nitrogen impurities, for example, the content of sulfur in the hydrocarbon oil can be as high as 3.0 wt%, the content of nitrogen can be as high as 2.0 wt%, and the content of metal impurities such as vanadium and nickel can be as high as 3000 ppm.

In the hydrocarbon oil catalytic cracking method of the present invention, the catalytic cracking conditions may be conventional in the art, and preferably include: the reaction temperature is 500 to 800 ℃, for example 550 to 680 ℃. The hydrocarbon oil can be one or more selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric wax oil, vacuum wax oil, DC wax oil, propane light/heavy deoiling, coker wax oil and coal liquefaction product.

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The X-ray diffraction (XRD) pattern was measured on a Nippon Denshi TTR-3 powder X-ray diffractometer. The instrument parameters are as follows: copper target (tube voltage 40kV, tube current 250mA), scintillation counter, step width 0.02 degree, scanning speed 0.4 (degree)/min. The ZSM-5 molecular sieve synthesized by the method of example 1 in CN1056818C is taken as a standard sample, and the crystallinity is determined as 100%. The relative crystallinity is expressed by percentage according to the ratio of the sum of the peak areas of five characteristic diffraction peaks of the X-ray diffraction spectra of the obtained product and the standard sample, wherein the 2 theta is between 22.5 and 25.0 degrees.

²⁷The analysis of the MAS-NMR spectrum was carried out on a Bruker model AVANCE III 600WB spectrometer. The instrument parameters are as follows: the diameter of the rotor is 4mm, the resonance frequency spectrum is 156.4MHz, the pulse width is 0.4 mus (corresponding to a 15-degree turning angle), the magic angle rotating speed is 12kHz, and the delay time is 1 s.²⁷The characteristic peak 1 at 54 + -3 pp m is assigned to the four-coordinate framework aluminum, and the characteristic peak 2 at 39 + -3 ppm is assigned to the phosphorus-stabilized framework aluminum (distorted four-coordinate framework aluminum). And each peak area is calculated by adopting an integration method after peak-splitting fitting is carried out on the characteristic peak.

X-ray photoelectron spectroscopy (XPS) was used to analyze the surface of molecular sieves and examine the migration of phosphorus compounds using an ESCALB 250 model X-ray photoelectron spectrometer from Thermo Fisher-VG. The instrument parameters are as follows: the excitation source was a monochromatized AlK α X-ray of 150W power, with the charge shift corrected for the C1s peak (284.8eV) from the contaminating carbon.

Temperature programmed desorption analysis (NH)₃TPD) characterization was carried out using an AutoChen II temperature programmed adsorption apparatus from Micromeritics. Weighing 0.1-0.2 g of sample, putting the sample into a quartz adsorption tube, introducing carrier gas (the flow rate of high-purity He. is 50mL/min), raising the temperature to 600 ℃ at the speed of 20 ℃/min, keeping the temperature for 2h, and removing water and air adsorbed on the sample; reducing the temperature to 100 ℃ at the speed of 20 ℃/min, and keeping the temperature for 30 min; switching the carrier gas to NH₃Keeping the temperature for 30min by using-He mixed gas to ensure that the sample is saturated by absorbing ammonia; reacting NH₃Switching the-He mixed gas into high-purity He carrier gas, and purging for 1h to desorb material resources and adsorb ammonia; then the temperature is raised to 600 ℃ at the speed of 10 ℃/min, and a temperature programmed desorption curve is obtained. The desorbed ammonia is detected by a thermal conductivity cell. Converting the temperature programmed desorption curve into NH₃After the desorption rate-temperature curve, the acid center density data is obtained by the spectrum resolution of the peak pattern.

The instruments and reagents used in the examples of the present invention are those commonly used by those skilled in the art unless otherwise specified.

The micro-reaction device is adopted to evaluate the influence of the catalytic cracking auxiliary agent on the yield of the low-carbon olefin in the catalytic cracking of the petroleum hydrocarbon. The prepared catalytic cracking assistant sample is aged for 17 hours at 800 ℃ under 100 percent water vapor in a fixed bed aging device, and is evaluated in a micro-reaction device, wherein the raw material oil is VGO or naphtha, and the evaluation conditions are that the reaction temperature is 620 ℃, the regeneration temperature is 620 ℃ and the agent-oil ratio is 3.2. Microreflective activity is determined using the ASTM D5154-2010 standard method.

The RIPP standard method can be found in petrochemical analysis, Yangcui and other editions, 1990 edition.

Some of the raw materials used in the examples had the following properties:

the raw material ZSM-5 molecular sieve was provided by Qilu division, a petrochemical catalyst of China, and had a relative crystallinity of 91.1%, a silica/alumina molar ratio of 24.1, and a specific surface area of 353m²(iv)/g, total pore volume 0.177 ml/g.

The pseudoboehmite is an industrial product produced by Shandong aluminum industry company, and the solid content is 60 percent by weight; the aluminum sol is an industrial product, Al, produced by the Qilu division of the medium petrochemical catalyst₂O₃The content was 21.5 wt%; the silica sol is an industrial product, SiO, produced by the middle petrochemical catalyst Qilu division₂The content was 28.9% by weight, Na₂The O content is 8.9 percent; the kaolin is kaolin specially used for a catalytic cracking catalyst produced by Suzhou kaolin company, and the solid content is 78 weight percent; the rectorite is produced by Taixiang famous stream rectorite development Limited company in Hubei province, and the content of the quartz sand<3.5 wt.% of Al₂O₃39.0 wt.% of Na₂The O content was 0.03% by weight, and the solid content was 77% by weight; SB aluminum hydroxide powder, manufactured by Condex, Germany, Al₂O₃The content was 75% by weight; gamma-alumina, manufactured by Condex, Germany, Al₂O₃The content was 95% by weight. Hydrochloric acid, chemical purity, concentration 36-38 wt%, and is produced in Beijing chemical plant.

The PSRY molecular sieve is an industrial product produced by Chang Ling division company of medium petrochemical catalyst, Na₂Content of O<1.5 wt.%, P₂O₅The content of the crystal cell is 0.8 to 1.2 wt%Constant number<2.456nm and crystallinity not less than 64%. The HRY-1 molecular sieve is an industrial product produced by Chang Ling division of medium petrochemical catalyst, La₂O₃The content is 11 to 13 wt%, and the unit cell constant<2.464nm and the crystallinity is more than or equal to 40 percent.

Examples 1 to 1

Example 1-1 illustrates a phosphorus modified ZSM-5 molecular sieve employed in the catalyst of the present invention.

Dissolving 16.2g diammonium hydrogen phosphate (analytically pure, the same below) in 60g deionized water, stirring for 0.5h to obtain phosphorus-containing aqueous solution, adding 113g HZSM-5 molecular sieve (provided by Qilu division of petrochemical catalyst, China) with relative crystallinity of 91.1%, silica/alumina molar ratio of 24.1, and Na₂O content 0.039 wt% and specific surface area 353m²(iv)/g, total pore volume 0.177ml/g, the same applies below), modified by impregnation, impregnated at 20 ℃ for 2 hours, dried in an oven at 110 ℃, externally pressurized and added with water, treated at 500 ℃, 0.5Mpa and 50% steam atmosphere for 0.5 hour to obtain a phosphorus modified ZSM-5 molecular sieve sample, designated as PSZ 1-1.

Examples 1 to 2

Examples 1-2 illustrate phosphorus modified ZSM-5 molecular sieves used in the catalysts of the invention.

The process is the same as the process of example 1-1 except that diammonium phosphate, HZSM-5 molecular sieve and water are mixed and beaten into slurry, and the temperature is raised to 100 ℃ and kept for 2 hours. The resulting phosphorus modified ZSM-5 molecular sieve sample was designated PSZ 1-2.

Comparative examples 1 to 1

Comparative examples 1-1 illustrate the conventional process of the prior art and the resulting comparative sample of phosphorus modified ZSM-5 molecular sieve.

The same as in example 1-1 except that the firing conditions were atmospheric pressure (apparent pressure 0MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of the phosphorus modified ZSM-5 molecular sieve was obtained and was identified as DBZ 1-1.

Comparative examples 1 to 2

Comparative examples 1-2 illustrate comparative samples of phosphorus modified ZSM-5 molecular sieves obtained by atmospheric hydrothermal calcination.

The same as in example 1-1 except that the firing conditions were atmospheric pressure (apparent pressure: 0 MPa). A comparative sample of phosphorus modified ZSM-5 molecular sieve was obtained and was identified as DBZ 1-2.

XRD crystallinity of PSZ1-1, PSZ1-2, DBZ1-1 and DBZ1-2 before and after being treated with 100% water vapor and 17h hydrothermal aging treatment at 800 ℃ is shown in Table 1-1.

Of PSZ1-1 and DBZ1-1²⁷Al MAS-NMR spectra of FIGS. 1 and 3, PSZ1-2 and DBZ1-2, respectively²⁷The Al MAS-NMR spectrum is characterized by 1 and 3, respectively, in which the chemical shift is ascribed to the four-coordinate framework aluminum at 54ppm and the chemical shift is ascribed to the four-coordinate framework aluminum in which phosphorus is bonded to aluminum (phosphorus-stabilized framework aluminum) at 39 ppm.²⁷The data of the peak area ratio of the Al MAS-NMR spectrum are shown in tables 1-2.

The surface XPS elemental analysis data for PSZ1-1, PSZ1-2, DBZ1-1, DBZ1-2 are shown in tables 1-3.

NH of PSZ1-1 subjected to hydrothermal aging for 17 hours at 800 ℃ under the condition of 100% water vapor₃The TPD spectrum is shown in FIG. 2. Comparative sample DBZ1-1 NH after hydrothermal aging at 800 ℃ under 100% water vapor condition for 17h₃The TPD spectrum is shown in FIG. 4. NH of PSZ1-1, PSZ1-2, DBZ1-1, DBZ1-2₃The specific gravity data of the area of the strong acid central peak occupying the total acid central peak area at the desorption temperature of more than 200 ℃ in the TPD spectrum are shown in tables 1 to 4.

TABLE 1-1

As can be seen from the table 1-1, the phosphorus modified ZSM-5 molecular sieve prepared by the method still has higher crystal retention after being subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the crystal retention is obviously higher than that of a contrast sample, and the crystal retention is improved by at least 5 percent.

Tables 1 to 2

Tables 1 to 3

Tables 1 to 4

Example 2-1

Example 2-1 illustrates the phosphorus-modified ZSM-5 molecular sieve and process employed in the catalyst of the present invention.

Dissolving 16.2g of diammonium hydrogen phosphate in 120g of deionized water at 50 ℃, stirring for 0.5h to obtain a phosphorus-containing aqueous solution, adding 113g of HZSM-5 molecular sieve, modifying by adopting a dipping method, dipping for 2h at 20 ℃, drying in an oven at 110 ℃, applying pressure to the outside, adding water, and carrying out pressurized hydrothermal roasting treatment for 2h at 600 ℃, 0.5Mpa and 30% of steam atmosphere to obtain a phosphorus-modified ZSM-5 molecular sieve sample, wherein the sample is marked as PSZ-2.

Examples 2 to 2

Examples 2-2 illustrate the phosphorus-modified ZSM-5 molecular sieve and process employed in the catalyst of the present invention.

The process is the same as the process of example 2-1 except that diammonium phosphate, HZSM-5 molecular sieve and water are mixed and beaten into slurry, and the temperature is raised to 70 ℃ and kept for 2 hours. The resulting phosphorus modified ZSM-5 molecular sieve sample was designated PSZ 2-2.

Comparative example 2-1

Comparative example 2-1 illustrates the current industry conventional process and the resulting phosphorus modified ZSM-5 comparative sample.

The same as in example 2-1 except that the firing conditions were atmospheric pressure (apparent pressure 0MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of the phosphorus-modified ZSM-5 molecular sieve was obtained and was identified as DBZ-2-1.

Comparative examples 2 to 2

Comparative examples 2-2 illustrate comparative samples of phosphorus modified ZSM-5 molecular sieves obtained by atmospheric hydrothermal calcination.

The same as in example 2-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of phosphorus modified ZSM-5 molecular sieve was obtained and was identified as DBZ-2-2.

XRD crystallinity of PSZ2-1, PSZ2-2, DBZ-2-1 and DBZ-2-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h is shown in Table 2-1.

Of PSZ1-2 and PSZ2-2²⁷Al MAS-NMR spectrum with the features of FIG. 1, DBZ2-1 and DBZ2-2²⁷The Al MAS-NMR spectrum is characterized by the same features as in FIG. 3.²⁷The data of the peak area ratio of the Al MAS-NMR spectrum are shown in Table 2-2.

The surface XPS elemental analysis data for PSZ2-1, PSZ2-2, DBZ2-1, DBZ2-2 are shown in Table 2-3, NH₃The specific gravity data of the area of the strong acid central peak occupying the total acid central peak area at the desorption temperature of more than 200 ℃ in the TPD spectrum are shown in tables 2 to 4.

PSZ2-1, PSZ2-2, DBZ2-1 and DBZ2-2 were evaluated for cracking of n-tetradecane, and the evaluation data are shown in tables 2 to 5.

TABLE 2-1

As can be seen from the table 2-1, the phosphorus-modified ZSM-5 molecular sieve prepared by the method still has higher crystal retention after being subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the crystal retention is obviously higher than that of a contrast sample, and the crystal retention is improved by at least 4 percentage points.

Tables 2 to 2

Tables 2 to 3

Tables 2 to 4

Example 3-1

Example 3-1 illustrates the phosphorus modified ZSM-5 molecular sieve employed in the catalyst of the present invention.

Dissolving 10.4g of phosphoric acid in 60g of deionized water at normal temperature, stirring for 2 hours to obtain a phosphorus-containing aqueous solution, adding 113g of HZSM-5 molecular sieve, modifying by adopting a dipping method, dipping for 4 hours at 20 ℃, drying in an oven at 110 ℃, externally applying pressure and adding water, and carrying out pressurized hydrothermal roasting treatment for 2 hours at 400 ℃, 0.3Mpa and 100% of steam atmosphere to obtain the phosphorus-modified ZSM-5 molecular sieve, wherein the mark is PSZ 3-1.

Examples 3 to 2

Example 3-2 illustrates the phosphorus modified ZSM-5 molecular sieve employed in the catalyst of the present invention.

The procedure of example 3-1 was repeated except that an aqueous solution of a phosphorus-containing compound at 80 ℃ was mixed with HZSM-5 molecular sieve heated to 80 ℃ and the mixture was subjected to calcination for 4 hours. The resulting phosphorus modified ZSM-5 molecular sieve sample was designated PSZ 3-2.

Comparative example 3-1

Comparative example 3-1 illustrates the current industry conventional process and the resulting phosphorus modified ZSM-5 comparative sample.

The same as in example 3-1 except that the firing conditions were atmospheric pressure (apparent pressure 0MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of the phosphorus modified ZSM-5 molecular sieve was obtained and was identified as DBZ 3-1.

Comparative examples 3 to 2

Comparative example 3-2 illustrates a comparative sample of phosphorus modified ZSM-5 molecular sieve obtained by hydrothermal calcination at atmospheric pressure.

The same as in example 3-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of phosphorus modified ZSM-5 molecular sieve was obtained and was identified as DBZ 3-2.

XRD crystallinity of PSZ3-1, PSZ3-2, PSZ DBZ3-1 and PSZ DBZ3-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h is shown in Table 3-1.

Of PSZ-3 and PSZ3-2²⁷Al MAS-NMR spectra having the features of FIG. 1, DBZ3-1 and DBZ3-2, respectively²⁷The Al MAS-NMR spectrum is characterized by the same features as in FIG. 3.²⁷The data of the peak area ratio of the Al MAS-NMR spectrum are shown in Table 3-2.

The surface XPS elemental analysis data for PSZ3-1, PSZ3-2, DBZ3-1, DBZ3-2 are shown in Table 3-3, NH₃The specific gravity data of the area of the strong acid central peak occupying the total acid central peak area at desorption temperatures above 200 ℃ in the TPD spectrum are shown in tables 3-4.

TABLE 3-1

As can be seen from the table 3-1, the phosphorus-modified ZSM-5 molecular sieve prepared by the method still has higher crystal retention after being subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the crystal retention is obviously higher than that of a contrast sample, and the crystal retention is improved by at least 10 percent.

TABLE 3-2

Tables 3 to 3

Tables 3 to 4

Example 4-1

Example 4-1 illustrates the phosphorus modified ZSM-5 molecular sieve employed in the catalyst of the present invention.

Dissolving 8.1g of diammonium hydrogen phosphate in 120g of deionized water at normal temperature, stirring for 0.5h to obtain a phosphorus-containing aqueous solution, adding 113g of HZSM-5 molecular sieve, modifying by adopting a dipping method, dipping for 2 hours at 20 ℃, drying in an oven at 110 ℃, applying pressure to the outside, adding water, and carrying out pressurized hydrothermal roasting treatment for 2h at 300 ℃, 0.4Mpa and 100% steam atmosphere to obtain a phosphorus-modified ZSM-5 molecular sieve sample, wherein the sample is marked as PSZ 4-1.

Example 4 to 2

Example 4-2 illustrates the phosphorus modified ZSM-5 molecular sieve employed in the catalyst of the present invention.

The procedure of the same materials, mixing, drying and calcining as in example 4-1 is different in that ammonium dihydrogen phosphate, HZSM-5 molecular sieve and water are mixed and beaten into slurry, and then the temperature is raised to 90 ℃ and kept for 2 h. The resulting phosphorus modified ZSM-5 molecular sieve sample was designated PSZ 4-2.

Comparative example 4-1

Comparative example 4-1 illustrates the current industry conventional process and the resulting phosphorus modified ZSM-5 comparative sample.

The same as in example 4-1 except that the firing conditions were atmospheric pressure (apparent pressure 0MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of the phosphorus modified ZSM-5 molecular sieve was obtained and was identified as DBZ 4-1.

Comparative examples 4 to 2

Comparative example 4-2 illustrates a comparative sample of phosphorus modified ZSM-5 molecular sieve obtained by hydrothermal calcination at atmospheric pressure.

The same as in example 4-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of phosphorus modified ZSM-5 molecular sieve was obtained and was identified as DBZ 4-2.

XRD crystallinity of PSZ4-1, PSZ4-2, DBZ4-1 and DBZ4-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h is shown in Table 4-1.

Of PSZ4-1 and PSZ4-2²⁷Al MAS-NMR spectra having the features of FIG. 1, DBZ-4-1 and DBZ-4-2, respectively²⁷The Al MAS-NMR spectrum is characterized by the same features as in FIG. 3.²⁷The data of the peak area ratio of the Al MAS-NMR spectrum are shown in Table 4-2.

The surface XPS elemental analysis data for PSZ4-1, PSZ4-2, DBZ4-1, DBZ4-2 are shown in Table 4-3, NH₃The specific gravity data of the area of the strong acid central peak occupying the total acid central peak area at the desorption temperature of more than 200 ℃ in the TPD spectrum are shown in the table 4-4.

TABLE 4-1

As can be seen from Table 4-1, the phosphorus-modified ZSM-5 molecular sieve prepared by the method still has higher crystal retention after being subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the crystal retention is obviously higher than that of a contrast sample, and the crystal retention is improved by at least 15 percent.

TABLE 4-2

Tables 4 to 3

Tables 4 to 4

Example 5-1

Example 5-1 illustrates the phosphorus modified ZSM-5 molecular sieve employed in the catalyst of the present invention.

Dissolving 8.5g of trimethyl phosphate in 80g of deionized water at 90 ℃, stirring for 1h to obtain a phosphorus-containing aqueous solution, adding 113g of HZSM-5 molecular sieve, modifying by adopting a dipping method, dipping for 8h at 20 ℃, drying in an oven at 110 ℃, externally applying pressure and adding water, and carrying out pressurized hydrothermal roasting treatment for 4h at 500 ℃, 0.8Mpa and 80% of steam atmosphere to obtain the phosphorus-modified ZSM-5 molecular sieve, wherein the mark is PSZ 5-1.

Examples 5 and 2

Example 5-2 illustrates the phosphorus modified ZSM-5 molecular sieve employed in the catalyst of the present invention.

The procedure of the same materials, mixing, drying and calcining as in example 5-1 is different in that trimethyl phosphate, HZSM-5 molecular sieve and water are mixed and beaten into slurry, and then the temperature is raised to 120 ℃ and kept for 8 hours. The resulting phosphorus modified ZSM-5 molecular sieve sample was designated PSZ 5-2.

Comparative example 5-1

Comparative example 5-1 illustrates the current industry conventional process and the resulting phosphorus modified ZSM-5 comparative sample.

The same as example 5-1 except that the firing conditions were atmospheric pressure (apparent pressure 0MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of the phosphorus modified ZSM-5 molecular sieve was obtained and was identified as DBZ 5-1.

Comparative examples 5 to 2

Comparative example 5-2 illustrates a comparative sample of phosphorus modified ZSM-5 molecular sieve obtained by hydrothermal calcination at atmospheric pressure.

The same as in example 5-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of phosphorus modified ZSM-5 molecular sieve was obtained and was identified as DBZ 5-2.

XRD crystallinity of PSZ5-1, PSZ5-2, DBZ5-1 and DBZ5-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h is shown in Table 5-1.

Of PSZ5-1 and PSZ5-2²⁷Al MAS-NMR spectrum with the features of FIG. 1, DBZ5-1 and DBZ5-2²⁷The Al MAS-NMR spectrum is characterized by the same features as in FIG. 3.²⁷The data of the peak area ratio of the Al MAS-NMR spectrum are shown in Table 5-2.

The surface XPS elemental analysis data for PSZ5-1, PSZ5-2, DBZ5-1, DBZ5-2 are shown in Table 5-3, NH₃The specific gravity data of the area of the strong acid central peak occupying the total acid central peak area at desorption temperatures above 200 ℃ in the TPD spectrum are shown in tables 5-4.

TABLE 5-1

As can be seen from Table 5-1, the phosphorus-modified ZSM-5 molecular sieve prepared by the method still has higher crystal retention after being subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the crystal retention is obviously higher than that of a contrast sample, and the crystal retention is improved by at least 5 percent.

TABLE 5-2

Tables 5 to 3

Tables 5 to 4

Example 6-1

Example 6-2 illustrates the phosphorus modified ZSM-5 molecular sieve employed in the catalyst of the present invention.

Dissolving 11.6g of boron phosphate in 100g of deionized water at 100 ℃, stirring for 3h to obtain a phosphorus-containing aqueous solution, adding 113g of HZSM-5 molecular sieve, modifying by adopting a dipping method, dipping for 2h at 20 ℃, drying in an oven at 110 ℃, applying pressure to the outside, adding water, and carrying out pressurized hydrothermal roasting treatment for 4h at 400 ℃, 0.3Mpa and 100% of steam atmosphere to obtain the phosphorus-modified ZSM-5 molecular sieve, wherein the mark is PSZ 6-1.

Example 6 to 2

The process is the same as the process of example 6-1 except that the boron phosphate, the HZSM-5 molecular sieve and water are mixed and beaten into slurry, and the temperature is raised to 150 ℃ and kept for 2 h. The resulting phosphorus modified ZSM-5 molecular sieve sample was designated PSZ 6-2.

Comparative example 6-1

Comparative example 6-1 illustrates the current industry conventional process and the resulting phosphorus modified ZSM-5 comparative sample.

The same as example 6-1 except that the firing conditions were atmospheric pressure (apparent pressure 0MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of the phosphorus modified ZSM-5 molecular sieve was obtained and was identified as DBZ 6-1.

Comparative examples 6 to 2

Comparative example 6-2 illustrates a comparative sample of phosphorus modified ZSM-5 molecular sieve obtained by hydrothermal calcination at atmospheric pressure.

The same as in example 6-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of phosphorus modified ZSM-5 molecular sieve was obtained and was identified as DBZ 6-2.

XRD crystallinity of PSZ6-1, PSZ6-2, PSZ DBZ6-1 and PSZ DBZ6-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h is shown in Table 6-1.

Of PSZ6-1 and PSZ6-2²⁷Al MAS-NMR spectrum with the features of FIG. 1, DBZ-6-1 and DBZ6-2²⁷The Al MAS-NMR spectrum is characterized by the same features as in FIG. 3.²⁷The data of the peak area ratio of the Al MAS-NMR spectrum are shown in Table 6-2.

The surface XPS elemental analysis data for PSZ6-1, PSZ6-2, DBZ6-1, DBZ6-2 are shown in Table 6-3, NH₃The specific gravity data of the area of the strong acid central peak occupying the total acid central peak area at desorption temperatures above 200 ℃ in the TPD spectrum are shown in tables 6-4.

TABLE 6-1

As can be seen from Table 6-1, the phosphorus-modified ZSM-5 molecular sieve prepared by the method still has higher crystal retention after being subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the crystal retention is obviously higher than that of a contrast sample, and the crystal retention is improved by at least 10 percent.

TABLE 6-2

Tables 6 to 3

Tables 6 to 4

Example 7-1

Example 7-1 illustrates the phosphorus modified ZSM-5 molecular sieve employed in the catalyst of the present invention.

Dissolving 14.2g of triphenylphosphine in 80g of deionized water at 100 ℃, stirring for 2h to obtain a phosphorus-containing aqueous solution, adding 113g of HZSM-5 molecular sieve, modifying by adopting an impregnation method, impregnating for 4h at 20 ℃, drying in an oven at 110 ℃, applying pressure to the outside, adding water, and carrying out pressurized hydrothermal roasting treatment for 2h at 600 ℃, 1.0Mpa and 30% of steam atmosphere to obtain the phosphorus-modified ZSM-5 molecular sieve, wherein the mark is PSZ 7-1.

Example 7-2

Example 7-2 illustrates the phosphorus modified ZSM-5 molecular sieve employed in the catalyst of the present invention.

The same materials, proportioning, drying and calcining as in example 7-1, except that the aqueous solution of the phosphorus compound at 80 ℃ was mixed and contacted with the HZSM-5 molecular sieve heated to 80 ℃ for 4 hours. The resulting phosphorus modified ZSM-5 molecular sieve sample was designated PSZ 7-2.

Comparative example 7-1

Comparative example 7-1 illustrates the current industry conventional process and the resulting phosphorus modified ZSM-5 comparative sample.

The same as example 7-1 except that the firing conditions after impregnation and drying were atmospheric pressure (apparent pressure 0MPa) and air firing in a muffle furnace at 550 ℃. A comparative sample of the phosphorus modified ZSM-5 molecular sieve was obtained and was identified as DBZ 7-1.

Comparative examples 7 to 2

Comparative example 7-2 illustrates a comparative sample of phosphorus modified ZSM-5 molecular sieve obtained by hydrothermal calcination at atmospheric pressure.

The same as example 7-1, except that the firing conditions after impregnation and drying were atmospheric pressure (apparent pressure: 0 MPa). A comparative sample of phosphorus modified ZSM-5 molecular sieve was obtained and was identified as DBZ 7-2.

XRD crystallinity of PSZ7-1, PSZ7-2, PSZ DBZ7-1 and PSZ DBZ7-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h is shown in Table 7-1.

PSZ-7 and PSZ7-2²⁷Al MAS-NMR spectrum with the features of FIG. 1, DBZ7-1 and DBZ7-2²⁷The Al MAS-NMR spectrum is characterized by the same features as in FIG. 3.²⁷The data of the peak area ratio of the MAS-NMR spectrum are shown in Table 7-2.

The surface XPS elemental analysis data of PSZ7-1, PSZ7-2, DBZ7-1 and DBZ7-2 are shown in Table 7-3, and NH of PSZ7-1, PSZ7-2, DBZ7-1 and DBZ7-2₃The specific gravity data of the area of the strong acid center peak occupying the total acid center peak area at desorption temperatures above 200 ℃ in the TPD spectrum are shown in tables 7-4.

TABLE 7-1

As can be seen from Table 7-1, the phosphorus-modified ZSM-5 molecular sieve prepared by the method still has higher crystal retention after being subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the crystal retention is obviously higher than that of a contrast sample, and the crystal retention is improved by at least 8 percent.

TABLE 7-2

Tables 7 to 3

Tables 7 to 4

Examples 8-11 illustrate the use of a phosphorus aluminum inorganic binder in the catalyst of the present invention.

Example 8

1.91 kg of pseudoboehmite (containing Al)₂O₃1.19 kg), 0.56 kg kaolin (0.5 kg on a dry basis) and 3.27 kg decationized water, stirring and adding 5.37 kg concentrated phosphoric acid (85% by mass) into the slurry, wherein the adding speed of the phosphoric acid is 0.04 kg phosphoric acid/min/kg alumina source, heating to 70 ℃, and then reacting for 45 minutes at the temperature to obtain the phosphorus-aluminum inorganic binder.The mixture ratio of the materials is shown in Table 8, and the sample number is Binder 1.

Examples 9 to 11

A phosphorus-aluminum inorganic Binder was prepared as in example 8, with the materials in the proportions shown in Table 8, and the sample numbers Binder2, Binder3, and Binder 4.

TABLE 8

Examples 12-18 illustrate the catalytic cracking catalysts of the present invention.

Example 12-1

Taking the phosphorus modified molecular sieve PSZ1-1, the Y-type molecular sieve (PSRY molecular sieve), kaolin and pseudo-boehmite prepared in the example 1-1, adding decationized water and alumina sol, pulping for 120 minutes to obtain slurry with the solid content of 30 weight percent, adding hydrochloric acid to adjust the pH value of the slurry to 3.0, further pulping for 45 minutes, then adding the phosphorus-aluminum inorganic Binder Binder1 prepared in the example 8, stirring for 30 minutes, spray-drying the obtained slurry to obtain microspheres, and roasting the microspheres for 1 hour at 500 ℃ to obtain a catalytic cracking catalyst sample with the serial number of CAZY1-1, wherein the serial number of the catalytic cracking catalyst sample is 40 percent of phosphorus modified ZSM-5 molecular sieve, 10 percent of PSRY molecular sieve, 18 percent of kaolin, 18 percent of Binder1 and 18 percent of pseudo-boehmite (prepared by Al)₂O₃Calculated as Al) 5%, alumina sol (calculated as Al)₂O₃Calculated) 9 percent. The reaction performance evaluation of 100% of balancing agent and the catalyst CAZY1-1 doped with the balancing agent is carried out by adopting a fixed bed micro-reaction device to illustrate the effect of the catalytic cracking reaction.

The catalyst CAZY1-1 was aged at 800 ℃ for 17 hours in a 100% steam atmosphere. The aged CAZY1-1 and industrial FCC equilibrium catalyst (FCC equilibrium catalyst of industrial grade DVR-3, light oil micro-reverse activity is 63) are mixed by 10% and 90% respectively. The mixture of the balancing agent and the catalyst is loaded into a fixed bed micro-reactor, the raw oil shown in the table 9 is subjected to catalytic cracking, and the evaluation conditions are that the reaction temperature is 620 ℃, the regeneration temperature is 620 ℃, and the agent-oil ratio is 3.2. The results of the reaction are given in Table 10.

TABLE 9

Example 12-2

The same as in example 12-1 except that the phosphorus-modified molecular sieve PSZ-1-1 was replaced with the phosphorus-modified molecular sieve PSZ-1-2 prepared in example 1-2, respectively. A catalyst sample was prepared, code number CAZY 1-2.

The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 10.

Comparative example 12-1

The difference from example 12-1 is that the phosphorus-modified molecular sieve PSZ-1-1 was replaced with comparative sample DBZ1-1 of comparative example 1-1. A comparative catalyst sample was prepared, code DCAZY 1-1.

Comparative examples 12 to 2

The difference from example 12-1 is that the phosphorus-modified molecular sieve PSZ-1-1 was replaced with comparative sample DBZ1-2 of comparative example 1-2. A comparative catalyst sample was prepared, code DCAZY 1-2.

Watch 10

Item	Example of blank test	Example 12-1	Example 12-2	Comparative example 12-1	Comparative examples 12 to 2
						Balance of materials, weight%
Liquefied gas	18.54	32.70	34.97	22.12	24.07
						Ethylene yield	1.39	3.47	3.78	2.76	2.95
Propylene yield	8.05	13.62	15.30	9.61	10.22

Example 13-1

The same as in example 12-1 except that the phosphorus-modified molecular sieve PSZ-1-1 was replaced with the phosphorus-modified molecular sieve PSZ-2-1 prepared in example 2-1. A catalytic cracking assistant sample is prepared, and the number is CAZY 2-1.

The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 11.

Example 13-2

The same as in example 13-1 except that the phosphorus-modified molecular sieve PSZ-2-1 was replaced with the phosphorus-modified molecular sieve PSZ-2-2 prepared in example 2-2. A catalytic cracking assistant sample is prepared, and the number is CAZY 2-2.

The evaluation was made in the same manner as in example 13-1, and the results are shown in Table 11.

Comparative example 13-1

The difference from example 13-1 is that the phosphorus-modified molecular sieve PSZ-2-1 was replaced with comparative sample DBZ2-1 of comparative example 2-1. A comparative sample of catalytic cracking aid was prepared, code DCAZY 2-1.

Comparative examples 13 to 2

The difference from example 13-1 is that the phosphorus-modified molecular sieve PSZ-2-1 was replaced with comparative sample DBZ2-2 of comparative example 2-2. A comparative sample of catalytic cracking aid was prepared, code DCAZY 2-2.

TABLE 11

Example 14-1

The same as in example 12-1 except that the phosphorus-modified molecular sieve PSZ-1-1 was replaced with the phosphorus-modified molecular sieve PSZ-3-1 prepared in example 3-1. A catalytic cracking assistant sample is prepared, and the number is CAZY 3-1.

The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 12.

Example 14-2

The same as in example 14-1 except that the phosphorus-modified molecular sieve PSZ-3-1 was replaced with the phosphorus-modified molecular sieve PSZ-3-2 prepared in example 3-2. A catalytic cracking assistant sample is prepared, and the number is CAZY 3-2.

The evaluation was made in the same manner as in example 14-1, and the results are shown in Table 12.

Comparative example 14-1

The difference from example 14-1 is that the phosphorus-modified molecular sieve PSZ-3-1 was replaced with comparative sample DBZ3-1 of comparative example 3-1. A comparative sample of catalytic cracking aid was prepared, code DCAZY 3-1.

Comparative examples 14 to 2

The difference from example 14-1 is that the phosphorus-modified molecular sieve PSZ-3-1 was replaced with comparative sample DBZ2-2 of comparative example 3-2. A comparative catalyst sample was prepared, code DCAZY 3-2.

TABLE 12

Item	Example of blank test	Example 14-1	Example 14-2	Comparative example 14-1	Comparative examples 14 to 2
						Balance of materials, weight%
Liquefied gas	18.54	33.92	35.48	21.29	23.50
						Ethylene yield	1.39	3.72	3.97	2.75	2.98
Propylene yield	8.05	14.80	16.25	9.68	10.45

Example 15-1

The same as in example 12-1 except that the phosphorus-modified molecular sieve PSZ-1-1 was replaced with the phosphorus-modified molecular sieve PSZ-4-1 prepared in example 4-1. A catalyst sample was prepared, code number CAZY 4-1.

The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 13.

Example 15-2

The same as in example 15-1 except that the phosphorus-modified molecular sieve PSZ-4-1 was replaced with the phosphorus-modified molecular sieve PSZ-4-2 prepared in example 4-2. A catalyst sample was prepared, code number CAZY 4-2.

The evaluation was made in the same manner as in example 15-1, and the results are shown in Table 13.

Comparative example 15-1

The difference from example 15-1 is that the phosphorus-modified molecular sieve PSZ-2-1 was replaced with comparative sample DBZ4-1 of comparative example 2-1. A comparative catalyst sample was prepared, code DCAZY 4-1.

Comparative examples 15 to 2

The difference from example 15-1 is that the phosphorus-modified molecular sieve PSZ-2-1 was replaced with comparative sample DBZ4-2 of comparative example 2-2. A comparative catalyst sample was prepared, code DCAZY 4-2.

Watch 13

Item	Example of blank test	Example 15-1	Example 15-2	Comparative example 15-1	Comparative examples 15 to 2
						Balance of materials, weight%
Liquefied gas	18.54	35.83	37.43	20.73	23.50
						Ethylene yield	1.39	3.93	4.18	2.68	2.98
Propylene yield	8.05	15.63	17.14	9.43	10.45

Example 16-1

The same as in example 12-1 except that the phosphorus-modified molecular sieve PSZ-1-1 was replaced with the phosphorus-modified molecular sieve PSZ-5-1 prepared in example 5-1. A catalyst sample was prepared, code number CAZY 5-1.

The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 14.

Example 16-2

The same as in example 16-1 except that the phosphorus-modified molecular sieve PSZ-5-1 was replaced with the phosphorus-modified molecular sieve PSZ-5-2 prepared in example 5-2. A catalyst sample was prepared, code number CAZY 5-2.

The evaluation was made in the same manner as in example 16-1, and the results are shown in Table 14.

Comparative example 16-1

The difference from example 16-1 is that the phosphorus-modified molecular sieve PSZ-5-1 was replaced with comparative sample DBZ5-1 of comparative example 5-1. A comparative catalyst sample was prepared, code DCAZY 5-1.

Comparative example 16-2

The difference from example 16-1 is that the phosphorus-modified molecular sieve PSZ-2-1 was replaced with comparative sample DBZ5-2 of comparative example 2-2. A comparative catalyst sample was prepared, code DCAZY 5-2.

TABLE 14

Item	Example of blank test	Example 16-1	Example 16-2	Comparative example 16-1	Comparative example 16-2
						Balance of materials, weight%
Liquefied gas	18.54	32.40	33.53	21.85	23.80
						Ethylene yield	1.39	3.55	3.75	2.82	3.02
Propylene yield	8.05	14.13	15.36	9.94	10.58

Example 17-1

The same as in example 12-1 except that the phosphorus-modified molecular sieve PSZ-1-1 was replaced with the phosphorus-modified molecular sieve PSZ-6-1 prepared in example 6-1. A catalyst sample was prepared, code number CAZY 6-1.

The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 15.

Example 17-2

The same as in example 17-1 except that the phosphorus-modified molecular sieve PSZ-6-1 was replaced with the phosphorus-modified molecular sieve PSZ-6-2 prepared in example 6-2. A catalyst sample was prepared, code number CAZY 6-2.

The evaluation was made in the same manner as in example 17-1, and the results are shown in Table 15.

Comparative example 17-1

The difference from example 17-1 is that the phosphorus-modified molecular sieve PSZ-2-1 was replaced with comparative sample DBZ2-1 of comparative example 6-1. A comparative catalyst sample was prepared, code DCAZY 6-1.

Comparative examples 17 to 2

The difference from example 17-1 is that the phosphorus-modified molecular sieve PSZ-2-1 was replaced with comparative sample DBZ2-2 of comparative example 6-2. A comparative catalyst sample was prepared, code DCAZY 6-2.

Watch 15

Item	Example of blank test	Example 17-1	Example 17-2	Comparative example 17-1	Comparative examples 17 to 2
						Balance of materials, weight%
Liquefied gas	18.54	33.54	34.70	20.45	23.20
						Ethylene yield	1.39	3.68	3.88	2.64	2.94
Propylene yield	8.05	14.63	15.89	9.30	10.32

Example 18-1

The same as in example 12-1 except that the phosphorus-modified molecular sieve PSZ-1-1 was replaced with the phosphorus-modified molecular sieve PSZ-7-1 prepared in example 7-1. A catalyst sample was prepared, code number CAZY 7-1.

The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 16.

Example 18-2

The same as in example 18-1 except that the phosphorus-modified molecular sieve PSZ-7-1 was replaced with the phosphorus-modified molecular sieve PSZ-7-2 prepared in example 7-2. A catalyst sample was prepared, code number CAZY 7-2.

The evaluation was made in the same manner as in example 18-1, and the results are shown in Table 16.

Comparative example 18-1

The difference from example 18-1 is that the phosphorus-modified molecular sieve PSZ-7-1 was replaced with comparative sample DBZ7-1 of comparative example 7-1. A comparative catalyst sample was prepared, code DCAZY 7-1.

Comparative example 18-2

The difference from example 18-1 is that the phosphorus-modified molecular sieve PSZ-7-1 was replaced with comparative sample DBZ7-2 of comparative example 7-2. A comparative catalyst sample was prepared, code DCAZY 7-2.

TABLE 16

Item	Example of blank test	Example 18-1	Example 18-2	Comparative example 18-1	Comparative example 18-2
						Balance of materials, weight%
Liquefied gas	18.54	31.25	33.14	19.89	22.01
						Ethylene yield	1.39	3.43	3.70	2.57	2.79
Propylene yield	8.05	13.63	15.18	9.05	9.79

Example 19-1

The difference from example 12-1 is that the aluminophosphate inorganic Binder was replaced with Binder2 prepared in example 9. The catalyst was obtained under the accession number CAZY 8-1.

The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 17.

Example 19-2

The difference from example 12-2 is that the aluminophosphate inorganic Binder was replaced with Binder2 prepared in example 9. The catalyst was obtained under the accession number CAZY 8-2.

Example 20-1

The difference from example 12-1 is that the aluminophosphate inorganic Binder was replaced with Binder3 prepared in example 10. The catalyst was obtained under the accession number CAZY 9-1.

Example 20-2

The difference from example 12-2 is that the aluminophosphate inorganic Binder was replaced with Binder3 prepared in example 10. The catalyst was obtained under the accession number CAZY 9-2.

Example 21-1

The difference from example 12-1 is that the aluminophosphate inorganic Binder was replaced with Binder4 prepared in example 11. The catalyst was obtained under the accession number CAZY 10-1.

Example 21-2

The difference from example 12-2 is that the aluminophosphate inorganic Binder was replaced with Binder4 prepared in example 11. The catalyst was obtained under the accession number CAZY 10-2.

TABLE 17

Example 22-1

The same as example 12-1, except that the phosphorus-modified ZSM-molecular sieve sample was PSZ 1-135 wt%, PSRY10 wt%, kaolin 18 wt%, aluminophosphate inorganic Binder Binder3 was 22 wt%, pseudoboehmite 10 wt%, and alumina sol 5 wt%. The catalyst was obtained under the accession number CAZY 11-1.

The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 18.

Example 22-2

The difference from example 12-1 is that PSZ1-1 was replaced with PSZ 1-2. The catalyst was obtained under the accession number CAZY 11-2.

Comparative example 22-1

The difference from example 22-1 is that PSZ1-1 was replaced with DBZ 1-1. A comparative catalyst sample was prepared, code DCAZ 11-1. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 18.

Comparative example 22-2

The difference from example 22-1 is that PSZ1-1 was replaced with DBZ 1-2. A comparative catalyst sample was prepared, code DCAZY 11-2. The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 18.

Watch 18

Example 23-1

The same as example 12-1, except that the phosphorus-modified ZSM-molecular sieve sample was PSZ 2-130 wt%, PSRY16 wt%, kaolin 24 wt%, aluminophosphate inorganic Binder Binder4 was 20 wt%, pseudoboehmite was 6 wt%, and silica sol was 10 wt%. The catalyst was obtained under the accession number CAZY 12-1.

The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 19.

Example 23-2

The difference from example 12-1 is that PSZ2-1 was replaced with PSZ 2-2. The catalyst was obtained under the accession number CAZY 12-2.

Comparative example 23-1

The difference from example 23-1 is that PSZ2-1 was replaced with DBZ 2-1. A comparative catalyst sample was prepared, code DCAZY 12-1.

Comparative examples 23 to 2

The difference from example 23-1 is that PSZ2-1 was replaced with DBZ 2-2. A comparative catalyst sample was prepared, code DCAZY 12-2.

Watch 19

Example 24-1

Mixing a binder alumina sol with kaolin, preparing the mixture into slurry with the solid content of 30 weight percent by using decationized water, uniformly stirring, adjusting the pH value of the slurry to 2.8 by using hydrochloric acid, standing and aging the slurry at 55 ℃ for 1 hour, adding the phosphorus modified ZSM-5 molecular sieve PSZ1-1 and the Y-type molecular sieve (PSRY) prepared in example 1 to form catalyst slurry (with the solid content of 35 weight percent), continuously stirring, and performing spray drying to prepare the microspherical catalyst. The microspherical catalyst was then calcined at 500 ℃ for 1 hour, washed with ammonium sulfate (where ammonium sulfate: microspherical catalyst: water 0.5:1:10) at 60 ℃ to a sodium oxide content of less than 0.25 wt%, rinsed with deionized water and filtered, and then dried at 110 ℃ to give the catalyst, code CAZY 13-1. The catalyst is prepared from phosphorus modified ZSM-5 molecular sieve PSZ-1-140%, PSRY molecular sieve 10%, kaolin 25%, and aluminum sol (Al₂O₃Calculated) 25 percent.

The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 20.

Example 24-2

The same as in example 24-1 except that the phosphorus-modified molecular sieve PSZ1-1 was replaced with the phosphorus-modified molecular sieve PSZ-1-2 prepared in example 1-2. A catalyst sample was prepared, code number CAZY 13-2.

Comparative example 24-1

The difference from example 24-1 is that the phosphorus-modified molecular sieve PSZ1-1 was replaced with comparative sample DBZ1-1 of comparative example 1-1. A comparative catalyst sample was prepared, code DCAZY 13-1.

Comparative example 24-2

The difference from example 24-1 is that the phosphorus-modified molecular sieve PSZ-1-1 was replaced with comparative sample DBZ1-2 of comparative example 1-2. A comparative catalyst sample was prepared, code DCAZY 13-2.

Watch 20

Item	Example of blank test	Example 24-1	Example 24-2	Comparative example 24-1	Comparative example 24-2
						Balance of materials, weight%
Liquefied gas	18.54	31.52	33.72	21.32	23.20
						Ethylene yield	1.39	3.33	3.62	2.64	2.83
Propylene yield	8.05	12.89	14.47	9.09	9.67

Example 25-1

The same as example 12-1 except that the Y-type molecular sieve (PSRY) was replaced with HRY-1. A catalyst sample was prepared, code number CAZY 14-1.

The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 21.

Example 25-2

The same as example 12-2 except that the Y-type molecular sieve (PSRY) was replaced with HRY-1. A catalyst sample was prepared, code number CAZY 14-1.

Comparative example 25-1

The difference from example 25-1 is that the phosphorus-modified molecular sieve PSZ1-1 was replaced with comparative sample DBZ1-1 of comparative example 1-1. A comparative catalyst sample was prepared, code DCAZY 14-1.

Comparative example 25-2

The difference from example 25-1 is that the phosphorus-modified molecular sieve PSZ-1-1 was replaced with comparative sample DBZ1-2 of comparative example 1-2. A comparative catalyst sample was prepared, code DCAZY 14-2.

TABLE 21

Item	Example of blank test	Example 25-1	Example 25-2	Comparative example 25-1	Comparative example 25-2
						Balance of materials, weight%
Liquefied gas	18.54	33.82	36.17	22.88	24.90
						Ethylene yield	1.39	3.60	3.93	2.87	3.07
Propylene yield	8.05	14.41	16.18	10.16	10.81

Example 26-1

The same as example 12-1 except that the Y-type molecular sieve (PSRY) was replaced with USY. A catalyst sample was prepared, code number CAZY 15-1.

The evaluation was made in the same manner as in example 12-1, and the results are shown in Table 22.

Example 26-2

The same as example 12-2 except that the Y-type molecular sieve (PSRY) was replaced with USY. A catalyst sample was prepared, code number CAZY 15-2.

Comparative example 26-1

The difference from example 26-1 is that the phosphorus-modified molecular sieve PSZ1-1 was replaced with comparative sample DBZ1-1 of comparative example 1-1. A comparative catalyst sample was prepared, code DCAZY 15-1.

Comparative example 26-2

The difference from example 26-1 is that the phosphorus-modified molecular sieve PSZ-1-1 was replaced with comparative sample DBZ1-2 of comparative example 1-2. A comparative catalyst sample was prepared, code DCAZY 15-2.

TABLE 22

Item	Example of blank test	Example 26-1	Example 26-2	Comparative example 26-1	Comparative example 26-2
						Balance of materials, weight%
Liquefied gas	18.54	31.19	33.36	21.11	22.97
						Ethylene yield	1.39	3.29	3.58	2.61	2.80
Propylene yield	8.05	12.75	14.32	8.99	9.56

Example 27-1 and example 27-2

Example 27-1 and example 27-2 used the catalysts CAZY1-1 and CAZY1-2 of example 12-1 and example 12-2, respectively. The feed oil for catalytic cracking was naphtha shown in Table 23.

The evaluation conditions were a reaction temperature of 620 ℃, a regeneration temperature of 620 ℃ and an agent-to-oil ratio of 3.2.

The weight composition of each catalytic cracking assistant-containing catalyst mixture and the reaction results are given in Table 22.

Comparative examples 27-1 and 27-2

The same as example 27-1 except that the catalytic control agents DCAZY1-1 and DCAZY1-2 of comparative example 12-1 and comparative example 12-2 were used, respectively.

The weight composition of the catalyst mixture and the reaction results for each comparative sample containing a catalytic cracking aid are shown in Table 24.

TABLE 23

Raw materials	Naphtha (a)
		Density (20 ℃ C.)/(g.m)^-3)	735.8
Vapor pressure/kPa	32
		Mass group composition/%)
Alkane hydrocarbons	51.01
		N-alkanes	29.40
Cycloalkanes	38.24
		Olefins	0.12
Aromatic hydrocarbons	10.52
		Distillation range/. degree.C
First run	45.5
		5％	72.5
10％	86.7
		30％	106.5
50％	120.0
		70％	132.7
90％	148.5
		95％	155.2
End point of distillation	166.5

Watch 24

The evaluation data in table 24 show that the catalyst containing the phosphorus modified ZSM-5 molecular sieve modified by the impregnation method in the example shows excellent performance of increasing the yield of liquefied gas and simultaneously increasing the yield of low carbon olefins when the catalyst containing the molecular sieve modified by the impregnation method in the example is subjected to catalytic cracking on different raw oils, wherein the yield of liquefied gas and low carbon olefins is obviously lower than that of the catalyst containing the molecular sieve modified by the impregnation method in the comparative example.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. A catalytic cracking catalyst, characterized in that the catalytic cracking catalyst contains 1-25 wt% of Y-type molecular sieve based on dry basis, 5-50 wt% of phosphorus modified ZSM-5 molecular sieve based on dry basis, 1-60 wt% of inorganic binder based on dry basis and 0-60 wt% of second clay optionally added based on dry basis, wherein the phosphorus modified ZSM-5 molecular sieve,²⁷in Al MAS-NMR, the ratio of the peak area of resonance signal with chemical shift of 39 +/-3 ppm to the peak area of resonance signal with chemical shift of 54ppm +/-3 ppm is more than or equal to 1, and the inorganic binder comprises phosphor-aluminum inorganic binder and/or other inorganic binders.

2. The catalyst of claim 1, wherein the Y-type molecular sieve comprises at least one of a PSRY molecular sieve, a PSRY-S molecular sieve, a PSRY molecular sieve containing rare earth, a PSRY-S molecular sieve containing rare earth, a USY molecular sieve containing rare earth, a REY molecular sieve, a REHY molecular sieve, and a HY molecular sieve.

3. The catalyst of claim 1, wherein said phosphorus-modified ZSM-5 molecular sieve has²⁷In the Al MAS-NMR, the ratio of the peak area of the resonance signal with the chemical shift of 39 +/-3 ppm to the peak area of the resonance signal with the chemical shift of 54ppm +/-3 ppm is not less than 1, the preferred ratio is not less than 10, and the more preferred ratio is 12-25.

4. The catalyst of claim 1, wherein the phosphorus modified ZSM-5 molecular sieve has a surface XPS elemental analysis of n1/n2 of 0.1 or less, preferably n1/n2 of 0.09 or less, more preferably n1/n2 of 0.08 or less, most preferably n1/n2 of 0.04 to 0.07, n1 represents the mole number of phosphorus, and n2 represents the total mole number of silicon and aluminum.

5. The catalyst according to claim 1, wherein the phosphorus modified ZSM-5 molecular sieve has an NH3-TPD spectrum, wherein the area of the strong acid central peak accounts for more than 40% of the total acid central peak area, preferably more than 42%, more preferably more than 45%, most preferably 48-85% of the total acid central peak area, at a desorption temperature of more than 200 ℃ after hydrothermal aging at 800 ℃ and 100% steam for 17 h.

6. The catalyst according to claim 1, wherein the phosphorus modified ZSM-5 molecular sieve has a ratio of 0.01 to 2, preferably 0.1 to 1.5, more preferably 0.2 to 1.5, when both phosphorus and aluminum are in molar terms.

7. A method of preparing a catalytic cracking catalyst, the method comprising: mixing and pulping the Y-type molecular sieve, the phosphorus modified ZSM-5 molecular sieve and the inorganic binder, spray-drying, and optionally roasting to obtain the catalytic cracking catalyst; wherein a second clay is added or not added to the mixing; the weight ratio of the Y-type molecular sieve, the phosphorus modified ZSM-5 molecular sieve, the inorganic binder and the second clay is (1-25): (5-50): (1-60): (0-60); the inorganic binder comprises a phosphor-aluminum inorganic binder and/or other inorganic binders; the phosphorus-modified ZSM-5 molecular sieve is obtained by contacting a phosphorus-containing compound solution with an HZSM-5 molecular sieve, drying, performing hydrothermal roasting treatment under the atmosphere environment of externally applied pressure and externally added water, and recovering a product; the contact is that an impregnation method is adopted to mix and contact a water solution of a phosphorus-containing compound with the temperature of 0-150 ℃ and an HZSM-5 molecular sieve with the temperature of 0-150 ℃ for at least 0.1 hour at the basically same temperature, or the contact is that the phosphorus-containing compound, the HZSM-5 molecular sieve and water are mixed and pulped and then are kept for at least 0.1 hour at the temperature of 0-150 ℃; the atmosphere environment has an apparent pressure of 0.01 to 1.0MPa and contains 1 to 100 percent of water vapor.

8. The method according to claim 7, wherein the phosphorus-containing compound is selected from an organic phosphide and/or an inorganic phosphide.

9. The process according to claim 7, wherein the organophosphate is selected from the group consisting of trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium hydroxide, triphenylethyl phosphonium bromide, triphenylbutyl phosphonium bromide, triphenylbenzyl phosphonium bromide, hexamethylphosphoric triamide, dibenzyl diethyl phosphonium, 1, 3-xylene bistrietyl phosphonium; the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.

10. The process according to claim 7, wherein the HZSM-5 molecular sieve contains Na₂O<0.1wt％。

11. The preparation method of claim 7, wherein the molar ratio of the phosphorus-containing compound to the HZSM-5 molecular sieve is 0.01-2; preferably, the molar ratio of the two is 0.1-1.5; more preferably, the molar ratio of the two is 0.2 to 1.5.

12. The method according to claim 7, wherein the contacting is carried out at 50 to 150 ℃, preferably 70 to 130 ℃ for 0.5 to 40 hours, with a water sieve weight ratio of 0.5 to 1.

13. The method according to claim 7, wherein the atmosphere has an apparent pressure of 0.1 to 0.8MPa, preferably 0.3 to 0.6MPa, and contains 30 to 100% of water vapor, preferably 60 to 100% of water vapor; the hydrothermal roasting treatment is carried out at 200-800 ℃, preferably 300-500 ℃.

14. The preparation method according to claim 7, wherein the phosphor-aluminum inorganic binder is phosphor-aluminum glue and/or a phosphor-aluminum inorganic binder containing first clay; the phosphorus-aluminum inorganic binder containing the first clay contains Al based on the dry weight of the phosphorus-aluminum inorganic binder containing the first clay₂O₃15-40% by weight, calculated as P, of an aluminium component₂O₅45-80% by weight of a phosphorus component and more than 0 and not more than 40% by weight of a first clay on a dry basis, and the phosphorus componentThe weight ratio of P/Al of the phosphorus-aluminum inorganic binder of the first clay is 1.0-6.0, the pH is 1-3.5, and the solid content is 15-60 wt%; the first clay comprises at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomaceous earth.

15. The method according to claim 7, wherein the second clay is at least one selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, hydrotalcite, bentonite, and diatomaceous earth.

16. The production method according to claim 7, wherein the catalyst contains 3 to 40 wt% of the aluminophosphate inorganic binder or 3 to 40 wt% of the aluminophosphate inorganic binder and 1 to 30 wt% of other inorganic binders, based on the dry basis of the catalyst, the other inorganic binders including at least one of pseudoboehmite, alumina sol, silica alumina sol and water glass.

17. The method according to claim 7, wherein the Y-type molecular sieve comprises at least one of a PSRY molecular sieve, a PSRY molecular sieve containing rare earth, a USY molecular sieve containing rare earth, a REY molecular sieve, a REHY molecular sieve and an HY molecular sieve.

18. The method of claim 7, wherein the method further comprises: washing and optionally drying the product obtained by roasting to obtain the catalytic cracking catalyst; wherein the roasting temperature of the first roasting treatment is 300-650 ℃, and the roasting time is 0.5-12 h.

19. The method of claim 7, further comprising preparing the first clay-containing aluminophosphate inorganic binder by: pulping an alumina source, the first clay and water to disperse into slurry with solid content of 5-48 wt%; wherein the alumina source is aluminum hydroxide and/or aluminum oxide which can be peptized by acid, relative to 15-40 part by weight of Al₂O₃(ii) an alumina source in an amount greater than 0 parts by weight and not greater than 40 parts by weight of the first clay on a dry basis; adding concentrated phosphoric acid to the slurry in a weight ratio of P/Al to 1-6 with stirring, and reacting the resulting mixed slurry at 50-99 ℃ for 15-90 minutes; in the P/Al, P is the weight of phosphorus in the phosphoric acid in terms of simple substance, and Al is the weight of aluminum in the alumina source in terms of simple substance.

20. A catalytic cracking catalyst prepared by the method of any one of claims 7 to 19.

21. Use of a catalytic cracking catalyst according to any one of claims 1 to 6 or 20.

22. The method of application according to claim 21, comprising: under the catalytic cracking reaction condition, the hydrocarbon oil is in contact reaction with the catalytic cracking catalyst, wherein the catalytic cracking reaction condition comprises the following steps: the reaction temperature is 500-800 ℃.

23. The use method according to claim 22, wherein the hydrocarbon oil is selected from one or more of crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric wax oil, vacuum wax oil, straight-flow wax oil, propane light/heavy deoiled, coker wax oil and coal liquefaction product.