CN114425430B - Catalytic cracking catalyst - Google Patents

Abstract

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

Description

Catalytic cracking catalyst

Technical field

The present invention relates to a catalytic cracking catalyst, and more specifically, the invention relates to a catalytic cracking catalyst containing Y-type molecular sieve and ZSM-5 molecular sieve.

Background technique

MFI structural molecular sieves, including ZSM-5 molecular sieves, are a widely used zeolite molecular sieve catalytic material developed by the American Mobil Company in 1972. This molecular sieve has a three-dimensional intersecting pore structure. The pores along the a-axis are straight pores with a cross-sectional size of 0.54×0.56nm, which is approximately circular. The pores along the b-axis are Z-shaped pores with a cross-sectional size of 0.51×0.56. nm, is an ellipse. Its pore is composed of ten-membered rings, and its size is between small-pore zeolite and large-pore zeolite. Therefore, this type of molecular sieve has unique shape-selective catalytic effect. It has a unique pore 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 low carbon content. , is widely used as catalyst and catalyst carrier, and has been successfully used in production processes such as alkylation, isomerization, disproportionation, catalytic cracking, methanol to gasoline, and methanol to olefins. This molecular sieve is introduced into catalytic cracking and catalytic cracking of carbon tetrahydrocarbons, showing excellent catalytic performance, and its molecular shape selectivity can be used to greatly increase the yield of low-carbon olefins.

Since 1983, ZSM-5 molecular sieve has been used in the catalytic cracking process as a catalytic cracking octane additive, aiming to improve the octane number of catalytic cracking gasoline and the selectivity of low-carbon olefins. US3758403 was the first to report the use of ZSM-5 as an active component to increase propylene production, that is, ZSM-5 and REY were used together as active components to prepare an FCC catalyst. US5997728 discloses the use of ZSM-5 molecular sieve as an additive to increase propylene production without any modification of the molecular sieve. The propylene yields of the above two technologies are not high. Although ZSM-5 molecular sieve has good shape-selective properties and isomerization properties, its shortcoming is poor hydrothermal stability and easy deactivation under harsh high-temperature hydrothermal conditions, which reduces catalytic performance.

In the 1980s, Mobil Company discovered that phosphorus could improve the hydrothermal stability of ZSM-5 molecular sieve. At the same time, phosphorus modified the ZSM-5 molecular sieve to increase the yield of low-carbon olefins. Conventional additives typically contain phosphorus-activated ZSM-5, which selectively converts primary cracking products (such as gasoline olefins) into C3 and C4 olefins. ZSM-5 molecular sieve is modified with an appropriate amount of inorganic phosphorus compounds after synthesis, which can stabilize the skeleton aluminum under harsh hydrothermal conditions.

A method for modifying ZSM-5 molecular sieve with phosphorus is disclosed in CN 106994364 A. The method is to first use one or more phosphorus-containing materials selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate. The compound is mixed with a ZSM-5 molecular sieve with a high alkali metal ion content to obtain a mixture with a phosphorus loading of at least 0.1 wt% calculated as P ₂ O ₅ . The mixture is dried, roasted, and then subjected to an ammonium salt step and a water washing step, so that The alkali metal ion content is reduced to less than 0.10wt%, and then undergoes drying and hydrothermal aging steps at 400-1000°C and 100% water vapor. The phosphorus-containing ZSM-5 molecular sieve obtained by this method has a high total acid content, excellent cracking conversion rate and propylene selectivity, and also has a high liquefied gas yield.

A method for modifying hierarchical pore ZSM-5 molecular sieve is disclosed in CN1506161A. The method includes following the conventional steps: synthesis → filtration → ammonium exchange → drying → roasting to obtain hierarchical pore ZSM-5 molecular sieve, and then The hierarchical pore ZSM-5 molecular sieve is modified with phosphoric acid, and then dried and roasted to obtain the phosphorus-modified hierarchical pore ZSM-5 molecular sieve. Among them, the P ₂ O ₅ holding amount is usually in the range of 1 to 7 wt%. However, phosphoric acid or ammonium phosphate salts will self-aggregate to form phosphorus species in different aggregate states during the roasting process. During the hydrothermal treatment, only the phosphate radicals entering the pores interact with the skeleton aluminum to retain the B acid center, reducing the distribution of phosphorus species.

Although using an appropriate amount of inorganic phosphide to modify the ZSM-5 molecular sieve can slow down the dealumination of the skeleton and improve the hydrothermal stability, the phosphorus atoms will combine with the twisted four-coordinate skeleton aluminum to form a weak B acid center, thereby achieving a higher It has high conversion rate of cracking long-chain alkanes and high selectivity of light olefins. However, excessive inorganic phosphide used to modify ZSM-5 molecular sieve will block the pores of the molecular sieve, reduce the pore volume and specific surface area, and Occupy a large number of strong B acid centers. Moreover, in the existing technology, during the roasting process, phosphoric acid or ammonium phosphate salts will self-aggregate to form phosphorus species in different aggregate states. The coordination between phosphorus and skeleton aluminum is insufficient, the utilization efficiency of phosphorus is low, and phosphorus modification is not always achieved. Satisfactory hydrothermal stability improvement results. Therefore, there is an urgent need for new technologies to promote the coordination of phosphorus and framework aluminum, improve the hydrothermal stability of phosphorus-modified ZSM-5 molecular sieves, and further improve the cracking activity.

Contents of the invention

One of the purposes of the present invention is to provide a catalytic cracking catalyst based on phosphorus-modified ZSM-5 molecular sieve with better hydrothermal stability as one of the active components; the second purpose is to provide a preparation method of the catalytic cracking catalyst ; The third purpose is to provide the application of the catalytic cracking catalyst in the catalytic cracking reaction of petroleum hydrocarbons, so as to obtain excellent cracking conversion rate and low carbon olefin yield, and at the same time have a high liquefied gas yield.

In order to achieve one of the above objects, the catalytic cracking catalyst provided by the first aspect of the present invention is characterized in that, based on the dry basis of the catalytic cracking catalyst, the catalytic cracking catalyst contains 1-25% by weight on a dry basis. Y-type molecular sieve, 5-50% by weight of phosphorus-modified ZSM-5 molecular sieve on a dry basis, 1-60% by weight of an inorganic binder on a dry basis and optionally 0-60% by weight on a dry basis. The second clay, wherein the phosphorus-modified ZSM-5 molecular sieve, in ²⁷ Al MAS-NMR, the ratio of the resonance signal peak area with a chemical shift of 39±3ppm and the resonance signal peak area with a chemical shift of 54ppm±3ppm is ≥1 , the inorganic binder includes phosphorus aluminum inorganic binder and/or other inorganic binders.

Preferably, the Y-type molecular sieve includes PSRY molecular sieve, PSRY-S molecular sieve, rare earth-containing PSRY molecular sieve, rare earth-containing PSRY-S molecular sieve, USY molecular sieve, rare earth-containing USY molecular sieve, REY molecular sieve, REHY molecular sieve and HY molecular sieve. At least one.

Preferably, in ^{the 27} Al MAS-NMR of the phosphorus-modified ZSM-5 molecular sieve, the ratio of the resonance signal peak area with a chemical shift of 39±3ppm and the resonance signal peak area with a chemical shift of 54ppm±3ppm is ≥1, and the preferred ratio is ≥10, and a more preferred ratio is 12-25.

In the surface XPS elemental analysis of the phosphorus-modified ZSM-5 molecular sieve, n1/n2≤0.1, preferably n1/n2≤0.09, more preferably n1/n2≤0.08, most preferably n1/n2 is 0.04~0.07, n1 represents The number of moles of phosphorus, n2 represents the total number of moles of silicon and aluminum.

The phosphorus-modified ZSM-5 molecular sieve, after hydrothermal aging at 800°C and 100% water vapor for 17 hours, in its NH3-TPD spectrum, the peak area of the strong acid center with a desorption temperature above 200°C accounts for the total acid The specific gravity of the central peak area is ≥40%, the preferred specific gravity is ≥42%, the more preferred specific gravity is ≥45%, and the most preferred specific gravity is 48% to 85%.

For the phosphorus-modified ZSM-5 molecular sieve, when phosphorus and aluminum are measured in moles, the ratio between the two is 0.01 to 2, the preferred ratio is 0.1 to 1.5, and the more preferred ratio is 0.2 to 1.5.

In order to achieve the second of the above objectives, the invention provides a method for preparing a catalytic cracking catalyst, which method includes: mixing Y-type molecular sieve, phosphorus-modified ZSM-5 molecular sieve and inorganic binder, and spray drying, and optionally Roasting treatment is performed to obtain the catalytic cracking catalyst; wherein, the second clay is added or not added to the mixing; on a dry basis, the Y-type molecular sieve, the phosphorus-containing modified ZSM-5 molecular sieve, the The weight ratio of the inorganic binder and the second clay is (1-25): (5-50): (1-60): (0-60); the inorganic binder includes phosphorus aluminum inorganic Binders and/or other inorganic binders; the phosphorus-modified ZSM-5 molecular sieve is made by contacting a phosphorus-containing compound solution with the HZSM-5 molecular sieve, and after drying, external pressure is applied and water is added externally. It is obtained by performing hydrothermal roasting treatment and recovering the product in an atmospheric environment; the contact is made by using an impregnation method to make the aqueous solution of the phosphorus-containing compound with a temperature of 0 to 150°C and the HZSM-5 molecular sieve of 0 to 150°C at basically the same temperature. Mix and contact with water for at least 0.1 hours, or the contact is to mix and beat the phosphorus-containing compound, HZSM-5 molecular sieve and water and then maintain it at 0-150°C for at least 0.1 hours; the apparent pressure of the described atmosphere is 0.01~1.0Mpa and containing 1~100% water vapor.

The phosphorus-containing compound is selected from organic phosphide and/or inorganic phosphide. The organic phosphorus compound is selected from the group consisting of trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphine bromide, tetrabutyl phosphine chloride, tetrabutyl phosphorus hydroxide, triphenylethyl bromide Phosphate, triphenylbutylphosphonium bromide, triphenylbenzylphosphorus bromide, hexamethylphosphoric triamide, dibenzyldiethylphosphonium, 1,3-xylenebistriethylphosphonium; The inorganic phosphide is selected from the group consisting of phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and boron phosphate.

In the HZSM-5 molecular sieve, Na ₂ O <0.1wt%.

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

The contact and water to sieve weight ratio are 0.5 to 1, and the contact is carried out at 50 to 150°C, preferably 70 to 130°C for 0.5 to 40 hours.

The apparent pressure of the described atmosphere is 0.1-0.8Mpa, preferably 0.3-0.6Mpa, and contains 30%-100% water vapor, preferably 60-100% water vapor; the hydrothermal roasting treatment is performed at 200 ~800°C, preferably 300-500°C.

The binder is a phosphorus aluminum inorganic binder and/or other inorganic binders. Preferably, the binder is preferably a phosphorus aluminum inorganic binder, and more preferably is a phosphorus aluminum glue and/or a phosphorus aluminum inorganic binder containing the first clay; with the first clay-containing phosphorus aluminum Based on the dry weight of the inorganic binder, the first clay-containing phosphorus aluminum inorganic binder contains 15-40 wt% aluminum component as Al ₂ O ₃ and 45-80 wt % as P ₂ O ₅ The phosphorus component and the first clay is greater than 0 and not more than 40% by weight on a dry basis, and the P/Al weight ratio of the first clay-containing phosphorus aluminum inorganic binder is 1.0-6.0, and the pH is 1- 3.5, the solid content is 15-60% by weight; the first clay includes at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomite. The other inorganic binder includes at least one of pseudo-boehmite, aluminum sol, silica-alumino sol and water glass. The second clay is at least one selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, halloysite, hydrotalcite, bentonite and diatomite.

Preferably, based on the dry basis of the catalytic cracking catalyst, it contains 3-40% by weight of phosphorus aluminum inorganic binder on a dry basis basis or 3-40% by weight of phosphorus aluminum inorganic binder and 1- 30% by weight of other inorganic binders.

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

The preparation method provided by the invention also includes: washing and optionally drying the product obtained by the roasting to obtain the catalytic cracking catalyst; wherein the roasting temperature of the first roasting process is 300-650°C, and the roasting time It is 0.5~12h.

Preferably, the preparation method of the present invention also includes the following steps to prepare the phosphorus aluminum inorganic binder containing the first clay: slurry the alumina source, the first clay and water to disperse the solid content to 5-48 wt. % slurry; wherein the alumina source is aluminum hydroxide and/or alumina that can be peptized by acid, relative to 15 to 40 parts by weight of the alumina source calculated as Al ₂ O ₃ , on a dry basis The dosage of the first clay is greater than 0 parts by weight and not more than 40 parts by weight; add concentrated phosphoric acid to the slurry according to the weight ratio of P/Al=1-6 under stirring, and make the resulting mixed slurry at 50- React at 99°C for 15-90 minutes; in P/Al, P is the weight of phosphorus in phosphoric acid in terms of elemental substance, and Al is the weight of aluminum in the alumina source in terms of elemental substance.

In order to achieve the third of the above objects, the present invention provides an application method of a catalytic cracking catalyst, which includes contacting and reacting hydrocarbon oil with the catalytic cracking catalyst under catalytic cracking reaction conditions, wherein the catalytic cracking reaction conditions include: a reaction temperature of 500-800℃. The hydrocarbon oil is selected from crude oil, naphtha, gasoline, atmospheric residual oil, vacuum residual oil, atmospheric wax oil, vacuum wax oil, DC wax oil, propane light/heavy deoiling, coking wax oil and coal One or more of the liquefied products.

The catalytic cracking catalyst provided by the invention contains a phosphorus-modified ZSM-5 molecular sieve with special physical and chemical parameters. The molecular sieve and the Y-type molecular sieve jointly serve as the active component of the catalyst and have a high cracking conversion rate in the catalytic cracking reaction of hydrocarbon oil. And it has the characteristics of high yield of low carbon olefins and liquefied gas.

Description of the drawings

Figure 1 is the ²⁷ Al MAS-NMR spectrum of the phosphorus-modified ZSM-5 molecular sieve sample PSZ1-1 in the catalytic cracking catalyst of the present invention.

Figure 2 is the NH ₃ -TPD spectrum of the phosphorus-modified ZSM-5 molecular sieve sample PSZ1-1 in the catalytic cracking catalyst of the present invention after hydrothermal aging at 800°C, 100% water vapor conditions for 17 hours.

Figure 3 shows the ²⁷ Al MAS-NMR spectrum of the phosphorus-modified ZSM-5 molecular sieve comparison sample DBZ1-1.

Figure 4 shows the NH ₃ -TPD spectrum of the phosphorus-modified ZSM-5 molecular sieve comparison sample DBZ1-1 after hydrothermal aging at 800°C, 100% water vapor conditions for 17 hours.

Detailed ways

The catalytic cracking catalyst of the present invention is characterized in that, based on the dry basis of the catalytic cracking catalyst, the catalytic cracking catalyst contains 1-25% by weight of Y-type molecular sieve on a dry basis, 5-50% by weight on a dry basis. % by weight of phosphorus modified ZSM-5 molecular sieve, 1-60% by weight of inorganic binder on a dry basis and optionally added 0-60% by weight of a second clay on a dry basis, wherein the phosphorus Modified ZSM-5 molecular sieve, in ²⁷ Al MAS-NMR, the ratio of the resonance signal peak area with a chemical shift of 39±3ppm and the resonance signal peak area with a chemical shift of 54ppm±3ppm is ≥1, and the inorganic binder includes phosphorus aluminum inorganic Binders and/or other inorganic binders.

In the catalytic cracking catalyst (hereinafter abbreviated as catalyst) provided by the invention, the Y-type molecular sieve preferably includes PSRY molecular sieve, rare earth-containing PSRY molecular sieve, USY molecular sieve, rare earth-containing USY molecular sieve, REY molecular sieve, REHY molecular sieve and HY At least one type of molecular sieve.

In the catalyst provided by the invention, in the phosphorus-modified ZSM-5 molecular sieve, in ²⁷ Al MAS-NMR, the ratio of the resonance signal peak area with a chemical shift of 39±3ppm and the resonance signal peak area with a chemical shift of 54ppm±3ppm is ≥1 , preferably ≥5, more preferably ≥10, and the most preferred ratio is 12-25.

Further, in the catalyst of the present invention, the phosphorus-modified ZSM-5 molecular sieve, in surface XPS elemental analysis, n1/n2≤0.1, where n1 represents the number of moles of phosphorus, n2 represents the total number of moles of silicon and aluminum, Preferably, n1/n2≤0.09, more preferably, n1/n2≤0.08, most preferably, n1/n2 is 0.04~0.07; this characterization parameter indicates the reduction of surface phosphorus species content in the molecular sieve, and also indicates the orientation of surface phosphorus species. The molecular sieve bulk phase migrates more, that is, the value of n1/n2 illustrates the dispersion effect of phosphorus species on the molecular sieve surface and the degree of migration from the ZSM-5 molecular sieve surface to the crystal. The smaller the value, the smaller the surface phosphorus species content, the phosphorus species. The species are well dispersed and have a high degree of inward migration, resulting in better hydrothermal stability of the molecular sieve.

Furthermore, in the catalyst of the present invention, the phosphorus-modified ZSM-5 molecular sieve, after hydrothermal aging at 800°C and 100% water vapor for 17 hours, has a desorption temperature of 200°C in its NH ₃ -TPD spectrum. The proportion of the above strong acid center peak area to the total acid center peak area is ≥40%, which shows that after 17 hours of hydrothermal aging at 800°C and 100% water vapor, it has a higher retention of strong acid centers, and thus the molecular sieve has a higher cracking ability active. Preferably, the specific gravity is ≥42%, more preferably, the specific gravity is ≥45%, and most preferably, the specific gravity is 48% to 85%.

In the catalyst of the present invention, the phosphorus content in the phosphorus-modified ZSM-5 molecular sieve, when both phosphorus and aluminum are measured in moles, the ratio between the two is 0.01 to 2; preferably, the ratio between the two is 0.1 to 1.5 ; More preferably, the ratio between the two is 0.2 to 1.5.

In the catalytic cracking catalyst of the present invention, clay is well known to those skilled in the art. The second clay can be selected from kaolin, metakaolin, diatomaceous earth, sepiolite, attapulgite, montmorillonite and rectorite. At least one, preferably one of kaolin, metakaolin and rectorite. Based on the total weight of the catalyst, 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.

In a specific embodiment of the catalyst of the present invention, on a dry basis, the catalyst includes 5-35% by weight of phosphorus aluminum inorganic binder, 1.5-20% by weight of Y-type molecular sieve, 10-45% by weight of Phosphorus modified ZSM-5 molecular sieve, 10-50% by weight of second clay and 5-28% by weight of other inorganic binders.

The invention also provides a preparation method of the catalyst, which method includes: mixing Y-type molecular sieve, phosphorus-modified ZSM-5 molecular sieve and inorganic binder, spray-drying, and optionally performing roasting treatment , to obtain the catalytic cracking catalyst; wherein, the second clay is added or not added to the mixing; on a dry basis, the Y-type molecular sieve, the phosphorus-modified ZSM-5 molecular sieve, the inorganic binder The weight ratio to the second clay is (1-25): (5-50): (1-60): (0-60); the inorganic binder includes phosphorus aluminum inorganic binder and/ or other inorganic binders; the phosphorus-modified ZSM-5 molecular sieve described therein is prepared by the following steps: contact the phosphorus-containing compound solution with the HZSM-5 molecular sieve, and after drying, apply external pressure and external It is obtained by performing hydrothermal roasting treatment and recovering the product in an atmosphere with added water; the contact is achieved by using an impregnation method to make an aqueous solution of a phosphorus-containing compound at a temperature of 0 to 150°C and a HZSM-5 molecular sieve of 0 to 150°C in a basic state. Mix and contact at the same temperature for at least 0.1 hours, or the contact is to mix and beat the phosphorus-containing compound, HZSM-5 molecular sieve and water and maintain it at 0 to 150°C for at least 0.1 hours; the described atmosphere environment, its surface The apparent pressure is 0.01~1.0Mpa and contains 1~100% water vapor.

The preparation steps used in the phosphorus-modified ZSM-5 molecular sieve promote the migration of surface phosphorus species to the bulk phase of the ZSM-5 molecular sieve; the phosphorus and the skeleton aluminum are fully coordinated, the skeleton aluminum is fully protected, and the molecular sieve has excellent hydrothermal stability sex.

In the preparation steps used in the phosphorus-modified ZSM-5 molecular sieve, the HZSM-5 molecular sieve is obtained by reducing the sodium of the microporous ZSM-5 molecular sieve through ammonium exchange to Na ₂ O <0.1wt%, and the silicon-aluminum ratio (oxidation The molar ratio of silicon to alumina (the same below) ranges from ≥10, usually between 10 and 200.

In the preparation steps used in the phosphorus-modified ZSM-5 molecular sieve, the phosphorus-containing compound is selected from organic phosphide and/or inorganic phosphide. The organic phosphorus compound is selected from the group consisting of trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphine bromide, tetrabutyl phosphine chloride, tetrabutyl phosphorus hydroxide, triphenylethyl bromide Phosphate, triphenylbutylphosphonium bromide, triphenylbenzylphosphorus bromide, hexamethylphosphoric triamide, dibenzyldiethylphosphonium, 1,3-xylenebistriethylphosphonium, so The inorganic phosphide is selected from the group consisting of 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 method of contact is to use an impregnation method to make an aqueous solution of a phosphorus-containing compound at a temperature of 0 to 150°C and HZSM-5 at a temperature of 0 to 150°C. The molecular sieves are contacted at substantially the same temperature for at least 0.1 hours. For example, the contact can be carried out in the normal temperature range of 0 to 30°C, preferably in a higher temperature range of 40°C or above, such as 50 to 150°C, more preferably 70 to 130°C, in order to obtain better The effect is that the phosphorus species are better dispersed, and the phosphorus is more likely to migrate into the HZSM-5 molecular sieve crystal and combine with the framework aluminum, further improving the coordination degree of phosphorus and the framework aluminum, and ultimately contributing to the improvement of the hydrothermal stability of the molecular sieve. The substantially same temperature means that the temperature difference between the respective temperatures of the aqueous solution of the phosphorus-containing compound and the HZSM-5 molecular sieve is ±5°C. For example, the temperature of the aqueous solution containing phosphorus compounds is 80°C, and the HZSM-5 molecular sieve needs to be heated to 75~85°C.

In the preparation steps of the phosphorus-modified ZSM-5 molecular sieve, the second method of contact is to mix the phosphorus-containing compound, the HZSM-5 molecular sieve and water and then maintain the mixture at 0 to 150°C for at least 0.1 hour. For example, after mixing, it is maintained at a normal temperature range of 0 to 30°C for at least 0.1 hours. Preferably, in order to obtain better results, that is, to achieve better dispersion of phosphorus species, phosphorus can more easily migrate into the molecular sieve crystals and combine with the framework aluminum, In order to further improve the coordination degree of phosphorus and framework aluminum, and ultimately improve the hydrothermal stability of the molecular sieve, the phosphorus-containing compound, HZSM-5 molecular sieve and water are mixed to maintain a temperature range of 0.1 in a higher temperature range above 40°C. hours, for example, in the temperature range of 50 to 150°C, more preferably in the temperature range of 70 to 130°C.

In the preparation steps used for the phosphorus-modified ZSM-5 molecular sieve, when the phosphorus-containing compound is measured as phosphorus and the HZSM-5 molecular sieve is measured as aluminum, the molar ratio between the two is 0.01 to 2; preferably, the molar ratio between the two is 0.1～1.5; more preferably, the molar ratio between the two is 0.2～1.5. In the described contact, the weight ratio of water to sieve is 0.5 to 1, and the preferred contact time is 0.5 to 40 hours.

In the preparation steps of the phosphorus-modified ZSM-5 molecular sieve, the hydrothermal roasting treatment is performed in an atmosphere with external pressure and external water added. The described atmospheric environment is obtained by externally applying pressure and externally applying water. The preferred superficial pressure is 0.1 to 0.8MPa, more preferably the superficial pressure is 0.3 to 0.6MPa, and preferably contains 30 to 100% water vapor, and more preferably contains 60~100% water vapor. The external pressure refers to applying a certain pressure from the outside during the hydrothermal roasting process of the prepared materials. For example, it can be carried out by introducing inert gas from the outside to maintain a certain back pressure. The amount of externally added water shall be such that the atmosphere contains 1 to 100% water vapor. The hydrothermal roasting treatment step is carried out at 200-800°C, preferably 300-500°C.

The catalyst of the present invention preferably contains 3-40% by weight of phosphorus-aluminum inorganic binder or 3-40% by weight of phosphorus-aluminum inorganic binder based on the dry basis of the catalyst. agent and 1-30% by weight of other inorganic binders.

The phosphorus aluminum inorganic binder is phosphorus aluminum glue and/or a phosphorus aluminum inorganic binder containing the first clay; based on the dry basis weight of the phosphorus aluminum inorganic binder containing the first clay, the phosphorus aluminum inorganic binder containing the first clay is used as the basis. The phosphorus aluminum inorganic binder of the first clay contains an aluminum component of 15-40% by _weight as _Al2O3 , a phosphorus component of _45-80 % by weight as _P2O5 and is greater than 0 and not More than 40% by weight of the first clay, and the P/Al weight ratio of the first clay-containing phosphorus aluminum inorganic binder is 1.0-6.0, the pH is 1-3.5, and the solid content is 15-60% by weight; The first clay includes 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 the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, halloysite, hydrotalcite, bentonite and diatomaceous earth.

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

The preparation method of the catalytic cracking catalyst also includes: subjecting the product obtained by spray drying to first roasting, washing and optional drying to obtain the catalyst; wherein the roasting temperature of the first roasting is 300-650 ℃, the roasting time is 0.5-8h; the temperature of the drying treatment is 100-200℃, and the drying time is 0.5-24h.

In the preparation method of the catalytic cracking catalyst, the method may further include preparing the phosphorus aluminum inorganic binder containing the first clay by using the following steps: slurrying the alumina source, the first clay and water to form a solid content. It is a slurry of 5-48% by weight; wherein the alumina source is aluminum hydroxide and/or alumina that can be peptized by acid, relative to 15-40 parts by weight of the alumina source calculated as Al ₂ O ₃ , the amount of the first clay on a dry basis is greater than 0 parts by weight and not more than 40 parts by weight; add concentrated phosphoric acid to the slurry according to the weight ratio of P/Al=1-6 under stirring, and make the resulting The mixed slurry is reacted at 50-99°C for 15-90 minutes; in P/Al, P is the weight of phosphorus in phosphoric acid in terms of elemental substance, and Al is the weight of aluminum in the alumina source in terms of elemental substance.

A specific embodiment of the phosphorus-aluminum inorganic binder in the present invention, based on the dry weight of the phosphorus-aluminum inorganic binder, preferably contains 15-35% by weight of aluminum based on Al ₂ O ₃ 50-75% by weight of _the phosphorus component as _P2O5 and 8-35% by weight of the first clay on a dry basis, and its P/Al weight ratio is preferably 1.2-6.0, more preferably 2.0 -5.0, the pH value is preferably 2.0-3.0. Another specific embodiment of the phosphorus-aluminum inorganic binder in the present invention is based on the dry weight of the phosphorus-aluminum inorganic binder. The phosphorus-aluminum inorganic binder includes Al ₂ O ₃ 20-40% by weight of the aluminum component and 60-80% by weight of _the phosphorus component as _P2O5 .

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

In a specific embodiment of the preparation method provided by the present invention, an inorganic binder (such as pseudo-boehmite, aluminum sol, silica sol, silica-alumino gel or a mixture of two or more thereof) can be mixed with the third Diclay (such as kaolin) and water (such as deoxygenated ionized water and/or deionized water) are mixed to form a slurry with a solid content of 10 to 50% by weight, stir evenly, and use inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid to slurry. Adjust the pH of the slurry to 1 to 4, maintain the pH value, and let it stand and age at 20 to 80°C for 0 to 2 hours, for example, after 0.3 to 2 hours, add aluminum sol and/or silica sol, and stir for 0.5 to 1.5 hours to form a colloid. Then add molecular sieves, which include the phosphorus-modified ZSM-5 molecular sieve and Y-type molecular sieve, to form a catalyst slurry. The solid content of the catalyst slurry is, for example, 20 to 45% by weight. The catalyst slurry is continuously stirred and then spray-dried to prepare a microsphere catalyst. The microsphere catalyst is then calcined, for example, at 350 to 650°C or 400 to 600°C, preferably 450 to 550°C for 0.5 to 6 hours or 0.5 to 2 hours, and then washed with ammonium sulfate (wherein, the washing temperature can be at 40 to 70°C , ammonium sulfate: microsphere catalyst: water = 0.2~0.8:1:5~15 weight ratio) until the sodium oxide content is less than 0.25% by weight, wash with water and filter, and then dry.

In another specific embodiment of the preparation method provided by the present invention, Y-type molecular sieve and phosphorus-modified ZSM-5 molecular sieve, phosphorus aluminum inorganic binder and other inorganic binders can be mixed, with or without adding a second clay , beating, spray drying.

The inorganic binder includes the phosphorus aluminum inorganic binder and the other inorganic binders. The weight ratio of the phosphorus aluminum inorganic binder and the other inorganic binders can be (3 -40): (1-30), preferably (5-35): (5-28), further preferably (10-30): (5-25); wherein the phosphorus aluminum inorganic binder can be Phosphorus aluminum glue and/or phosphorus aluminum inorganic binder containing the first clay; the other inorganic binders may include at least one of pseudo-boehmite, aluminum sol, silica-alumina sol and water glass.

The preparation method of the catalytic cracking catalyst of the present invention can mix and beat the phosphorus-containing modified ZSM-5 molecular sieve, phosphorus aluminum inorganic binder and other inorganic binders. There is no special requirement for the order of adding the materials. For example, phosphorus aluminum can be Inorganic binders, other inorganic binders, molecular sieves, and second clay are mixed (when the second clay is not included, the relevant adding steps can be omitted) and beaten. Preferably, the second clay, molecular sieves, and other inorganic binders are first mixed. The phosphorus-aluminum inorganic binder is added after the binder is mixed and beaten, which is beneficial to improving the activity and selectivity of the catalyst.

The preparation method of the catalytic cracking catalyst of the present invention also includes the step of spray drying the slurry obtained by the beating. The method of spray drying is well known to those skilled in the art, and there are no special requirements in this disclosure.

Further, the method of the present invention may also include preparing the phosphate-aluminum inorganic binder containing the first clay by using the following steps: slurry the alumina source, the first clay and water to disperse the solid content to 5-48 wt. % slurry; wherein the alumina source is aluminum hydroxide and/or alumina that can be peptized by acid, relative to 15 to 40 parts by weight of the alumina source calculated as Al ₂ O ₃ , on a dry basis The dosage of the first clay is greater than 0 parts by weight and not more than 40 parts by weight; add concentrated phosphoric acid to the slurry according to the weight ratio of P/Al=1-6 under stirring, and make the resulting mixed slurry at 50- React at 99°C for 15-90 minutes; in P/Al, P is the weight of phosphorus in phosphoric acid in terms of elemental substance, and Al is the weight of aluminum in the alumina source in terms of elemental substance. The alumina source may be selected from the group consisting of rho-alumina, x-alumina, eta-alumina, γ-alumina, κ-alumina, σ-alumina, θ-alumina, gibbsite, and At least one of almanite, nordiaspore, diaspore, boehmite and pseudo-boehmite, the aluminum component in the first clay-containing phosphoaluminum inorganic binder is derived from the Alumina source. The first clay may be classified into one or more types of high alumina, sepiolite, attapulgite, rectorite, montmorillonite and diatomite, preferably rectorite. The concentration of the concentrated phosphoric acid may be 60-98% by weight, more preferably 75-90% by weight. The feeding rate of phosphoric acid is preferably 0.01-0.10kg phosphoric acid/minute/kg alumina source, and more preferably 0.03-0.07kg phosphoric acid/minute/kg alumina source.

In the above embodiment, the introduction of the first clay-containing phosphorus aluminum inorganic binder not only improves the mass transfer and heat transfer between materials during the preparation process, but also avoids uneven local instantaneous violent reactions of the materials. When the binder is fixed due to exothermic super-stability, the bonding performance of the obtained binder is equivalent to that of the phosphorus-aluminum binder prepared by the method without introducing clay; and this method introduces clay, especially the retort with layered structure. Soil improves the heavy oil conversion ability of the catalyst, making the resulting catalyst more selective.

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

The invention further provides a method for catalytic cracking of hydrocarbon oil. When used in the catalytic cracking process, in a specific embodiment, the catalytic cracking catalyst can be added separately to the catalytic cracking reactor, for example, under catalytic cracking conditions, the hydrocarbon oil is contacted and reacted with the catalytic cracking catalyst of the present invention; used for In another specific embodiment of the catalytic cracking process, the catalyst can be mixed with a catalytic cracking catalyst. For example, the hydrocarbon oil can 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 present invention may account for no more than 30% by weight of the total amount of the above mixture, preferably 1-25% by weight, more preferably 3-15% by weight. The catalytic cracking catalyst provided by the present invention can be used for various hydrocarbon oil catalysis lysis. The hydrocarbon oil can be selected from various petroleum fractions, such as crude oil, naphtha, catalytic gasoline, atmospheric residual oil, vacuum residual oil, atmospheric wax oil, vacuum wax oil, DC wax oil, propane light/heavy One or more of deoiling, coking wax oil and coal liquefaction products. The hydrocarbon oil may contain heavy metal impurities such as nickel and vanadium as well as sulfur and nitrogen impurities. For example, the sulfur content in the hydrocarbon oil may be as high as 3.0% by weight, the nitrogen content may be as high as 2.0% by weight, and the content of metal impurities such as vanadium and nickel may be as high as 3000 ppm.

In the hydrocarbon oil catalytic cracking method of the present invention, the catalytic cracking conditions can be conventional in the art, and preferably include: reaction temperature of 500 to 800°C, such as 550 to 680°C. The hydrocarbon oil used can be selected from crude oil, naphtha, gasoline, atmospheric residual oil, vacuum residual oil, atmospheric wax oil, vacuum wax oil, direct flow wax oil, propane light/heavy deoiling, coking wax oil and One or more of the coal liquefaction products.

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

X-ray diffraction (XRD) spectra were measured on a Japanese Rigaku TTR-3 powder X-ray diffractometer. Instrument parameters: copper target (tube voltage 40kV, tube current 250mA), scintillation counter, step width 0.02°, scan rate 0.4(°)/min. The ZSM-5 molecular sieve synthesized by the method of Example 1 in CN1056818C was used as a standard sample, and its crystallinity was set as 100%. The relative crystallinity is expressed as a percentage by the sum of the peak areas of five characteristic diffraction peaks with 2θ between 22.5 and 25.0° in the X-ray diffraction spectrum of the obtained product and the standard sample.

²⁷ Al MAS-NMR spectrum analysis was measured on a Bruker AVANCE III 600WB spectrometer. Instrument parameters: rotor diameter 4mm, resonance spectrum 156.4MHz, pulse width 0.4μs (corresponding to 15° chamfering angle), magic angle rotation speed 12kHz, delay time 1s. ²⁷ Al MAS-NMR spectrum characteristics, characteristic peak 1 at 54±3ppm is attributed to four-coordinated framework aluminum, and characteristic peak 2 at 39±3ppm is attributed to phosphorus-stabilized framework aluminum (twisted four-coordinated framework aluminum). The area of each peak was calculated using the integration method after performing peak split fitting on the characteristic peaks.

X-ray photoelectron spectroscopy (XPS) was used to analyze the surface of the molecular sieve and examine the migration of phosphorus compounds, using the ESCALAB 250 X-ray photoelectron spectrometer of Thermo Fisher-VG Company. Instrument parameters: The excitation source is monochromated AlKα X-ray with a power of 150W, and the charge shift is corrected by the C1s peak (284.8eV) from contaminated carbon.

Temperature programmed desorption analysis (NH ₃ -TPD) was used for characterization using Micromeritics' AutoChenⅡ temperature programmed adsorption instrument. Weigh 0.1~0.2g of the sample, put it into a quartz adsorption tube, pass in the carrier gas (high purity He. Flow rate 50mL/min), raise it to 600℃ at a rate of 20℃/min, keep the temperature constant for 2h, and remove the adsorbed gas on the sample. Water and air; reduce to 100°C at a rate of 20°C/min and keep the temperature constant for 30 minutes; switch the carrier gas to NH ₃ -He mixed gas and keep the temperature constant for 30 minutes to allow the sample to absorb ammonia to reach saturation; switch the NH ₃ -He mixed gas to High-purity He carrier gas was purged for 1 hour to adsorb ammonia using desorption force; then the temperature was raised to 600°C at a rate of 10°C/min to obtain a programmed temperature-increasing desorption curve. The desorbed ammonia is detected using a thermal conductivity cell. After converting the programmed temperature desorption curve into an NH ₃ desorption rate-temperature curve, the acid center density data was obtained by analyzing the peak shape.

Unless otherwise specified, the instruments and reagents used in the examples of the present invention are all commonly used by those skilled in the art.

A micro-reaction device is used to evaluate the impact of the catalytic cracking aid of the present invention on the yield of light olefins in the catalytic cracking of petroleum hydrocarbons. The prepared catalytic cracking additive sample was aged at 800°C and 100% water vapor for 17 hours on a fixed bed aging device, and then evaluated on a micro-reaction device. The raw material oil was VGO or naphtha, and the evaluation conditions were a reaction temperature of 620°C. , regeneration temperature 620℃, agent-oil ratio 3.2. Microreactive activity was measured using the ASTM D5154-2010 standard method.

The specific RIPP standard method of the present invention can be found in "Petrochemical Analytical Methods", edited by Yang Cuiding et al., 1990 edition.

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

The raw material ZSM-5 molecular sieve is provided by Sinopec Catalyst Company Qilu Branch. The relative crystallinity is 91.1%, the silicon oxide/alumina molar ratio is 24.1, the specific surface area is 353m ² /g, and the total pore volume is 0.177ml/g.

Pseudo-boehmite is an industrial product produced by Shandong Aluminum Company, with a solid content of 60% by weight; aluminum sol is an industrial product produced by Sinopec Catalyst Qilu Branch, with an Al ₂ O ₃ content of 21.5% by weight; silica sol is produced by Sinopec Catalyst Qilu Branch The industrial products produced by the company have a SiO ₂ content of 28.9% by weight and a Na ₂ O content of 8.9%; kaolin is a special kaolin for catalytic cracking catalyst produced by Suzhou Kaolin Company, with a solid content of 78% by weight; Retoite is Hubei Zhongxiang celebrity Retoite Produced by Development Co., Ltd., quartz sand content <3.5 wt%, Al ₂ O ₃ content 39.0 wt %, Na ₂ O content 0.03 wt %, solid content 77 wt %; SB aluminum hydroxide powder, produced by Condex Company, Germany, Al The content of ₂ O ₃ is 75% by weight; γ-alumina is produced by Condex Company of Germany, and the content of Al ₂ O ₃ is 95% by weight. Hydrochloric acid, chemically pure, concentration 36-38% by weight, produced by Beijing Chemical Factory.

PSRY molecular sieve is an industrial product produced by Sinopec Catalyst Changling Branch. The Na ₂ O content is <1.5 wt%, the P ₂ O ₅ content is 0.8 to 1.2 wt%, the unit cell constant is <2.456nm, and the crystallinity is ≥64%. HRY-1 finished molecular sieve is an industrial product produced by Sinopec Catalyst Changling Branch. The La ₂ O ₃ content is 11 to 13% by weight, the unit cell constant is <2.464nm, and the crystallinity is ≥40%.

Unless otherwise specified, the instruments and reagents used in the examples of the present invention are all commonly used by those skilled in the art.

Example 1-1

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

Dissolve 16.2g diammonium hydrogen phosphate (Tianjin Guangfu Technology Development Co., Ltd., analytical grade, the same below) in 60g deionized water, stir for 0.5h to obtain a phosphorus-containing aqueous solution, and add 113g HZSM-5 molecular sieve (Sinopec Catalyst Company Qilu Provided by the branch, the relative crystallinity is 91.1%, the silicon oxide/alumina molar ratio is 24.1, the Na ₂ O content is 0.039% by weight, the specific surface area is 353m ² /g, the total pore volume is 0.177ml/g, the same below), Modified by the impregnation method, immersed at 20°C for 2 hours and dried in an oven at 110°C, external pressure was applied and water was added, and treated at 500°C, 0.5Mpa, and 50% water vapor atmosphere for 0.5h to obtain the phosphorus The modified ZSM-5 molecular sieve sample is designated as PSZ1-1.

Example 1-2

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

The materials, proportions, drying and roasting are the same as in Example 1-1, except that after mixing diammonium hydrogen phosphate, HZSM-5 molecular sieve and water into a slurry, the mixture is heated to 100°C and maintained for 2 hours. The obtained phosphorus-modified ZSM-5 molecular sieve sample was designated as PSZ1-2.

Comparative example 1-1

Comparative Example 1-1 illustrates the existing industrial conventional method and the obtained phosphorus-modified ZSM-5 molecular sieve comparison sample.

It is the same as Example 1-1, except that the roasting conditions are normal pressure (apparent pressure 0 MPa) and air roasting in a muffle furnace at 550°C. The obtained phosphorus-modified ZSM-5 molecular sieve comparison sample is designated as DBZ1-1.

Comparative Example 1-2

Comparative Example 1-2 illustrates a comparative sample of phosphorus-modified ZSM-5 molecular sieve obtained by hydrothermal roasting under normal pressure.

It is the same as Example 1-1, except that the roasting condition is normal pressure (apparent pressure 0 MPa). A comparative sample of phosphorus-modified ZSM-5 molecular sieve was obtained, designated as DBZ1-2.

The XRD crystallinity of PSZ1-1, PSZ1-2, DBZ1-1, and DBZ1-2 before and after hydrothermal aging treatment at 800°C, 100% water vapor, and 17 hours is shown in Table 1-1.

^{The 27} Al MAS-NMR spectra of PSZ1-1 and DBZ1-1 are shown in Figure 1 and Figure 3 respectively. ^{The 27} AlMAS-NMR spectra of PSZ1-2 and DBZ1-2 have the same characteristics as Figure 1 and Figure 3 respectively. In the figure, Chemistry The shift at 54 ppm is attributed to four-coordinated framework aluminum, while the chemical shift at 39 ppm is attributed to four-coordinated framework aluminum in which phosphorus is combined with aluminum (phosphorus-stabilized framework aluminum). The peak area ratio data of ²⁷ Al MAS-NMR spectrum are shown in Table 1-2.

The surface XPS elemental analysis data of PSZ1-1, PSZ1-2, DBZ1-1, and DBZ1-2 are shown in Table 1-3.

The NH ₃ -TPD spectrum of PSZ1-1 after hydrothermal aging at 800°C, 100% water vapor conditions for 17 hours is shown in Figure 2. The NH ₃ -TPD spectrum of comparative sample DBZ1-1 after hydrothermal aging at 800°C, 100% water vapor conditions, and 17 hours is shown in Figure 4. In the NH ₃ -TPD spectra of PSZ1-1, PSZ1-2, DBZ1-1, and DBZ1-2, the ratio of the peak area of strong acid centers to the peak area of total acid centers when the desorption temperature is above 200°C is shown in Table 1-4.

Table 1-1

It can be seen from Table 1-1 that the phosphorus-modified ZSM-5 molecular sieve prepared by the method of the present invention still has a high crystal retention after hydrothermal aging treatment at 800°C, 100% water vapor, and 17 hours, and the crystal retention is significantly higher than Compared with the sample, the crystal retention is increased by at least 5 percentage points.

Table 1-2

Table 1-3

Table 1-4

Example 2-1

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

Take 16.2g of diammonium hydrogen phosphate and dissolve it in 120g of deionized water at 50°C. Stir for 0.5h to obtain a phosphorus-containing aqueous solution. Add 113g of HZSM-5 molecular sieve and modify it by impregnation. Dip at 20°C for 2 hours and then at 110°C. Dry it in a lower oven, apply external pressure and add water, and perform hydrothermal roasting treatment under pressure at 600°C, 0.5Mpa, and 30% water vapor atmosphere for 2 hours. The obtained phosphorus-modified ZSM-5 molecular sieve sample is designated as PSZ-2.

Example 2-2

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

The materials, proportions, drying and roasting are the same as those in Example 2-1, except that after mixing diammonium hydrogen phosphate, HZSM-5 molecular sieve and water into a slurry, the mixture is heated to 70°C and maintained for 2 hours. The obtained phosphorus-modified ZSM-5 molecular sieve sample was designated as PSZ2-2.

Comparative example 2-1

Comparative Example 2-1 illustrates the existing industrial conventional method and the obtained phosphorus-modified ZSM-5 comparative sample.

It is the same as Example 2-1, except that the roasting conditions are normal pressure (apparent pressure 0 MPa) and air roasting in a muffle furnace at 550°C. The obtained phosphorus-modified ZSM-5 molecular sieve comparison sample is designated as DBZ-2-1.

Comparative Example 2-2

Comparative Example 2-2 illustrates a comparative sample of phosphorus-modified ZSM-5 molecular sieve obtained by hydrothermal roasting under normal pressure.

Same as Example 2-1, except that the roasting condition is normal pressure (apparent pressure 0 MPa). A comparative sample of phosphorus-modified ZSM-5 molecular sieve was obtained, which was designated as DBZ-2-2.

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

^{The 27} Al MAS-NMR spectra of PSZ1-2 and PSZ2-2 have the characteristics of Figure 1, and ^{the 27} AlMAS-NMR spectra of DBZ2-1 and DBZ2-2 have the same characteristics as Figure 3. The peak area ratio data of ²⁷ Al MAS-NMR spectrum are shown in Table 2-2.

The surface XPS elemental analysis data of PSZ2-1, PSZ2-2, DBZ2-1, and DBZ2-2 are shown in Table 2-3. In the NH ₃ -TPD spectrum, the area of the strong acid center peaks with a desorption temperature above 200°C accounts for the total acid center peaks. The area proportion data are shown in Table 2-4.

PSZ2-1, PSZ2-2, DBZ2-1, and DBZ2-2 were evaluated for n-tetradecane cracking. The evaluation data are shown in Table 2-5.

table 2-1

It can be seen from Table 2-1 that the phosphorus-modified ZSM-5 molecular sieve prepared by the method of the present invention still has a high crystal retention after hydrothermal aging treatment at 800°C, 100% water vapor, and 17 hours, and the crystal retention is significantly higher than Compared with the sample, the crystal retention is increased by at least 4 percentage points.

Table 2-2

Table 2-3

Table 2-4

Example 3-1

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

Dissolve 10.4g of phosphoric acid in 60g of deionized water at room temperature, stir for 2 hours, and obtain a phosphorus-containing aqueous solution. Add 113g of HZSM-5 molecular sieve, modify it by dipping, soak at 20°C for 4 hours, and then dry in an oven at 110°C. Afterwards, external pressure was applied and water was added, and the phosphorus-modified ZSM-5 molecular sieve was obtained by pressurized hydrothermal roasting at 400°C, 0.3Mpa, and 100% water vapor atmosphere for 2 hours, which was designated as PSZ3-1.

Example 3-2

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

The materials, proportions, drying and roasting are the same as in Example 3-1, except that the aqueous solution of the phosphorus-containing compound at 80°C is mixed and contacted with the HZSM-5 molecular sieve heated to 80°C for 4 hours. The obtained phosphorus-modified ZSM-5 molecular sieve sample was designated as PSZ3-2.

Comparative example 3-1

Comparative Example 3-1 illustrates the existing industrial conventional method and the obtained phosphorus-modified ZSM-5 comparative sample.

It is the same as Example 3-1, except that the roasting conditions are normal pressure (apparent pressure 0 MPa) and air roasting in a muffle furnace at 550°C. The obtained phosphorus-modified ZSM-5 molecular sieve comparison sample is designated as DBZ3-1.

Comparative Example 3-2

Comparative Example 3-2 illustrates a comparative sample of phosphorus-modified ZSM-5 molecular sieve obtained by hydrothermal roasting under normal pressure.

Same as Example 3-1, except that the roasting condition is normal pressure (apparent pressure 0 MPa). A comparative sample of phosphorus-modified ZSM-5 molecular sieve was obtained, designated as DBZ3-2.

The XRD crystallinity of PSZ3-1, PSZ3-2, DBZ3-1, and DBZ3-2 before and after hydrothermal aging treatment at 800°C, 100% water vapor, and 17 hours is shown in Table 3-1.

^{The 27} Al MAS-NMR spectra of PSZ-3 and PSZ3-2 have the characteristics of Figure 1 respectively, and ^{the 27} AlMAS-NMR spectra of DBZ3-1 and DBZ3-2 have the same characteristics as Figure 3. The peak area ratio data of ²⁷ Al MAS-NMR spectrum are shown in Table 3-2.

The surface XPS elemental analysis data of PSZ3-1, PSZ3-2, DBZ3-1, and DBZ3-2 are shown in Table 3-3. In the NH ₃ -TPD spectrum, the area of the strong acid center peaks with a desorption temperature above 200°C accounts for the total acid center peaks. The area proportion data are shown in Table 3-4.

Table 3-1

It can be seen from Table 3-1 that the phosphorus-modified ZSM-5 molecular sieve prepared by the method of the present invention still has a high crystal retention after hydrothermal aging treatment at 800°C, 100% water vapor, and 17 hours, and the crystal retention is significantly higher than Compared with the sample, the crystal retention is increased by at least 10 percentage points.

Table 3-2

Table 3-3

Table 3-4

Example 4-1

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

Dissolve 8.1g of diammonium hydrogen phosphate in 120g of deionized water at room temperature, stir for 0.5h to obtain a phosphorus-containing aqueous solution, add 113g of HZSM-5 molecular sieve, modify it by dipping, soak at 20℃ for 2 hours and then at 110℃ Dry it in a lower oven, apply external pressure and add water, and perform hydrothermal roasting treatment under pressure at 300°C, 0.4Mpa, and 100% water vapor atmosphere for 2 hours. The obtained phosphorus-modified ZSM-5 molecular sieve sample is designated as PSZ4-1.

Example 4-2

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

The materials, proportions, drying and roasting are the same as in Example 4-1, except that after mixing ammonium dihydrogen phosphate, HZSM-5 molecular sieve and water into a slurry, the temperature is raised to 90°C and maintained for 2 hours. The obtained phosphorus-modified ZSM-5 molecular sieve sample was designated as PSZ4-2.

Comparative example 4-1

Comparative Example 4-1 illustrates the existing industrial conventional method and the obtained phosphorus-modified ZSM-5 comparative sample.

The same as Example 4-1, except that the roasting conditions are normal pressure (apparent pressure 0 MPa) and air roasting in a muffle furnace at 550°C. The obtained phosphorus-modified ZSM-5 molecular sieve comparison sample is designated as DBZ4-1.

Comparative Example 4-2

Comparative Example 4-2 illustrates a comparative sample of phosphorus-modified ZSM-5 molecular sieve obtained by hydrothermal roasting under normal pressure.

Same as Example 4-1, except that the roasting condition is normal pressure (apparent pressure 0 MPa). A comparative sample of phosphorus-modified ZSM-5 molecular sieve was obtained, designated as DBZ4-2.

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

^{The 27} Al MAS-NMR spectra of PSZ4-1 and PSZ4-2 have the characteristics of Figure 1 respectively, and ^{the 27} Al MAS-NMR spectra of DBZ-4-1 and DBZ-4-2 have the same characteristics as Figure 3. The peak area ratio data of ²⁷ Al MAS-NMR spectrum are shown in Table 4-2.

The surface XPS elemental analysis data of PSZ4-1, PSZ4-2, DBZ4-1, and DBZ4-2 are shown in Table 4-3. In the NH ₃ -TPD spectrum, the peak area of the strong acid center with a desorption temperature above 200°C accounts for the total acid center peak area. The specific gravity data is shown in Table 4-4.

Table 4-1

It can be seen from Table 4-1 that the phosphorus-modified ZSM-5 molecular sieve prepared by the method of the present invention still has a high crystal retention after hydrothermal aging treatment at 800°C, 100% water vapor, and 17 hours, and the crystal retention is significantly higher than Compared with the sample, the crystal retention is increased by at least 15 percentage points.

Table 4-2

Table 4-3

Table 4-4

Example 5-1

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

Dissolve 8.5g trimethyl phosphate in 80g deionized water at 90°C, stir for 1 hour to obtain a phosphorus-containing aqueous solution, add 113g HZSM-5 molecular sieve, modify it by dipping method, soak at 20°C for 8 hours and then at 110°C After drying in the oven, external pressure is applied and water is added, and the phosphorus-modified ZSM-5 molecular sieve obtained is hydrothermal roasted under pressure at 500°C, 0.8Mpa, and 80% water vapor for 4 hours, and is designated as PSZ5-1.

Example 5-2

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

The materials, proportions, drying and roasting are the same as in Example 5-1, except that trimethyl phosphate, HZSM-5 molecular sieve and water are mixed to form a slurry, and then the temperature is raised to 120°C and maintained for 8 hours. The obtained phosphorus-modified ZSM-5 molecular sieve sample was designated as PSZ5-2.

Comparative example 5-1

Comparative Example 5-1 illustrates the existing industrial conventional method and the obtained phosphorus-modified ZSM-5 comparative sample.

It is the same as Example 5-1, except that the roasting conditions are normal pressure (apparent pressure 0 MPa) and air roasting in a muffle furnace at 550°C. The obtained phosphorus-modified ZSM-5 molecular sieve comparison sample is designated as DBZ5-1.

Comparative example 5-2

Comparative Example 5-2 illustrates a comparative sample of phosphorus-modified ZSM-5 molecular sieve obtained by hydrothermal roasting under normal pressure.

Same as Example 5-1, except that the roasting condition is normal pressure (apparent pressure 0 MPa). A comparative sample of phosphorus-modified ZSM-5 molecular sieve was obtained, designated as DBZ5-2.

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

^{The 27} Al MAS-NMR spectra of PSZ5-1 and PSZ5-2 have the characteristics of Figure 1, and ^{the 27} AlMAS-NMR spectra of DBZ5-1 and DBZ5-2 have the same characteristics as Figure 3. The peak area ratio data of ²⁷ Al MAS-NMR spectrum are shown in Table 5-2.

The surface XPS elemental analysis data of PSZ5-1, PSZ5-2, DBZ5-1, and DBZ5-2 are shown in Table 5-3. In the NH ₃ -TPD spectrum, the peak area of strong acid centers with a desorption temperature above 200°C accounts for the total acid center peaks. The area proportion data are shown in Table 5-4.

Table 5-1

It can be seen from Table 5-1 that the phosphorus-modified ZSM-5 molecular sieve prepared by the method of the present invention still has a high crystal retention after hydrothermal aging treatment at 800°C, 100% water vapor, and 17 hours, and the crystal retention is significantly higher than Compared with the sample, the crystal retention is increased by at least 5 percentage points.

Table 5-2

Table 5-3

Table 5-4

Example 6-1

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

Take 11.6g of boron phosphate and dissolve it in 100g of deionized water at 100°C. Stir for 3 hours to obtain a phosphorus-containing aqueous solution. Add 113g of HZSM-5 molecular sieve and modify it by impregnation. After immersing at 20°C for 2 hours, remove it at 110°C. Dry in an oven, apply external pressure and add water, and perform hydrothermal roasting treatment under pressure at 400°C, 0.3Mpa, and 100% water vapor atmosphere for 4 hours. The obtained phosphorus-modified ZSM-5 molecular sieve is designated as PSZ6-1.

Example 6-2

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

The materials, proportions, drying and roasting are the same as in Example 6-1, except that boron phosphate, HZSM-5 molecular sieve and water are mixed into a slurry and then heated to 150°C and maintained for 2 hours. The obtained phosphorus-modified ZSM-5 molecular sieve sample was designated as PSZ6-2.

Comparative example 6-1

Comparative Example 6-1 illustrates the existing industrial conventional method and the obtained phosphorus-modified ZSM-5 comparative sample.

It is the same as Example 6-1, except that the roasting conditions are normal pressure (apparent pressure 0 MPa) and air roasting in a muffle furnace at 550°C. The obtained phosphorus-modified ZSM-5 molecular sieve comparison sample is designated as DBZ6-1.

Comparative Example 6-2

Comparative Example 6-2 illustrates a comparative sample of phosphorus-modified ZSM-5 molecular sieve obtained by hydrothermal roasting under normal pressure.

Same as Example 6-1, except that the roasting condition is normal pressure (apparent pressure 0 MPa). A comparative sample of phosphorus-modified ZSM-5 molecular sieve was obtained, designated as DBZ6-2.

The XRD crystallinity of PSZ6-1, PSZ6-2, DBZ6-1, and DBZ6-2 before and after hydrothermal aging treatment at 800°C, 100% water vapor, and 17 hours is shown in Table 6-1.

^{The 27} Al MAS-NMR spectra of PSZ6-1 and PSZ6-2 have the characteristics of Figure 1, and ^{the 27} AlMAS-NMR spectra of DBZ-6-1 and DBZ6-2 have the same characteristics as Figure 3. The peak area ratio data of ²⁷ Al MAS-NMR spectrum are shown in Table 6-2.

The surface XPS elemental analysis data of PSZ6-1, PSZ6-2, DBZ6-1, and DBZ6-2 are shown in Table 6-3. In the NH ₃ -TPD spectrum, the area of the strong acid center peaks with a desorption temperature above 200°C accounts for the total acid center peaks. The area proportion data are shown in Table 6-4.

Table 6-1

It can be seen from Table 6-1 that the phosphorus-modified ZSM-5 molecular sieve prepared by the method of the present invention still has a high crystal retention after hydrothermal aging treatment at 800°C, 100% water vapor, and 17 hours, and the crystal retention is significantly higher than Compared with the sample, the crystal retention is increased by at least 10 percentage points.

Table 6-2

Table 6-3

Table 6-4

Example 7-1

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

Take 14.2g triphenylphosphorus and dissolve it in 80g deionized water at 100°C. Stir for 2 hours to obtain a phosphorus-containing aqueous solution. Add 113g HZSM-5 molecular sieve and modify it by the impregnation method. After immersing it at 20°C for 4 hours, add it to 110 Dry in an oven at ℃, apply external pressure and add water, and perform hydrothermal roasting treatment under pressure at 600°C, 1.0Mpa, and 30% water vapor atmosphere for 2 hours. The obtained phosphorus-modified ZSM-5 molecular sieve is designated as PSZ7-1.

Example 7-2

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

The materials, proportions, drying and roasting are the same as in Example 7-1, except that the aqueous solution of the phosphorus-containing compound at 80°C is mixed and contacted with the HZSM-5 molecular sieve heated to 80°C for 4 hours. The obtained phosphorus-modified ZSM-5 molecular sieve sample was designated as PSZ7-2.

Comparative Example 7-1

Comparative Example 7-1 illustrates the existing industrial conventional method and the obtained phosphorus-modified ZSM-5 comparative sample.

It is the same as Example 7-1, except that the roasting conditions after impregnation and drying are normal pressure (apparent pressure 0 MPa) and air roasting in a muffle furnace at 550°C. The obtained phosphorus-modified ZSM-5 molecular sieve comparison sample is designated as DBZ7-1.

Comparative Example 7-2

Comparative Example 7-2 illustrates a comparative sample of phosphorus-modified ZSM-5 molecular sieve obtained by hydrothermal roasting under normal pressure.

Same as Example 7-1, except that the roasting conditions after impregnation and drying are normal pressure (apparent pressure 0 MPa). A comparative sample of phosphorus-modified ZSM-5 molecular sieve was obtained, designated as DBZ7-2.

The XRD crystallinity of PSZ7-1, PSZ7-2, DBZ7-1, and DBZ7-2 before and after hydrothermal aging treatment at 800°C, 100% water vapor, and 17 hours is shown in Table 7-1.

^{The 27} Al MAS-NMR spectra of PSZ-7 and PSZ7-2 have the characteristics of Figure 1, and ^{the 27} AlMAS-NMR spectra of DBZ7-1 and DBZ7-2 have the same characteristics as Figure 3. The peak area ratio data of ²⁷ Al 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. In the NH ₃ -TPD spectra of PSZ7-1, PSZ7-2, DBZ7-1, and DBZ7-2, When the desorption temperature is above 200°C, the proportion of strong acid center peak area to total acid center peak area is shown in Table 7-4.

Table 7-1

It can be seen from Table 7-1 that the phosphorus-modified ZSM-5 molecular sieve prepared by the method of the present invention still has a high crystal retention after hydrothermal aging treatment at 800°C, 100% water vapor, and 17 hours, and the crystal retention is significantly higher than Compared with the sample, the crystal retention is increased by at least 8 percentage points.

Table 7-2

Table 7-3

Table 7-4

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

Example 8

Slurry 1.91 kg of pseudo-boehmite (containing Al ₂ O ₃ , 1.19 kg), 0.56 kg of kaolin (0.5 kg on a dry basis) and 3.27 kg of decationized water for 30 minutes. Add 5.37 kg of concentrated phosphoric acid (mass) to the slurry under stirring. Concentration 85%), add phosphoric acid at a rate of 0.04 kg phosphoric acid/minute/kg alumina source, raise the temperature to 70°C, and then react at this temperature for 45 minutes to prepare the phosphorus aluminum inorganic binder. The material ratio is shown in Table 8, and the sample number is Binder1.

Examples 9-11

The phosphorus aluminum inorganic binder was prepared according to the method of Example 8. The material ratio is shown in Table 8, and the sample numbers are Binder2, Binder3, and Binder4.

Table 8

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

Example 12-1

Take the phosphorus modified molecular sieve PSZ1-1, Y-type molecular sieve (PSRY molecular sieve), kaolin and pseudo-boehmite prepared in Example 1-1, add decationized water and aluminum sol and beat for 120 minutes to obtain a solid content of 30% by weight. slurry, add hydrochloric acid to adjust the pH value of the slurry to 3.0, and then continue beating for 45 minutes. Then add the phosphorus aluminum inorganic binder Binder1 prepared in Example 8. After stirring for 30 minutes, spray-dry the obtained slurry to obtain microspheres. Calculate at 500°C for 1 hour to obtain the catalytic cracking catalyst sample of the present invention, numbered CAZY1-1, with a proportion of 40% phosphorus-modified ZSM-5 molecular sieve, 10% PSRY molecular sieve, 18% kaolin, 18% Binder1, Pseudo-boehmite (calculated as Al ₂ O ₃ ) 5%, aluminum sol (calculated as Al ₂ O ₃ ) 9%. A fixed-bed micro-reaction device was used to evaluate the reaction performance of 100% balance agent and balance agent-incorporated catalyst CAZY1-1 to illustrate the catalytic cracking reaction effect.

Catalyst CAZY1-1 was aged for 17 hours at 800°C and 100% water vapor atmosphere. The aged CAZY1-1 was mixed with an industrial FCC equilibrium catalyst (industrial brand DVR-3 FCC equilibrium catalyst, light oil micro reaction activity of 63) at a weight ratio of 10% and 90% respectively. The balance agent and catalyst mixture were put into the fixed-bed micro-reactor, and the feed oil shown in Table 9 was catalytically cracked. The evaluation conditions were reaction temperature 620°C, regeneration temperature 620°C, and agent-oil ratio 3.2. Table 10 gives the reaction results.

Table 9

Example 12-2

Same as Example 12-1, except that the phosphorus modified molecular sieve PSZ-1-1 is replaced by the phosphorus modified molecular sieve PSZ-1-2 prepared in Example 1-2. A catalyst sample was prepared, numbered CAZY1-2.

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

Comparative example 12-1

It is the same as Example 12-1, except that the phosphorus modified molecular sieve PSZ-1-1 is replaced by the comparative sample DBZ1-1 of Comparative Example 1-1. A catalyst comparison sample was prepared, numbered DCAZY1-1.

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

Comparative example 12-2

It is the same as Example 12-1, except that the phosphorus modified molecular sieve PSZ-1-1 is replaced by the comparative sample DBZ1-2 of Comparative Example 1-2. A catalyst comparison sample was prepared, numbered DCAZY1-2.

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

Table 10

project Blank test case Example 12-1 Example 12-2 Comparative example 12-1 Comparative example 12-2 Material balance, 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

Same as Example 12-1, except that the phosphorus modified molecular sieve PSZ-1-1 is replaced by the phosphorus modified molecular sieve PSZ-2-1 prepared in Example 2-1. A sample of catalytic cracking aid was prepared, numbered CAZY2-1.

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

Example 13-2

Same as Example 13-1, except that the phosphorus modified molecular sieve PSZ-2-1 is replaced by the phosphorus modified molecular sieve PSZ-2-2 prepared in Example 2-2. A sample of catalytic cracking aid was prepared, numbered CAZY2-2.

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

Comparative example 13-1

It is the same as Example 13-1, except that the phosphorus modified molecular sieve PSZ-2-1 is replaced by the comparative sample DBZ2-1 of Comparative Example 2-1. A comparative sample of catalytic cracking aid was prepared, numbered DCAZY2-1.

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

Comparative example 13-2

Same as Example 13-1, except that the phosphorus modified molecular sieve PSZ-2-1 is replaced by the comparative sample DBZ2-2 of Comparative Example 2-2. A comparative sample of catalytic cracking aid was prepared, numbered DCAZY2-2.

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

Table 11

Example 14-1

Same as Example 12-1, except that the phosphorus modified molecular sieve PSZ-1-1 is replaced by the phosphorus modified molecular sieve PSZ-3-1 prepared in Example 3-1. A sample of catalytic cracking aid was prepared, numbered CAZY3-1.

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

Example 14-2

Same as Example 14-1, except that the phosphorus modified molecular sieve PSZ-3-1 is replaced by the phosphorus modified molecular sieve PSZ-3-2 prepared in Example 3-2. A sample of catalytic cracking aid was prepared, numbered CAZY3-2.

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

Comparative example 14-1

It is the same as Example 14-1, except that the phosphorus modified molecular sieve PSZ-3-1 is replaced by the comparative sample DBZ3-1 of Comparative Example 3-1. A comparative sample of catalytic cracking aid was prepared, numbered DCAZY3-1.

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

Comparative Example 14-2

It is the same as Example 14-1, except that the phosphorus modified molecular sieve PSZ-3-1 is replaced by the comparative sample DBZ2-2 of Comparative Example 3-2. A catalyst comparison sample was prepared, numbered DCAZY3-2.

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

Table 12

project Blank test case Example 14-1 Example 14-2 Comparative example 14-1 Comparative Example 14-2 Material balance, 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

Same as Example 12-1, except that the phosphorus modified molecular sieve PSZ-1-1 is replaced by the phosphorus modified molecular sieve PSZ-4-1 prepared in Example 4-1. A catalyst sample was prepared, numbered CAZY4-1.

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

Example 15-2

Same as Example 15-1, except that the phosphorus modified molecular sieve PSZ-4-1 is replaced by the phosphorus modified molecular sieve PSZ-4-2 prepared in Example 4-2. A catalyst sample was prepared, numbered CAZY4-2.

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

Comparative example 15-1

It is the same as Example 15-1, except that the phosphorus modified molecular sieve PSZ-2-1 is replaced by the comparative sample DBZ4-1 of Comparative Example 2-1. A catalyst comparison sample was prepared, numbered DCAZY4-1.

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

Comparative example 15-2

It is the same as Example 15-1, except that the phosphorus modified molecular sieve PSZ-2-1 is replaced by the comparative sample DBZ4-2 of Comparative Example 2-2. A catalyst comparison sample was prepared, numbered DCAZY4-2.

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

Table 13

project Blank test case Example 15-1 Example 15-2 Comparative example 15-1 Comparative example 15-2 Material balance, 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

Same as Example 12-1, except that the phosphorus modified molecular sieve PSZ-1-1 is replaced by the phosphorus modified molecular sieve PSZ-5-1 prepared in Example 5-1. A catalyst sample was prepared, numbered CAZY5-1.

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

Example 16-2

Same as Example 16-1, except that the phosphorus modified molecular sieve PSZ-5-1 is replaced by the phosphorus modified molecular sieve PSZ-5-2 prepared in Example 5-2. A catalyst sample was prepared, numbered CAZY5-2.

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

Comparative example 16-1

Same as Example 16-1, except that the phosphorus modified molecular sieve PSZ-5-1 is replaced by the comparative sample DBZ5-1 of Comparative Example 5-1. A catalyst comparison sample was prepared, numbered DCAZY5-1.

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

Comparative Example 16-2

Same as Example 16-1, except that the phosphorus modified molecular sieve PSZ-2-1 is replaced by the comparative sample DBZ5-2 of Comparative Example 2-2. A catalyst comparison sample was prepared, numbered DCAZY5-2.

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

Table 14

project Blank test case Example 16-1 Example 16-2 Comparative example 16-1 Comparative Example 16-2 Material balance, 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

Same as Example 12-1, except that the phosphorus modified molecular sieve PSZ-1-1 is replaced by the phosphorus modified molecular sieve PSZ-6-1 prepared in Example 6-1. A catalyst sample was prepared, numbered CAZY6-1.

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

Example 17-2

Same as Example 17-1, except that the phosphorus modified molecular sieve PSZ-6-1 is replaced by the phosphorus modified molecular sieve PSZ-6-2 prepared in Example 6-2. A catalyst sample was prepared, numbered CAZY6-2.

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

Comparative Example 17-1

It is the same as Example 17-1, except that the phosphorus modified molecular sieve PSZ-2-1 is replaced by the comparative sample DBZ2-1 of Comparative Example 6-1. A catalyst comparison sample was prepared, numbered DCAZY6-1.

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

Comparative Example 17-2

Same as Example 17-1, except that the phosphorus modified molecular sieve PSZ-2-1 is replaced by the comparative sample DBZ2-2 of Comparative Example 6-2. A catalyst comparison sample was prepared, numbered DCAZY6-2.

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

Table 15

project Blank test case Example 17-1 Example 17-2 Comparative Example 17-1 Comparative Example 17-2 Material balance, 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

Same as Example 12-1, except that the phosphorus modified molecular sieve PSZ-1-1 is replaced by the phosphorus modified molecular sieve PSZ-7-1 prepared in Example 7-1. A catalyst sample was prepared, numbered CAZY7-1.

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

Example 18-2

Same as Example 18-1, except that the phosphorus modified molecular sieve PSZ-7-1 is replaced by the phosphorus modified molecular sieve PSZ-7-2 prepared in Example 7-2. A catalyst sample was prepared, numbered CAZY7-2.

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

Comparative Example 18-1

It is the same as Example 18-1, except that the phosphorus modified molecular sieve PSZ-7-1 is replaced by the comparative sample DBZ7-1 of Comparative Example 7-1. A catalyst comparison sample was prepared, numbered DCAZY7-1.

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

Comparative Example 18-2

Same as Example 18-1, except that the phosphorus modified molecular sieve PSZ-7-1 is replaced by the comparative sample DBZ7-2 of Comparative Example 7-2. A catalyst comparison sample was prepared, numbered DCAZY7-2.

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

Table 16

project Blank test case Example 18-1 Example 18-2 Comparative example 18-1 Comparative Example 18-2 Material balance, 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

It is the same as Example 12-1, except that the phosphorus aluminum inorganic binder is replaced by Binder2 prepared in Example 9. The catalyst was prepared, number CAZY8-1.

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

Example 19-2

It is the same as Example 12-2, except that the phosphorus aluminum inorganic binder is replaced by Binder2 prepared in Example 9. The catalyst was prepared, number CAZY8-2.

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

Example 20-1

It is the same as Example 12-1, except that the phosphorus aluminum inorganic binder is replaced by Binder3 prepared in Example 10. The catalyst was prepared, numbered CAZY9-1.

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

Example 20-2

It is the same as Example 12-2, except that the phosphorus aluminum inorganic binder is replaced by Binder3 prepared in Example 10. The catalyst was prepared, number CAZY9-2.

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

Example 21-1

It is the same as Example 12-1, except that the phosphorus aluminum inorganic binder is replaced by Binder 4 prepared in Example 11. The catalyst was prepared, number CAZY10-1.

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

Example 21-2

It is the same as Example 12-2, except that the phosphorus aluminum inorganic binder is replaced by Binder 4 prepared in Example 11. The catalyst was prepared, number CAZY10-2.

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

Table 17

Example 22-1

Same as Example 12-1, except that the phosphorus modified ZSM-molecular sieve sample PSZ1-1 is 35% by weight, PSRY10% by weight, kaolin 18% by weight, phosphorus aluminum inorganic binder Binder3 is 22% by weight, and pseudo-boehmite is 10% by weight, aluminum sol is 5% by weight. The catalyst was prepared, number CAZY11-1.

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

Example 22-2

Same as Example 12-1, except that PSZ1-1 is replaced by PSZ1-2. The catalyst was prepared, number CAZY11-2.

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

Comparative example 22-1

Same as Example 22-1, except that PSZ1-1 is replaced with DBZ1-1. A catalyst comparison sample was prepared, numbered DCAZ11-1. The evaluation was the same as in Example 12-1, and the results are shown in Table 18.

Comparative Example 22-2

Same as Example 22-1, except that PSZ1-1 is replaced with DBZ1-2. A catalyst comparison sample was prepared, numbered DCAZY11-2. The evaluation was the same as in Example 12-1, and the results are shown in Table 18.

Table 18

Example 23-1

Same as Example 12-1, except that the phosphorus modified ZSM-molecular sieve sample PSZ2-1 is 30 wt%, PSRY16 wt%, kaolin is 24 wt%, phosphorus aluminum inorganic binder Binder4 is 20 wt%, and pseudo-boehmite is 6% by weight and 10% by weight of silica sol. The catalyst was prepared, number CAZY12-1.

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

Example 23-2

Same as Example 12-1, except that PSZ2-1 is replaced with PSZ2-2. The catalyst was prepared, number CAZY12-2.

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

Comparative example 23-1

Same as Example 23-1, except that PSZ2-1 is replaced with DBZ2-1. A catalyst comparison sample was prepared, numbered DCAZY12-1.

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

Comparative Example 23-2

Same as Example 23-1, except that PSZ2-1 is replaced with DBZ2-2. A catalyst comparison sample was prepared, numbered DCAZY12-2.

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

Table 19

Example 24-1

Mix the binder aluminum sol with kaolin, and use decationized water to make a slurry with a solid content of 30% by weight. Stir evenly. Use hydrochloric acid to adjust the pH value of the slurry to 2.8, and let it stand for aging at 55°C for 1 hour. Then, the phosphorus-modified ZSM-5 molecular sieve PSZ1-1 and Y-type molecular sieve (PSRY) prepared in Example 1 were added to form a catalyst slurry (solid content: 35% by weight), and the mixture was continuously stirred and spray-dried to prepare a microsphere catalyst. The microsphere catalyst is then calcined at 500°C for 1 hour, and then washed with ammonium sulfate at 60°C (ammonium sulfate:microsphere catalyst:water=0.5:1:10) until the sodium oxide content is less than 0.25% by weight, and then Rinse and filter with deionized water, and then dry at 110°C to obtain the catalyst, number CAZY13-1. The catalyst ratio is 40% of phosphorus modified ZSM-5 molecular sieve PSZ-1-1, 10% of PSRY molecular sieve, 25% of kaolin, and 25% of aluminum sol (calculated as Al ₂ O ₃ ).

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

Example 24-2

Same as Example 24-1, except that the phosphorus modified molecular sieve PSZ1-1 is replaced by the phosphorus modified molecular sieve PSZ-1-2 prepared in Example 1-2. A catalyst sample was prepared, numbered CAZY13-2.

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

Comparative Example 24-1

It is the same as Example 24-1, except that the phosphorus modified molecular sieve PSZ1-1 is replaced by the comparative sample DBZ1-1 of Comparative Example 1-1. A catalyst comparison sample was prepared, numbered DCAZY13-1.

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

Comparative Example 24-2

It is the same as Example 24-1, except that the phosphorus modified molecular sieve PSZ-1-1 is replaced by the comparative sample DBZ1-2 of Comparative Example 1-2. A catalyst comparison sample was prepared, numbered DCAZY13-2.

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

Table 20

project Blank test case Example 24-1 Example 24-2 Comparative Example 24-1 Comparative Example 24-2 Material balance, 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

Same as Example 12-1, except that the Y-type molecular sieve (PSRY) is replaced with HRY-1. A catalyst sample was prepared, numbered CAZY14-1.

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

Example 25-2

Same as Example 12-2, except that the Y-type molecular sieve (PSRY) is replaced with HRY-1. A catalyst sample was prepared, numbered CAZY14-1.

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

Comparative example 25-1

It is the same as Example 25-1, except that the phosphorus modified molecular sieve PSZ1-1 is replaced by the comparative sample DBZ1-1 of Comparative Example 1-1. A catalyst comparison sample was prepared, numbered DCAZY14-1.

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

Comparative Example 25-2

It is the same as Example 25-1, except that the phosphorus modified molecular sieve PSZ-1-1 is replaced by the comparative sample DBZ1-2 of Comparative Example 1-2. A catalyst comparison sample was prepared, numbered DCAZY14-2.

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

Table 21

project Blank test case Example 25-1 Example 25-2 Comparative example 25-1 Comparative Example 25-2 Material balance, 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

Same as Example 12-1, except that the Y-type molecular sieve (PSRY) is replaced by USY. A catalyst sample was prepared, numbered CAZY15-1.

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

Example 26-2

Same as Example 12-2, except that the Y-type molecular sieve (PSRY) is replaced by USY. A catalyst sample was prepared, numbered CAZY15-2.

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

Comparative Example 26-1

It is the same as Example 26-1, except that the phosphorus modified molecular sieve PSZ1-1 is replaced by the comparative sample DBZ1-1 of Comparative Example 1-1. A catalyst comparison sample was prepared, numbered DCAZY15-1.

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

Comparative Example 26-2

It is the same as Example 26-1, except that the phosphorus modified molecular sieve PSZ-1-1 is replaced by the comparative sample DBZ1-2 of Comparative Example 1-2. A catalyst comparison sample was prepared, numbered DCAZY15-2.

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

Table 22

project Blank test case Example 26-1 Example 26-2 Comparative Example 26-1 Comparative Example 26-2 Material balance, 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, 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 raw material oil for catalytic cracking is naphtha shown in Table 23.

The evaluation conditions are reaction temperature 620°C, regeneration temperature 620°C, and agent-oil ratio 3.2.

Table 22 shows the weight composition and reaction results of each catalyst mixture containing catalytic cracking promoter.

Comparative Example 27-1, Comparative Example 27-2

Same as Example 27-1, except that the catalytic contrast agents DCAZY1-1 and DCAZY1-2 of Comparative Example 12-1 and Comparative Example 12-2 were respectively used.

Table 24 shows the weight composition and reaction results of each catalyst mixture containing the catalytic cracking aid comparative sample.

Table 23

raw material Naphtha Density(20℃)/(gm ^-3 ) 735.8 Vapor pressure/kPa 32 Mass family composition/% paraffins 51.01 normal alkanes 29.40 Naphthenic 38.24 Alkenes 0.12 Aromatic hydrocarbons 10.52 Distillation range/℃ initial distillation 45.5 5% 72.5 10% 86.7 30% 106.5 50% 120.0 70% 132.7 90% 148.5 95% 155.2 final boiling point 166.5

Table 24

The evaluation data in Table 24 shows that the catalyst containing the phosphorus-modified ZSM-5 molecular sieve modified by the impregnation method of the embodiment shows excellent performance in producing liquefied gas while being rich in low-carbon olefins when catalytically cracking different feed oils, including the comparative example For catalysts using molecular sieves modified by the impregnation method, the yields of liquefied gas and light olefins are significantly lower.

The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details of the above embodiments. Within the scope of the technical concept of the present invention, a variety of simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the specific technical features described in the above-mentioned specific embodiments can be combined in any suitable manner as long as there is no contradiction. In order to avoid unnecessary repetition, various possible combinations are not further described in the present invention.

In addition, any combination of various embodiments of the present invention can also be carried out. As long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (38)

1. A catalytic cracking catalyst comprising, on a dry basis, 1 to 25 wt.% of a Y-type molecular sieve, 5 to 50 wt.% of a phosphorus-modified ZSM-5 molecular sieve, 1 to 60 wt.% of an inorganic binder, on a dry basis, and optionally 0 to 60 wt.% of a second clay, on a dry basis; wherein, the phosphorus modified ZSM-5 molecular sieve, ²⁷ in Al MAS-NMR, the ratio of the resonance signal peak area with the chemical shift of 39+/-3 ppm to the resonance signal peak area with the chemical shift of 54 ppm+/-3 ppm is more than or equal to 1, and the molecular sieve is subjected to hydrothermal aging at 800 ℃ under the condition of 100% water vapor for 17 hours and then NH ₃ In the TPD spectrum, the desorption temperature is inThe specific gravity of the central peak area of the strong acid above 200 ℃ to the total central peak area of the acid is more than or equal to 40%; the inorganic binder is at least one of phosphorus aluminum inorganic binder, pseudo-boehmite, aluminum sol, silicon aluminum sol and water glass.

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 rare earth-containing PSRY-S molecular sieve, a USY molecular sieve, a rare earth-containing USY molecular sieve, a REY molecular sieve, a REHY molecular sieve, and an HY molecular sieve.

3. The catalyst of claim 1 wherein said ²⁷ In Al MAS-NMR, the ratio of the resonance signal peak area with the chemical shift of 39+ -3 ppm to the resonance signal peak area with the chemical shift of 54 ppm+ -3 ppm is not less than 10.

4. The catalyst of claim 1 wherein said ²⁷ In Al MAS-NMR, the ratio of the resonance signal peak area with a chemical shift of 39.+ -.3 ppm to the resonance signal peak area with a chemical shift of 54 ppm.+ -.3 ppm is 12 to 25.

5. The catalyst according to claim 1, wherein in the phosphorus-modified ZSM-5 molecular sieve, n1/n2 is less than or equal to 0.1, n1 represents the mole number of phosphorus, and n2 represents the total mole number of silicon and aluminum in the surface XPS elemental analysis.

6. The catalyst according to claim 5, wherein n1/n2 is not more than 0.09.

7. The catalyst according to claim 6, wherein n1/n2 is not more than 0.08.

8. The catalyst according to claim 7, wherein n1/n2 is 0.04 to 0.07.

9. The catalyst of claim 1 wherein said NH is ₃ In the TPD spectrum, the desorption temperature is 200 DEG CThe proportion of the upper strong acid center peak area to the total acid center peak area is more than or equal to 42 percent.

10. The catalyst of claim 1 wherein said NH is ₃ In the TPD spectrum, the specific gravity of the strong acid center peak area with the desorption temperature of more than 200 ℃ to the total acid center peak area is more than or equal to 45 percent.

11. The catalyst of claim 1 wherein said NH is ₃ In the TPD spectrum, the specific gravity of the strong acid center peak area with the desorption temperature of more than 200 ℃ to the total acid center peak area is 48-85 percent.

12. The catalyst of claim 1 wherein the phosphorus-modified ZSM-5 molecular sieve has a ratio of 0.01 to 2 when phosphorus and aluminum are both present on a molar basis.

13. The catalyst of claim 1 wherein the phosphorus-modified ZSM-5 molecular sieve has a ratio of 0.1 to 1.5 when phosphorus and aluminum are both present on a molar basis.

14. The catalyst of claim 1 wherein the phosphorus-modified ZSM-5 molecular sieve has a ratio of 0.2 to 1.5 when phosphorus and aluminum are both present on a molar basis.

15. A process for preparing a catalytic cracking catalyst according to any one of claims 1 to 14, which comprises: mixing, pulping and spray drying a Y-type molecular sieve, a phosphorus modified ZSM-5 molecular sieve and an inorganic binder, and optionally roasting to obtain the catalytic cracking catalyst; wherein a second clay is added or not added to the mixture; the weight ratio of the Y-type molecular sieve to the phosphorus modified ZSM-5 molecular sieve to the inorganic binder to the second clay is (1-25): (5-50): (1-60): (0-60); the inorganic binder is at least one of phosphorus-aluminum inorganic binder, pseudo-boehmite, aluminum sol, silicon-aluminum sol and water glass; the phosphorus modified ZSM-5 molecular sieve is obtained by contacting phosphorus-containing compound solution with an HZSM-5 molecular sieve, drying, performing hydrothermal roasting treatment under external applied pressure and external water-added atmosphere, and recovering a product; the contact is to mix and contact the aqueous solution of the phosphorus-containing compound with the temperature of 0-150 ℃ and the HZSM-5 molecular sieve with the temperature of 0-150 ℃ for at least 0.1 hour by adopting an immersion method, or the contact is to mix and pulp the phosphorus-containing compound, the HZSM-5 molecular sieve and water and then keep the mixture for at least 0.1 hour at the temperature of 0-150 ℃; the apparent pressure of the atmosphere environment is 0.01-1.0 Mpa and contains 1-100% of water vapor.

16. The process according to claim 15, wherein the phosphorus-containing compound is selected from the group consisting of organic phosphides and/or inorganic phosphides.

17. The process according to claim 16, wherein the organic phosphorus compound is selected from the group consisting of trimethyl phosphate, triphenylphosphine, trimethyl phosphite, tetrabutyl phosphine bromide, tetrabutyl phosphine chloride, tetrabutyl phosphine hydroxide, triphenyl ethyl phosphine bromide, triphenyl butyl phosphine bromide, triphenyl benzyl phosphine bromide, hexamethylphosphoric triamide, dibenzyldiethylphosphoric, 1, 3-xylyl bistriethyl phosphorus; the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.

18. The preparation method of claim 15, wherein in the HZSM-5 molecular sieve, na ₂ O<0.1wt％。

19. The process according to claim 15, wherein the molar ratio of the phosphorus-containing compound to HZSM-5 molecular sieve to aluminum is 0.01 to 2.

20. The process according to claim 15, wherein the molar ratio of the phosphorus-containing compound to HZSM-5 molecular sieve to aluminum is 0.1 to 1.5.

21. The process according to claim 15, wherein the molar ratio of the phosphorus-containing compound to HZSM-5 molecular sieve to aluminum is 0.2 to 1.5.

22. The process according to claim 15, wherein the contacting is carried out at 50 to 150 ℃ for 0.5 to 40 hours with a water sieve weight ratio of 0.5 to 1.

23. The process of claim 22 wherein said contacting is at a temperature of from 70 to 130 ℃.

24. The process according to claim 15, wherein the apparent pressure of the atmosphere is 0.1 to 0.8Mpa; the hydrothermal roasting treatment is carried out at 200-800 ℃.

25. The process according to claim 24, wherein the apparent pressure of the atmosphere is 0.3 to 0.6Mpa.

26. The process according to claim 15, wherein said atmosphere comprises 30% to 100% water vapor.

27. The process according to claim 26, wherein said atmosphere comprises 60 to 100% water vapor.

28. The process according to claim 24, wherein the hydrothermal baking treatment is carried out at 300 to 500 ℃.

29. The preparation method of claim 15, wherein the phosphorus-aluminum inorganic binder is phosphorus-aluminum glue and/or phosphorus-aluminum inorganic binder containing first clay; the first clay-containing phosphorus-aluminum inorganic binder contains, based on the dry weight of the first clay-containing phosphorus-aluminum inorganic binder, al ₂ O ₃ 15-40 wt% of aluminum component, calculated as P ₂ O ₅ 45-80 wt% of a phosphorus component on a dry basis0 to not more than 40 wt% of a first clay, wherein the P/Al weight ratio of the phosphorus-aluminum inorganic binder containing the first clay is 1.0 to 6.0, the pH is 1 to 3.5, and the solid content is 15 to 60 wt%; the first clay includes at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, and diatomaceous earth.

30. The process according to claim 15, 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.

31. The preparation method according to claim 15, wherein the catalyst comprises 3 to 40 wt% of an inorganic binder of phosphorus-aluminum or 3 to 40 wt% of an inorganic binder of phosphorus-aluminum and 1 to 30 wt% of at least one of pseudo-boehmite, alumina sol, silica-alumina sol and water glass on a dry basis of the catalyst.

32. The method of preparing according to claim 15, wherein the Y-type molecular sieve comprises at least one of a PSRY molecular sieve, a rare earth-containing PSRY molecular sieve, a USY molecular sieve, a rare earth-containing USY molecular sieve, a REY molecular sieve, a REHY molecular sieve, and an HY molecular sieve.

33. The method of manufacturing according to claim 15, wherein the method further comprises: washing and optionally drying the product obtained by the roasting treatment to obtain the catalytic cracking catalyst; wherein the roasting temperature of the roasting treatment is 300-650 ℃ and the roasting time is 0.5-12 h.

34. The method of preparing according to claim 29, further comprising preparing the first clay-containing phosphorus aluminum inorganic binder by: pulping and dispersing an alumina source, the first clay and water into slurry with a 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 15-40In parts by weight of Al ₂ O ₃ An alumina source in an amount of greater than 0 parts by weight and no more than 40 parts by weight, based on dry weight of the first clay; adding concentrated phosphoric acid to the slurry with stirring according to the weight ratio of P/Al=1-6, and reacting the obtained mixed slurry at 50-99 ℃ for 15-90 minutes; wherein P in the P/Al is the weight of phosphorus in phosphoric acid in terms of simple substance, and Al is the weight of aluminum in the alumina source in terms of simple substance.

35. A catalytic cracking catalyst prepared by the method of any one of claims 15-34.

36. A catalytic cracking process, characterized in that the catalyst is a catalytic cracking catalyst according to any one of claims 1 to 14 or claim 35.

37. The catalytic cracking process according to claim 36, comprising: contacting 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 ℃.

38. The catalytic cracking method according to claim 37, wherein the hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric wax oil, vacuum wax oil, straight run wax oil, coker wax oil, and coal liquefied product.