A catalytic cracking catalyst and a method for preparing the same

Abstract

The present application belongs to the field of catalyst preparation, and relates to a catalytic cracking catalyst and a preparation method thereof. The catalytic cracking catalyst comprises 10-70 wt% of a cracking active component, 10-60 wt% of a binder and 10-70 wt% of clay, wherein the cracking active component comprises 5-100 wt% of a first Y-type molecular sieve and 0-95 wt% of a second molecular sieve; the first Y-type molecular sieve is a modified kaolin-based metacrystalline molecular sieve, and the sodium oxide content thereof is less than 2 wt%. The preparation method of the catalyst comprises the steps of beating, spray drying, washing, filtering and drying the cracking active component comprising the modified kaolin-based metacrystalline molecular sieve, the binder and the clay. The catalyst is used for heavy oil catalytic cracking reaction, and has good coke selectivity and high heavy oil conversion rate.

Description

Technical Field

[0001] This invention relates to a catalytic cracking catalyst, and more particularly to a low-coke catalytic cracking catalyst and its preparation method. Background Technology

[0002] Catalytic cracking (FCC) is a crucial secondary processing step in crude oil, playing a vital role in the refining industry. In FCC, heavy fractions, such as vacuum distillate or even heavier residues, react in the presence of a catalyst to produce high-value-added products like liquefied petroleum gas (LPG), gasoline, and diesel. This process typically requires catalytic materials with high cracking activity. Y-type zeolites, due to their excellent shape-selective catalytic properties and high cracking reactivity, are widely used in catalytic cracking reactions. Y-type zeolites are obtained through two techniques: one technique involves first synthesizing Y-type zeolites using alkaline silica-alumina gel, then mixing the Y-type zeolites with a matrix and spray-drying to obtain microsphere catalysts. The Y-type zeolites synthesized using alkaline silica-alumina gel are characterized by high molecular sieve content and a high silica-to-alumina ratio, and can exhibit various reaction characteristics through different modification methods. The other technique is in-situ crystallization, which first forms microspheres, then crystallizes them to generate molecular sieves, directly obtaining catalyst microspheres containing both active components (molecular sieves) and non-molecular sieve components. Catalysts synthesized using in-situ crystallization exhibit strong resistance to heavy metal contamination, high activity index, and good hydrothermal and structural stability. However, currently, Y-type molecular sieves synthesized through in-situ crystallization have relatively high coke yields when used for heavy oil conversion.

[0003] Bao Xiaojun's CN103043680A uses natural kaolin and natural diatomite minerals as the sole silicon and aluminum sources for molecular sieve synthesis, and these minerals serve as the matrix for molecular sieve growth, forming crystalline products through in-situ crystallization. In this composite material, the mass percentage of NaY molecular sieve is 25% to 50%, and the silicon-to-aluminum ratio of the NaY molecular sieve is 3 to 5.5.

[0004] Zheng Shuqin (Synthesis of hierarchical porous catalytic materials by hydrothermal crystallization of Si-Al gel and kaolin, Acta Petrolei Sinica (Petroleum Processing), V30(1), 32-37) reported the hydrothermal synthesis of hierarchical porous catalytic materials by Si-Al gel and kaolin. The method is to prepare Si-Al gel by using water glass and sodium aluminate as silicon source and aluminum source respectively, then spray it with kaolin to form spheres, and then synthesize it.

[0005] The above disclosure does not address how to reduce the coke selectivity of catalysts containing in-situ crystallized Y-type molecular sieves in heavy oil conversion. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to address the issue of high coking in in-situ crystallized Y-type molecular sieve catalytic cracking catalysts in the prior art, and to provide a catalytic cracking catalyst with low coking under the condition of high heavy oil conversion rate, which contains molecular sieve active components based on kaolin crystallization.

[0007] A catalytic cracking catalyst comprises: 10-70 wt% of a cracking active component, 10-60 wt% of a binder, and 10-70 wt% of clay, wherein the cracking active component comprises 5-100 wt% of a first Y-type molecular sieve and 0-95 wt% of a second molecular sieve, wherein the first Y-type molecular sieve is a modified kaolin-based transcrystalline molecular sieve, and the modified kaolin-based transcrystalline molecular sieve is obtained by modifying the kaolin-based transcrystalline molecular sieve.

[0008] The described kaolin-based molecular sieve, measured by X-ray diffraction, has a crystallinity of ≥60% based on peak height, with a ratio of K1 (0.76-0.89) to that based on peak area. The silicon-to-alumina ratio (S / A ratio) determined by the cell constant a0 is 5.0-5.5, with a ratio of K2 (0.87-0.93) to that determined by chemical methods. All S / A ratios are molar ratios of silicon oxide to aluminum oxide. The crystallinity based on peak height is ≥80%, with K1 = 0.80-0.89 or K1 = 0.80-0.85. K2 = 0.87-0.92 or K2 = 0.88-0.90.

[0009] In a preferred embodiment, the molecular sieve based on kaolin crystallization has K1 = 0.77-0.88 and K2 = 0.87-0.91.

[0010] In one embodiment, the molecular sieve based on kaolin crystallization has a mesopore rate of 10-20%.

[0011] In one embodiment, the silicon-to-aluminum ratio of the kaolin-based molecular sieve, determined by the cell constant a0, is 5.2-5.5.

[0012] In a preferred embodiment, the modified kaolin-based molecular sieve contains rare earth elements (the rare earth-containing modified Y-type molecular sieve is also called a rare earth-containing kaolin-based molecular sieve), and its rare earth content, calculated as RE2O3, is preferably 10%-20% by weight. With the rare earth content of the modified kaolin-based molecular sieve within this range, the catalytic cracking catalyst can exhibit higher heavy oil conversion activity.

[0013] This invention provides a method for preparing a catalytic cracking catalyst, comprising the following steps:

[0014] (S1) Preparation of modified molecular sieves based on kaolin crystallization;

[0015] (S2) Forming a slurry from clay, including modified kaolin-based molecular sieves and optional second molecular sieves, and a binder;

[0016] (S3) Spray dry the slurry obtained in step S2.

[0017] According to the preparation method of the catalytic cracking catalyst provided by the present invention, the modified kaolin-based molecular sieve is a modified kaolin-based molecular sieve (also known as an in-situ crystallization synthesized molecular sieve) obtained by modification treatment.

[0018] According to the preparation method of the catalytic cracking catalyst provided by the present invention, the modified kaolin-based molecular sieve can be obtained by modifying the kaolin-based molecular sieve. The kaolin-based molecular sieve is a Y-type molecular sieve composite material. Measured by X-ray diffraction, the crystallinity of the kaolin-based molecular sieve (or the Y-type molecular sieve composite material) by peak height method is ≥60%, and the ratio of the crystallinity by peak area method is K1, K1 = 0.76-0.89; the silicon-to-aluminum ratio determined by cell constant a0 is 5.0-5.5, and the ratio of the silicon-to-aluminum ratio determined by chemical method is K2, K2 = 0.87-0.90. All silicon-to-aluminum ratios are molar ratios of silicon oxide and aluminum oxide. The modified kaolin-based molecular sieve is a molecular sieve material obtained by modifying the kaolin-based molecular sieve. The modification process reduces the sodium oxide content in the kaolin-based molecular sieve to below 2% by weight. The modification process can be, for example, ion exchange.

[0019] The kaolin-based molecular sieve of the present invention has spherical-like structures of 5-20 micrometers, wherein the crystallinity by peak height method is ≥60%, that is, the mass percentage content of NaY molecular sieve is at least 60%. Preferably, the crystallinity by peak height method is greater than 75%, more preferably ≥80%.

[0020] According to basic crystallization knowledge, the difference between the crystallinity determined by the peak height method and the crystallinity determined by the peak area method is related to the grain size. The Y-type molecular sieve composite material (hereinafter referred to as the composite material) described in this invention has a set grain size coefficient K1, where K1 = S 峰高 / S 峰面积 K1 is the ratio of the crystallinity obtained by the peak height method to the crystallinity obtained by the peak area method. The value of K1 indicates the size of the grains; a larger K1 value indicates a larger grain size. The preferred K1 value is 0.80-0.89, and more preferably 0.80-0.85.

[0021] The molar ratio of silicon oxide to aluminum oxide calculated using the cell constant a0 is the framework silicon-aluminum ratio of the molecular sieve, while the molar ratio of silicon oxide to aluminum oxide determined by chemical methods is the overall silicon-aluminum ratio of the composite material. The molecular sieve based on kaolin crystallization described in this invention has a framework silicon-aluminum ratio of 5.0-5.5, preferably 5.2-5.5, calculated using the cell constant a0, while the overall silicon-aluminum ratio determined by chemical methods is the macroscopic silicon-aluminum ratio of the entire material. Both the framework silicon-aluminum ratio and the overall silicon-aluminum ratio are related to the integrity and purity of the molecular sieve framework in the composite material. The molecular sieve based on kaolin crystallization described in this invention is obtained from metakaolin crystallization, where a portion of the metakaolin is in the intermediate stage of crystallization into a Y-type molecular sieve. Therefore, an intermediate system number K2 is defined, i.e., K2 = framework silicon-aluminum ratio / overall silicon-aluminum ratio. The magnitude of the K2 value indicates the degree of composite material composition; the smaller the K2 value, the more intermediates are contained. The preferred value of K2 is 0.87-0.92, and the more preferred value is 0.88-0.90.

[0022] The molecular sieve based on kaolin crystallization (also known as Y-type molecular sieve composite material) of the present invention preferably has K1 = 0.77-0.88, for example K1 = 0.81-0.88 or K1 = 0.86-0.88 and K2 = 0.87-0.91.

[0023] In this invention, pores with a diameter greater than 0.8 nm are defined as mesopores or macropores. The molecular sieve based on kaolin crystallization described in this invention has a suitable mesopore-to-macropore ratio, wherein the macropore ratio is 10-20%.

[0024] According to the preparation method of the catalytic cracking catalyst provided by the present invention, the molecular sieve based on kaolin crystallization is a Y-type molecular sieve composite material. One preparation method includes the following steps: (1) calcining and dehydrating kaolin at 500-900℃ to convert it into metakaolin, pulverizing it, and preparing metakaolin powder with a particle size of less than 10 micrometers; (2) adding sodium silicate, a directing agent, sodium hydroxide solution and water to the metakaolin powder to prepare a molar ratio of (1-2.5) Na2O:Al2 O3:(4-9)SiO2:(40-100)H2O reaction raw material A, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0; (3) the reaction raw material A is crystallized under stirring at 88-98℃, and after the crystallization time reaches 1-70h, a second silicon source is added to obtain reaction raw material B, wherein the second silicon source accounts for 0.1-10% by weight of the total silicon feed, all calculated as silicon oxide; (4) the reaction raw material B is crystallized under stirring at 88-98℃ and the product is recovered.

[0025] According to the preparation method of the catalytic cracking catalyst provided by the present invention, in the method for preparing molecular sieves based on kaolin crystallization, the directing agent can be synthesized according to conventional methods, such as those described in USP3574538, USP3639099, USP3671191, USP4166099, and EUP0435625. The molar composition of the directing agent is: (10-17)SiO2:(0.7-1.3)Al2O3:(11-18)Na2O:(200-350)H2O. During synthesis, the raw materials are aged at 4-35℃, preferably 4-20℃, to obtain the directing agent.

[0026] According to the preparation method of the catalytic cracking catalyst provided by the present invention, in the preparation method of the molecular sieve based on kaolin crystallization, the second silicon source has a sodium content of 0.01%-10% by weight (Na2O), preferably <1% by weight. Considering cost control, the preferred second silicon source is solid silica gel. The solid silica gel is included in the total synthesis ratio, and the solid silica gel used can be solid silica gel with different pore sizes. Based on pore size, there are fine-pore silica gel, coarse-pore silica gel, and mesoporous silica gel between the two. Conventionally, silica gel with an average pore size below 1.5-2.0 nm is called fine-pore silica gel (e.g., type A solid silica gel from Qingdao Ocean Chemical Group Special Silica Gel Factory), and silica gel with an average pore size above 4.0-5.0 nm is called coarse-pore silica gel (e.g., type C solid silica gel from Qingdao Ocean Chemical Group Special Silica Gel Factory); furthermore, silica gel with an average pore size above 10.0 nm is called extra-coarse-pore silica gel, and silica gel with an average pore size below 0.8 nm is called extra-fine-pore silica gel (e.g., type B solid silica gel from Qingdao Ocean Chemical Group Special Silica Gel Factory). The second silicon source can also be liquid silicone. When liquid silicone is used as the second silicon source, preferably, the SiO2 content therein is at least 30%.

[0027] According to the preparation method of the catalytic cracking catalyst provided by the present invention, the method for preparing the molecular sieve based on kaolin crystallization involves crystallizing a multi-level porous Y-type molecular sieve composite material product containing a certain number of medium and large pores under stirring. The crystallization stirring speed can be, but is not limited to, 50-1000 rpm, preferably 300-500 rpm, and the time can be 16-48 hours, preferably 24-32 hours. The drying temperature of the zeolite after crystallization is 100-120℃.

[0028] According to the method for preparing catalytic cracking catalyst provided by the present invention, in the method for preparing molecular sieve based on kaolin crystallization, the second silicon source accounts for 0.1-10% by weight of the total silicon feed, preferably 4-10% by weight, based on silicon oxide.

[0029] According to the method for preparing catalytic cracking catalyst provided by the present invention, in the method for preparing molecular sieves based on kaolin crystallization, sodium silicate and a second silicon source are added to the synthesis preparation system at different stages, particularly the second silicon source being added during the crystal growth period. This invention combines the method of adding different silicon sources at different stages of the crystallization process to control the synthesis ratio with in-situ crystallization synthesis technology of kaolin (using natural minerals as the main aluminum and silicon sources). By using the silicon source to change the crystal growth environment, two completely different material ratios are used in the crystal nucleation period and the crystal growth period. In the crystal nucleation period, the method of this invention uses a larger sodium-to-silicon ratio (Na₂O / SiO₂) in the material, which is beneficial to the rapid nucleation of Y-type molecular sieves. In the crystal growth period, a low-sodium or sodium-free silicon source is added to increase the silicon-to-aluminum ratio (SiO₂ / Al₂O₃) in the synthesized material while decreasing the sodium-to-silicon ratio (Na₂O / SiO₂). This shortens the crystallization time and is beneficial to increasing the silicon-to-aluminum ratio of the product, raising the framework silicon-to-aluminum ratio to 5.0-5.5.

[0030] According to the method for preparing the catalytic cracking catalyst provided by the present invention, in the step (4) of preparing the molecular sieve based on kaolin crystallization, the product is recovered after crystallization to obtain the molecular sieve based on kaolin crystallization. The recovery typically includes a filtration step, and optionally may also include one or more processes such as washing, drying, and calcination.

[0031] According to the method for preparing the catalytic cracking catalyst provided by the present invention, the modified molecular sieve based on kaolin crystallization is prepared by means of: subjecting the above-mentioned recovered product to a modification treatment, such as ion exchange, to obtain the modified molecular sieve based on kaolin crystallization.

[0032] According to the method for preparing the catalytic cracking catalyst provided by the present invention, the obtained kaolin-based molecular sieve can be treated by any method capable of reducing the sodium content therein to ensure that the sodium oxide content does not exceed 2% by weight. For example, modified kaolin-based molecular sieves can be obtained by ion exchange. The ion exchange can be performed using ammonium salt and / or rare earth salt solutions; the present invention has no particular requirements. Preferably, the ion exchange results in the obtained modified kaolin-based molecular sieve having a rare earth content (RE2O3) of 10%-20% by weight and a sodium oxide content of less than 2% by weight. In one embodiment, the kaolin-based molecular sieve is mixed with an exchange solution and stirred at 20-90°C for 10-120 minutes. This process can be performed once or multiple times, and the exchange solution in each exchange can contain ammonium ions, rare earth ions, or both. Preferably, the concentration of ammonium salt in the exchange solution is 5-700 g / L, for example 5-100 g / L, and / or the concentration of rare earth salt, calculated as RE2O3, is 5-400 g / L, for example 5-200 g / L. The ammonium salt is, for example, one or more of ammonium chloride, ammonium nitrate, and ammonium sulfate. The rare earth salt is, for example, one or more of rare earth chloride and rare earth nitrate. The rare earth may include one or more of lanthanide and actinide rare earth elements, for example, one or more of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, TB, Dy, Ho, Er, Tm, Yb, and Lu.

[0033] According to the preparation method of the catalytic cracking catalyst provided by the present invention, the molecular sieve based on kaolin crystallization may further include one or more steps of filtration, washing, drying and calcination after ion exchange. These steps may refer to filtration, washing, drying and calcination methods well known to those skilled in the art.

[0034] The method for preparing catalytic cracking catalyst provided by the present invention, wherein step S2 involves forming a slurry from clay, modified kaolin-based molecular sieve, optional second molecular sieve, and binder, can be achieved by mixing clay, modified kaolin-based molecular sieve, optional second molecular sieve, binder, and water, and stirring until homogeneous.

[0035] According to the preparation method of the catalytic cracking catalyst provided by the present invention, in step S3, the slurry obtained in step S2 is spray-dried to obtain catalyst microspheres. The catalyst microspheres can be further calcined and / or washed, with the washing performed before and / or after calcination. The spray drying, washing, and calcination can be carried out according to existing methods for spray drying and calcination in the production of catalytic cracking catalysts. For example, the washing may be performed with an ammonium salt solution, and the calcination may be carried out at 350-650°C for 1-4 hours.

[0036] The catalytic cracking catalyst provided by this invention exhibits good coke selectivity, reducing coke selectivity while maintaining high hydrocarbon-oil conversion catalytic activity. Preferably, the catalytic cracking catalyst provided by this invention also possesses even higher hydrocarbon-oil conversion activity and / or liquid product yield. Detailed Implementation

[0037] The following detailed embodiments and examples are provided to further illustrate the present invention. It should be understood that the detailed embodiments and examples described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0038] The catalytic cracking catalyst provided by the present invention comprises: 10-70 wt%, for example 20-60 wt% or 25-65 wt%, a cracking active component, 10-60 wt%, for example 20-45 wt%, a binder, and 10-70 wt%, for example 20-60 wt% or 25-55 wt%, clay, wherein the cracking active component comprises 5-100 wt%, for example 40-100 wt%, a first Y-type molecular sieve and 0-95 wt%, for example 0-60 wt%, a second molecular sieve.

[0039] The catalytic cracking catalyst provided by this invention may further contain a second molecular sieve, preferably an octahedral zeolite and / or a molecular sieve with a five-membered ring structure. The octahedral zeolite is, for example, one or more of HY, REY, REHY, USY, REUSY, DASY, and REDASY. The molecular sieve with a five-membered ring structure is, for example, a BEA-structured molecular sieve, an MFI-structured molecular sieve, or mordenite, preferably one or more of a BEA-structured molecular sieve and an MFI-structured molecular sieve. The BEA-structured molecular sieve can be obtained by amine-free crystallization or by calcining a molecular sieve prepared using a template agent method; for example, the BEA-structured molecular sieve is, for example, a β-molecular sieve. The MFI-structured molecular sieve is, for example, at least one of rare-earth-containing MFI-structured molecular sieves, phosphorus-containing MFI-structured molecular sieves, iron-containing MFI-structured molecular sieves, and phosphorus- and transition metal-containing MFI-structured molecular sieves. The mordenite is, for example, at least one of high-silica mordenite or low-silica mordenite.

[0040] The catalytic cracking catalyst provided by the present invention contains clay, which may be one or more of the following: kaolin, hydrous kaolin, montmorillonite, diatomite, halloysite, quasi-haloysite, soapstone, rettosite, sepiolite, attapulgite, hydrotalcite, and bentonite.

[0041] The catalytic cracking catalyst provided by the present invention contains a binder, which may be selected from one or more of silica sol, alumina sol, boehmite (hereinafter referred to as boehmite), and metal-modified boehmite.

[0042] In the catalytic cracking catalyst provided by the present invention, the first Y-type molecular sieve is a modified molecular sieve based on kaolin crystallization, preferably a molecular sieve based on kaolin crystallization containing rare earth elements, wherein the rare earth content is 10%-20% by weight (RE2O3) and the sodium oxide content is no more than 2% by weight, preferably no more than 1.5% by weight.

[0043] In one embodiment, the modified kaolin-based molecular sieve is prepared according to the following steps:

[0044] (1) Kaolin is calcined at 500-900℃ to dehydrate and transform into metakaolin, which is then crushed to make powder with a particle size of less than 10 micrometers.

[0045] (2) Sodium silicate, a directing agent, sodium hydroxide solution and water are added to metakaolin powder to prepare a reaction slurry, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0.

[0046] (3) After the reaction slurry prepared in (2) is crystallized at 88-98℃ for 1-70h, for example 5-40h, 6-30h or 8-16h, solid silica gel is added, wherein the mass ratio of solid silica gel to metakaolin is 0.01-1.0.

[0047] (4) The reaction raw materials obtained in (3) are crystallized under stirring at 88-98℃ for 1-20h, for example 8-20h or 12-16h. Then, the mixture is filtered and dried to obtain the in-situ crystallized molecular sieve based on kaolin crystallization.

[0048] (5) The obtained in-situ crystallized molecular sieve based on kaolin crystallization is contacted with ammonium salt and / or rare earth salt solution for ion exchange, filtered, washed, dried, and calcined to obtain a modified molecular sieve based on kaolin crystallization. The rare earth content in the modified molecular sieve based on kaolin crystallization is preferably 10%-20% by weight (RE2O3), and the sodium oxide content is less than 2% by weight. The contact can be performed once or multiple times. Each contact exchange can be performed with a solution containing both rare earth ions and ammonium ions, or with a solution containing only one type of ion for ammonium ion exchange or rare earth ion exchange.

[0049] In one embodiment, the in-situ crystallization synthesized molecular sieve based on kaolinite transcrystallization contains 20%-30% by mass of an intermediate that is a transcrystallization intermediate from metakaolinite to Y-type molecular sieve. Due to the presence of this intermediate, K2 is in the range of 0.87-0.93.

[0050] The purpose of this invention is to provide a catalyst with good catalytic activity. When the catalyst is applied to a catalytic cracking reaction, the catalyst can achieve at least one, two, three or all of the following properties: (1) good anti-wear properties, (2) low coke selectivity, (3) high heavy oil conversion and high total liquid yield, and (4) strong resistance to metal contamination. The catalyst can be used for the catalytic cracking of hydrocarbon oils (e.g., heavy oil), for example for the production of low-carbon olefins.

[0051] To achieve the above objectives, the present invention provides the following six sets of technical solutions:

[0052]

Group A

[0053] 1. A catalytic cracking catalyst, comprising: 10-70 wt% of a cracking active component, 10-60 wt% of a binder, and 10-70 wt% of clay, wherein the cracking active component comprises 5-100 wt% of a first Y-type molecular sieve and 0-95 wt% of a second molecular sieve; wherein the first Y-type molecular sieve is a modified kaolin-based molecular sieve obtained by modifying a kaolin-based molecular sieve, and its sodium oxide content is less than 2 wt%.

[0054] 2. The catalytic cracking catalyst according to technical solution 1 of Group A, wherein the molecular sieve based on kaolin crystallization has a crystallinity of ≥60% as measured by X-ray diffraction using the peak height method, and the ratio of the crystallinity to that of the peak area method is K1, K1 = 0.76-0.89; the silicon-aluminum ratio determined by the cell constant a0 is 5.0-5.5, and the ratio of the silicon-aluminum ratio determined by the chemical method is K2, K2 = 0.87-0.93, wherein the silicon-aluminum ratio is the molar ratio of silicon oxide to aluminum oxide.

[0055] 3. The catalytic cracking catalyst according to technical solution 2 of Group A, wherein the crystallinity of the peak height method is ≥80%.

[0056] 4. The catalytic cracking catalyst according to technical solution 2 of group A, wherein K1 = 0.80-0.89.

[0057] 5. The catalytic cracking catalyst according to technical solution 2 of group A, wherein K1 = 0.80-0.85.

[0058] 6. The catalytic cracking catalyst according to technical solution 2 of group A, wherein K2 = 0.87-0.92.

[0059] 7. The catalytic cracking catalyst according to technical solution 2 of group A, wherein K2 = 0.88-0.90.

[0060] 8. The catalytic cracking catalyst according to technical solution 2 of group A, wherein K1 = 0.77-0.88 and K2 = 0.87-0.91.

[0061] 9. The catalytic cracking catalyst according to technical solution 2 of Group A, wherein the mesopores of the molecular sieve based on kaolin crystallization are 10-20%.

[0062] 10. The catalytic cracking catalyst according to technical solution 2 of group A, wherein the silicon-to-aluminum ratio measured by the cell constant a0 is 5.2-5.5.

[0063] 11. The catalytic cracking catalyst according to technical solution 1 or 2 of Group A, wherein the molecular sieve based on kaolin crystallization is prepared by the following steps:

[0064] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, and then crushed into metakaolin powder with a particle size of less than 10 micrometers.

[0065] (2) Add a directing agent, sodium silicate, sodium hydroxide solution and water to the metakaolin powder to prepare reaction raw material A, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0, and the ratio of reaction raw material A is (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O molar ratio;

[0066] (3) After crystallizing reaction raw material A at 88-98℃ for 1-70h with stirring, a second silicon source is added to obtain reaction raw material B, wherein the second silicon source accounts for 0.1-10% by weight of the total silicon feed, based on silicon oxide.

[0067] (4) Crystallize the reaction raw material B under stirring at 88-98℃ and recover the product.

[0068] 12. The catalytic cracking catalyst according to any one of the technical solutions 1-11 in Group A, wherein the modified molecular sieve based on kaolin crystallization contains rare earth elements, and the rare earth content in the modified molecular sieve based on kaolin crystallization is 10%-20% by weight (RE2O3).

[0069] 13. The catalytic cracking catalyst according to technical solution 1 of Group A, wherein the second molecular sieve is selected from octahedral zeolite and / or molecular sieves with a five-membered ring structure; for example, the octahedral zeolite is one or more of HY, REY, REHY, USY, REUSY, DASY, and REDASY; the molecular sieve with a five-membered ring structure includes one or more of BEA structure molecular sieves, MFI structure molecular sieves, and mordenite; the binder is selected from one or more of silica sol, alumina sol, borosilicate, and metal-modified borosilicate; the clay is one or more of kaolin, montmorillonite, diatomaceous earth, halloysite, quasi-haloysite, soapstone, rettosite, sepiolite, attapulgite, hydrotalcite, and bentonite.

[0070] 14. A method for preparing the catalytic cracking catalyst according to any one of the technical solutions 1-13 in Group A, comprising the following steps:

[0071] (1) Preparation of modified molecular sieves based on kaolin crystallization;

[0072] (2) Forming a slurry from clay, cracking active components and binder; wherein the cracking active components include the modified kaolin-based molecular sieve and an optional second molecular sieve;

[0073] (3) Spray dry the slurry obtained in step (2).

[0074] 15. The method for preparing a catalytic cracking catalyst according to technical solution 14 of Group A, wherein the method for preparing the modified molecular sieve based on kaolin crystallization includes the following steps:

[0075] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, which is then crushed to produce metakaolin powder with a particle size of less than 10 micrometers.

[0076] (2) Add sodium silicate, a directing agent, sodium hydroxide solution and water to metakaolin powder to prepare reaction raw material A with a ratio of (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0.

[0077] (3) The reaction raw material A is crystallized under stirring at 88-98℃. After the crystallization time reaches 1-70h, a second silicon source is added to obtain the reaction raw material B. The second silicon source accounts for 0.1%-10% of the total silicon feed amount, all calculated as silicon oxide.

[0078] (4) Crystallize reaction material B under stirring at 88-98℃ and recover the product;

[0079] (5) The recovered products are subjected to ion exchange.

[0080] 16. The method for preparing a catalytic cracking catalyst according to technical solution 15 of Group A, wherein the composition of the directing agent is: (10-17)SiO2:(0.7-1.3)Al2O3:(11-18)Na2O:(200-350)H2O.

[0081] 17. The preparation method according to technical solution 15 of group A, wherein the sodium content of the second silicon source is less than 1% by weight, calculated as Na2O.

[0082] 18. The method for preparing a catalytic cracking catalyst according to technical solution 15 or 17 of Group A, wherein the second silicon source is solid silica gel.

[0083] 19. The method for preparing a catalytic cracking catalyst according to technical solution 18 of Group A, wherein the average pore size of the solid silica gel is 1.5-2.0 nm, or the average pore size of the solid silica gel is 4.0-5.0 nm, or the average pore size of the solid silica gel is above 10.0 nm, or the average pore size of the solid silica gel is below 0.8 nm.

[0084] 20. The method for preparing a catalytic cracking catalyst according to technical solution 15 or 17 of Group A, wherein the second silicon source is liquid silica gel.

[0085] 21. The method for preparing a catalytic cracking catalyst according to technical solution 20 of Group A, wherein the mass content of SiO2 in the liquid silica gel is 1-30%.

[0086] 22. The method for preparing a catalytic cracking catalyst according to technical solution 15 of Group A, wherein, based on silicon oxide, the second silicon source accounts for 4-10% by weight of the total silicon feed.

[0087] 23. The method for preparing catalytic cracking catalyst according to technical solution 15 of Group A, wherein the ion exchange in step (5) is ammonium ion exchange and / or rare earth ion exchange.

[0088] 24. The method for preparing catalytic cracking catalyst according to technical scheme 15 or 23 of Group A, wherein the ion exchange product obtained in step (5) is further calcined.

[0089] 25. The method for preparing a catalytic cracking catalyst according to technical solution 15 or 24 of Group A, wherein the ion exchange includes rare earth ion exchange, and the rare earth content in the modified molecular sieve based on kaolin crystallization obtained in step (5) is 10%-20% by weight (RE2O3) and the sodium oxide content is less than 2% by weight.

[0090] 26. A catalytic cracking method, comprising the step of contacting and reacting a hydrocarbon oil with a catalytic cracking catalyst as described in any one of the technical solutions 1-13 of Group A.

[0091] Group B

[0092] 1. A silicon-aluminum material, the anhydrous weight chemical formula of which is: (0-1)Na2O·(15-50)Al2O3·(85-50)SiO2, the most probable pore size is 10-100nm, the specific surface area is 150-600m2 / g, the pore volume is 0.5-1.5ml / g, and the proportion of pore volume with a pore size greater than 10nm to the total pore volume is 70%-98%.

[0093] 2. The silicon-aluminum material according to technical solution 1 of Group B, wherein the silicon-aluminum material contains boehmite grains, and the average size of the boehmite grains is 1.5nm-3.5nm.

[0094] 3. The silicon-aluminum material according to technical solution 1 of Group B, wherein the pore volume of the silicon-aluminum material is 0.8-1.5 ml / g.

[0095] 4. The silicon-aluminum material according to technical solution 1 of Group B, wherein the specific surface area of ​​the silicon-aluminum material is 280-450 m2 / g.

[0096] 5. The silicon-aluminum material according to technical solution 1 of group B, wherein the weight ratio of SiO2 to Al2O3 in the silicon-aluminum material is 2-4:1.

[0097] 6. The method for preparing silicon-aluminum material according to any one of technical solutions 1-5 in Group B includes the following steps:

[0098] (1) At room temperature to 95°C, the alkaline silicon source is gradually added to the acidic aluminum source according to the weight ratio of SiO2:Al2O3=(50-85):(50-15);

[0099] (2) After all the alkaline silicon source is added to the acidic aluminum source, an alkaline solution is added until the pH of the slurry is 8-10.5, and then aged at 50-95℃ for 1-10 hours to obtain a solid precipitate;

[0100] (3) The solid precipitate is contacted with a solution containing ammonium salt and / or acid, and filtered to obtain a silicon-aluminum material with a sodium content of less than 1% by weight based on Na2O. The solid precipitate may or may not be dried before contacting the solution containing ammonium salt and / or acid.

[0101] 7. The method for preparing silicon-aluminum materials according to technical solution 6 of Group B, wherein the acidic aluminum source is selected from aluminum sulfate, aluminum chloride, aluminum sol, and acidic hydrolysis products of aluminum metal alkoxides, and the aluminum metal alkoxides are, for example, aluminum isopropoxide, aluminum sec-butoxide, aluminum triethanolamine, etc., one or more of these.

[0102] 8. The method for preparing silicon-aluminum materials according to technical solution 6 of Group B, wherein the alkaline silicon source is selected from alkaline silica sol, water glass, sodium silicate, alkaline hydrolysis products of silicon ester, and the silicon ester is one or more such as methyl orthosilicate, tetraethyl orthosilicate, isopropyl orthosilicate, butyl orthosilicate.

[0103] 9. The method for preparing silicon-aluminum materials according to technical solution 6 of group B, wherein the alkaline solution is one or more of ammonia water, sodium hydroxide solution, potassium hydroxide solution, and sodium aluminate solution, and is more preferably sodium aluminate solution.

[0104] 10. The method for preparing silicon-aluminum materials according to technical solution 6 of Group B, wherein the contact treatment process of the solid precipitate with a solution containing ammonium salt and / or acid includes: contacting the obtained solid precipitate with the solution containing ammonium salt at room temperature to 100°C according to the weight ratio of dry basis of solid precipitate: ammonium salt: H2O = 1:(0.05-0.1):(5-30).

[0105] 11. The method for preparing silicon-aluminum materials according to technical solution 6 or 10 of Group B, wherein the ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium bicarbonate.

[0106] 12. The method for preparing silicon-aluminum materials according to technical solution 6 of Group B, wherein the solution containing ammonium salt and / or acid is an acid solution, and the contact treatment of the solid precipitate with the solution containing ammonium salt and / or acid is to contact the solid precipitate with the acid solution at room temperature to 100°C for at least 0.5 hours, for example, 0.5-2 hours, according to the weight ratio of solid precipitate dry basis: acid: H2O = 1:(0.03-0.3):(5-30), and the exchange can be performed once or multiple times.

[0107] 13. The method for preparing silicon-aluminum materials according to technical solution 6 or 12 of Group B, wherein the acid is one or more of sulfuric acid, hydrochloric acid or nitric acid.

[0108] 14. The method for preparing silicon-aluminum materials according to any one of technical solutions 6-13 in Group B, wherein the process of contact treatment with a solution containing ammonium salt and / or acid is performed once or multiple times, each contact lasting 0.5-1 hour, until the sodium oxide content in the solid precipitate is less than 1% by weight.

[0109] 15. The silicon-aluminum material obtained by the silicon-aluminum material preparation method described in any one of the technical solutions 6-14 of Group B.

[0110] 16. A catalytic cracking catalyst, comprising 10 wt%-70 wt% of a cracking active component, 1 wt%-20 wt% of a silica-alumina material, 10 wt%-60 wt% of a binder, and 10 wt%-70 wt% of clay; wherein the cracking active component comprises 25 wt%-100 wt% of a first Y-type molecular sieve and 0-75 wt% of a second molecular sieve; wherein the first Y-type molecular sieve is a Y-type molecular sieve synthesized in situ by crystallization with a sodium oxide content of less than 2 wt%, and the silica-alumina material is any one of technical solutions 1-5 of Group B or the silica-alumina material described in technical solution 15 of Group B.

[0111] 17. The catalytic cracking catalyst according to technical solution 16 of Group B, wherein the Y molecular sieve synthesized by in-situ crystallization of kaolin with a sodium oxide content of less than 2% by weight contains rare earth elements, wherein the rare earth element content is 10%-20% by weight as RE2O3.

[0112] 18. The catalytic cracking catalyst according to technical solution 16 or 17 of Group B, wherein the Y molecular sieve synthesized by in-situ crystallization of kaolin with a sodium oxide content of less than 2% by weight is a modified molecular sieve based on kaolin crystallization, wherein the modified molecular sieve based on kaolin crystallization is obtained by reducing the sodium content and / or introducing rare earth elements, and the sodium oxide content of the modified molecular sieve based on kaolin crystallization is less than 2% by weight.

[0113] 19. The catalytic cracking catalyst according to technical solution 18 of Group B, wherein the molecular sieve based on kaolin crystallization has a crystallinity of ≥60% as measured by X-ray diffraction using the peak height method, and the ratio of the crystallinity to that of the peak area method is K1, K1 = 0.76-0.89; the silicon-aluminum ratio determined by the cell constant a0 is 5.0-5.5, and the ratio of the silicon-aluminum ratio determined by the chemical method is K2, K2 = 0.87-0.93, wherein the silicon-aluminum ratio is the molar ratio of silicon oxide to aluminum oxide.

[0114] 20. The catalytic cracking catalyst according to technical solution 19 of Group B, wherein the crystallinity of the peak height method is ≥80%.

[0115] 21. The catalytic cracking catalyst according to technical solution 19 of group B, wherein K1 = 0.77-0.88 and K2 = 0.87-0.91.

[0116] 22. The catalytic cracking catalyst according to technical solution 19 or 21 of Group B, wherein K1 = 0.80-0.89 or K1 = 0.80-0.85.

[0117] 23. The catalytic cracking catalyst according to technical solutions 19, 21 or 22 of Group B, wherein K2 = 0.87-0.92 or K2 = 0.88-0.90.

[0118] 24. The catalytic cracking catalyst according to technical solution 19 of Group B, wherein the mesopores of the molecular sieve based on kaolin crystallization are 10-20%.

[0119] 25. The catalytic cracking catalyst according to technical solution 19 of Group B, wherein the silicon-to-aluminum ratio determined by the cell constant a0 is 5.2-5.5.

[0120] 26. The catalytic cracking catalyst according to technical solution 18 of Group B, wherein the molecular sieve based on kaolin crystallization is prepared by the following steps:

[0121] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, and then crushed into metakaolin powder with a particle size of less than 10 micrometers.

[0122] (2) Add a directing agent, sodium silicate, sodium hydroxide solution and water to the metakaolin powder to prepare reaction raw material A, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0, and the molar ratio of reaction raw material A is (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O;

[0123] (3) After crystallizing reaction raw material A at 88-98℃ for 1-70h with stirring, a second silicon source is added to obtain reaction raw material B, wherein the second silicon source accounts for 0.1-10% by weight of the total silicon feed, based on silicon oxide.

[0124] (4) Crystallize the reaction raw material B under stirring at 88-98℃ and recover the product.

[0125] 27. The catalytic cracking catalyst according to technical solution 16 of Group B, wherein the second molecular sieve is selected from octahedral zeolite and / or molecular sieves with a five-membered ring structure, for example, the octahedral zeolite is one or more of HY, REY, REHY, USY, REUSY, DASY, and REDASY, and the molecular sieve with a five-membered ring structure includes one or more of BEA structure molecular sieves, MFI structure molecular sieves, and mordenite; the binder is selected from one or more of silica sol, alumina sol, borosilicate, and metal-modified borosilicate; and the clay is one or more of kaolin, montmorillonite, diatomaceous earth, halloysite, quasi-haloysite, soapstone, rettosite, sepiolite, attapulgite, hydrotalcite, and bentonite.

[0126] 28. A method for preparing a catalytic cracking catalyst, characterized by comprising the following steps:

[0127] Clay, silica-alumina material, cracking active component and binder are formed into a slurry and spray-dried; wherein the silica-alumina material is any one of technical solutions 1-5 of Group B or the silica-alumina material described in technical solution 15 of Group B, and the cracking active component includes a first Y-type molecular sieve and an optional second molecular sieve; wherein the first Y-type molecular sieve is a Y molecular sieve synthesized in situ by crystallization with a sodium oxide content of less than 2% by weight.

[0128] 29. The method for preparing a catalytic cracking catalyst according to technical solution 28 of Group B, wherein the first Y-type molecular sieve is a modified molecular sieve based on kaolin crystallization, and the preparation method of the modified molecular sieve based on kaolin crystallization includes the following steps:

[0129] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, which is then crushed to produce metakaolin powder with a particle size of less than 10 micrometers.

[0130] (2) Add sodium silicate, a directing agent, sodium hydroxide solution and water to metakaolin powder to prepare reaction raw material A with a ratio of (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0.

[0131] (3) The reaction raw material A is crystallized under stirring at 88-98℃. After the crystallization time reaches 1-70h, a second silicon source is added to obtain the reaction raw material B. The second silicon source accounts for 0.1%-10% of the total silicon feed amount, all calculated as silicon oxide.

[0132] (4) Crystallize reaction material B under stirring at 88-98℃ and recover the product;

[0133] (5) The recovered products are subjected to ion exchange.

[0134] 30. The preparation method according to technical solution 29 of group B, wherein the molar composition of the directing agent is: (10-17)SiO2:(0.7-1.3)Al2O3:(11-18)Na2O:(200-350)H2O.

[0135] 31. The preparation method according to technical solution 29 of group B, wherein the sodium content of the second silicon source is less than 1% by weight, calculated as Na2O.

[0136] 32. The preparation method according to technical solution 29 or 31 of Group B, wherein the second silicon source is solid silicone and / or liquid silicone.

[0137] 33. The preparation method according to technical solution 32 of Group B, wherein the average pore size of the solid silica gel is below 0.8 nm, or the average pore size of the solid silica gel is 1.5-2.0 nm, or the average pore size of the solid silica gel is 4.0-5.0 nm, or the average pore size of the solid silica gel is above 10.0 nm; and the SiO2 mass content in the liquid silica gel is 1%-30%.

[0138] 34. According to the preparation method of technical solution 29 in Group B, wherein, based on silicon oxide, the second silicon source accounts for 4%-10% by weight of the total silicon feed.

[0139] 35. The method for preparing catalytic cracking catalyst according to technical solution 29 of Group B, wherein the ion exchange in step (5) is ammonium ion exchange and / or rare earth ion exchange; preferably, the ion exchange product obtained in step (5) is further calcined.

[0140] 36. The method for preparing a catalytic cracking catalyst according to technical solution 29 or 35 of Group B, wherein the ion exchange includes rare earth ion exchange, and the rare earth content in the modified molecular sieve based on kaolin crystallization obtained in step (5) is 10%-20% by weight (RE2O3) and the sodium oxide content is less than 2% by weight.

[0141] 37. The catalytic cracking catalyst obtained by the method for preparing the catalytic cracking catalyst according to any one of the technical solutions 28-36 in Group B.

[0142] Group C

[0143] 1. A zirconium sol comprising 0.5%-20% by mass of ZrO2, a stabilizer, an alkaline cation, and water, wherein the molar ratio of the stabilizer to Zr is 1-6, and the zirconium sol has a pH of 1-7.

[0144] 2. The zirconium sol according to technical solution 1 of group C, characterized in that the zirconium sol particles are between 5nm and 15nm in size, with an average particle size of about 10nm (about 10nm means 10±2nm), and a concentration of over 90%.

[0145] 3. The zirconium sol according to technical solution 1 or 2 of Group C, characterized in that the zirconium sol is dried at 100°C for 6 hours and calcined at 600°C for 2-6 hours for heat treatment, and the resulting product contains both monoclinic and tetragonal phases, with the preferred ratio of monoclinic to tetragonal phase being 0.05-0.6:1; and / or the zirconium sol is dried at 100°C for 6 hours and calcined at 800°C for 2-6 hours for heat treatment, and the resulting product contains ZrO2 in the tetragonal phase.

[0146] 4. The zirconium sol according to technical solution 1 of group C, characterized in that the stabilizer is an organic acid, preferably one or more of glycolic acid, oxalic acid, acetic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, and citric acid.

[0147] 5. The zirconium sol according to technical solution 1 of group C, characterized in that the alkaline cation is a nitrogen-containing cation, such as ammonium ions or nitrogen-containing cations formed by the hydrolysis of water-soluble organic bases, wherein the water-soluble organic bases are one or more of the following: methylamine, dimethylamine, trimethylamine, methanolamine, diethanolamine, triethanolamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltriethylammonium hydroxide, monomethyltriethanolammonium hydroxide, and monomethyltributylammonium hydroxide.

[0148] 6. The zirconium sol according to technical solution 1 of group C, characterized in that the molar ratio of the alkaline cation to Zr is 1-8.

[0149] 7. The zirconium sol according to technical solution 1 of group C, characterized in that the zirconium sol further contains inorganic acid radicals and / or alcohols, wherein the molar ratio of the inorganic acid radicals and / or alcohols to Zr is 1-6:1; preferably, the inorganic acid radicals are one or more of sulfate, chloride, and nitrate, and the alcohols are one or more of methanol, ethanol, propanol, and butanol.

[0150] 8. The zirconium sol according to technical solution 1 of group C, characterized in that the pH value of the zirconium sol is 2-4.

[0151] 9. A method for preparing zirconium sol, comprising the following steps:

[0152] (1) Prepare a zirconium source solution with a concentration of 0.5%-20% by mass based on ZrO2;

[0153] (2) A stabilizer is added to the zirconium source solution to obtain a first mixed solution; wherein the molar ratio of the stabilizer to zirconium is 1-6:

[0154] (3) At room temperature -50℃, an alkaline solution is added to the first mixed solution to obtain zirconium sol, wherein the amount of alkaline solution used is such that the pH value of the zirconium sol is 1-7.

[0155] 10. The method for preparing zirconium sol according to technical solution 9 of group C, characterized in that an alkaline solution is slowly added to a first mixed solution to obtain a clear and transparent zirconium sol; the slow addition may be dropwise addition or the addition rate may be controlled at 0.05 ml-50 ml alkaline solution / min / L of the first mixed solution.

[0156] 11. The method for preparing zirconium sol according to technical solution 9 of group C, characterized in that the zirconium source is one or more of inorganic zirconium salts or organic zirconium salts, wherein the inorganic zirconium salt is one or more of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, zirconium nitrate, zirconium oxynitrate, zirconium oxysulfate, and zirconium oxycarbonate; and the organic zirconium salt is one or more of zirconium n-propoxide, zirconium isopropoxide, zirconium ethoxide, and zirconium butoxide.

[0157] 12. The method for preparing zirconium sol according to technical solution 9 of group C, characterized in that the stabilizer is an organic acid that can form a coordination polymer with zirconium, and the stabilizer is preferably at least one of glycolic acid, acetic acid, oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, citric acid, etc., more preferably one or more of acetic acid, oxalic acid or citric acid.

[0158] 13. The method for preparing zirconium sol according to technical solution 9 of group C, characterized in that the alkaline solution is selected from ammonia water or an aqueous solution of a water-soluble organic base, wherein the water-soluble organic base is, for example, one or more of methylamine, dimethylamine, trimethylamine, methanolamine, diethanolamine, triethanolamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltriethylammonium hydroxide, monomethyltriethanolammonium hydroxide, and monomethyltributylammonium hydroxide.

[0159] 14. Zirconium sol obtained by any one of the zirconium sol preparation methods described in any one of the technical solutions 9-13 in Group C.

[0160] 15. A heavy oil cracking catalyst, comprising, on a dry basis by mass: 10%-60% by mass of a cracking active component, 20%-60% by mass of a binder, and 10%-70% by mass of clay; wherein the binder comprises 1%-50% by mass of zirconium sol and 50%-99% by mass of a second binder, wherein the zirconium sol is preferably the zirconium sol described in any one of technical solutions 1-9 of Group C or the zirconium sol described in technical solution 14 of Group C; preferably, the cracking active component comprises 70%-100% by mass of a Y-type molecular sieve and 0-30% by mass of a second molecular sieve.

[0161] 16. The heavy oil cracking catalyst according to technical solution 15 of group C, characterized in that the second binder is one or more of alumina sol, alumina, and metal-modified alumina.

[0162] 17. The heavy oil cracking catalyst according to technical solution 15 of Group C, characterized in that the rare earth content in the Y-type molecular sieve is 0-20% by mass, and the cell constant of the Y-type molecular sieve is 2.430 nm-2.480 nm; the clay is one or more of kaolin, montmorillonite, diatomite, halloysite, quasi-haloysite, soapstone, rettosite, sepiolite, attapulgite, hydrotalcite, and bentonite.

[0163] 18. The heavy oil cracking catalyst according to technical solution 15 of Group C, characterized in that the Y-type molecular sieve is one or more of DASY molecular sieve, rare earth-containing DASY molecular sieve, USY molecular sieve, rare earth-containing USY molecular sieve, REY molecular sieve, HY molecular sieve, REHY molecular sieve, and Y-type molecular sieve synthesized by in-situ crystallization of modified kaolin; the sodium oxide content of the Y-type molecular sieve synthesized by in-situ crystallization of modified kaolin is less than 2% by mass.

[0164] 19. The heavy oil cracking catalyst according to technical solution 15 of Group C, characterized in that the Y-type molecular sieve includes a first Y-type molecular sieve and an optional third Y-type molecular sieve; wherein the first Y-type molecular sieve is a modified kaolin-based molecular sieve obtained by modification treatment of a molecular sieve based on kaolin crystallization, and its sodium oxide content is less than 2% by mass; the modification treatment includes ultrastabilization treatment and / or ion exchange treatment; the third Y-type molecular sieve is selected from one or more of HY, REY, REHY, USY, REUSY, DASY, and REDASY.

[0165] 20. The heavy oil cracking catalyst according to technical solution 15 of group C, characterized in that the second molecular sieve is a molecular sieve with a five-membered ring structure, which may include one or more of BEA structure molecular sieves, MFI type molecular sieves, and mordenite, preferably one or more of BEA structure molecular sieves and MFI type molecular sieves; the BEA structure molecular sieve may be obtained by amine-free crystallization or by calcining a molecular sieve prepared by a template agent method, for example, a Beta molecular sieve; the MFI structure molecular sieve includes at least one of rare earth-containing MFI molecular sieves, phosphorus-containing MFI molecular sieves, and iron-containing MFI molecular sieves; the mordenite includes at least one of high-silica mordenite or low-silica mordenite.

[0166] 21. The heavy oil cracking catalyst according to technical solution 19 of Group C, wherein the molecular sieve based on kaolin crystallization has a crystallinity of ≥60% as measured by X-ray diffraction using the peak height method, and the ratio of the crystallinity to that of the peak area method is K1, K1 = 0.76-0.89; the silicon-aluminum ratio determined by the cell constant a0 is 5.0-5.5, and the ratio of the silicon-aluminum ratio determined by the chemical method is K2, K2 = 0.87-0.93, wherein the silicon-aluminum ratio is the molar ratio of silicon oxide to aluminum oxide.

[0167] 22. The heavy oil cracking catalyst according to technical solution 22 of Group C, wherein the crystallinity of the peak height method is ≥80%.

[0168] 23. The heavy oil cracking catalyst according to technical solution 22 of Group C, wherein K1 = 0.80-0.89.

[0169] 24. The heavy oil cracking catalyst according to technical solution 22 of Group C, wherein K1 = 0.80-0.85.

[0170] 25. The heavy oil cracking catalyst according to technical solution 22 of Group C, wherein K2 = 0.87-0.92.

[0171] 26. The heavy oil cracking catalyst according to technical solution 22 of Group C, wherein K2 = 0.88-0.90.

[0172] 27. The heavy oil cracking catalyst according to technical solution 22 of Group C, wherein K1 = 0.77-0.88 and K2 = 0.87-0.91.

[0173] 28. The heavy oil cracking catalyst according to technical solution 22 of Group C, wherein the mesopores of the molecular sieve based on kaolin crystallization are 10-20%.

[0174] 29. The heavy oil cracking catalyst according to technical solution 22 of Group C, wherein the silicon-to-aluminum ratio determined by the cell constant a0 is 5.2-5.5.

[0175] 30. The heavy oil cracking catalyst according to technical solution 22 of group C, wherein the molecular sieve based on kaolin crystallization is prepared by the following steps:

[0176] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, and then crushed into metakaolin powder with a particle size of less than 10 micrometers.

[0177] (2) Add a directing agent, sodium silicate, sodium hydroxide solution and water to the metakaolin powder to prepare reaction raw material A, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0, and the ratio of reaction raw material A is (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O molar ratio;

[0178] (3) After crystallizing reaction raw material A at 88-98℃ for 1-70h with stirring, a second silicon source is added to obtain reaction raw material B, wherein the second silicon source accounts for 0.1-10% by mass of the total silicon feed, based on silicon oxide.

[0179] (4) Crystallize the reaction raw material B under stirring at 88-98℃ and recover the product.

[0180] 31. The heavy oil cracking catalyst according to technical solution 19 of Group C, wherein the modified molecular sieve based on kaolin crystallization contains rare earth elements, and the rare earth content of the modified molecular sieve based on kaolin crystallization is 10%-20% by mass, calculated as RE2O3.

[0181] 32. The preparation method of the heavy oil cracking catalyst of technical solution 15 in Group C includes forming a mixture of zirconium sol, second binder, clay, cracking active component and water, and spray drying, wherein the cracking active component includes a molecular sieve, and the molecular sieve includes a Y-type molecular sieve and an optional second molecular sieve.

[0182] 33. The method for preparing a heavy oil cracking catalyst according to technical solution 32 of Group C, characterized in that the second binder comprises aluminum sol and aluminum oxide, and the method for preparing the heavy oil cracking catalyst comprises the following steps:

[0183] (S1) The zirconium sol and aluminum sol are first mixed to form a first sol. Preferably, the pH value of the first sol is controlled to be 2.5-3.5.

[0184] (S2) Prepare clay slurry and cracking active component slurry respectively;

[0185] (S3) Mix the clay slurry, cracking active component slurry, the first sol, and aluminum oxide, and disperse them evenly (e.g., by stirring, homogenizing, or grinding) to obtain the second colloidal mixture;

[0186] (S4) Spray dry the second colloidal mixture obtained in step (S3).

[0187] 34. The method for preparing heavy oil cracking catalyst according to technical solution 33 of Group C, wherein the Y-type molecular sieve includes a modified molecular sieve based on kaolin crystallization, and the preparation method of the modified molecular sieve based on kaolin crystallization includes the following steps:

[0188] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, which is then crushed to produce metakaolin powder with a particle size of less than 10 micrometers.

[0189] (2) Add sodium silicate, a directing agent, sodium hydroxide solution and water to metakaolin powder to prepare reaction raw material A with a ratio of (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0;

[0190] (3) Crystallize reaction raw material A under stirring at 88-98℃. After the crystallization time reaches 1-70h, add a second silicon source to obtain reaction raw material B. The second silicon source accounts for 0.1%-10% of the total silicon feed amount, all calculated as silicon oxide.

[0191] (4) Crystallize reaction material B under stirring at 88-98℃ and recover the product;

[0192] (5) The recovered products are subjected to ion exchange and / or ultrastabilization treatment.

[0193] 35. The method for preparing heavy oil cracking catalyst according to technical solution 34 of Group C, wherein the composition of the directing agent is: (10-17)SiO2:(0.7-1.3)Al2O3:(11-18)Na2O:(200-350)H2O.

[0194] 36. The method for preparing heavy oil cracking catalyst according to technical solution 34 of Group C, wherein the second silicon source has a sodium content of <1% by mass (calculated as Na2O).

[0195] 37. The method for preparing heavy oil cracking catalyst according to technical solution 34 or 36 of Group C, wherein the second silicon source is solid silica gel; wherein the average pore size of the solid silica gel is 1.5-2.0 nm, or the average pore size of the solid silica gel is 4.0-5.0 nm, or the average pore size of the solid silica gel is above 10.0 nm, or the average pore size of the solid silica gel is below 0.8 nm.

[0196] 38. The method for preparing heavy oil cracking catalyst according to technical solution 34 or 36 of Group C, wherein the second silicon source is liquid silica gel, and the mass content of SiO2 in the liquid silica gel is 1-30%.

[0197] 39. The method for preparing heavy oil cracking catalyst according to technical solution 34 of Group C, wherein, based on silicon oxide, the second silicon source accounts for 4-10% of the total silicon feed.

[0198] 40. The method for preparing heavy oil cracking catalyst according to technical solution 34 of Group C, wherein the ion exchange in step (5) is ammonium ion exchange and / or rare earth ion exchange.

[0199] 41. The method for preparing heavy oil cracking catalyst according to technical scheme 34 or 40 of Group C, wherein the product obtained in step (5) is further roasted.

[0200] 42. The method for preparing heavy oil cracking catalyst according to technical scheme 34 or 41 of Group C, wherein the ion exchange includes rare earth ion exchange, and the rare earth content in the modified molecular sieve based on kaolin crystallization obtained in step (5) is 10%-20% by mass as RE2O3, and the sodium oxide content is less than 2% by mass.

[0201] Group D

[0202] 1. A metal-resistant catalytic cracking catalyst, comprising, based on the dry weight of the catalytic cracking catalyst: 10-70 wt% of cracking active components, 1-20 wt% of zirconium oxide binder, 1-20 wt% of silica sol binder, 0-50 wt% of alumina-based binder, and 10-70 wt% of clay.

[0203] 2. The catalytic cracking catalyst according to technical solution 1 of group D, characterized in that the zirconium oxide binder is zirconium sol, the zirconium sol comprising 0.5 wt%-20 wt%, for example 5-15 wt%, of ZrO2, stabilizer, alkaline cation and water, wherein the molar ratio of stabilizer to Zr is 1-6, and the pH value of the zirconium sol is 1-7.

[0204] 3. The catalytic cracking catalyst according to technical solution 2 of group D, characterized in that the zirconium sol particles are between 5nm and 15nm in size, have an average particle size of 10±2nm, and a concentration of over 90%.

[0205] 4. The catalytic cracking catalyst according to technical solution 2 of group D, characterized in that the zirconium sol is dried at 100°C for 6 hours and calcined at 600°C for 2-6 hours for heat treatment, and the resulting product contains both monoclinic and tetragonal phases, with the preferred ratio of monoclinic to tetragonal phase being 0.05-0.6:1; and / or the zirconium sol is dried at 100°C for 6 hours and calcined at 800°C for 2-6 hours for heat treatment, and the resulting product contains ZrO2 in the tetragonal phase.

[0206] 5. The catalytic cracking catalyst according to technical solution 2 of group D, characterized in that the stabilizer in the zirconium sol is one or more of glycolic acid, oxalic acid, acetic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, citric acid, etc.

[0207] 6. The catalytic cracking catalyst according to technical solution 2 of group D, characterized in that, in the zirconium sol, the alkaline cation is an ammonium ion or a nitrogen-containing cation formed by the hydrolysis of a water-soluble organic base, and the water-soluble organic base is one or more of the following: methylamine, dimethylamine, trimethylamine, methanolamine, diethanolamine, triethanolamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltriethylammonium hydroxide, monomethyltriethanolammonium hydroxide, and monomethyltributylammonium hydroxide.

[0208] 7. The catalytic cracking catalyst according to technical solution 2 of group D, characterized in that, in the zirconium sol, the molar ratio of the alkaline cation to Zr is 1-8.

[0209] 8. The catalytic cracking catalyst according to technical solution 2 of group D, characterized in that the zirconium sol further contains inorganic acid radicals and / or alcohols, wherein the molar ratio of the inorganic acid radicals and / or alcohols to Zr is 1-6; the inorganic acid radicals are, for example, one or more of sulfate, chloride, and nitrate; and the alcohols are, for example, one or more of methanol, ethanol, propanol, and butanol.

[0210] 9. The catalytic cracking catalyst according to technical solution 2 of group D, characterized in that the pH value of the zirconium sol is 1.5-5, preferably 2-3.

[0211] 10. The catalytic cracking catalyst according to technical solution 1 of group D, characterized in that the pH value of the silica sol is 1.5-3.5, and the silica sol particle size is 2nm-20nm; the content of SiO2 in the silica sol is preferably 5%-15% by weight; in one embodiment, the silica sol is a silica sol prepared by direct acidification of water glass, and the pH value of the silica sol is 1.5-3.

[0212] 11. The catalytic cracking catalyst according to technical solution 1 of group D, characterized in that the alumina binder is one or more of alumina sol, alumina, phosphorus and / or metal-modified alumina.

[0213] 12. The catalytic cracking catalyst according to technical solution 1 of group D, characterized in that the cracking active component comprises 70%-100% by weight of a Y-type molecular sieve and 0-30% by weight of a second molecular sieve; the Y-type molecular sieve has a cell constant of 2.430 nm-2.480 nm and a rare earth content of 0-20% by weight (calculated as RE2O3); the second molecular sieve is a molecular sieve with a five-membered ring structure; the clay is one or more of kaolin, montmorillonite, diatomite, halloysite, quasi-haloysite, soapstone, rettoitite, sepiolite, attapulgite, hydrotalcite, and bentonite.

[0214] 13. The catalytic cracking catalyst according to technical solution 12 of group D, characterized in that the Y-type molecular sieve is a modified molecular sieve based on kaolin crystallization obtained by modification treatment, and its sodium oxide content is less than 2% by weight, wherein the modification treatment includes ultrastabilization treatment and / or ion exchange treatment.

[0215] 14. The heavy oil cracking catalyst according to technical solution 13 of group D, wherein the molecular sieve based on kaolin crystallization has a crystallinity of ≥60% as measured by X-ray diffraction using the peak height method, and the ratio of the crystallinity to that of the peak area method is K1, K1 = 0.76-0.89; the silicon-aluminum ratio determined by the cell constant a0 is 5.0-5.5, and the ratio of the silicon-aluminum ratio determined by the chemical method is K2, K2 = 0.87-0.93, wherein the silicon-aluminum ratio is the molar ratio of silicon oxide to aluminum oxide.

[0216] 15. The heavy oil cracking catalyst according to technical solution 14 of group D, wherein the crystallinity of the peak height method is ≥80%.

[0217] 16. The heavy oil cracking catalyst according to technical solution 14 of group D, wherein the molecular sieve based on kaolin crystallization has K1 = 0.77-0.88 and K2 = 0.87-0.91.

[0218] 17. The heavy oil cracking catalyst according to technical solution 14 of group D, wherein the mesopore size of the molecular sieve based on kaolin crystallization is 10-20%.

[0219] 18. The heavy oil cracking catalyst according to technical solution 14 of group D, wherein the silicon-to-aluminum ratio of the molecular sieve based on kaolin crystallization is 5.2-5.5 as determined by the cell constant a0.

[0220] 19. The heavy oil cracking catalyst according to technical solution 14 of group D, wherein, in the preparation process of the catalytic cracking catalyst, the zirconium oxide binder and the silica sol binder are first mixed, and then mixed with the cracking active component, clay and alumina-based binder.

[0221] 20. The heavy oil cracking catalyst according to technical solution 14 of Group D, wherein the modified molecular sieve based on kaolin crystallization contains rare earth elements, and the rare earth content of the modified molecular sieve based on kaolin crystallization is 10%-20% by weight (RE2O3).

[0222] 21. A method for preparing a catalytic cracking catalyst according to any one of the technical solutions 1-20 in Group D, comprising:

[0223] A mixture of zirconium sol and silica sol is formed; the mixture of zirconium sol and silica sol, cracking active components, clay, and optional alumina binder form a slurry; spray drying is performed; the cracking active components include Y-type molecular sieves and optional second molecular sieves.

[0224] 22. The method for preparing a catalytic cracking catalyst according to technical solution 21 of group D, characterized in that it includes the following steps:

[0225] (s1) Zirconium sol and silica sol are mixed, preferably with the pH value of the mixture controlled at 2.5-3.5;

[0226] (s2) Prepare clay slurry;

[0227] (s3) Preparation of molecular sieve slurry;

[0228] (s4) Mix the clay slurry, molecular sieve slurry, the mixture obtained in step (s1), and alumina binder;

[0229] (s5) Disperse the slurry obtained in step (s4) evenly and spray dry it.

[0230] 23. The method for preparing a catalytic cracking catalyst according to technical solution 21 or 22 of Group D, characterized in that the method for preparing the zirconium sol includes the following steps:

[0231] (1) Prepare a zirconium source solution with a concentration of 0.5%-20% by weight, for example 5-15% by weight, based on ZrO2.

[0232] (2) Add a stabilizer to the zirconium source solution and stir at room temperature to 90°C for 0.5-3 hours to obtain a first mixed solution; wherein the molar ratio of stabilizer to zirconium is 1-6:

[0233] (3) At room temperature -50℃, an alkaline solution is added to the first mixed solution to obtain zirconium sol, wherein the amount of alkaline solution used is such that the pH value of the zirconium sol is 1-7.

[0234] 24. The method for preparing a catalytic cracking catalyst according to technical solution 23 of group D, characterized in that, in the method for preparing zirconium sol, an alkaline solution is slowly added to a first mixed solution to obtain a clear and transparent zirconium sol; the slow addition is either dropwise addition or the alkaline solution addition rate is controlled to be 0.05 ml-50 ml alkaline solution / min / L of the first mixed solution; preferably, the amount of alkaline solution added makes the pH value of the zirconium sol 1.5-5, for example, 2-3.

[0235] 25. The method for preparing a catalytic cracking catalyst according to technical solution 23 of Group D, characterized in that the zirconium source is one or more of inorganic zirconium salts or organic zirconium salts, wherein the inorganic zirconium salt is one or more of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, zirconium nitrate, zirconium oxynitrate, zirconium oxysulfate, and zirconium oxycarbonate; and the organic zirconium salt is one or more of zirconium n-propoxide, zirconium isopropoxide, zirconium ethoxide, and zirconium butoxide.

[0236] 26. The method for preparing a catalytic cracking catalyst according to technical solution 23 of group D, characterized in that the stabilizer is one or more of glycolic acid, acetic acid, oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, and citric acid.

[0237] 27. The method for preparing a catalytic cracking catalyst according to technical solution 23 of group D, characterized in that the alkaline solution is selected from ammonia water or an aqueous solution of a water-soluble organic base, wherein the water-soluble organic base is, for example, one or more of methylamine, dimethylamine, trimethylamine, methanolamine, diethanolamine, triethanolamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltriethylammonium hydroxide, monomethyltriethanolammonium hydroxide, and monomethyltributylammonium hydroxide.

[0238] 28. The method for preparing a catalytic cracking catalyst according to technical solution 21 of group D, wherein the Y-type molecular sieve includes a modified molecular sieve based on kaolin crystallization, and the method for preparing the modified molecular sieve based on kaolin crystallization includes the following steps:

[0239] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, which is then crushed to produce metakaolin powder with a particle size of less than 10 micrometers.

[0240] (2) Add sodium silicate, a directing agent, sodium hydroxide solution and water to metakaolin powder to prepare reaction raw material A with a ratio of (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O, wherein the weight ratio of the directing agent to metakaolin is 0.01-1.0.

[0241] (3) The reaction raw material A is crystallized under stirring at 88-98℃. After the crystallization time reaches 1-70h, a second silicon source is added to obtain the reaction raw material B. The second silicon source accounts for 0.1%-10% of the total silicon feed amount, all calculated as silicon oxide.

[0242] (4) The reaction raw material B is crystallized under stirring at 88-98℃ and the product is recovered to obtain a molecular sieve based on kaolin crystallization;

[0243] (5) The recovered molecular sieve based on kaolin crystallization is subjected to ion exchange and / or ultrastabilization treatment.

[0244] 29. The method for preparing a catalytic cracking catalyst according to technical solution 28 of group D, wherein the composition of the directing agent is: (10-17)SiO2:(0.7-1.3)Al2O3:(11-18)Na2O:(200-350)H2O.

[0245] 30. The method for preparing a catalytic cracking catalyst according to technical solution 28 of group D, wherein the second silicon source has a sodium content of <1% by weight (calculated as Na2O) and is calculated as silicon oxide, and the second silicon source accounts for 4-10% by weight of the total silicon feed.

[0246] 31. The method for preparing a catalytic cracking catalyst according to technical solution 28 or 30 of Group D, wherein, in the method for preparing the modified molecular sieve based on kaolin crystallization, the second silicon source is solid silica gel and / or liquid silica gel; wherein, the average pore size of the solid silica gel is 1.5-2.0 nm, or the average pore size of the solid silica gel is 4.0-5.0 nm, or the average pore size of the solid silica gel is above 10.0 nm, or the average pore size of the solid silica gel is below 0.8 nm, and the SiO2 weight content in the liquid silica gel is 1-30%.

[0247] 32. The method for preparing catalytic cracking catalyst according to technical solution 28 of group D, wherein the ion exchange in step (5) is ammonium ion exchange and / or rare earth ion exchange.

[0248] 33. The method for preparing a catalytic cracking catalyst according to technical solution 28 or 32 of Group D, wherein the ion exchange includes rare earth ion exchange, and the rare earth content in the modified molecular sieve based on kaolin crystallization obtained in step (5) is 10%-20% by weight (RE2O3) and the sodium oxide content is less than 2% by weight.

[0249] Group E

[0250] 1. A catalytic cracking catalyst for producing high levels of low-carbon olefins, comprising: 10%-60% by weight of a cracking active component on a dry basis, 20%-60% by weight of a binder on a dry basis, and 0%-70% by weight of a second clay on a dry basis; wherein, based on the dry weight of the binder, the binder comprises 1%-50% by weight of zirconium sol, 50%-99% by weight of phosphorus-aluminum inorganic binder, and 0-45% by weight of a third binder on a dry basis.

[0251] The cracking active component includes a first molecular sieve and an optional second molecular sieve, wherein the first molecular sieve is a five-membered ring molecular sieve; on a dry basis, the first molecular sieve accounts for more than 70% of the cracking active component; preferably, the cracking active component contains 70-100% by weight of the first molecular sieve and 0-30% by weight of the second molecular sieve.

[0252] The zirconium sol comprises 0.5%-20% by mass of ZrO2, a stabilizer, an alkaline cation, and water, wherein the molar ratio of the stabilizer to Zr is 1-6, and the pH value of the zirconium sol is 1-7.

[0253] The phosphorus-aluminum inorganic binder contains 15-40% by weight of alumina source component (based on Al2O3), 45-80% by weight of phosphorus component (based on P2O5), and 0-40% by weight of first clay (based on dry basis). Its P / Al weight ratio is 1-6, pH value is 1-3.5, and solid content is 15-60% by weight.

[0254] 2. The catalytic cracking catalyst according to technical solution 1 of group E, characterized in that the third binder is selected from one or more of silica sol, alumina sol, aluminosilicate gel, alumina, and metal-modified alumina.

[0255] 3. The catalytic cracking catalyst according to technical solution 1 of group E, characterized in that the first molecular sieve is one or more of MFI structure molecular sieve, BEA structure molecular sieve, and mordenite.

[0256] 4. The catalytic cracking catalyst according to technical solution 1 of group E, characterized in that the second molecular sieve is a Y-type molecular sieve, and the rare earth content in the Y-type molecular sieve is 0-20% by weight, preferably 0-12% by weight.

[0257] 5. The catalytic cracking catalyst according to technical solution 1 or 4 of group E, characterized in that the Y-type molecular sieve is one or more of DASY molecular sieve, rare earth-containing DASY molecular sieve, USY molecular sieve, rare earth-containing USY molecular sieve, REY molecular sieve, HY molecular sieve, REHY molecular sieve, and Y-type molecular sieve synthesized by in-situ crystallization of modified kaolin.

[0258] 6. The catalytic cracking catalyst according to technical solution 1 or 5 of group E, characterized in that the second molecular sieve is an ion-modified ultrastable molecular sieve based on kaolin crystallization; based on the weight of the catalytic cracking catalyst, the content of the ion-modified ultrastable molecular sieve based on kaolin crystallization in the catalytic cracking catalyst is preferably 1-10% by weight.

[0259] 7. The catalytic cracking catalyst according to technical solution 1 of group E, characterized in that the second clay is one or more of kaolin, montmorillonite, diatomite, halloysite, quasi-haloysite, soapstone, attapulgite, sepiolite, attapulgite, hydrotalcite, and bentonite; the first clay is one or more of kaolin, montmorillonite, diatomite, halloysite, quasi-haloysite, soapstone, attapulgite, sepiolite, attapulgite, hydrotalcite, and bentonite, preferably one or more of kaolin, sepiolite, attapulgite, attapulgite, montmorillonite, and diatomite.

[0260] 8. The catalytic cracking catalyst according to technical solution 1 of group E, characterized in that the preparation method of the phosphorus aluminum inorganic binder includes:

[0261] (1) The alumina source, the first clay and water are slurried and dispersed into a slurry with a solid content of 8-45% by weight; the alumina source is aluminum hydroxide and / or alumina that can be dissolved by acid, and the weight ratio of the first clay on a dry basis to the alumina source on an Al2O3 basis is 0-40:15-40.

[0262] (2) Add concentrated phosphoric acid to the slurry obtained in step (1) under stirring at a weight ratio of P / Al = 1-6; wherein the concentration of the concentrated phosphoric acid is, for example, 50-98% by weight.

[0263] (3) React the slurry obtained in step (2) at a temperature of 50-99℃ for 15-90 minutes.

[0264] 9. The catalytic cracking catalyst according to technical solution 8 of group E, characterized in that the phosphorus aluminum inorganic binder comprises 15-35% by weight of Al2O3 derived from the alumina source, 50-75% by weight of P2O5 and 0-35% by weight of a first clay on a dry basis, for example, 5-30% by weight of a first clay.

[0265] 10. The catalytic cracking catalyst according to technical solution 1 or 8 of group E, characterized in that the P / Al weight ratio is 2-5.

[0266] 11. The catalytic cracking catalyst according to technical solution 8 of group E, characterized in that the alumina source is one or more of p-alumina, χ-alumina, η-alumina, γ-alumina, κ-alumina, δ-alumina, θ-alumina, gibbsite, boehmite, diaspore, boehmite, boehmite, and pseudoboehmite.

[0267] 12. The catalytic cracking catalyst according to technical solution 1 of group E, characterized in that the zirconium sol particles are between 5 nm and 15 nm in size, have an average particle size of 10 ± 2 nm, and a concentration of more than 90%.

[0268] 13. The zirconium sol according to technical solution 1 or 12 of Group E, characterized in that the zirconium sol is dried at 100°C for 6 hours and calcined at 600°C for 2-6 hours for heat treatment, and the resulting product contains both monoclinic and tetragonal phases, with the ratio of monoclinic to tetragonal phase preferably being 0.05-0.6:1; and / or the zirconium sol is dried at 100°C for 6 hours and calcined at 800°C for 2-6 hours for heat treatment, and the resulting product contains ZrO2 in the tetragonal phase.

[0269] 14. The catalytic cracking catalyst according to technical solution 1 of group E, characterized in that the stabilizer is one or more of glycolic acid, oxalic acid, acetic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, and citric acid.

[0270] 15. The catalytic cracking catalyst according to technical solution 1 of group E, characterized in that the alkaline cation is an ammonium ion or a nitrogen-containing cation formed by the hydrolysis of a water-soluble organic base, wherein the water-soluble organic base is one or more of the following: methylamine, dimethylamine, trimethylamine, methanolamine, diethanolamine, triethanolamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltriethylammonium hydroxide, monomethyltriethanolammonium hydroxide, and monomethyltributylammonium hydroxide.

[0271] 16. The catalytic cracking catalyst according to technical solution 1 of group E, characterized in that the molar ratio of the alkaline cation to Zr is 1-8.

[0272] 17. The catalytic cracking catalyst according to technical solution 1 of group E, characterized in that the zirconium sol further contains inorganic acid radicals and / or alcohols, wherein the molar ratio of the inorganic acid radicals and / or alcohols to Zr is 1-6:1; preferably, the inorganic acid radicals are one or more of sulfate, chloride, and nitrate, and the alcohols are one or more of methanol, ethanol, propanol, and butanol.

[0273] 18. The zirconium sol according to technical solution 1 of group E, characterized in that the pH value of the zirconium sol is 2-4.

[0274] 19. The catalytic cracking catalyst according to technical solution 1 of group E, characterized in that the zirconium sol is prepared by a method comprising the following steps:

[0275] (1) Prepare a zirconium source solution with a concentration of 0.5%-20% by mass based on ZrO2;

[0276] (2) A stabilizer is added to the zirconium source solution to obtain a first mixed solution; wherein the molar ratio of the stabilizer to zirconium is 1-6:

[0277] (3) At room temperature -50℃, an alkaline solution is added to the first mixed solution to obtain zirconium sol, wherein the amount of alkaline solution used is such that the pH value of the zirconium sol is 1-7.

[0278] 20. The catalytic cracking catalyst according to technical solution 1 of group E, wherein the preparation method of the modified molecular sieve based on kaolin crystallization includes the following steps:

[0279] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, which is then crushed to produce metakaolin powder with a particle size of less than 10 micrometers.

[0280] (2) Add sodium silicate, a directing agent, sodium hydroxide solution and water to metakaolin powder to prepare reaction raw material A with a ratio of (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0;

[0281] (3) The reaction raw material A is crystallized under stirring at 88-98℃. After the crystallization time reaches 1-70h, a second silicon source is added to obtain the reaction raw material B. The second silicon source accounts for 0.1%-10% of the total silicon feed amount, all calculated as silicon oxide.

[0282] (4) The reaction raw material B is crystallized under stirring at 88-98℃ and the product is recovered to obtain a molecular sieve based on kaolin crystallization;

[0283] (5) Obtain molecular sieves based on kaolin crystallization and perform ion exchange and / or ultrastabilization treatment.

[0284] 21. A method for preparing the catalytic cracking catalyst according to any one of the technical solutions 1-20 in Group E, comprising: forming a slurry from cracking active components, binder, water and optional clay, and spray drying.

[0285] 22. The method for preparing the catalytic cracking catalyst according to technical solution 21 of group E, characterized in that it includes the following steps:

[0286] (S1) Obtain molecular sieve slurry.

[0287] (S2) Obtain the second clay slurry.

[0288] (S3) Obtain zirconium sol.

[0289] (S4) Obtain the phosphorus aluminum inorganic binder.

[0290] (S5) Mix the molecular sieve slurry, the second clay slurry, the zirconium sol, the phosphorus aluminum inorganic binder, and optionally the third binder;

[0291] (S6) Spray dry the slurry obtained in step (S5).

[0292] 23. A catalytic cracking method, comprising the step of contacting heavy oil with a catalytic cracking catalyst as described in any one of the technical solutions 13-20 of Group E.

[0293] Group F

[0294] A composite material, characterized in that the composite material comprises zirconium sol and aluminosilicate materials, wherein, based on the total amount of the composite material and on a dry basis, the content of zirconium sol is 30-80% by weight and the content of aluminosilicate materials is 20-70% by weight.

[0295] 2. The composite material according to technical solution 1 of group F, wherein the particle size of the zirconium sol is between 5-15 nm, the average particle size is 8-12 nm, and the concentration is above 90%.

[0296] 3. The composite material according to technical solution 1 or 2 of group F, wherein the method for preparing the zirconium sol includes:

[0297] (a) A solution containing a zirconium source is mixed with an acid to obtain a first mixture;

[0298] (b) Add an alkaline solution to the first mixture to obtain zirconium sol.

[0299] 4. The composite material according to technical solution 3 of group F, wherein, in step (a), the concentration of the solution containing the zirconium source, calculated as ZrO2, is 0.5-20% by weight;

[0300] Preferably, in step (a), the molar ratio of the zirconium source solution to the acid, calculated as Zr element, is 1:1-6;

[0301] Preferably, the mixing conditions in step (a) include: a temperature of 20-90°C and a time of 0.5-3 hours;

[0302] Preferably, the acid in step (a) is an organic acid, more preferably at least one of glycolic acid, acetic acid, oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid and citric acid, and even more preferably acetic acid and / or citric acid;

[0303] Preferably, the zirconium source is an inorganic zirconium salt and / or an organic zirconium salt;

[0304] More preferably, the inorganic zirconium salt is selected from at least one of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, zirconium nitrate, zirconium oxynitrate, zirconium oxysulfate, and zirconium oxycarbonate.

[0305] More preferably, the organozirconium salt is selected from at least one of zirconium n-propoxide, zirconium isopropoxide, zirconium ethoxide, and zirconium butoxide.

[0306] 5. The composite material according to technical solution 3 or 4 of group F, wherein the amount of alkali solution added in step (b) makes the pH value of the zirconium sol 1-7, preferably 1.5-5, and more preferably 2-3;

[0307] Preferably, the alkaline solution in step (b) is ammonia and / or a water-soluble organic base;

[0308] More preferably, the water-soluble organic base is selected from at least one of methylamine, dimethylamine, trimethylamine, methanolamine, diethanolamine, triethanolamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltriethylammonium hydroxide, monomethyltriethanolammonium hydroxide, and monomethyltributylammonium hydroxide.

[0309] 6. The composite material according to any one of the technical solutions 1-5 in Group F, wherein the expression of the silicon-aluminum material, in terms of the weight ratio of oxides, is (0-1)Na2O·(15-50)Al2O3·(85-50)SiO2;

[0310] Preferably, the silicon-aluminum material has an average pore size of 10-100 nm, a specific surface area of ​​150-600 m² / g, and a pore volume of 0.5-1.5 cm³ / g.

[0311] 7. The composite material according to any one of technical solutions 1-6 in Group F, wherein the preparation method of the silicon-aluminum material includes:

[0312] (i) Mixing a silicon source with an aluminum source to obtain a mixture containing both silicon and aluminum sources;

[0313] (ii) Add an alkaline solution to the mixture containing the silicon source and the aluminum source to obtain a slurry, and then age the slurry to obtain a solid precipitate;

[0314] (iii) The solid precipitate is contacted with an ammonium salt or an acid to obtain a silicon-aluminum material.

[0315] 8. The composite material according to technical solution 7 of group F, wherein in step (i), the molar ratio of silicon source (calculated as SiO2) to aluminum source (calculated as Al2O3) is 50-85:50-15.

[0316] Preferably, the mixing conditions in step (i) include a temperature of 20-95°C;

[0317] Preferably, the silicon source in step (i) is an alkaline silicon source, more preferably one or more of alkaline silica sol, water glass, sodium silicate, and alkaline hydrolysis products of metal alkoxides of silicon;

[0318] Preferably, the aluminum source in step (i) is an acidic aluminum source, more preferably one or more of aluminum sulfate, aluminum chloride, aluminum sol, and acidic hydrolysis products of aluminum metal alkoxides.

[0319] 9. The composite material according to technical solution 7 or 8 of group F, wherein the amount of alkali solution added in step (ii) makes the pH value of the slurry 8-10.5;

[0320] Preferably, the aging conditions in step (ii) include: a temperature of 50-95°C and a time of 1-10 hours;

[0321] Preferably, the alkaline solution in step (ii) is selected from at least one of ammonia water, sodium hydroxide solution, potassium hydroxide solution and sodium aluminate solution.

[0322] 10. The composite material according to any one of the technical solutions 7-9 of Group F, wherein, in step (iii), the solid precipitate is contacted with the ammonium salt by mixing the solid precipitate with the ammonium salt and water to perform ammonium exchange;

[0323] Preferably, the weight ratio of the solid precipitate to the ammonium salt and water on a dry basis is 1:0.05-0.1:5-30;

[0324] Preferably, the ammonium exchange conditions result in the sodium content of the silicon-aluminum material being less than 1% by weight;

[0325] More preferably, the conditions for ammonium exchange include: a temperature of 20-100℃, 1-3 exchanges, and a time of 0.5-1h for each exchange.

[0326] Preferably, the ammonium salt is selected from at least one of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, and ammonium bicarbonate.

[0327] 11. The composite material according to any one of the technical solutions 7-9 of Group F, wherein in step (iii), the solid precipitate is contacted with acid by mixing the solid precipitate with acid and water for acid treatment;

[0328] Preferably, the weight ratio of the solid precipitate to acid and water on a dry basis is 1:0.03-0.3:5-30;

[0329] Preferably, the acid treatment conditions result in the sodium content of the silicon-aluminum material being less than 1% by weight;

[0330] More preferably, the acid treatment conditions include: a temperature of 20-100°C and a time of at least 0.5 h, more preferably 1-3 h;

[0331] Preferably, the acid is selected from at least one of sulfuric acid, hydrochloric acid, and nitric acid.

[0332] 12. A catalytic cracking catalyst, characterized in that the catalyst comprises a molecular sieve, an aluminum-based binder, clay, and a composite material as described in any one of the technical solutions 1-11 of Group F, wherein, based on the total amount of the catalyst, the content of the molecular sieve is 10-70% by weight, the content of the aluminum-based binder is 5-30% by weight, the content of the clay is 10-70% by weight, and the content of the composite material is 6-50% by weight.

[0333] The molecular sieve includes a first molecular sieve and an optional second molecular sieve. Based on the total amount of the molecular sieve, the content of the first molecular sieve is 70-100% by weight and the content of the second molecular sieve is 0-30% by weight.

[0334] The first molecular sieve is a Y-type molecular sieve, wherein the content of rare earth elements in the Y-type molecular sieve is 0-20% by weight; the second molecular sieve is a molecular sieve with a five-membered ring structure.

[0335] 13. The catalyst according to technical solution 12 of group F, wherein the Y-type molecular sieve is at least one of HY molecular sieve, REY molecular sieve, molecular sieve based on kaolin crystallization, REHY molecular sieve, USY molecular sieve, REUSY molecular sieve, DASY molecular sieve and REDASY molecular sieve;

[0336] Preferably, the first molecular sieve is a REY molecular sieve and / or a rare earth element modified molecular sieve based on kaolin crystallization;

[0337] More preferably, the content of the rare earth element in the molecular sieve based on kaolin crystallization is 10-20% by weight;

[0338] Preferably, the rare earth element is selected from at least one of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and more preferably La.

[0339] 14. The catalyst according to technical solution 12 of group F, wherein the ratio of the crystallinity obtained by peak height method to the crystallinity obtained by peak area method in the molecular sieve based on kaolin crystallization is 0.76-0.89.

[0340] Preferably, in the molecular sieve based on kaolin crystallization, the ratio of the silicon-aluminum ratio calculated using the cell constant to the silicon-aluminum ratio determined by chemical methods is 0.87-0.93.

[0341] Preferably, the mesoporous and macroporous ratio of the molecular sieve based on kaolin crystallization is 10-20%.

[0342] 15. The catalyst according to any one of technical solutions 12-14 in Group F, wherein the preparation method of the molecular sieve based on kaolin crystallization includes:

[0343] (1) Kaolin is roasted to obtain metakaolin, and then the metakaolin is mixed with sodium silicate solution, directing agent and alkali solution to obtain mixed slurry;

[0344] (2) The mixed slurry is first crystallized and then mixed with solid silica gel, and then second crystallized and dried to obtain a molecular sieve based on kaolin crystallization.

[0345] 16. The catalyst according to technical solution 15 of group F, wherein, in step (1), the calcination conditions include: a temperature of 500-900℃ and a time of 1-10h;

[0346] Preferably, the mass ratio of the guiding agent to metakaolin in step (1) is 0.01-1.

[0347] 17. The catalyst according to technical solution 15 or 16 of group F, wherein, in step (2), the conditions for the first crystallization include: a temperature of 88-98°C and a time of 1-70h;

[0348] Preferably, the mass ratio of the solid silica gel to metakaolin in step (2) is 0.01-1;

[0349] Preferably, the conditions for the second crystallization in step (2) include: a temperature of 88-98°C and a time of 1-20h.

[0350] 18. The catalyst according to any one of technical solutions 12-17 in Group F, wherein the molecular sieve with the five-membered ring structure is selected from at least one of BEA-type molecular sieve, MFI-type molecular sieve and mordenite-type molecular sieve, more preferably BEA-type molecular sieve and / or MFI-type molecular sieve.

[0351] Preferably, the MFI molecular sieve is selected from at least one of rare earth-containing MFI molecular sieves, phosphorus-containing MFI molecular sieves, and iron-containing MFI molecular sieves.

[0352] Preferably, the mordenite zeolite molecular sieve is a high-silica mordenite zeolite molecular sieve and / or a low-silica mordenite zeolite molecular sieve.

[0353] 19. The catalyst according to any one of technical solutions 12-18 in Group F, wherein the aluminum-based binder is selected from at least one of aluminum sol, aluminum oxide, and metal-modified aluminum.

[0354] Preferably, the clay is one or more of the following: kaolin, hydrous kaolin, montmorillonite, diatomaceous earth, halloysite, soapstone, rettosite, sepiolite, attapulgite, hydrotalcite, and bentonite.

[0355] 20. A method for preparing a catalytic cracking catalyst, characterized in that the method comprises: mixing a molecular sieve, a composite material as described in any one of the technical solutions 1-11 of Group F, or a zirconium sol and a silicon-aluminum material forming the composite material, an aluminum-based binder, and clay, and then sequentially drying and calcining the mixture to obtain the catalytic cracking catalyst;

[0356] The amounts of the molecular sieve, composite material, aluminum-based binder, and clay are such that, based on the total amount of the catalyst, the content of the molecular sieve is 10-70% by weight, the content of the composite material is 6-50% by weight, the content of the aluminum-based binder is 5-30% by weight, and the content of the clay is 10-70% by weight.

[0357] The molecular sieve includes a first molecular sieve and an optional second molecular sieve. Based on the total amount of the molecular sieve, the content of the first molecular sieve is 70-100% by weight and the content of the second molecular sieve is 0-30% by weight.

[0358] The first molecular sieve is a Y-type molecular sieve, wherein the content of rare earth elements in the Y-type molecular sieve is 0-20% by weight; the second molecular sieve is a molecular sieve with a five-membered ring structure.

[0359] More specifically, to achieve the above objectives, the present invention provides the following technical solution:

[0360] 1. A catalytic cracking catalyst, comprising: 10-70 wt% of a cracking active component, 10-60 wt% of a binder, and 10-70 wt% of clay, wherein the cracking active component comprises 5-100 wt% of a first Y-type molecular sieve and 0-95 wt% of a second molecular sieve; wherein the first Y-type molecular sieve is a modified kaolin-based molecular sieve obtained by modifying a kaolin-based molecular sieve, and its sodium oxide content is less than 2 wt%.

[0361] 2. The catalytic cracking catalyst according to technical solution 1, wherein the molecular sieve based on kaolin crystallization, measured by X-ray diffraction, has a crystallinity of ≥60% by peak height method, and the ratio of crystallinity measured by peak area method is K1, K1 = 0.76-0.89; the silicon-to-aluminum ratio determined by cell constant a0 is 5.0-5.5, and the ratio of the silicon-to-aluminum ratio determined by chemical method is K2.

[0362] K2 = 0.87-0.93, where the silicon-aluminum ratio refers to the molar ratio of silicon oxide to aluminum oxide.

[0363] 3. The catalytic cracking catalyst according to technical solution 2, wherein the crystallinity of the peak height method is ≥80%.

[0364] 4. The catalytic cracking catalyst according to any one of technical solutions 2-3, wherein K1 = 0.80-0.89, for example, K1 = 0.80-0.85.

[0365] 5. The catalytic cracking catalyst according to any one of technical solutions 2-4, wherein K2 = 0.87-0.92, for example, K2 = 0.88-0.90.

[0366] 6. The catalytic cracking catalyst according to any one of technical solutions 2-5, wherein K1 = 0.77-0.88 and K2 = 0.87-0.91.

[0367] 7. The catalytic cracking catalyst according to any one of technical solutions 2-6, wherein the mesopore rate of the molecular sieve based on kaolin crystallization is 10-20%.

[0368] 8. The catalytic cracking catalyst according to any one of technical solutions 2-7, wherein the silicon-to-aluminum ratio determined by the cell constant a0 is 5.2-5.5.

[0369] 9. The catalytic cracking catalyst according to any one of technical solutions 1-7, wherein the molecular sieve based on kaolin crystallization is prepared by the following steps:

[0370] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, and then crushed into metakaolin powder with a particle size of less than 10 micrometers.

[0371] (2) Add a directing agent, sodium silicate, sodium hydroxide solution and water to the metakaolin powder to prepare reaction raw material A, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0, and the ratio of reaction raw material A is (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O molar ratio;

[0372] (3) After crystallizing reaction raw material A at 88-98℃ for 1-70h with stirring, a second silicon source is added to obtain reaction raw material B, wherein the second silicon source accounts for 0.1-10% by weight of the total silicon feed, based on silicon oxide.

[0373] (4) Crystallize the reaction raw material B under stirring at 88-98℃ and recover the product.

[0374] 10. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the modified kaolin-based molecular sieve contains rare earth elements, and the rare earth content in the modified kaolin-based molecular sieve is 10%-20% by weight (RE2O3).

[0375] 11. The catalytic cracking catalyst according to the foregoing technical solution, wherein the second molecular sieve is selected from octahedral zeolite and / or molecular sieves with a five-membered ring structure; for example, the octahedral zeolite is one or more of HY, REY, REHY, USY, REUSY, DASY, and REDASY; the molecular sieve with a five-membered ring structure includes one or more of BEA structure molecular sieves, MFI structure molecular sieves, and mordenite; the binder is selected from one or more of zirconium sol, silica sol, alumina sol, borosilicate, and metal-modified borosilicate; the clay is one or more of kaolin, montmorillonite, diatomaceous earth, halloysite, quasi-haloysite, soapstone, rettoite, sepiolite, attapulgite, hydrotalcite, and bentonite.

[0376] 12. A method for preparing the catalytic cracking catalyst according to any one of the foregoing technical solutions, comprising the following steps:

[0377] (1) Preparation of modified molecular sieves based on kaolin crystallization;

[0378] (2) Forming a slurry from clay, cracking active components and binder; wherein the cracking active components include the modified kaolin-based molecular sieve and an optional second molecular sieve;

[0379] (3) Spray dry the slurry obtained in step (2).

[0380] 13. The method for preparing the catalytic cracking catalyst according to technical solution 12, wherein the method for preparing the modified molecular sieve based on kaolin crystallization includes the following steps:

[0381] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, which is then crushed to produce metakaolin powder with a particle size of less than 10 micrometers.

[0382] (2) Add sodium silicate, a directing agent, sodium hydroxide solution and water to metakaolin powder to prepare reaction raw material A with a ratio of (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0.

[0383] (3) The reaction raw material A is crystallized under stirring at 88-98℃. After the crystallization time reaches 1-70h, a second silicon source is added to obtain the reaction raw material B. The second silicon source accounts for 0.1%-10% of the total silicon feed amount, all calculated as silicon oxide.

[0384] (4) Crystallize reaction material B under stirring at 88-98℃ and recover the product;

[0385] (5) The recovered products are subjected to ion exchange.

[0386] 14. The catalytic cracking catalyst according to technical solution 9 or the catalytic cracking catalyst preparation method according to technical solution 13, wherein the composition of the directing agent is: (10-17)SiO2:(0.7-1.3)Al2O3:(11-18)Na2O:(200-350)H2O.

[0387] 15. The preparation method according to technical solution 13, wherein the second silicon source has a sodium content of less than 1% by weight, calculated as Na2O.

[0388] 16. The method for preparing a catalytic cracking catalyst according to any one of technical solutions 13-15, wherein the second silicon source is solid silica gel.

[0389] 17. The method for preparing a catalytic cracking catalyst according to technical solution 16, wherein the average pore size of the solid silica gel is 1.5-2.0 nm, or the average pore size of the solid silica gel is 4.0-5.0 nm, or the average pore size of the solid silica gel is above 10.0 nm, or the average pore size of the solid silica gel is below 0.8 nm.

[0390] 18. The method for preparing a catalytic cracking catalyst according to any one of technical solutions 13-17, wherein the second silicon source is liquid silica gel.

[0391] 19. The method for preparing a catalytic cracking catalyst according to technical solution 18, wherein the mass content of SiO2 in the liquid silica gel is 1-30%.

[0392] 20. The method for preparing a catalytic cracking catalyst according to any one of technical solutions 13-19, wherein, based on silicon oxide, the second silicon source accounts for 4-10% by weight of the total silicon feed.

[0393] 21. The method for preparing a catalytic cracking catalyst according to any one of technical solutions 13-20, wherein the ion exchange in step (5) is ammonium ion exchange and / or rare earth ion exchange.

[0394] 22. The method for preparing a catalytic cracking catalyst according to any one of technical solutions 13-21, wherein the ion exchange product obtained in step (5) is further calcined.

[0395] 23. The method for preparing a catalytic cracking catalyst according to any one of technical solutions 13-22, wherein the ion exchange includes rare earth ion exchange, and the rare earth content in the modified molecular sieve based on kaolin crystallization obtained in step (5) is 10%-20% by weight (RE2O3) and the sodium oxide content is less than 2% by weight.

[0396] 24. A catalytic cracking method, comprising the step of contacting and reacting hydrocarbon oil with the catalytic cracking catalyst described in any one of technical solutions 1-11.

[0397] 25. The catalytic cracking catalyst according to any one of the aforementioned technical solutions 1-11, wherein the catalytic cracking catalyst comprises a silicon-aluminum material, the anhydrous weight chemical expression of which is: (0-1)Na2O·(15-50)Al2O3·(85-50)SiO2, the most probable pore size is 10-100nm, the specific surface area is 150-600m2 / g, the pore volume is 0.5-1.5ml / g, and the proportion of pore volume with a pore size greater than 10nm to the total pore volume is 70%-98%.

[0398] 26. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the silicon-aluminum material contains boehmite grains, and the average size of the boehmite grains is 1.5nm-3.5nm.

[0399] 27. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the pore volume of the silicon-aluminum material is 0.8-1.5 ml / g.

[0400] 28. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the specific surface area of ​​the silicon-aluminum material is 280-450 m2 / g.

[0401] 29. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the weight ratio of SiO2 to Al2O3 of the silicon-aluminum material is 2-4:1.

[0402] 30. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the silicon-aluminum material is prepared by the following method, the method comprising the following steps:

[0403] (1) At room temperature to 95°C, the alkaline silicon source is gradually added to the acidic aluminum source according to the weight ratio of SiO2:Al2O3=(50-85):(50-15);

[0404] (2) After all the alkaline silicon source is added to the acidic aluminum source, an alkaline solution is added until the pH of the slurry is 8-10.5, and then aged at 50-95℃ for 1-10 hours to obtain a solid precipitate;

[0405] (3) The solid precipitate is contacted with a solution containing ammonium salt and / or acid, and filtered to obtain a silicon-aluminum material with a sodium content of less than 1% by weight based on Na2O. The solid precipitate may or may not be dried before contacting the solution containing ammonium salt and / or acid.

[0406] 31. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein, in the method for preparing the silicon-aluminum material, the acidic aluminum source is selected from aluminum sulfate, aluminum chloride, aluminum sol, and acidic hydrolysis products of aluminum metal alkoxides, and the aluminum metal alkoxides are, for example, aluminum isopropoxide, aluminum sec-butoxide, aluminum triethanolamine, etc., one or more of these.

[0407] 32. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein, in the method for preparing the silicon-aluminum material, the alkaline silicon source is selected from alkaline silica sol, water glass, sodium silicate, alkaline hydrolysis products of silica esters, and the silica ester is, for example, one or more of methyl orthosilicate, tetraethyl orthosilicate, isopropyl orthosilicate, butyl orthosilicate, etc.

[0408] 33. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein, in the method for preparing the silicon-aluminum material, the alkaline solution is one or more of ammonia water, sodium hydroxide solution, potassium hydroxide solution, and sodium aluminate solution, and is more preferably sodium aluminate solution.

[0409] 34. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein, in the method for preparing the silicon-aluminum material, the contact treatment process of the solid precipitate with the solution containing ammonium salt and / or acid includes: contacting the obtained solid precipitate with the solution containing ammonium salt at room temperature to 100°C according to the weight ratio of dry basis of solid precipitate: ammonium salt: H2O = 1:(0.05-0.1):(5-30).

[0410] 35. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein, in the method for preparing the silicon-aluminum material, the ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, and ammonium bicarbonate.

[0411] 36. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein, in the method for preparing the silicon-aluminum material, the solution containing ammonium salt and / or acid is an acid solution, and the contact treatment of the solid precipitate with the solution containing ammonium salt and / or acid is based on the dry basis of the solid precipitate:

[0412] The solid precipitate is contacted with the acid solution at a weight ratio of acid:H2O = 1:(0.03-0.3):(5-30) for at least 0.5 hours, for example, 0.5-2 hours, at room temperature to 100°C. The exchange may be performed once or multiple times.

[0413] 37. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein, in the method for preparing the silicon-aluminum material, the acid is one or more of sulfuric acid, hydrochloric acid, or nitric acid.

[0414] 38. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein, in the method for preparing the silicon-aluminum material, the process of contact treatment with a solution containing ammonium salt and / or acid is performed once or multiple times, with each contact lasting 0.5-1 hour, until the sodium oxide content in the solid precipitate is less than 1% by weight.

[0415] 39. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the catalytic cracking catalyst comprises 10 wt%-70 wt% of cracking active components, 1 wt%-20 wt% of silicon-aluminum material, 10 wt%-60 wt% of binder and 10 wt%-70 wt% of clay; wherein the cracking active components comprise 25 wt%-100 wt% of a first Y-type molecular sieve and 0-75 wt% of a second molecular sieve; wherein the first Y-type molecular sieve is a Y-type molecular sieve synthesized in situ with a sodium oxide content of less than 2 wt%, and the silicon-aluminum material is the silicon-aluminum material according to any one of the foregoing technical solutions.

[0416] 40. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the Y molecular sieve synthesized by in-situ crystallization of kaolin with a sodium oxide content of less than 2% by weight contains rare earth elements, wherein the rare earth element content is 10%-20% by weight as RE2O3.

[0417] 41. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein the Y molecular sieve synthesized by in-situ crystallization of kaolin with a sodium oxide content of less than 2% by weight is a modified molecular sieve based on kaolin crystallization, wherein the modified molecular sieve based on kaolin crystallization is obtained by reducing the sodium content and / or introducing rare earth elements, and the sodium oxide content of the modified molecular sieve based on kaolin crystallization is less than 2% by weight.

[0418] 42. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein the molecular sieve based on kaolin crystallization, measured by X-ray diffraction, has a crystallinity of ≥60% by peak height method, and the ratio of crystallinity measured by peak area method is K1, K1 = 0.76-0.89; the silicon-aluminum ratio determined by cell constant a0 is 5.0-5.5, and the ratio of silicon-aluminum ratio determined by chemical method is K2, K2 = 0.87-0.93, wherein the silicon-aluminum ratio is the molar ratio of silicon oxide to aluminum oxide.

[0419] 43. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the crystallinity of the peak height method is ≥80%.

[0420] 44. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein K1 = 0.77-0.88 and K2 = 0.87-0.91.

[0421] 45. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein K1 = 0.80-0.89 or K1 = 0.80-0.85.

[0422] 46. ​​The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein K2 = 0.87-0.92 or K2 = 0.88-0.90.

[0423] 47. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the mesopore rate of the molecular sieve based on kaolin crystallization is 10-20%.

[0424] 48. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the silicon-to-aluminum ratio measured by the cell constant a0 is 5.2-5.5.

[0425] 49. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the molecular sieve based on kaolin crystallization is prepared by the following steps:

[0426] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, and then crushed into metakaolin powder with a particle size of less than 10 micrometers.

[0427] (2) Add a directing agent, sodium silicate, sodium hydroxide solution and water to the metakaolin powder to prepare reaction raw material A, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0, and the molar ratio of reaction raw material A is (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O;

[0428] (3) After crystallizing reaction raw material A at 88-98℃ for 1-70h with stirring, a second silicon source is added to obtain reaction raw material B, wherein the second silicon source accounts for 0.1-10% by weight of the total silicon feed, based on silicon oxide.

[0429] (4) Crystallize the reaction raw material B under stirring at 88-98℃ and recover the product.

[0430] 50. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the second molecular sieve is selected from octahedral zeolite and / or molecular sieves with a five-membered ring structure, for example, the octahedral zeolite is one or more of HY, REY, REHY, USY, REUSY, DASY, and REDASY, and the molecular sieve with a five-membered ring structure includes one or more of BEA structure molecular sieves, MFI structure molecular sieves, and mordenite; the binder is selected from one or more of silica sol, alumina sol, borosilicate, and metal-modified borosilicate; and the clay is one or more of kaolin, montmorillonite, diatomaceous earth, halloysite, quasi-haloysite, soapstone, rettosite, sepiolite, attapulgite, hydrotalcite, and bentonite.

[0431] 51. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the catalytic cracking catalyst is prepared by the following preparation method, characterized in that it includes the following steps:

[0432] Clay, silica-alumina material, cracking active component and binder are formed into a slurry and spray-dried; wherein the silica-alumina material is the silica-alumina material described in any of the foregoing technical solutions, and the cracking active component includes a first Y-type molecular sieve and an optional second molecular sieve; wherein the first Y-type molecular sieve is a Y molecular sieve synthesized in situ by crystallization with a sodium oxide content of less than 2% by weight.

[0433] 52. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein in the method for preparing the catalytic cracking catalyst, the first Y-type molecular sieve is a modified molecular sieve based on kaolin crystallization, and the method for preparing the modified molecular sieve based on kaolin crystallization includes the following steps:

[0434] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, which is then crushed to produce metakaolin powder with a particle size of less than 10 micrometers.

[0435] (2) Add sodium silicate, a directing agent, sodium hydroxide solution and water to metakaolin powder to prepare reaction raw material A with a ratio of (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0.

[0436] (3) The reaction raw material A is crystallized under stirring at 88-98℃. After the crystallization time reaches 1-70h, a second silicon source is added to obtain the reaction raw material B. The second silicon source accounts for 0.1%-10% of the total silicon feed amount, all calculated as silicon oxide.

[0437] (4) Crystallize reaction material B under stirring at 88-98℃ and recover the product;

[0438] (5) The recovered products are subjected to ion exchange.

[0439] 53. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein in the preparation method of the catalytic cracking catalyst, the molar composition of the directing agent is: (10-17)SiO2:(0.7-1.3)Al2O3:(11-18)Na2O:(200-350)H2O.

[0440] 54. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the sodium content of the second silicon source is <1% by weight, calculated as Na2O.

[0441] 55. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein in the method for preparing the catalytic cracking catalyst, the second silicon source is solid silica gel and / or liquid silica gel.

[0442] 56. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein in the preparation method of the catalytic cracking catalyst, the average pore size of the solid silica gel is less than 0.8 nm, or the average pore size of the solid silica gel is 1.5-2.0 nm, or the average pore size of the solid silica gel is 4.0-5.0 nm, or the average pore size of the solid silica gel is greater than 10.0 nm; and the SiO2 mass content in the liquid silica gel is 1%-30%.

[0443] 57. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein in the preparation method of the catalytic cracking catalyst, the second silicon source accounts for 4%-10% by weight of the total silicon feed, based on silicon oxide.

[0444] 58. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein in the method for preparing the catalytic cracking catalyst, the ion exchange in step (5) is ammonium ion exchange and / or rare earth ion exchange; preferably, the ion exchange product obtained in step (5) is further calcined.

[0445] 59. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein in the method for preparing the catalytic cracking catalyst, the ion exchange includes rare earth ion exchange, and the rare earth content in the modified molecular sieve based on kaolin crystallization obtained in step (5) is 10%-20% by weight (RE2O3) and the sodium oxide content is less than 2% by weight.

[0446] 60. The catalytic cracking catalyst according to any one of the aforementioned technical solutions 1-11, wherein the binder comprises a zirconium sol, the zirconium sol comprising 0.5%-20% by mass of ZrO2, a stabilizer, an alkaline cation, and water, wherein the molar ratio of the stabilizer to Zr is 1-6, and the pH value of the zirconium sol is 1-7.

[0447] 61. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein the zirconium sol particles are between 5nm and 15nm in size, have an average particle size of about 10nm (about 10nm means 10±2nm), and have a concentration of over 90%.

[0448] 62. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the zirconium sol is dried at 100°C for 6 hours and calcined at 600°C for 2-6 hours for heat treatment, and the resulting product contains both monoclinic and tetragonal phases, with the preferred ratio of monoclinic to tetragonal phase being 0.05-0.6:1; and / or the zirconium sol is dried at 100°C for 6 hours and calcined at 800°C for 2-6 hours for heat treatment, and the resulting product contains ZrO2 in the tetragonal phase.

[0449] 63. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the stabilizer is an organic acid, and the stabilizer is preferably one or more of glycolic acid, oxalic acid, acetic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, and citric acid.

[0450] 64. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the alkaline cation is a nitrogen-containing cation, such as ammonium ions or a nitrogen-containing cation formed by the hydrolysis of a water-soluble organic base, wherein the water-soluble organic base is one or more of the following: methylamine, dimethylamine, trimethylamine, methanolamine, diethanolamine, triethanolamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltriethylammonium hydroxide, monomethyltriethanolammonium hydroxide, and monomethyltributylammonium hydroxide.

[0451] 65. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the molar ratio of the alkaline cation to Zr is 1-8.

[0452] 66. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the zirconium sol further contains inorganic acid radicals and / or alcohols, and the molar ratio of the inorganic acid radicals and / or alcohols to Zr is 1-6:1; preferably, the inorganic acid radicals are one or more of sulfate, chloride, and nitrate, and the alcohols are one or more of methanol, ethanol, propanol, and butanol.

[0453] 67. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the pH value of the zirconium sol is 2-4.

[0454] 68. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the zirconium sol is prepared by the following preparation method, comprising the following steps:

[0455] (1) Prepare a zirconium source solution with a concentration of 0.5%-20% by mass based on ZrO2;

[0456] (2) A stabilizer is added to the zirconium source solution to obtain a first mixed solution; wherein the molar ratio of the stabilizer to zirconium is 1-6:

[0457] (3) At room temperature -50℃, an alkaline solution is added to the first mixed solution to obtain zirconium sol, wherein the amount of alkaline solution used is such that the pH value of the zirconium sol is 1-7.

[0458] 69. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein an alkaline solution is slowly added to the first mixed solution to obtain a clear and transparent zirconium sol; the slow addition may be dropwise addition or the addition rate may be controlled at 0.05 ml-50 ml alkaline solution / min / L of the first mixed solution.

[0459] 70. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the zirconium source is one or more of inorganic zirconium salts or organic zirconium salts, wherein the inorganic zirconium salt is one or more of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, zirconium nitrate, zirconium oxynitrate, zirconium oxysulfate, and zirconium oxycarbonate; and the organic zirconium salt is one or more of zirconium n-propoxide, zirconium isopropoxide, zirconium ethoxide, and zirconium butoxide.

[0460] 71. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the stabilizer is an organic acid that can form a coordination polymer with zirconium, and the stabilizer is preferably at least one of glycolic acid, acetic acid, oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, citric acid, etc., more preferably one or more of acetic acid, oxalic acid or citric acid.

[0461] 72. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the alkaline solution is selected from ammonia water or an aqueous solution of a water-soluble organic base, and the water-soluble organic base is, for example, one or more of methylamine, dimethylamine, trimethylamine, methanolamine, diethanolamine, triethanolamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltriethylammonium hydroxide, monomethyltriethanolammonium hydroxide, and monomethyltributylammonium hydroxide.

[0462] 73. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the catalyst is a heavy oil cracking catalyst, comprising, on a dry basis by mass: 10%-60% by mass of cracking active components, 20%-60% by mass of binder, and 10%-70% by mass of clay; wherein the binder comprises 1%-50% by mass of zirconium sol and 50%-99% by mass of a second binder, wherein the zirconium sol is preferably the zirconium sol according to any one of the foregoing technical solutions; preferably, the cracking active components comprise 70%-100% by mass of Y-type molecular sieve and 0-30% by mass of a second molecular sieve.

[0463] 74. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein the second binder is one or more of alumina sol, alumina, and metal-modified alumina.

[0464] 75. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the rare earth content in the Y-type molecular sieve is 0-20% by mass, and the cell constant of the Y-type molecular sieve is 2.430nm-2.480nm; the clay is one or more of kaolin, montmorillonite, diatomite, halloysite, quasi-haloysite, soapstone, rettosite, sepiolite, attapulgite, hydrotalcite, and bentonite.

[0465] 76. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the Y-type molecular sieve is one or more of DASY molecular sieve, rare earth-containing DASY molecular sieve, USY molecular sieve, rare earth-containing USY molecular sieve, REY molecular sieve, HY molecular sieve, REHY molecular sieve, and Y-type molecular sieve synthesized by in-situ crystallization of modified kaolin; the sodium oxide content of the Y-type molecular sieve synthesized by in-situ crystallization of modified kaolin is less than 2% by mass.

[0466] 77. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the Y-type molecular sieve includes a first Y-type molecular sieve and an optional third Y-type molecular sieve; wherein the first Y-type molecular sieve is a modified kaolin-based molecular sieve obtained by modification treatment of a kaolin-based molecular sieve, and its sodium oxide content is less than 2% by mass, the modification treatment includes ultrastabilization treatment and / or ion exchange treatment; the third Y-type molecular sieve is selected from one or more of HY, REY, REHY, USY, REUSY, DASY and REDASY.

[0467] 78. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the second molecular sieve is selected from a molecular sieve having a five-membered ring structure, such as one or more of BEA structure molecular sieves, MFI type molecular sieves, and mordenite, preferably one or more of BEA structure molecular sieves and MFI type molecular sieves; the BEA structure molecular sieve can be obtained by amine-free crystallization, or it can be obtained by calcining a molecular sieve prepared by a template agent method, for example, a Beta molecular sieve; the MFI structure molecular sieve includes at least one of rare earth-containing MFI molecular sieves, phosphorus-containing MFI molecular sieves, and iron-containing MFI molecular sieves; the mordenite includes at least one of high-silica mordenite or low-silica mordenite.

[0468] 79. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein the molecular sieve based on kaolin crystallization has a crystallinity of ≥60% as measured by X-ray diffraction using the peak height method, and the ratio of the crystallinity to that of the peak area method is K1, K1 = 0.76-0.89; the silicon-to-aluminum ratio determined by the cell constant a0 is 5.0-5.5, and the ratio of the silicon-to-aluminum ratio determined by the chemical method is K2, K2 = 0.87-0.93, wherein the silicon-to-aluminum ratio is the molar ratio of silicon oxide to aluminum oxide.

[0469] 80. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the crystallinity of the peak height method is ≥80%.

[0470] 81. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein K1 = 0.80-0.89, for example, K1 = 0.80-0.85.

[0471] 82. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein K2 = 0.87-0.92, for example, K2 = 0.88-0.90.

[0472] 83. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein K1 = 0.77-0.88 and K2 = 0.87-0.91.

[0473] 84. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the mesopore rate of the molecular sieve based on kaolin crystallization is 10-20%.

[0474] 85. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the silicon-to-aluminum ratio measured by the cell constant a0 is 5.2-5.5.

[0475] 86. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the molecular sieve based on kaolin crystallization is prepared by the following steps:

[0476] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, and then crushed into metakaolin powder with a particle size of less than 10 micrometers.

[0477] (2) Add a directing agent, sodium silicate, sodium hydroxide solution and water to the metakaolin powder to prepare reaction raw material A, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0, and the ratio of reaction raw material A is (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O molar ratio;

[0478] (3) After crystallizing reaction raw material A at 88-98℃ for 1-70h with stirring, a second silicon source is added to obtain reaction raw material B, wherein the second silicon source accounts for 0.1-10% by mass of the total silicon feed, based on silicon oxide.

[0479] (4) Crystallize the reaction raw material B under stirring at 88-98℃ and recover the product.

[0480] 87. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the modified molecular sieve based on kaolin crystallization contains rare earth elements, and the rare earth content of the modified molecular sieve based on kaolin crystallization is 10%-20% by mass, calculated as RE2O3.

[0481] 88. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the preparation method of the heavy oil cracking catalyst includes forming a mixture of the zirconium sol, the second binder, clay, the cracking active component and water, and spray drying the mixture, wherein the cracking active component includes a molecular sieve, and the molecular sieve includes a Y-type molecular sieve and an optional second molecular sieve.

[0482] 89. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein in the method for preparing the heavy oil cracking catalyst, the second binder comprises alumina sol and aluminum oxide, and the method for preparing the heavy oil cracking catalyst comprises the following steps:

[0483] (S1) The zirconium sol and aluminum sol are first mixed to form a first sol. Preferably, the pH value of the first sol is controlled to be 2.5-3.5.

[0484] (S2) Prepare clay slurry and cracking active component slurry respectively;

[0485] (S3) Mix the clay slurry, cracking active component slurry, the first sol, and aluminum oxide, and disperse them evenly (e.g., by stirring, homogenizing, or grinding) to obtain the second colloidal mixture;

[0486] (S4) Spray dry the second colloidal mixture obtained in step (S3).

[0487] 90. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein in the method for preparing the heavy oil cracking catalyst, the Y-type molecular sieve includes a modified molecular sieve based on kaolin crystallization, and the method for preparing the modified molecular sieve based on kaolin crystallization includes the following steps:

[0488] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, which is then crushed to produce metakaolin powder with a particle size of less than 10 micrometers.

[0489] (2) Add sodium silicate, a directing agent, sodium hydroxide solution and water to metakaolin powder to prepare reaction raw material A with a ratio of (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0;

[0490] (3) Crystallize reaction raw material A under stirring at 88-98℃. After the crystallization time reaches 1-70h, add a second silicon source to obtain reaction raw material B. The second silicon source accounts for 0.1%-10% of the total silicon feed amount, all calculated as silicon oxide.

[0491] (4) Crystallize reaction material B under stirring at 88-98℃ and recover the product;

[0492] (5) The recovered products are subjected to ion exchange and / or ultrastabilization treatment.

[0493] 91. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein in the preparation method of the heavy oil cracking catalyst, the composition of the directing agent is: (10-17)SiO2:(0.7-1.3)Al2O3:(11-18)Na2O:(200-350)H2O.

[0494] 92. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein in the method for preparing the heavy oil cracking catalyst, the second silicon source has a sodium content of <1% by mass, calculated as Na2O.

[0495] 93. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein in the method for preparing the heavy oil cracking catalyst, the second silicon source is solid silica gel; wherein the average pore size of the solid silica gel is 1.5-2.0 nm, or the average pore size of the solid silica gel is 4.0-5.0 nm, or the average pore size of the solid silica gel is above 10.0 nm, or the average pore size of the solid silica gel is below 0.8 nm.

[0496] 94. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein in the method for preparing the heavy oil cracking catalyst, the second silicon source is liquid silica gel, and the mass content of SiO2 in the liquid silica gel is 1-30%.

[0497] 95. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein in the method for preparing the heavy oil cracking catalyst, the second silicon source accounts for 4-10% of the total silicon feed, based on silicon oxide.

[0498] 96. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein in the method for preparing the heavy oil cracking catalyst, the ion exchange in step (5) is ammonium ion exchange and / or rare earth ion exchange.

[0499] 97. The catalytic cracking catalyst described in any of the aforementioned technical solutions, wherein in the method for preparing the heavy oil cracking catalyst, the product obtained in step (5) is further calcined.

[0500] 98. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein in the method for preparing the heavy oil cracking catalyst, the ion exchange includes rare earth ion exchange, and the rare earth content in the modified molecular sieve based on kaolin crystallization obtained in step (5) is 10%-20% by mass as RE2O3, and the sodium oxide content is less than 2% by mass.

[0501] 99. The catalytic cracking catalyst according to any one of the aforementioned technical solutions 1-11, wherein the catalyst is a metal-resistant catalytic cracking catalyst, and based on the dry weight of the catalytic cracking catalyst, it comprises: 10-70% by weight of cracking active component, 1-20% by weight of zirconium oxide binder, 1-20% by weight of silica sol binder, 0-50% by weight of alumina-based binder and 10-70% by weight of clay.

[0502] 100. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the zirconium oxide binder is zirconium sol, the zirconium sol comprising 0.5 wt%-20 wt%, for example 5-15 wt%, of ZrO2, stabilizer, alkaline cation and water, wherein the molar ratio of stabilizer to Zr is 1-6, and the pH value of the zirconium sol is 1-7.

[0503] 101. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the zirconium sol particles are between 5nm and 15nm in size, have an average particle size of 10±2nm, and a concentration of more than 90%.

[0504] 102. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the zirconium sol is dried at 100°C for 6 hours and calcined at 600°C for 2-6 hours for heat treatment, and the resulting product contains both monoclinic and tetragonal phases, with the preferred ratio of monoclinic to tetragonal phase being 0.05-0.6:1; and / or the zirconium sol is dried at 100°C for 6 hours and calcined at 800°C for 2-6 hours for heat treatment, and the resulting product contains ZrO2 in the tetragonal phase.

[0505] 103. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the stabilizer in the zirconium sol is one or more of glycolic acid, oxalic acid, acetic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, citric acid, etc.

[0506] 104. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein in the zirconium sol, the alkaline cation is an ammonium ion or a nitrogen-containing cation formed by the hydrolysis of a water-soluble organic base, and the water-soluble organic base is one or more of methylamine, dimethylamine, trimethylamine, methanolamine, diethanolamine, triethanolamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltriethylammonium hydroxide, monomethyltriethanolammonium hydroxide, and monomethyltributylammonium hydroxide.

[0507] 105. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the molar ratio of the alkaline cation to Zr in the zirconium sol is 1-8.

[0508] 106. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the zirconium sol further contains inorganic acid radicals and / or alcohols, and the molar ratio of the inorganic acid radicals and / or alcohols to Zr is 1-6; the inorganic acid radicals are, for example, one or more of sulfate, chloride, and nitrate; and the alcohols are, for example, one or more of methanol, ethanol, propanol, and butanol.

[0509] 107. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the pH value of the zirconium sol is 1.5-5, preferably 2-3.

[0510] 108. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the silica sol has a pH value of 1.5-3.5 and a silica sol particle size of 2nm-20nm; the content of SiO2 in the silica sol is preferably 5%-15% by weight; in one embodiment, the silica sol is a silica sol prepared by direct acidification of water glass, and the pH value of the silica sol is 1.5-3.

[0511] 109. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the alumina binder is one or more of alumina sol, borosilicate, phosphorus and / or metal-modified borosilicate.

[0512] 110. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the cracking active component comprises 70%-100% by weight of a Y-type molecular sieve and 0-30% by weight of a second molecular sieve; the Y-type molecular sieve has a cell constant of 2.430 nm-2.480 nm and a rare earth content of 0-20% by weight as RE2O3; the second molecular sieve is a molecular sieve with a five-membered ring structure; the clay is one or more of kaolin, montmorillonite, diatomite, halloysite, quasi-haloysite, soapstone, palygorskite, sepiolite, attapulgite, hydrotalcite, and bentonite.

[0513] 111. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the Y-type molecular sieve is a modified molecular sieve based on kaolin crystallization obtained by modification treatment, and its sodium oxide content is less than 2% by weight, wherein the modification treatment includes ultrastabilization treatment and / or ion exchange treatment.

[0514] 112. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein the molecular sieve based on kaolin crystallization has a crystallinity of ≥60% as measured by X-ray diffraction using the peak height method, and the ratio of the crystallinity to that measured by the peak area method is K1, K1 = 0.76-0.89; the silicon-aluminum ratio determined by the cell constant a0 is 5.0-5.5, and the ratio of the silicon-aluminum ratio determined by the chemical method is K2, K2 = 0.87-0.93, wherein the silicon-aluminum ratio is the molar ratio of silicon oxide to aluminum oxide.

[0515] 113. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the crystallinity of the peak height method is ≥80%.

[0516] 114. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the molecular sieve based on kaolin crystallization has K1 = 0.77-0.88 and K2 = 0.87-0.91.

[0517] 115. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the mesopore rate of the molecular sieve based on kaolin crystallization is 10-20%.

[0518] 116. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the silicon-to-aluminum ratio of the molecular sieve based on kaolin crystallization is 5.2-5.5 as determined by the cell constant a0.

[0519] 117. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein, in the preparation process of the catalytic cracking catalyst, the zirconium oxide binder and the silica sol binder are first mixed, and then mixed with the cracking active component, clay and alumina-based binder.

[0520] 118. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the modified molecular sieve based on kaolin crystallization contains rare earth elements, and the rare earth content of the modified molecular sieve based on kaolin crystallization is 10%-20% by weight (RE2O3).

[0521] 119. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the catalytic cracking catalyst is prepared by the following method, the preparation method comprising:

[0522] A mixture of zirconium sol and silica sol is formed; the mixture of zirconium sol and silica sol, cracking active components, clay, and optional alumina binder form a slurry; spray drying is performed; the cracking active components include Y-type molecular sieves and optional second molecular sieves.

[0523] 120. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the following steps are included:

[0524] (s1) Zirconium sol and silica sol are mixed, preferably with the pH value of the mixture controlled at 2.5-3.5;

[0525] (s2) Prepare clay slurry;

[0526] (s3) Preparation of molecular sieve slurry;

[0527] (s4) Mix the clay slurry, molecular sieve slurry, the mixture obtained in step (s1), and alumina binder;

[0528] (s5) Disperse the slurry obtained in step (s4) evenly and spray dry it.

[0529] 121. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the method for preparing the zirconium sol includes the following steps:

[0530] (1) Prepare a zirconium source solution with a concentration of 0.5%-20% by weight, for example 5-15% by weight, based on ZrO2.

[0531] (2) Add a stabilizer to the zirconium source solution and stir at room temperature to 90°C for 0.5-3 hours to obtain a first mixed solution; wherein the molar ratio of stabilizer to zirconium is 1-6:

[0532] (3) At room temperature -50℃, an alkaline solution is added to the first mixed solution to obtain zirconium sol, wherein the amount of alkaline solution used is such that the pH value of the zirconium sol is 1-7.

[0533] 122. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein, in the zirconium sol preparation method, an alkaline solution is slowly added to a first mixed solution to obtain a clear and transparent zirconium sol; the slow addition is dropwise addition or controlling the addition rate of the alkaline solution to be 0.05 ml-50 ml alkaline solution / min / L of the first mixed solution; preferably, the amount of alkaline solution added makes the pH value of the zirconium sol 1.5-5, for example, 2-3.

[0534] 123. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the zirconium source is one or more of inorganic zirconium salts or organic zirconium salts, wherein the inorganic zirconium salt is one or more of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, zirconium nitrate, zirconium oxynitrate, zirconium oxysulfate, and zirconium oxycarbonate; and the organic zirconium salt is one or more of zirconium n-propoxide, zirconium isopropoxide, zirconium ethoxide, and zirconium butoxide.

[0535] 124. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the stabilizer is one or more of glycolic acid, acetic acid, oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, and citric acid.

[0536] 125. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the alkaline solution is selected from ammonia water or an aqueous solution of a water-soluble organic base, and the water-soluble organic base is, for example, one or more of methylamine, dimethylamine, trimethylamine, methanolamine, diethanolamine, triethanolamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltriethylammonium hydroxide, monomethyltriethanolammonium hydroxide, and monomethyltributylammonium hydroxide.

[0537] 126. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the Y-type molecular sieve comprises a modified kaolin-based molecular sieve, and the preparation method of the modified kaolin-based molecular sieve comprises the following steps:

[0538] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, which is then crushed to produce metakaolin powder with a particle size of less than 10 micrometers.

[0539] (2) Add sodium silicate, a directing agent, sodium hydroxide solution and water to metakaolin powder to prepare reaction raw material A with a ratio of (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O, wherein the weight ratio of the directing agent to metakaolin is 0.01-1.0.

[0540] (3) The reaction raw material A is crystallized under stirring at 88-98℃. After the crystallization time reaches 1-70h, a second silicon source is added to obtain the reaction raw material B. The second silicon source accounts for 0.1%-10% of the total silicon feed amount, all calculated as silicon oxide.

[0541] (4) The reaction raw material B is crystallized under stirring at 88-98℃ and the product is recovered to obtain a molecular sieve based on kaolin crystallization;

[0542] (5) The recovered molecular sieve based on kaolin crystallization is subjected to ion exchange and / or ultrastabilization treatment.

[0543] 127. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the composition of the directing agent is: (10-17)SiO2:(0.7-1.3)Al2O3:(11-18)Na2O:(200-350)H2O.

[0544] 128. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein the second silicon source has a sodium content of <1% by weight (calculated as Na2O, calculated as silicon oxide), and the second silicon source accounts for 4-10% by weight of the total silicon feed.

[0545] 129. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein, in the preparation method of the modified molecular sieve based on kaolin crystallization, the second silicon source is solid silica gel and / or liquid silica gel; wherein, the average pore size of the solid silica gel is 1.5-2.0 nm, or the average pore size of the solid silica gel is 4.0-5.0 nm, or the average pore size of the solid silica gel is above 10.0 nm, or the average pore size of the solid silica gel is below 0.8 nm, and the SiO2 weight content in the liquid silica gel is 1-30%.

[0546] 130. The catalytic cracking catalyst described in any of the aforementioned technical solutions, wherein the ion exchange in step (5) is ammonium ion exchange and / or rare earth ion exchange.

[0547] 131. The catalytic cracking catalyst described in any of the aforementioned technical solutions, wherein the ion exchange includes rare earth ion exchange, and the rare earth content in the modified molecular sieve based on kaolin crystallization obtained in step (5) is 10%-20% by weight (RE2O3) and the sodium oxide content is less than 2% by weight.

[0548] 132. The catalytic cracking catalyst according to any one of the aforementioned technical solutions 1-11, wherein the catalyst is a catalytic cracking catalyst that produces more low-carbon olefins, comprising: 10%-60% by weight of cracking active components on a dry basis, 20%-60% by weight of binder on a dry basis, and 0%-70% by weight of second clay on a dry basis; wherein, based on the dry weight of the binder, the binder comprises 1%-50% by weight of zirconium sol, 50%-99% by weight of phosphorus aluminum inorganic binder, and 0-45% by weight of third binder on a dry basis;

[0549] The cracking active component includes a first molecular sieve and an optional second molecular sieve, wherein the first molecular sieve is a five-membered ring molecular sieve; on a dry basis, the first molecular sieve accounts for more than 70% of the cracking active component; preferably, the cracking active component contains 70-100% by weight of the first molecular sieve and 0-30% by weight of the second molecular sieve.

[0550] The zirconium sol comprises 0.5%-20% by mass of ZrO2, a stabilizer, an alkaline cation, and water, wherein the molar ratio of the stabilizer to Zr is 1-6, and the pH value of the zirconium sol is 1-7.

[0551] The phosphorus-aluminum inorganic binder contains 15-40% by weight of alumina source component (based on Al2O3), 45-80% by weight of phosphorus component (based on P2O5), and 0-40% by weight of first clay (based on dry basis). Its P / Al weight ratio is 1-6, pH value is 1-3.5, and solid content is 15-60% by weight.

[0552] 133. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the third binder is selected from one or more of silica sol, alumina sol, aluminosilicate gel, alumina, and metal-modified alumina.

[0553] 134. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the first molecular sieve is one or more of MFI structure molecular sieve, BEA structure molecular sieve, and mordenite.

[0554] 135. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the second molecular sieve is a Y-type molecular sieve, and the rare earth content in the Y-type molecular sieve is 0-20% by weight, preferably 0-12% by weight.

[0555] 136. The catalytic cracking catalyst described in any of the foregoing technical solutions, wherein the Y-type molecular sieve is one or more of DASY molecular sieve, rare earth-containing DASY molecular sieve, USY molecular sieve, rare earth-containing USY molecular sieve, REY molecular sieve, HY molecular sieve, REHY molecular sieve, and Y-type molecular sieve synthesized by in-situ crystallization of modified kaolin.

[0556] 137. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the second molecular sieve is an ion-modified ultrastable molecular sieve based on kaolin crystallization; based on the weight of the catalytic cracking catalyst, the content of the ion-modified ultrastable molecular sieve based on kaolin crystallization in the catalytic cracking catalyst is preferably 1-10% by weight.

[0557] 138. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the second clay is one or more of kaolin, montmorillonite, diatomite, halloysite, quasi-haloysite, soapstone, attapulgite, sepiolite, attapulgite, hydrotalcite, and bentonite; and the first clay is one or more of kaolin, montmorillonite, diatomite, halloysite, quasi-haloysite, soapstone, attapulgite, sepiolite, attapulgite, hydrotalcite, and bentonite, wherein the first clay is preferably one or more of kaolin, sepiolite, attapulgite, attapulgite, montmorillonite, and diatomite.

[0558] 139. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the method for preparing the phosphorus-aluminum inorganic binder includes:

[0559] (1) The alumina source, the first clay and water are slurried and dispersed into a slurry with a solid content of 8-45% by weight; the alumina source is aluminum hydroxide and / or alumina that can be dissolved by acid, and the weight ratio of the first clay on a dry basis to the alumina source on an Al2O3 basis is 0-40:15-40.

[0560] (2) Add concentrated phosphoric acid to the slurry obtained in step (1) under stirring at a weight ratio of P / Al = 1-6; wherein the concentration of the concentrated phosphoric acid is, for example, 50-98% by weight.

[0561] (3) React the slurry obtained in step (2) at a temperature of 50-99℃ for 15-90 minutes.

[0562] 140. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the phosphorus aluminum inorganic binder comprises 15-35% by weight of Al2O3 derived from the alumina source, 50-75% by weight of P2O5 and 0-35% by weight of a first clay, for example 5-30% by weight of a first clay on a dry basis.

[0563] 141. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the P / Al weight ratio is 2-5.

[0564] 142. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the alumina source is one or more of p-alumina, χ-alumina, η-alumina, γ-alumina, κ-alumina, δ-alumina, θ-alumina, gibbsite, boehmite, diaspore, boehmite, boehmite, and pseudoboehmite.

[0565] 143. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the zirconium sol particles are between 5nm and 15nm in size, have an average particle size of 10±2nm, and a concentration of more than 90%.

[0566] 144. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the zirconium sol is dried at 100°C for 6 hours and calcined at 600°C for 2-6 hours for heat treatment, and the resulting product contains both monoclinic and tetragonal phases, with the ratio of monoclinic to tetragonal phase preferably being 0.05-0.6:1; and / or the zirconium sol is dried at 100°C for 6 hours and calcined at 800°C for 2-6 hours for heat treatment, and the resulting product contains ZrO2 in the tetragonal phase.

[0567] 145. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the stabilizer is one or more of glycolic acid, oxalic acid, acetic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, and citric acid.

[0568] 146. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the alkaline cation is an ammonium ion or a nitrogen-containing cation formed by the hydrolysis of a water-soluble organic base, and the water-soluble organic base is one or more of the following: methylamine, dimethylamine, trimethylamine, methanolamine, diethanolamine, triethanolamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltriethylammonium hydroxide, monomethyltriethanolammonium hydroxide, and monomethyltributylammonium hydroxide.

[0569] 147. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the molar ratio of the alkaline cation to Zr is 1-8.

[0570] 148. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the zirconium sol further contains inorganic acid radicals and / or alcohols, and the molar ratio of the inorganic acid radicals and / or alcohols to Zr is 1-6:1; preferably, the inorganic acid radicals are one or more of sulfate, chloride, and nitrate, and the alcohols are one or more of methanol, ethanol, propanol, and butanol.

[0571] 149. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the pH value of the zirconium sol is 2-4.

[0572] 150. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the zirconium sol is prepared by a preparation method comprising the following steps:

[0573] (1) Prepare a zirconium source solution with a concentration of 0.5%-20% by mass based on ZrO2;

[0574] (2) A stabilizer is added to the zirconium source solution to obtain a first mixed solution; wherein the molar ratio of the stabilizer to zirconium is 1-6:

[0575] (3) At room temperature -50℃, an alkaline solution is added to the first mixed solution to obtain zirconium sol, wherein the amount of alkaline solution used is such that the pH value of the zirconium sol is 1-7.

[0576] 151. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the preparation method of the modified molecular sieve based on kaolin crystallization includes the following steps:

[0577] (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, which is then crushed to produce metakaolin powder with a particle size of less than 10 micrometers.

[0578] (2) Add sodium silicate, a directing agent, sodium hydroxide solution and water to metakaolin powder to prepare reaction raw material A with a ratio of (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0;

[0579] (3) The reaction raw material A is crystallized under stirring at 88-98℃. After the crystallization time reaches 1-70h, a second silicon source is added to obtain the reaction raw material B. The second silicon source accounts for 0.1%-10% of the total silicon feed amount, all calculated as silicon oxide.

[0580] (4) The reaction raw material B is crystallized under stirring at 88-98℃ and the product is recovered to obtain a molecular sieve based on kaolin crystallization;

[0581] (5) Obtain molecular sieves based on kaolin crystallization and perform ion exchange and / or ultrastabilization treatment.

[0582] 152. The catalytic cracking catalyst according to any one of the aforementioned technical solutions 1-11, wherein the catalytic cracking catalyst contains a composite material, the composite material comprising zirconium sol and silicon-aluminum material, wherein, based on the total amount of the composite material, on a dry basis, the content of zirconium sol is 30-80% by weight and the content of silicon-aluminum material is 20-70% by weight.

[0583] 153. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the zirconium sol has a particle size between 5-15 nm, an average particle size of 8-12 nm, and a concentration of over 90%.

[0584] 154. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the method for preparing the zirconium sol includes:

[0585] (a) A solution containing a zirconium source is mixed with an acid to obtain a first mixture;

[0586] (b) Add an alkaline solution to the first mixture to obtain zirconium sol.

[0587] 155. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein, in step (a), the concentration of the solution containing the zirconium source, calculated as ZrO2, is 0.5-20% by weight;

[0588] Preferably, in step (a), the molar ratio of the zirconium source solution to the acid, calculated as Zr element, is 1:1-6;

[0589] Preferably, the mixing conditions in step (a) include: a temperature of 20-90°C and a time of 0.5-3 hours;

[0590] Preferably, the acid in step (a) is an organic acid, more preferably at least one of glycolic acid, acetic acid, oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid and citric acid, and even more preferably acetic acid and / or citric acid;

[0591] Preferably, the zirconium source is an inorganic zirconium salt and / or an organic zirconium salt;

[0592] More preferably, the inorganic zirconium salt is selected from at least one of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, zirconium nitrate, zirconium oxynitrate, zirconium oxysulfate, and zirconium oxycarbonate.

[0593] More preferably, the organozirconium salt is selected from at least one of zirconium n-propoxide, zirconium isopropoxide, zirconium ethoxide, and zirconium butoxide.

[0594] 156. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the amount of alkaline solution added in step (b) makes the pH value of the zirconium sol 1-7, preferably 1.5-5, and more preferably 2-3;

[0595] Preferably, the alkaline solution in step (b) is ammonia and / or a water-soluble organic base;

[0596] More preferably, the water-soluble organic base is selected from at least one of methylamine, dimethylamine, trimethylamine, methanolamine, diethanolamine, triethanolamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltriethylammonium hydroxide, monomethyltriethanolammonium hydroxide, and monomethyltributylammonium hydroxide.

[0597] 157. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the expression of the silicon-aluminum material, in terms of the weight ratio of oxides, is (0-1)Na2O·(15-50)Al2O3·(85-50)SiO2;

[0598] Preferably, the silicon-aluminum material has an average pore size of 10-100 nm, a specific surface area of ​​150-600 m² / g, and a pore volume of 0.5-1.5 cm³ / g.

[0599] 158. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the method for preparing the silicon-aluminum material includes:

[0600] (i) Mixing a silicon source with an aluminum source to obtain a mixture containing both silicon and aluminum sources;

[0601] (ii) Add an alkaline solution to the mixture containing the silicon source and the aluminum source to obtain a slurry, and then age the slurry to obtain a solid precipitate;

[0602] (iii) The solid precipitate is contacted with an ammonium salt or an acid to obtain a silicon-aluminum material.

[0603] 159. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein, in step (i), the molar ratio of silicon source (calculated as SiO2) to aluminum source (calculated as Al2O3) is 50-85:50-15;

[0604] Preferably, the mixing conditions in step (i) include a temperature of 20-95°C;

[0605] Preferably, the silicon source in step (i) is an alkaline silicon source, more preferably one or more of alkaline silica sol, water glass, sodium silicate, and alkaline hydrolysis products of metal alkoxides of silicon;

[0606] Preferably, the aluminum source in step (i) is an acidic aluminum source, more preferably one or more of aluminum sulfate, aluminum chloride, aluminum sol, and acidic hydrolysis products of aluminum metal alkoxides.

[0607] 160. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the amount of alkaline solution added in step (ii) makes the pH value of the slurry 8-10.5;

[0608] Preferably, the aging conditions in step (ii) include: a temperature of 50-95°C and a time of 1-10 hours;

[0609] Preferably, the alkaline solution in step (ii) is selected from at least one of ammonia water, sodium hydroxide solution, potassium hydroxide solution and sodium aluminate solution.

[0610] 161. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein, in step (iii), the solid precipitate is contacted with the ammonium salt by mixing the solid precipitate with the ammonium salt and water to perform ammonium exchange;

[0611] Preferably, the weight ratio of the solid precipitate to the ammonium salt and water on a dry basis is 1:0.05-0.1:5-30;

[0612] Preferably, the ammonium exchange conditions result in the sodium content of the silicon-aluminum material being less than 1% by weight;

[0613] More preferably, the conditions for ammonium exchange include: a temperature of 20-100℃, 1-3 exchanges, and a time of 0.5-1h for each exchange.

[0614] Preferably, the ammonium salt is selected from at least one of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, and ammonium bicarbonate.

[0615] 162. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein in step (iii), the solid precipitate is contacted with acid by mixing the solid precipitate with acid and water for acid treatment;

[0616] Preferably, the weight ratio of the solid precipitate to acid and water on a dry basis is 1:0.03-0.3:5-30;

[0617] Preferably, the acid treatment conditions result in the sodium content of the silicon-aluminum material being less than 1% by weight;

[0618] More preferably, the acid treatment conditions include: a temperature of 20-100°C and a time of at least 0.5 h, more preferably 1-3 h;

[0619] Preferably, the acid is selected from at least one of sulfuric acid, hydrochloric acid, and nitric acid.

[0620] 163. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the catalyst comprises molecular sieve, aluminum-based binder, clay and the aforementioned composite material, wherein, based on the total amount of the catalyst, the content of molecular sieve is 10-70% by weight, the content of aluminum-based binder is 5-30% by weight, the content of clay is 10-70% by weight, and the content of composite material is 6-50% by weight.

[0621] The molecular sieve includes a first molecular sieve and an optional second molecular sieve. Based on the total amount of the molecular sieve, the content of the first molecular sieve is 70-100% by weight and the content of the second molecular sieve is 0-30% by weight.

[0622] The first molecular sieve is a Y-type molecular sieve, wherein the content of rare earth elements in the Y-type molecular sieve is 0-20% by weight; the second molecular sieve is a molecular sieve with a five-membered ring structure.

[0623] 164. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the Y-type molecular sieve is at least one of HY molecular sieve, REY molecular sieve, molecular sieve based on kaolin crystallization, REHY molecular sieve, USY molecular sieve, REUSY molecular sieve, DASY molecular sieve and REDASY molecular sieve;

[0624] Preferably, the first molecular sieve is a REY molecular sieve and / or a rare earth element modified molecular sieve based on kaolin crystallization;

[0625] More preferably, the content of the rare earth element in the molecular sieve based on kaolin crystallization is 10-20% by weight;

[0626] Preferably, the rare earth element is selected from at least one of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and more preferably La.

[0627] 165. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the ratio of the crystallinity obtained by the peak height method to the crystallinity obtained by the peak area method in the molecular sieve based on kaolin crystallization is 0.76-0.89;

[0628] Preferably, in the molecular sieve based on kaolin crystallization, the ratio of the silicon-aluminum ratio calculated using the cell constant to the silicon-aluminum ratio determined by chemical methods is 0.87-0.93.

[0629] Preferably, the mesoporous and macroporous ratio of the molecular sieve based on kaolin crystallization is 10-20%.

[0630] 166. The catalytic cracking catalyst according to any one of the foregoing technical solutions, wherein the preparation method of the molecular sieve based on kaolin crystallization includes:

[0631] (1) Kaolin is roasted to obtain metakaolin, and then the metakaolin is mixed with sodium silicate solution, directing agent and alkali solution to obtain mixed slurry;

[0632] (2) The mixed slurry is first crystallized and then mixed with solid silica gel, and then second crystallized and dried to obtain a molecular sieve based on kaolin crystallization.

[0633] 167. The catalytic cracking catalyst according to any of the aforementioned technical solutions, wherein, in step (1), the calcination conditions include: a temperature of 500-900℃ and a time of 1-10h;

[0634] Preferably, the mass ratio of the guiding agent to metakaolin in step (1) is 0.01-1.

[0635] 168. The catalytic cracking catalyst described in any of the aforementioned technical solutions, wherein, in step (2), the conditions for the first crystallization include: a temperature of 88-98°C and a time of 1-70 h;

[0636] Preferably, the mass ratio of the solid silica gel to metakaolin in step (2) is 0.01-1;

[0637] Preferably, the conditions for the second crystallization in step (2) include: a temperature of 88-98°C and a time of 1-20h.

[0638] 169. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the molecular sieve with the five-membered ring structure is selected from at least one of BEA-type molecular sieve, MFI-type molecular sieve and mordenite-type molecular sieve, more preferably BEA-type molecular sieve and / or MFI-type molecular sieve;

[0639] Preferably, the MFI molecular sieve is selected from at least one of rare earth-containing MFI molecular sieves, phosphorus-containing MFI molecular sieves, and iron-containing MFI molecular sieves.

[0640] Preferably, the mordenite zeolite molecular sieve is a high-silica mordenite zeolite molecular sieve and / or a low-silica mordenite zeolite molecular sieve.

[0641] 170. The catalytic cracking catalyst according to any of the foregoing technical solutions, wherein the aluminum-based binder is selected from at least one of aluminum sol, borosilicate, and metal-modified borosilicate;

[0642] Preferably, the clay is one or more of the following: kaolin, hydrous kaolin, montmorillonite, diatomaceous earth, halloysite, soapstone, rettosite, sepiolite, attapulgite, hydrotalcite, and bentonite.

[0643] Example

[0644] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, all raw materials used are commercially available.

[0645] The specifications of the raw materials used in the catalyst preparation example are as follows:

[0646] DASY molecular sieve: Sinopec Catalysts Qilu Branch, with Na2O content of 1.02 wt%, rare earth content (calculated as RE2O3) of 2.3 wt%, and silicon-aluminum ratio (SiO2 / Al2O3 molar ratio) of 10.4.

[0647] REY molecular sieve: a product of Sinopec Catalysts Qilu Branch, with a rare earth content (calculated as RE2O3) of 16-17.6% by weight;

[0648] SOY-8 molecular sieve: Qilu Catalyst Branch, rare earth content (calculated as RE2O3) is 8% by weight.

[0649] ZRP-1 molecular sieve: Qilu Catalyst Branch, P2O5 content is 5% by mass;

[0650] ZSP-3 molecular sieve: Sinopec Catalysts Qilu Branch, with P2O5 content of 3.02 wt%, (SiO2 / Al2O3) of 45%, and Na2O content of 0.02 wt%.

[0651] β molecular sieve: Qilu Catalyst Branch, silicon-aluminum ratio (SiO2:Al2O3 molar ratio) 25.

[0652] Ammonia water: Sinopharm Group, analytical grade, 28% by weight.

[0653] Zirconium oxychloride octahydrate: commercially available from Aldrich, analytical grade, 98.5%;

[0654] Glacial acetic acid: Sinopharm Group, analytical grade, 99% by weight.

[0655] Oxalic acid: Sinopharm Group, analytical grade, 99% by mass;

[0656] Acetic acid: Sinopharm Group, analytical grade, 99%;

[0657] Kaolin: Solid content 75% by weight, produced by China Kaolin Co., Ltd. (Suzhou);

[0658] Aluminum sulfate: Sinopharm Group, analytical grade, 99%;

[0659] Aluminum sol: a product of Qilu Branch of Sinopec Catalyst Co., Ltd., with a solid content of 23-25% by weight.

[0660] Boehmite (abbreviated as boehmite): a product of Shandong Aluminum Company, with a solid content of 65-75% by weight;

[0661] Sodium hydroxide: Sinopharm Group, analytical grade, 99% by mass;

[0662] Triethanolamine: Sinopharm Group, analytical grade, 99% by weight

[0663] Water glass: Qilu Catalyst Branch, SiO2 250g / L.

[0664] Hydrochloric acid: Sinopharm Group, analytical grade, 36% by weight

[0665] Zirconium oxychloride: commercially available from Aldrich, analytical grade, purity 98.5% by weight;

[0666] Zirconium isopropoxide: Sinopharm Group, analytical grade, 99% by weight

[0667] Nitrogen adsorption method (GB / T5816-1995) for determining specific surface area; nitrogen adsorption method (RIPP151-90) for determining pore volume. In nitrogen adsorption method, pores with a diameter greater than 0.8 nm are defined as mesopores and macropores. The formula for calculating the mesopore ratio is (V total pores - V micropores) / V total pores × 100%.

[0668] The elemental content in catalysts and molecular sieves was determined by XRF, while the specific surface area and pore volume were determined by low-temperature nitrogen adsorption-desorption method.

[0669] The cell constant a0 was determined according to the RIPP 145-90 standard method. The skeletal silicon-to-aluminum ratio was calculated from the cell constant a0 (Å) using the following formula: SiO2 / Al2O3 (molar ratio) = 2 × (25.858 - a0) / (a0 - 24.191).

[0670] In the examples, the NaY zeolite content in the composite material was determined according to the RIPP 146-90 standard method (the RIPP standard method can be found in "Analytical Methods for Petrochemical Products (RIPP Test Methods)", edited by Yang Cuiding et al., Science Press, 1990, the same below).

[0671] The wear index of the catalyst was determined using the RIPP28-90 and RIPP29-90 methods in "Analytical Methods for Petrochemicals, RIPP Test Method" (edited by Yang Cuiding, Science Press, published in 1990).

[0672] The average size of the grains is determined by randomly measuring the size of 50 grains and taking their arithmetic mean.

[0673] Preparation of directing agent

[0674] Take 250 kg of sodium silicate solution (containing 20.05 wt% SiO2 and 6.41 wt% Na2O), and slowly add 120 kg of sodium aluminate solution (containing 3.15 wt% Al2O3 and 21.1 wt% Na2O) at 30°C with rapid stirring. Stir for 1 hour, then age at 20°C for 48 hours to obtain the directing agent. The directing agent composition is 16Na2O:Al2O3:15SiO2:320H2O.

[0675] Preparation of molecular sieves based on kaolin crystallization

[0676] Zeolite Material A

[0677] 100 kg of pulverized metakaolin powder was mixed with 400 kg of sodium silicate solution (containing 20.05 wt% SiO2 and 6.41 wt% Na2O), 60 kg of a directing agent, and 100 kg of 5 wt% sodium hydroxide solution under stirring. The mixture was heated to 95°C and stirred at this constant temperature. After 8 hours, 10 kg of solid silica gel (Qingdao Ocean Chemical Group Special Silica Gel Factory, Type A) was added, and the mixture was further crystallized for 12 hours. The stirring speed during addition and crystallization was 400 rpm. After crystallization, the crystallization tank was rapidly cooled, filtered, and washed with water until the pH of the washing solution was less than 10. The mixture was then dried at 120°C for 2 hours to obtain zeolite material A.

[0678] The crystallinity of zeolite material A measured by X-ray diffraction, the K1 value (ratio of crystallinity measured by peak height to crystallinity measured by peak area), the silicon-aluminum ratio determined by cell constant a0, the K2 value (ratio of silicon-aluminum ratio determined by cell constant a0 to silicon-aluminum ratio determined by chemical method), and the medium-to-large porosity are shown in Table 1.

[0679] Zeolite Material B

[0680] 100 kg of pulverized metakaolin powder was mixed with 380 kg of sodium silicate solution (containing 20.05 wt% SiO2 and 6.41 wt% Na2O), 60 kg of a directing agent, and 100 kg of 5 wt% sodium hydroxide solution under stirring. The mixture was heated to 93°C and stirred at this constant temperature. After 8 hours, 15 kg of solid silica gel (Qingdao Ocean Chemical Group Special Silica Gel Factory, Type A) was added, and the mixture was further crystallized for 14 hours. The stirring speed during addition and crystallization was 400 rpm. After crystallization, the crystallization tank was rapidly cooled, filtered, and washed with water until the pH of the washing solution was less than 10. The mixture was then dried at 120°C for 2 hours to obtain zeolite material B.

[0681] The crystallinity of zeolite material B measured by X-ray diffraction, the K1 value (ratio of crystallinity by peak height method to crystallinity by peak area method), the silicon-aluminum ratio determined by cell constant a0, the K2 value (ratio of silicon-aluminum ratio determined by cell constant a0 to silicon-aluminum ratio determined by chemical method), and the medium-to-large porosity are shown in Table 1.

[0682] Zeolite material C

[0683] 100 kg of pulverized metakaolin powder was mixed with 360 kg of sodium silicate solution (containing 20.05 wt% SiO2 and 6.41 wt% Na2O), 60 kg of a directing agent, and 100 kg of 5 wt% sodium hydroxide solution under stirring. The mixture was heated to 95°C and stirred at this constant temperature. After 8 hours, 20 kg of solid silica gel (Qingdao Ocean Chemical Group Special Silica Gel Factory, Type A) was added, and the mixture was further crystallized for 16 hours. The stirring speed during addition and crystallization was 400 rpm. After crystallization, the crystallization tank was rapidly cooled, filtered, and washed with water until the pH of the washing solution was less than 10. The mixture was then dried at 120°C for 2 hours to obtain zeolite material C.

[0684] The crystallinity of zeolite material C measured by X-ray diffraction, the K1 value (ratio of crystallinity by peak height method to crystallinity by peak area method), the silicon-aluminum ratio determined by cell constant a0, the K2 value (ratio of silicon-aluminum ratio determined by cell constant a0 to silicon-aluminum ratio determined by chemical method), and the medium-to-large porosity are shown in Table 1.

[0685] Zeolite material D (comparison)

[0686] This comparative example illustrates the situation where two silicon sources are added to the reaction system at once.

[0687] 100 kg of pulverized metakaolin powder was mixed with 400 kg of sodium silicate solution (containing 20.05 wt% SiO2 and 6.41 wt% Na2O), 60 kg of a directing agent, 105 kg of 5 wt% sodium hydroxide solution, and 10 kg of solid silica gel (Qingdao Ocean Chemical Group Special Silica Gel Factory, Type A) under stirring. The mixture was heated to 94℃ and stirred at a constant temperature for 24 hours, with a stirring speed of 400 rpm during both feeding and crystallization. After crystallization, the crystallization tank was rapidly cooled, filtered, and washed with water until the pH of the washing solution was less than 10. The mixture was then dried at 120℃ for 2 hours to obtain zeolite material D.

[0688] The crystallinity of zeolite material D was measured by X-ray diffraction. The values ​​are shown in Table 1: the crystallinity determined by peak height method (K1 value), the ratio of crystallinity determined by peak height method to crystallinity determined by peak area method, the silicon-to-aluminum ratio determined by cell constant a0, the ratio of silicon-to-aluminum ratio determined by cell constant a0 to silicon-to-aluminum ratio determined by chemical method (K2 value), and the medium-to-large porosity. Zeolite material D has low crystallinity and contains impurities.

[0689] Zeolite material E (comparison)

[0690] This comparative example illustrates the case where no second silicon source was added.

[0691] 100 kg of pulverized metakaolin powder was mixed with 400 kg of sodium silicate solution (containing 20.05 wt% SiO2 and 6.41 wt% Na2O), 60 kg of a directing agent, and 100 kg of 5 wt% sodium hydroxide solution under stirring. The mixture was heated to 94°C and stirred at a constant temperature for 24 hours, with a stirring speed of 400 rpm during both the addition and crystallization processes. After crystallization, the crystallization tank was rapidly cooled, filtered, and washed with water until the pH of the washing solution was less than 10. The mixture was then dried at 120°C for 2 hours to obtain zeolite material E.

[0692] The crystallinity of zeolite material E was measured by X-ray diffraction. The values ​​are shown in Table 1: crystallinity by peak height method (K1 value), the ratio of crystallinity by peak height method to crystallinity by peak area method, the silicon-to-aluminum ratio determined by cell constant a0, the ratio of the silicon-to-aluminum ratio determined by cell constant a0 to the silicon-to-aluminum ratio determined by chemical method (K2 value), and the medium-to-large porosity. Zeolite material E has good crystallinity, but its silicon-to-aluminum ratio is relatively low.

[0693] Zeolite material F (comparison)

[0694] This comparative example illustrates the preparation of NaY molecular sieves according to the method in CN101468803A.

[0695] 189 mL of deionized water, 86.6 g of directing agent, 130 mL of aluminum sulfate solution (product of Changling Refinery Catalyst Plant, specific gravity 1.28, Al2O3 content 88.2 g / L) and 100 mL of sodium aluminate solution (product of Changling Refinery Catalyst Plant, specific gravity 1.23, Al2O3 content 102 g / L, Na2O content 151.9 g / L) were added to 401 mL of sodium silicate. After vigorous stirring for 30 minutes, the mixture was allowed to stand at 100 °C for 33 hours to crystallize. The product was recovered and denoted as zeolite material F.

[0696] The crystallinity of zeolite material F was measured by X-ray diffraction, the K1 value (ratio of crystallinity by peak height method to crystallinity by peak area method), the silicon-aluminum ratio determined by cell constant a0, the K2 value (ratio of silicon-aluminum ratio determined by cell constant a0 to silicon-aluminum ratio determined by chemical method), and the medium-to-large porosity are shown in Table 1.

[0697] Table 1

[0698]

[0699] silicon-aluminum materials

[0700] Silicon-aluminum material A

[0701] At room temperature (25℃), with stirring, water glass solution (SiO2 concentration 250 g / L) was added dropwise to aluminum sulfate solution (aluminum sulfate solution concentration as Al2O3 was 90 g / L) in a weight ratio of SiO2:Al2O3 = 75:25. After the addition was complete, sodium hydroxide solution (concentration 300 g / L) was added until the pH of the slurry reached 10, and then aged at 50℃ for 6 hours. The resulting solid precipitate was dried at 120℃ for 6 hours, then washed with ammonium chloride solution (concentration 50 g / L), and filtered to obtain silicon-aluminum material A with a sodium content of less than 1%. Its elemental analysis chemical weight composition is 0.2Na2O·25Al2O3·74.8SiO2; specific surface area is 324 m². 2 / g, pore volume 1.26cm 3 / g, with 82% having a pore size greater than 10nm, the average size of the pseudoboehmite grains in the material is 2.2nm, and the approximate pore size is 33.2nm.

[0702] Silicon-aluminum material B

[0703] At 50℃ and under stirring, water glass solution (SiO2 concentration 250 g / L) was added dropwise to aluminum sulfate solution (aluminum sulfate solution concentration as Al2O3 was 90 g / L) in a SiO2:Al2O3 weight ratio of 60:30. After the addition was complete, sodium hydroxide solution (concentration 300 g / L) was added until the pH of the slurry reached 9.5, and then aged at 70℃ for 8 hours. The resulting solid precipitate was dried at 120℃ for 6 hours, then washed with ammonium chloride solution, and filtered to obtain silicon-aluminum material B with a sodium content of less than 1% by weight. Its elemental analysis chemical composition was 0.1Na2O·25.2Al2O3·59.7SiO2; specific surface area was 331 m². 2 / g, pore volume 1.30cm 3 / g, with 75% having a pore size greater than 10nm, and the pseudoboehmite grains in the material being 2.8nm, with a possible pore size of 26.4nm.

[0704] Silicon-aluminum material C (comparison)

[0705] (1) Using Al2(SO4)3 solution with a concentration of 90gAl2O3 / L and NaAlO2 solution with a concentration of 102gAl2O3 / L and a caustic ratio of 2.5 as reaction raw materials, the mixture was stirred vigorously in a co-current gelation method, and the system temperature was controlled at 40℃ and the system pH value was 9.0. The gel slurry was collected and measured. (2) Water glass with a concentration of 60gSiO2 / L was added to the gel slurry under stirring at a weight ratio of SiO2:Al2O3 = 1:2. The mixture was heated to 60℃ and aged for 3 hours to obtain the first solid precipitate. (3) NH4Cl and deionized water were added to the first solid precipitate at a weight ratio of precipitate dry basis:ammonium salt:H2O = 1:0.5:12. The mixture was then aged at 60℃. Sodium ions were removed from the precipitate by ion exchange at ℃. The exchange was repeated once, each time for 0.5 hours, until the sodium oxide content was less than 0.3%, and a second solid precipitate was obtained; (4) The obtained second solid precipitate was then mixed with water at a weight ratio of precipitate dry basis: H2O = 1:8 and pulped. Phosphoric acid and magnesium nitrate were added at a weight ratio of P2O5:MgO: material dry basis = 0.033:0.022:1. The mixture was then reacted at 80℃ for 1 hour. After filtration and washing with water, it was dried at 120℃ for 10 hours to obtain silicon-aluminum material C, which has a pseudo-boehmite structure. The elemental analysis chemical composition is 0.12Na2O·65.1Al2O3·28.2SiO2·3.2P2O5·2.1MgO; the specific surface area is 391m². 2 / g, pore volume 0.97cm 3 / g, average pore size 9.9nm.

[0706] Silicon-aluminum material D (comparison)

[0707] (1) Using a 90g / L Al2O3 / L Al2(SO4)3 solution and a 25% by weight ammonia solution as reaction raw materials, the Al2(SO4)3 solution and ammonia solution were mixed and gelled under vigorous stirring in a co-current gelling method. The system temperature was controlled at 40℃ and the system pH value was 9.5. The gelling slurry was collected and measured. (2) Under stirring conditions, water glass with a concentration of 102g / L SiO2 was added to the gelling slurry at a weight ratio of SiO2:Al2O3 = 1:2.6. The temperature was raised to 70℃ and aged for 2 hours to obtain the first solid precipitate. (3) The first solid precipitate was mixed according to the following ratio: precipitate dry basis: ammonium salt: H2O = The sodium ions were removed by ion exchange of the solid precipitate at 60°C with a weight ratio of 1:0.8:15. The sodium oxide was washed down to 0.3% to obtain a second solid precipitate. (4) The precipitate (filter cake) of the second solid precipitate was re-watered and pulped. Then, it was mixed with phosphoric acid at a weight ratio of P2O5: the dry basis of the second solid precipitate = 0.05:1. The mixture was heated to 60°C and stirred for 1 hour. After filtration, it was dried at 120°C for 10 hours to obtain silicon-aluminum material D, which has a pseudo-boehmite structure. The elemental analysis chemical composition is 0.12Na2O·62.5Al2O3·31.7SiO2·5.0P2O5; the specific surface area is 413m². 2 / g, pore volume 0.97cm 3 / g, average pore size 9.4nm.

[0708] Zirconium sol

[0709] Zirconium sol A

[0710] Add 130g of deionized water to a beaker, then add 125g of zirconium oxychloride and stir for 10 minutes. Add 93g of acetic acid and stir for 30 minutes to obtain a mixed solution. Then, slowly add ammonia water to the above solution using a peristaltic pump. Control the pump speed (i.e., the ammonia water addition rate) at 5mL / min and control the pH value of the obtained product to 2.5 to obtain clear and transparent zirconium sol A.

[0711] Based on the TEM image of the zirconium sol A prepared according to the present invention, the particle size of the obtained zirconium sol is between 5-15 nm, the average particle size is about 10 nm, and the concentration is above 90%.

[0712] Zirconium sol B

[0713] Add 130g of deionized water to a beaker, then add 125g of zirconium oxychloride and stir for 10 minutes. Add 70g of oxalic acid and stir for 30 minutes to obtain a mixed solution. Then, slowly add ammonia water to the above solution using a peristaltic pump at a speed of 5mL / min and control the pH value to 2.5 to obtain clear and transparent zirconium sol B.

[0714] Zirconium sol C

[0715] Add 170g of deionized water to a beaker, then add 176g of zirconium isopropoxide and stir for 10 minutes. Add 70g of oxalic acid and stir for 30 minutes to obtain a mixed solution. Then, slowly add triethanolamine to the solution using a pump at a rate of 5mL / min and maintain the pH at 2.5 to obtain a clear and transparent zirconium sol C.

[0716] Zirconium sol D (comparison)

[0717] Add 130g of deionized water to a beaker, then add 125g of zirconium oxychloride and stir for 10 minutes. Then slowly add ammonia water to the solution using a peristaltic pump at a speed of 5mL / min to form a precipitate suspension with pH=1.2, which is denoted as zirconium sol D.

[0718] Zirconium sol E (comparison)

[0719] Add 35.38 g of ZrOCl2·8H2O to a beaker, and then add 9.77 g of a 45% by weight sodium hydroxide solution at a Zr to sodium hydroxide molar ratio of 1:1. Stir at 60°C for 60 minutes to obtain the first contact product after the reaction. Then, at 40°C, add Zr:H... + Add 19.41 g of 31% hydrochloric acid at a ratio of 1:1.5, then stir at 40°C for 60 minutes to obtain the second contact material. Then, at 40°C, follow the Zr:H ratio... + 19.41 g of hydrochloric acid with a concentration of 31% by weight was added to the second contact material in a ratio of 1:1.5, and the mixture was stirred at 40°C for 60 minutes to obtain zirconium sol E.

[0720] Zirconium sol F (comparison)

[0721] Zirconium sol D was prepared according to the above preparation method, and then dried at 120°C for 12 hours and calcined at 600°C for 4 hours to obtain zirconium oxide powder F (for the sake of terminology, it is also referred to as zirconium sol F in this article).

[0722] The properties of zirconium sol AE are shown in the table below.

[0723] Zirconium sol number A B C D E <![CDATA[ZrO2, mass %]]> 10.8 11.9 11.3 13.4 16.3 pH value 2.5 2.5 2.5 1.2 2.5 Molar ratio of base cations to Zr 2 1.67 1.74 0.6 1 stabilizer to Zr molar ratio 4 4 4 0 0 Average particle size, nm 10 9.8 9.7 Particle size range, nm 8-10 8-10 8-10 Concentration, % 95 93 92 The ratio of monoclinic phases to tetragonal phases* 0.4:1 0.35:1 0.3:1

[0724] * The sample was dried at 100℃ for 6 hours and then calcined at 600℃ for 4 hours.

[0725] Catalyst preparation

[0726] Example 1

[0727] (1) Preparation of rare earth modified molecular sieve based on kaolin crystallization: Zeolite material A was added to deionized water and slurried to obtain a molecular sieve slurry with a solid content of 10% by weight; Lanthanum chloride was added to water and slurried to form a lanthanum chloride solution with a La2O3 concentration of 5% by weight; The lanthanum chloride solution was added to the molecular sieve slurry, and the weight ratio of lanthanum chloride (calculated as La2O3) to molecular sieve (on a dry basis) was 1:6; The mixture was stirred at 70°C for 1 hour, filtered, washed, dried at 150°C for 8 hours, and calcined at 500°C for 4 hours to obtain a rare earth modified molecular sieve based on kaolin crystallization (which can also be referred to as "rare earth modified molecular sieve" in this paper).

[0728] (2) Catalyst preparation: The catalyst formulation is shown in the table below. The formulation composition in the table is on a dry basis, and the rare earth content in the rare earth modified molecular sieve is calculated as RE2O3. First, kaolin is slurried with water to obtain a kaolin slurry with a solid content of 20% by weight; the rare earth modified molecular sieve is slurried with water and dispersed with a homogenizer to obtain a rare earth modified molecular sieve slurry with a solid content of 35% by weight; the kaolin slurry and the rare earth modified molecular sieve slurry are mixed and stirred, and then 10% by weight of aluminum oxide (wherein the aluminum oxide, the molar ratio of HCl to aluminum oxide calculated as Al2O3 is 0.2) is added, stirred for 10 minutes, and finally aluminum sol is added and stirred for 30 minutes to obtain the catalyst slurry. The catalyst slurry was spray-dried to obtain catalyst microspheres. The obtained catalyst microspheres were calcined at 500℃ for 2 hours and then washed with an ammonium sulfate solution with a concentration of 2% by weight. The weight ratio of ammonium sulfate solution to dry catalyst microspheres was 10:1 to obtain catalytic cracking catalyst C1.

[0729] Examples 2-6

[0730] Catalysts C2-C6 were prepared according to the method in Example 1. Rare-earth modified molecular sieves were obtained by adjusting the weight ratio of lanthanum chloride (calculated as La2O3) to molecular sieves (on a dry basis) or by performing multiple processes. The zeolite materials used and the rare-earth content in the obtained rare-earth modified molecular sieves are shown in the table below. ZSP-3 molecular sieve was slurried with water to form a ZSP-3 molecular sieve slurry with a solid content of 35% by weight. This slurry was mixed with kaolin slurry and rare-earth modified molecular sieve slurry, and then the aluminum oxide was added. After stirring for 10 minutes, aluminum sol was added, and the mixture was stirred for 30 minutes. The mixture was then spray-dried and subjected to calcination and washing. The catalyst formulation is shown in the table below.

[0731] Comparative Examples 1-4

[0732] Catalysts D1 to D4 of Comparative Examples 1 to 4 were prepared according to the method of Example 1. The catalyst formulations are shown in the table below. In the catalysts of Comparative Examples 2 to 4, the contents of rare earth modified molecular sieves, the rare earth content in the rare earth modified molecular sieves, and the Na2O content in the rare earth modified molecular sieves are respectively the percentage contents of rare earth modified molecular sieves obtained after rare earth exchange of zeolite materials D to F in the catalyst, the rare earth content in the corresponding rare earth modified molecular sieves, and the sodium oxide content.

[0733]

[0734] Example 7

[0735] (1) Preparation of rare earth modified molecular sieve based on kaolin crystallization: carried out in a manner similar to Example 1.

[0736] (2) Catalyst preparation: The catalyst formulation is shown in the table below. The formulation composition in the table is on a dry basis, and the rare earth content in the rare earth modified molecular sieve is calculated as RE2O3. First, kaolin is slurried to obtain a kaolin slurry with a solid content of 20% by weight; the rare earth modified molecular sieve is slurried with water and dispersed with a homogenizer to obtain a rare earth modified molecular sieve slurry with a solid content of 35% by weight; the kaolin slurry and the rare earth modified molecular sieve slurry are mixed and stirred, and then silicon-aluminum material is added, followed by the addition of 10% by weight of aluminum hydrate (wherein the aluminum hydrate, the molar ratio of HCl to boehmite calculated as Al2O3 is 0.2), stirred for 10 minutes, and then aluminum sol is added and stirred for 30 minutes. The catalyst slurry was spray-dried to obtain catalyst microspheres. The obtained catalyst microspheres were calcined at 500℃ for 2 hours and then washed with an ammonium sulfate solution with a concentration of 2% by weight. The weight ratio of ammonium sulfate solution to dry catalyst microspheres was 10:1 to obtain catalytic cracking catalyst C7.

[0737] Examples 8-12 and Comparative Examples 5-10

[0738] Catalysts C8-C12 and D5-D10 of Examples 8-12 and Comparative Examples 5-10 were prepared according to the preparation methods of Examples 2-6 and Comparative Examples 1-4. The catalyst formulations are shown in the table below.

[0739]

[0740] Examples 13-18 and Comparative Examples 11-14

[0741] The catalyst was prepared according to the following method, and the catalyst formulation is shown in the table below.

[0742] First, kaolin was pulped to obtain a slurry with a solid content of 20% by mass. DASY molecular sieve and ZSP-3 molecular sieve were separately pulped with water and dispersed using a homogenizer to obtain slurries with solid contents of 35% by mass for both DASY and ZSP-3 molecular sieves. The kaolin slurry and molecular sieve slurry were mixed and stirred, and then 10% by mass of alumina (where the molar ratio of HCl to boehmite calculated as Al2O3 was 0.2) was added and stirred for 10 minutes to obtain a first mixed slurry. Zirconium sol and alumina sol were mixed and then added to the first mixed slurry and stirred for 30 minutes to obtain a catalyst slurry. The catalyst microspheres were spray-dried and then calcined at 500℃ for 2 hours to obtain a catalytic cracking catalyst.

[0743]

[0744]

[0745] Example 19

[0746] (1) Preparation of rare earth modified molecular sieve based on kaolin crystallization: Zeolite material A was added to deionized water and slurried to obtain a molecular sieve slurry with a solid content of 10% by weight; Lanthanum chloride was added to water and slurried to form a lanthanum chloride solution with a La2O3 concentration of 5% by weight; The lanthanum chloride solution was added to the molecular sieve slurry, and the weight ratio of lanthanum chloride (calculated as La2O3) to molecular sieve (on a dry basis) was 1:6; The mixture was stirred at 70°C for 1 hour, filtered, washed, dried at 150°C for 8 hours, calcined at 500°C for 4 hours, and the catalyst was washed again with 5% ammonium sulfate on a dry basis to finally obtain a rare earth modified molecular sieve based on kaolin crystallization with less than 2% sodium oxide.

[0747] (2) Catalyst preparation: The catalyst formulation is shown in the table below. The formulation composition in the table is on a dry basis, and the rare earth content in the rare earth modified molecular sieve is calculated as RE2O3. First, kaolin and water are slurried to obtain a kaolin slurry with a solid content of 20% by mass. Rare earth modified molecular sieve is slurried with water and dispersed using a homogenizer to obtain a rare earth modified molecular sieve slurry with a solid content of 35% by mass. The kaolin slurry and the rare earth modified molecular sieve slurry are mixed and stirred, and then 10% by mass of aluminum oxide (where the molar ratio of HCl to aluminum oxide, calculated as Al2O3, is 0.2) is added and stirred for 10 minutes. Finally, a mixture of aluminum sol and zirconium sol is added and stirred for 30 minutes to obtain a catalyst slurry. The catalyst slurry is spray-dried, and the obtained catalyst microspheres are calcined at 500°C for 2 hours. Then, they are exchange-washed with a 2% by mass ammonium sulfate solution, wherein the mass ratio of ammonium sulfate solution to dry catalyst microspheres is 10:1. After drying, the catalytic cracking catalyst C19 is obtained.

[0748] Examples 20-24

[0749] The catalyst was prepared according to the method of Example 19, and the catalyst formulation is shown in the table below. ZRP-1 molecular sieve was slurried with water to form a ZRP-1 molecular sieve slurry with a solid content of 35% by mass. This slurry was then mixed with kaolin slurry and modified molecular sieve slurry based on kaolin crystallization. The aluminum oxide was then added, and after stirring for 10 minutes, aluminum sol and zirconium sol were added and stirred for 30 minutes. The mixture was then spray-dried and subjected to the calcination, washing, and drying processes described above.

[0750] Comparative Example 15

[0751] Catalyst D15 was prepared according to the method of Example 19, and the catalyst formulation is shown in the table below.

[0752]

[0753]

[0754] Examples 25-29 and Comparative Examples 16-21

[0755] The catalyst was prepared according to the following method, and the catalyst formulation is shown in the table below.

[0756] (1) Preparation of acidic silica sol: 25g of water glass was diluted with 75g of water and stirred for 10 minutes. Then, 5g of hydrochloric acid was quickly added and stirred for 10 minutes to obtain a clear and transparent silica sol with a SiO2 content of 5% by weight and a pH of 2.5. This is denoted as S1. The silica sol particles are 4nm in size.

[0757] (2) Catalyst preparation: First, kaolin was slurried to prepare a kaolin slurry with a solid content of 20% by weight. SOY molecular sieve and ZSP-3 molecular sieve were taken, and water was added separately to slurry them. They were dispersed using a homogenizer to obtain SOY molecular sieve slurry and ZSP-3 molecular sieve slurry with solid contents of 35% by weight, respectively. The kaolin slurry, SOY molecular sieve slurry and ZSP-3 molecular sieve slurry were mixed and stirred. Then, 10% by weight of alumina (biopyrite acidified with hydrochloric acid, acid-alumina ratio (HCl:Al2O3) was added. The molar ratio of boehmite to 0.2 was used to stir the mixture for 10 minutes to obtain the first slurry. Zirconium sol and the above-mentioned acidic silica sol S1 were mixed (pH 2.5) and added to the first slurry. The mixture was stirred for 30 minutes to obtain the second slurry. The second slurry was spray-dried to obtain catalyst microspheres. The obtained catalyst microspheres were calcined at 500°C for 2 hours and then washed with ammonium sulfate solution (ammonium sulfate accounted for 6% of the dry mass of the catalyst in each wash) until the sodium oxide content in the catalyst was less than 0.2% by mass, thus obtaining the catalytic cracking catalyst.

[0758]

[0759] Example 30

[0760] The catalyst formulation is shown in the table below.

[0761] (1) Preparation of silica sol: carried out in a manner similar to that of Example 25.

[0762] (2) Preparation of rare earth modified kaolin-based molecular sieves: carried out in a manner similar to that of Example 19.

[0763] (3) Catalyst preparation: carried out in a manner similar to that of Example 19.

[0764] Examples 31-34

[0765] The catalyst was prepared according to the method of Example 30, and the catalyst formulation is shown in the table below. ZSP-3 molecular sieve was slurried with water to form a ZSP-3 molecular sieve slurry with a solid content of 35% by weight, which was then mixed with kaolin slurry and modified molecular sieve slurry based on kaolin crystallization, and then mixed with a mixture of zirconium sol, silica sol and alumina sol (if any).

[0766] Comparative Examples 22-24

[0767] The catalyst was prepared according to the method in Example 30 of the catalyst preparation, and the catalyst formulation is shown in the table below.

[0768]

[0769] Examples 35-37

[0770] The catalyst was prepared according to the following method, and the catalyst formulation is shown in the table below.

[0771] (1) Preparation of aluminum phosphate colloid: Boehmite, kaolin and water were slurried and dispersed into a slurry with a solid content of 15% by weight (the weight ratio of clay to boehmite based on dry basis was 1:1 based on Al2O3); concentrated phosphoric acid (H3PO4 concentration of 85% by weight) was added to the slurry under stirring at a weight ratio of P / Al=3, and the mixture was reacted at 70℃ for 30 minutes to obtain aluminum phosphate colloid.

[0772] (2) First, kaolin is pulped to obtain a kaolin slurry with a solid content of 20% by weight. DASY molecular sieve and ZSP-3 molecular sieve are taken separately, added to water, and pulped. They are then dispersed using a homogenizer to obtain DASY molecular sieve slurry and ZSP-3 molecular sieve slurry with a solid content of 35% by weight, respectively. The kaolin slurry, DASY molecular sieve slurry, and molecular sieve slurry are mixed and stirred. Then, aluminum oxide with a solid content of 10% by weight (wherein HCl reacts with Al) is added. The molar ratio (acid-aluminum ratio) of pseudoboehmite based on 2O3 was 0.2. After stirring for 10 minutes, a first catalyst slurry was obtained. Aluminum sol, zirconium sol, and phosphorus aluminum sol were mixed and then added to the first catalyst slurry. After stirring for 30 minutes, a second catalyst slurry was obtained. The second catalyst slurry was spray-dried to obtain catalyst microspheres. The obtained catalyst microspheres were calcined at 500℃ for 2 hours and then washed once with ammonium sulfate at 6% of the catalyst dry weight to obtain the catalytic cracking catalyst.

[0773] Examples 38-40

[0774] The catalyst was prepared according to the following method, and the catalyst formulation is shown in the table below.

[0775] (1) Preparation of phosphorus aluminum glue: Boehmite, kaolin and water are slurried and dispersed into a slurry with a solid content of 15% by weight (the weight ratio of clay to boehmite based on dry basis is 1:1). Under stirring, concentrated phosphoric acid (85% by weight) is added to the above slurry according to the weight ratio of P / Al = 4. The mixture is reacted at 80°C for 20 minutes to obtain phosphorus aluminum glue.

[0776] (2) First, kaolin was pulped to prepare a slurry with a solid content of 20% by weight. DASY molecular sieve and ZSP-3 molecular sieve were taken, and water was added to each to make a slurry. The slurries were then dispersed using a homogenizer to obtain DASY molecular sieve slurry and ZSP-3 molecular sieve slurry with a solid content of 35% by weight. The kaolin slurry, DASY molecular sieve slurry and ZSP-3 molecular sieve slurry were mixed and stirred. Then, 10% by weight of aluminum oxide (acidified with hydrochloric acid, with an acid-aluminum ratio of 0.2) was added and stirred for 10 minutes to obtain a slurry containing molecular sieve and kaolin. Aluminum sol, zirconium sol and phosphorus aluminum sol were mixed and added to the above slurry containing molecular sieve and kaolin. The mixture was stirred for 30 minutes to obtain a catalyst slurry. The catalyst slurry was spray-dried, and the obtained catalyst microspheres were calcined at 500℃ for 2 hours. Then, the microspheres were washed once with ammonium sulfate at 6% by weight of the catalyst dry basis to obtain the catalytic cracking catalyst.

[0777] Comparative Examples 25-29

[0778] The catalyst was prepared according to the method in Example 35 of the catalyst preparation, and the catalyst formulation is shown in the table below.

[0779]

[0780] Example 41

[0781] (1) Preparation of rare earth-modified ultrastable molecular sieves based on kaolin crystallization:

[0782] Zeolite material A was reacted with silicon tetrachloride gas at a weight ratio of SiCl4:zeolite material A (dry basis) of 0.4:1 at 450℃ for 2 hours. After washing and filtration, a gas-phase ultrastable molecular sieve based on kaolin crystallization (referred to as ultrastable molecular sieve) with a cell constant of 2.456 was obtained. The ultrastable molecular sieve was then slurried with deionized water to form an ultrastable molecular sieve slurry with a solid content of 10% by weight. Lanthanum chloride was then slurried with water to form a La₂O₃ concentration of 5%. A lanthanum chloride solution (in weight percentages) was prepared. The lanthanum chloride solution was added to an ultrastable molecular sieve slurry, with a lanthanum chloride (as La2O3) to molecular sieve (dry basis) weight ratio of 1:20. The mixture was stirred at 70°C for 1 hour, filtered, washed, dried at 150°C for 8 hours, and calcined at 500°C for 4 hours. The mixture was then washed with ammonium sulfate solution, with an ammonium sulfate to molecular sieve dry basis weight ratio of 1:20, to obtain a rare earth-modified ultrastable molecular sieve based on kaolin crystallization (referred to as rare earth-modified ultrastable molecular sieve).

[0783] (2) Preparation of aluminum phosphate colloid: Boehmite, kaolin and water are slurried to obtain a slurry with a solid content of 15% by weight. Concentrated phosphoric acid (85% by weight) is added to the slurry under stirring according to the weight ratio of P / Al=3. The mixture is reacted at 70°C for 30 minutes to obtain aluminum phosphate colloid.

[0784] (3) Catalyst preparation: According to the catalyst formula in the table below, kaolin was first slurried to obtain a kaolin slurry with a solid content of 20% by weight; rare earth modified ultrastable molecular sieve and ZSP-3 molecular sieve were taken, water was added separately and slurries were made, and dispersed with a homogenizer to obtain rare earth modified ultrastable molecular sieve slurry and ZSP-3 molecular sieve slurry with a solid content of 35% by weight; the kaolin slurry, rare earth modified ultrastable molecular sieve slurry and ZSP-3 molecular sieve slurry were mixed and stirred, and then 10% by weight of aluminum oxide (aluminum oxide to aluminum oxide ratio of 0.2 molar ratio) was added and stirred for 10 minutes. Then zircon sol A, aluminum sol and the above-mentioned phosphorus aluminum colloid were added and stirred for 30 minutes. The mixture was spray dried to obtain catalyst microspheres. The obtained catalyst microspheres were calcined at 500℃ for 2 hours to obtain catalytic cracking catalyst C41.

[0785] Examples 42-43

[0786] The catalyst was prepared according to the method of Example 41, and the catalyst formulation is shown in the table below.

[0787] Example 44

[0788] (1) Preparation of rare earth-modified ultrastable molecular sieves based on kaolin crystallization:

[0789] Zeolite material A was calcined at 650℃ and 100% vol% water vapor for 12 hours to obtain an ultrastable molecular sieve based on kaolin crystal transformation (hereinafter referred to as ultrastable molecular sieve) with a cell constant of 2.455 nm. The ultrastable molecular sieve was slurried with deionized water to obtain a slurry with a solid content of 10% by weight. Lanthanum chloride was slurried with water to form a lanthanum chloride solution with a La2O3 concentration of 5% by weight. The lanthanum chloride solution was added to the ultrastable molecular sieve slurry, with a weight ratio of lanthanum chloride (based on La2O3) to molecular sieve (based on dry basis) of 1:20. The mixture was stirred at 70℃ for 1 hour, filtered and washed, dried at 150℃ for 8 hours, and calcined at 500℃ for 4 hours. The mixture was then washed with ammonium sulfate solution, with a weight ratio of ammonium sulfate to molecular sieve dry basis of 1:20, to obtain a rare earth modified ultrastable molecular sieve based on kaolin crystal transformation (hereinafter referred to as rare earth modified ultrastable molecular sieve).

[0790] (2) Preparation of phosphorus aluminum sol: Boehmite, kaolin and water were slurried and dispersed into a slurry with a solid content of 15% by weight (the weight ratio of clay on a dry basis to alumina source on an Al2O3 basis was 1:1). Concentrated phosphoric acid was added to the slurry under stirring at a weight ratio of P / Al = 4. The mixture was stirred at 80°C for 20 minutes to obtain phosphorus aluminum sol.

[0791] (3) Catalyst preparation: According to the catalyst formula in the table below, kaolin was first slurried, and the solid content of the resulting kaolin slurry was 40% by weight. Aluminum sol was added and slurried. Rare earth modified ultrastable molecular sieve and ZSP-3 molecular sieve were taken, and water was added to slurry respectively. They were dispersed with a homogenizer to obtain rare earth modified ultrastable molecular sieve slurry and ZSP-3 molecular sieve slurry with solid contents of 35% by weight respectively. The kaolin slurry, rare earth modified ultrastable molecular sieve slurry and ZSP-3 molecular sieve were mixed and stirred. Then, the phosphorus aluminum sol obtained in step (2) was added and stirred for 10 minutes. Finally, the aluminum sol was added to the above catalyst mixture slurry and stirred for 30 minutes. The mixture was spray-dried and the obtained catalyst microspheres were calcined at 500℃ for 2 hours to obtain catalytic cracking catalyst C44.

[0792] Examples 45-46

[0793] The catalyst was prepared according to the method of Example 44, and the catalyst formulation is shown in the table below. In the preparation of rare earth modified ultrastable molecular sieve based on kaolin crystallization, the preparation method is the same as that of Example 44, except for the different rare earth content.

[0794] Comparative Examples 30-31

[0795] The catalyst was prepared according to the method of Example 44, and the formulation is shown in the table below. The rare earth-modified ultrastable molecular sieve was prepared based on zeolite materials D and E.

[0796]

[0797] Examples 47-50

[0798] The catalyst was prepared according to the method in Example 7, and the catalyst formulation is shown in the table below.

[0799] Comparative Example 32

[0800] The catalyst was prepared according to the method of Comparative Example 5, and the catalyst formulation is shown in the table below.

[0801]

[0802] Catalyst evaluation

[0803] The catalysts were evaluated for the following feedstocks.

[0804] The composition and physical properties of the crude oil are shown in the table below:

[0805] project Wu-mixed three-fuel oil <![CDATA[Density (20 °C), g / cm 3 > 0.9044 Refractive index (20℃) 1.5217 <![CDATA[Viscosity (100 °C), mm 2 / s]]> 9.96 Freezing point, ℃ 40 Aniline point, ℃ 95.8 C, weight % 85.98 H, weight % 12.86 S, weight % 0.55 N, weight % 0.18 Residual char, m% 3 Distillation range, °C Initial boiling point 243 5％ 294 10％ 316 30％ 395 50％ 429 70％ 473 90％ -

[0806] project Hydrogenated oil <![CDATA[Density (20 °C), g / cm 3 > 0.9334 Refractive index (70℃) 1.5061 Four components, m% Saturated hydrocarbons 55.6 Aromatics 30 gelatin 14.4 Asphalt ＜0.1 Freezing point, ℃ 34 Metal content, ppm Ca 3.9

[0807] Fe 1.1 Mg ＜0.1 Na 0.9 Ni 3.1 Pb ＜0.1 V 0.5 C m% 86.88 H m% 11.94 S m% 0.7 residual carbon m% 1.77

[0808] The catalyst was deactivated by aging at 800°C and 100% steam for 24 hours. It was then evaluated on a fixed fluidized bed microreactor (ACE).

[0809] The evaluation conditions were: reaction temperature 500℃, agent-to-oil ratio (by weight) 6, and WHSV 16h. -1 ,

[0810] Wherein, conversion rate = gasoline yield + liquefied petroleum gas yield + dry gas yield + coke yield

[0811] Total liquid yield = Gasoline yield + LPG yield + Recycle oil yield

[0812] Coke selectivity = Coke yield / Conversion rate × 100

[0813] Coking factor = Coke yield × (1 - Conversion rate) / Conversion rate × 100

[0814] The coking factor is an important indicator for evaluating the coke selectivity of catalysts. The smaller the coking factor, the better the coke selectivity of the catalyst.

[0815] Using Wu-Hun-3 feedstock as the feedstock, the evaluation results are listed in the table below:

[0816] catalyst C1 C2 C3 C4 C5 C6 D1 D2 D3 D4 Microreactive, % 75 73 71 70 72 77 68 58 62 65 Dry gas wt% 1.51 2.45 3.47 4.02 2.98 1.62 2.57 1.87 2.15 2.32 liquefied petroleum gas (LPG) wt% 14.56 19.09 22.21 24.25 17.65 16.16 20.06 15.56 18.27 18.01 <![CDATA[C5 + Gasoline wt% 52.82 47.11 43.56 39.46 45.86 53.98 43.04 39.44 41.18 43.01 Circulating oil wt% 15.81 16.09 16.13 17.43 18.46 14.41 17.68 21.59 19.42 18.85 Oil slurry wt% 9.14 9.18 8.65 8.76 9.32 7.99 10.24 15.26 12.82 11.47 coke wt% 6.16 6.08 5.98 6.08 5.73 6.04 6.41 6.28 6.16 6.34 Conversion rate / weight% 75.05 74.73 75.22 73.81 72.22 77.8 72.08 63.15 67.76 69.68 Total liquid yield / weight % 83.19 82.29 81.9 81.14 81.97 84.55 80.78 76.59 78.87 79.87 Coke selectivity % 8.21 8.14 7.95 8.24 7.93 7.76 8.89 9.94 9.09 9.1 Coking factor 2.05 2.06 1.97 2.16 2.2 1.72 2.48 3.66 2.93 2.76

[0817] The catalyst was deactivated by aging at 800°C and 100% steam for 24 hours. It was then evaluated on a fixed fluidized bed microreactor (ACE).

[0818] The evaluation conditions were: reaction temperature 500℃, agent-to-oil ratio (by weight) 6, and WHSV 16h. -1 ,

[0819] Wherein, conversion rate = gasoline yield + liquefied petroleum gas yield + dry gas yield + coke yield

[0820] Coke selectivity = Coke yield / Conversion rate × 100

[0821] Coking factor = Coke yield × (1 - Conversion rate) / Conversion rate × 100

[0822] Using Wu-Hun-3 feedstock as the feedstock, the evaluation results are listed in the table below:

[0823] catalyst C19 C20 C21 C22 C23 C24 D15 Dry gas wt% 1.49 1.98 2.64 2.05 1.94 1.89 1.48 liquefied petroleum gas (LPG) wt% 15.5 16.89 18.48 16.68 17.59 16.85 15.45 C5+ gasoline wt% 51.95 49.62 47.53 49.71 47.68 52.82 46.64 Circulating oil wt% 16.73 16.85 17.02 16.82 17.45 14.43 18.34 Oil slurry wt% 8.47 8.73 8.65 8.92 9.41 8.12 11.51 coke wt% 5.86 5.93 5.68 5.82 5.93 5.89 6.58 Conversion rate / weight% 74.8 74.42 74.33 74.26 73.14 77.45 70.15 Coke selectivity % 7.83 7.97 7.64 7.84 8.11 7.6 9.38 Coking factor 1.97 2.04 1.96 2.02 2.18 1.71 2.8 Wear index, m% / h 0.8 0.9 0.7 0.6 1 0.9 5.8

[0824] The catalyst was deactivated by aging at 800°C and 100% steam for 17 hours. It was then evaluated on a fixed fluidized bed microreactor (ACE).

[0825] The evaluation conditions were: reaction temperature 520℃, agent-to-oil ratio (by weight) 4, and WHSV = 16h. -1 ,

[0826] Wherein, conversion rate = gasoline yield + liquefied petroleum gas yield + dry gas yield + coke yield

[0827] Coke selectivity = Coke yield / Conversion rate × 100

[0828] Coking factor = Coke yield × (1 - Conversion rate) / Conversion rate × 100

[0829] The evaluation results using hydrotreated oil as feedstock are listed in the table below:

[0830] catalyst C7 C8 C9 C10 C11 C12 D5 D6 D7 D8 D9 D10 Microreactive, % 75 74 71 72 70 76 65 66 60 68 64 63 Dry gas wt% 1.44 2.05 2.51 2.11 1.98 1.74 1.28 1.32 1.02 1.48 1.24 1.18 liquefied petroleum gas (LPG) wt% 15.66 16.69 17.56 16.71 16.48 16.26 14.98 15.01 13.12 15.49 14.79 14.42 C5+ gasoline wt% 51.97 50.91 49.82 51.05 49.89 52.47 47.01 47.12 43.42 47.91 46.87 46.25 Circulating oil wt% 16.61 16.09 15.81 15.89 16.48 16.02 18.24 18.13 20.82 17.31 18.37 18.81 Oil slurry wt% 8.27 8.18 7.94 8.17 8.86 7.39 11.25 11.21 13.94 10.64 11.64 11.82 coke wt% 6.05 6.08 6.36 6.07 6.31 6.12 7.24 7.21 7.68 7.17 7.09 7.52 Conversion rate / weight% 75.12 75.73 76.25 75.94 74.66 76.59 70.51 70.66 65.24 72.05 69.99 69.37 Coke selectivity % 8.05 8.03 8.34 7.99 8.45 7.99 10.27 10.2 11.77 9.95 10.13 10.84 Coking factor 2 1.95 1.98 1.92 2.14 1.87 3.03 2.99 4.09 2.78 3.04 3.32

[0831] The catalyst was deactivated by aging at 800°C and 100% steam for 15 hours. It was then evaluated on a fixed fluidized bed microreactor (ACE).

[0832] The evaluation conditions were: reaction temperature 500℃, agent-to-oil ratio (by weight) 6, and WHSV = 16h. -1 ,

[0833] Wherein, conversion rate = gasoline yield + liquefied petroleum gas yield + dry gas yield + coke yield

[0834] The evaluation results using hydrotreated oil as feedstock are listed in the table below:

[0835] catalyst C30 C31 C32 C33 C34 D22 D23 D24

[0836] Microreactive, % 76 75 77 75 77 70 68 71 Dry gas wt% 1.61 2.07 2.38 2.17 2.42 1.91 1.48 1.86 liquefied petroleum gas (LPG) wt% 14.23 15.19 16.01 15.79 15.41 15.22 14.31 15.17 C5+ gasoline wt% 52.13 51.06 51.87 50.28 51.92 46.11 47.76 47.22 Circulating oil wt% 15.61 15.71 14.34 15.84 14.01 19.23 19.03 18.03 Oil slurry wt% 9.83 9.73 8.84 9.54 9.91 11.17 11.01 11.25 coke wt% 6.59 6.24 6.56 6.38 6.33 6.36 6.41 6.47 Conversion rate / weight% 74.56 74.56 76.82 74.62 76.08 69.6 69.96 70.72 Total liquid yield / weight % Coke selectivity % 8.84 8.37 8.54 8.55 8.32 9.14 9.16 9.15 Coking factor 2.25 2.13 1.98 2.17 1.99 2.78 2.75 2.68

[0837] The catalyst was impregnated using the Michael method, with heavy metals of 1000 μg / g nickel and 3000 μg / g vanadium as the contaminants. After aging at 780℃ with 100% vol% steam for 4 hours, the contaminated catalyst was evaluated on an ACE device under the following conditions: reaction temperature 500℃, catalyst-to-oil ratio (by weight) 6, and WHSV = 16 h. -1 .

[0838] The evaluation results using hydrotreated oil as feedstock are listed in the table below:

[0839] catalyst C30 C31 C32 C33 C34 D22 D23 D24 Microreactive, % 67 66 67 65 67 59 57 60 Dry gas wt% 1.41 1.45 1.52 1.32 1.47 1.23 1.92 1.34 liquefied petroleum gas (LPG) wt% 12.32 12.53 13.73 13.12 13.63 11.13 11.15 11.98 C5+ gasoline wt% 47.01 46.22 46.91 44.81 46.17 40.12 39.89 41.01 Circulating oil wt% 20.43 21.11 19.82 21.58 19.89 27.31 26.71 25.54 Oil slurry wt% 11.51 11.15 10.61 11.31 11.13 11.83 12.08 11.68 coke wt% 7.32 7.54 7.41 7.86 7.71 8.38 8.25 8.45 Conversion rate / weight% 68.06 67.74 69.57 67.11 68.98 60.86 61.21 62.78

[0840] The catalyst was deactivated by aging at 800°C and 100% steam for 12 hours. It was then evaluated on a fixed fluidized bed microreactor (ACE).

[0841] The evaluation conditions were: reaction temperature 550℃, agent-to-oil ratio (by weight) 6, and WHSV 16h. -1 ,

[0842] Wherein, conversion rate = gasoline yield + liquefied petroleum gas yield + dry gas yield + coke yield

[0843] Low-carbon olefin selectivity = (propylene + ethylene) yield / conversion rate × 100%

[0844] Coke selectivity = Coke yield / Conversion rate × 100

[0845] Coking factor = Coke yield × (1 - Conversion rate) / Conversion rate × 100

[0846] Ethylene concentration = ethylene yield / dry gas yield

[0847] Propylene concentration = propylene yield / liquefied gas yield

[0848] Using Wu-Hun-3 feedstock as the feedstock, the evaluation results are listed in the table below:

[0849]

[0850] The catalyst was deactivated by aging at 800°C and 100% steam for 15 hours. It was then evaluated on a fixed fluidized bed microreactor (ACE).

[0851] The evaluation conditions were: reaction temperature 500℃, agent-to-oil ratio (by weight) 6, and WHSV = 16h.-1 ,

[0852] The evaluation results using hydrotreated oil as feedstock are listed in the table below:

[0853] catalyst C47 C48 C49 C50 D32 Microreactive, % 77 79 78 75 70 Dry gas wt% 1.62 2.15 1.75 2.02 1.91 liquefied petroleum gas (wt%) 14.85 16.31 15.83 16.21 15.22 C5+ gasoline wt% 52.64 52.75 52.95 51.72 46.11 Circulating oil wt% 16.09 15.58 15.12 15.72 19.23 Oil slurry wt% 8.65 7.49 8.47 8.22 11.17 coke wt% 6.15 5.72 5.88 6.11 6.36 Conversion rate / weight% 75.26 76.93 76.41 76.06 69.6

[0854] Total liquid yield / weight % 83.58 84.64 83.9 83.65 80.56 Coke selectivity % 8.17 7.44 7.7 8.03 9.14 Coking factor 2.02 1.72 1.82 1.92 2.78 Wear index, m% / h 0.7 0.6 0.9 0.9 -

[0855] The catalyst was impregnated using the Michael method, with heavy metals of 1000 μg / g nickel and 3000 μg / g vanadium as the contaminants. After aging at 780℃ with 100% vol% steam for 4 hours, the contaminated catalyst was evaluated on an ACE device under the following conditions: reaction temperature 500℃, catalyst-to-oil ratio (by weight) 6, and WHSV = 16 h. -1 .

[0856] The evaluation results using hydrotreated oil as feedstock are listed in the table below:

[0857] catalyst C47 C48 C49 C50 D32 Microreactive, % by weight 69 70 69 66 59 Dry gas yield, % by weight 1.51 1.98 1.72 1.92 1.23 LPG yield, % by weight 13.31 15.84 14.53 14.25 11.13 C5+ gasoline yield, % by weight 47.24 46.47 46.24 46.12 40.12 Circulating oil yield, % by weight 20.44 19.08 20.06 20.56 27.31 Oil slurry yield, % by weight 10.67 10.12 10.62 10.72 11.83 Coke yield, % by weight 6.83 6.51 6.83 6.43 8.38 Conversion rate, weight % 68.89 70.8 69.32 68.72 60.86

Claims

1. A catalytic cracking catalyst, comprising: The mixture comprises 10-70 wt% of a cracking active component, 10-60 wt% of a binder, and 10-70 wt% of clay on a dry basis, wherein the cracking active component includes 5-100 wt% of a first Y-type molecular sieve and 0-95 wt% of a second molecular sieve; wherein the first Y-type molecular sieve is a modified kaolin-based molecular sieve obtained by modifying a kaolin-based molecular sieve, and its sodium oxide content is less than 2 wt%. The molecular sieve based on kaolin crystallization, measured by X-ray diffraction, has a crystallinity of ≥60% according to the peak height method, and the ratio of crystallinity measured by the peak area method is K1, where K1 = 0.76-0.89; the silicon-to-aluminum ratio determined by the cell constant a0 is 5.0-5.5, and the ratio of the silicon-to-aluminum ratio determined by the chemical method is K2, where K2 = 0.87-0.

93. All silicon-to-aluminum ratios refer to the molar ratio of silicon oxide to aluminum oxide. The preparation method of the molecular sieve based on kaolin crystallization includes the following steps: (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, and then crushed into metakaolin powder with a particle size of less than 10 micrometers. (2) Add a directing agent, sodium silicate, sodium hydroxide solution and water to the metakaolin powder to prepare reaction raw material A, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.0, and the ratio of reaction raw material A is (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O molar ratio; (3) After crystallizing reaction raw material A at 88-98℃ for 1-70h with stirring, a second silicon source is added to obtain reaction raw material B, wherein the second silicon source accounts for 0.1-10% by weight of the total silicon feed, based on silicon oxide. (4) Crystallize the reaction raw material B under stirring at 88-98℃ and recover the product. The molar composition of the directing agent is: (10-17)SiO2:(0.7- 1.3)Al2O3:(11-18)Na2O:(200-350)H2O.

2. The catalytic cracking catalyst according to claim 1, wherein, The crystallinity obtained by the peak height method is ≥80%.

3. The catalytic cracking catalyst according to claim 1, wherein, The K1 is 0.80-0.

89.

4. The catalytic cracking catalyst according to claim 3, wherein, The K1 is 0.80-0.

85.

5. The catalytic cracking catalyst according to claim 1, wherein, The K2 is 0.87-0.

92.

6. The catalytic cracking catalyst according to claim 5, wherein, The K2 is 0.88-0.

90.

7. The catalytic cracking catalyst according to claim 1, wherein, The values ​​are K1 = 0.77-0.88 and K2 = 0.87-0.

91.

8. The catalytic cracking catalyst according to claim 1, wherein, The molecular sieve based on kaolin crystallization has a mesopore rate of 10-20%.

9. The catalytic cracking catalyst according to claim 1, wherein, The silicon-to-aluminum ratio, as determined by the cell constant a0, is 5.2-5.

5.

10. The catalytic cracking catalyst according to claim 1, wherein, The modified kaolin-based molecular sieve contains rare earth elements, and the rare earth content in the modified kaolin-based molecular sieve, calculated as RE2O3, is 10%-20% by weight.

11. The catalytic cracking catalyst according to claim 1, wherein, The second molecular sieve is selected from octahedral zeolite and / or molecular sieves with a five-membered ring structure; the octahedral zeolite is one or more of HY, REY, REHY, USY, REUSY, DASY, and REDASY; the molecular sieve with a five-membered ring structure includes one or more of BEA structure molecular sieves, MFI structure molecular sieves, and mordenite; the binder is selected from one or more of zirconium sol, silica sol, alumina sol, acidified pseudoboehmite, and metal-modified pseudoboehmite; the clay is one or more of kaolin, montmorillonite, diatomaceous earth, halloysite, pseudo-halosite, soapstone, rettoitite, sepiolite, attapulgite, hydrotalcite, and bentonite; or The catalytic cracking catalyst comprises 10%-70% by weight (dry basis) of cracking active components, 1%-20% by weight (dry basis) of silicon-aluminum material, 10%-60% by weight (dry basis) of binder, and 10%-70% by weight (dry basis) of clay; wherein the cracking active components include 25%-100% by weight of a first Y-type molecular sieve and 0-75% by weight of a second molecular sieve; the first Y-type molecular sieve is a modified kaolin-based molecular sieve with a sodium oxide content of less than 2% by weight; the silicon-aluminum material has the following anhydrous gravimetric chemical expression: (0-1)Na₂O·(15-50)Al₂O₃·(85-50)SiO₂, a most probable pore size of 10-100 nm, and a specific surface area of ​​150-600 m². 2 / g, with a pore volume of 0.5-1.5mL / g, and the proportion of pore volume with a pore size greater than 10nm to the total pore volume is 70%-98%; or The catalytic cracking catalyst comprises: 10%-60% by mass (dry basis) of a cracking active component, 20%-60% by mass (dry basis) of a binder, and 10%-70% by mass (dry basis) of clay; wherein the binder comprises 1%-50% by mass of zirconium sol and 50%-99% by mass of a second binder, the zirconium sol comprising 0.5%-20% by mass of ZrO2, a stabilizer, an alkaline cation, and water, wherein the molar ratio of the stabilizer to Zr is 1-6, and the pH value of the zirconium sol is 1-7; the cracking active component comprises 70%-100% by mass of a first Y-type molecular sieve and 0-30% by mass of a second molecular sieve; or Based on the dry weight of the catalytic cracking catalyst, the catalytic cracking catalyst comprises: 10-70 wt% cracking active components, 1-20 wt% zirconium oxide binder, 1-20 wt% silica sol binder, 0-50% alumina-based binder, and 10-70 wt% clay. The zirconium oxide binder is zirconium sol, which comprises 0.5 wt%-20 wt% ZrO2, stabilizer, alkaline cation, and water, wherein the molar ratio of stabilizer to Zr is 1-6, and the pH value of the zirconium sol is 1-7. The cracking active components comprise 70 wt%-100 wt% of a first Y-type molecular sieve and 0-30 wt% of a second molecular sieve.

12. A method for preparing the catalytic cracking catalyst according to claim 1, comprising the following steps: (1) Preparation of modified molecular sieves based on kaolin crystallization; (2) Forming a slurry from clay, cracking active components and binder; wherein the cracking active components include the modified kaolin-based molecular sieve and an optional second molecular sieve; (3) Spray dry the slurry obtained in step (2).

13. The preparation method according to claim 12, wherein, The method for preparing the modified kaolin-based molecular sieve includes the following steps: (1) Kaolin is calcined and dehydrated at 500-900℃ to convert it into metakaolin, which is then crushed to produce metakaolin powder with a particle size of less than 10 micrometers. (2) Add sodium silicate, a directing agent, sodium hydroxide solution and water to metakaolin powder to prepare reaction raw material A with a molar ratio of (1-2.5)Na2O:Al2O3:(4-9)SiO2:(40-100)H2O, wherein the mass ratio of the directing agent to metakaolin is 0.01-1.

0. (3) The reaction raw material A is crystallized under stirring at 88-98℃. After the crystallization time reaches 1-70h, a second silicon source is added to obtain the reaction raw material B. The second silicon source accounts for 0.1%-10% of the total silicon feed amount, all of which are calculated as silicon oxide. (4) Crystallize reaction material B under stirring at 88-98℃ and recover the product; (5) The recovered products are subjected to ion exchange.

14. The preparation method according to claim 13, wherein, The second silicon source is solid silicone.

15. The preparation method according to claim 14, wherein, The solid silicone has an average pore size of 1.5-2.0 nm, or an average pore size of 4.0-5.0 nm, or an average pore size of 10.0 nm or more, or an average pore size of 0.8 nm or less.

16. The preparation method according to claim 13, wherein, The second silicon source is liquid silicone.

17. The preparation method according to claim 16, wherein, The SiO2 content in the liquid silica gel is 1-30% by mass.

18. The preparation method according to claim 13, wherein, The second silicon source accounts for 4-10% by weight of the total silicon feed, based on silicon oxide.

19. The preparation method according to claim 13, wherein, The ion exchange mentioned in step (5) is ammonium ion exchange and / or rare earth ion exchange.

20. The preparation method according to claim 13, wherein, The ion exchange product obtained in step (5) is further calcined.

21. The preparation method according to claim 13, wherein, The ion exchange includes rare earth ion exchange, and the rare earth content in the modified kaolin-based molecular sieve obtained in step (5) is 10%-20% by weight (RE2O3) and the sodium oxide content is less than 2% by weight.

22. A catalytic cracking method comprising the step of contacting a hydrocarbon oil with a catalytic cracking catalyst according to any one of claims 1-11.

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