CN105148984B - A kind of catalytic cracking catalyst and its preparation method and application - Google Patents

Abstract

The invention provides a catalytic cracking catalyst, its preparation method and application. Based on the total weight of the catalytic cracking catalyst, the catalytic cracking catalyst contains 1-60% by weight of cracking active components, 1-50% by weight of mesoporous active silicon-phosphorus-aluminum materials, and 1-70% by weight of clay and 1-70% by weight of the binder; the mesoporous active silicon-phosphorus-aluminum material has a pseudo-boehmite crystal phase structure, and the anhydrous chemical expression in terms of the weight ratio of the oxide is: (0-0.2) Na ₂ O·(50‑86)Al ₂ O ₃ ·(12‑50)SiO ₂ ·(0.5‑10)P ₂ O ₅ , the specific surface area is 200‑600m ² /g, and the pore volume is 0.5‑1.8cm ³ / g, the average pore diameter is 8-18nm; based on the total weight of the cracking active component, the cracking active component contains 30-99% by weight of the first molecular sieve component and 1-70% by weight of the second molecular sieve component. The catalytic cracking catalyst not only has lower coke selectivity and higher catalytic cracking activity in the process of catalytic cracking of heavy oil, but also can obtain higher yield of diesel oil.

Description

A kind of catalytic cracking catalyst and its preparation method and application

technical field

The invention relates to a catalytic cracking catalyst, a preparation method of the catalytic cracking catalyst and an application of the catalytic cracking catalyst in heavy oil catalytic cracking.

Background technique

Catalytic cracking (FCC) is an important secondary processing process of crude oil and occupies a pivotal position in the oil refining industry. In the catalytic cracking process, heavy fractions (such as vacuum distillate oil or residues of heavier components) react in the presence of catalysts and are converted into high value-added products such as liquefied gas, gasoline, and diesel oil. In this process, it usually requires Catalytic materials with high cracking activity are used. Microporous zeolite catalytic materials are widely used in petroleum refining and processing industries due to their excellent shape-selective catalytic performance and high cracking reactivity. With the depletion of petroleum resources and the requirements of environmental protection, especially the growing trend of crude oil becoming heavier and the market's large demand for light oil products, more and more attention is paid to the depth of heavy oil and residual oil in the petroleum processing industry processing.

For improving the conversion rate, enhancing the conversion capacity of heavy oil, and reducing the further conversion of middle distillates and naphtha, traditional microporous molecular sieve catalytic materials show obvious diffusion-limiting effects on larger raw material molecules due to their small pores, making Pure microporous molecular sieve catalytic materials are not suitable for catalytic cracking of heavy distillate oils such as heavy oil and residual oil, so it is necessary to use materials with large pore size, no diffusion restriction on reactant molecules and high cracking activity. Therefore, the research and development of mesoporous and macroporous catalytic materials has attracted more and more attention. In addition, in the field of catalytic cracking, silicon-alumina materials are widely used due to their strong acid centers and good cracking performance.

CN1565733A discloses a mesoporous silicon-aluminum material, the mesoporous silicon-alumina material has a pseudoboehmite crystal phase structure, and the anhydrous chemical expression in terms of the weight ratio of oxides is: (0-0.3) _Na2O ·(40-90)Al ₂ O ₃ ·(10-60)SiO ₂ , with a specific surface area of 200-400m ² /g, a pore volume of 0.5-2.0mL/g, and an average pore diameter of 8-20nm. The pore size is 5-15nm. The preparation of the mesoporous silica-alumina material does not require the use of organic templates, the synthesis cost is low, and the obtained mesoporous silica-alumina material has high cracking activity and hydrothermal stability, and shows good macromolecular cracking in catalytic cracking reactions performance.

CN1854258A discloses a fluidized cracking catalyst, the fluidized cracking catalyst contains 3-20% by weight of acid-treated mesoporous silica-alumina material, the mesoporous silica-alumina material has a pseudo-boehmite crystal phase structure, to oxidize The anhydrous chemical expression based on the weight ratio of the substance is: (0-0.3)Na ₂ O·(40-90)Al ₂ O ₃ ·(10-60)SiO ₂ , the specific surface area is 200-400m ² /g, The pore volume is 0.5-2.0mL/g, the average pore diameter is 8-20nm, and the most probable pore diameter is 5-15nm.

CN1978593A discloses a cracking catalyst, which contains a mesoporous material, and the anhydrous compound composition of the mesoporous material is (0-0.3) Na ₂ O·(40-85 )Al ₂ O ₃ ·(10-55)SiO ₂ ·(1-20)M _x O _y , wherein metal M is selected from the periodic table IIA, IB, IIB, IVB, VB, VIB, VIIB, VIIIB or lanthanum It is one of the rare earth elements. The mesoporous material has a pseudo-boehmite crystal phase structure, a specific surface area of 200-400m ² /g, a pore volume of 0.5-2.0mL/g, and an average pore diameter of 8-20nm. The pore size can be 5-15nm. The catalyst can be directly used in a catalytic cracking reaction, and under conventional FCC operating conditions, it can not only increase the conversion rate of crude oil and heavy oil, but also effectively reduce the sulfur content of FCC gasoline.

CN102078821A discloses a cracking catalyst containing a mesoporous silicon-aluminum material, wherein the cracking catalyst is composed of a cracking active component, clay, a binder and a mesoporous silicon-aluminum material, and the mesoporous silicon-aluminum material has pseudo-thin water The crystal phase structure of bauxite, the anhydrous chemical expression based on the weight ratio of oxides is: (0-0.3) Na ₂ O · (40-90) Al ₂ O ₃ · (10-60) SiO ₂ , specific surface area The pore volume is 200-400m ² /g, the pore volume is 0.5-2.0mL/g, the average pore diameter is 8-20nm, the most probable pore diameter is 5-15nm, and the binder is silica sol and/or aluminum sol. Although the cracking catalyst has the advantages of low production cost and better crude oil conversion ability compared with the conventional catalyst using pseudo-boehmite, its coke selectivity is poor.

Contents of the invention

The purpose of the present invention is to provide a new catalytic cracking catalyst with lower coke selectivity, higher cracking activity and higher diesel oil yield, the preparation method of the catalytic cracking catalyst and the catalytic cracking catalyst Application of catalyst in catalytic cracking of heavy oil.

The invention provides a catalytic cracking catalyst, wherein, based on the total weight of the catalytic cracking catalyst, the catalytic cracking catalyst contains 1-60% by weight of cracking active components, 1-50% by weight of mesopore activity A silicon phosphorus aluminum material, 1-70% by weight of clay and a binder of 1-70% by weight; the mesoporous active silicon phosphorus aluminum material has a pseudoboehmite crystal phase structure, and the mesoporous active silicon phosphorus aluminum The anhydrous chemical expression in terms of the weight ratio of oxides in the material is: (0-0.2)Na ₂ O·(50-86)Al ₂ O ₃ ·(12-50)SiO ₂ ·(0.5-10)P ₂ O ₅ , and the specific surface area of the mesoporous active silicon-phosphorus-aluminum material is 200-600m ² /g, the pore volume is 0.5-1.8cm ³ /g, and the average pore diameter is 8-18nm;

Based on the total weight of the cracking active component, the cracking active component contains 30-99% by weight of the first molecular sieve component and 1-70% by weight of the second molecular sieve component, and the first molecular sieve group Divided into ultra-stable Y-type molecular sieves containing magnesium, the second molecular sieve component is one or more of rare earth-containing DASY molecular sieves, REY molecular sieves and MFI molecular sieves;

The magnesium content calculated as magnesium oxide in the magnesium-containing ultra-stable Y-type molecular sieve is 0.1-25% by weight;

The expression of the anhydrous chemical composition in terms of the molar ratio of oxides in the molecular sieve with the MFI structure is: (0.01-0.25)RE ₂ O ₃ ·(0.005-0.02)Na ₂ O·Al ₂ O ₃ ·(0.2-1.0 )P ₂ O ₅ ·(35-120)SiO ₂ , the adsorption weight ratio of the molecular sieve to n-hexane and cyclohexane is 4-5:1.

The present invention also provides a method for preparing the catalytic cracking catalyst, which comprises mixing and beating the cracking active component, mesoporous active silicon-phosphorus-aluminum material, clay and binder, followed by spray drying, washing, Filter and dry.

In addition, the present invention also provides the application of the catalytic cracking catalyst in heavy oil catalytic cracking.

The catalytic cracking catalyst provided by the present invention increases the content of mesopores in the catalytic cracking catalyst by using specific cracking active components and specific mesoporous active silicon-phosphorus-aluminum materials together with clay and binder, which is beneficial to the formation of heavy oil macromolecules. Diffusion and cracking, the catalytic cracking catalyst is especially suitable for catalytic cracking of heavy oil, in the process of catalytic cracking of heavy oil, it can not only show lower coke selectivity and higher catalytic cracking activity, but also can obtain higher yield of diesel oil .

Other features and advantages of the present invention will be described in detail in the following detailed description.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. In the attached picture:

Figure 1 is the X-ray diffraction spectrum of the mesoporous active silicon-phosphorus-aluminum material obtained in Preparation Example 1.

Detailed ways

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

The invention provides a catalytic cracking catalyst, wherein, based on the total weight of the catalytic cracking catalyst, the catalytic cracking catalyst contains 1-60% by weight of cracking active components, 1-50% by weight of mesopore activity A silicon phosphorus aluminum material, 1-70% by weight of clay and a binder of 1-70% by weight; the mesoporous active silicon phosphorus aluminum material has a pseudoboehmite crystal phase structure, and the mesoporous active silicon phosphorus aluminum The anhydrous chemical expression in terms of the weight ratio of oxides in the material is: (0-0.2)Na ₂ O·(50-86)Al ₂ O ₃ ·(12-50)SiO ₂ ·(0.5-10)P ₂ O ₅ , and the specific surface area of the mesoporous active silicon-phosphorus-aluminum material is 200-600m ² /g, the pore volume is 0.5-1.8cm ³ /g, and the average pore diameter is 8-18nm;

Based on the total weight of the cracking active component, the cracking active component contains 30-99% by weight of the first molecular sieve component and 1-70% by weight of the second molecular sieve component, and the first molecular sieve group Divided into ultra-stable Y-type molecular sieves containing magnesium, the second molecular sieve component is one or more of rare earth-containing DASY molecular sieves, REY molecular sieves and MFI molecular sieves;

The magnesium content calculated as magnesium oxide in the magnesium-containing ultra-stable Y-type molecular sieve is 0.1-25% by weight;

The expression of the anhydrous chemical composition in terms of the molar ratio of oxides in the molecular sieve with the MFI structure is: (0.01-0.25)RE ₂ O ₃ ·(0.005-0.02)Na ₂ O·Al ₂ O ₃ ·(0.2-1.0 )P ₂ O ₅ ·(35-120)SiO ₂ , the adsorption weight ratio of the molecular sieve to n-hexane and cyclohexane is 4-5:1.

In the present invention, the specific surface area, pore volume and average pore diameter are all measured by the low-temperature nitrogen adsorption-desorption method, and the instrument used is a physicochemical adsorption instrument ASAP2400 from Micro meritics of the United States.

According to the catalytic cracking catalyst provided by the present invention, preferably, based on the total weight of the catalytic cracking catalyst, the catalytic cracking catalyst contains 10-50% by weight of cracking active components, 5-40% by weight of mesopore activity Silicon phosphorus aluminum material, 10-60% by weight of clay and 10-60% by weight of binder, controlling the content of the above-mentioned components within the preferred range can make the catalytic cracking catalyst obtained have better comprehensive performance .

According to the catalytic cracking catalyst provided by the present invention, in order to enable the first molecular sieve component and the second molecular sieve component to play a better synergistic effect, preferably, based on the total weight of the cracking active components, the The cracking active component contains 45-95% by weight of the first molecular sieve component and 5-55% by weight of the second molecular sieve component.

The magnesium content in the magnesium-containing ultra-stable Y-type molecular sieve, calculated as magnesium oxide, is 0.1-25% by weight, preferably 0.5-25% by weight, more preferably 5-10% by weight. The magnesium-containing ultra-stable Y-type molecular sieve can be obtained commercially, or can be prepared according to various methods known to those skilled in the art, for example, it can be prepared according to the method disclosed in CN1297018A. Specifically, the magnesium-containing ultra-stable Y-type molecular sieve can be prepared according to the following two methods: (1) magnesium compounds (for example, selected from magnesium oxide, magnesium chloride, magnesium sulfate and nitric acid) after being dissolved or fully wet-milled At least one of magnesium) is uniformly dispersed in ultra-stable Y-type molecular sieve (USY molecular sieve) slurry, with or without ammonia water, mixed uniformly, dried and roasted; (2) the ultra-stable Y-type molecular sieve after fully wet grinding (USY molecular sieve) is uniformly dispersed in a solution of magnesium compound (for example, at least one selected from magnesium chloride, magnesium sulfate and magnesium nitrate), and ammonia water is added to mix evenly, followed by filtering, washing, drying and roasting.

The rare earth-containing DASY molecular sieve refers to a rare earth-containing hydrothermal ultrastable molecular sieve, wherein the rare earth content in the rare earth-containing DASY molecular sieve may be 1.5-3% by weight calculated as rare earth oxide (RE ₂ O ₃ ). The rare earth-containing DASY molecular sieve can be various commercially available products, for example, it can be DASY2.0 molecular sieve purchased from Sinopec Catalyst Qilu Branch.

The REY molecular sieve refers to a rare earth Y-type molecular sieve, which can be various commercially available REY molecular sieve products, for example, can be purchased from Sinopec Catalyst Qilu Branch.

The X-ray diffraction spectrum data of the molecular sieve with the MFI structure are shown in Table 1 below:

Table 1

d value (×10 ^-1 nm) Relative intensity value (I/I ₀ ) 11.2±0.2 vs. 10.1±0.2 m 9.8±0.2 VW 3.85±0.04 vs. 3.81±0.04 S 3.75±0.04 W 3.72±0.04 m 3.65±0.04 m 3.60±0.04 W

The relative intensity values represented by the symbols in Table 1 are as follows: VS: 80-100%; S: 60-80%; M: 40-60%; W: 20-40%; VW: <20%.

In addition, in the molecular sieve with the MFI structure, the rare earths are included in the molecular sieve crystals, wherein the rare earths come from the rare earth-containing faujasite crystal seeds used in the synthesis of the molecular sieves with the MFI structure. In the MFI structure molecular sieve, phosphorus is chemically combined with aluminum in the molecular sieve framework, and the MFI structure molecular sieve has a coordination corresponding to Al(4Si) in the ²⁷ Al NMR spectrum (that is, Al originates from the formation of four Si atoms through oxygen and Tetrahedral structure), the chemical shift is 55ppm spectral peak, and has the spectral peak corresponding to Al(4P) coordination (that is, Al atom forms tetrahedral structure through oxygen and four P atoms), chemical shift is 39ppm; In the ³¹ P NMR spectrum, the molecular sieve with the MFI structure has a peak corresponding to the P(4Al) coordination (that is, the interaction between the PO ₄ tetrahedron and the adjacent AlO ₄ tetrahedron) with a chemical shift of -29ppm. Preferably, the phosphorus in the molecular sieve with the MFI structure is evenly distributed in the molecular sieve crystal phase, which is specifically reflected in: the analysis results of the transmission electron microscope-energy dispersive spectrum (TEM-EDS) show that the phosphorus content in any single crystal particle is related to the molecular sieve body Phosphorus content in the phase is similar.

The adsorption weight ratio of the MFI structure molecular sieve to n-hexane and cyclohexane is 4-5:1, under the conditions of adsorption temperature of 40°C, adsorption time of 3 hours, and adsorption phase pressure P/P ₀ =0.20-0.25 , the adsorption capacity of the molecular sieve with MFI structure is 98-105 mg/g for n-hexane, and the adsorption capacity for cyclohexane is 20-25 mg/g. The adsorption weight ratio (4-5) is significantly higher than that of ZSM-5 zeolite (2-2.5).

In addition, the molecular sieve with MFI structure can be obtained commercially, or can be prepared according to various methods known to those skilled in the art, for example, it can be prepared according to the method disclosed in CN1147420A.

According to the catalytic cracking catalyst provided by the present invention, preferably, the specific surface area of the mesoporous active silicon-phosphorus-aluminum material is 250-550m ² /g, the pore volume is 0.6-1.6cm ³ /g, and the average pore diameter is 9-15nm.

The mesoporous active silicon-phosphorus-aluminum material can be prepared according to the following method: neutralize the aluminum source and alkaline solution at room temperature to 85°C to form a gel, control the pH of the gel to be 7-11, and then use SiO ₂ : Al ₂ O ₃ =1:1-7.5 weight ratio Add silicon source to the gelling slurry, then age at room temperature to 90°C for 1-5 hours, then mix the aged solid precipitate with ammonium salt or acid After _the solution is contacted, it is filtered to obtain a solid product with a sodium oxide content of less than 0.3% by weight, and then the solid product is contacted with a phosphorus source, and the contact product is dried; the amount of the phosphorus source in terms of _P2O5 is the same as the The dry basis weight ratio of the solid product is 0.005-0.1:1.

In the preparation method of the above-mentioned mesoporous active silicon-phosphorus-aluminum material, the steps before obtaining the solid product can be carried out with reference to the method disclosed in CN1565733A.

Specifically, the aluminum source may be various existing substances that can be converted into alumina, for example, may be selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.

The alkaline solution can be various existing alkaline substances, for example, it can be selected from one or more of ammonia water, sodium hydroxide solution, potassium hydroxide solution and sodium metaaluminate solution. Wherein, the concentration of the alkaline solution can be conventionally selected in the art, and will not be repeated here.

The silicon source can be various existing substances that can be converted into silicon oxide, for example, it can be selected from one or more of water glass, sodium silicate, tetraethoxy silicon and silicon oxide.

The present invention has no particular limitation on the method of contacting the solid precipitate with ammonium salt, for example, it may include contacting the solid precipitate on its dry basis: ammonium salt: H ₂ O = 1:0.1-1:5- A weight ratio of 30 was exchanged at room temperature to 100°C. Wherein, the number of times of said contacting can be 1-3 times, and the contacting time for each time can be 0.5-1 hour, specifically, the content of sodium oxide in the obtained solid product should be less than 0.3% by weight.

In addition, the type of the ammonium salt can be conventionally selected in the art, for example, it can be selected from one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium bicarbonate.

The present invention does not specifically limit the method of contacting the solid precipitate with an acidic solution, for example, it may include contacting the solid precipitate on a dry basis: acid: H ₂ O = 1:0.03-0.3:5-30 The weight ratio was exchanged at room temperature to 100 °C for at least 0.2 hours.

In addition, the type of the acidic solution can be a conventional choice in the art, usually an inorganic acid, for example, the acid in the acidic solution can be selected from one or more of sulfuric acid, hydrogen chloride and nitric acid.

According to the catalytic cracking catalyst provided by the present invention, wherein, the contact between the solid product and the phosphorus source can be carried out in the presence of water, and the contact method includes: using the solid product on its dry basis: water=1: Mixing and beating at a weight ratio of 5-20, adding a phosphorus source and reacting at room temperature to 90° C. for 0.2-5 hours, preferably 0.5-3 hours, and then filtering and washing the obtained contact product. In addition, the contact between the solid product and the phosphorus source may also be mixing and grinding the solid product and the phosphorus source. The conditions for drying the contact product of the solid product and the phosphorus source generally include: the drying temperature may be 100-150° C., and the drying time may be 10-20 hours. In addition, optionally, the preparation method of the mesoporous active silicon-phosphorus-aluminum material may also include roasting the dried product, and the conditions of the roasting generally include that the roasting temperature may be 500-700°C, and the roasting time may be 1-4 Hour.

The type of the phosphorus source can be conventionally selected in the art, for example, it can be selected from one or more of ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid.

The clay can be various existing clays that can be used in catalytic cracking catalysts, for example, can be selected from kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, retortite, One or more of sepiolite, attapulgite, hydrotalcite and bentonite.

The binder can be various existing binders that can be used in catalytic cracking catalysts, for example, it can be selected from one or more of silica sol, alumina sol and pseudo-boehmite.

In addition, the catalytic cracking catalyst may also contain additional rare earths. The added rare earth is formed by additionally adding rare earth chloride during the process of preparing the catalytic cracking catalyst. In the catalytic cracking catalyst, the added rare earth usually exists in the form of rare earth oxide (RE ₂ O ₃ ). Based on the dry weight of the catalytic cracking catalyst, the content of the added rare earth in the form of rare earth oxide may be 0-3% by weight, preferably 0.5-2% by weight. Wherein, the rare earth elements in the added rare earths refer to various conventional rare earth elements involved in the field of catalytic cracking catalysts, such as lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, etc.

The preparation method of the catalytic cracking catalyst provided by the invention comprises mixing and beating the above-mentioned cracking active component, mesoporous active silicon-phosphorus-aluminum material, clay and binder, and then performing spray drying, washing, filtering and drying in sequence. In addition, when the catalytic cracking catalyst also contains external rare earth, the preparation method of the catalytic cracking catalyst provided by the present invention also includes combining the rare earth chloride with the cracking active component, mesoporous active silicon phosphorus aluminum material, clay and The binders are mixed and beaten together, followed by spray drying, washing, filtering and drying in sequence.

According to the preparation method of the catalytic cracking catalyst provided by the present invention, the cracking active component, the mesoporous active silicon-phosphorus-aluminum material, the clay and the binder, and the optionally contained rare earth chloride are mixed and beaten, and the subsequent spray drying, Washing, filtering and drying, the implementation methods of these operations can be implemented by conventional methods, and their specific implementation methods are described in detail in CN1916166A, CN1098130A, CN1362472A, CN1727442A, CN1132898C and CN1727445A, and the present invention is incorporated here for reference. In addition, generally, after the spray-drying and before washing, the preparation method of the catalytic cracking catalyst usually further includes the step of roasting the spray-dried product. The calcination conditions generally include a calcination temperature of 500-700° C. and a calcination time of 1-4 hours.

In addition, the present invention also provides the application of the above catalyst for catalytic cracking in heavy oil catalytic cracking.

The present invention will be described in detail below by way of examples.

The raw materials used in the following preparation examples, comparative preparation examples, embodiments and comparative examples are as follows:

Hydrochloric acid is produced by Beijing Chemical Plant, chemically pure, and its concentration is 36% by weight;

Sodium silicate is commercially available with a _SiO2 concentration of 26.0% by weight and a modulus of 3.2;

Kaolin is a product of Suzhou Kaolin Company, and its solid content is 74.0% by weight;

Pseudoboehmite is an industrial product of Shandong Aluminum Plant, with a solid content of 62.0% by weight;

The aluminum sol is _a product of Sinopec Catalyst Qilu Branch, and the _Al2O3 content is 21.5% by weight;

The ultra-stable Y-type molecular sieve containing magnesium is prepared according to the method in Example 1 of CN1297018A, wherein the magnesium content calculated as magnesium oxide is 6.1% by weight;

DASY2.0 molecular sieve is produced by Sinopec Catalyst Qilu Branch;

REY molecular sieve is produced by Sinopec Catalyst Qilu Branch;

Molecular sieve with MFI structure was prepared according to the method in Example 1 of CN1147420A.

Rare earth chloride was purchased from Baotou Steel Rare Earth High Technology Co., Ltd., and the rare earth elements were La and Ce.

In the following preparation examples, comparative preparation examples, examples and comparative examples:

The specific surface area, pore volume and average pore diameter were all measured by low-temperature nitrogen adsorption-desorption method, and the instrument used was ASAP2400 physicochemical adsorption instrument from Micro meritics company in the United States. The contents of Na ₂ O, Al ₂ O ₃ , SiO ₂ , and P ₂ O ₅ in mesoporous active silicon-phosphorus-aluminum materials were determined by X-ray fluorescence method (see "Petrochemical Analysis Methods (RIPP Experimental Methods)", edited by Yang Cuiding et al., Science Press, published in 1990).

Preparation Example 1

This preparation example is used to illustrate the mesoporous active silicon-phosphorus-aluminum material provided by the present invention and its preparation method.

Using the Al ₂ (SO ₄ ) ₃ solution with a concentration of 90gAl ₂ O ₃ /L and the NaAlO ₂ solution with a concentration of 102gAl ₂ O ₃ /L and a caustic ratio of 2.5 as the reaction raw materials, co-flow gelation at 85°C and control The pH value of gelling is 9.5, collect a certain amount of gelling slurry, add sodium water glass with a concentration of _60gSiO2 /L in the ratio of SiO ₂ : Al ₂ O ₃ = 1: 6.56 under stirring, heat up to 70°C and age for 2 hours, a solid precipitate was obtained. Use NH ₄ Cl solution to carry out ion exchange on the solid precipitate at 60°C at a weight ratio of solid precipitate (dry basis): NH ₄ Cl: H ₂ O = 1:0.8:15 to remove sodium ions, and repeat the ion exchange Twice, for 0.5 hours each time, after filtration, a solid product with a sodium oxide content of less than 0.3% by weight was obtained, and then the solid product was mixed with the solid product (dry basis): H ₂ O=1:8 weight ratio Mix with water for beating, and add diammonium hydrogen phosphate according to the weight ratio of P ₂ O ₅ : solid product dry basis = 0.022:1, then react at 70°C for 1 hour, filter and wash with water, and dry at 120°C for 10 hours to obtain medium Pore-active silicon-phosphorus-aluminum material, denoted as A-1.

The mesoporous active silicon-phosphoraluminum material A-1 has a pseudo-boehmite structure, and its X-ray diffraction spectrum is shown in FIG. 1 . Measured by X-ray fluorescence analysis, the chemical composition of mesoporous active silicon-phosphorus-aluminum material A-1 in terms of weight ratio of oxides is: 0.11Na ₂ O·84.0Al ₂ O ₃ ·12.8SiO ₂ ·2.1P ₂ O ₅ . The specific surface area of the mesoporous active silicon phosphorus aluminum material A-1 is 501m ² /g, the pore volume is 1.51cm ³ /g, and the average pore diameter is 12.1nm.

Preparation example 2

This preparation example is used to illustrate the mesoporous active silicon-phosphorus-aluminum material provided by the present invention and its preparation method.

Prepare the mesoporous active silicon-phosphorus-aluminum material according to the method of Preparation Example 1, the difference is that the amount of diammonium hydrogen phosphate is such that P ₂ O ₅ : solid product dry basis = 0.095:1, then react at 70°C for 2 hours, and filter After washing with water, dry at 120° C. for 10 hours to obtain a mesoporous active silicon-phosphorus-aluminum material, denoted as A-2.

The mesoporous active silicon phosphorus aluminum material A-2 has a pseudoboehmite structure, and its X-ray diffraction spectrum is similar to that of the mesoporous active silicon phosphorus aluminum material A-1. Measured by X-ray fluorescence analysis, the chemical composition of mesoporous active silicon-phosphorus-aluminum material A-2 in terms of weight ratio of oxides is: 0.09Na ₂ O·78.1Al ₂ O ₃ ·12.3SiO ₂ ·9.3P ₂ O ₅ . The specific surface area of the mesoporous active silicon phosphorus aluminum material A-2 is 487m ² /g, the pore volume is 1.33cm ³ /g, and the average pore diameter is 10.9nm.

Preparation example 3

This preparation example is used to illustrate the mesoporous active silicon-phosphorus-aluminum material provided by the present invention and its preparation method.

Using the Al ₂ (SO ₄ ) ₃ solution with a concentration of 90gAl ₂ O ₃ /L and the NaAlO ₂ solution with a concentration of 102gAl ₂ O ₃ /L and a caustic ratio of 1.7 as the reaction raw materials, co-flow gelation at 60°C and control The gelling pH is 10.5, collect quantitative gelling slurry, add sodium water glass with a concentration of _60gSiO2 /L in the ratio of SiO ₂ :Al ₂ O ₃ =1:2.47 under stirring, heat up to 60°C and age for 3 hours, a solid precipitate was obtained. Ion-exchange the solid precipitate at 60°C with NH ₄ Cl solution at a weight ratio of solid precipitate (dry basis): NH ₄ Cl: H ₂ O = 1:1:10 to remove sodium ions, and use a large amount of deionized Rinse with water until the sodium oxide content is lower than 0.3%, and then mix the obtained solid product with water according to the weight ratio of solid product (dry basis): H ₂ O = 1:10, and dry according to P ₂ O ₅ : solid product Add ammonium dihydrogen phosphate at a weight ratio of 0.052:1, react at 70°C for 2 hours, filter and wash with water, and dry at 120°C for 10 hours to obtain a mesoporous active silicon-phosphorus-aluminum material, which is designated as A-3.

The mesoporous active silicon phosphorus aluminum material A-3 has a pseudoboehmite structure, and its X-ray diffraction pattern is similar to that of the mesoporous active silicon phosphorus aluminum material A-1. Measured by X-ray fluorescence analysis, the chemical composition of mesoporous active silicon-phosphorus-aluminum material A-3 in terms of weight ratio of oxides is: 0.08Na ₂ O·67.3Al ₂ O ₃ ·27.3SiO ₂ ·5.1P ₂ O ₅ . The specific surface area of the mesoporous active silicon phosphorus aluminum material A-3 is 373m ² /g, the pore volume is 1.07cm ³ /g, and the average pore diameter is 11.5nm.

Preparation Example 4

This preparation example is used to illustrate the mesoporous active silicon-phosphorus-aluminum material provided by the present invention and its preparation method.

Using the Al ₂ (SO ₄ ) ₃ solution with a concentration of 90gAl ₂ O ₃ /L and the NaAlO ₂ solution with a concentration of 102gAl ₂ O ₃ /L and a caustic ratio of 1.7 as the reaction raw materials, co-flow gelation at 40°C and control The pH value of the gel is 9.0, collect the quantitative gel slurry, add sodium water glass with a concentration of 60gSiO ₂ /L in the ratio of SiO ₂ : Al ₂ O ₃ = 1: 1.52 under stirring, raise the temperature to 80°C and age for 1.5 hours , a solid precipitated product was obtained. Use NH ₄ Cl solution to remove sodium ions by ion-exchanging the solid precipitate at 60°C according to the weight ratio of solid precipitate (dry basis): NH ₄ Cl: H ₂ O = 1:1:12, and use a large amount of deionized water Rinse until the sodium oxide content is less than 0.3% by weight, then directly mix the solid product with a sodium oxide content of less than 0.3% by weight with phosphoric acid at a weight ratio of P ₂ O ₅ : solid product dry basis = 0.008:1, and grind evenly Dry at 120° C. for 10 hours to obtain a mesoporous active silicon-phosphor-aluminum material. Record it as A-4.

The mesoporous active silicon phosphorus aluminum material A-4 has a pseudoboehmite structure, and its X-ray diffraction pattern is similar to that of the mesoporous active silicon phosphorus aluminum material A-1. Measured by X-ray fluorescence analysis, the chemical composition of the mesoporous active silicon-phosphorus-aluminum material A-4 is: 0.14Na ₂ O·59.3Al ₂ O ₃ ·39.1SiO ₂ ·0.8P ₂ O ₅ . The specific surface area of the mesoporous active silicon phosphorus aluminum material A-4 is 320m ² /g, the pore volume is 0.78cm ³ /g, and the average pore diameter is 9.7nm.

Preparation Example 5

This preparation example is used to illustrate the mesoporous active silicon-phosphorus-aluminum material provided by the present invention and its preparation method.

First put the Al ₂ (SO ₄ ) ₃ solution with a quantitative concentration of 90gAl ₂ O ₃ /L in a beaker, add ammonia water drop by drop under vigorous stirring until the pH of the system is 10.5, and the gelling temperature is 40 ℃; under stirring, add sodium water glass with a concentration of 60gSiO ₂ /L to the obtained gelled slurry according to the ratio of SiO ₂ : Al ₂ O ₃ =1:1.05, raise the temperature to 70 ℃ and age for 3 hours to obtain a solid Precipitate. Then the obtained solid precipitate was exchanged at 60° C. for 30 minutes according to the weight ratio of solid precipitate (dry basis): HCl: H ₂ O = 1: 0.08: 10, filtered and washed with water so that the sodium oxide content was lower than 0.3%, and a solid was obtained. The product is marked as SA-L5, and then the obtained solid product is mixed with water at a weight ratio of solid product (dry basis): H ₂ O = 1:8 for beating, and according to P ₂ O ₅ : solid product dry basis = 0.016: Add phosphoric acid at a weight ratio of 1, react at 60°C for 2 hours, filter and wash with water, and dry at 120°C for 10 hours to obtain a mesoporous active silicon-phosphorus-aluminum material, which is designated as A-5.

The mesoporous active silicon-phosphor-aluminum material A-5 has a pseudo-boehmite structure, and its X-ray diffraction pattern is similar to that of the mesoporous active silicon-phosphorus-aluminum material A-1. Measured by X-ray fluorescence analysis, the chemical composition of mesoporous active silicon-phosphorus-aluminum material A-5 in terms of weight ratio of oxides is: 0.12Na ₂ O·50.2Al ₂ O ₃ ·48.0SiO ₂ ·1.5P ₂ O ₅ . The specific surface area of the mesoporous active silicon phosphorus aluminum material A-5 is 289m ² /g, the pore volume is 0.64cm ³ /g, and the average pore diameter is 8.8nm.

Comparative Preparation Example 1

This comparative preparation example is used to illustrate the mesoporous silica-alumina material and its preparation method.

The mesoporous silica-alumina material was prepared according to the method of Preparation Example 1, except that the step of mixing and beating the solid product with water at a weight ratio of solid product (dry basis): H ₂ O = 1:8 was not included, Instead, the solid product with a sodium oxide content of less than 0.3% by weight was directly dried at 120° C. for 10 hours as a reference mesoporous active silica-alumina material, which was designated as DA-1.

The mesoporous active silicon-aluminum material DA-1 has a pseudo-boehmite structure, and its X-ray diffraction pattern is similar to that of the mesoporous active silicon-phosphoraluminum material A-1. Measured by X-ray fluorescence analysis, the chemical composition of the mesoporous active silicon-aluminum material DA-1 in terms of weight ratio of oxides is: 0.19Na ₂ O·81.9Al ₂ O ₃ ·16.7SiO ₂ . The specific surface area of the mesoporous active silica-alumina material DA-1 is 514m ² /g, the pore volume is 1.45cm ³ /g, and the average pore diameter is 11.3nm.

Example 1

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

Mix 19 parts by weight of pseudo-boehmite on a dry basis with deionized water for beating, and add hydrochloric acid to the resulting slurry for peptization. The acid-aluminum ratio (weight) is 0.20:1, and then the temperature is raised to 65 ℃ acidification for 1 hour, then add respectively 28 parts by weight of kaolin slurry (solid content is 25% by weight) on dry basis, 13 parts by weight of aluminum sol on dry basis and 10 parts by weight on dry basis of The slurry (solid content is 18% by weight) of the mesoporous active silicon-phosphorus-aluminum material A-1 prepared by Preparation Example 1 was stirred for 20 minutes, and then 20 parts by weight of the magnesium-containing superfine powder was added thereto on a dry basis. The mixed slurry (solid content: 35% by weight) of stable Y-type molecular sieve and 9 parts by weight of the REY molecular sieve on a dry basis was continuously stirred and then spray-dried to prepare a microsphere catalyst. Then the microsphere catalyst was calcined at 500° C. for 1 hour, and then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05: 1:10) until the Na ₂ O content is less than 0.25% by weight, then rinse with deionized water and filter, and then dry at 110°C to obtain the catalytic cracking catalyst C1, wherein the total amount of the catalytic cracking catalyst C1 Based on weight, the catalytic cracking catalyst C1 contains 10% by weight of mesoporous active silicon-phosphorus-aluminum material, 20% by weight of magnesium-containing ultra-stable Y-type molecular sieve, 9% by weight of REY molecular sieve, 28% by weight of kaolin, 33% by weight _{Al2O3 binder} .

Comparative example 1

This comparative example is used to illustrate the reference catalytic cracking catalyst and its preparation method.

The catalytic cracking catalyst was prepared according to the method of Example 1, the difference was that the mesoporous active silicon-phosphorus-aluminum material A-1 prepared by Preparation Example 1 was used by the same weight part of the mesoporous active silicon-aluminum material DA prepared by Comparative Preparation Example 1 -1 instead, to obtain a reference catalytic cracking catalyst CB1, wherein, based on the total weight of the reference catalytic cracking catalyst CB1, the reference catalytic cracking catalyst CB1 contains 10% by weight of mesoporous active silica-alumina materials, 20% by weight of ultra-stable Y-type molecular sieve containing magnesium, 9% by weight of REY molecular sieve, 28% by weight of kaolin, and 33% by weight of Al ₂ O ₃ binder.

Comparative example 2

This comparative example is used to illustrate the reference catalytic cracking catalyst and its preparation method.

Catalytic cracking catalyst was prepared according to the method of Example 1, the difference was that the mesoporous active silicon-phosphor-aluminum material A-1 was not added, and the mesoporous active silicon-phosphoraluminum material A-1 was replaced with kaolin of the same dry basis weight to obtain Reference catalytic cracking catalyst CB2, wherein, based on the total weight of the reference catalytic cracking catalyst CB2, the reference catalytic cracking catalyst CB2 contains 20% by weight of magnesium-containing ultra-stable Y-type molecular sieve, 9% by weight REY molecular sieve, 38% by weight of kaolin, 33% by weight of Al ₂ O ₃ binder.

Example 2

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

20 parts by weight of kaolin on a dry basis are mixed with deionized water for beating, then 20 parts by weight of pseudo-boehmite are added on a dry basis, and hydrochloric acid is added for peptization in the obtained slurry, the acid-aluminum ratio (weight ) was 0.20:1, then the temperature was raised to 65°C for acidification for 1 hour, and then 5 parts by weight of aluminum sol on a dry basis and 30 parts by weight on a dry basis of the mesoporous activity prepared by Preparation Example 2 were added respectively. The slurry of silicon phosphorus aluminum material A-2 (solid content is 20% by weight), was stirred for 20 minutes, then added thereto the ultra-stable Y-type molecular sieve containing magnesium of 20 parts by weight on a dry basis, 3 parts by weight of the DASY2.0 molecular sieve and 2 parts by weight of the molecular sieve with the MFI structure (solid content: 35% by weight) on a dry basis, continued to stir and then spray-dried to make a microsphere catalyst. Then the microsphere catalyst was calcined at 500° C. for 1 hour, and then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05: 1:10) until the Na ₂ O content is less than 0.25% by weight, then rinse with deionized water and filter, and then dry at 110°C to obtain catalytic cracking catalyst C2, wherein the total amount of catalytic cracking catalyst C2 Based on weight, the catalytic cracking catalyst C2 contains 30% by weight of mesoporous active silicon-phosphorus-aluminum material, 20% by weight of magnesium-containing ultra-stable Y-type molecular sieve, 3% by weight of DASY2.0 molecular sieve, 2% by weight of Molecular sieve with MFI structure, 20% by weight of kaolin, and 25% by weight of Al ₂ O ₃ binder.

Example 3

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

28 parts by weight of kaolin on a dry basis are mixed with deionized water for beating, then 28 parts by weight of pseudo-boehmite are added on a dry basis, and hydrochloric acid is added for peptization in the obtained slurry, the acid-aluminum ratio (weight ) was 0.20:1, then the temperature was raised to 65° C. for acidification for 1 hour, and then the slurry (solid content 25% by weight), stirred for 20 minutes, then added 7 parts by weight of the magnesium-containing ultra-stable Y-type molecular sieve on a dry basis, and the DASY2.0 molecular sieve of 15 parts by weight on a dry basis The mixed slurry (solid content is 35% by weight) and 2 parts by weight of rare earth chloride solution in terms of rare earth oxides were continuously stirred and then spray-dried to prepare a microsphere catalyst. Then the microsphere catalyst was calcined at 500° C. for 1 hour, and then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05: 1:10) until the Na ₂ O content is less than 0.25% by weight, then rinse with deionized water and filter, and then dry at 110°C to obtain catalytic cracking catalyst C3, wherein the total amount of catalytic cracking catalyst C3 Based on weight, the catalytic cracking catalyst C3 contains 20% by weight of mesoporous active silicon-phosphorus-aluminum material, 7% by weight of magnesium-containing ultra-stable Y-type molecular sieve, 15% by weight of DASY2.0 molecular sieve, 28% by weight of Kaolin, 28 wt% Al ₂ O ₃ binder, 2 wt% rare earth oxide.

Example 4

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

40 parts by weight of kaolin on a dry basis, 15 parts by weight on a dry basis of aluminum sol and 15 parts by weight on a dry basis of the mesoporous active silicon-phosphorus-aluminum material A-4 prepared by Preparation Example 4 The slurry (solid content is 20% by weight) was mixed and beaten, stirred for 120 minutes, and then added 15 parts by weight of the magnesium-containing ultra-stable Y-type molecular sieve on a dry basis and 15 parts by weight on a dry basis. The mixed slurry of the DASY2.0 molecular sieve (solid content: 35% by weight) was continuously stirred and then spray-dried to prepare a microsphere catalyst. Then the microsphere catalyst was calcined at 500° C. for 1 hour, and then washed with (NH ₄ ) ₂ SO ₄ solution at 60° C. (wherein, (NH ₄ ) ₂ SO ₄ : microsphere catalyst: H ₂ O=0.05: 1:10) until the Na ₂ O content is less than 0.25% by weight, then rinse with deionized water and filter, and then dry at 110°C to obtain catalytic cracking catalyst C4, wherein, the total amount of catalytic cracking catalyst C4 Based on weight, the catalytic cracking catalyst C4 contains 15% by weight of mesoporous active silicon-phosphorus-aluminum material, 15% by weight of magnesium-containing ultra-stable Y-type molecular sieve, 15% by weight of DASY2.0 molecular sieve, 40% by weight of Kaolin, 15% by weight _{Al2O3 binder} .

Example 5

This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.

(1) Preparation of silica sol:

Dilute 1.7L of hydrochloric acid with 8.0kg of decationized water, dilute 7.7kg of sodium water glass with 8.0kg of decationized water, and slowly add the diluted sodium water glass into the above dilute hydrochloric acid solution under stirring to obtain _a SiO concentration of 7.8% by weight silica sol with a pH of 2.8.

(2) preparation of catalytic cracking catalyst:

Add 10 parts by weight of kaolin on a dry basis to the above-mentioned silica sol of 20 parts by weight on a dry basis, and add 40 parts by weight on a dry basis of the mesoporous active silicon phosphorus prepared by Preparation Example 5 after stirring for 1 h The slurry (solid content is 18% by weight) of aluminum material A-5 is mixed and beaten, and then adds 20 parts by weight of the ultra-stable Y-type molecular sieve containing magnesium on a dry basis, and 5 parts by weight on a dry basis. A mixed slurry of 5 parts by weight of the DASY2.0 molecular sieve and 5 parts by weight of the REY molecular sieve (solid content: 30% by weight) on a dry basis was continuously stirred and then spray-dried to prepare a microsphere catalyst. Then the microsphere catalyst was washed with (NH ₄ ) ₂ SO ₄ solution (wherein, (NH ₄ ) ₂ SO ₄ :microsphere catalyst:H ₂ O=0.05:1:10) at 60°C to reach the Na ₂ O content less than 0.25% by weight, followed by rinsing with deionized water and filtering, and then drying at 110°C to obtain catalytic cracking catalyst C5, wherein, based on the total weight of catalytic cracking catalyst C5, the catalytic cracking catalyst C5 contains 40% by weight of mesoporous active silicon-phosphorus-aluminum material, 20% by weight of magnesium-containing ultra-stable Y-type molecular sieve, 5% by weight of DASY2.0 molecular sieve, 5% by weight of REY molecular sieve, 10% by weight of kaolin, 20% by weight _SiO2 binder.

Comparative example 3

This comparative example is used to illustrate the reference catalytic cracking catalyst and its preparation method.

The solid product SA-L5 obtained in Preparation Example 5 was dried at 120° C., and then calcined at 550° C. for 2 hours to obtain a mesoporous silica-alumina material, which was designated as SSA-5. The catalytic cracking catalyst is prepared according to the method of Example 5, the difference is that the mesoporous active silicon-phosphor-aluminum material A-5 prepared by Preparation Example 5 is replaced with the same weight portion of the mesoporous active silicon-aluminum material SSA-5 to obtain a reference Catalytic cracking catalyst CB3. Wherein, based on the total weight of the reference catalytic cracking catalyst CB3, the reference catalytic cracking catalyst CB3 contains 40% by weight of mesoporous silica-alumina material, 20% by weight of magnesium-containing ultra-stable Y-type molecular sieve, 5% by weight of DASY2.0 molecular sieve, 5% by weight of REY molecular sieve, 10% by weight of kaolin, 20% by weight of SiO ₂ binder.

Example 6-10

Examples 6-10 are used to illustrate the performance test of the catalytic cracking catalyst provided by the present invention.

The catalytic cracking catalysts C1-C5 prepared above were aged for 12 hours under the conditions of 800°C and 100% water vapor respectively, and then filled in a small-scale fixed fluidized bed ACE device (purchased from KTI Company of the United States), and the filling amounts were respectively Both are 9g. Then, under the conditions of reaction temperature of 500°C, space velocity of 16h ^-1 , and agent-to-oil weight ratio of 5:1, the feedstock oil shown in Table 2 was subjected to catalytic cracking reaction, and the reaction results are listed in Table 3. Among them, coke selectivity refers to the ratio of coke yield to conversion.

Comparative example 4-6

Comparative Examples 4-6 are used to illustrate the performance tests of the reference catalytic cracking catalysts.

Carry out catalytic cracking reaction to stock oil according to the method for embodiment 6-10, difference is, catalytic cracking catalyst C1-C5 is replaced with the referenced catalytic cracking catalyst CB1, CB2 and CB3 of same weight part respectively, and reaction result is listed in Table 3.

Table 2

table 3

The results in Table 3 illustrate that the catalyst provided by the present invention can significantly improve the selectivity of coke and has higher cracking activity compared with the catalyst with the same zeolite content but without mesoporous active silicon-phosphorus-aluminum materials. Compared with the catalyst with the same molar content but the mesoporous active material used is different from the mesoporous active silicon-phosphorus-aluminum material of the present invention, the coke yield of the catalyst provided by the present invention is reduced, and the coke selectivity is obviously improved. It can be seen that the catalytic cracking catalyst provided by the present invention can not only show better coke selectivity and higher catalytic cracking activity in the process of catalytic cracking of heavy oil, but also can obtain higher yield of diesel oil.

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

In addition, it should be noted that the various specific technical features described in the above specific implementation manners may be combined in any suitable manner if there is no contradiction. In order to avoid unnecessary repetition, various possible combinations are not further described in the present invention.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (14)

1. a kind of catalytic cracking catalyst, which is characterized in that described to urge on the basis of the total weight of the catalytic cracking catalyst Fluidized cracking catalysts contain mesopore activity silicon phosphor-aluminum material, the 1-70 of the cracking activity constituent element of 1-60 weight %, 1-50 weight % The clay of weight % and the binding agent of 1-70 weight %；The mesopore activity silicon phosphor-aluminum material has boehmite crystalline phase knot Structure, in the mesopore activity silicon phosphor-aluminum material using the anhydrous chemical expression of the weight ratio meter of oxide as：(0-0.2)Na₂O· (50-86)Al₂O₃·(12-50)SiO₂·(0.5-10)P₂O₅, and the specific surface area of the mesopore activity silicon phosphor-aluminum material is 200-600m²/ g, pore volume 0.5-1.8cm³/ g, average pore size 8-18nm；

On the basis of the total weight of the cracking activity constituent element, the cracking activity constituent element contains first point of 30-99 weight % Second molecular sieve component of sub- screen banks point and 1-70 weight %, first molecular sieve component are the super-stable Y molecular sieves containing magnesium, Second molecular sieve component is the DASY molecular sieves containing rare earth, REY molecular sieves and one kind or more in MFI structure molecular sieve Kind；

Using the content of magnesium that magnesia is counted as 0.1-25 weight % in the super-stable Y molecular sieves containing magnesium；

In the MFI structure molecular sieve using the anhydrous chemical of the molar ratio computing of oxide form expression formula as：(0.01-0.25) RE₂O₃·(0.005-0.02)Na₂O·Al₂O₃·(0.2-1.0)P₂O₅·(35-120)SiO₂, the molecular sieve is to n-hexane and ring The absorption weight ratio of hexane is 4-5：1.

2. catalytic cracking catalyst according to claim 1, wherein, using the total weight of the catalytic cracking catalyst as base Standard, the catalytic cracking catalyst contain the mesopore activity silicon phosphorus aluminium of the cracking activity constituent element of 10-50 weight %, 5-40 weight % The binding agent of material, the clay of 10-60 weight % and 10-60 weight %.

3. catalytic cracking catalyst according to claim 1, wherein, the specific surface area of the mesopore activity silicon phosphor-aluminum material For 250-550m²/ g, pore volume 0.6-1.6cm³/ g, average pore size 9-15nm.

4. according to the catalytic cracking catalyst described in any one in claim 1-3, wherein, the mesopore activity silicon phosphorus aluminium Material is prepared in accordance with the following methods：

Silicon source and alkaline solution are controlled into the pH value of plastic as 7-11, according still further to SiO at 85 DEG C and plastic in room temperature₂： Al₂O₃=1：The weight ratio of 1-7.5 adds in silicon source into plastic slurries, then then will in room temperature to when ageing 1-5 is small at 90 DEG C It is aged after obtained solid sediment is contacted with ammonium salt or acid solution and filters, obtain sodium oxide content less than 0.3 weight %'s Then the solid product with phosphorus source is contacted, and product of contact is dried by solid product again；Phosphorus source is with P₂O₅The use of meter Amount and the weight ratio of the butt of the solid product are 0.005-0.1：1.

5. catalytic cracking catalyst according to claim 4, wherein, source of aluminium is selected from aluminum nitrate, aluminum sulfate and chlorination One or more in aluminium；The alkaline solution is selected from ammonium hydroxide, sodium hydroxide solution, potassium hydroxide solution and sodium aluminate solution In one or more；One or more of the silicon source in waterglass, sodium metasilicate, tetraethoxy-silicane and silica.

6. catalytic cracking catalyst according to claim 4, wherein, the method that the solid sediment is contacted with ammonium salt Including：The solid sediment is pressed into its butt：Ammonium salt：H₂O=1：0.1-1：The weight ratio of 5-30 room temperature at 100 DEG C into Row exchanges.

7. catalytic cracking catalyst according to claim 4, wherein, the ammonium salt is selected from ammonium chloride, ammonium sulfate, nitric acid One or more in ammonium, ammonium carbonate and ammonium hydrogen carbonate.

8. catalytic cracking catalyst according to claim 4, wherein, the solid sediment is contacted with acid solution Method includes：The solid sediment is pressed into its butt：Acid：H₂O=1：0.03-0.3：The weight ratio of 5-30 is in room temperature to 100 Exchanged at DEG C at least 0.2 it is small when.

9. catalytic cracking catalyst according to claim 4, wherein, the acid in the acid solution is selected from sulfuric acid, chlorination One or more in hydrogen and nitric acid.

10. catalytic cracking catalyst according to claim 4, wherein, the contact between the solid product and phosphorus source exists It is carried out in the presence of water, the contact method includes：The solid product is pressed into its butt：Water=1：The weight ratio mixing of 5-20 Mashing adds phosphorus source and in room temperature to when reaction 0.2-5 is small at 90 DEG C.

11. catalytic cracking catalyst according to claim 4, wherein, phosphorus source be selected from ammonium phosphate, diammonium hydrogen phosphate, One or more in ammonium dihydrogen phosphate and phosphoric acid.

12. according to the catalytic cracking catalyst described in any one in claim 1-3, wherein, with the cracking activity constituent element Total weight on the basis of, the cracking activity constituent element contains the first molecular sieve component of 45-95 weight % and 5-55 weight % Second molecular sieve component.

13. the preparation method of the catalytic cracking catalyst in claim 1-12 described in any one, this method is included by described in Cracking activity constituent element, mesopore activity silicon phosphor-aluminum material, clay and binding agent are mixed with beating, be then spray-dried successively again, Washing, filtering and drying.

14. application of the catalytic cracking catalyst in claim 1-12 described in any one in heavy oil catalytic cracking.