Catalytic cracking catalyst having high-porosity structure and / or being resistant to vanadium, and preparation method therefor

Abstract

The present invention belongs to the technical field of the petrochemical industry, and relates to a catalytic cracking catalyst having a high-porosity structure and / or being resistant to vanadium, and a preparation method therefor. The catalyst is obtained by means of in-situ crystallization on an aluminosilicate composite material containing magnesium and / or vanadium reactive metal to form a molecular sieve, wherein the aluminosilicate composite material containing magnesium and / or vanadium reactive metal is obtained by activating kaolinite-rich and carbon-containing minerals that serve as a raw material and then performing spray molding. The present invention is beneficial to the industrial production of the synthesis of a small-grain Y-type molecular sieve on an aluminosilicate composite material containing magnesium and / or vanadium reactive metal, and achieves the exposure of more active centers, an increase in the number of exposed orifices and shortened micropore channels; therefore, cracking products are easier to strip and diffuse, secondary cracking of gasoline is reduced, better cracking reaction activity for heavy oil and heavy metal pollution resistance are achieved, a higher yield of light oil (gasoline and liquefied gas) is obtained, and fewer coke by-products are produced.

Description

Catalytic cracking catalyst with high porosity structure and / or resistance to vanadium and its preparation method TECHNICAL FIELD

[0001] The present application relates to a catalytic cracking catalyst with high porosity structure and / or resistance to vanadium and its preparation method. BACKGROUND

[0002] With the world's crude oil becoming heavier and poorer, heavy oil and residual oil have become the main processing raw materials used in the catalytic cracking process. Because heavy oil contains more gum, asphaltene and heavy metals, it requires the FCC catalyst to have higher matrix activity, stronger metal pollution resistance, better catalytic activity and selectivity, among which the FCC catalyst containing Y-type zeolite is the largest type of catalyst in use.

[0003] Currently, there are two forms of Y-type molecular sieve cracking catalysts produced in the industry, the first of which is a semi-synthetic binder type, that is, the Y-type molecular sieve is modified by exchange and mixed with kaolin and a binder to be sprayed and formed. The second is an in-situ crystallization type, that is, the kaolin microspheres are calcined at high temperature and then hydrothermally crystallized in an alkaline system, so that Y-type molecular sieves grow on the inner and outer surfaces of the microspheres, and then the finished catalyst is obtained by modification. The in-situ crystallization type has the following characteristics compared with the semi-synthetic binder type catalyst: (1) Y-type molecular sieves and matrix are generated simultaneously by in-situ crystallization and are connected by chemical bonds, which have higher thermal and hydrothermal stability; (2) Y-type molecular sieves are uniformly distributed on the surface of the matrix pores, and the crystal size is about ten times smaller than that of NaY synthesized by the gel method, which greatly improves the accessibility and cracking performance of heavy oil feedstocks; (3) the kaolin microspheres calcined at high temperature contain aluminum-rich spinel structures, which have excellent resistance to vanadium and nickel pollution and mechanical grinding ability. Thus, the in-situ crystallization type cracking catalyst has advantages for processing heavy oil feedstocks. The precursor of the in-situ crystallization type catalyst, kaolin microspheres, is the key to the preparation technology.

[0004] A series of patents related to the preparation of cracking catalysts by in-situ crystallization have been applied by Engelhard Company of the United States since the 1960s, such as US3503900, US3506594, US3663165, US4493902, US4965233, US5023220. In addition to Engelhard Company of the United States, other applicants have also applied a series of patents related to the preparation of cracking catalysts by in-situ crystallization, such as CN1232862A (Lanzhou Refining and Chemical General Factory of Sinopec); CN1778676A, CN102019196A, CN102019197B, CN102895988A (China Petroleum and Natural Gas Corporation); CN109312238B (BASF Corporation); CN100528351C (Engelhard Company) and the like.

[0005] Kaolin is a clay or clay rock dominated by kaolinite group clay minerals. According to the texture, plasticity and mass fraction of sandy quality, kaolin ore types are divided into hard kaolin (hard texture, no plasticity, plasticity after crushing and fine grinding), soft kaolin (soft texture, strong plasticity, sandy mass fraction <50%), and sandy kaolin (soft texture, weak plasticity, sandy mass fraction >50%), see “People’s Republic of China Geological and Mining Industry Standard DZ / T 0206-2000”. Due to sedimentation and other processes during mineral formation, sedimentary kaolin can have a high carbon content.

[0006] Coal gangue refers to rock with dry ash content >50% produced during the process of coal mine well construction, development and excavation, coal mining and coal washing (see “People’s Republic of China National Standard GB / T 29162-2012”), also known as carbonaceous kaolin. The chemical composition of coal gangue varies slightly in content and type depending on the place of origin, and is usually dominated by Al2O3, SiO2, and contains varying amounts of Na2O, K2O, MgO, CaO, Fe2O3, TiO2, etc. (Wang Xiaoli, “Coal Gangue Synthesized Zeolite Adsorbent and Its Adsorption Performance Research”, Science Press, June 2022). In recent years, there have been some new developments in the synthesis of molecular sieves from coal gangue. For example, Bu, Naijing et al. synthesized NaY zeolite from coal gangue (Bu, Naijing et al. “Synthesis of NaY zeolite from coal gangue and its characterization for lead removal from aqueous solution.” Advanced Powder Technology 31.7 (2020): 2699-2710); Han, Jinfeng et al. synthesized SSZ-13 zeolite from coal gangue (Han, Jinfeng, et al. “Synthesis of zeolite SSZ-13 from coal gangue via ultrasonic pretreatment combined with hydrothermal growth method.” Ultrasonics Sonochemistry 59 (2019): 104703). However, none of them involved the preparation of catalysts by in-situ crystallization.

[0007] Fireclay clay, also known as disordered kaolinite, is a natural aluminosilicate material with kaolinite as the main mineral component. It is mainly composed of Al and Si elements, and usually contains a small amount of other elements such as Fe, Mg, and Ti. The carbon content of some clays can be as high as about 3wt%.

[0008] The technical core of the preparation of the in-situ crystallized catalyst is: first, a solid material mainly composed of kaolin and its derivatives is prepared, and then under certain synthesis conditions, a molecular sieve is generated "in-situ" on the solid material through a liquid-solid reaction, and then through post-processing, a catalyst meeting the requirements is obtained. However, there has been no great improvement in the composition and preparation process of kaolin microspheres, and the two-stage calcination method of the early Engelhard Company has basically been continued. The problems of high energy consumption, high cost, and low crystallinity have not been solved.

[0009] The feedstock of catalytic cracking often contains vanadium, which can react with aluminum in the molecular sieve, destroying the structure of the molecular sieve and making the performance of the cracking catalyst worse. The prior art often adds vanadium reactive metals that can react with vanadium to form specific compounds to reduce the damage of vanadium to the molecular sieve on the catalyst. However, the prior art does not involve how to obtain an in-situ crystallized catalyst with better anti-vanadium effect. SUMMARY

[0010] The first object of the present application is to provide an aluminosilicate composite material containing magnesium and / or vanadium reactive metal (also referred to herein as "reactive microspheres"), which has at least one of the following characteristics, preferably all of the following characteristics:

[0011] (a) optionally, the specific surface area of the composite material is 20-60m 2 / g, such as 20-35m 2 / g, or 23-32m 2 / g, or 25-35m 2 / g, or 42-49m 2 / g;

[0012] (b) the content of the composite material is

[0013] the silicon content calculated as SiO2 is 30-70wt%, such as 40-60wt%, or 45.56-55.38wt%,

[0014] the aluminum content calculated as Al2O3 is 20-60wt%, such as 30-50wt%, or 32.61-49.26wt%,

[0015] a magnesium content of 0.5 to 15 wt%, such as 0.7 to 10 wt%, or 0.87 to 8.75 wt%, and / or a vanadium reactive metal content of 0.5 to 15 wt%, such as 0.7 to 10 wt%, or 0.7 to 5 wt%, or 0.8 to 4.1 wt%, as oxide (M x O y ) of 0.4 to 1.8 wt%, such as 0.6 to 1.2 wt%, or 0.7 to 1.15 wt%, or 0.71 to 1.14 wt%, and

[0016] Optionally, a sodium content of 0.1 to 15 wt%, such as 1 to 10 wt%, or 1.55 to 7.16 wt%, as Na2O;

[0017] Optionally, a sodium content of 0.1 to 15 wt%, such as 1 to 10 wt%, or 1.55 to 7.16 wt%, as Na2O;

[0018] (c) a content of tetrahedrally and pentahedrally coordinated Al2O3 of 25 to 90 wt%, such as 30 to 85 wt%, or 40 to 80 wt%, or 41.7 to 75.6 wt%, as Al2O3 in the composite material;

[0019] (d) optionally, a content of SiO2 having a Q 4 (0Al) structure of 20 to 95 wt%, such as 30 to 95 wt%, or 25 to 90 wt%, or 35 to 90 wt%, or 30 to 80 wt%, or 40 to 85 wt%, or 40 to 75%, or 30.3 to 75.1 wt%, as SiO2 in the composite material;

[0020] (e) Preferably, in the composite material, a complex salt of magnesium and aluminium in the form of MgAl2O4 is present (if the magnesium as MgO is in the above range), and optionally, the content of MgAl2O4 is 1 to 40 wt%, such as 2 to 25 wt%, or 2.1 to 21.6 wt%, as 100 wt% of the total weight of the composite material, and / or in the composite material, a complex salt of vanadium reactive metal and aluminium in the form of metal oxide is present (if the vanadium reactive metal as oxide is in the above range), and optionally, the content of the complex salt of vanadium reactive metal and aluminium is 0.5 to 40 wt%, such as 0.55 to 20 wt%, or 0.6 to 10 wt%, or 0.65 to 5 wt%, or 0.7 to 4.3 wt%, as 100 wt% of the total weight of the composite material;

[0021] In the present application, the vanadium reactive metal is selected from at least one of the group VA metals (such as bismuth, antimony), group II B metals (such as zinc, cadmium), group VI B metals (such as chromium, molybdenum, tungsten), group VII B metals (such as manganese, technetium, rhenium), group VIII metals (such as iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum), group III B metals (such as rare earth metals, i.e. scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium) (M represents the vanadium reactive metal, x represents the coordination number of M, and Y represents the coordination number of O, for group VA metals, group VI B metals, group III B metals, group VIII metals, x is 2 and y is 3; for group VII B metals, x is 1 and y is 2; for group II B metals, x is 1 and y is 1), preferably one or more of Bi, Mn, Zn, Ce, La, more preferably La,

[0022] Optionally, the composite further has at least one, preferably all, of the following characteristics:

[0023] (f) the sphericity of the composite is 85-100%, such as 90-99%, or 91-95%, or 92-97%, or 92.5-96.2%;

[0024] (g) the attrition index of the composite is 2.0-5.0% / h, such as 2.0-4.0% / h, or 3.0-4.0% / h, or 3.2-4.0% / h;

[0025] (h) the average particle size of the composite is 50-100 μm, such as 60-90 μm, or 70-80 μm, or 72-78 μm;

[0026] (i) the pore volume of the composite is 0.02-0.1 mL / g, such as 0.035-0.085 mL / g, or 0.05-0.1 mL / g, or 0.06-0.09 mL / g, or 0.04-0.07 mL / g, or 0.045-0.095 mL / g, or 0.06-0.09 mL / g.

[0027] A second object of the present application is to provide a catalyst comprising, in terms of total weight of the catalyst, 100 wt%:

[0028] 50-70 wt%, such as 57-67 wt%, or 58-65 wt%, or 60.04-63.61 wt% of silicon (as SiO2);

[0029] 20-30 wt%, such as 21-28 wt%, or 23-26 wt%, such as 21.22-26.5 wt% of aluminium (as Al2O3);

[0030] 0.2-8wt%, such as 0.3-5.5wt%, or 0.38-5.2wt% of magnesium (as MgO), and / or 0.2-15wt%, or 0.2-8wt%, or 1-8wt%, or 0.3-5.5wt%, or 0.8-5.2wt%, or 0.7-3.95% of vanadium reactive metal (as oxide MxOy);

[0031] Optionally, 0.3-2wt%, such as 0.35-1wt%, or 0.4-0.92wt%, or 0.3-1wt%, or 0.6-1wt% of titanium (as Ti02);

[0032] Optionally, 0.01-2wt%, such as 0.1-0.4wt%, or 0.12-0.26wt%, or 5-15wt%, or 7-11wt%, or 8-11wt%, or 8-10.88wt% of Na (as Na20);

[0033] Optionally, 0-0.01wt%, or 1-25wt%, such as 6-15wt%, or 9.01-11.98wt% of exchanged rare earth (as rare earth oxide RE203);

[0034] In the catalyst, there is a complex salt of magnesium and aluminium in the form of MgAl204, if the magnesium as MgO is in the above range, and optionally, the content of MgAl204is 0.5-20wt%, such as 0.75-15wt%, or 0.94-12.85wt%, based on 100wt% of the total weight of the catalyst, and / or in the catalyst, there is a complex salt of vanadium reactive metal and aluminium in the form of metal oxide, if the vanadium reactive metal as oxide is in the above range, and optionally, the content of the complex salt of vanadium reactive metal and aluminium is 0.5-20wt%, such as 0.75-15wt%, or 0.75-7.5wt%, or 0.76-3.35wt%, based on 100wt% of the total weight of the catalyst;

[0035] wherein

[0036] When the content of Na (as Na20) is 0.01-2wt%, or 0.1-0.4wt%, the content of exchanged rare earth (as rare earth oxide RE203) is 1-25wt%, or 0.5-20wt%, or 1-15wt%, or 6-15wt%, or 9.01-11.98wt%;

[0037] When the content of Na (as Na20) is 5-15wt%, or 7-11wt%, or 8-11wt%, the content of exchanged rare earth (as rare earth oxide RE203) is 0-0.01wt%.

[0038] For example, the rare earth is one or more of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y) and scandium (Sc), preferably the rare earth is one or more of yttrium, lanthanum, cerium, praseodymium and neodymium, more preferably one or more of La, Ce and Y; for example, the rare earth oxide is one or more of La2O3, CeO2and Y2O3.

[0039] When the vanadium reactive metal comprises a rare earth, the catalyst comprises rare earth in the molecular sieve crystalline cell (referred to as exchanged rare earth) and / or rare earth as a vanadium reactive metal outside the molecular sieve crystalline particle, the content of the rare earth refers to the content of the exchanged rare earth, excluding the rare earth as a vanadium reactive metal.

[0040] Preferably, the catalyst has at least one of the following characteristics, preferably all of the following characteristics:

[0041] (1) attrition index = 0.5-3.0% / h, such as 0.7-2.2% / h, or 0.8-2.1% / h, or 1.0-3.0% / h, or 1.8-2.1% / h, or 0.5-2.0% / h, or 1.0-3.0% / h, or 0.6-1.5% / h, or 0.8-1.1% / h, or 1.5-2.2% / h;

[0042] (2) specific surface area = 400-1000 m 2 / g, such as 400-800 m 2 / g, or 450-700 m 2 / g, or 600-970 m 2 / g, or 600-960 m 2 / g, or 630-960 m 2 / g, or 640-955 m 2 / g, or 600-750 m 2 / g, or 600-860 m 2 / g, or 611.9-851.3 m 2 / g, or 730-860 m 2 / g, or 720-840 m 2 / g, or 650-850 m 2 / g, or 732.6-851.3 m 2 / g, or 611.9-737.8 m 2 / g;

[0043] (3) Pore Volume = 0.2-0.6 mL / g, such as 0.2-0.55 mL / g, or 0.25-0.55 mL / g, 0.25-0.5 mL / g, or 0.3-0.6 mL / g, or 0.3-0.5 mL / g, or 0.4-0.5 mL / g, or 0.41-0.46 mL / g, or 0.41-0.44 mL / g, or 0.38-0.48 mL / g;

[0044] (4) Crystallinity = 55-90%, such as 60-90%, or 60-78%, or 60-75%, or 60-67%, or 61-75%, or 65-75%;

[0045] (5) Unit Cell Parameter = 2.454-2.473 nm, such as 2.457-2.470 nm, or 2.460-2.467 nm, or 2.460-2.466 nm, or 2.461-2.467 nm, or 2.463-2.467 nm;

[0046] Optionally, the catalyst further has at least one, and preferably all, of the following characteristics:

[0047] (6) Framework silica-to-alumina ratio (molar ratio of Si02 / Al203) = 2.0-7.0, such as 3.0-6.7, or 4.0-6.3, or 4.8-6.3, or 2.0-6.0, or 5.0-6.2, or 5.0-6.1, or 5.1-6.1, or 5.0-6.0;

[0048] (7) Pore Volume = 0.2-0.6 mL / g, such as 0.2-0.55 mL / g, or 0.25-0.55 mL / g, 0.25-0.5 mL / g, or 0.3-0.6 mL / g, or 0.3-0.5 mL / g, or 0.4-0.5 mL / g, or 0.41-0.46 mL / g, or 0.41-0.44 mL / g, or 0.38-0.48 mL / g;

[0049] (8) Mesopore Volume = 20-40%, such as 25-37%, or 25-36%, or 25-35%, or 26-36%, or 25.1-34.2%, or 25.1-35.9%, or 25.1-36%, or 25.1-37.2%, or 25.7-36.2%, or 25.7-35.9%, or 26-37.9%, or 26.8-35.5%;

[0050] (9) Trimethylpyridine acidity = 100-500 μmol / g, such as 280-411 μmol / g, or 250-450 μmol / g, or 280-420 μmol / g, or 280-413 μmol / g;

[0051] The catalyst is obtained by in-situ crystallization of a molecular sieve on the magnesium-containing and / or vanadium-containing reactive metal aluminosilicate composite material of the present application, preferably the molecular sieve is an X-type molecular sieve, a Y-type molecular sieve, or an A-type molecular sieve, more preferably the molecular sieve is a Y-type molecular sieve, and more particularly preferably the molecular sieve is a NaY-type molecular sieve or a REY-type molecular sieve.

[0052] In the present application, the high porosity refers to a meso-macroporosity of 20%-40% of the catalyst. The meso-macroporosity is determined by nitrogen adsorption method for pore volume, and is calculated by the following formula:

[0053] Meso-macroporosity = (V 总孔 -V 微孔 ) / V 总孔 x 100%, wherein

[0054] Micropore: pore size < 2 nm;

[0055] Meso-pore: pore size 2-50 nm;

[0056] Macropore: pore size > 50 nm.

[0057] Further preferably, in the pore size distribution curve of the catalyst, there is one meso-pore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0058] A third object of the present application is to provide a calcined aluminosilicate material (also referred to herein as "activated kaolin") obtained by calcining particles of a kaolinite-rich and carbon-containing mineral substance having a particle size in the range of 0.1-3.0 microns at a temperature in the range of 400-920°C, for example 450-900°C, further for example 500-800°C.

[0059] A fourth object of the present application is to provide a method for preparing a magnesium-containing and / or vanadium-containing reactive metal aluminosilicate composite material, comprising the following steps: (1) washing, crushing and grinding a kaolinite-rich and carbon-containing mineral substance, screening out the fraction having a particle size in the range of 0.1-3.0 microns, and calcining at a temperature in the range of 400-920°C for 1-8 hours to obtain a calcined aluminosilicate material; (2) slurrying the calcined aluminosilicate material, a binder, a modifier, and water together to form a slurry, and then (high pressure) spray forming to obtain the magnesium-containing and / or vanadium-containing reactive metal aluminosilicate composite material.

[0060] A fifth object of the present application is to provide a method for preparing the catalyst of the present application, which comprises steps (1) and (2) of the method for preparing the magnesium-containing and / or vanadium-containing reactive metal-containing aluminosilicate composite material of the present application, and further comprises (3) mixing the magnesium-containing and / or vanadium-containing reactive metal-containing aluminosilicate composite material with a silicon source, an alkali source, a directing agent, and water, and then performing in-situ hydrothermal crystallization to obtain a catalyst containing a NaY-type molecular sieve (preferably a catalyst containing a NaY-type molecular sieve); and optionally, (4) filtering, washing, and performing rare earth exchange and / or optional ammonium salt exchange and / or phosphorus exchange (e.g., performing rare earth exchange and optional ammonium salt exchange and / or phosphorus exchange), drying, and calcining the catalyst containing a NaY-type molecular sieve (e.g., a catalyst containing a NaY-type molecular sieve) to obtain a modified molecular sieve catalyst, such as a catalyst containing a rare earth-modified Y-type molecular sieve.

[0061] A sixth object of the present application is to apply the catalyst of the present application in the production of light oil from heavy oil catalytic cracking. The heavy oil catalytic cracking catalyst of the present application has strong heavy oil conversion capacity, high light oil yield, and low coke selectivity. The heavy oil can be a heavy oil containing vanadium.

[0062] The present application has the following advantages:

[0063] (1) The catalytic cracking catalyst of the present application is obtained by hydrothermal crystallization of reactive microspheres. The reactive microspheres have mesoporous and macroporous structures, and the zeolite catalyst can be hydrothermally formed on the mesoporous and macroporous structures, and the molecular sieve uniformly grows on the inner and outer surfaces of the microsphere matrix, which greatly improves the utilization rate of the molecular sieve, has good accessibility of active centers, increases the cracking activity of the catalyst for heavy oil macromolecules, and is more conducive to the heavy oil catalytic cracking reaction.

[0064] (2) The reactive microspheres prepared in the present application are formed by high-pressure spraying after beating the active kaolin clay, a binder, water, and a modifier together to form a slurry. The active kaolin clay is prepared by activating and depolymerizing carbon-containing kaolin clay, and has high active silicon (Q 4 (0Al) structure SiO2) and active aluminum (tetrahedral and pentahedral Al2O3), and the hydrothermal crystallization product has higher crystallinity and more cracking active centers.

[0065] (3) The catalyst preparation method provided by the present application uses the reactive microspheres for in-situ crystallization, and the molecular sieve uniformly grows on the inner and outer surfaces of the microsphere matrix, so that a catalyst with higher mesoporous and macroporous content and porosity and higher specific surface area can be obtained.

[0066] (4) The vanadium-containing reactive metal-containing aluminosilicate composite material has high active silicon (Q 4The hydrothermal crystallization product has higher crystallinity and more cracking active centers, and can form more pore structures and mesopore and macropore structures.

[0067] (5) The catalyst substrate of the present application contains a vanadium reactive metal oxide capable of reacting with vanadium, which can react with vanadium to fix vanadium, such as vanadium in heavy oil, thereby reducing the opportunity for vanadium to react with the aluminum in the framework of the molecular sieve, and has strong resistance to vanadium poisoning in combination with large porosity.

[0068] Other features and advantages of the present application will be described in detail in the following specific embodiments. BRIEF DESCRIPTION OF DRAWINGS

[0069] Figure 1 is a pore size distribution curve of the crystallized microspheres obtained in Preparation Example 2.1, in which there is one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0070] Figure 2 is a pore size distribution curve of the crystallized microspheres obtained in Preparation Example 2.8, in which there is one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively. DETAILED DESCRIPTION

[0071] The following detailed description of the application is provided. It should be understood that the detailed description is merely illustrative and explanatory thereof and is not intended to limit the application.

[0072] In a first aspect of the present application, the present application provides a magnesium-containing and / or vanadium reactive metal-containing aluminosilicate composite material (also referred to herein as "reactive microspheres"). The composite material has at least one of the following characteristics, and preferably has all of the following characteristics:

[0073] (a) optionally, the specific surface area of the composite material is 20-60 m 2 / g, such as 20-35 m 2 / g, or 23-32 m 2 / g, or 25-35 m 2 / g, or 42-49 m 2 / g;

[0074] (b) the content of the composite material is 0.1-5 wt%, such as 0.5-3 wt%, or 1-2 wt%, based on the total weight of the composite material being 100 wt%;

[0075] the silicon content, calculated as SiO2, is 30-70 wt%, such as 40-60 wt%, or 45.56-55.38 wt%,

[0076] aluminium content of 20 to 60 wt%, such as 30 to 50 wt%, or 32.61 to 49.26 wt% as Al2O3,

[0077] magnesium content of 0.5 to 15 wt%, such as 0.7 to 10 wt%, or 0.87 to 8.75 wt% as MgO, and / or vanadium reactive metal content of 0.5 to 15 wt%, such as 0.7 to 10 wt%, or 0.7 to 5 wt%, or 0.8 to 4.1 wt% as oxide (M x O y ) as oxide (M 4

[0078] optionally titanium content of 0.4 to 1.8 wt%, such as 0.6 to 1.2 wt%, or 0.7 to 1.15 wt%, or 0.71 to 1.14 wt% as TiO2, and

[0079] optionally sodium content of 0.1 to 15 wt%, such as 1 to 10 wt%, or 1.55 to 7.16 wt% as Na2O;

[0080] (c) tetrahedrally and pentahedrally coordinated Al2O3 content of 25 to 90 wt%, such as 30 to 85 wt%, or 40 to 80 wt%, or 41.7 to 75.6 wt% as Al2O3 in said composite material;

[0081] (d) optionally SiO2 content of 20 to 95 wt%, such as 30 to 95 wt%, or 25 to 90 wt%, or 35 to 90 wt%, or 30 to 80 wt%, or 40 to 85 wt%, or 40 to 75 wt%, or 30.3 to 75.1 wt% as SiO2 having Q 4 (0Al) structure in said composite material;

[0082] (e) preferably, in the composite material, there is a complex salt of magnesium and aluminium present as MgAl2O4 if the magnesium is in the above range as MgO, and optionally, the MgAl2O4 content is 1 to 40 wt%, such as 2 to 25 wt%, or 2.1 to 21.6 wt% based on the total weight of the composite material as 100 wt%, and / or in the composite material, there is a complex salt of vanadium reactive metal and aluminium present as metal oxide if the vanadium reactive metal is in the above range as oxide, and optionally, the complex salt of vanadium reactive metal and aluminium content is 0.5 to 40 wt%, such as 0.55 to 20 wt%, or 0.6 to 10 wt%, or 0.65 to 5 wt%, or 0.7 to 4.3 wt% based on the total weight of the composite material as 100 wt%;

[0083] The composite can further have at least one, preferably all of the following characteristics:

[0084] (f) the sphericity of the composite is 85-100%, such as 90-99%, or 91-95%, or 92-97%, or 92.5-96.2%;

[0085] (g) the attrition index of the composite is 2.0-5.0% / h, such as 2.0-4.0% / h, or 3.0-4.0% / h, or 3.2-4.0% / h;

[0086] (h) the average particle size of the composite is 50-100 pm, such as 60-90 pm, or 70-80 pm, or 72-78 pm;

[0087] (i) the pore volume of the composite is 0.02-0.1 mL / g, such as 0.035-0.085 mL / g, or 0.05-0.1 ml / g, or 0.06-0.09 mL / g, or 0.04-0.07 mL / g, or 0.045-0.095 mL / g, or 0.06-0.09 mL / g.

[0088] In a second aspect of the application, the present application provides a catalyst. The catalyst comprises, in terms of total weight of the catalyst as 100 wt%, on an elemental basis:

[0089] 50-70 wt%, such as 57-67 wt%, or 58-65 wt%, or 60.04-63.61 wt% of silicon (as Si02);

[0090] 20-30 wt%, such as 21-28 wt%, or 23-26 wt%, such as 21.22-26.5 wt% of aluminium (as AI2O3);

[0091] 0.2-8 wt%, such as 0.3-5.5 wt%, or 0.38-5.2 wt% of magnesium (as MgO), and / or 0.2-15 wt%, or 0.2-8 wt%, or 1-8 wt%, or 0.3-5.5 wt%, or 0.8-5.2 wt%, or 0.7-3.95% of vanadium reactive metal (as oxide MxOy);

[0092] Optionally, 0.3-2 wt%, such as 0.35-1 wt%, or 0.4-0.92 wt%, or 0.3-1 wt%, or 0.6-1 wt% of titanium (as Ti02);

[0093] Optionally, 0.01-2 wt%, such as 0.1-0.4 wt%, or 0.12-0.26 wt%, or 5-15 wt%, or 7-11 wt%, or 8-11 wt%, or 8-10.88 wt% of Na (as Na2O);

[0094] Optionally, 0-0.01 wt%, or 1-25 wt%, such as 6-15 wt%, or 9.01-11.98 wt% of rare earth (or referred to as exchange rare earth, as rare earth oxide RE2O3).

[0095] In the catalyst, there is a complex salt of magnesium and aluminum existing in the form of MgAl2O4 (if the magnesium as MgO is within the above range), and optionally, the content of MgAl2O4 is 0.5-20 wt%, such as 0.75-15 wt%, or 0.94-12.85 wt%, based on 100 wt% of the total weight of the catalyst, and / or in the catalyst, there is a complex salt of vanadium reactive metal and aluminum existing in the form of metal oxide (if the vanadium reactive metal as oxide is within the above range), and optionally, the content of the complex salt of vanadium reactive metal and aluminum is 0.5-20 wt%, such as 0.75-15 wt%, or 0.75-7.5 wt%, or 0.76-3.35 wt%, based on 100 wt% of the total weight of the catalyst.

[0096] When the content of Na (as Na2O) is 0.01-2 wt%, or 0.1-0.4 wt%, the content of exchange rare earth (as rare earth oxide RE2O3) is 1-25 wt%, or 0.5-20 wt%, or 1-15 wt%, or 6-15 wt%, or 9.01-11.98 wt%;

[0097] When the content of Na (as Na2O) is 5-15 wt%, or 7-11 wt%, or 8-11 wt%, the content of exchange rare earth (as rare earth oxide RE2O3) is 0-0.01 wt%.

[0098] The rare earth can be one or more of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y), and scandium (Sc), preferably, the rare earth is one or several of yttrium, lanthanum, cerium, praseodymium, and neodymium, more preferably, one or more of La, Ce, and Y. For example, the rare earth oxide can be one or several of La2O3, CeO2, and Y2O3.

[0099] The catalyst can also have at least one, preferably all of the following characteristics:

[0100] (1) Abrasion index = 0.5-3.0% / h, such as 0.7-2.2% / h, or 0.8-2.1% / h, or 1.0-3.0% / h, or 1.8-2.1% / h, or 0.5-2.0% / h, or 1.0-3.0% / h, or 0.6-1.5% / h, or 0.8-1.1% / h, or 1.5-2.2% / h;

[0101] (2) Specific surface area = 400-1000 m 2 / g, such as 400-800 m 2 / g, or 450-700 m 2 / g, or 600-970 m 2 / g, or 600-960 m 2 / g, or 630-960 m 2 / g, or 640-955 m 2 / g, or 600-750 m 2 / g, or 600-860 m 2 / g, or 611.9-851.3 m 2 / g, or 730-860 m 2 / g, or 720-840 m 2 / g, or 650-850 m 2 / g, or 732.6-851.3 m 2 / g, or 611.9-737.8 m 2 / g;

[0102] (3) Pore volume = 0.2-0.6 mL / g, such as 0.2-0.55 mL / g, or 0.25-0.55 mL / g, 0.25-0.5 mL / g, or 0.3-0.6 mL / g, or 0.3-0.5 mL / g, or 0.4-0.5 mL / g, or 0.41-0.46 mL / g, or 0.41-0.44 mL / g, or 0.38-0.48 mL / g;

[0103] (4) Crystallinity = 55-90%, such as 60-90%, or 60-78%, or 60-75%, or 60-67%, or 61-75%, or 65-75%;

[0104] (5) Cell parameters = 2.454-2.473 nm, such as 2.457-2.470 nm, or 2.460-2.467 nm, or 2.460-2.466 nm, or 2.461-2.467 nm, or 2.463-2.467 nm.

[0105] The catalyst can further have at least one, preferably all, of the following characteristics:

[0106] (6) a framework silica-to-alumina ratio (molar ratio of Si02 / Al203) = 2.0-7.0, such as 3.0-6.7, or 4.0-6.3, or 4.8-6.3, or 2.0-6.0, or 5.0-6.2, or 5.0-6.1, or 5.1-6.1, or 5.0-6.0;

[0107] (7) a porosity = 3%-30%, such as 3%-20%, or 5%-20%, or 5%-12%, or 8%-20%, or 9.2%-19.4%, or 9.1%-18.5%, or 9.2%-18.2%, or 9.8%-18.2%, or 9.4%-19.4%, or 9.0%-19.5%;

[0108] (8) optionally, a meso-macroporosity = 20%-40%, such as 25%-37%, or 25%-36%, or 25%-35%, or 26%-36%, or 25.1%-34.2%, or 25.1%-35.9%, or 25.1%-36%, or 25.1%-37.2%, or 25.7%-36.2%, or 25.7%-35.9%, or 26-37.9%, or 26.8%-35.5%.

[0109] (9) optionally, the catalyst has a quantity of trimethylpyridine acid of 100-500 μιηοΐ / g, such as 280-411 μιηοΐ / g, or 250-450 μιηοΐ / g, or 280-420 μιηοΐ / g, or 280-413 μιηοΐ / g.

[0110] The catalyst can be obtained by in-situ crystallization of a molecular sieve on the magnesium- and / or vanadium-reactive metal-containing aluminosilicate composite material described in the first aspect of the present invention, preferably the molecular sieve is an X-type molecular sieve, a Y-type molecular sieve, or an A-type molecular sieve, more preferably the molecular sieve is a Y-type molecular sieve.

[0111] There is one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively, in the pore size distribution curve of the catalyst.

[0112] According to a preferred embodiment of the second aspect of the present invention, the catalyst is obtained by in-situ crystallization of a molecular sieve on the magnesium- and / or vanadium-reactive metal-containing aluminosilicate composite material described in the first aspect of the present invention, the obtained molecular sieve is a NaY-type molecular sieve. The catalyst comprises, on an elemental basis, 100 wt% of the total weight of the catalyst:

[0113] 58-65wt%, such as 60.5-62.7wt%, or 60-62.7wt% silicon (as Si02);

[0114] 21-28wt%, such as 23.5-26.5wt%, or 23.5-26.6wt% aluminium (as AI2O3);

[0115] 0.3-5.5wt% magnesium (as MgO), and / or 0.2-10wt%, such as 0.3-8wt%, or 1-8wt%, or 0.3-5.5wt%, or 0.5-5.2wt%, or 0.7-3.9wt% vanadium reactive metal (as oxide);

[0116] 5-15wt%, or 7-11wt%, or 8-11.5wt%, or 8-10.88wt% sodium (as Na20);

[0117] Optionally, 0.3-1.1wt%, such as 0.35-1wt%, or 0.4-1wt%, or 0.6-1wt%, or 0.4-0.95wt%, or 0.51-0.92wt% titanium (as Ti02).

[0118] In the catalyst, there is a complex salt of magnesium and aluminium present in the form of MgAI2O4 (if the magnesium as MgO is in the above range), and optionally, the content of MgAI2O4 is 0.75-15wt%, such as 1.2-13wt%, such as 1.24-12.85wt%, based on 100wt% of the total weight of the catalyst, and / or in the catalyst, there is a complex salt of vanadium reactive metal and aluminium present in the form of metal oxide (if the vanadium reactive metal as oxide is in the above range), and optionally, the content of the complex salt of vanadium reactive metal and aluminium is 0.75-15wt%, such as 0.75-7.5wt%, or 0.76-3.33wt%, based on 100wt% of the total weight of the catalyst.

[0119] The catalyst can have at least one, preferably all of the following characteristics:

[0120] (1) attrition index = 0.5-3.0% / h, such as 0.7-2.2% / h, or 0.8-2.1% / h, or 1.0-3.0% / h, or 1.8-2.1% / h, or 0.5-2.0% / h, or 1.0-3.0% / h, or 0.6-1.5% / h, or 0.8-1.1% / h, or 1.5-2.2% / h;

[0121] (2) specific surface area = 400-1000m2 / g, such as 400-800 m 2 / g, or 450-700 m 2 / g, or 600-970 m 2 / g, or 600-960 m 2 / g, or 630-960 m 2 / g, or 640-955 m 2 / g, or 600-750 m 2 / g, or 600-860 m 2 / g, or 611.9-851.3 m 2 / g, or 730-860 m 2 / g, or 720-840 m 2 / g, or 650-850 m 2 / g, or 732.6-851.3 m 2 / g, or 611.9-737.8 m 2 / g;

[0122] (3) Pore Volume = 0.2-0.6 mL / g, such as 0.2-0.55 mL / g, or 0.25-0.55 mL / g, 0.25-0.5 mL / g, or 0.3-0.6 mL / g, or 0.3-0.5 mL / g, or 0.4-0.5 mL / g, or 0.41-0.46 mL / g, or 0.41-0.44 mL / g, or 0.38-0.48 mL / g;

[0123] (4) Crystallinity = 55-90%, such as 60-90%, or 60-78%, or 60-75%, or 60-67%, or 61-75%, or 65-75%;

[0124] (5) Unit Cell Parameter = 2.454-2.473 nm, such as 2.457-2.470 nm, or 2.460-2.467 nm, or 2.460-2.466 nm, or 2.461-2.467 nm, or 2.463-2.467 nm.

[0125] Still further, the catalyst further has at least one, and preferably all, of the following characteristics:

[0126] (6) Framework silica-to-alumina ratio (molar ratio of Si02 / Al203) = 2.0-7.0, such as 3.0-6.7, or 4.0-6.3, or 4.8-6.3, or 2.0-6.0, or 5.0-6.2, or 5.0-6.1, or 5.1-6.1, or 5.0-6.0;

[0127] (7) porosity = 3-30%, such as 3-20%, or 5-20%, or 5-12%, or 8-20%, or 9.2-19.4%, or 9.1-18.5%, or 9.2-18.2%, or 9.8-18.2%, or 9.4-19.4%, or 9.0-19.5%;

[0128] (8) meso-macroporosity = 20-40%, such as 25-37%, or 25-36%, or 25-35%, or 26-36%, or 25.1-34.2%, or 25.1-35.9%, or 25.1-36%, or 25.1-37.2%, or 25.7-36.2%, or 25.7-35.9%, or 26-37.9%, or 26.8-35.5%.

[0129] According to another preferred embodiment of the second aspect of the application, the catalyst is obtained by crystallization in situ of a molecular sieve on the magnesium- and / or vanadium- reactive metal containing aluminosilicate composite material described in the first aspect of the application and by modification with rare earths, the obtained molecular sieve being a REY type molecular sieve.

[0130] The catalyst comprises, in terms of total weight of the catalyst, 100 wt%, elements

[0131] 55-68 wt%, such as 56-67 wt%, or 58-65 wt%, or 59-67 wt%, or 60-64 wt%, or 60.04-63.61 wt% of silicon (as Si02);

[0132] 21-28 wt%, such as 21-26 wt%, or 23-27 wt%, or 21.22-25.58 wt% of aluminum (as Al203);

[0133] 0.3-5.5 wt%, such as 0.3-5 wt%, or 0.38-4.95 wt% of magnesium (as MgO), and / or 0.3-8 wt%, or 0.3-5.5 wt%, or 0.5-5.2 wt%, or 1-8 wt%, or 0.84-3.95 w% of vanadium reactive metal (as oxide);

[0134] Optionally, 0.3-1 wt%, such as 0.35-0.95 wt%, or 0.40-0.91 wt%, or 0.6-0.91 wt% of titanium (as Ti02);

[0135] Optionally, 0.01-2 wt%, such as 0.1-0.3 wt%, or 0.12-0.26 wt% of sodium (as Na20);

[0136] 6-15 wt%, such as 9-12 wt%, or 9.01-11.98 wt% of rare earth (or exchanged rare earth, calculated as rare earth oxide RE2O3).

[0137] For example, rare earth elements are one or more of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y), and scandium (Sc). Preferably, rare earth elements are one or more of yttrium, lanthanum, cerium, praseodymium, and neodymium. More preferably, rare earth elements are one or more of La, Ce, and Y. For example, rare earth oxides are one or more of La2O3, CeO2, and Y2O3.

[0138] The catalyst contains a complex salt of magnesium and aluminum in the form of MgAl2O4 (if the magnesium content, calculated as MgO, is within the above range), and optionally, the content of MgAl2O4 is 0.75-15 wt%, such as 0.9-12.5 wt%, or 0.94-12.23 wt%, based on 100 wt% of the total weight of the catalyst, and / or the catalyst contains a complex salt of vanadium reactive metal and aluminum in the form of metal oxides (if the vanadium reactive metal, calculated as oxide, is within the above range), and optionally, the content of the complex salt of vanadium reactive metal and aluminum is 0.75-15 wt%, such as 0.75-7.5 wt%, or 0.77-3.35 wt%, based on 100 wt% of the total weight of the catalyst.

[0139] Preferably, the catalyst has at least one of the following characteristics, and preferably all of the following characteristics:

[0140] (1) Wear index = 0.5-3.0% / h, such as 0.7-2.2% / h, or 0.8-2.1% / h, or 1.0-3.0% / h, or 1.8-2.1% / h, or 0.5-2.0% / h, or 1.0-3.0% / h, or 0.6-1.5% / h, or 0.8-1.1% / h, or 1.5-2.2% / h;

[0141] (2) Specific surface area = 400 - 1000 m² 2 / g, such as 400-800m 2 / g, or 450-700m 2 / g, or 600-970m 2 / g, or 600-960m 2 / g, or 630-960m 2 / g, or 640-955m 2 / g, or 600-750m2 / g, or 600-860 m 2 / g, or 611.9-851.3 m 2 / g, or 730-860 m 2 / g, or 720-840 m 2 / g, or 650-850 m 2 / g, or 732.6-851.3 m 2 / g, or 611.9-737.8 m 2 / g;

[0142] (3) Pore Volume = 0.2-0.6 mL / g, such as 0.2-0.55 mL / g, or 0.25-0.55 mL / g, 0.25-0.5 mL / g, or 0.3-0.6 mL / g, or 0.3-0.5 mL / g, or 0.4-0.5 mL / g, or 0.41-0.46 mL / g, or 0.41-0.44 mL / g, or 0.38-0.48 mL / g;

[0143] (4) Crystallinity = 55-90%, such as 60-90%, or 60-78%, or 60-75%, or 60-67%, or 61-75%, or 65-75%;

[0144] (5) Unit Cell Parameter = 2.454-2.473 nm, such as 2.457-2.470 nm, or 2.460-2.467 nm, or 2.460-2.466 nm, or 2.461-2.467 nm, or 2.463-2.467 nm.

[0145] Still further, the catalyst further has at least one, and preferably all, of the following characteristics:

[0146] (6) Framework silica-to-alumina ratio (molar ratio of Si02 / Al203) = 2.0-7.0, such as 3.0-6.7, or 4.0-6.3, or 4.8-6.3, or 2.0-6.0, or 5.0-6.2, or 5.0-6.1, or 5.1-6.1, or 5.0-6.0;

[0147] (7) Pore Volume = 0.2-0.6 mL / g, such as 0.2-0.55 mL / g, or 0.25-0.55 mL / g, 0.25-0.5 mL / g, or 0.3-0.6 mL / g, or 0.3-0.5 mL / g, or 0.4-0.5 mL / g, or 0.41-0.46 mL / g, or 0.41-0.44 mL / g, or 0.38-0.48 mL / g;

[0148] (8) mesopore volume = 20-40%, such as 25-37%, or 25-36%, or 25-35%, or 26-36%, or 25.1-34.2%, or 25.1-35.9%, or 25.1-36%, or 25.1-37.2%, or 25.7-36.2%, or 25.7-35.9%, or 26-37.9%, or 26.8-35.5%;

[0149] (9) trimethylpyridine acidity = 100-500 μmol / g, such as 280-411 μmol / g, or 250-450 μmol / g, or 280-420 μmol / g, or 280-413 μmol / g.

[0150] In a third aspect of the present application, the present application provides a calcined aluminosilicate material (also referred to herein as "activated kaolin"). The calcined aluminosilicate material is obtained by calcining particles of a kaolinite-rich and carbonaceous mineral at a temperature in the range of 400-920°C, such as 450-900°C, further such as 500-800°C, the particles having a particle size in the range of 0.1-3.0 microns, such as 0.1-2.5 microns, further such as 0.5-2.0 microns.

[0151] In a fourth aspect of the present application, the present application provides a method of preparing the magnesium-containing and / or vanadium-containing reactive metal aluminosilicate composite material of the first aspect of the present application, comprising the steps of:

[0152] (1) washing, crushing and grinding a kaolinite-rich and carbonaceous mineral, sieving out a fraction having a particle size in the range of 0.1-3.0 microns, such as 0.1-2.5 microns, further such as 0.5-2.0 microns, and calcining the fraction at a temperature in the range of 400-920°C, such as 450-900°C, further such as 500-890°C or 500-800°C, for a period of 1-8 hours, such as 2-8 hours, 1.5-6 hours, further such as 1.8-5.1 hours or 2-4 hours, to obtain a calcined aluminosilicate material;

[0153] (2) the calcined aluminosilicate material, a binder, a modifier, and water are slurried together to form a slurry, and the slurry is high pressure (e.g., 1-10 MPa, preferably 3-7 MPa absolute pressure) spray formed to form the magnesium-containing and / or vanadium reactive metal-containing aluminosilicate composite material. The binder can be one or more of water glass, sodium silicate, sodium pyrophosphate, silica sol, alumina sol, silica-alumina gel, silica-alumina sol, phospho-alumina gel, phospho-alumina sol, and acid-activated pseudoboehmite. The modifier can be one or more of magnesium nitrate, basic magnesium carbonate, magnesium carbonate; and / or a precursor of a vanadium reactive metal oxide, such as one or more of a vanadium reactive metal nitrate, a vanadium reactive metal basic carbonate, a vanadium reactive metal carbonate. The binder can be added in an amount (as oxide) of 2-20 wt% of the total mass (dry basis) of the kaolin clay (i.e., the calcined aluminosilicate material or calcined kaolin clay). The modifier can be added in an amount (as oxide) of 0.1-15 wt%, or 0.1-10 wt%, such as 0.5-15 wt%, or 0.5-8 wt%, such as 0.5-8 wt%, or 1-8 wt% of the total mass (dry basis) of the kaolin clay (calcined aluminosilicate material or calcined kaolin clay). The amount of water added is not particularly limited in the present application, as long as the slurry obtained is suitable for high pressure spray forming.

[0154] The calcined aluminosilicate material described in the third and fourth aspects of the present application has the following properties:

[0155] a BET specific surface area of 35-56 m 2 / g, such as 40-50 m 2 / g, or 42-49 m 2 / g, or 44-48 m 2 / g;

[0156] a total pore volume of 0.04-0.08 cc / g, such as 0.05-0.07 cc / g;

[0157] a particle size of 0.1-3.0 microns;

[0158] a content of tetrahedrally and pentahedrally coordinated Al2O3 of 25-90 wt%, such as 40-80 wt%, or 50-80 wt%, or 40.1-76.2 wt%, or 41.1-75.2 wt%, based on the Al2O3 in the calcined aluminosilicate material;

[0159] a content of Q 4SiO2in the (0Al) structure in an amount of 30-95 wt%, such as 40-90 wt%, or 41.3-80.0 wt%, or 41.3-80.1 wt%, or 55-75 wt%;

[0160] Optionally, Na in an amount of 0.01-0.4 wt% as Na2O, such as 0.02-0.4 wt%, or 0.024-0.308 wt%;

[0161] Optionally, K in an amount of 0.02-0.4 wt% as K2O, such as 0.04-0.2 wt%, or 0.0537-0.154 wt%;

[0162] Optionally, the sum of Na and K in an amount of not more than 0.5 wt% as Na2O and as K2O, such as 0.06-0.5 wt%, or 0.0935-0.46 wt%;

[0163] Optionally, Mg in an amount of 0.015-0.5 wt% as MgO, such as 0.05-0.15 wt%, or 0.078-0.106 wt%;

[0164] Al in an amount of 30-60 wt% as Al2O3, such as 40-50 wt%, or 45.5-46.6 wt%;

[0165] Si in an amount of 30-60 wt% as SiO2, such as 45-55 wt%, or 49.7-52 wt%;

[0166] Optionally, Ca in an amount of 0.03-1.5 wt% as CaO, such as 0.1-0.4 wt%, or 0.158-0.288 wt%;

[0167] Optionally, Ti in an amount of 0.5-5 wt% as TiO2, such as 0.6-2 wt%, or 0.799-1.34 wt%;

[0168] Optionally, Fe in an amount of 0.05-1.2 wt% as Fe2O3, such as 0.15-0.8 wt%, or 0.211-0.578 wt%.

[0169] The kaolinite-rich and carbon-containing mineral matter described in the third and fourth aspects of the application includes, but is not limited to, kaolin, fireclay, and coal gangue.

[0170] According to the present application, the kaolinite-rich and carbon-containing mineral substance (based on its total weight of 100 wt%) has the following properties: a kaolinite content higher than 50 wt%, such as higher than 60 wt%, or higher than 70 wt%, or higher than 80 wt%; a carbon content of 0.5-20 wt%, such as 0.7-14 wt%, or 0.5-10 wt%, or 1.0-8.0 wt%; optionally, a titanium dioxide content of 0.1-3.0 wt%, such as 0.5-2.0 wt%, or 0.7-1.5 wt%; optionally, an iron oxide content of 0.05-3.0 wt%, such as 0.2-1.0 wt%; optionally, a sum of sodium oxide and potassium oxide content of 0.01-0.5 wt%.

[0171] Preferably, the kaolinite-rich and carbon-containing mineral substance is a coal gangue having one or more or all of the following properties:

[0172] based on 100 wt% of the coal gangue before ignition,

[0173] a kaolinite content higher than 80 wt%;

[0174] a carbon content of 0.5-15 wt%, such as 0.8-9.2 wt%;

[0175] a BET specific surface of 15-33 m 2 / g, such as 19-26 m 2 / g;

[0176] a total pore volume of 0.08-0.15 cc / g, such as 0.09-0.12 cc / g, or 0.098-0.116 cc / g;

[0177] a quartz sand content of 0.5-3 wt%, such as 0.9-2 wt%;

[0178] optionally, based on 100 wt% of the coal gangue after ignition, the coal gangue after ignition has:

[0179] a Na content of 0.01-0.4 wt% as Na2O, such as 0.02-0.4 wt%, or 0.024-0.308 wt%; and / or

[0180] a K content of 0.02-0.4 wt% as K2O, such as 0.04-0.2 wt%, or 0.0537-0.154 wt%; and / or

[0181] a sum of Na and K content of not more than 0.5 wt% as Na2O and as K2O, such as 0.06-0.5 wt%, or 0.0935-0.46 wt%; and / or

[0182] Mg, in terms of MgO, is present in an amount of 0.015-0.5 wt%, such as 0.05-0.15 wt%, or 0.078-0.106 wt%; and / or

[0183] Al, in terms of Al2O3, is present in an amount of 30-60 wt%, such as 40-50 wt%, or 45.5-46.6 wt%; and / or

[0184] Si, in terms of SiO2, is present in an amount of 30-60 wt%, such as 45-55 wt%, or 49.7-52 wt%; and / or

[0185] Ca, in terms of CaO, is present in an amount of 0.03-1.5 wt%, such as 0.1-0.4 wt%, or 0.158-0.288 wt%; and / or

[0186] Ti, in terms of TiO2, is present in an amount of 0.5-5 wt%, such as 0.6-2 wt%, or 0.799-1.34 wt%; and / or

[0187] Fe, in terms of Fe2O3, is present in an amount of 0.05-1.2 wt%, such as 0.15-0.8 wt%, or 0.211-0.578 wt%.

[0188] In a fifth aspect of the present application, the present application provides a method for preparing the catalyst described in the second aspect of the present application, which comprises the steps (1) and (2) in the method described in the fourth aspect of the present application and further comprises (3) mixing the magnesium-containing and / or vanadium-containing reactive metal aluminosilicate composite material obtained in step (2) with a silicon source, an alkali source, a directing agent, and water, and then performing in-situ hydrothermal crystallization to obtain a catalyst containing a Na-type molecular sieve (e.g., a catalyst containing a NaY-type molecular sieve); and optionally, (4) filtering, washing, and exchanging, drying and calcining the catalyst containing a Na-type molecular sieve (e.g., a catalyst containing a NaY-type molecular sieve) to obtain a catalyst containing a rare earth modified molecular sieve (e.g., a catalyst containing a rare earth modified Y-type molecular sieve such as a REY molecular sieve). The exchanging includes, for example, rare earth exchange and / or ammonium salt exchange and / or phosphorus exchange, for example, performing rare earth exchange and optional ammonium salt exchange and / or phosphorus exchange.

[0189] In the preparation of the catalyst containing a Na-type molecular sieve (e.g., a NaY-type molecular sieve), the yield of fine powder having a particle size of not more than 20 μm is not more than 10 wt%, such as 1-10 wt%, or 2-9 wt%.

[0190] The catalyst containing NaY-type molecular sieve and the catalyst containing rare earth modified Y-type molecular sieve of the present application have the following properties: crystallinity > 60%; unit cell parameter = 2.454-2.473 nm, such as 2.457-2.470 nm, or 2.460-2.467 nm, or 2.460-2.466 nm, or 2.461-2.467 nm, or 2.463-2.467 nm; relative crystalline retention after 17 hours aging at 800°C, 1 atm pressure and 100% water vapor atmosphere is 30%-50%.

[0191] In step (3), the conditions of the hydrothermal crystallization include: temperature is 80-105°C, such as 85-105°C; time is 1-160 hours, such as 8-80 hours.

[0192] In step (3), the weight ratio of the silicon source (calculated as SiO2) to the magnesium-containing and / or vanadium-containing reactive metal-containing aluminosilicate composite material (calculated as dry basis) is (0.1-10):1, (0.3-3):1, (0.6-2.5):1; the weight ratio of the alkali source (calculated as MB2O, MB represents alkali metal) to the magnesium-containing and / or vanadium-containing reactive metal-containing aluminosilicate composite material (calculated as dry basis) is (0.01-1):1, (0.04-0.7):1, or (0.07-0.4):1; the weight ratio of the directing agent (calculated as Al2O3) to the magnesium-containing and / or vanadium-containing reactive metal-containing aluminosilicate composite material (calculated as dry basis) is (0.001-2):1, (0.003-0.1):1, (0.005-0.05):1; and the weight ratio of water to the magnesium-containing and / or vanadium-containing reactive metal-containing aluminosilicate composite material (calculated as dry basis) is (3-100):1, (5-65):1, (7-30):1.

[0193] In step (3), the directing agent can be obtained by aging sodium silicate, sodium aluminate and sodium hydroxide and water in a molar ratio of (11-16) Na2O·Al2O3·(10-16) SiO2·(100-350) H2O at room temperature to 70°C for 5-50 hours.

[0194] In step (3), the silicon source can be one or more of water glass, sodium silicate, silica gel and organosilicon. The alkali source can be sodium hydroxide and / or potassium hydroxide, for example.

[0195] In step (4), the conditions of the exchange include: adjusting pH = 2-6 with acid, and performing the exchange at 50-95°C. The acid can be one or more of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid.

[0196] The exchange can be rare earth exchange and / or ammonium exchange and / or phosphorus exchange. Preferably, the exchange comprises rare earth exchange and optional ammonium salt exchange and / or phosphorus exchange, to obtain a catalyst comprising a rare earth modified molecular sieve (e.g. a catalyst comprising a rare earth modified Y-type molecular sieve).

[0197] In step (4), the temperature of calcination is 500-950°C, for example 650-800°C; the time of calcination is 1-8 hours, for example 2-4 hours; the temperature of drying is 120-400°C, for example 150-200°C; the time of calcination is 1-8 hours, for example 2-4 hours.

[0198] In step (4), the exchange can be carried out 1-3 times, the calcination can be carried out 1-3 times, and the drying can be carried out 1-3 times, and after the exchange, the drying and / or calcination is carried out, if drying, the drying is carried out first, then the calcination is carried out; or only the calcination is carried out, without drying; or only the drying is carried out, without calcination; if there is no drying, the calcination is carried out directly;

[0199] The rare earth exchange, the ammonium salt exchange, and the phosphorus exchange can be carried out by conventional methods known in the art, and the present application is not particularly limited thereto.

[0200] In step (4), in the rare earth exchange, the rare earth can be one or more of nitrate, chloride, and hydroxide of the rare earth, and the rare earth is one or more of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y), and scandium (Sc), preferably, the rare earth is one or more of yttrium, lanthanum, cerium, praseodymium, and neodymium, more preferably, one or more of La, Ce, and Y;

[0201] In the ammonium salt exchange, the ammonium salt used is one or more of ammonium sulfate, ammonium chloride, ammonium nitrate, and ammonium phosphate.

[0202] In the phosphorus exchange, a phosphorus-containing compound is used. The phosphorus-containing compound can be phosphorous inorganic acid, salts of phosphorous inorganic acid, and mixtures thereof, for example, phosphorous acid (H3PO3), phosphoric acid (H3PO4), phosphite, phosphate, and mixtures thereof. Although any soluble salt (such as alkali metal salt and ammonium salt) of phosphorous acid and phosphoric acid can be used, the use of ammonium salt is preferred because the use of alkali metal salt requires the subsequent removal of alkali metal from the catalyst.

[0203] The sequence of the ammonium salt exchange, the phosphorus exchange, and the rare earth exchange is generally ammonium exchange first, then phosphorus exchange, and finally rare earth exchange.

[0204] Optionally but preferably, the method for preparing the catalyst further comprises a step of gas phase ultra-stabilization and / or hydrothermal ultra-stabilization. The method for gas phase ultra-stabilization and / or hydrothermal ultra-stabilization is well known to those skilled in the art.

[0205] In the present application, the rare earths can exist in at least two kinds, one of which is a rare earth as a vanadium reactive metal, which reacts with vanadium to form a rare earth vanadate compound to fix vanadium and avoid the reaction of vanadium with aluminum in the molecular sieve and the matrix to destroy the framework structure of the molecular sieve and the matrix structure. The other is an exchange rare earth, which enters the cage of the molecular sieve by exchange of rare earth to stabilize the framework structure of the molecular sieve and improve the hydrothermal stability of the molecular sieve.

[0206] According to the present application, the content of the rare earths (or the content of the exchange rare earths) refers to the content of the rare earths other than the rare earth as a vanadium reactive metal. The content of the rare earth as a vanadium reactive metal is included in the vanadium reactive metal, and the rare earth introduced before crystallization is as a vanadium reactive metal.

[0207] In the sixth aspect of the present application, the present application provides an application of the catalyst described in the second aspect of the present application in the production of light oil from heavy oil catalytic cracking. In the process of producing light oil from heavy oil catalytic cracking using the catalyst of the present application, the heavy oil is contacted with the catalyst for reaction, the reaction temperature is 450-550℃; the weight hourly space velocity is 5-30 hours-1; the catalyst to oil ratio is 1-15 (weight ratio); and the heavy oil is one or more of atmospheric residue, atmospheric gas oil, vacuum residue, vacuum gas oil, coking wax oil, light heavy deasphalted oil, hydrogenated LCO, hydrogenated cracking tail oil, hydrogenated VGO, hydrogenated residue, and intermediate base crude oil. -1

[0208] In the present application, the carbon content of the kaolinite-rich and carbon-containing mineral (such as coal gangue) refers to the fixed carbon content, which can be determined according to GB / T 212-2008 Coal Industrial Analysis Method.

[0209] In the present application, the elemental content of the aluminosilicate and the catalyst is determined by X-ray fluorescence spectrometry.

[0210] ​The unit cell constant, relative crystallinity: unit cell constant, relative crystallinity in the present application are determined by X-ray powder diffraction method (XRD) using RIPP 145-90, RIPP 146-90 standard method (see "Petroleum and Chemical Industry Analysis Method" (RIPP Test Method) Yang Cuiding et al. ed., Science Press, 1990). The framework silicon aluminum ratio of the zeolite is calculated by the following formula: SiO2 / Al2O3=(2.5858-a0)×2 / (a0-2.4191) wherein, a0 is the unit cell constant (or unit cell parameter), unit: nm; the total silicon aluminum ratio of the zeolite is calculated according to the Si and Al element content determined by X-ray fluorescence spectrometry. The relative crystallinity in the present application is determined by taking RIPP 146-90 external standard as the reference, and the determination method of the relative crystallinity is described in RIPP 146-90 method in "Petroleum and Chemical Industry Analysis Method" (RIPP Test Method) (Yang Cuiding et al. ed., Science Press, 1990).

[0211] The measurement method of the content of four-coordinated and five-coordinated Al2O3 in the present application: using Bruker AVANCE III 600MHz resonator for determination, using 4mm ZrO2 rotor, rotation speed is 12kHz, pulse width is 0.51μs, sampling number is 5000. 27 Al NMR spectrum, wherein the integral area of each coordinated aluminum element is calculated (for example, using MATLAB software), and then the content of four and five coordinated aluminum is calculated.

[0212] Q 4 The measurement method of the content of SiO2 with (0Al) structure: Si coordination environment analysis is characterized by Si solid nuclear magnetic, Bruker AVANCE III 500MHz resonator is used for determination, using 7mm ZrO2 rotor, rotation speed is 5kHz, pulse width is 2.03μs, sampling number is 3000, 29 The resonance peaks of Si spectrum appearing at -90.56ppm, -104.3ppm, -110.98ppm correspond to Si(4Al), Si(1Al) and Si(0Al) coordination environment respectively. The mass fraction or molar fraction is calculated by the resonance peak appearing at -110.98ppm / total peak area.

[0213] The catalyst porosity in the present application: the porosity of the catalyst is tested by μ-CT, the image is collected by using Brook microCT system (SkyScan 1172), the X-ray focal spot size (nominal) used is 35 μm, the energy is 50 kV, and the working current is 370 μA. The exposure time is 700 milliseconds. The image pixel size is 0.20 microns. When measuring, the microspheres with a diameter of about 70 μm are randomly selected. The microspheres with a diameter of about 70 microns are measured. The continuously acquired tomographic data are used to observe and analyze the size, structure and distribution of the pores / channels inside the microspherical catalyst. About 460 μ-CT tomographic images are subjected to image reconstruction and data processing using NRecon Server (version 1.7.3.0; Brook, Billerica, MA) and CT Analyzer (version 1.13; Brook, Billerica, MA).

[0214] The determination method of the pore structure is as follows: according to the standard method of RIPP 151-90 “Petroleum and Chemical Industry Analysis Method (RIPP Test Method)” (Yang Cuiding et al., Science Press, published in 1990), the total pore volume of the molecular sieve is determined according to the adsorption isotherm, then the micropore volume of the molecular sieve is determined according to the T plotting method according to the adsorption isotherm, and the secondary pore volume is obtained by subtracting the micropore volume from the total pore volume. The mesopore specific surface area and the specific surface area (total specific surface area), pore volume and pore size distribution are measured by low-temperature nitrogen adsorption capacity method, using an ASAP2420 adsorber of Micromeritics Company of the United States, the sample is vacuum degassed at 100°C and 300°C for 0.5h and 6h respectively, and N2 adsorption-desorption test is carried out at 77.4K temperature. The adsorption and desorption amounts of nitrogen under different specific pressure conditions are obtained, and the N2 adsorption-desorption isotherm curve is obtained. The BET specific surface area (total specific surface area) is calculated by using the BET formula, and the micropore area is calculated by t-plot.

[0215] The catalyst acidity is determined by infrared method of 2,4,6-trimethylpyridine adsorption.

[0216] 2,4,6-trimethylpyridine test instrument: CPCP-7070-B infrared in-situ transient analysis platform (Tianjin Xianquan Trade Development Co., Ltd.), infrared model: BRUKER (Bruker) TENSOR II, sample mass: 5 mg, tablet diameter: 7 mm, resolution: 4 cm -1 , scanning time: 32 Scans, experimental process:

[0217] 1, sample tablet, 350°C treatment for 30 minutes under high vacuum (pressure is 5.4×10 -6 mbar),

[0218] 2, drop to room temperature, adsorb pyridine for 30 minutes,

[0219] 3. Vacuum (6.3 x 10 -6 mbar) desorption for 10 minutes,

[0220] 4. Temperature increase to 200°C desorption for 30 minutes, determination of total acid amount.

[0221] The sphericity in the present application: the sphericity is expressed by sphericity index SPHT, which refers to the ratio of the surface area of a sphere with the same volume as the object and the surface area of the object. The sphericity calculation formula is as follows: sphericity index SPHT = 4πA 2 / P 2 wherein A is the projected area of the particle, and P is the projected perimeter of the particle. The sphericity of the catalytic cracking catalyst is tested by using the Camsizer XT dynamic digital imaging particle analyzer of Germany Leici Company, two digital camera lens reference lenses CCD-B and focusing lenses CCD-Z are used, and the falling sample particles are shot at a shooting speed of 300 pictures per second. Through software analysis, the particle images captured by the two lenses are statistically calculated to obtain the sphericity index SPHT of the sample.

[0222] The particle size is determined by the laser particle size analyzer method according to Q / SYLS 0519 (2002).

[0223] The MgAl2O4 content is calculated by XRD phase peak area (instrument: Empyrean. Test conditions: tube voltage 40 kV, tube current 40 mA, Cu target Kα radiation, 2θ scanning range 5°-70°, scanning rate 2(°) / min. Peak position is 39.2°, 31.6°, 56.4°). Other metal-aluminum composite salts are also calculated by XRD phase peak area.

[0224] In the present application, the rare earth metal refers to scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

[0225] When the vanadium reactive metal comprises rare earth, the catalyst comprises rare earth in the molecular sieve cell (referred to as exchanged rare earth) and / or rare earth as a vanadium reactive metal outside the molecular sieve crystal grain, the amount of rare earth as a vanadium reactive metal can be measured by XRD method, and the content of rare earth oxide is calculated by peak area (instrument: Empyrean. Test conditions: tube voltage 40 kV, tube current 40 mA, Cu target Kα radiation, 2θ scanning range 5°-70°, scanning speed 2(°) / min. Peak position is 39.2°, 31.6°, 56.4°). The total mass fraction of rare earth oxide is measured by X-ray fluorescence method (NB / SH / T 0950-2017 Determination of lanthanum oxide and cerium oxide content in catalytic cracking catalyst - X-ray fluorescence spectrometry, Japanese science ZSX fluorescence analyzer, voltage 50 kV, rhodium target, LiF 200 crystal, current 50 mA), the mass fraction of exchanged rare earth is equal to the total mass fraction of rare earth oxide minus the mass fraction of rare earth as a vanadium reactive metal.

[0226] The attrition index in the present application: the attrition index is obtained according to NB / SH / T0943-2017 "Determination of attrition performance of FCC catalysts - air jet method".

[0227] The measurement method of the parameters mentioned in the present application can also be determined with reference to "Petroleum and Chemical Analysis Methods (RIPP Test Methods)" (Yang Cuiding et al., Science Press, published in 1990), as well as various industry standards such as Q / SYLS 0518 / 0519 / 0520 / 0521 / 0568 / 0573 / 0580 / 0586 / 0589 / 0596 / 0600 / 0641.

[0228] Examples

[0229] The present application will be further illustrated by the following examples, but the present application is not limited in any way by the following examples.

[0230] If not specified, the specifications of the chemical reagents used are chemically pure.

[0231] Carbon-containing kaolin is provided by Shanxi Shuozhou Jinkun Mining Co., Ltd. The properties of the carbon-containing kaolin used in the examples are shown in Table 1 below, wherein the elemental analysis is carried out after calcination according to the method recommended in GB / T 35986-2018 "Determination of loss on ignition of coal gangue", except that 1 kg of sample is calcined in a muffle furnace for 4 hours, with the maximum temperature controlled at about 600°C.

[0232] Common kaolin is Suzhou kaolin produced by China Kaolin Co., Ltd., and its properties are shown in Table 1 below.

[0233] Water glass: produced by Zichuan Catalyst Factory of Qilu Petrochemical Company, SiO2 mass fraction: 20.01%, Na2O mass fraction: 6.32%;

[0234] Alkaline liquor: aqueous solution of NaOH, Na2O content 40wt%;

[0235] Silica sol: acidic silica sol produced by Beijing Chemical Factory, pH value 3.0, SiO2 mass fraction 15.66wt%, Na2O mass fraction 0.58wt%;

[0236] Alumina sol: produced by Qilu Branch of Sinopec Catalyst Co., Ltd., Al2O3 mass fraction 19.4wt%;

[0237] Pseudo-boehmite: produced by Shandong Aluminum Factory, Al2O3 content 68.3wt%.

[0238] Table 1: Properties of kaolin as raw material

[0239] (I) Preparation examples and comparative preparation examples of reactive microspheres

[0240] Preparation examples 1.1-1.10: Preparation of reactive microspheres MB-1 to MB-10 of the present application

[0241] The carbon-containing kaolin as raw material (see Table 1) was washed with water, crushed and ground, and the fraction having a particle size of 0.1-3.0 microns was sieved by two-stage separation of cyclone and cloth bag. The obtained kaolin having a particle size of 0.1-3.0 microns was calcined at a temperature of about 400 to about 900°C for 1-8 hours according to the conditions of Table 2 to produce activated kaolin (designated as activated kaolin Q1-Q5, properties see Table 2). The activated kaolin, a binder (for example, water glass, silica sol and / or alumina sol), a magnesium salt or a vanadium reactive metal salt, and water were mixed and then spray-dried to obtain reactive microspheres MB-1 to MB-10 having a particle size of 20-150 microns, i.e., magnesium-containing silicoaluminate composite materials of the present application (see Table 3A) or vanadium reactive metal-containing silicoaluminate composite materials of the present application (see Table 3B).

[0242] Table 2: Properties of activated kaolin

[0243] Table 3A

[0244] Table 3B

[0245] Comparative preparation example 1.1: Preparation of comparative reactive microspheres CMB-1

[0246] Comparative Preparation Example 1.1 was conducted according to the procedure of the above preparation example, except that the calcination was conducted after the forming (including mixing and spray drying) rather than before. Specifically, the carbon-containing kaolin clay was washed with water, broken up and ground, and the portion having a particle size of 0.1-3.0 microns was separated by two stages of separation, cyclone and baghouse. The resulting kaolin clay having a particle size of 0.1-3.0 microns, binder, magnesium salt and water were mixed and spray dried to form microspheres having a particle size of 20-150 microns. The resulting microspheres were calcined according to the conditions of Table 3C to form reactive microspheres CMB-1, a comparative silicoaluminate composite material.

[0247] Comparative Preparation Example 1.2: Preparation of Comparative Reactive Microspheres CMB-2

[0248] Comparative Preparation Example 1.2 was conducted according to the procedure of the above preparation example, except that the carbon-containing kaolin clay was replaced with ordinary kaolin clay having a carbon content of zero.

[0249] Comparative Preparation Example 1.3: Preparation of Comparative Reactive Microspheres CMB-3

[0250] Comparative Preparation Example 1.3 was conducted according to the procedure of the above preparation example, except that the slurry for spray forming did not contain the magnesium salt.

[0251] Comparative Preparation Example 1.4: Preparation of Comparative Reactive Microspheres CMB-4

[0252] Comparative Preparation Example 1.4 was conducted according to the procedure of the above preparation example, except that after the carbon-containing kaolin clay was washed with water, broken up and ground, the portion having a particle size of about 5-10 microns was separated. The resulting kaolin clay having a particle size of about 5-10 microns was calcined at a temperature of about 400 to about 900°C for 1-8 hours according to the conditions of Table 3C to form activated kaolin clay. The activated kaolin clay, silica sol, magnesium salt and water were mixed and spray dried to form reactive microspheres CMB-4, a comparative silicoaluminate composite material, having a particle size of about 20-150 microns.

[0253] Table 3C

[0254] Comparative Preparation Example 1.5: Preparation of Comparative Reactive Microspheres CMB-5

[0255] Comparative Preparation Example 1.5 was conducted according to the method of the above preparation examples, except that the calcination was conducted after the forming (including mixing and spray drying) rather than before. Specifically, the carbon-containing kaolin clay was washed with water, broken up and ground, and the portion having a particle size of 0.1-3.0 microns was screened by two stages of separation, cyclone and cloth bag. The resulting kaolin clay having a particle size of 0.1-3.0 microns, binder, vanadium reactive metal salt, and water were mixed and spray dried to form microspheres having a particle size of 20-150 microns. The resulting microspheres were calcined according to the conditions of Table 3D to form reactive microspheres CMB-5, a comparative silicoaluminate composite.

[0256] Comparative Preparation Example 1.6: Preparation of Comparative Reactive Microspheres CMB-6

[0257] Comparative Preparation Example 1.6 was conducted according to the method of the above preparation examples, except that the carbon-containing kaolin clay was replaced with ordinary kaolin clay (which has a carbon content of zero).

[0258] Comparative Preparation Example 1.7: Preparation of Comparative Reactive Microspheres CMB-7

[0259] Comparative Preparation Example 1.7 was conducted according to the method of the above preparation examples, except that the slurry for spray forming did not contain magnesium salt and vanadium reactive metal salt.

[0260] Comparative Preparation Example 1.8: Preparation of Comparative Reactive Microspheres CMB-8

[0261] Comparative Preparation Example 1.8 was conducted according to the method of the above preparation examples, except that after the carbon-containing kaolin clay was washed with water, broken up and ground, the portion having a particle size of about 5-10 microns was screened. The resulting kaolin clay having a particle size of about 5-10 microns was calcined at a temperature of about 400 to about 900°C for 1-8 hours according to the conditions of Table 3D to form activated kaolin clay. The activated kaolin clay, silica sol, vanadium reactive metal salt, and water were mixed and spray dried to form reactive microspheres CMB-8, a comparative silicoaluminate composite, having a particle size of about 20-150 microns.

[0262] Table 3D

[0263] (B) Preparation Examples and Comparative Preparation Examples of Crystallized Microspheres and Catalysts

[0264] In the following Preparation Examples and Comparative Preparation Examples of Crystallized Microspheres and Catalysts, a directing agent was prepared as follows: about 45.3 kilograms of water glass was slowly added to about 32.2 kilograms of sodium metaaluminate solution (containing 3.19 wt% Al2O3, 21.96 wt% Na2O) at 30°C under rapid stirring, stirred for 1 hour, and aged at 50°C for 48 hours to obtain the directing agent.

[0265] Preparation Example 2.1

[0266] About 40.0 g of the directing agent and about 1.0 g of the alkali liquor were mixed uniformly and allowed to stand at about 40°C for about 1.5 hours to obtain a mixture of the directing agent and the alkali liquor; about 12.0 g of the reactive microspheres MB-1 and about 2.5 g of the alkali liquor were mixed uniformly and allowed to stand at about 95°C for about 1.5 hours, then the above mixture of the directing agent and the alkali liquor, and about 46.2 g of the water glass were added, and about 23.3 g of water was added, and after mixing uniformly, the crystallization was continued for about 8 hours, and then the crystallized microspheres containing NaY-type molecular sieves were obtained by filtration, water washing, and drying, and were recorded as NaY-1. The XRD diffraction pattern of the obtained crystallized microspheres (which had diffraction peaks at 2θ angles of 6.2°, 15.6°, 20.3°, 23.6°, 26.0°, and 31.4°) and the standard NaY pattern were compared, and it was confirmed that the molecular sieves on the obtained crystallized microspheres were NaY molecular sieves. The properties of the crystallized microspheres are listed in Table 4A. In the pore size distribution curve of the crystallized microspheres, there were mesopore peaks in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm.

[0267] The above crystallized microspheres were modified by an exchange and calcination procedure to obtain a catalyst, which was recorded as REY-1. The properties of the catalyst REY-1 are listed in Table 4B. In the pore size distribution curve of the catalyst, there were mesopore peaks in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm. The pore size distribution curve of the catalyst REY-1 is shown in Figure 1.

[0268] The exchange and calcination procedure is a conventional technical means well known to those skilled in the art, and the present application does not have a particular limitation thereon. The exchange and calcination procedure, for example, includes a one-exchange-one-calcination process, a two-exchange-one-calcination process, a two-exchange-two-calcination process, a three-exchange-two-calcination process, and a three-exchange-three-calcination process. The exchange can be an ammonium salt exchange or a rare earth exchange, etc. Between the exchange and the calcination, further modification, such as phosphorus modification, can be performed. After each exchange, drying can be optionally performed. The maximum temperature used in the calcination process is usually 450°C-1100°C, for example, 500°C, 600°C, 700°C, 800°C, 900°C, 1000°C. The temperature of the drying process can be 150°C-400°C, for example, 200°C, 250°C, 300°C, 350°C.

[0269] In the present example, a three-exchange-two-calcination process was used as follows:

[0270] One-exchange-one-calcination:

[0271] (1) The crystallized microspheres containing NaY-type molecular sieves were washed with neutral water, and the obtained filter cake was slurried, and the slurry of the crystallized microspheres containing NaY-type molecular sieves was adjusted to a pH value of about 3.0-5.0 at about 25°C using a hydrochloric acid solution, and the reaction was continued for about 5-60 minutes;

[0272] (2) adding soluble rare earth salt to the slurry of the crystallized microspheres with a weight ratio of NaY type molecular sieve: rare earth oxide: H2O = about 1: about (0.01-0.25): about (5-30) to perform a first exchange, the pH of the slurry being about 3.0-4.0, maintaining the temperature at about 85-120°C, and reacting for about 60-120 minutes;

[0273] (3) filtering the slurry obtained in step (2), and washing the filter cake of the crystallized microspheres with a soluble ammonium salt having a dry mass of about 10-60% and a concentration of about 100-200 g / L, and distilled water in an amount of about 2-10 times the dry mass of the crystallized microspheres, after the slurry of the crystallized microspheres has been completely separated by filtration;

[0274] (4) calcining the filter cake of the crystallized microspheres in a two-stage temperature-controlled rotary furnace, the first stage having a calcination temperature of about 300-500°C, and the second stage having a calcination temperature of about 500-700°C, the residence time of the crystallized microspheres in each stage being about 1-2 hours, and the water vapor being 0-100% water vapor, to obtain the first-exchanged and first-calcined crystallized microspheres.

[0275] second exchange and second calcination

[0276] (1) slurrying the crystallized microspheres obtained after rare earth ion exchange with distilled water in an amount of about 5-10 times the dry mass of the crystallized microspheres, and adding a soluble ammonium salt in an amount of about 10-50% of the dry mass of the crystallized microspheres and an organic acid in an amount of about 1-5% to the slurry of the crystallized microspheres, the reaction temperature of the slurry of the crystallized microspheres being about 85-120°C, the reaction time being about 60-120 minutes, the pH of the slurry being about 3.0-5.0, and the organic acid being one or more of oxalic acid, citric acid, or EDTA;

[0277] (2) filtering the slurry of the crystallized microspheres obtained in step (1) after the reaction in step (1) has ended, and washing the filter cake of the crystallized microspheres with a soluble ammonium salt having a dry mass of about 10-60% and a concentration of about 100-200 g / L, and distilled water in an amount of about 2-10 times the dry mass of the crystallized microspheres, after the slurry of the crystallized microspheres has been completely separated by filtration;

[0278] (3) calcining the filter cake of the crystallized microspheres in a rotary furnace, the calcination temperature being about 500-700°C, the residence time of the crystallized microspheres in the rotary furnace being about 2-4 hours, and the water vapor being about 10-100% water vapor, to obtain the second-exchanged and second-calcined crystallized microspheres.

[0279] third exchange

[0280] (1) The crystallized microspheres obtained after ion exchange of rare earth ions are slurried with about 5-10 times the dry mass of the crystallized microspheres in distilled water, and about 10-50% of the dry mass of the crystallized microspheres and about 1-5% of an organic acid are added to the slurry of the crystallized microspheres, and the slurry is reacted at a temperature of about 85-120°C for about 60-120 minutes. The pH of the slurry is about 2.5-4.0, and the organic acid is one or more of oxalic acid, citric acid, or EDTA.

[0281] (2) After the reaction of step (1) is complete, the slurry of the crystallized microspheres obtained in step (1) is filtered, and the filtered cake of the crystallized microspheres is washed with about 10-60% of a soluble ammonium salt having a concentration of about 100-200 g / L and about 5-10 times the dry mass of the crystallized microspheres in distilled water, and dried at about 120°C to obtain the crystallized microspheres containing rare earth Y after three ion exchanges and two calcinations.

[0282] Preparation Example 2.2

[0283] About 5.4 g of the directing agent and about 2.2 g of the alkali solution are mixed and allowed to stand at about 71°C for about 2.3 hours to obtain a mixture of the directing agent and the alkali solution. About 12 g of the reactive microspheres MB-2 and about 2.5 g of the alkali solution are mixed and allowed to stand at about 88°C for about 3.5 hours, and then the above mixture of the directing agent and the alkali solution and about 59.8 g of the water glass are added. After about 48.4 g of water is added and mixed, the mixture is allowed to crystallize for about 10 hours, filtered, washed with water, and dried to obtain the crystallized microspheres containing NaY-type molecular sieves, which are designated as NaY-2. The XRD diffraction pattern of the obtained crystallized microspheres is compared with that of a standard NaY pattern to confirm that the molecular sieves on the obtained crystallized microspheres are NaY molecular sieves. The properties of the crystallized microspheres are listed in Table 4A. In the pore size distribution curve of the crystallized microspheres, there are mesopore peaks in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm.

[0284] The above crystallized microspheres are modified according to the "three ion exchanges and two calcinations" method similar to that of Preparation Example 2.1 to obtain a catalyst, which is designated as REY-2. The properties of the catalyst REY-2 are listed in Table 4B. In the pore size distribution curve of the catalyst, there are mesopore peaks in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm.

[0285] Preparation Example 2.3

[0286] about 2.2 g of alkali solution were mixed well and kept at about 70°C for about 2.1 hours to obtain a mixture of directing agent and alkali solution; about 12 g of reactive microspheres MB-3 were mixed well with about 6.5 g of alkali solution and kept at about 92°C for about 1.5 hours, then the above mixture of directing agent and alkali solution, and about 120 g of silica sol were added, and about 79.6 g of water was added, and the mixture was kept at about 92°C for about 11 hours. The product was filtered, washed with water and dried to obtain crystallized microspheres containing NaY-type molecular sieves, which were designated as NaY-3. The XRD diffraction pattern of the obtained crystallized microspheres was compared with that of standard NaY, and it was confirmed that the molecular sieves on the obtained crystallized microspheres were NaY molecular sieves. The properties of the crystallized microspheres were listed in Table 4A. In the pore size distribution curve of the crystallized microspheres, there were three mesopore peaks in the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0287] The above crystallized microspheres were modified by a "three-exchange and two-calcination" method similar to that of Preparation Example 2.1 to obtain a catalyst, which was designated as REY-3. The properties of the catalyst REY-3 were listed in Table 4B. In the pore size distribution curve of the catalyst, there were three mesopore peaks in the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0288] Preparation Example 2.4

[0289] about 0.5 g of alkali solution were mixed well and kept at about 45°C for about 3.8 hours to obtain a mixture of directing agent and alkali solution; about 12 g of reactive microspheres MB-4 were mixed well with about 2.0 g of alkali solution and kept at about 85°C for about 1.8 hours, then the above mixture of directing agent and alkali solution, and about 55.7 g of water glass were added, and about 46.0 g of water was added, and the mixture was kept at about 85°C for about 18 hours. The product was filtered, washed with water and dried to obtain crystallized microspheres containing NaY-type molecular sieves, which were designated as NaY-4. The XRD diffraction pattern of the obtained crystallized microspheres was compared with that of standard NaY, and it was confirmed that the molecular sieves on the obtained crystallized microspheres were NaY molecular sieves. The properties of the crystallized microspheres were listed in Table 4A. In the pore size distribution curve of the crystallized microspheres, there were three mesopore peaks in the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0290] The above crystallized microspheres were modified by a "three-exchange and two-calcination" method similar to that of Preparation Example 2.1 to obtain a catalyst, which was designated as REY-4. The properties of the catalyst REY-4 were listed in Table 4B. In the pore size distribution curve of the catalyst, there were three mesopore peaks in the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0291] Preparation Example 2.5

[0292] About 20.6 g of the directing agent and about 8.0 g of the alkali solution were mixed well and allowed to stand at about 65°C for about 0.5 hour to obtain a mixture of the directing agent and the alkali solution; about 12 g of the reactive microspheres MB-5 and about 2.5 g of the alkali solution were mixed well and allowed to stand at about 85°C for about 3.8 hours, then the above mixture of the directing agent and the alkali solution and about 180 g of the silica sol were added, and about 77.0 g of water was added, followed by mixing well, and the crystallization was further carried out for about 9 hours, followed by filtration, washing with water and drying, to obtain crystallized microspheres containing NaY-type molecular sieves, which were designated as NaY-5. The XRD diffractogram of the obtained crystallized microspheres was compared with that of a standard NaY, and it was confirmed that the molecular sieves on the obtained crystallized microspheres were NaY molecular sieves. The properties of the crystallized microspheres are shown in Table 4A. In the pore size distribution curve of the crystallized microspheres, there were mesopore peaks in each of the ranges of 3-4 nm, 5-8 nm and 10-25 nm.

[0293] The above crystallized microspheres were modified by the "three-interaction and two-calcination" method similar to that of Preparation Example 2.1 to obtain a catalyst, which was designated as REY-5. The properties of the catalyst REY-5 are shown in Table 4B. In the pore size distribution curve of the catalyst, there were mesopore peaks in each of the ranges of 3-4 nm, 5-8 nm and 10-25 nm.

[0294] Comparative Preparation Example 2.1

[0295] A catalytic cracking catalyst was prepared by the same method as that of Preparation Example 2.2, except that the reactive microspheres CMB-1 were used instead of MB-2 to obtain crystallized microspheres, which were designated as CNaY-1. The prepared crystallized microspheres were modified by the "three-interaction and two-calcination" method similar to that of Preparation Example 2.1 to obtain a comparative catalyst, which was designated as CREY-1.

[0296] The properties of the crystallized microspheres are shown in Table 4A. In the pore size distribution curve of the crystallized microspheres, there were mesopore peaks in each of the ranges of 3-4 nm, 5-8 nm and 10-25 nm. The properties of the catalyst CREY-1 are shown in Table 4B. In the pore size distribution curve of the catalyst, there were mesopore peaks in each of the ranges of 3-4 nm, 5-8 nm and 10-25 nm.

[0297] Comparative Preparation Example 2.2

[0298] A catalytic cracking catalyst was prepared by the same method as that of Preparation Example 2.3, except that the reactive microspheres CMB-2 were used instead of MB-3 to obtain crystallized microspheres, which were designated as CNaY-2. The prepared crystallized microspheres were modified by the "three-interaction and two-calcination" method similar to that of Preparation Example 2.1 to obtain a comparative catalyst, which was designated as CREY-2.

[0299] The properties of the crystallized microspheres are listed in Table 4A. In the pore size distribution curve of the crystallized microspheres, there is not one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively. The properties of the catalyst CREY-2 are listed in Table 4B. In the pore size distribution curve of the catalyst, there is not one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0300] Comparative Preparation Example 2.3

[0301] A catalytic cracking catalyst was prepared in the same manner as in Preparation Example 2.1, except that the reactive microspheres CMB-3 were used instead of MB-1 to obtain crystallized microspheres, which are designated as CNaY-3. The prepared crystallized microspheres were modified in the same manner as in Preparation Example 2.1 to obtain a comparative catalyst, which is designated as CREY-3.

[0302] The properties of the crystallized microspheres are listed in Table 4A. In the pore size distribution curve of the crystallized microspheres, there is not one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively. The properties of the catalyst CREY-3 are listed in Table 4B. In the pore size distribution curve of the catalyst, there is not one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0303] Comparative Preparation Example 2.4

[0304] About 1.7 kg of pseudo-boehmite and water were mixed uniformly, and concentrated hydrochloric acid (chemical purity, produced by Beijing Chemical Plant) with a concentration of 36 wt% was added under stirring at an acid-alumina ratio (molar ratio of HCl to pseudo-boehmite in terms of alumina) of 0.2. The obtained mixture was aged at a temperature of about 70°C for 1.5 hours to obtain aged pseudo-boehmite, and the alumina content of the aged pseudo-boehmite was 12 wt%. About 3 kg of rare earth modified Y-type molecular sieve (provided by Qilu Catalysis Branch Company, crystallinity 92%), about 0.55 kg of aluminum sol, about 2.3 kg of kaolin, and the above-mentioned aged pseudo-boehmite were mixed uniformly with deionized water to prepare a slurry with a solid content of about 32 wt%, and then spray dried to obtain a comparative catalyst, which is designated as CREY-4.

[0305] The properties of the catalyst CREY-4 are listed in Table 4B. In the pore size distribution curve of the catalyst, there is not one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0306] Comparative Preparation Example 2.5

[0307] A catalytic cracking catalyst was prepared in the same manner as in Preparation Example 2.1, except that reactive microspheres CMB-4 were used instead of MB-1 to obtain crystallized microspheres, designated CNaY-5. The prepared crystallized microspheres were modified in a similar "three exchange two calcination" manner as in Preparation Example 2.1 to obtain a comparative catalyst, designated CREY-5.

[0308] The properties of the crystallized microspheres are listed in Table 4A. In the pore size distribution curve of the crystallized microspheres, there were not one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively. The properties of the catalyst CREY-5 are listed in Table 4B. In the pore size distribution curve of the catalyst, there were not one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0309] Preparation Example 2.6

[0310] The crystallized microspheres NaY-1 were modified in a similar "three exchange two calcination" manner as in Preparation Example 2.1. The obtained three exchange two calcined rare earth Y containing crystallized microspheres were contacted with silicon tetrachloride gas at a weight ratio of about 1 : (0.1-0.7) and at a gas phase ultrastable reaction temperature of about 200°C-650°C for a reaction time of about 10 minutes-300 minutes to obtain gas phase ultrastable modified rare earth Y containing crystallized microspheres, designated catalyst REY-6. The properties of the catalyst REY-6 are listed in Table 4B. In the pore size distribution curve of the catalyst, there were one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0311] Preparation Example 2.7

[0312] The crystallized microspheres NaY-1 were modified in a similar "three exchange two calcination" manner as in Preparation Example 2.1. The obtained three exchange two calcined rare earth Y containing crystallized microspheres were treated by calcination under an atmosphere of about 50% by volume water vapor (i.e., about 50% by volume water vapor + about 50% by volume nitrogen) at a reaction temperature of about 400°C-650°C for a reaction time of about 10 minutes-300 minutes to obtain hydrothermally ultrastable modified rare earth Y containing crystallized microspheres, designated catalyst REY-7. The properties of the catalyst REY-7 are listed in Table 4B. In the pore size distribution curve of the catalyst, there were one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0313] Table 4A: Properties of Crystallized Microspheres

[0314] Table 4A (continued)

[0315] Table 4B: Properties of Catalysts

[0316] Table 4B (continued)

[0317] Catalyst Preparation Example 2.8

[0318] A mixture of 80 g of the directing agent and 2.0 g of the alkali solution was prepared by mixing them well and standing at about 40°C for 1.5 hours. A mixture of 24 g of the reactive microspheres MB-6 and 5 g of the alkali solution was prepared by mixing them well and standing at 95°C for 1.5 hours. The mixture of the directing agent and the alkali solution and 92.5 g of the water glass were added to the mixture of the reactive microspheres and the alkali solution. After mixing well, 46.8 g of water was added, and the mixture was crystallized for 7.5 hours. The crystallized microspheres were filtered, washed with water, and dried to obtain crystallized microspheres containing NaY-type molecular sieves, which were designated as NaY-6. The XRD pattern of the obtained crystallized microspheres, which had diffraction peaks at 6.2°, 15.6°, 20.3°, 23.6°, 26.0°, and 31.4° in terms of the 2Θ angle, was identical with that of the standard NaY pattern, which confirmed that the molecular sieves on the obtained crystallized microspheres were NaY molecular sieves. The properties of the crystallized microspheres are shown in Table 4C. In the pore size distribution curve of the crystallized microspheres, there were mesopore peaks in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm.

[0319] The above crystallized microspheres were modified by the "three mixing and two calcining" method similar to that of Preparation Example 2.1 to obtain a catalyst, which was designated as REY-8. The properties of the catalyst REY-8 are shown in Table 4D. In the pore size distribution curve of the catalyst, there were mesopore peaks in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm. The pore size distribution curve of the catalyst REY-8 is shown in Fig. 2.

[0320] Catalyst Preparation Example 2.9

[0321] A mixture of 10.8 g of the directing agent and 4.4 g of the alkali solution was prepared by mixing them well and standing at about 70°C for 2.5 hours. A mixture of 24 g of the reactive microspheres MB-7 and 5.0 g of the alkali solution was prepared by mixing them well and standing at about 90°C for about 3.5 hours. The mixture of the directing agent and the alkali solution was added to the mixture of the reactive microspheres and the alkali solution. After mixing well, about 98 g of water was added, and the mixture was crystallized for 9.5 hours. The crystallized microspheres were filtered, washed with water, and dried to obtain crystallized microspheres containing NaY-type molecular sieves, which were designated as NaY-7. The XRD pattern of the obtained crystallized microspheres was identical with that of the standard NaY pattern, which confirmed that the molecular sieves on the obtained crystallized microspheres were NaY molecular sieves. The properties of the crystallized microspheres are shown in Table 4C. In the pore size distribution curve of the crystallized microspheres, there were mesopore peaks in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm.

[0322] The above crystallized microspheres were modified by the "three-interaction and two-calcination" method similar to that of Preparation Example 2.1 to obtain a catalyst, noted as REY-9. The properties of the catalyst REY-9 are listed in Table 4D. In the pore size distribution curve of the catalyst, there are three mesopore peaks in the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0323] Catalyst Preparation Example 2.10

[0324] About 32 g of the directing agent and about 1.0 g of the alkali solution were mixed uniformly and allowed to stand at about 48°C for about 3.5 hours to obtain a mixture of the directing agent and the alkali solution; about 24 g of the reactive microspheres MB-9 and about 4.0 g of the alkali solution were mixed uniformly and allowed to stand at about 88°C for about 2.0 hours, then the above mixture of the directing agent and the alkali solution and about 111.5 g of the water glass were added, and about 95.0 g of water was added, and the mixture was allowed to stand uniformly, and then the crystallization was continued for about 17 hours, followed by filtration, water washing and drying to obtain the crystallized microspheres containing the NaY type molecular sieves, noted as NaY-9. The XRD diffraction pattern of the obtained crystallized microspheres was compared with that of the standard NaY, and it was confirmed that the molecular sieves on the obtained crystallized microspheres were NaY molecular sieves. The properties of the crystallized microspheres are listed in Table 4C. In the pore size distribution curve of the crystallized microspheres, there are three mesopore peaks in the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0325] The above crystallized microspheres were modified by the "three-interaction and two-calcination" method similar to that of Preparation Example 2.1 to obtain a catalyst, noted as REY-9. The properties of the catalyst REY-9 are listed in Table 4D. In the pore size distribution curve of the catalyst, there are three mesopore peaks in the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0326] Catalyst Preparation Example 2.11

[0327] About 32 g of the directing agent and about 1.0 g of the alkali solution were mixed uniformly and allowed to stand at about 48°C for about 3.5 hours to obtain a mixture of the directing agent and the alkali solution; about 24 g of the reactive microspheres MB-9 and about 4.0 g of the alkali solution were mixed uniformly and allowed to stand at about 88°C for about 2.0 hours, then the above mixture of the directing agent and the alkali solution and about 111.5 g of the water glass were added, and about 95.0 g of water was added, and the mixture was allowed to stand uniformly, and then the crystallization was continued for about 17 hours, followed by filtration, water washing and drying to obtain the crystallized microspheres containing the NaY type molecular sieves, noted as NaY-9. The XRD diffraction pattern of the obtained crystallized microspheres was compared with that of the standard NaY, and it was confirmed that the molecular sieves on the obtained crystallized microspheres were NaY molecular sieves. The properties of the crystallized microspheres are listed in Table 4C. In the pore size distribution curve of the crystallized microspheres, there are three mesopore peaks in the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0328] The above crystallized microspheres were modified by the similar "three-interaction and two-calcination" process as in Preparation Example 2.1 to obtain a catalyst, noted as REY-11. The properties of the catalyst REY-11 are listed in Table 4D. In the pore size distribution curve of the catalyst, there are three mesopore peaks in the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0329] Preparation Example 2.12

[0330] About 41 g of the directing agent and about 16 g of the alkali solution were mixed uniformly and allowed to stand at about 66°C for about 1.8 hours to obtain a mixture of the directing agent and the alkali solution; about 24 g of the reactive microspheres MB-10 and about 5.0 g of the alkali solution were mixed uniformly and allowed to stand at about 89°C for about 4.5 hours, then the above mixture of the directing agent and the alkali solution, and about 360 g of the silica sol were added, and about 154.0 g of water was added, followed by mixing uniformly, and then crystallization was continued for about 9 hours, followed by filtration, water washing, and drying to obtain crystallized microspheres containing NaY molecular sieves, noted as NaY-10. The XRD diffraction pattern of the obtained crystallized microspheres was compared with that of the standard NaY pattern, and it was confirmed that the molecular sieves on the obtained crystallized microspheres were NaY molecular sieves. The properties of the crystallized microspheres are listed in Table 4C. In the pore size distribution curve of the crystallized microspheres, there are three mesopore peaks in the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0331] The above crystallized microspheres were modified by the similar "three-interaction and two-calcination" process as in Preparation Example 2.1 to obtain a catalyst, noted as REY-11. The properties of the catalyst REY-11 are listed in Table 4D. In the pore size distribution curve of the catalyst, there are three mesopore peaks in the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0332] Comparative Preparation Example 2.6

[0333] A catalytic cracking catalyst was prepared by the same method as in Preparation Example 2.9, except that the reactive microspheres CMB-5 were used instead of MB-7 to obtain crystallized microspheres, noted as CNaY-6. The obtained crystallized microspheres were modified by the similar "three-interaction and two-calcination" process as in Preparation Example 2.1 to obtain a comparative catalyst, noted as CREY-6.

[0334] The properties of the crystallized microspheres are listed in Table 4C. In the pore size distribution curve of the crystallized microspheres, there are not three mesopore peaks in the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively. The properties of the catalyst CREY-6 are listed in Table 4D. In the pore size distribution curve of the catalyst, there are not three mesopore peaks in the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0335] Comparative Preparation Example 2.7

[0336] A catalytic cracking catalyst was prepared in the same manner as in Preparation Example 2.10, except that reactive microspheres CMB-6 were used instead of MB-8 to obtain crystallized microspheres, designated CNaY-7. The prepared crystallized microspheres were modified in the same manner as in Preparation Example 2.1, "three exchange and two calcination", to obtain a comparative catalyst, designated CREY-7.

[0337] The properties of the crystallized microspheres are listed in Table 4C. In the pore size distribution curve of the crystallized microspheres, there was no mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively. The properties of the catalyst CREY-2 are listed in Table 4D. In the pore size distribution curve of the catalyst, there was no mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0338] Comparative Preparation Example 2.8

[0339] A catalytic cracking catalyst was prepared in the same manner as in Preparation Example 2.8, except that reactive microspheres CMB-7 were used instead of MB-6 to obtain crystallized microspheres, designated CNaY-8. The prepared crystallized microspheres were modified in the same manner as in Preparation Example 2.1, "three exchange and two calcination", to obtain a comparative catalyst, designated CREY-8.

[0340] The properties of the crystallized microspheres are listed in Table 4C. In the pore size distribution curve of the crystallized microspheres, there was no mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively. The properties of the catalyst CREY-3 are listed in Table 4D. In the pore size distribution curve of the catalyst, there was no mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0341] Comparative Preparation Example 2.9

[0342] About 1.7 kg of pseudo-boehmite and water were mixed well, and concentrated hydrochloric acid (chemical purity, produced by Beijing Chemical Plant) with a concentration of 36 wt% was added under stirring, with an acid-alumina ratio (molar ratio of HCl to pseudo-boehmite in terms of alumina) of 0.2. The resulting mixture was aged at about 70°C for 1.5 hours to obtain aged pseudo-boehmite. About 0.12 kg of a lanthanum rare earth chloride solution (lanthanum oxide mass fraction of 16.5%) was added, and stirring was performed for 40 minutes to obtain aged pseudo-boehmite containing rare earth, with an alumina content of 11.8 wt%. About 3 kg of a rare earth modified Y-type molecular sieve (provided by Qilu Catalysis Branch Company, with a crystallinity of 92%), about 0.55 kg of an aluminum sol, about 2.3 kg of kaolin, and the above-mentioned aged pseudo-boehmite containing rare earth were mixed well with deionized water to prepare a slurry with a solid content of about 32 wt%, and then spray drying was performed to obtain a comparative catalyst, which is denoted as CREY-9.

[0343] The properties of the catalyst CREY-9 are listed in Table 4D. In the pore size distribution curve of the catalyst, there is not one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0344] Comparative Preparation Example 2.10

[0345] A catalytic cracking catalyst was prepared by using the same method as in Preparation Example 2.8, except that the reactive microspheres CMB-8 were used instead of MB-6 to obtain crystallized microspheres, which are denoted as CNaY-10. The prepared crystallized microspheres were modified by a “three-interaction and two-calcination” method similar to that in Preparation Example 2.1 to obtain a comparative catalyst, which is denoted as CREY-10.

[0346] The properties of the crystallized microspheres are listed in Table 4C. In the pore size distribution curve of the crystallized microspheres, there is not one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively. The properties of the catalyst CREY-5 are listed in Table 4D. In the pore size distribution curve of the catalyst, there is not one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0347] Preparation Example 2.13

[0348] The crystallized microspheres NaY-6 were modified by the "three-exchange two-calcination" method similar to that of Preparation Example 2.8. The obtained three-exchange two-calcination modified rare earth Y containing crystallized microspheres were contacted with silicon tetrachloride gas at a weight ratio of about 1 : (0.1-0.7), and the gas phase ultrastable reaction temperature was about 200°C-650°C, and the reaction time was about 10 minutes-300 minutes, to obtain gas phase ultrastable modified rare earth Y containing crystallized microspheres, which were recorded as catalyst REY-13. The properties of the catalyst REY-13 are listed in Table 4D. In the pore size distribution curve of the catalyst, there was one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0349] Preparation Example 2.14

[0350] The crystallized microspheres NaY-6 were modified by the "three-exchange two-calcination" method similar to that of Preparation Example 2.8. The obtained three-exchange two-calcination modified rare earth Y containing crystallized microspheres were treated by calcination under an atmosphere of about 50% by volume of water vapor (i.e., about 50% by volume of water vapor + about 50% by volume of nitrogen) for about 4.5 hours, at a reaction temperature of about 400°C-650°C, and a reaction time of about 10 minutes-300 minutes, to obtain hydrothermally ultrastable modified rare earth Y containing crystallized microspheres, which were recorded as catalyst REY-14. The properties of the catalyst REY-14 are listed in Table 4D. In the pore size distribution curve of the catalyst, there was one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively.

[0351] Table 4C: Properties of Crystallized Microspheres

[0352] ND: not measured.

[0353] Table 4C (continued)

[0354] Table 4D: Properties of Catalysts

[0355] Note: In Table 4D, M (representing vanadium reactive metal) is the case of rare earth, the content of M oxide is measured by XRD method, and the content of M oxide is calculated by peak area. The total content of rare earth oxide is measured by X-ray fluorescence method, and the exchanged rare earth is equal to the total content of rare earth oxide - the content of M oxide.

[0356] Table 4D (continued)

[0357] (III) Test Examples

[0358] 3.1. Relative crystalline retention and light oil microreactor activity test MAT

[0359] The catalysts shown in Table 5A (referred to as fresh catalysts) were treated in an aging device under the conditions of about 800°C / about 100% steam for about 17 hours, respectively, and then subjected to light oil micro- reaction activity test MAT. The relative crystallinity of the molecular sieve before and after aging of the catalyst was analyzed by XRD method and the relative crystallinity retention after aging was calculated, and the results are shown in Table 5A.

[0360] The fresh catalysts were respectively contaminated by impregnation method according to the nickel content of 2000 ppm and the vanadium content of 6000 ppm in the contaminated catalyst, and then treated under the conditions of about 800°C / about 100% steam for 4 hours, and then subjected to light oil micro- reaction activity test MAT.

[0361] The reaction conditions of the light oil micro- reaction activity test MAT were as follows: Dagang light diesel oil with a distillation range of 235-335°C was used as the raw material, the catalyst to oil ratio was 3.2 (by weight), the weight space velocity was 16h -1 , and the temperature was 460°C. The reaction products were analyzed by gas chromatography.

[0362] Among them, the light oil micro- reaction activity (MA) is calculated by the following formula:

[0363] The light oil micro- reaction activity (MA) = (C5 below gas production + C5-221°C gasoline production + coke production) / total feed amount x 100% = C5 below gas yield + C5-221°C gasoline yield + coke yield.

[0364] As can be seen from Table 5A, under the same conditions, the catalysts with high porosity structure and / or vanadium resistance provided by the present application have high activity after being contaminated by metals in catalytic cracking, and good resistance to heavy metals V and Ni.

[0365] At the same time, the catalysts with high porosity structure and / or vanadium resistance provided by the present application have higher relative crystallinity retention compared with the comparative catalysts after being aged under harsh conditions of about 800°C, about 100% by volume steam, and about 17 hours in a naked state in catalytic cracking, indicating that the Y-type molecular sieve in the catalyst with high porosity structure provided by the present application has higher hydrothermal stability in catalytic cracking.

[0366] Table 5A

[0367] The catalysts shown in Table 5B (referred to as fresh catalysts) were treated in an aging device under the conditions of about 800°C / about 100% steam for about 17 hours, respectively, and then subjected to light oil micro- reaction activity test MAT. The relative crystallinity of the molecular sieve before and after aging of the catalyst was analyzed by XRD method and the relative crystallinity retention after aging was calculated, and the results are shown in Table 5B.

[0368] The fresh catalyst was contaminated by impregnation method according to the vanadium content of 10,000 ppm by mass in the contaminated catalyst, and then treated at about 800°C and about 100% steam for 4 hours, followed by light oil micro-reaction activity test MAT.

[0369] The reaction conditions of the light oil micro-reaction activity test MAT were as follows: Dagang light diesel oil with a distillation range of 235-335°C was used as the raw material, the catalyst / oil ratio was 3.2 (by weight), the weight hourly space velocity was 16 h -1 , and the temperature was 460°C. The reaction products were analyzed by gas chromatography.

[0370] The light oil micro-reaction activity (MA) was calculated by the following formula:

[0371] The light oil micro-reaction activity (MA) = (C5 and below gas yield + C5-221°C gasoline yield + coke yield) / total amount of feedstock x 100% = C5 and below gas yield + C5-221°C gasoline yield + coke yield.

[0372] As can be seen from Table 5B, under the same modification conditions, the catalysts with high porosity structure and / or vanadium resistance provided by the present application have high activity and good heavy metal V resistance performance after being contaminated by metals in catalytic cracking.

[0373] Meanwhile, the catalysts with high porosity structure and / or vanadium resistance provided by the present application have higher relative crystallinity retention compared with the comparative catalysts after being aged under harsh conditions of about 800°C, about 100% by volume steam, and about 17 hours in a bare state in catalytic cracking, indicating that the Y-type molecular sieve in the high porosity structure catalyst provided by the present application has higher hydrothermal stability in catalytic cracking.

[0374] Table 5B

[0375] 3.2. Heavy oil catalytic cracking test

[0376] The catalysts REY-1 to REY-14 and CREY-1 to CREY-10 prepared above were respectively aged at 800°C and 100% steam for 17 hours, and then filled in a fixed fluidized bed FFB device (manufactured by Sinopec Yanchuan Company) to evaluate the reaction performance of the catalytic cracking catalyst, and the filling amount of the catalyst was 150 g. Then, under the conditions of a reaction temperature of 510°C, a weight hourly space velocity of 12 h -1 , and a catalyst / oil ratio (by weight) of 6, the raw material oil shown in Table 6 was injected into the fixed fluidized bed FFB device to perform catalytic cracking reaction. The composition of the reaction products was analyzed, and the conversion rate (= dry gas yield + liquefied gas yield + gasoline yield + coke yield) was calculated, and the results are shown in Table 7 below.

[0377] From Table 7, it can be seen that the catalytic cracking catalyst with the high porosity structure provided by the application has better cracking effect when used for catalytic cracking of heavy oil, has higher conversion rate, and the sum of gasoline and LPG yield is high, the diesel yield and slurry oil yield are low, and the coke factor (coke factor = coke yield x (1 - conversion rate) / conversion rate x 100) is obviously low.

[0378] Table 6

[0379] Table 7

Claims

1. An aluminosilicate composite material containing magnesium and / or vanadium reactive metals, characterized in that The composite material has at least one, preferably all of the following characteristics: (a) optionally, the specific surface area of the composite material is 20-60 m 2 / g, such as 20-35 m 2 / g, or 23-32 m 2 / g, or 25-35 m 2 / g, or 42-49 m 2 / g. (b) the composite material has, based on the total weight of the composite material being 100 wt%, from 0.5 to 40 wt%, such as from 0.55 to 20 wt%, or from 0.6 to 10 wt%, or from 0.65 to 5 wt%, or from 0.7 to 4.3 wt% of a complex salt of the vanadium reactive metal and aluminium, if the vanadium reactive metal is within the above range as an oxide, and optionally from 1 to 40 wt%, such as from 2 to 25 wt%, or from 2.1 to 21.6 wt% of MgAI2O4, if the magnesium is within the above range as MgO, and / or the composite material has, based on the total weight of the composite material being 100 wt%, from 20 to 60 wt%, such as from 30 to 50 wt%, or from 32.61 to 49.26 wt% of AI2O3, and from 30 to 70 wt%, such as from 40 to 60 wt%, or from 45.56 to 55.38 wt% of SiO2, and from 20 to 60 wt%, such as from 30 to 50 wt%, or from 32.61 to 49.26 wt% of AI2O3, and a magnesium content of 0.5 to 15 wt%, such as 0.7 to 10 wt%, or 0.87 to 8.75 wt%, and / or a vanadium reactive metal content of 0.5 to 15 wt%, such as 0.7 to 10 wt%, or 0.7 to 5 wt%, or 0.8 to 4.1 wt%, calculated as oxide (M x O y ) wherein the vanadium reactive metal is selected from at least one of the group consisting of VA group metal, II B group metal, VI B group metal, VII B group metal, VIII group metal, III B group metal, preferably one or more of Bi, Mn, Zn, Ce, La, more preferably La; M represents the vanadium reactive metal, x represents the coordination number of M, and y represents the coordination number of O, for VA group metal, VI B group metal, III B group metal, VIII group metal, x is 2 and y is 3; for VII B group metal, x is 1 and y is 2; for II B group metal, x is 1 and y is 1 ; optionally from 0.4 to 1.8 wt%, such as from 0.6 to 1.2 wt%, or from 0.7 to 1.15 wt%, or from 0.71 to 1.14 wt% of TiO2, and optionally from 0.1 to 15 wt%, such as from 1 to 10 wt%, or from 1.55 to 7.16 wt% of Na2O, and (c) the composite material has, based on AI2O3 in the composite material, from 25 to 90 wt%, such as from 30 to 85 wt%, or from 40 to 80 wt%, or from 41.7 to 75.6 wt% of AI2O3 in tetrahedral and pentahedral coordination; (d) optionally, having a content of Si02in the composite of 20-95 wt%, such as 30-95 wt%, or 25-90 wt%, or 35-90 wt%, or 30-80 wt%, or 40-85 wt%, or 40-75%, or 30.3-75.1 wt% of Si02having the Q 4 (0Al) structure. (d) optionally, having a content of Si02in the composite of 20-95 wt%, such as 30-95 wt%, or 25-90 wt%, or 35-90 wt%, or 30-80 wt%, or 40-85 wt%, or 40-75%, or 30.3-75.1 wt% of Si02having the Q 4 (0Al) structure. (e) preferably, in the composite material, there is a complex salt of magnesium and aluminium in the form of MgAI2O4 if the magnesium is within the above range as MgO, and optionally from 1 to 40 wt%, such as from 2 to 25 wt%, or from 2.1 to 21.6 wt% of MgAI2O4, based on the total weight of the composite material being 100 wt%, and / or in the composite material, there is a complex salt of the vanadium reactive metal and aluminium in the form of metal oxide if the vanadium reactive metal is within the above range as an oxide, and optionally from 0.5 to 40 wt%, such as from 0.55 to 20 wt%, or from 0.6 to 10 wt%, or from 0.65 to 5 wt%, or from 0.7 to 4.3 wt% of the complex salt of the vanadium reactive metal and aluminium, based on the total weight of the composite material being 100 wt%; optionally, the composite material further has at least one, preferably all of the following characteristics: (f) the composite material has a sphericity of from 85 to 100%, such as from 90 to 99%, or from 91 to 95%, or from 92 to 97%, or from 92.5 to 96.2%; and (g) the composite material has a wear index of from 2.0 to 5.0% / h, such as from 2.0 to 4.0% / h, or from 3.0 to 4.0% / h, or from 3.2 to 4.0% / h; and (h) the composite material has an average particle size of 50-100 pm, such as 60-90 pm, or 70-80 pm, or 72-78 pm; (i) the composite material has a pore volume of 0.02-0.1 mL / g, such as 0.035-0.085 mL / g, or 0.05-0.1 ml / g, or 0.06-0.09 mL / g, or 0.04-0.07 mL / g, or 0.045-0.095 mL / g, or 0.06-0.09 mL / g.

2. A catalyst characterized in that said catalyst (on an elemental basis) comprises, based on the total weight of the catalyst being 100 wt%: 50-70 wt%, such as 57-67 wt%, or 58-65 wt%, or 60.04-63.61 wt% of silicon (on Si02 basis); 20-30 wt%, such as 21-28 wt%, or 23-26 wt%, such as 21.22-26.5 wt% of aluminium (on AI2O3 basis); 0.2-8 wt%, such as 0.3-5.5 wt%, or 0.38-5.2 wt% of magnesium (on MgO basis), and / or 0.2-15 wt%, or 0.2-8 wt%, or 1-8 wt%, or 0.3-5.5 wt%, or 0.8-5.2 wt%, or 0.7-3.95% of vanadium reactive metal (on oxide MxOy basis), wherein the vanadium reactive metal is selected from at least one of a VA group metal, a group II B metal, a group VI B metal, a group VII B metal, a group VIII metal, a group III B metal, preferably one or more of Bi, Mn, Zn, Ce, La, more preferably La; M represents the vanadium reactive metal, x represents the coordination number of M, and y represents the coordination number of O, for a VA group metal, a group VI B metal, a group III B metal, a group VIII metal, x is 2 and y is 3; for a group VII B metal, x is 1 and y is 2; for a group II B metal, x is 1 and y is 1 ; optionally, 0.3-2 wt%, such as 0.35-1 wt%, or 0.4-0.92 wt%, or 0.3-1 wt%, or 0.6-1 wt% of titanium (on Ti02 basis); optionally, 0.01-2 wt%, such as 0.1-0.4 wt%, or 0.12-0.26 wt%, or 5-15 wt%, or 7-11 wt%, or 8-11 wt%, or 8-10.88 wt% of Na (on Na20 basis); optionally, 0-0.01 wt%, or 1-25 wt%, such as 6-15 wt%, or 9.01-11.98 wt% of exchanged rare earth (on rare earth oxide RE203 basis); In the catalyst, there is a complex salt of magnesium and aluminum existing in the form of MgAl2O4 (if the magnesium in terms of MgO is within the above range), and optionally, the content of MgAl2O4 is 0.5-20 wt%, such as 0.75-15 wt%, or 0.94-12.85 wt%, based on 100 wt% of the total weight of the catalyst, and / or in the catalyst, there is a complex salt of vanadium reactive metal and aluminum existing in the form of metal oxide (if the vanadium reactive metal in terms of oxide is within the above range), and optionally, the content of the complex salt of vanadium reactive metal and aluminum is 0.5-20 wt%, such as 0.75-15 wt%, or 0.75-7.5 wt%, or 0.76-3.35 wt%, based on 100 wt% of the total weight of the catalyst; wherein when the content of Na (in terms of Na2O) is 0.01-2 wt%, or 0.1-0.4 wt%, the content of exchanged rare earth (in terms of rare earth oxide RE2O3) is 1-25 wt%, or 0.5-20 wt%, or 1-15 wt%, or 6-15 wt%, or 9.01-11.98 wt%; when the content of Na (in terms of Na2O) is 5-15 wt%, or 7-11 wt%, or 8-11 wt%, the content of exchanged rare earth (in terms of rare earth oxide RE2O3) is 0-0.01 wt%; for example, the rare earth is one or more of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y) and scandium (Sc), preferably, the rare earth is one or several of yttrium, lanthanum, cerium, praseodymium and neodymium, more preferably, one or more of La, Ce, and Y; for example, the rare earth oxide is one or several of La2O3, CeO2, and Y2O3; Preferably, the catalyst has at least one of the following characteristics, preferably all of the following characteristics: (1) attrition index = 0.5-3.0% / h, such as 0.7-2.2% / h, or 0.8-2.1% / h, or 1.0-3.0% / h, or 1.8-2.1% / h, or 0.5-2.0% / h, or 1.0-3.0% / h, or 0.6-1.5% / h, or 0.8-1.1% / h, or 1.5-2.2% / h; (2) Specific surface area = 400-1000 m 2 / g, such as 400-800 m 2 / g, or 450-700 m 2 / g, or 600-970 m 2 / g, or 600-960 m 2 / g, or 630-960 m 2 / g, or 640-955 m 2 / g, or 600-750 m 2 / g, or 600-860 m 2 / g, or 611.9-851.3 m 2 / g, or 730-860 m 2 / g, or 720-840 m 2 / g, or 650-850 m 2 / g, or 732.6-851.3 m 2 / g, or 611.9-737.8 m 2 / g; (3) pore volume = 0.2-0.6 mL / g, such as 0.2-0.55 mL / g, or 0.25-0.55 mL / g, 0.25-0.5 mL / g, or 0.3-0.6 mL / g, or 0.3-0.5 mL / g, or 0.4-0.5 mL / g, or 0.41-0.46 mL / g, or 0.41-0.44 mL / g, or 0.38-0.48 mL / g; (4) crystallinity = 55-90%, such as 60-90%, or 60-78%, or 60-75%, or 60-67%, or 61-75%, or 65-75%; (5) unit cell parameter = 2.454-2.473 nm, such as 2.457-2.470 nm, or 2.460-2.467 nm, or 2.460-2.466 nm, or 2.461-2.467 nm, or 2.463-2.467 nm; Optionally, the catalyst further has at least one, preferably all, of the following characteristics: (6) framework silica to alumina ratio (molar ratio of Si02 / Al203) = 2.0-7.0, such as 3.0-6.7, or 4.0-6.3, or 4.8-6.3, or 2.0-6.0, or 5.0-6.2, or 5.0-6.1, or 5.1-6.1, or 5.0-6.0; (7) porosity = 3%-30%, such as 3%-20%, or 5%-20%, or 5%-12%, or 8%-20%, or 9.2%-19.4%, or 9.1%-18.5%, or 9.2%-18.2%, or 9.8%-18.2%, or 9.4%-19.4%, or 9.0%-19.5%; (8) mesopore fraction = 20%-40%, such as 25%-37%, or 25%-36%, or 25%-35%, or 26%-36%, or 25.1%-34.2%, or 25.1%-35.9%, or 25.1%-36%, or 25.1%-37.2%, or 25.7%-36.2%, or 25.7%-35.9%, or 26-37.9%, or 26.8%-35.5%; (9) optionally, trimethylpyridine acidity = 100-500 μmol / g, such as 280-411 μmol / g, or 250-450 μmol / g, or 280-420 μmol / g, or 280-413 μmol / g; Still more preferably, the catalyst is obtained by in situ crystallization of a molecular sieve on the magnesium-containing and / or reactive metal-containing aluminosilicate composite material of the preceding claim 1, preferably the molecular sieve is an X-type molecular sieve, a Y-type molecular sieve, or an A-type molecular sieve, more preferably the molecular sieve is a Y-type molecular sieve; Further preferably, there is one mesopore peak in each of the ranges of 3-4 nm, 5-8 nm, and 10-25 nm, respectively, in the pore size distribution curve of the catalyst.

3. Catalyst according to claim 2, characterized in that Optionally but preferably, the catalyst is obtained by in situ crystallization of a molecular sieve on the magnesium-containing and / or reactive metal-containing aluminosilicate composite material of the preceding claim 1, the molecular sieve being a NaY-type molecular sieve; The catalyst comprises, on an elemental basis and based on the total weight of the catalyst being 100 wt%,: 58-65 wt%, such as 60.5-62.7 wt%, or 60-62.7 wt% of silicon (as Si02); 21-28 wt%, such as 23.5-26.5 wt%, or 23.5-26.6 wt% of aluminium (as Al203); 0.3-5.5 wt%, such as 0.5-5.2 wt% of magnesium (as MgO), and / or 0.2-10 wt%, such as 0.3-8 wt%, or 1-8 wt%, or 0.3-5.5 wt%, or 0.5-5.2 wt%, or 0.7-3.9 wt% of vanadium reactive metal (as oxide); 5-15 wt%, such as 7-11 wt%, or 8-11.5 wt%, or 8-10.88 wt% of sodium (as Na20); Optionally, 0.3-1.1 wt%, such as 0.35-1 wt%, or 0.4-1 wt%, or 0.6-1 wt%, or 0.4-0.95 wt%, or 0.51-0.92 wt% of titanium (as Ti02); In the catalyst, there is a complex salt of magnesium and aluminium present in the form of MgAl204, if the magnesium is in the above range as MgO, and optionally, the content of MgAl204is 0.75-15 wt%, such as 1.2-13 wt%, such as 1.24-12.85 wt%, based on 100 wt% of the total weight of the catalyst, and / or in the catalyst, there is a complex salt of vanadium reactive metal and aluminium present in the form of metal oxide, if the vanadium reactive metal is in the above range as oxide, and optionally, the content of the complex salt of vanadium reactive metal and aluminium is 0.75-15 wt%, such as 0.75-7.5 wt%, or 0.76-3.33 wt%, based on 100 wt% of the total weight of the catalyst; Preferably, the catalyst has at least one, preferably all, of the following characteristics: (1) attrition index = 0.5-3.0% / h, such as 0.7-2.2% / h, or 0.8-2.1% / h, or 1.0-3.0% / h, or 1.8-2.1% / h, or 0.5-2.0% / h, or 1.0-3.0% / h, or 0.6-1.5% / h, or 0.8-1.1% / h, or 1.5-2.2% / h; (2) Specific surface area = 400-1000 m 2 / g, such as 400-800 m 2 / g, or 450-700 m 2 / g, or 600-970 m 2 / g, or 600-960 m 2 / g, or 630-960 m 2 / g, or 640-955 m 2 / g, or 600-750 m 2 / g, or 600-860 m 2 / g, or 611.9-851.3 m 2 / g, or 730-860 m 2 / g, or 720-840 m 2 / g, or 650-850 m 2 / g, or 732.6-851.3 m 2 / g, or 611.9-737.8 m 2 / g; (3) pore volume = 0.2-0.6 mL / g, such as 0.2-0.55 mL / g, or 0.25-0.55 mL / g, 0.25-0.5 mL / g, or 0.3-0.6 mL / g, or 0.3-0.5 mL / g, or 0.4-0.5 mL / g, or 0.41-0.46 mL / g, or 0.41-0.44 mL / g, or 0.38-0.48 mL / g; (4) crystallinity = 55-90%, such as 60-90%, or 60-78%, or 60-75%, or 60-67%, or 61-75%, or 65-75%; (5) unit cell parameter = 2.454-2.473 nm, such as 2.457-2.470 nm, or 2.460-2.467 nm, or 2.460-2.466 nm, or 2.461-2.467 nm, or 2.463-2.467 nm; Optionally, the catalyst further has at least one, preferably all, of the following characteristics: (6) framework silica to alumina ratio (molar ratio Si02 / Al203) = 2.0-7.0, such as 3.0-6.7, or 4.0-6.3, or 4.8-6.3, or 2.0-6.0, or 5.0-6.2, or 5.0-6.1, or 5.1-6.1, or 5.0-6.0; (7) porosity = 3-30%, such as 3-20%, or 5-20%, or 5-12%, or 8-20%, or 9.2-19.4%, or 9.1-18.5%, or 9.2-18.2%, or 9.8-18.2%, or 9.4-19.4%, or 9.0-19.5%; (8) meso-macroporosity = 20-40%, such as 25-37%, or 25-36%, or 25-35%, or 26-36%, or 25.1-34.2%, or 25.1-35.9%, or 25.1-36%, or 25.1-37.2%, or 25.7-36.2%, or 25.7-35.9%, or 26-37.9%, or 26.8-35.5%.

4. Catalyst according to claim 2, characterized in that Optionally, but preferably, the catalyst is obtained by in situ crystallization of a molecular sieve on the aforementioned magnesium- and / or vanadium-reactive metal-containing aluminosilicate composite material of claim 1 and by modification with a rare earth, the obtained molecular sieve being a REY-type molecular sieve; said catalyst comprising, in terms of total weight of the catalyst, 100 wt%, 55-68 wt%, such as 56-67 wt%, or 58-65 wt%, or 59-67 wt%, or 60-64 wt%, or 60.04-63.61 wt% of silicon (as Si02); 21-28 wt%, such as 21-26 wt%, or 23-27 wt%, or 21.22-25.58 wt% of aluminum (as Al203); 0.3-5.5 wt%, such as 0.3-5 wt%, or 0.38-4.95 wt% of magnesium (as MgO), and / or 0.3-8 wt%, or 0.3-5.5 wt%, or 0.5-5.2 wt%, or 1-8 wt%, or 0.84-3.95 w% of vanadium reactive metal (as oxide); optionally, 0.3-1 wt%, such as 0.35-0.95 wt%, or 0.40-0.91 wt%, or 0.6-0.91 wt% of titanium (as Ti02); Optionally, 0.01-2 wt%, such as 0.1-0.3 wt%, or 0.12-0.26 wt% of sodium (as Na2O); 6-15 wt%, such as 9-12 wt%, or 9.01-11.98 wt% of exchanged rare earth (as rare earth oxide RE2O3); for example, the rare earth is one or more of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y), and scandium (Sc), preferably, the rare earth is one or more of yttrium, lanthanum, cerium, praseodymium, and neodymium, more preferably, one or more of La, Ce, and Y; for example, the rare earth oxide is one or more of La2O3, CeO2, and Y2O3; In the catalyst, there is a complex salt of magnesium and aluminum existing in the form of MgAl2O4 (if the magnesium as MgO is within the above range), and optionally, the content of MgAl2O4 is 0.75-15 wt%, such as 0.9-12.5 wt%, or 0.94-12.23 wt%, based on 100 wt% of the total weight of the catalyst, and / or in the catalyst, there is a complex salt of vanadium reactive metal and aluminum existing in the form of metal oxide (if the vanadium reactive metal as oxide is within the above range), and optionally, the content of the complex salt of vanadium reactive metal and aluminum is 0.75-15 wt%, such as 0.75-7.5 wt%, or 0.77-3.35 wt%, based on 100 wt% of the total weight of the catalyst; Preferably, the catalyst has at least one of the following characteristics, preferably all of the following characteristics: (1) attrition index = 0.5-3.0% / h, such as 0.7-2.2% / h, or 0.8-2.1% / h, or 1.0-3.0% / h, or 1.8-2.1% / h, or 0.5-2.0% / h, or 1.0-3.0% / h, or 0.6-1.5% / h, or 0.8-1.1% / h, or 1.5-2.2% / h; (2) Specific surface area = 400-1000 m 2 / g, such as 400-800 m 2 / g, or 450-700 m 2 / g, or 600-970 m 2 / g, or 600-960 m 2 / g, or 630-960 m 2 / g, or 640-955 m 2 / g, or 600-750 m 2 / g, or 600-860 m 2 / g, or 611.9-851.3 m 2 / g, or 730-860 m 2 / g, or 720-840 m 2 / g, or 650-850 m 2 / g, or 732.6-851.3 m 2 / g, or 611.9-737.8 m 2 / g; (3) pore volume = 0.2-0.6 mL / g, such as 0.2-0.55 mL / g, or 0.25-0.55 mL / g, 0.25-0.5 mL / g, or 0.3-0.6 mL / g, or 0.3-0.5 mL / g, or 0.4-0.5 mL / g, or 0.41-0.46 mL / g, or 0.41-0.44 mL / g, or 0.38-0.48 mL / g; (4) crystallinity = 55-90%, such as 60-90%, or 60-78%, or 60-75%, or 60-67%, or 61-75%, or 65-75%; (5) unit cell parameter = 2.454-2.473 nm, such as 2.457-2.470 nm, or 2.460-2.467 nm, or 2.460-2.466 nm, or 2.461-2.467 nm, or 2.463-2.467 nm; Optionally, the catalyst further has at least one, preferably all, of the following characteristics: (6) framework silica to alumina ratio (molar ratio of Si02 / Al203) = 2.0-7.0, such as 3.0-6.7, or 4.0-6.3, or 4.8-6.3, or 2.0-6.0, or 5.0-6.2, or 5.0-6.1, or 5.1-6.1, or 5.0-6.0; (7) porosity = 3-30%, such as 3-20%, or 5-20%, or 5-12%, or 8-20%, or 9.2-19.4%, or 9.1-18.5%, or 9.2-18.2%, or 9.8-18.2%, or 9.4-19.4%, or 9.0-19.5%; (8) optionally, meso-macroporosity = 20-40%, such as 25-37%, or 25-36%, or 25-35%, or 26-36%, or 25.1-34.2%, or 25.1-35.9%, or 25.1-36%, or 25.1-37.2%, or 25.7-36.2%, or 25.7-35.9%, or 26-37.9%, or 26.8-35.5%; (9) trimethylpyridine acidity = 100-500 μmol / g, such as 280-411 μmol / g, or 250-450 μmol / g, or 280-420 μmol / g, or 280-413 μmol / g.

5. A calcined aluminosilicate material characterized in that The calcined aluminosilicate material is obtained by calcining particles of a kaolinite-rich and carbon-containing mineral substance having a particle size in the range of 0.1-3.0 micrometers (e.g. 0.1-2.5 micrometers, further e.g. 0.5-2.0 micrometers) at 400-920°C, such as 450-900°C, further e.g. 500-800°C, Preferably, the kaolinite-rich and carbon-containing mineral substance comprises / consists of kaolin, fireclay and coal gangue, and / or Preferably, the kaolinite-rich and carbon-containing mineral substance (based on its total weight of 100 wt%) has the following properties: kaolinite content higher than 50 wt%, such as higher than 60 wt%, or higher than 70 wt%, or higher than 80 wt%; carbon content of 0.5-20 wt%, such as 0.7-14 wt%, or 0.5-10 wt%, or 1.0-8.0 wt%; titania content of 0.1-3.0 wt%, such as 0.5-2.0 wt%, or 0.7-1.5 wt%; iron oxide content of 0.05-3.0 wt%, such as 0.2-1.0 wt%; sum of sodium oxide and potassium oxide content of 0.01-0.5 wt%; More preferably, the kaolinite-rich and carbon-containing mineral is a coal gangue having the following properties: based on 100 wt% of the coal gangue before ignition, a kaolinite content higher than 80 wt%; a carbon content of 0.5-15 wt%, such as 0.8-9.2 wt%; BET specific surface of 15-33 m 2 / g, for example 19-26 m 2 / g; a total pore volume of 0.08-0.15 cc / g, such as 0.09-0.12 cc / g, or 0.098-0.116 cc / g; a quartz sand content of 0.5-3 wt%, such as 0.9-2 wt%; based on 100 wt% of the coal gangue after ignition, a Na content of 0.01-0.4 wt% as Na2O, such as 0.02-0.4 wt%, or 0.024-0.308 wt%; a K content of 0.02-0.4 wt% as K2O, such as 0.04-0.2 wt%, or 0.0537-0.154 wt%; a sum of Na and K content of not more than 0.5 wt% as Na2O and as K2O, such as 0.06-0.5 wt%, or 0.0935-0.46 wt%; a Mg content of 0.015-0.5 wt% as MgO, such as 0.05-0.15 wt%, or 0.078-0.106 wt%; an Al content of 30-60 wt% as Al2O3, such as 40-50 wt%, or 45.5-46.6 wt%; a Si content of 30-60 wt% as SiO2, such as 45-55 wt%, or 49.7-52 wt%; a Ca content of 0.03-1.5 wt% as CaO, such as 0.1-0.4 wt%, or 0.158-0.288 wt%; a Ti content of 0.5-5 wt% as TiO2, such as 0.6-2 wt%, or 0.799-1.34 wt%; a Fe content of 0.05-1.2 wt% as Fe2O3, such as 0.15-0.8 wt%, or 0.211-0.578 wt%; and / or Preferably, the calcined aluminosilicate material has the following properties: BET specific surface of 35-56 m 2 / g, such as 40-50 m 2 / g, or 42-49 m 2 / g, or 44-48 m 2 / g; a total pore volume of 0.04-0.08 cc / g, such as 0.05-0.07 cc / g; a particle size of 0.1-3.0 microns; a content of tetrahedrally and pentahedrally coordinated Al2O3 of 25-90 wt% based on Al2O3 in the calcined aluminosilicate material, such as 40-80 wt%, or 50-80 wt%, or 40.1-76.2 wt%, or 41.1-75.2 wt%; having Q 4 a content of SiO2in the structure of Q (0Al) of 30-95 wt%, such as 40-90 wt%, or 41.3-80.0 wt%, or 41.3-80.1 wt%, or 55-75 wt%; a Na content of 0.01-0.4 wt% as Na2O, such as 0.02-0.4 wt%, or 0.024-0.308 wt%; a K content of 0.02-0.4 wt% as K2O, such as 0.04-0.2 wt%, or 0.0537-0.154 wt%; a sum of Na and K content of not more than 0.5 wt% as Na2O and as K2O, such as 0.06-0.5 wt%, or 0.0935-0.46 wt%; Mg in an amount of 0.015-0.5 wt% MgO, such as 0.05-0.15 wt%, or 0.078-0.106 wt%; Al in an amount of 30-60 wt% AI2O3, such as 40-50 wt%, or 45.5-46.6 wt%; Si in an amount of 30-60 wt% SiO2, such as 45-55 wt%, or 49.7-52 wt%; Ca in an amount of 0.03-1.5 wt% CaO, such as 0.1-0.4 wt%, or 0.158-0.288 wt%; Ti in an amount of 0.5-5 wt% TiO2, such as 0.6-2 wt%, or 0.799-1.34 wt%; Fe in an amount of 0.05-1.2 wt% Fe2O3, such as 0.15-0.8 wt%, or 0.211-0.578 wt%.

6. A method of making the Mg-containing and / or V-containing reactive metal aluminosilicate composite material of the preceding claim 1, comprising the steps of: (1) washing, crushing and grinding a kaolinite-rich and carbon-containing mineral, sieving out a fraction having a particle size in the range of 0.1-3.0 microns (such as 0.1-2.5 microns, further such as 0.5-2.0 microns), and calcining the sieved fraction at a temperature in the range of 400-920 °C, such as 450-900 °C, further such as 500-800 °C, for a time in the range of 1-8 hours, such as 2-8 hours, 1.5-6 hours, further such as 2-4 hours, to obtain a calcined aluminosilicate material; Preferably, the kaolinite-rich and carbon-containing mineral comprises / consists of kaolin, fireclay and coal gangue, and / or Preferably, the kaolinite-rich and carbon-containing mineral has the following properties (based on 100 wt% of the total weight of the mineral): a kaolinite content higher than 50 wt%, such as higher than 60 wt%, or higher than 70 wt%, or higher than 80 wt%; a carbon content in the range of 0.5-20 wt%, such as 0.5-10 wt%, 1.0-8.0 wt%, or 0.7-14 wt%; a titania content in the range of 0.1-3.0 wt%, such as 0.5-2.0 wt%; an iron oxide content in the range of 0.05-3.0 wt%, such as 0.2-1.0 wt%; a sum of sodium oxide and potassium oxide content in the range of 0.01-0.5 wt%; More preferably, the kaolinite-rich and carbon-containing mineral is a coal gangue having the following properties: based on 100 wt% of the coal gangue before ignition, a kaolinite content higher than 80 wt%; a carbon content in the range of 0.5-15 wt%, such as 0.8-9.2 wt%; BET specific surface of 15-33 m 2 / g, such as 19-26 m 2 / g; a total pore volume in the range of 0.08-0.15 cc / g, such as 0.09-0.12 cc / g, or 0.098-0.116 cc / g; a quartz sand content in the range of 0.5-3 wt%, such as 0.9-2 wt%; based on 100 wt% of the coal gangue after ignition, a sodium content in the range of 0.01-0.4 wt% Na2O, such as 0.02-0.4 wt%, or 0.024-0.308 wt%; K in an amount of 0.02-0.4 wt% as K2O, such as 0.04-0.2 wt%, or 0.0537-0.154 wt%; Na and K in a combined amount of no more than 0.5 wt% as Na2O and as K2O, such as 0.06-0.5 wt%, or 0.0935-0.46 wt%; Mg in an amount of 0.015-0.5 wt% as MgO, such as 0.05-0.15 wt%, or 0.078-0.106 wt%; Al in an amount of 30-60 wt% as Al2O3, such as 40-50 wt%, or 45.5-46.6 wt%; Si in an amount of 30-60 wt% as SiO2, such as 45-55 wt%, or 49.7-52 wt%; Ca in an amount of 0.03-1.5 wt% as CaO, such as 0.1-0.4 wt%, or 0.158-0.288 wt%; Ti in an amount of 0.5-5 wt% as TiO2, such as 0.6-2 wt%, or 0.799-1.34 wt%; Fe in an amount of 0.05-1.2 wt% as Fe2O3, such as 0.15-0.8 wt%, or 0.211-0.578 wt%; and / or Preferably, the calcined aluminosilicate material has the following properties: BET specific surface of 35-56 m 2 / g, such as 40-50 m 2 / g, or 42-49 m 2 / g, or 44-48 m 2 / g; a total pore volume of 0.04-0.08 cc / g, such as 0.05-0.07 cc / g; a particle size of 0.1-3.0 microns; Al2O3 in an amount of 25-90 wt% as Al2O3, such as 40-80 wt%, or 50-80 wt%, or 40.1-76.2 wt%, or 41.1-75.2 wt%; having Q 4 a content of SiO2in the structure of Q (0Al) of 30-95 wt%, such as 40-90 wt%, or 41.3-80.0 wt%, or 41.3-80.1 wt%, or 55-75 wt%; Na in an amount of 0.01-0.4 wt% as Na2O, such as 0.02-0.4 wt%, or 0.024-0.308 wt%; K in an amount of 0.02-0.4 wt% as K2O, such as 0.04-0.2 wt%, or 0.0537-0.154 wt%; Na and K in a combined amount of no more than 0.5 wt% as Na2O and as K2O, such as 0.06-0.5 wt%, or 0.0935-0.46 wt%; Mg in an amount of 0.015-0.5 wt% as MgO, such as 0.05-0.15 wt%, or 0.078-0.106 wt%; Al in an amount of 30-60 wt% as Al2O3, such as 40-50 wt%, or 45.5-46.6 wt%; Si in an amount of 30-60 wt% as SiO2, such as 45-55 wt%, or 49.7-52 wt%; Ca in an amount of 0.03-1.5 wt% as CaO, such as 0.1-0.4 wt%, or 0.158-0.288 wt%; Ti in an amount of 0.5-5 wt% as TiO2, such as 0.6-2 wt%, or 0.799-1.34 wt%; Fe content of 0.05 to 1.2 wt% as Fe2O3, such as 0.15 to 0.8 wt%, or 0.211 to 0.578 wt%; (2) mixing the calcined aluminosilicate material, the binder, the modifier, and water to form a slurry, and then spray forming the slurry at high pressure (e.g., 1 to 10 MPa, preferably 3 to 7 MPa) to obtain the magnesium-containing and / or vanadium reactive metal-containing aluminosilicate composite material; Preferably, the binder is added in an amount of 2 to 20 wt% of the total mass of the calcined aluminosilicate material, the modifier is added in an amount of 0.1 to 10 wt% of the total mass of the calcined aluminosilicate material, such as 0.5 to 8 wt%; the binder is one or more of water glass, sodium silicate, sodium pyrophosphate, silica sol, alumina sol, silica-alumina gel, silica-alumina sol, phosphorus-aluminum gel, phosphorus-aluminum sol, and acidified pseudo-boehmite; the modifier is one or more of magnesium nitrate, basic magnesium carbonate, and magnesium carbonate, and / or the modifier is a precursor of a vanadium reactive metal oxide, such as one or more of a vanadium reactive metal nitrate, a vanadium reactive metal basic carbonate, a vanadium reactive metal carbonate, or a vanadium reactive metal chloride.

7. A method for preparing the catalyst of any one of the preceding claims 2 to 4, the method comprising the steps (1) and (2) of the method of claim 6 and further comprising: (3) mixing the magnesium-containing and / or vanadium reactive metal-containing aluminosilicate composite material obtained in step (2) with a silica source (such as one or more selected from the group consisting of water glass, sodium silicate, colloidal silica, and organosilica), an alkali source (such as sodium hydroxide and potassium hydroxide), a directing agent, and water, and then subjecting the mixture to in-situ hydrothermal crystallization to obtain the catalyst containing a Na-type molecular sieve such as NaY-type molecular sieve; Preferably, the yield of fine powder having a particle size of not more than 20 μm produced in the preparation of the catalyst containing a Na-type molecular sieve such as NaY-type molecular sieve is not more than 10 wt%; the hydrothermal crystallization is carried out under conditions including: a temperature of 80 to 105°C, such as 85 to 105°C; a time of 1 to 160 hours, such as 8 to 80 hours; a weight ratio of the silica source (calculated as SiO2) to the magnesium-containing and / or vanadium reactive metal-containing aluminosilicate composite material (calculated as dry basis) of (0.1 to 10): 1, (0.3 to 3): 1, (0.6 to 2.5): 1; a weight ratio of the alkali source (calculated as MB2O, wherein MB represents an alkali metal) to the magnesium-containing and / or vanadium reactive metal-containing aluminosilicate composite material (calculated as dry basis) of (0.01 to 1): 1, (0.04 to 0.7): 1, (0.07 to 0.4): 1; a weight ratio of the directing agent (calculated as Al2O3) to the magnesium-containing and / or vanadium reactive metal-containing aluminosilicate composite material (calculated as dry basis) of (0.001 to 2): 1, (0.003 to 0.1): 1, (0.005 to 0.05): 1; The weight ratio of water to the magnesium-containing and / or vanadium-containing reactive metal-containing aluminosilicate composite material (dry basis) is (3-100):1, (5-65):1, (7-30):1; The directing agent is obtained by aging sodium silicate, sodium aluminate and sodium hydroxide and water in the following molar ratio (11-16) Na2O·Al2O3·(10-16) SiO2·(100-350) H2O at room temperature to 70°C for 5-50 hours; Optionally, (4) filtering, washing, and exchanging, such as rare earth exchanging and / or ammonium salt exchanging and / or phosphorus exchanging, drying and calcining, of the catalyst containing Na-containing molecular sieve, such as NaY-type molecular sieve, preferably, the exchanging comprises rare earth exchanging and optional ammonium salt exchanging and / or phosphorus exchanging, drying and calcination, to obtain a catalyst containing rare earth modified molecular sieve, such as rare earth modified Y-type molecular sieve; Preferably, the catalyst has a crystallinity > 60%; a unit cell parameter = 2.454-2.473 nm, such as 2.457-2.470 nm, or 2.460-2.467 nm, or 2.460-2.466 nm, or 2.461-2.467 nm, or 2.463-2.467 nm; and a relative crystalline retention of 30%-50% after 17 hours of aging at 800°C, 1 atm pressure and 100% water vapor atmosphere.

8. The method according to claim 7, characterized in that, The step (4) is performed, wherein the conditions of the exchanging include: adjusting pH = 2-6 with an acid, and the exchanging is performed at 50-95°C; the temperature of the calcination is 500-950°C, such as 650-800°C; the time of the calcination is 1-8 hours, such as 2-4 hours; the temperature of the drying is 120-400°C, such as 150-200°C; the time of the calcination is 1-8 hours, such as 2-4 hours; the exchanging is performed 1-3 times, the calcination is performed 1-3 times, and the drying is performed 1-3 times, and the drying and / or calcination is performed after the exchanging, and if the drying is performed, the drying is performed first, and then the calcination is performed; or only the calcination is performed, and the drying is not performed; or only the drying is performed, and the calcination is not performed; and if the drying is not performed, the calcination is performed directly; Preferably, the acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; Preferably, the rare earth used in the rare earth exchanging is one or more of nitrate rare earth, chloride rare earth, and hydroxide rare earth, and the rare earth is one or more of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y), and scandium (Sc), preferably, the rare earth is one or more of yttrium, lanthanum, cerium, praseodymium, and neodymium, more preferably, one or more of La, Ce, and Y; The ammonium salt used in the ammonium salt exchanging is one or more of ammonium sulfate, ammonium chloride, ammonium nitrate, and ammonium phosphate.

9. Use of the catalyst of any one of claims 2-4 in the production of light oil from heavy oil catalytic cracking.

10. Use according to claim 9, wherein, comprising reacting a heavy oil with the catalyst at a temperature of 450 to 550°C, a weight hourly space velocity of 5 to 30 hours, a catalyst to oil ratio of 1 to 15 (weight ratio), the heavy oil being one or more of atmospheric residue, atmospheric gas oil, vacuum residue, vacuum gas oil, coker gas oil, light heavy deasphalted oil, hydrocracked LCO, hydrocracking tail oil, hydrocracked VGO, hydrocracked residue, intermediate base crude oil -1 ,

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