FR3012125A1 - - Google Patents

Abstract

The present invention relates to a metal-modified Y zeolite, its preparation and use. Said zeolite contains from 1 to 15% by weight of a Group IVB metal as the oxide and is characterized in that the ratio of the group IVB metal content of the zeolite surface to the metal content of the IVB group of the interior of the zeolite is not greater than 0.2; and / or in that the ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum in the zeolite network structure is (0.1 to 0.8): 1 .

Description

TECHNICAL FIELD The present invention relates to a metal modified Y zeolite, its preparation and its use.  Background As the catalytic cracking feed becomes increasingly heavy, it is essential that the catalytic cracking catalyst has both superior activity and superior thermal and hydrothermal stabilities to increase heavy conversion and non-contamination capabilities. heavy metals.  Therefore, it is necessary that the main active component in the catalytic cracking catalyst, i.e. zeolite Y, has high thermal and hydrothermal stabilities, and remains an appropriate contribution of acidic active centers.  Rare earth modified (RE) Y zeolite has high relative thermal and hydrothermal stabilities, and is widely used in FCC catalyst (Fluid Catalytic Cracking).  However, the sudden spike in the price of rare earths is resulting in a significant increase in the cost of the FCC catalyst.  Therefore, it is desirable to introduce other metal ions into zeolite Y, to reduce the rare earth content in zeolite Y and to ensure hydrothermal stability comparable to zeolite Y with a high rare earth content. .  CN1350887A, CN1765492A and US2007010698A1 disclose methods for preparing metal-modified Y zeolites.  However, in comparison to the rare earth modified Y zeolite, the metal-modified Y zeolites above have poor thermal and hydrothermal stabilities.  Documents CN101898144A and CN101134576A propose the modification of the zeolite Y framework in order to increase the thermal and hydrothermal stabilities of Y zeolites.  However, metal-modified Y zeolites other than the resulting rare earths produce a low gasoline yield in catalytic cracking.  SUMMARY Solving the problems of the prior art, the present invention provides a metal modified Y zeolite and method of preparation thereof.  The metal-modified Y zeolite is modified by rare earth-free metal elements, and has a thermal and hydrothermal stability comparable to the rare earth-modified Y zeolite.  And when used in the catalytic cracking catalyst, the catalyst may exhibit excellent properties in cracking activity, gasoline yield, and coke selectivity.  In one aspect, the present invention relates to a metal-modified Y zeolite, characterized in that: the ratio of the group IVB metal content of the zeolite surface to the IVB metal content of the interior of the zeolite zeolite is not greater than 0.2; and / or the ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum in the zeolite network structure is (0.1 to 0.8): 1.  In another aspect, the present invention relates to a process for preparing the metal-modified Y zeolite, comprising the following steps: (1) a zeolite Y raw material is dewatered so that the raw material has a content of water by weight not exceeding 5%; (2) zeolite Y obtained in step (1) is contacted with a mixture of a Group IVB metal-containing compound and an organic solvent, and the resulting mixture is optionally filtered and / or dried; (3) zeolite Y obtained in step (2) is calcined at 300 to 700 ° C, preferably for at least 0.5 hours, for example 0.5 to 5 hours; (4) the zeolite Y obtained in step (3) is brought into contact with an aqueous acidic solution and then calcined at 400 to 800 ° C under a steam condition of 1 to 100% for 0.5 to 5 hours for producing the metal-modified Y zeolite containing the Group IVB metal; the concentration of acid, as H +, is 0.1 to 2.0 mol / l.  In another aspect, the present invention relates to a process for preparing the metal-modified Y zeolite, comprising the following steps: (1) zeolite Y is treated by contacting with an acidic solution and / or an aqueous solution of EDTA; said acid being an organic acid and / or an inorganic acid; (2) the product obtained in step (1) is dehydrated at a temperature below 400 ° C, so that the water content in the zeolite is not greater than 5% by weight; (3) the zeolite obtained in step (2) is impregnated with a metal in an organic solvent; (4) the metal-impregnated Y zeolite obtained in step (3) and an organic solvent are added in a tank at a solid-liquid weight ratio of 1: (5 to 50) and mixed, an inert gas such as one or more of the nitrogen and helium is introduced into the vessel, and the vessel is maintained at a pressure of 0 to 2.0 MPa (gauge pressure) at a temperature in the range of room temperature to 200 ° C for at least one hour, for example 1 to 48 hours; filtration and / or drying are optionally conducted, preferably filtration and drying are conducted; (5) the zeolite obtained in step (4) is calcined; the calcination is conducted in an inert gas atmosphere, the calcination temperature is 300 to 700 ° C, the calcination time is at least 0.5 hours, for example 0.5 to 5 hours.  In another aspect, the present invention also relates to a catalytic cracking catalyst containing the metal modified zeolite Y and its method of preparation.  Specifically, the present invention involves the following technical solutions:  A metal-modified Y zeolite, which contains 1 to 15% by weight of a Group IVB metal as the oxide, in which the metal-modified Y zeolite has a ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum in the network structure of 0.1 to 0.8, for example 0.2 to 0.8.  2.  Metal-modified zeolite Y according to solution 1, which has a specific surface area of 600 to 850 m2 / g or 600 to 750 m2 / g, an elemental mesh size a0 of 2,448 to 2,458 nm or 2,450 to 2,455 nm, a crystallinity not less than 60%, and optionally a S102 / Al2O3 molar ratio (Si / Ald'ossature atomic ratio) of 5 to 50 and the percentage between the secondary pores (pore diameter 6 to 20 nm) and the total secondary pores (diameter pore size of 2 to 100 nm) being 30 to 50% or 50% to 65%.  3.  A metal-modified Y zeolite according to any one of the preceding solutions, wherein the modifying metal is Ti and / or Zr, wherein with respect to the unmodified Y zeolite, the antisymmetric valency vibration frequency (1050 to 1150 cm-1) and the symmetrical valence vibration frequency (750 to 820 cm-1) in the infrared spectrum of the metal-modified Y zeolite do not shift to red in a downward direction.  4.  A metal-modified Y zeolite according to any one of the preceding solutions, which has a formula of anhydrous chemical composition, as oxide and by weight, of (0-2) Na2O- (1-15) MO2- (10-) 25) Al2O3- (65-75) 5iO2 4 3012125 (0.1-1.2) Na2O- (1-10) MO2- (20-24) Al2O3- (67-74) SiO2, wherein M is a metal group IVB, selected from one or more of Ti, Zr, Hf and Rf.  5.  A metal-modified Y zeolite according to any one of the preceding solutions, wherein the Group IVB metal is Ti and / or Zr, and the metal-modified Y zeolite is free of both framework Ti and Zr frame.  6.  A metal-modified Y zeolite according to any one of the preceding solutions, wherein the ratio of the Group IVB metal content of the zeolite surface to the Group IVB metal content of the interior of the zeolite is not greater than 0.2.  7.  A metal-modified Y zeolite according to any one of the preceding solutions wherein the Group IVB metal content as the oxide is from 1 to 10% by weight.  8.  A metal-modified Y zeolite according to any one of the preceding solutions, wherein the Group IVB metal comprises Ti and / or Zr.  9.  A process for preparing a metal-modified Y zeolite, comprising the steps of: (1) zeolite Y is contacted with an acid solution and / or an aqueous EDTA solution; said acid being an organic acid and / or an inorganic acid; (2) the product obtained in step (1) is dehydrated at a temperature below 400 ° C, so that the water content in the zeolite is not greater than 5% by weight; (3) the zeolite obtained in step (2) is impregnated with a metal in an organic solvent; (4) the metal-impregnated zeolite Y obtained in step (3) and an organic solvent are added in a vessel at a solid-liquid weight ratio of 1: 5 to 50, an inert gas is introduced into the vessel, and the vessel is maintained at a pressure of 0 to 2.0 MPa, preferably 0.1 to 2 MPa (gauge pressure) at a temperature in the range of room temperature to 200 ° C for at least one hour; filtration and / or drying are optionally conducted; (5) the zeolite obtained in step (4) is calcined; the calcination is conducted in an inert gas atmosphere, the calcination temperature is 300 to 700 ° C, the calcination time is 0.5 to 5 hours.  10.  A process according to any one of the preceding solutions, wherein in step (1) zeolite Y is one or more of zeolite NaY, NaHY, NaNH4Y, NH4Y, HY, USY, DASY, zeolite Y exchanged once - Once calcined, a zeolite Y exchanged twice - calcined twice, and a zeolite Y exchanged twice - calcined once.  11.  A process according to any one of the preceding solutions wherein in step (1) zeolite Y is contacted with the acidic solution in a solid-liquid weight ratio of 1: 5 to 1:20 at a temperature in a range from room temperature to 100 ° C for at least 0.5 hours, then filtered and washed; the acid solution has an acid concentration, as W, of 0.1 to 1 mol / L.  12.  A method according to any one of the preceding solutions, wherein the contact time is 0.5 to 3 hours; the acid is an inorganic acid and / or an organic acid; wherein the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid; and the organic acid is one or more of formic acid, acetic acid, oxalic acid, citric acid.  13.  A process according to any one of the preceding solutions wherein in step (2), the dehydration is for calcining the zeolite obtained in step (1) at 200 to 400 ° C for 2 to 10 hours.  14.  A process according to any one of the preceding solutions, wherein in step (3) the impregnation with the metal in the organic solvent comprises mixing the organic solvent in which a Group IVB metal-containing compound is dissolved with the zeolite obtained in step (2), and the resulting mixture is stored for at least 0.5 hours, wherein the solid-liquid weight ratio of zeolite Y and organic solvent is 1: (0.5 to 5).  15.  A process according to any one of the preceding solutions wherein in step (3) the resulting mixture is stored at rest or stirred for 0.5 to 12 hours.  16.  A process according to any one of the preceding solutions wherein in step (3) the solid-liquid weight ratio of zeolite Y and organic solvent is 1: 1 to 2.  17.  A process according to any one of the preceding solutions, wherein the Group IVB metal-containing compound is a Ti-containing compound and / or a Zr-containing compound; the Ti-containing compound is one or more of titanium sulphate, titanyl sulphate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate, and ammonium fluotitanate, and the Zr-containing compound is one or more among zirconium tetrachloride, zirconium sulphate, zirconium nitrate, zirconium oxychloride, zirconium acetate, and zirconium isopropoxide.  18.  A process according to any one of the preceding solutions wherein in step (4) the vessel is stored for 1 to 48 hours.  19.  A process according to any one of the preceding solutions wherein in step (4) the pressure is 0.5 to 1.5 MPa, the temperature is from room temperature to 150 ° C, the time is 4 at 24 hours, and the solid-liquid weight ratio of the zeolite and the organic solvent is 1: 5 to 30.  20.  A process according to any one of the preceding solutions wherein in step (5) the calcination temperature is 450 to 650 ° C, and the calcination time is 1 to 4 hours.  21.  A process according to any one of the preceding solutions, wherein the organic solvent of step (3) and / or (4) has a water content of not more than 5% by weight.  22.  A process according to any one of the preceding solutions, wherein the organic solvent of step (3) and / or (4) has a water content of not more than 3% by weight; and the zeolite Y obtained in step (2) has a water content of not more than 3% by weight.  23.  A process according to any one of the preceding solutions, wherein the organic solvent is one or more of alkanes, aromatic hydrocarbons, alcohols, ketones, ethers, esters, halogenated alkanes such as chlorinated alkanes.  24.  A process according to any one of the preceding solutions, wherein the organic solvent has a normal boiling point of 40 to 100 ° C.  25.  A process according to any one of the preceding solutions, wherein the organic solvent is preferably one or more of n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol. , acetone, butanone, and trichloromethane.  26.  A process for preparing a metal-modified Y zeolite, comprising the following steps: (1) a zeolite Y raw material is dewatered so that the raw material has a water content by weight of no more than 5%; (2) the dehydrated zeolite Y obtained in step (1) is contacted with a mixture of a Group IVB metal-containing compound and an organic solvent, and the resulting mixture is optionally filtered and / or dried; (3) zeolite Y obtained in step (2) is calcined at 300 to 700 ° C; (4) the zeolite Y obtained in step (3) is contacted with an aqueous acidic solution and then calcined at 400 to 800 ° C to produce the metal-modified zeolite Y containing the Group IVB metal; the concentration of acid, as H +, is 0.1 to 2.0 mol / l.  27.  A process according to any one of the preceding solutions, wherein in step (2), the mixture weight ratio of the Group IVB metal-containing compound, zeolite Y and the organic solvent is 0.01 to 0 , 15: 1: 1 to 50, wherein the weight of the Group IVB metal-containing compound is calculated as the oxide, and zeolite Y is calculated in a dry base.  28.  A process according to any one of the preceding solutions, wherein in step (2), the compound weight ratio containing the Group IVB metal (as oxide): zeolite Y (dry base): organic solvent is 0.01 to 0.1: 1: 5 to 30.  29.  A process according to any one of the preceding solutions, wherein in step (2), the procedure for contacting the dried zeolite Y obtained in step (1) with the group IVB metal-containing compound and the Organic solvent and optional filtration and / or drying comprises the following steps: the Group IVB metal-containing compound, the organic solvent and the Y zeolite are mixed and contacted at a temperature in a range of 100 ° ambient temperature C for at least 0.5 hours, then optionally filtered, and then optionally dried.  30.  A process according to any one of the preceding solutions wherein in step (2), the procedure for contacting the dried zeolite Y obtained in step (1) with the mixture of the group IVB metal-containing compound and the optional organic and filtering and / or drying solvent of the resulting mixture is conducted once or more than once.  31.  Process according to any one of the preceding solutions, in which in step (3), the calcination temperature is from 350 to 650 ° C, the calcination time is from 2 to 4 hours, the calcination atmosphere is a dried air and / or inert gas.  32.  A process according to any one of the preceding solutions, wherein in step (4), the contacting condition of the Y zeolite obtained in step (3) and the aqueous acid solution comprises the following characteristics: ratio by weight (solid-liquid ratio) between the zeolite Y obtained in step (3) and the aqueous acid solution is from 1: 5 to 20, the contact temperature is in a range from room temperature to 100 ° C the contact time is at least 0.5 hours; the aqueous acid solution has an acid concentration, as H +, of 0.1 to 2 mol / L.  33.  A process according to any one of the preceding solutions, wherein the aqueous acidic solution has an acid concentration, as H +, of 0.5 to 2 moles / L.  34.  A process according to any one of the preceding solutions, wherein the organic solvent is one or more of alkanes, aromatic hydrocarbons, alcohols, ketones, ethers, esters, halogenated alkanes such as chlorinated alkanes.  35.  A process according to any one of the preceding solutions, wherein the organic solvent is selected from one or more of n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, methanol, and the like. isopropanol, acetone, butanone, trichloromethane.  36.  A process according to any one of the preceding solutions, wherein the organic solvent has a normal boiling point of 40 to 100 ° C.  37.  A process according to any one of the preceding solutions, wherein the organic solvent has a water content of not more than 5% by weight.  38.  A process according to any one of the preceding solutions, wherein the organic solvent has a water content of not more than 1% by weight.  39.  A process according to any one of the preceding solutions wherein in step (2) the contacting temperature of the dehydrated zeolite Y obtained in step (1) and the mixture of the group IVB metal-containing compound and organic solvent is a temperature that allows the organic solvent to be in a liquid state.  40.  A method according to any one of the preceding solutions, wherein the group IVB metal-containing compound comprises a Ti-containing compound and / or a Zr-containing compound.  41.  A process according to any one of the preceding solutions, wherein the Ti-containing compound is one or more of titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate, fluotitanate. ammonium, and the Zr-containing compound is one or more of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, zirconium acetate and zirconium isopropoxide.  42.  A process according to any one of the preceding solutions wherein in step (1) the zeolite Y raw material is one or more of a NaY zeolite, a NaHY zeolite, a NaNH4Y zeolite, an NH4Y zeolite and a HY zeolite. .  43.  A process according to any one of the preceding solutions, wherein in step (1), the raw zeolite material Y has a water content, after dehydration, of not more than 1% by weight.  3012125 '44.  A process according to any one of the preceding solutions wherein in step (4) the calcination is conducted in a steam atmosphere of 1 to 100%.  45.  A metal-modified Y zeolite according to any one of the solutions 1 to 8 which is obtained or obtainable by the process of any of the solutions 9 to 44.  46.  Catalytic cracking catalyst, based on the weight of the catalyst, containing 10 to 60% by weight of a metal-modified Y zeolite, 10 to 60% by weight of a clay and 5 to 50% by weight of a binder, wherein said metal-modified Y zeolite is the metal-modified Y zeolite of any of the solutions 1 to 8.  47.  Catalytic cracking catalyst according to solution 46, wherein the catalytic cracking catalyst contains 20 to 55% by weight of Group IVB metal-modified zeolite Y, 15 to 60% by weight of the clay and 10 to 40% by weight of the binder.  48.  A catalytic cracking catalyst according to solution 46, wherein the catalyst further contains other molecular sieves customarily used in the catalytic cracking catalyst, said other molecular sieves include molecular sieves of type Y, molecular sieves with MFI structure, and SAPO molecular sieves.  49.  A catalytic cracking catalyst according to solution 46, wherein the content of other molecular sieves conventionally used in the catalytic cracking catalyst is not more than 40% by weight, such as 1 to 35% by weight.  50.  A method of preparing the catalytic cracking catalyst, which comprises the steps of preparing a metal-modified Y zeolite, mixing and slurrying the metal-modified Y zeolite and a clay and a binder, and spray-drying the resulting mixture, in wherein said metal-modified Y zeolite is prepared according to the method of any of the solutions 9 to 44.  51.  A method according to solution 50, wherein the clay is selected from one or more of kaolin, halloysite, rectorite, diatomite, montmorillonite, bentonite and sepiolite; and the binder is selected from one or more of hydrated alumina, alumina sol, pseudobohemite, bohemite, alumina monohydrate, alumina trihydrate, and amorphous aluminum hydroxide.  52.  A solution according to any one of the above solutions 1 to 51, wherein the metal-modified Y zeolite contains substantially none of V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Ir, Ni, Pd, Pt, Cu, Zn, Ag, Au, Cd, Hg, Sc and Y.  Brief Description of the Drawings Fig. 1 is a Fourier transform infrared (FT-FT) spectrum for type Y zeolite (Y) and metal modified Y zeolites prepared in Examples B. 1. 1. 2, 8. 1. 1. 6 and B. 1. 2. 4.  Figure 2 is a 27AI nuclear magnetic resonance spectrum (27AI NMR) for type Y zeolite (Y) and metal modified Y zeolites prepared in Examples B. 1. 1. 2, B. 1. 2. 2 and B. 1. 2. 5.  DETAILED DESCRIPTION Zeolite Modified The first metal-modified Y zeolite according to the present invention is characterized in that the ratio of the Group IVB metal content of the zeolite surface to the Group IVB metal content of the interior of the zeolite is not greater than 0.2; for example 0.001 to 0.2; or 0.02 to 0.18.  The second metal-modified Y zeolite according to the present invention is characterized in that the ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum in the zeolite network structure is ( 0.1 to 0.8): 1; (0.2 to 0.8): 1; (0.2 to 0.6): 1; (0.1 to 0.6): 1; or (0.2 to 0.5): 1.  The third metal-modified Y zeolite according to the present invention is characterized in that the ratio of the group IVB metal content of the zeolite surface to the group IVB metal content of the interior of the zeolite is not more than 0.2; for example 0.001 to 0.2; or 0.02 to 0.18; and the ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum in the zeolite network structure is (0.1 to 0.8): 1; (0.2 to 0.8): 1; (0.2 to 0.6): 1; (0.1 to 0.6): 1; or (0.2 to 0. 5): 1.  The three metal-modified Y zeolites above are further characterized by one or more of the following characteristics: (1) Group IVB metal content, as oxide and with respect to metal-modified Y zeolite: 1 to 15% by weight, or 1 to 10% by weight; (2) specific surface area: 600 to 850 m2 / g, 600 to 750 m2 / g, or 630 to 730 m2 / g; (3) elementary mesh size (expressed as a0): 2.488 to 2.458 nm, 2.50 to 2.455 nm; 2.499 to 2.455 nm; or 2,449 to 2,452nm; (4) crystallinity: not less than 60%, for example 60 to 120%, or 60 to 95%; and (5) SiO 2 / Al 2 O 3 molar ratio: 5 to 50, 5 to 20, 5 to 8, 5 to 6 (6) the percentage between the secondary pores (pore diameter 6 to 20 nm) and the total secondary pores ( pore diameter of 2 to 100 nm) being 30 to 50% or 50% to 65%, for example 35%, 40%, 45%, 50%, 55%, 60%.  According to the present invention, the Group IVB metal is selected from one or more of Ti, Zr, Hf and Rf, for example one or more of Ti, Zr and Hf, preferably Ti and / or Zr.  According to the present invention, as the oxide and by weight, the metal-modified zeolite Y has a formula of anhydrous chemical composition, as oxide and by weight, of (0-2) Na2O- (1-15) M02- (10-25) Al2O3- (65-75) SiO2, or (0, 1-1.2) Na2O. (1-10) M02. (20-24) A1203. (67-74) SiO2; wherein M is a Group IVB metal selected from one or more of Ti, Zr, Hf and Rf.  In the metal-modified Y zeolite according to the present invention, most of the Group IVB metal ions are located within the zeolite, and a small amount of ions are present on the surface of the zeolite.  The ratio of the Group IVB metal content of the zeolite surface to the Group IVB metal content of the interior of the zeolite is not greater than 0.2.  In the present invention, including the following examples, the methods of zeolite analysis are as follows: The Group IVB metal content of the zeolite surface refers to the Group IVB metal content which can be measured in depth from 2 to 5 nm from the surface of the zeolite using X-ray photoelectron spectroscopy (XPS).  The Group IVB metal content of the interior of the zeolite refers to the difference between the Group IVB metal content of the zeolite mass and the Group IVB metal content of the zeolite surface.  The Group IVB metal content of the zeolite mass is the Group IVB metal content in the zeolite that can be obtained via a chemical analysis method.  The ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum refers to the ratio of the spectral peak area to a chemical shift of 40 to that to a chemical shift of 60. , measured by MAS NMR 27AI.  Secondary pores are determined and measured according to the standardized method RIPP151-90.  Reference can be made to Analytical Methods in Petrochemical Industry (RIPP Experiment Techniques), Yang Cuiding et al, Science Press, 1990.  The elemental content is determined by X-ray fluorescence spectrometry.  The specific area is determined by the BET method.  Elementary mesh size and crystallinity are determined by X-ray diffraction according to the standard methods RIPP145-90 and RIPP146-90 respectively.  Reference can be made to Analytical Methods in Petrochemical Industry (RIPP Experiment Techniques), Yang Cuiding et al, Science Press, 1990.  The SiO 2 / Al 2 O 3 molar ratio (i.e., Si / Al atomic ratio of framework) is determined according to the standardized method SH / T0339-92.  The present invention relates to a process for preparing the metal-modified Y zeolite, comprising the following steps: (1) a zeolite Y raw material is dewatered so that the raw material has a content in water by weight, not more than 5%; (2) the dehydrated zeolite Y obtained in step (1) is contacted with a mixture of a Group IVB metal-containing compound and an organic solvent, and the resulting mixture is optionally filtered and / or dried; (3) zeolite Y obtained in step (2) is calcined at 300 to 700 ° C, preferably for at least 0.5 hours, for example 0.5 to 5 hours; (4) the zeolite Y obtained in step (3) is brought into contact with an aqueous acidic solution and then calcined at 400 to 800 ° C. in a steam condition of 1 to 100% for 0.5 to 5 hours in order to producing the metal-modified Y zeolite containing the Group IVB metal; the concentration of acid, as H +, is 0.1 to 2.0 mol / l.  The metal-modified Y zeolite prepared by the above-mentioned method is characterized by one or more of the following: (1) Most Group IVB metal ions are located within the zeolite, while a small amount of ions are present on the surface of the zeolite; (2) the ratio of the Group IVB metal content of the zeolite surface to the Group IVB metal content of the interior of the zeolite is not greater than 0.2; (3) the ratio of the Group IVB metal content of the zeolite surface to the Group IVB metal content of the interior of the zeolite is 0.001 to 0.2; (4) the ratio of the Group IVB metal content of the zeolite surface to the Group IVB metal content of the interior of the zeolite is 0.02 to 0.18; (5) the ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum in the zeolite network structure is (0.2 to 0.8): 1; (6) the ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum in the zeolite network structure is (0.2 to 0.6): 1; (7) the ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum in the zeolite network structure is (0.1 to 0.6): 1; and (8) the ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum in the zeolite network structure is (0.2 to 0.5): 1.  Step (1): Dehydration The raw zeolite material Y may be one or more of zeolite NaY, zeolite NH4Y, zeolite HY, zeolite NaNH4Y and zeolite NaHY, preferably zeolite NaY.  The zeolite NaY can be synthesized by crystallization.  After removal of the mother liquor, the crystallized zeolite can be used in the present invention directly or after washing.  NaY zeolite may be commercially available or may be prepared according to the method of the prior art, for example, the method disclosed in USP3671191.  The zeolite NaNH4Y is a zeolite obtained by exchange of zeolite NaY with NH4 + to a certain extent.  The NaHY zeolite can be obtained by calcining the NaNH4Y zeolite or by exchanging the NaY zeolite with H + to a certain extent.  The dehydration is preferably conducted at a temperature of not higher than 400 ° C.  Dehydration can be done by drying or calcining.  Drying can be a conventional drying method or a vacuum drying method.  When using the calcination to dehydrate, the calcination temperature is preferably not higher than 400 ° C, for example 200 to 400 ° C, usually 250 to 350 ° C.  The conventional drying method includes heat drying, air drying, flash drying or spray drying.  The drying temperature is usually not more than 200 ° C, for example 80 to 200 ° C.  The dehydrated zeolite preferably has a water content of not more than 3% by weight, preferably not more than 1% by weight.  Step (2): Contacting - Optional Filtration - Optional Drying In step (2), the dried zeolite Y obtained in step (1) is contacted with a mixture of a metal-containing compound of the group IVB and an organic solvent for introducing the modifying metal into the zeolite.  The method of contacting comprises mixing and slurrying a mixture of a Group IVB metal-containing compound and an organic solvent and zeolite Y, which is ion-exchanged at room temperature. exchange (or contact temperature).  After contact, filtration is optionally conducted.  Then, drying is optionally conducted.  The contact can be done once or more than once.  The "more than once" contact means that the zeolite obtained by the preceding treatment is contacted with a mixture of an organic solvent and a modifier metal compound; and after each contact, filtration is optional, and drying is optional.  In the case of "more than once" contact, it is best to dry after the last contact.  In the case of "more than once" contact, zeolite Y obtained by filtration may be treated directly with a Group IVB metal-containing compound and an organic solvent, or may be dried and / or calcined, and then treated. with a compound containing a Group IVB metal and an organic solvent.  There may be at least one temperature point in the exchange temperature range at which point the solvent may be present in a liquid state.  In each contact, the Group IVB metal-containing compound weight ratio (as oxide): zeolite Y (dry basis): organic solvent is (0.01 to 0.15): 1: (1 to 50 ), or (0.01 to 0.14): 1: (5 to 30), or (0.02 to 0.11): 1: (5 to 25), or (0.01 to 0.1) : 1: (5 to 30).  The contact time is for example at least 0.5 hours, for example 0.5 to 5 hours, or 1.5 to 3.5 hours.  The contact temperature may be a temperature at which the organic solvent is in a liquid state.  The exchange temperature may be a temperature range in which the organic solvent is in a liquid state.  Usually, the exchange temperature may be a temperature range, whose lower point is greater than the solidification point of the organic solvent, and whose upper point is lower than the boiling point of the organic solvent.  For example, the exchange temperature is from room temperature to a temperature which is 20 ° C lower than the normal boiling point of the organic solvent; from 0 to 100 ° C; from room temperature to 100 ° C; from 0 to 100 ° C and below 20 ° C to the normal boiling point of the organic solvent; and room temperature at 100 ° C and 20 ° C lower than the normal boiling point of the organic solvent.  The ambient temperature is 15 to 40 ° C.  The normal boiling point means the boiling point at 1 atm.  The drying temperature is usually not more than 200 ° C, for example from 0 to 200 ° C, for example from room temperature to 150 ° C, from room temperature to 120 ° C, from 100 to 120 ° C.  The drying time can be from 4 to 48 hours, from 12 to 48 hours.  The Group IVB metal may be one or more of Ti, Zr and Hf, preferably Ti and / or Zr.  The Group IVB metal-containing compound may be one or more compounds containing Ti and / or Zr, for example a Ti-containing compound, a Zr-containing compound or a Ti and Zr-containing compound.  The Group IVB metal-containing compound is preferably soluble in the organic solvent used, for example, its solubility in the organic solvent is not less than 0.1 g of the Group IVB metal-containing compound / 100 g of the solvent organic.  The Ti-containing compound may be one or more of titanium sulphate, titanyl sulphate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate, and ammonium fluotitanate, the Zr containing compound may be one or several of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, zirconium acetate, and zirconium isopropoxide.  The organic solvent has a water content of not more than 5% by weight, preferably not more than 1% by weight, for example not more than 0.1% by weight, not more than 0.01% by weight. , or not more than 0.001% by weight.  Preferably, in the organic solvent, the content of organic substance as a solvent is not less than 95% by weight, preferably not less than 99% by weight.  The organic solvent may be one or more of alkanes, aromatic hydrocarbons, alcohols, ketones, ethers, esters, halogenated alkanes such as chlorinated alkanes.  The normal boiling point of the organic solvent (1 atm) is preferably 40 to 100 ° C, which is both favorable for the dispersion of the metal component, and favorable for removing the organic solvent.  The organic solvent may be, for example, one or more of n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone, and the like. trichloromethane.  Step (3): Calcination The calcination temperature may be, for example, 300 to 700 ° C, 350 to 650 ° C, 400 to 620 ° C or 450 to 600 ° C.  The calcination time may be for example 0.5 to 5 hours, 1 to 5 hours, 2 to 4 hours.  The calcination atmosphere may be, for example, a dried air atmosphere, and / or an inert gas atmosphere, preferably an inert gas atmosphere.  The inert gas may be nitrogen and / or helium.  In the case of dried air, the water content therein is below 1% by volume, for example below 0.5% by volume.  Step (4): Acid Treatment - Calcination The contacting temperature of the aqueous acid solution with zeolite Y obtained in step (3) is in a range of room temperature to 100 ° C, for example 75 to 95 ° C.  The contact time is not less than 0.2 hours, for example 0.5 to 5 hours.  The solid-liquid contact ratio (the weight ratio of the zeolite to the aqueous acid solution) is from 1: 5 to 20, for example 1: 6 to 14.  The concentration of the aqueous acid solution used, as I-1 +, is 0.1 to 2 mol / L, 0.5 to 2 mol / L, 0.5 to 1.5 mol / L.  After contact, filtration is performed.  After filtration, the zeolite contacted with the acid is washed with water to remove the free acid, and then dried and calcined.  The calcination temperature is 400 to 800 ° C, 500 to 600 ° C.  The calcination atmosphere is a 1 to 100% vapor condition.  The calcination time is 0.5 to 5 hours, or 1 to 3 hours.  The acid used in step (4) is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, acetic acid, formic acid, preferably one or more of hydrochloric acid, oxalic acid and formic acid.  In another aspect, the present invention relates to a process for preparing the metal-modified Y zeolite, which comprises the following steps: (1) zeolite Y is treated by contacting with an acidic solution and / or an aqueous solution of 'EDTA; wherein said acid is an organic acid and / or an inorganic acid; (2) the product obtained in step (1) is dehydrated at a temperature below 400 ° C, so that the water content in the zeolite is not more than 5% by weight; (3) the zeolite obtained in step (2) is impregnated with a metal in an organic solvent; (4) the metal-impregnated Y zeolite obtained in step (3) and an organic solvent are added to a tank at a solid-liquid weight ratio of 1: 5 to 50, an inert gas such as nitrogen and / or the helium is introduced into the tank, and the tank is kept at a pressure of 0 to 2.0 MPa (gauge pressure) at a temperature in the range of room temperature to 200 ° C for at least one hour, for example from 1 to 48 hours; filtration and / or drying are optionally conducted, and filtration and drying are preferably conducted; (5) the zeolite obtained in step (4) is calcined; the calcination is conducted in an inert gas atmosphere, the calcination temperature is 300 to 700 ° C, the calcination time is 0.5 to 5 hours, or greater than 0.5 hour.  The metal-modified Y zeolite prepared by the above-mentioned method is characterized by one or more characteristics selected from: (1) most of the Group IVB metal ions are located within the zeolite, while a small number of amount of ions are present on the surface of the zeolite; (2) the ratio of the Group IVB metal content of the zeolite surface to the Group IVB metal content of the interior of the zeolite is not greater than 0.2; (3) the ratio of the Group IVB metal content of the zeolite surface to the Group IVB metal content of the interior of the zeolite is 0.001 to 0.2; (4) the ratio of the Group IVB metal content of the zeolite surface to the Group IVB metal content of the interior of the zeolite is 0.02 to 0.18; (5) the ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum in the zeolite network structure is (0.2 to 0.8): 1; (6) the ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum in the zeolite network structure is (0.2 to 0.6): 1; (7) the ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum in the zeolite network structure is (0.1 to 0.6): 1; and (8) the ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum in the zeolite network structure is (0.2 to 0.5): 1.  Step (1): Contact The zeolite Yen as starting material can be one or more of NaY, NaHY, NaNH4Y, Ni-14Y, HY, USY, zeolite Y exchanged once - calcined once, DASY zeolite a zeolite Y exchanged twice - calcined twice, a zeolite Y exchanged twice - calcined once.  The zeolite Y exchanged once - calcined once may be for example the zeolite Y obtained by subjecting a zeolite NaY to an exchange - a calcination; the zeolite DASY may be, for example, the zeolite Y obtained by subjecting a zeolite Y to calcination in the presence of steam; the zeolite Y exchanged twice - calcined twice may be, for example, the zeolite Y obtained by subjecting a zeolite NaY to two exchanges - two calcinations; the zeolite Y exchanged twice - calcined once may for example be zeolite Y obtained by subjecting a zeolite NaY to two exchanges - calcination; and preferably, the exchange is conducted with H + and / or NH4 + The weight ratio between zeolite Y (dry basis) and acid solution (aqueous acid solution) or aqueous EDTA solution (solid-liquid ratio ) is 1: 5 to 20.  The contact temperature is in a range of room temperature to 100 ° C.  The contact time is at least 0.5 hours, for example 0.5 to 3 hours.  After contact, filtration and washing can be done.  The acid concentration of the acid solution as H + is 0.1 to 1 mole / L, 0.2 to 0.5 mole / L or 0.5 to 1 mole / L.  The acid may be an inorganic acid and / or an organic acid.  The inorganic acid may be one or more of hydrochloric acid, sulfuric acid and nitric acid; the organic acid may be one or more of formic acid, acetic acid, oxalic acid, citric acid.  In step (1), the washing can be done with water such as deionized water and distilled water to remove the acid in the zeolite.  For example, the weight ratio of water to zeolite may be from 5 to 20: 1.  The treated zeolite obtained in step (1) has an Na2O content of not more than 4.0% by weight and preferably not more than 2.0% by weight.  Step (2): Calcination The treated zeolite obtained in step (1) can be calcined to remove the adsorbed water.  By calcination, the water content in the zeolite is not more than 5% by weight, for example not more than 3% by weight.  The calcination temperature may be 200 ° C to 400 ° C, for example 300 to 350 ° C.  The calcination time can be from 2 to 10 hours, for example from 2 to 4 hours.  The solids content of the calcined zeolite is not less than 95% by weight, not less than 97% by weight, or 97 to 99.9% by weight.  Step (3) The metal-impregnated zeolite in an organic solvent comprises mixing the Group IVB metal-containing compound in the organic solvent and zeolite, and preserving the mixture for at least 0.5 hours, for example 0.5 to 12 hours with agitation or without agitation (at rest).  For example, the mixture can be stored with stirring for 0.5 to 12 hours.  Then the next step can be conducted, for example, continuing with step (4), or repeating step (3).  The introduction of one or more modifying metals into zeolite Y can be achieved by one or more impregnation.  The solid-liquid weight ratio between the zeolite Y and the organic solvent can be 1: (0.5 to 5), 1: (1 to 2), 1: (1 to 4) or 1: (1.1 to 1.6).  The impregnation temperature is a temperature that can cause the organic solvent to be in a liquid state.  The impregnation can be done in the manner of isometric impregnation or excessive impregnation.  The impregnation temperature is not particularly limited, for example, the impregnation can be done at room temperature.  The Group IVB metal is selected from one or more of Ti, Zr, Hf and Rf, preferably Ti and / or Zr.  The Group IVB metal-containing compound may be one or more of a Ti-containing compound, a Zr-containing compound, a Hf-containing compound and a Rf-containing compound, for example a Ti-containing compound and / or a Zr-containing compound.  The Group IVB metal-containing compound may be an inorganic salt and / or an organometallic compound of the Group IVB metal, for example, the Ti-containing compound may be one or more of titanium sulfate, titanyl sulfate, tetrachloride of titanium, titanium trichloride, tetrabutyl titanate and ammonium fluotitanate.  The Zr-containing compound may be one or more of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, zirconium acetate and zirconium isopropoxide.  The organic solvent has a water content of not more than 5% by weight, or not more than 3% by weight, or not more than 1% by weight.  The organic solvent may be one or more of alkanes, aromatic hydrocarbons, alcohols, ketones, ethers, esters, halogenated alkanes such as chlorinated alkanes.  The organic solvent may have a normal boiling point of 40 to 100 ° C.  The organic solvent is preferably one or more of n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone, trichloromethane.  Step (4): introduction of an inert gas - optional filtration - optional drying The impregnated zeolite and the organic solvent are placed in a reaction vessel such as an autoclave.  The solid-liquid weight ratio between the zeolite and the organic solvent is 1: (5 to 50), for example 1: (5 to 30) or 1: (5 to 10).  In general, the organic solvent used in step (4) is identical to that used in step (3).  An inert gas such as nitrogen and helium can be introduced into the reaction vessel.  The pressure of the reaction vessel (gauge pressure) is 0.0 to 2.0 MPa, or 0.5 to 1.5 MPa.  The temperature of the reaction vessel ranges from room temperature to 200 ° C, ambient temperature to 150 ° C, or ambient temperature to 90 ° C.  The substances in the reaction vessel can be kept at rest or with stirring for at least 1 hour, usually 1 to 48 hours, 2 to 24 hours, or 4 to 24 hours.  Then, filtration and / or drying can be optionally conducted.  Filtration and drying are preferably conducted so that the zeolite can be separated from the organic solvent.  Filtration and drying can be conducted in a conventional manner.  The existing drying process can be adopted, such as air drying, flash drying and spray drying.  For example, the drying temperature may be from 100 to 200 ° C.  For example, the drying time can be from 1 second to 2 days, for example from 6 to 24 hours.  Step (5): calcination The zeolite obtained in step (4) is calcined; the calcination is conducted in an inert gas atmosphere, the calcination temperature is 300 to 700 ° C, the calcination time is 0.5 to 5 hours, or more than 0.5 hour.  The calcination is conducted in an inert gas atmosphere.  The calcination temperature is 300 to 700 ° C, 450 to 650 ° C or 500 to 600 ° C.  The calcination time is 0.5 to 5 hours, or 1 to 4 hours.  The inert gas comprises one or more of nitrogen and helium.  The present invention further relates to a catalytic cracking catalyst, based on the total weight of the catalyst, containing 20 to 60% by weight of the Group IVB metal-modified zeolite Y according to the present invention, 10 to 60% by weight of a clay and 5 to 50% by weight of a binder.  The present invention also relates to a method of preparing the catalytic cracking catalyst, which comprises the steps of mixing and slurrying the metal-modified Y zeolite according to the present invention and a clay and binder, and spray-drying the resulting mixture.  For example, deionized water, the clay and the binder can be mixed and slurried, and the resulting slurry is added the modified Y zeolite.  Spray drying and calcination technologies are well known in the art, and therefore will not be discussed in detail.  According to the present invention, the clay is selected from one or more of kaolin, halloysite, rectorite, diatomite, montmorillonite, bentonite, and sepiolite, which are well known in the art.  According to the present invention, the binder designates a substance which can form a heat-resistant inorganic oxide after calcination.  The heat-resistant inorganic oxide comprises one or more of alumina, silica, amorphous silica-alumina, preferably alumina.  The binder is preferably selected from one or more of dehydrated alumina, alumina sol, pseudobohemite, bohemite, alumina trihydrate, alumina monohydrate, and amorphous aluminum hydroxide.  These different binders can mutate in the form of γ-Al 2 O 3 after calcination.  These binders are well known in the art.  The IVB metal-modified Y zeolite according to the present invention has high crystallinity, a large specific surface area and high thermal and hydrothermal stability.  According to the present invention, zeolite Y is modified by the Group IV metal without using the expensive rare earth material.  And modified zeolite Y according to the present invention can impart thermal and hydrothermal stability comparable to or greater than rare earth modified Y zeolite.  The modified zeolite Y according to the present invention can be used in the catalytic cracking catalyst to replace the rare earth modified zeolite Y.  The cost of the catalyst can be remarkably reduced.  The catalytic cracking catalyst according to the present invention has excellent performance in cracking activities, gasoline yield and coke selectivity.  Example In the following examples, the ambient temperature used is 15 to 40 ° C such as 26 ° C.  The microactivity (MA) of light oil is measured according to the standardized method RIPP92-90, where 5 g of the catalyst is used.  The reaction temperature is 460 ° C.  The feed is a light straight-run diesel having a distillation range of 235 to 337 ° C.  The product composition is analyzed by gas chromatography.  Depending on the product composition, the microactivity is calculated as follows: microactivity (MA) of light oil = (the gasoline output ( <216 ° G) + gas outlet + coke outlet) / load inlet x 100% In the Examples and Comparative Examples, the starting materials used are commercially available and their detailed technical characteristics are as follows. Raw materials of zeolite, industrial product, available from Sinopec Catalyst, Qilu division. ReCI3 (mixed rare earth chloride), industrial grade, available from Sinopec Catalyst, Qilu Division. Other agents: chemically pure, unless otherwise indicated. The secondary pore volume is measured according to the standardized method RIPP151-90. Reference can be made to Analytical Methods in Petrochemical Industry (RIPP Experiment Techniques), Yang Cuiding et al, Science Press, 1990. According to the adsorption isotherm, the total pore volume of the zeolite is measured. Then the micropore volume of the zeolite is measured from the adsorption isotherm according to the T-tracing method. The total pore volume minus the micropore volume equals the secondary pore volume, and the percentage between the pores. secondary (pore diameter 6 to 20 nm) and total secondary pores (pore diameter 2 to 100 nm) is calculated from the secondary pore distribution of the zeolite. A.1 Modification of the zeolite Example A.1.1.1 200 g of NaY zeolite were calcined at 300 ° C. for 3 hours (after calcination, the water content was 1% by weight). After cooling to room temperature, it was placed in 2000 g of ethanol (the content of ethanol = 99.9% by weight). The resulting slurry was stirred homogeneously. To the slurry was added 10.5 g of zirconium nitrate (Zr (NO 3) 4.5H 2 O). Then, the resulting mixture was stirred at room temperature for 2 hours, and filtered. The filter cake was dried in a cooker at 100 ° C for 24 hours and then calcined at 600 ° C for 2 hours. The above calcined zeolite Y was added to 2000 g of an aqueous inorganic acid solution with an acid concentration of 1.0 mol / L (a dilute hydrochloric acid solution). The resulting mixture was homogeneously mixed, stirred at 80 ° C for 3 hours, then filtered, washed with deionized water (the weight of the wash water was 15 times the weight of the dry base of the zeolite), and filtered. The filter cake was removed, and calcined in 100% steam at 600 ° C for 1 hour. Finally, Zr-modified zeolite was obtained and designated Zr (2) Y, whose properties are shown in Table A1. Example A.1.1.2 200 g NaY zeolite was evacuated at 200 ° C under 0.001 Pa for 4 hours. After cooling to room temperature (water content = 0.5% by weight), it was placed in 1500 g of ethanol (ethanol content = 99.9% by weight). The resulting slurry was homogeneously stirred. To the slurry was added 15.7 g of zirconium oxychloride (ZrOC12-8H2O). Then, the resulting mixture was stirred at room temperature for 3 hours and filtered. The filter cake was dried in a cooker at 100 ° C for 24 hours and then calcined at 500 ° C for 3 hours. The above calcined zeolite Y was added to 1500 g of an aqueous solution of oxalic acid with an acid concentration of 2.0 mol / l. The resultant mixture was homogeneously mixed, heated to 90 ° C, stirred for 1 hour, then filtered and washed with deionized water (the weight of wash water was 15 times higher). the weight of the dry base of the zeolite). The filter cake was removed, and calcined in 100% steam at 500 ° C for 2 hours. Finally, Zr-modified zeolite was obtained and designated Zr (4) Y, whose properties are shown in Table A1. Example A.1.1.3 200 g of NaY zeolite was calcined at 300 ° C for 3 hours. After cooling to room temperature (water content = 1% by weight), it was placed in 1000 g of n-hexane (n-hexane content = 99.5% by weight). The resulting slurry was homogeneously mixed. To the slurry was added 37.8 g of zirconium isopropoxide. The resulting mixture was stirred at room temperature for 3 hours, and filtered. The filter cake was dried in a cooker at 120 ° C for 48 hours, and calcined at 500 ° C (in a dry air atmosphere, the water content in the air was not greater than 0.2% by volume) for 4 hours. The calcined zeolite Y was added above to 1000 g of an aqueous solution of inorganic acid (sulfuric acid) with an acid concentration of 0.5 mol / L. The resulting mixture was mixed at 80 ° C for 3 hours, then filtered and washed with deionized water (the weight of the wash water was 20 times the weight of the dry base of the zeolite ). The filter cake was removed and calcined at 500 ° C in a 100% steam atmosphere for 3 hours. Finally, Zr-modified zeolite was obtained and designated Zr (8) Y, whose properties are shown in Table A1. Example A.1.1.4 200 g of NaY zeolite were calcined at 300 ° C. during 3 hours. After cooling to room temperature, it was placed in 1000 g of butanone (butanone content = 99.5% by weight). The resulting slurry was homogeneously stirred. To the slurry was added 14.2 g of titanium tetrachloride. The resulting mixture was stirred at room temperature for 2 hours, and filtered. The filter cake was dried in a cooker at 120 ° C for 24 hours and then calcined at 450 ° C in a nitrogen atmosphere for 4 hours. The calcined zeolite Y was added above to 1000 g of an aqueous solution of inorganic acid (hydrochloric acid) with an acid concentration of 0.5 mol / L. The mixture was homogeneously mixed, stirred at 80 ° C for 2 hours, then filtered and washed with deionized water (the weight of the wash water was 10 times the weight of the base). dry zeolite). The filter cake was removed, and calcined at 500 ° C in a 100% steam atmosphere for 2 hours. Finally, the Ti-modified zeolite was obtained and named Ti (4) Y, whose properties are shown in Table A1. Example A.1.1.5 Vacuum in 200 g of NaY zeolite at 300 ° C under 0.001 Pa for 4 hours. After cooling to room temperature, it was placed in 2000 g of cyclohexane (cyclohexane content = 99.9% by weight). The resulting slurry was homogeneously stirred. To the slurry was added 63.9 g of tetrabutyl titanate. The resulting mixture was stirred at room temperature for 3 hours and filtered. The filter cake was dried at 100 ° C in a cooker for 48 hours and then calcined at 600 ° C in a nitrogen atmosphere for 2 hours. The above calcined zeolite Y was added to 2000 g of an aqueous solution of oxalic acid with an acid concentration of 1.5 mol / L. The mixture was homogeneously mixed, stirred at 90 ° C for 1 hour, then filtered and washed with deionized water (the weight of the wash water was 20 times the weight of the base). dry zeolite). The filter cake was removed and then calcined at 600 ° C in a 100% steam atmosphere for 2 hours. Finally, the Ti-modified zeolite was obtained and named Ti (10) Y, whose properties are shown in Table A1. Example A.1.1.6 Vacuum was performed in 200 g of NaY zeolite at 300 ° C at 0.001 Pa for 4 hours. After cooling to room temperature, it was placed in 3000 g of ethanol (ethanol content = 99.9% by weight). The resulting slurry was homogeneously stirred. To the slurry was added 3.6 g of titanium tetrachloride and 31.5 g of zirconium nitrate. The resulting mixture was stirred at room temperature for 3 hours, and filtered. The filter cake was dried at 100 ° C in a cooker for 48 hours and then calcined at 550 ° C in a nitrogen atmosphere for 3 hours. The above calcined zeolite Y was added to 3000 g of an aqueous solution of inorganic acid (nitric acid) with an acid concentration of 1.0 mol / L. The mixture was homogeneously mixed, stirred at 80 ° C for 2 hours, then filtered and washed with deionized water (the weight of the wash water was 20 times the weight of the base). dry zeolite). The filter cake was removed, and calcined at 550 ° C in a 100% steam atmosphere for 3 hours. Finally, the zeolite modified with Ti and Zr was obtained and called Ti-Zr-Y, whose properties are shown in Table A1. Example A.1.1.7 A modified zeolite according to Example A.1.1.4 was prepared except that after treatment with the inorganic acid, the filter cake was first dried and then calcined at 500 ° C in an air atmosphere to produce the modified zeolite Ti (4) Y-1. Example A.1.2.1 200 g of NaY zeolite and 2000 g of deionized water were mixed and slurried. To the resulting slurry was added 45 mL of a 270 g / L RECI3 solution. The mixture was adjusted with dilute hydrochloric acid at pH = 3.8, warmed to 80 ° C for one hour exchange. After filtration and washing, the resulting filter cake was calcined at 500 ° C for 3 hours. The resulting zeolite Y was then mixed and slurried with 2000 g of deionized water. To the slurry was added 45 g of ammonium sulfate. The mixture was adjusted with dilute hydrochloric acid at pH = 4.0, and warmed to 80 ° C for one hour exchange. After filtration and washing, the resulting filter cake was calcined at 600 ° C in a 100% steam atmosphere for 3 hours. Finally, RE-modified zeolite was obtained and designated RE (8) Y, whose properties are shown in Table A1. Example A.1.2.2 200 g of NaY zeolite were placed in 2000 g deionized water. The resulting slurry was homogeneously mixed. To the slurry, 31.4 grams of zirconium oxychloride ZrOC12-8H20 was added. The mixture was warmed to 90 ° C, stirred for 3 hours and filtered. The filter cake was dried at 100 ° C in a cooker for 12 hours, and calcined at 500 ° C for 3 hours. The calcined zeolite Y was then mixed and slurried with 2000 g of deionized water. To the resulting slurry was added 45 g of ammonium sulfate. The mixture was adjusted with dilute hydrochloric acid at pH = 4.0, warmed to 80 ° C for 1 hour exchange. After filtration and washing, the filter cake was calcined at 500 ° C in a 100% steam atmosphere for 2 hours. Finally, Zr-modified zeolite was obtained and designated Zr (W) Y, whose properties are shown in Table A1. Example A.1.2.3 A modified zeolite was prepared according to Example A. 1.2.2, except that 14.2 g of titanium tetrachloride was used in place of 31.4 g of zirconium oxychloride ZrOC12.8H20. Finally, the Ti-modified zeolite was obtained and named Ti (W) Y, whose properties are shown in Table A1. Example A.1.2.4 A Zr-modified Y zeolite according to Example 1 of CN101134576A was prepared. Finally, Zr-modified zeolite was obtained and designated Zr (G) Y, whose properties are shown in Table A1. Example A.1.2.5 200 g of NH4USY (Si / Al atomic ratio = 5.2) was added to 500 g of absolute ethanol with vigorous stirring to form a suspension, to which 50 g / L of a solution of butyl titanate - absolute ethanol (as TiO2) with violent stirring. The mixture was air-dried overnight with stirring. The resulting sample was calcined at 500 ° C for 5 hours to produce Ti-modified zeolites with a titanium content of 2.4 wt.% And 9.1 wt.%, Referred to as DT2 and DT9. Table A1 Physical and chemical properties of metal-modified Y zeolites Example A.1.1.X 1 2 3 4 5 6 7 Sample Zr (2) Y Zr (4) Y Zr (8) Y Ti (4) Y Ti (10) Y Ti-Zr-Y Ti (4) Y-1 a0, nm 2,452 2,450 2,449 2,451 2,449 2,449 2,455 crystallinity,% 77.6 73.7 70.3 72.6 69.1 68.8 73.0 Na2O, % by weight 1.0 0.9 0.7 0.9 0.8 1.0 0.9 A1203, `) / 0 by weight 22.8 22.5 21.8 22.8 21.3 20.9 22.8 SiO2, wt% 73.6 72.5 69.7 72.1 68.8 70.5 72.0 ZrO2, wt% 2.1 3.8 7.3 0 0 5.5 0 TiO2 ,% by weight 0 0 0 3,7 8,6 1,9 3,7 RE203,% by weight 0 0 0 0 0 0 0 0 specific surface area, m2 / g 676 710 690 726 702 640 722 network failure temperature, The ratio of the Group IVB metal content of the zeolite surface to the Group IVB metal content of the interior of the zeolite 0.05 0.10 0.12 0, 08 0.16 0.15 0.10 ratio of deformed tetrahedral coordination framework aluminum to 0.42 tetrahedral coordination framework aluminum , 3 0.5 0.4 0.4 0.6 0.5 0.3 Percentage between secondary pores (pore diameter 6 to 20 nm) and total secondary pores (pore diameter 2 to 100 nm) 48.2 50.6 57.8 52.4 62.4 64.5 51.8 Table A1 (continued) Example A.1.2.X 1 2 3 4 5 Sample RE (8) Y Zr (W) Y Ti (W) Y Zr (G) Y DT2 DT9 α0, nm 2,451 2,450 2,452 2,451 2,458 2,448 crystallinity,% 62.7 50.6 53.9 64.2 69.9 63.0 Na2O, wt% 1.0 0.8 1 , 0 0.8 1.1 1.2 Al 2 O 3, wt.% 21.7 21.9 21.8 20.8 21.2 21.8 SiO 2, wt.% 70.5 69.9 72.8 70, 74.8 67.2 ZrO 2, wt.% 0 7.0 0 7.5 0 0 TiO 2, wt.% 0 3.9 0 2.4 9.1 RE203, wt.% 6.6 0 0 0 0 0 specific surface area, m2 / g 640 548 526 624 535 520 grid failure temperature, ° C 1043 1028 1015 1030 1036 1036 ratio of the group IVB metal content of the zeolite surface to the metal content of the group IVB from interior of zeolite - 1.8 1,2 - 1,0 1,3 ratio between deformed tetrahedral coordination framework aluminum and aluminum tetrahedral coordination framework - 0.05 0.06 0.02 0.01 0.04 A.2 Stability of the modified zeolite The modified Y zeolites prepared according to Examples A.1.1.1 to A.1.1.7 and A.1.2.1 to A.1.2.5 at 800 ° C in a 100% vapor condition for 8 hours to determine the crystallinity and specific surface area, and the retention of crystallinity and the retention of specific area. The results are listed in Table A2. The aged zeolites were subjected to the microactivity (MA) test of light oil. The results are listed in Table A2. Table A2 Physical and chemical properties of metal-modified Y zeolites after hydrothermal aging Example A.2.1.X 1 2 3 4 5 6 7 zeolite Y Zr (2) Y Zr (4) Y Zr (8) Y Ti (4) Y Ti (10) Y Ti-Zr-Y Ti (4) Y-1 Retention of crystallinity,% 60.5 62.1 64.7 63.9 65.9 66.3 63.2 Specific area retention,% 62.4 65.0 66.7 64.1 67.8 68.0 65.2 800 ° C / 8 h, activity 81 84 86 85 86 87 84 Table A2 (continued) Example A.2.2.X 1 2 3 4 5 Zeolite Y RE (8) Y Zr (W) Y Ti (W) Y Zr (G) Y DT2 DT9 Retention of crystallinity,% 63.2 45.5 50.2 60.8 60.2 62.0 Retention specific area,% 65.5 50.8 51.6 64.9 61.6 62.9 800 ° C / 8 h, activity 84 75 75 80 70 72 Example A.2.1.8 According to example A.1.1 .5 Ti-modified Y zeolites having Ti contents (such as TiO2) of 1 wt.%, 2 wt.%, 7 wt.%, 12 wt.%, 15 wt.% Were prepared. The physical and chemical properties are listed in Table A3. These Ti-modified Y zeolites were aged at 800 ° C under a 100% vapor condition for 8 hours to determine crystallinity and specific surface area, and the retention of crystallinity and specific surface retention were calculated. The aged zeolites were subjected to the microactivity (MA) test of light oil. The results are listed in Table A3. Example A.2.2.6 According to Example A.1.2.1, RE-modified Y zeolites having ER contents of 1% by weight, 2% by weight, 12% by weight, 15% were prepared. in weight. The physical and chemical properties are listed in Table A3. RE-modified Y zeolites were aged at 800 ° C under a 100% vapor condition for 8 hours to determine crystallinity and specific surface area, and the retention of crystallinity and specific surface retention were calculated. The aged zeolites were subjected to the microactivity (MA) test of light oil. The results are listed in Table A3. Table A3 Example A.2.1.8 Example A.2.2.6 TiO2, wt% 1.0 2.0 7.0 12.0 15.0 0 0 0 0 RE203, wt% 0 0 0 0 0 1 0 2.0 12.0 15.0 Na 2 O, wt.% 1.1 0.9 1.1 0.9 0.9 1.0 1.0 0.9 0.9 Al 2 O 3, wt.% 23, 2 22.8 21.4 19.2 16.5 22.0 21.8 20.2 17.2 SiO2,% by weight 73.3 72.8 68.7 66.9 67.1 74.5 73, 5 66.0 66.2 a0, nm 2,449 2,450 2,452 2,455 2,455 2,455 2,457 2,458 2,460 Crystallinity,% 71.2 70.6 72.8 71.1 69.8 70.2 68.4 62.2 60.8 area Specific, m 2 / g 674 680 690 666 645 620 653 560 490 Mains failure temperature, ° C 1042 1045 1050 1046 1046 1030 1044 1045 1045 ratio of the metal content of group IVB of the surface of the zeolite to the content of Group IVB metal from within the zeolite 0.02 0.05 0.12 0.15 0.17 Zeolite No. Ti (1) Y Ti (2) Y Ti (7) Y Ti (12) Y Ti (15) Y After hydrothermal aging Retention of crystallinity,% 62.2 61.2 63.6 66.0 64.5 60.0 63.4 66.2 65.0 Specific area retention,% 61.9 63 , 8 63.4 67.7 66.6 62.2 64 , 65.9 800.8 ° C / 8 h, activity 82 85 87 85 85 80 82 83 83 34 3012125 A.3 Catalyst Example A.3.1.1 The modified Y zeolite prepared according to the present invention was used. Zr (8) Y, as an active component for preparing the catalyst according to the conventional method of preparing the catalytic cracking catalyst. The preparation was the following. According to a zeolite ratio (dry basis): kaolin (dry base): pseudobohemite (as A1203): alumina sol (as Al 2 O 3) of 38: 34: 20: 8, we mixed and put in boiled the kaolin and decationate water. To the resulting slurry, the alumina sol was added, and pseudobohemite was added with continued stirring. After stirring for 30 minutes, a liquor containing the zeolite was added to the colloid. The resulting mixture was homogeneously mixed, spray-dried and shaped to produce a catalyst, designated Cl. The catalyst was pretreated at 800 ° C under a 100% steam condition for 17 hours. The pretreated catalyst was then tested on a small scale fixed fluidized bed (CFA) for catalyst evaluation. The load for evaluation was Wuhun III, whose properties are shown in Table A4. The reaction temperature, catalyst-oil ratio, WHSV and the evaluation result are listed in Table A5. where, conversion = gasoline yield + liquefied gas yield + dry gas yield + coke yield coke selectivity = coke yield * 100 / conversion Example A.3.2.1 A catalyst was prepared according to Example A. 3.1.1, except that the same amount of RE (8) Y zeolite was used instead of zeolite Zr (8) Y to produce a catalyst called DC1. DC1 was then evaluated according to Example A.3.1.1. The evaluation result is listed in Table A5. Example A.3.2.2 A catalyst was prepared according to Example A.3.1.1, except that the same amount of Zr (W) Y zeolite was used in place of Zr (8) Y zeolite for produce a catalyst called DC2. Then DC2 was evaluated according to example A.3.1.1. The evaluation result is listed in Table A5.

Table A4 Wuhun III Charge Density (20 ° C), g / cm3 0.9044 Refraction (20 ° C) 1.5217 Viscosity (100 ° C), mm2 / s 9.96 Freezing Point, ° C 40 Point d aniline, ° C 95.8 ° C, wt.% 85.98 ° H, wt.% 12.86 S, wt.% 0.55 N, wt.% 0.18 Residual carbon, wt.% 3.0 Distillation range, ° C Initial distillation point% 243% 294 30% 316 50% 395 70% 429 90% 473 Table A5 Example A.3.1.1 A.3.2.1 A.3.2.2 Catalyst Cl DC1 DC2 Temp. reaction temperature, 500 500 500 Catalyst-oil weight ratio 5 VSHP, 1.1-1 16 16 16 Production distribution,% by weight Dry gas 1.15 1.10 1.18 liquefied gas 11.15 11, 66 12.03 coke 4.02 5.45 4.65 petrol 56.40 53.08 50.30 diesel 20.17 21.46 23.02 36 3012125 Heavy oil 7.11 7.25 8.82 Conversion,% by weight 72.72 71.29 68.16 Selectivity of coke 5.53 7.64 6.82 Example A.3.1.2 According to Example A.1.1.1, the amount of zirconium nitrate used was adjusted to preparing Zr-modified zeolite Y, designated Zr (6) Y, wherein the ratio of the amount of zirconium nitrate used (as ZrO 2) to the weight amount of the zeolite was 6: 100 by weight. 323 g of pseudobohemite (having a solids content of 62% by weight) and 1343 g of deionized water were mixed. The mixture was stirred for 15 minutes and homogeneously mixed to produce a pseudobohemite slurry, the pH value of which was adjusted with hydrochloric acid diluted to 3.5. The resulting slurry was aged at room temperature for 6 hours. To the aged slurry was added 447 g of kaolin (having a solids content of 76% by weight) and 372 g of alumina sol (having an alumina content of 21.5% by weight). The resulting slurry was stirred for 60 minutes. To the above slurry was added a slurry formed by slurrying 380 g (dry basis) of the zeolite Zr (6) Y modified above and 880 g of deionized water. The resulting mixture was stirred for 60 minutes to produce a catalyst slurry, which was spray-dried and shaped, and calcined at 550 ° C for 1 hour to produce a catalytic cracking catalyst, referred to as C11. The ZrO 2 content of Catalyst C11, measured by XRF, was 2.2% by weight. Example A.3.1.3 Zr modified zeolite Y was prepared according to Example A.1.1.2, designated Zr (10) Y, where ZrO 2: zeolite = 10: 100. 421 g of kaolin (having a solids content of 76% by weight), 465 g of alumina sol (having an alumina content of 21.5% by weight) and 732 g of deionized water were added. they were slurried in a slurry tank, to which was added 1667 g of an acidified pseudobohemite (acidified with hydrochloric acid, the molar ratio hydrochloric acid / alumina = 0.15, and having a content solid material of 12% by weight). After stirring for 60 minutes, a slurry formed by slurrying 380 g (dry basis) of the zeolite Zr (10) Y modified above and 880 g of deionized water was added to the vessel. The resulting mixture was stirred for 60 minutes to produce a catalyst slurry, which was spray-dried and shaped, and calcined at 550 ° C for 1 hour to produce a catalytic cracking catalyst, referred to as C21. The ZrO 2 content of catalyst C21, measured by XRF, was 3.5% by weight. Example A.3.1.4 447 g of kaolin, 372 g of alumina sol and 800 g of deionized water were mixed and slurried for 60 minutes. After addition of 1667 g of an acidified pseudoboehmite, the resulting slurry was further stirred for 60 minutes. To the resulting mixture was added a slurry formed by slurrying 380 g (dry basis) of the zeolite Ti (2) Y modified above and 880 g of deionized water. The resulting mixture was stirred for 60 minutes to produce a catalyst slurry, which was spray-dried and shaped, and calcined at 650 ° C for 2 hours to produce a catalytic cracking catalyst, referred to as C31. The TiO2 content of catalyst C31, measured by XRF, was 0.75% by weight. Example A.3.1.5 447 g of kaolin, 372 g of alumina sol and 800 g of deionized water were mixed and slurried for 60 minutes. After addition of 1667 g of an acidified pseudoboehmite, the resulting slurry was further stirred for 60 minutes. To the resulting mixture was added a slurry formed by slurrying 380 g (dry basis) of the modified Ti (4) Y zeolite and 880 g of deionized water. The resulting mixture was stirred for 60 minutes to produce a catalyst slurry, which was spray dried and shaped, and calcined at 650 ° C for 2 hours to produce a catalytic cracking catalyst, referred to as C41. The TiO2 content of catalyst C41, measured by XRF, was 1.5% by weight. Example A.3.1.6 A catalyst was prepared according to Example A.3.1.5, except that the same amount of Ti (4) Y-1 was used instead of Ti (4) Y zeolite. to produce the catalyst, called C41-1. Example A.3.1.7 A catalyst was prepared according to Example A.3.1.5, except that a REY zeolite prepared according to the prior method was used (molar ratio SiO 2 / Al 2 O 3 = 5.1, content rare earth = 3.8% by weight, Na 2 O content = 0.4% by weight) in place of a part of the Ti (4) Y zeolite. The ratio by weight of the REY zeolite prepared according to the prior method and the Ti (4) Y zeolite was 1: 1 to produce a catalyst, referred to as C41-2. Example A.3.1.8 According to Example A.1.1.4, the amount of titanium tetrachloride used was adjusted to prepare Ti-modified Y zeolite, referred to as Ti (8) Y, where the ratio of the amount used of titanium tetrachloride (such as TiO 2) and the amount by weight of the zeolite was 8: 100 by weight. 421 g of kaolin, 698 g of alumina sol and 900 g of deionized water were mixed and slurried for 60 minutes. After addition of 1250 g of an acidified pseudoboehmite, the resulting slurry was further stirred for 60 minutes. To the resulting mixture was added a slurry formed by slurrying 380 g (dry basis) of the zeolite Ti (8) Y modified above and 800 g of deionized water. The resulting mixture was stirred for 60 minutes to produce a catalyst slurry, which was spray dried and shaped, and calcined at 700 ° C for 2 hours to produce a catalytic cracking catalyst, referred to as C51. The TiO2 content of the C51 catalyst, as measured by XRF, was 3.0% by weight. Example A.3.1.9 The same starting materials were used as those used in Example A.3.1.2, with the exception of the metal modified Y zeolite. 355 g of pseudobohemite and 1478 g of deionized water were mixed and stirred for 30 minutes to produce a pseudobohemite slurry, the pH of which was adjusted with a suitable amount of hydrochloric acid diluted to 3.8. The resulting slurry was aged at 60 ° C for 2 hours. To the aged slurry, 395 grams of kaolin and 465 grams of alumina sol were added. The resulting mixture was stirred for 60 minutes. To the slurry was then added a slurry formed by slurrying 380 g (dry basis) of the zeolite Ti-Zr-Y modified above and 880 g of deionized water. The resulting mixture was stirred for 60 minutes to produce a catalyst slurry, which was spray-dried and shaped, and calcined at 600 ° C for 3 hours to produce a catalytic cracking catalyst, referred to as C61. . Example A.3.2.3 A catalyst was prepared according to Example A.3.1.8 except that the same amount of RE (8) Y zeolite was used in place of zeolite Ti (8) Y for produce a catalyst, called DC11. The RE203 content of the catalyst DC11, measured by XRF, was 2.32% by weight. Example A.3.2.4 A catalyst was prepared according to Example A.3.1.8, except that the same amount of Ti (W) Y zeolite was used in place of the Ti (8) Y zeolite for produce a catalyst, called DC21. The TiO2 content of the DC21 catalyst, measured by XRF, was 2.40% by weight. Example A.3.2.5 A catalyst was prepared according to Example A.3.1.2, except that the same amount of Zr (W) Y zeolite was used in place of Zr (6) Y zeolite for produce a catalyst, called DC31. The ZrO 2 content of the DC31 catalyst, measured by XRF, was 2.18% by weight. Catalysts C11-C61 and DC11 were pretreated at DC at 800 ° C under a 100% steam condition for 8 hours. The pretreated catalyst was then tested on a small scale fixed fluidized bed (CFA) for catalyst evaluation. The load for evaluation was Wuhun III, whose properties are shown in Table A4. The reaction temperature, catalyst-oil ratio, WHSV and the evaluation result are listed in Table A6 where conversion = gasoline yield + liquefied gas yield + dry gas yield + coke yield.

Table A6 Evaluation result Example A.3.1.2 A.3.1.3 A.3.1.4 A.3.1.5 A.3.1.6 A.3.1.7 A.3.1.8 A.3.1.9 A. 3.2.3 A.3.2.4 A.3.2.5 Catalysts C11 C21 C31 C41 C41-1 C41-2 C51 C61 DC11 DC21 DC31 Zeolites Zr (6) Y Zr (10) Y Ti (2) Y Ti (4) Y Ti (4) Y-1 Ti (4) Y REY Ti (8) Y Ti-Zr-Y RE (8) Y Ti (W) Y Zr (W) Y Temp. reaction temperature, ° C 500 500 500 500 500 500 500 500 500 500 500 Catalyst-oil weight ratio 8.04 8.04 8.04 8.04 8.04 8.04 8.04 8.04 8.04 8 , 04 8.04 WHSV, h-1 16 16 16 16 16 16 16 16 16 16 16 Production distribution,% by weight Dry gas 1.35 1.32 1.33 1.34 1.33 1.3 1, 32 1,35 1,34 1,34 1,35 liquefied gas 14,04 13,61 13,30 14,43 14,21 13,96 14,52 14,26 13,58 13,35 13,72 coke 6 , 71 6.86 7.52 7.05 7.13 7.42 6.76 6.71 8.02 7.29 7.12 gasoline 54.11 53.52 52.98 53.44 53.25 53 51 53.24 53.87 52.22 49.87 50.55 diesel 16.76 16.84 16.96 16.65 16.94 16.71 16.94 16.84 16.89 17.19 17.37 Heavy oil 7.03 7.85 7.91 7.09 7.14 7.1 7.22 6.97 7.95 10.96 9.89 Total 100 100 100 100 100 100 100 100 100 100 100 Conversion,% weight 76.21 75.31 75.13 76.26 75.92 76.19 75.84 76.19 75.16 71.85 72.74 coke / conversion 0.08805 0.09109 0.10009 0.09245 0.09391 0.09739 0.08980 0.08807 0.10671 0.10146 0.09788 41 3012125 B.1 Zeolite modification Example B.1.1.1 (1) At room temperature, the mixture was stirred and stirred. 200 g of NaY zeolite (dry base, 75% by weight) and 1500 ml of a hydrochloric acid solution having a molar concentration of 0.5 mol / L for 30 minutes. After filtration, the filter cake was washed with 1500 ml of deionized water to produce an acid-treated NaY zeolite, which had an Na2O content of 3.5% by weight; (2) The acid-treated NaY zeolite was calcined at 300 ° C for 3 hours to produce a zeolite having a solids content of 96% by weight, referred to as F1; (3) 5.23 g of zirconium nitrate Zr (NO 3) 4.5H 2 O was dissolved in 200 g of ethanol (analytically pure, ethanol content = 99.9% by weight) to produce an impregnating liquor. The impregnating liquor and treated zeolite F1 were homogeneously mixed and stored at room temperature for 1 hour. (4) The product of step (3) and 800 ml of ethanol were mixed and transferred to an autoclave, into which nitrogen was introduced. The pressure was maintained at 0.5 MPa. Then, the mixture was kept at room temperature for 12 hours. After filtration, the filter cake was heat-dried at 100 ° C for 24 hours. (5) The product of step (4) was calcined in a nitrogen atmosphere at 500 ° C. for 4 hours to produce Zr-modified zeolite Y, designated ZrY (1), whose properties are shown in FIG. Table B2. Example B.1.1.2 to Example B.1.1.7 With reference to Example B.1.1.1, zeolites modified according to the process of the present invention were prepared. Operating conditions and product properties are shown in Table B2. Example B.1.1.8 A zeolite modified according to Example B.1.1.1 was prepared, except that in step (4) nitrogen was introduced and the pressure (gauge pressure) was maintained at 0 MPa. The modified zeolite obtained ZrY (1) -1, whose properties are shown in Table B2.

Example B.1.1.9 A modified zeolite according to Example B.1.1.1 was prepared except that in step (1): (1) at room temperature, 200 g of NaY zeolite (dry basis, 75% by weight) and 1500 ml of an EDTA solution having a molar concentration of 0.5 mol / L for 30 minutes. After filtration, the filter cake was washed with 1500 ml of deionized water to produce an acid-treated NaY zeolite, which had an Na2O content of 3.5% by weight; Steps (2) to (5) were identical to those in Example B.1.1.1. The modified zeolite obtained ZrY (1) -2, whose properties are shown in Table B2. Example B.1.2.1 200 g of NaY zeolite (the same as that of Example B.1.1.1) and 2000 g of deionized water were slurried. To the slurry was added 60 g of ammonium sulfate. The resulting slurry was adjusted with hydrochloric acid diluted to pH = 4.0, heated to 80 ° C and exchanged for 1 hour. After filtration and washing with water, the filter cake was calcined at 550 ° C in a 100% steam atmosphere for 2 hours. The above procedure was repeated twice to produce a modified Y zeolite. Next, the resulting zeolite Y was slurried and 2000 g of deionized water. To the slurry was added 45 mL of RECI3 solution (270 g / L). The resulting slurry was adjusted with hydrochloric acid diluted to pH = 3.8, heated to 80 ° C and exchanged for 1 hour. To the mixture was added 45 g of ammonium sulfate, and the resulting mixture was stirred for 1 hour. After filtration and washing, the filter cake was calcined at 550 ° C in a 100% steam atmosphere for 2 hours. Finally, a rare earth-modified REY zeolite was obtained and was named REY, whose properties are shown in Table B3. Example B.1.2.2 The zeolite modified according to B.1.1.2 was prepared except that the same amount of zirconium oxychloride ZrOC12.8H20 was dissolved in 200 g of deionized water. Finally, Zr-modified zeolite was obtained and designated Zr (W) Y, whose properties are shown in Table B3.

Example B.1.2.3 200 grams of NaY zeolite and 2,000 grams of deionized water were slurried. To the resulting slurry, 60 g of NH 4 Cl was added. The slurry was adjusted to pH 3.8, heated to 80 ° C, and exchanged for 2 hours. After filtration and washing with water, the filter cake was calcined at 600 ° C under a 100% steam condition for 2 hours. The calcined zeolite was slurried and 2000 g deionized water. To the resulting slurry, 45 g of NH 4 Cl and 31.4 g of zirconium oxychloride ZrOCl 2 · 8H 2 O was added to conduct a second ion exchange at substantially the same temperature and for the same time as the first exchange. After filtration and washing with water, the filter cake was calcined at 600 ° C under a 100% steam condition for 2 hours. Finally, Zr-modified zeolite was obtained and designated Zr (J) Y, whose properties are shown in Table B3. Example B.1.2.4 A Zr-modified Y zeolite according to Example 1 of CN101134576A was prepared. Finally, Zr-modified zeolite was obtained and designated Zr (G) Y, whose properties are shown in Table B3. Example B.1.2.5 200 g of zeolite DASY0.0 was added to 500 g of absolute ethanol with vigorous stirring to form a suspension, to which was added 50 g / L of a solution of butyl titanate - ethanol absolute (as TiO2) with violent stirring. The mixture was air-dried overnight with stirring. The resulting sample was calcined at 500 ° C for 5 hours to produce Ti-modified zeolites with a titanium content of 7.9 wt.%, Referred to as Ti (D) Y. It could be seen from the IR-TF spectra of zeolites Y modified in FIG. 1 that the antisymmetric valence vibration frequency (1050 to 1150 cm -1) and the symmetric valence vibration frequency (750 to 820 cm -1) 1) zeolite Zr (G) Y provided in the prior art (e.g., Example 8.1.2.4) exhibited a redshift in a downward frequency direction, showing that Zr had entered the framework structure zeolite Y. The modified Y zeolites provided by the present invention (eg, ZrY and TiY) did not show the redshift, showing that Zr and Ti had not entered the backbone structure of the present invention. zeolite. From the Y-NMR spectra of modified Y zeolites Y in FIG. 2 it could be seen that the modified Y zeolite had a large amount of tetrahedral coordination framework aluminum (chemical shift 60) and little hexahedral coordination framework aluminum. (chemical shift 0). In comparison with zeolite Y, the zetolically coordinated zeolite ZrY framework aluminum peak prepared by the organic solution impregnation method became wider and shifted to the lower chemical shift, showing that Zr entering the zeolite interacted with the zeolite backbone [Al04]. This interaction caused the tetrahedral coordination framework aluminum spectrum peak to shift to a higher field, while the distorted tetrahedral coordination framework aluminum spectrum peak was noticeable (chemical shift 40). The ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum could be, for example, 0.1 to 0.6. The zeolites Zr (W) Y and Ti (D) Y, prepared according to Example B.1.2.2 (impregnation of aqueous solution) and Example B.1.2.5, showed no significant change of aluminum peak. of deformed tetrahedral coordination framework, showing that Zr or Ti had little interaction with the zeolite framework [Al04], and that the ratio of deformed tetrahedral coordination framework aluminum to aluminum tetrahedral coordination framework was less than 0.1. It could be seen that the modification method according to the present invention was more favorable for metal ions to enter the interior of the zeolite, interact with the zeolite backbone [A104], and have a stabilizing effect on the structure. framework of the zeolite.

Table B1 Raw material NaY DASY (0,0) Once exchanged - calcined once Elemental composition,% by weight Na2O 12.8 1,2 3,7 Al203 21,9 23,6 23,4 SiO2 64,4 71 , 7 72.0 Elementary mesh size, nm 2,466 2,448 2,453 Crystallinity,% 81.6 65.6 78.0 Total specific area, m2 / g 762 620 644 Total pore volume, mL / g 0.377 0.353 0.352 46 Table B2 Example B.1.1.1 B.1.1.2 B.1.1.3 8.1.1.4 B.1.1.5 Raw material zeolite Y NaY DASY (0.0) exchanged once - calcined once exchanged once - calcined once NaY (1) Concentration of acidic solution, mole / L 0.5 0.1 1.0 0.2 0.5 Acidic acidic acid oxalic acid sulfuric acid hydrochloric acid hydrochloric acid hydrochloric acid Weight ratio acid solution: zeolite 10 10 10 10 10 in Na 2 O after treatment, wt.% 3.5 0.6 1.2 0.8 3.5 Step Calcination temperature, ° C 300 300 350 350 300 (2) Calcination time, hours 3 3 3 3 3 water,% by weight 4 3 1.5 1.5 4 Step Compound cont Group IVB metal zirconium nitrate zirconium oxychloride zirconium isopropoxide zirconium isopropoxide titanium tetrachloride (3) Ethanol solvent ethanol n-hexane n-hexane butanone Water content in the solvent,% by weight 0,1 0,1 0.2 0.2 0.3 Solvent ratio: zeolite 1.3 1.5 1.5 1.2 1.3 w O 1-1 1-1 U1 47 Ratio by weight metal salt (as oxide): zeolite 0.01 0.03 0.06 0.10 0.02 Solvent used ethanol ethanol n-hexane n-hexane butanone Ratio by weight solvent: zeolite 5.1 10.0 10.0 10.0 5, 1 Inert gas introduced nitrogen nitrogen nitrogen nitrogen nitrogen Pressure, MPa 0.5 1.0 0.5 0.8 0.5 Temperature, ° C 26 25 60 25 25 Time, time 12 8 5 8 5 How resting agitation stirring resting agitation Drying temperature, ° C 100 120 120 120 100 Drying time, time 24 6 6 6 12 Inert gas nitrogen nitrogen nitrogen nitrogen nitrogen Calculation temperature, ° C 500 550 550 550 500 Calcination time, time 4 2 3 3 3 Zeolite Y modified by metal, No. Zr Y (1) ZrY (3) ZrY (6) ZrY (10) TiY (2) Na 2 O, wt.% 1.0 0.5 0.8 0.6 1.2 Al 2 O 3, wt%, 3 23.5 22.2 20.5 22.8 SiO2, wt.% 73.8 72.8 70.5 67.8 73.1 ZrO2, wt.% 0.9 2.8 6.1 10.5 TiO2, wt.% 2.2 48 a0, nm 2,456 2,448 2,450 2,452 2,451 Crystallinity,% 78.8 64.7 70.6 72.2 76.9 Surface area, m2 / g 710 616 624 635 702 failure temperature of network, ° C 1048 1050 1045 1047 1044 Ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum 0.2 0.3 0.5 0.6 0.2 Percentage of pores 32.5 42.8 48.7 50.3 38.6 secondary (pore diameter 6 to 20 nm) and total secondary pores (pore diameter 2 to 100 nm) 49 Table B2 (continued) Example B. 1.1.6 B.1.1.7 8.1.1.8 B.1.1.9 Step (1) Raw material of zeolite Y once exchanged - calcined once exchanged once calcined once NaY NaY Concentration of acid solution, mole / L 1, 0 1.0 0.5 0.5 Acetic acid oxalic acid acid hydrochloric EDTA Weight ratio acid solution: zeolite 10 10 10 Na 2 0% after treatment, wt% 1.0 1.0 3.5 3.5 Step (2) Calcination temperature, ° C 350 350 300 300 Calcination time, hours 3 3 3 3 Water content,% by weight 1.8 1.5 4 4 Step (3) Group IVB metal-containing compound butyl titanate zirconium nitrate titrate zirconium nitrate butyl nitrate + nitrate of zirconium Solvent cyclohexane ethanol ethanol ethanol Water content in the solvent,% by weight 0.2 0.1 0.1 0.1 Ratio by weight solvent: zeolite 1.5 1.5 1.3 1.3 w 0 1 -1 Ni 1-1 Ni U1 50 Ratio by weight metal salt (as oxide): zeolite 0.10 0.08 0.01 0.01 Step (4) Solvent used cyclohexane ethanol ethanol ethanol Solvent ratio: zeolite 10.0 8.0 5.1 5.1 Inert gas introduced nitrogen nitrogen nitrogen nitrogen Pressure, MPa 0.5 1.5 0.0 0.5 Temperature, ° C 25 80 26 26 Time, time 10 24 12 12 Way Rest Agitation Rest Rest Rest Stage (4 ) Drying temperature, ° C 120 120 100 100 Drying time, time 6 24 24 24 Stage (5) Inert gas nitrogen nitrogen nitrogen nitrogen Calcination temperature, ° C 550 550 500 500 Calcination time, hour 2 3 4 4 Zeolite Y modified by metal, No. TiY (10) Ti-Zr-Y ZrY (1) -1 ZrY (1) -2 Na 2 O, wt% 1.0 0.8 1.0 0.9 Al 2 O 3,% by weight 21.5 21.9 23.2 23.4 SiO2, wt% 67.1 69.0 73.9 73.6 ZrO2, wt.% 3.8 0.9 0.9 TiO2, wt.% 9, 8 4.0 51 a0, nm 2.455 2.45 2.44 2.455 crystallinity, c1 / 0 73.5 72.9 71.5 77.7 Surface area, m2 / g 642 639 700 699 network failure temperature, ° C 1045 1050 1045 1048 ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum 0.5 0.5 0.2 0.2 Percentage between secondary pores (pore diameter 6 to 20 nm) and total secondary pores (pore diameter from 2 to 100 nm) 49.8 44.4 35.4 33.9 52 Table B3 Example B.1.2.1 8.1.2.2 8.1.2.3 B.1.2.4 8.1.2 . Zeolite Y No. REY Zr (W) Y Zr (J) Y Zr (G) Y Ti (D) Y Na2O,% by weight 1.2 0.8 0.6 0.5 1 Al2O3, wt% 21 , 20.6 21.8 20.8 21.5 SiO2, ° A) by weight 70.5 70.2 71 70.7 69.3 ZrO2,% by weight 8 6.2 7.5 TiO2,% by weight weight 7,9 RE203, wt.% 6.6 a0, nm 2,451 2,45 2,452 2,451 2,453 crystallinity,% 62.7 51.9 55.7 60.2 59.6 specific area, m2 / g 640 536 548 624 610 network failure temperature, ° C 1043 1027 1028 1041 1033 ratio of deformed tetrahedral coordination framework aluminum to tetrahedral coordination framework aluminum 0.05 0.01 0.02 0.01 B. Stability of the modified zeolite The modified Y zeolites prepared according to Examples B.2.1.1 to 8.2.1.9 and B.2.2.1 to B.2.2.5 were aged at 800 ° C under a 100% vapor condition. for 8 hours and 17 hours, respectively, to determine the crystallinity and the specific surface area, and the retention of crystallinity and specific surface retention were calculated. The aged zeolites were subjected to the microactivity (MA) test of light oil. The results are listed in Table B4. Table B4 Example B.2.1.X 1 2 3 4 5 6 7 8 9 zeolite Y ZrY (1) ZrY (3) ZrY (6) ZrY (10) TiY (2) TiY (10) Ti-Zr-Y ZrY ( 1) -1 ZrY (1) -2 retention of crystallinity at 800 ° C / 8 h, `) / 0 61.2 62.8 63.7 68.4 63.1 67.5 68.6 62.0 61 , 8 retention of crystallinity at 800 ° C / 17 h,% 55.5 57.0 56.7 62.5 57.6 60.1 60 56.5 56.1 retention of specific area at 800 ° C / 8 h , ') / 0 62.0 61.3 62.9 69.6 66.1 68 69.6 62.8 61.0 specific area retention at 800 ° C / 17 h,% 57.2 56.7 57 , 6 63.9 59.6 62.2 62.8 57.0 56.4 activity at 800 ° C / 8 h,% 80 82 84 87 85 86 87 80 80 activity at 800 ° C / 17 h,% 76 77 79 82 79 80 81 75 77 Table B4 (continued) Example B.2.2.X 1 2 3 4 5 zeolite Y REY Zr (W) Y Zr (J) Y Zr (G) Y Ti (D) Y crystallinity retention at 800 ° C / 8 h,% 63.2 50.4 50.5 60.8 61.6 retention of crystallinity at 800 ° C / 17 h,% 56.5 45.8 42.5 52.9 53 retention of specific area at 67.1 58 54.2 64.9 62.4 54 800 ° C / 8 h,% retention of specific area at 800 ° C / 17 h,% 61.2 52 , 6 49.8 58.2 59.1 activity at 800 ° C / 8 h,% 85 75 72 80 72 activity at 800 ° C / 17 h,% 79 68 65 75 66 55 3012125 B.3 Catalyst Example B. 3.1.1 The modified zeolite Y prepared according to the present invention, Zr (6) Y, was used as the active component for preparing the catalyst according to the conventional method of preparing the catalytic cracking catalyst. The preparation was the following. According to a zeolite ratio (dry basis): kaolin (dry base): pseudobohemite (as Al 2 O 3): alumina sol (as Al 2 O 3) of 38: 34: 20: 8, it was mixed and put into boiled the kaolin and decationate water. To the resulting slurry, the alumina sol was added, and pseudobohemite was further added with continuous stirring. After stirring for 30 minutes, a liquor containing the zeolite was added to the colloid. The resulting mixture was homogeneously mixed, spray-dried and shaped to produce a so-called Cl catalyst. Evaluation of heavy oil cracking performance: The catalyst was pretreated at 800 ° C. under a condition of 100% steam for 8 hours. Then, the pretreated catalyst was tested on a small scale fixed fluidized bed (CFA) for catalyst evaluation. The feedstock for the evaluation was a ZhengHai mixed vacuum gas oil (VGO) oil and DaQing atmospheric residue (80:20 by weight), whose properties are shown in Table B5. Reaction time = 500 ° C, WHSV = 16 h-1, catalyst-oil weight ratio = 45. The evaluation result is listed in Table B6 where, conversion = gasoline yield + liquefied gas yield + yield dry gas + coke yield coke selectivity = coke yield x 100 / conversion.

56 Table B5 ZhengHai vacuum gas oil load DaQing atmospheric residue Density (20 ° C), g / cm3 0.9154 0.8906 Refraction (70 ° C) 1.4926 1.4957 (20 ° C) Viscosity (100 ° C) C) mm2 / s 6.962 24.84 Composition SARA, ° A) Hydrocarbons saturated 64.0 51.2 Aromatic hydrocarbons 32.0 29.7 Resin 4.0 18.3 Asphaltene 0.0 0.8 Freezing point, ° C 35 43 Aniline point, ° C 82.0> 105 C, wt% 85.38 86.54 H, wt% 12.03 13.03 S, wt% 2.0 0.13 N, % by weight 0.16 0.3 Residual carbon% 0.18 4.3 Distillation range, ° C Initial distillation 329 282 5% 363 351 10% 378 370 30% 410 482 50% 436 553 70% 462 - 90% 501 - Example B.3.1.2 A catalyst was prepared according to Example B.3.1.1 except that the same amount of TiY zeolite (2) was used in place of ZrY zeolite (6). ) to produce a catalyst C2. Then, the evaluation of C2 was carried out according to example B.3.1.1. The evaluation result is listed in Table B6.

Example 8.3.2.1 to Example B.3.2.3 A series of catalysts was prepared according to Example B.3.1.1, except that the same amount of REY zeolite, the same amount of zeolite, was used respectively. Zr (W) Y, and the same amount of zeolite Ti (D) Y in place of zeolite ZrY (6) to produce catalysts DC1, DC2 and DC3. Then the evaluation of DC1 to DC3 was carried out according to example B.3.1.1. The evaluation result is listed in Table B6. Table B6 Example 8.3.1.1 B.3.1.2 B.3.2.1 B.3.2.2 B.3.2.3 Zeolite No. ZrY (6) TiY (2) REY Zr (W) Y Ti (D) Y Catalyst Cl C2 DC1 DC2 DC3 Temp. reaction ratio, 500 500 500 500 500 Catalyst-oil weight ratio 5 VSHP, h-1 16 16 16 16 16 Production distribution,% by weight Dry gas 1.40 1.39 1.38 1 , 39 1.37 liquefied gas 17.15 16.92 16.53 16.44 16.98 coke 4.52 4.75 5.35 5.16 5.33 gasoline 50.80 49.98 49.70 45, 62 48.29 diesel 17.85 18.76 18.64 19.97 18.73 heavy oil 8.28 8.20 8.40 11.42 9.30 conversion,% by weight 73.87 73.04 72, 96 68.61 71.97 Total liquid yield,% by weight 85.80 85.66 84.87 82.03 84.00 Coke selectivity 6.12 6.50 7.33 7.52 7.41 Example B. 3.1.3 A Zr-modified zeolite Y according to Example B.1.1.1, Zr (2) Y, was prepared in which the zirconium nitrate weight ratio (as ZrO 2): zeolite Y = 0.02: 1. 323 g of pseudoboehmite and 1343 g of deionized water were mixed and stirred for 15 minutes to produce a pseudobohemite slurry. The slurry was adjusted with dilute hydrochloric acid (having a concentration of 15% by weight) to a pH of 3.5, and aged at room temperature for 6 hours. To the aged slurry, 421 grams of kaolin and 465 grams of alumina sol were added. After stirring for 60 minutes, a slurry formed by slurrying 380 g (dry basis) of the zeolite ZrY (2) modified above and 800 g of deionized water was added to the resulting slurry. The resulting mixture was stirred for 60 minutes to produce a catalyst slurry, which was spray-dried and shaped, and calcined at 550 ° C for 2 hours to produce a catalytic cracking catalyst, referred to as C17. The ZrO2 content of the C17 catalyst, measured by X-ray fluorescence, was 0.75% by weight. Example B.3.1.4 421 g of kaolin, 465 g of alumina sol and 732 g of deionized water were added and slurried in a slurry tank, to which was added 1667 g of a pseudoboehmite acidified. After stirring for 60 minutes, a slurry formed by slurrying 380 g (dry basis) of the Zr (6) Y zeolite modified above and 800 g of deionized water was added to the vessel. The resulting mixture was stirred for 60 minutes to produce a catalyst slurry, which was spray dried and shaped, and calcined at 550 ° C for 1 hour to produce a catalytic cracking catalyst, referred to as C18. The ZrO 2 content of the C18 catalyst, measured by X-ray fluorescence, was 2.18% by weight. Example B.3.1.5 421 g of kaolin, 558 g of alumina sol and 800 g of deionized water were mixed and slurried for 60 minutes. After addition of 1500 g of an acidified pseudoboehmite, the resulting slurry was further stirred for 60 minutes. To the resulting mixture was added a slurry formed by slurrying 380 g (dry basis) of the zeolite ZrY (10) modified above and 800 g of deionized water. The resulting mixture was mixed for 60 minutes to produce a catalyst slurry, which was spray-dried and shaped, and calcined at 650 ° C for 2 hours to produce a catalytic cracking catalyst, referred to as C19. The ZrO 2 content of catalyst C19, measured by X-ray fluorescence, was 3.52% by weight. Example B.3.1.6 According to Example B.2.1.5, a Ti-modified Y zeolite was prepared and called TiY (8), in which during the impregnation of step (3), the weight ratio of titanium tetrachloride (as TiO2) to zeolite was 0.08: 1. 421 g of kaolin and 380 g of deionized water were mixed and slurried for 60 minutes. After addition of 1667 g of an acidified pseudoboehmite, the resulting slurry was further stirred for 30 minutes. To the resulting mixture was added a slurry formed by slurrying 380 g (dry basis) of the zyolite TiY (8) modified above and 800 g of deionized water. After stirring for 60 minutes, 465 g of alumina sol were added to the resulting slurry. The resulting mixture was stirred for 30 minutes to produce a catalyst slurry, which was spray-dried and shaped, and calcined at 700 ° C for 2 hours to produce a catalytic cracking catalyst, referred to as C20. The TiO2 content of the C20 catalyst, measured by X-ray fluorescence, was 3.02% by weight. Example B.3.1.7 According to Example B.2.1.5, a Ti-modified Y zeolite was prepared and named TiY (4), in which during the impregnation of step (3), the weight ratio of titanium tetrachloride (as TiO2) to zeolite was 0.04: 1. 323 g of pseudobohemite and 1478 g of deionized water were mixed. The mixture was stirred for 30 minutes to produce a pseudobohemite slurry, the pH value of which was adjusted with a suitable amount of hydrochloric acid diluted to 3.8. The resulting slurry was aged at 60 ° C for 2 hours. To the aged slurry, 421 grams of kaolin and 465 grams of alumina sol were added. The resulting slurry was stirred for 60 minutes. To the above slurry was added a slurry formed by slurrying 380 g (dry basis) of the zyolite TiY (4) modified above and 800 g of deionized water. The resulting mixture was stirred for 60 minutes to produce a catalyst slurry, which was spray-dried and shaped, and calcined at 600 ° C for 3 hours to produce a catalytic cracking catalyst, referred to as C21. The TiO2 content of catalyst C21, measured by X-ray fluorescence, was 1.48% by weight. Example B.3.1.8 According to Example B.2.1.5, an Hf-modified zeolite Y was prepared and designated HfY (6), in which during the impregnation of step (3), the weight ratio of hafnium nitrate (as HfO2) to zeolite was 0.06: 1. 421 g of kaolin and 380 g of deionized water were mixed and slurried for 60 minutes. After adding 1667 g of an acidified pseudoboehmite, the resulting slurry was further stirred for 30 minutes. To the resulting mixture was added a slurry formed by slurrying 380 g (dry basis) of the above modified HFY zeolite (6) and 800 g of deionized water. After stirring for 60 minutes, 465 g of alumina sol were added to the resulting slurry. The resultant mixture was stirred for 30 minutes to produce a catalyst slurry, which was spray-dried and shaped, and calcined at 700 ° C for 2 hours to produce a catalytic cracking catalyst, referred to as C22. The HfO2 content of the C22 catalyst, measured by X-ray fluorescence, was 2.11% by weight. Example B.3.1.9 421 g of kaolin and 380 g of deionized water were mixed and slurried for 60 minutes. After adding 1667 g of an acidified pseudoboehmite, the resulting slurry was further stirred for 30 minutes. To the resulting mixture was added a slurry formed by slurrying 380 g (dry basis) of the zeolite Ti-Zr-Y modified above and 800 g of deionized water. After stirring for 60 minutes, 465 g of alumina sol were added to the resulting slurry. The resultant mixture was stirred for 30 minutes to produce a catalyst slurry, which was spray-dried and shaped, and calcined at 700 ° C for 2 hours to produce a catalytic cracking catalyst, referred to as C23. The contents of TiO2 and ZrO2 of catalyst C23, measured by X-ray fluorescence, were 1.50% by weight and 1.48% by weight respectively. Example B.3.1.10 to Example 8.3.1.12 A series of catalysts was prepared according to Example B.3.1.3, except that the same amount of ZrY (1), the same amount of ZrY was used respectively. (1) -1 and the same amount of ZrY (1) -2 instead of zeolite ZrY (2) to produce catalysts C24, C25 and C26. Example B.3.2.4 A catalyst was prepared according to Example B.3.1.4 except that the same amount of Zr (W) Y zeolite was used in place of ZrY zeolite (6) to produce the catalyst DC14. The ZrO 2 content of the DC14 catalyst, measured by X-ray fluorescence, was 2.19% by weight. Example B.3.2.5 500 g of NaY zeolite (dry basis) and 6000 g of deionized water were mixed and slurried. To the resulting slurry, 200 g of NH 4 Cl was added. The mixture was adjusted to pH = 3.8, heated to 80 ° C for 2 hours, filtered and washed with water. The above procedure was repeated three times. The resulting filter cake was calcined at 600 ° C in a 100% steam atmosphere for 2 hours. The calcined zeolite Y and 6,000 g of deionized water were then mixed and slurried. To the slurry was added 150 g of NH4Cl and 95.1 g of titanium tetrachloride. The mixture was warmed to 80 ° C for an exchange for 3 hours. After filtration and washing, the resulting filter cake was calcined at 600 ° C in a 100% steam atmosphere for 2 hours. Finally, a zeolite was obtained and called zeolite Ti (J) Y. A catalyst was prepared according to Example B.3.1.6 except that the same amount of Ti (J) Y zeolite was used in place of the TiY zeolite (8) to produce the DC15 catalyst. The TiO2 content of the DC15 catalyst, measured by X-ray fluorescence, was 1.72% by weight. Example B.3.2.6 200 g of NaY zeolite and 2000 g of deionized water were mixed and slurried. To the resulting slurry was added 45 mL of a 270 g / L RECI3 solution. The mixture was adjusted with dilute hydrochloric acid at pH = 3.8, warmed to 80 ° C for one hour exchange. After filtration and washing, the resulting filter cake was calcined at 500 ° C for 3 hours. Then, the resulting zeolite Y and 2000 g of deionized water were mixed and slurried. To the slurry was added 45 g of ammonium sulfate. The mixture was adjusted with dilute hydrochloric acid at pH = 4.0, and warmed to 80 ° C for one hour exchange. After filtration and washing, the resulting filter cake was calcined at 600 ° C in a 100% steam atmosphere for 3 hours. Finally, RE-modified zeolite was obtained and was named REY (8). According to a zeolite ratio (dry basis): kaolin (dry base): pseudobohemite (as Al 2 O 3): alumina sol (as Al 2 O 3) of 38: 34: 20: 8, we mixed and put in boiled the kaolin and decationate water. To the resulting slurry, the alumina sol was added, and pseudobohemite was added with continued stirring. After stirring for about 30 minutes, a liquor containing the zeolite was added to the colloid. The resultant mixture was homogeneously mixed, spray-dried and shaped to produce a catalyst, referred to as DC16. Catalysts C17 to C26 and DC14 to DC16 were pretreated at 800 ° C under a 100% steam condition for 17 hours. Then, the pretreated catalysts were tested on a small scale fixed fluidized bed (CFA) for evaluation of the catalyst. The load for evaluation was Wuhun III, whose properties are shown in Table B7. Reaction temperature = 500 ° C, and catalyst-oil weight ratio = 5. The evaluation result is listed in Table B8 where, conversion = gasoline yield + liquefied gas yield + dry gas yield + fuel efficiency coke Coke selectivity = coke yield / conversion. Table B7 Charge properties Wuhun III charge Density (20 ° C), g / cm3 0,9044 Refraction (20 ° C) 1,5217 Viscosity (100 ° C), mm2 / s 9,96 Freezing point, ° C 40 Aniline point, ° C 95.8 C, wt% 85.98 H, wt% 12.86 S, wt% 0.55 N, wt% 0.18 Residual carbon, wt% 3.0 Distillation range, ° C Initial distillation point 243 5% 294 10% 316 30% 395 50% 429 70% 473 90% - Table B8 Evaluation result Example 8.3.1.3 B.3.1.4 B.3.1 .5 B.3.1.6 B.3.1.7 8.3.1.8 8.3.1.9 Catalyst No. C17 C18 C19 C20 C21 C22 C23 Modified Y-zeolite No. ZrY (2) ZrY (6) ZrY (10) TiY (8) TiY (4) HfY (6) Ti-Zr-Y Reaction time, ° C 500 500 500 500 500 500 500 Catalyst-oil ratio (weight) 5 5 5 5 5 5 WHSV, h-1 16 16 16 16 16 16 16 Production distribution,% by weight Dry gas 1,25 1,12 1,29 1,22 1,10 1,18 1,20 Liquefied gas 12,04 13,05 11,53 12,09 12,41 12, 48 12.35 Coke 5.09 4.26 4.95 4.96 5.01 4.85 4.99 Petrol 53.99 54.61 54.59 54.44 54.07 53.9 5 54.11 Diesel 21.41 20.98 21.58 21.34 21.84 21.69 21.36 Heavy oil 6.22 5.98 6.06 5.95 5.57 5.85 5.99 Total 100 100 100 100 100 100 100 Conversion% by weight 72.37 73.04 72.36 72.71 72.59 72.46 72.65 Coke / Conversion 0.07033 0.05832 0.06841 0.06822 0, 06902 0.06693 0.06869 63 Table B8 Evaluation result (continued) Example B.3.1.10 B.3.1.11 B.3.1.12 B.3.2.4 B.3.2.5 8.3.2.6 Catalyst No. C24 C25 C26 DC14 DC15 DC16 Modified Y zeolite ZrY (1) ZrY (1) -1 ZrY (1) -2 Zr (W) Y Ti (J) Y RE (8) Y Reaction temperature, ° C 500 500 500 500 500 500 Catalyst-oil ratio (weight) 5 VSHP, h-1 16 16 16 16 16 16 Production distribution,% by weight Dry gas 1.21 1.22 1.23 1.32 1, 18 1.10 Liquefied gas 11.81 11.79 11.89 11.78 12.03 11.66 Coke 4.62 4.52 4.71 5.88 5.25 5.45 Gasoline 54.15 54.21 54.48 50.57 50.30 53.08 Diesel 21.88 21.91 21.28 22.01 22.12 21.46 Heavy Oil 6.33 6.35 6.41 8.44 9.12 7, 25 Total 100 100 100 100 100 100 Conversion,% by weight 71.79 71.74 72.31 69.55 68.76 71.29 Coke / Conversion 0.06435 0.06301 0.06514 0.08454 0.07635 0.0764 64 65

Claims (51)

Claims 1. A metal-modified zeolite Y which contains 1 to 15% by weight of a Group IVB metal as the oxide, wherein the metal-modified Y zeolite has a ratio of deformed tetrahedral coordination and tetrahedral coordination framework aluminum in the network structure from 0.1 to 0.8, for example 0.2 to 0.8. The metal-modified Y zeolite according to claim 1, which has a specific surface area of 600 to 850 m2 / g or 600 to 750 m2 / g, an elemental mesh size a0 of 2,448 to 2,458 nm or 2,450 to 2,455 nm, a crystallinity not less than 60%, and optionally a SiO 2 / Al 2 O 3 molar ratio of 5 to 50 and the percentage between the secondary pores (pore diameter 6 to 20 nm) and the total secondary pores (pore diameter of 2 to 100 nm ) being 30 to 50% or 50% to 65%. A metal-modified Y zeolite according to claim 1, wherein the modifying metal is Ti and / or Zr, wherein relative to the unmodified zeolite Y, the antisymmetric valence vibration frequency (1050 to 1150 cm -1) 1) and the symmetrical valence vibration frequency (750 to 820 cm-1) in the infrared spectrum of the metal-modified Y zeolite do not shift to red in a downward direction. A metal-modified Y zeolite according to claim 1 or 3, which has an anhydrous chemical composition formula, as oxide and by weight, of (0-2) Na 2 O- (1-15) M02- (10-). 25) Al 2 O 3 - (65-75) SiO 2 (0.1-1.2) Na 2 O- (1-10) M02- (20-24) Al 2 O 3 - (67-74) SiO 2, wherein M is a metal of the group IVB, selected from one or more of Ti, Zr, Hf and Rf. The metal-modified Y zeolite of claim 1, wherein the Group IVB metal is Ti and / or Zr, and the metal-modified Y zeolite is free of both framework Ti and framework Zr. The metal-modified Y zeolite of claim 1, wherein the ratio of the Group IVB metal content of the zeolite surface to the Group IVB metal content of the interior of the zeolite is not greater than at 0.2. 66 3012125 The metal-modified Y zeolite of claim 1, wherein the Group IVB metal content as the oxide is from 1 to 10% by weight. The metal-modified Y zeolite of claim 1, wherein the Group IVB metal comprises Ti and / or Zr. A process for preparing a metal-modified Y zeolite, comprising the following steps: (1) zeolite Y is contacted with an acid solution and / or an aqueous EDTA solution; said acid being an organic acid and / or an inorganic acid; (2) the product obtained in step (1) is dehydrated at a temperature below 400 ° C, so that the water content in the zeolite is not greater than 5% by weight; (3) the zeolite obtained in step (2) is impregnated with a metal in an organic solvent; (4) the metal-impregnated zeolite Y obtained in step (3) and an organic solvent are added in a vessel at a solid-liquid weight ratio of 1: 5 to 50, an inert gas is introduced into the vessel, and the vessel is maintained at a pressure of 0 to 2.0 MPa, preferably 0.1 to 2 MPa (gauge pressure) at a temperature in the range of room temperature to 200 ° C for at least one hour; filtration and / or drying are optionally conducted; (5) the zeolite obtained in step (4) is calcined; the calcination is conducted in an inert gas atmosphere, the calcination temperature is 300 to 700 ° C, the calcination time is 0.5 to 5 hours. The process according to claim 9, wherein in step (1), zeolite Y is one or more of zeolite NaY, NaHY, NaNH4Y, NH4Y, HY, USY, DASY, once exchanged zeolite Y - calcined once, a zeolite Y exchanged twice - calcined twice, and a zeolite Y exchanged twice - calcined once. The process according to claim 9, wherein in step (1) zeolite Y is contacted with the acidic solution in a solid-to-liquid weight ratio of 1: 5 to 1:20 at a temperature in a range from room temperature to 100 ° C for at least 0.5 hours, then filtered and washed; the acid solution has an acid concentration, as H +, of 0.1 to 1 mol / L. 67 3012125 The method of claim 11, wherein the contact time is 0.5 to 3 hours; the acid is an inorganic acid and / or an organic acid; wherein the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid; and the organic acid is one or more of formic acid, acetic acid, oxalic acid, citric acid. 13. The method of claim 9, wherein in step (2), the dehydration is intended to calcine the zeolite obtained in step (1) at 200 to 400 ° C for 2 to 10 hours. The process according to claim 9, wherein in step (3), the impregnation with the metal in the organic solvent comprises the mixture of the organic solvent in which a compound containing the Group IVB metal is dissolved with the zeolite obtained. in step (2), and the resulting mixture is stored for at least 0.5 hours, wherein the solid-liquid weight ratio of zeolite Y and organic solvent is 1: (0.5 to 5) . 15. The method of claim 14, wherein in step (3), the resulting mixture is stored at rest or stirred for 0.5 to 12 hours. The process according to claim 14, wherein in step (3), the solid-liquid weight ratio of zeolite Y and organic solvent is 1: 1 to 2. The method of claim 14, wherein the group IVB metal-containing compound is a Ti-containing compound and / or a Zr-containing compound; the Ti-containing compound is one or more of titanium sulphate, titanyl sulphate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate, and ammonium fluotitanate, and the Zr-containing compound is one or more among zirconium tetrachloride, zirconium sulphate, zirconium nitrate, zirconium oxychloride, zirconium acetate, and zirconium isopropoxide. 18. The method of claim 9, wherein in step (4), the vessel is stored for 1 to 48 hours. 19. The method of claim 9, wherein in step (4), the pressure is 0.5 to 1.5 MPa, the temperature is from room temperature to 150 ° C, the time is from 4 to 24 hours, and the solid-liquid weight ratio of zeolite and organic solvent is from 1: 5 to 30. 20. The method of claim 9, wherein in step (5), the calcination temperature is 450-650 ° C, and the calcining time is 1-4 hours. 21. The process according to claim 9, wherein the organic solvent has a water content of not more than 5% by weight. 22. The process according to claim 21, wherein the organic solvent has a water content of not more than 3% by weight; and the zeolite Y obtained in step (2) has a water content of not more than 3% by weight. The process according to any one of claims 9 to 22, wherein the organic solvent is one or more of alkanes, aromatic hydrocarbons, alcohols, ketones, ethers, esters, halogenated alkanes such as alkanes. chlorinated. 24. The process according to claim 23, wherein the organic solvent has a normal boiling point of 40 to 100 ° C. 25. The process according to claim 23, wherein the organic solvent is preferably one or more of n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, propylene glycol, and the like. acetone, butanone, and trichloromethane. 26. A process for preparing a metal-modified Y zeolite, comprising the following steps: (1) a zeolite Y raw material is dewatered so that the raw material has a water content by weight no greater than 5 % (2) the dehydrated zeolite Y obtained in step (1) is contacted with a mixture of a Group IVB metal-containing compound and an organic solvent, and the resulting mixture is optionally filtered and / or dried; (3) zeolite Y obtained in step (2) is calcined at 300 to 700 ° C; (4) the zeolite Y obtained in step (3) is contacted with an aqueous acidic solution and then calcined at 400 to 800 ° C to produce the metal-modified zeolite Y containing the Group IVB metal; the concentration of acid, as H +, is 0.1 to 2.0 mol / L. 27. The method of claim 26, wherein in step (2), the weight ratio of mixture between the group IVB containing compound, zeolite Y and the organic solvent is 0.01 to 0.15. : 1: 1-50, wherein the weight of the Group IVB metal-containing compound is calculated as the oxide, and the zeolite Y is calculated in a dry base. 28. The method of claim 26, wherein in step (2), the weight ratio containing the Group IVB metal (as oxide): zeolite Y (dry basis): organic solvent is 0, 01 to 0.1: 1: 5 to 30. 29. The method of claim 26, wherein in step (2), the procedure for contacting the dehydrated zeolite Y obtained in step (1) with the compound containing the group IVB metal and the organic solvent. and optional filtration and / or drying comprises: the Group IVB metal-containing compound, the organic solvent and the Y zeolite are mixed and contacted at a temperature in a range of room temperature to 100 ° C for at least 0 , 5 hours, then optionally filtered, and then optionally dried. 30. The method of claim 26 or 29, wherein in step (2), the procedure for contacting the dried zeolite Y obtained in step (1) with the mixture of the compound containing the group IVB metal. and the optional organic and filtering and / or drying solvent of the resulting mixture is conducted once or more than once. 31. The method of claim 26, wherein in step (3), the calcination temperature is 350 to 650 ° C, the calcination time is 2 to 4 hours, the calcination atmosphere is a dried air and / or an inert gas. 32. The method of claim 26, wherein in step (4), the condition of bringing the zeolite Y obtained in step (3) into contact with the aqueous acid solution comprises the following characteristics: weight (solid-liquid ratio) between the zeolite Y obtained in step (3) and the aqueous acid solution is from 1: 5 to 20, the contact temperature is in a range from room temperature to 100 ° C, the contact time is at least 0.5 hours; the aqueous acid solution has an acid concentration, as H +, of 0.1 to 2 mol / L. 70 3012125 33. The process according to claim 26, wherein the aqueous acid solution has an acid concentration, as H +, of 0.5 to 2 mol / L. The process according to claim 26, wherein the organic solvent is one or more of alkanes, aromatic hydrocarbons, alcohols, ketones, ethers, esters, halogenated alkanes such as chlorinated alkanes. The process according to claim 26, wherein the organic solvent is selected from one or more of n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, amine acetone, butanone, trichloromethane. 36. The process of claim 26, wherein the organic solvent has a normal boiling point of 40 to 100 ° C. 37. A process according to any one of claims 26 to 36, wherein the organic solvent has a water content of not more than 5% by weight. 38. The process according to claim 26, wherein the organic solvent has a water content of not more than 1% by weight. 39. A method according to any one of claims 26 to 38, wherein in step (2), the contacting temperature of the dried zeolite Y obtained in step (1) and the mixture of the compound containing the Group IVB metal and organic solvent is a temperature that allows the organic solvent to be in a liquid state. 40. The method of claim 26, wherein the group IVB metal-containing compound comprises a Ti-containing compound and / or a Zr-containing compound. 41. The process according to claim 40, wherein the Ti-containing compound is one or more of titanium sulphate, titanyl sulphate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate, ammonium fluotitanate, and the Zr-containing compound is one or more of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, zirconium acetate and zirconium isopropoxide. 42. The process according to claim 26, wherein in step (1) the zeolite Y raw material is one or more of a NaY zeolite, a NaHY zeolite, a NaNH4Y zeolite, an NH4Y zeolite and a HY zeolite. 43. The process according to claim 26, wherein in step (1), the raw zeolite material Y has a water content, after dehydration, of not more than 1% by weight. 44. The process according to claim 26, wherein in step (4) the calcination is conducted in a steam atmosphere of 1 to 100%. 45. A metal-modified Y zeolite according to any one of claims 1 to 8 which is obtained or obtainable by the process of any one of claims 9 to 44. 46. Catalytic cracking catalyst, based on the weight of the catalyst, containing 10 to 60% by weight of a metal-modified Y zeolite, 10 to 60% by weight of a clay and 5 to 50% by weight of a binder, wherein said metal-modified Y zeolite is the metal-modified Y zeolite of any one of claims 1 to 8. 47. Catalytic cracking catalyst according to claim 46, wherein the catalytic cracking catalyst contains 20 to 55% by weight of the Group IVB metal-modified zeolite Y, 15 to 60% by weight of the clay and 10 to 40% by weight of the binder. 48. Catalytic cracking catalyst according to claim 46, wherein the catalyst further contains other molecular sieves conventionally used in the catalytic cracking catalyst, said other molecular sieves include molecular sieves of type Y, molecular sieves with MFI structure. , and SAPO molecular sieves. 49. A catalytic cracking catalyst according to claim 46, wherein the content of other molecular sieves conventionally used in the catalytic cracking catalyst is not more than 40% by weight, such as 1 to 35% by weight. 72 3012125 50. A method of preparing the catalytic cracking catalyst, which comprises the steps of preparing a metal-modified Y zeolite, mixing and slurrying the metal-modified Y zeolite and a clay and a binder, and spray-drying the resulting mixture. wherein said metal-modified Y zeolite is prepared according to the method of any one of claims 9 to 44. 51. The method of claim 50, wherein the clay is selected from one or more of kaolin, halloysite, rectorite, diatomite, montmorillonite, bentonite and sepiolite; and the binder is selected from one or more hydrated alumina, alumina sol, pseudobohemite, bohemite, alumina monohydrate, alumina trihydrate, and amorphous aluminum hydroxide.