RU2670744C2 - Metal modified zeolite of y-type and method for producing thereof - Google Patents

Abstract

FIELD: metallurgy.SUBSTANCE: present invention relates to a metal-modified zeolite of the Y-type for use as a catalytic cracking catalyst, which contains 1–15 wt. % of the group IVB metal based on the oxide, the ratio of the deformed tetrahedrally coordinated alumina to tetrahedrally coordinated framework aluminum in the crystal lattice structure of the zeolite is 0.1–0.8. Invention also relates to two variants of a process for its preparation and a catalyst based on this zeolite.EFFECT: for use as catalytic cracking catalyst.52 cl, 2 dwg, 45 ex, 14 tbl

Description

The technical field to which the invention relates.

The present invention relates to a zeolite of type Y, modified by metals, the method of its production and its use.

The level of technology

When conducting catalytic cracking, the raw materials become more and more enriched with heavy compounds; it is important for catalytic cracking catalyst to have both high activity and high thermal and hydrothermal stability to increase the ability to convert heavy compounds and reduce heavy metal contamination. Consequently, it is required that the main active component of the catalytic cracking catalyst, namely, Y-type zeolite, possess high thermal and hydrothermal stability and make a corresponding contribution to the active acid sites.

The rare earth metals (RE) type Y zeolite has a rather high thermal and hydrothermal stability and is widely used in the preparation of FCC catalysts (liquid catalytic cracking). However, the sharp rise in prices for rare earth metals leads to a significant increase in the cost of the FCC catalyst. Therefore, it is desirable to introduce other metal ions into the Y-type zeolite, reduce the content of rare-earth elements in the Y-type zeolite, and ensure hydrothermal stability, comparable to the hydrothermal stability of the Y-containing rare-earth zeolite.

In the applications CN 1350887 A, CN 1765492 A and US 2007010698 A1, methods have been proposed for the preparation of zeolites of type Y modified with metals. However, compared with rare-earth-modified zeolite Y, these metal-modified zeolites have low thermal and hydrothermal stability.

In the applications CN 101898144A and CN 101134576A a modification of the skeleton of type Y zeolites is proposed with the aim of increasing the thermal and hydrothermal stability of these zeolites. However, the obtained zeolites of type Y, modified with non-rare-earth metals, result in catalytic cracking in the production of a gasoline fraction in a low yield.

DISCLOSURE OF INVENTION

To solve the problems of the prior art, the present invention proposes a zeolite of type Y, modified by metals, and a method for producing it. Such a zeolite of type Y, modified by metals, is modified by non-rare-earth elements and has thermal and hydrothermal stability, comparable to the same properties of zeolite of type Y, modified by rare-earth elements. When used as a catalyst for catalytic cracking, this catalyst has excellent cracking activity, provides a high yield of gasoline and selectivity for coke.

In accordance with one aspect, the present invention provides for a zeolite of type Y modified by metals, characterized in that: the ratio of the content of metal of group IVB on the surface of zeolite to the content of metal of group IVB in the pores inside the zeolite is not more than 0.2; and / or the ratio of the content of the deformed tetrahedrally coordinated aluminum atom in the framework to the content of the tetrahedrally coordinated aluminum atom of the framework in the structure of the zeolite lattice is (0.1–0.8): 1.

According to another aspect, this invention relates to a method for producing a zeolite of type Y, modified by metals, which includes the following stages:

(1) the crude type Y zeolite is dehydrated to produce a crude zeolite with a water content of not more than 5% by weight;

(2) the type Y zeolite obtained in step (1) is contacted with a mixture of a compound containing a metal of the IVB group and an organic solvent, and the resulting mixture is optionally filtered and / or dried;

(3) Y-type zeolite obtained in step (2) is calcined at a temperature of 300-700 ° C, preferably for at least 0.5 hours, for example, within 0.5-5 hours;

(4) Y-type zeolite obtained in step (3) is contacted with an aqueous acid solution and then calcined at a temperature of 400-800 ° C in an atmosphere containing 1-100% steam for 0.5-5 hours to obtain a Y-type zeolite metal modified metal containing group IVB; while the concentration of H + in the acid solution is 0.1-2.0 mol / l.

According to another aspect of the present invention provides a method for producing a zeolite of type Y, modified by metals, which includes the following stages:

(1) Y-type zeolite is treated by contacting with an acid solution and / or an aqueous solution of EDTA (ethylenediaminetetraacetic acid); wherein said acid is an organic and / or inorganic acid;

(2) the product obtained in stage (1) is subjected to dehydration at a temperature below 400 ° C so that the water content in the zeolite is no more than 5 weight. %;

(3) the zeolite obtained in step (2) is impregnated with a solution of a metal in an organic solvent;

(4) Y-type zeolite impregnated with the metal solution obtained in step (3) and the organic solvent is added to the reaction vessel with a weight ratio of solid to liquid of 1: (5-50) and stirred, an inert gas is introduced into the vessel, such as one or more gases selected from nitrogen and helium, and the vessel is kept under a pressure of 0-2.0 MPa (gauge pressure) at a temperature ranging from room temperature to 200 ° C for at least one hour, for example, for 1- 48 h; then optionally filtering and drying the product.

(5) the zeolite obtained in step (4) is calcined; the calcination is carried out in an inert gas atmosphere, the calcination temperature is 300-700 ° C, the calcination time is at least 0.5 hours, for example, 0.5-5 hours

According to another aspect of the invention, there is also provided a catalytic cracking catalyst comprising a type Y zeolite modified with metals and a method for producing it.

Specifically, this invention provides the following technical solutions:

1. Zeolite type Y, modified by metals, which contains 1-14 weight. The% of group IVB metal calculated on the oxide, while the zeolite of type Y modified by metals, has the ratio of the content of the deformed tetrahedrally coordinated aluminum atom in the frame to the content of the tetrahedrally coordinated aluminum atom of the framework in the crystal lattice structure equal to 0.1-0.8, for example, 0.2-0.8.

2. Zeolite of type Y, modified by metals, according to the previous decision, which has the value of specific surface area equal to 600-850 m ² / g or 600-750 m ² / g, the size of the unit cell parameter of zeolite a0 equal to 2.448-2.458 nm or 2.450- 2.455 nm, the degree of crystallinity is not less than 60% and, optionally, the molar ratio of SiO ₂ / Al ₂ O ₃ (the ratio of Si / Al atoms in the frame) is 5-50, while the ratio of the number of secondary pores (with a pore diameter of 6-20 nm) to the total number of secondary pores (with a pore diameter of 2-100 nm) is 30-50% or 50-65%.

3 Metal modified type Y zeolite according to any one of the previous solutions, in which the modifying metal is Ti and / or Zr, while compared to unmodified type Y zeolite, the frequency of asymmetric stretching vibrations (1050-1150 cm ^-1 ) and the frequency of symmetrical stretching vibrations (750–820 cm ^–1 ) in the infrared spectrum of a metal-modified zeolite of type Y do not have a shift to the long wavelength region (red shift) in the direction of the lower frequency.

4. A zeolite of type Y, modified by metals, according to any one of the previous solutions, which in the form of oxides has the following chemical composition (by weight) (0-2) Na ₂ O⋅ (1-15) MO ₂ (10-25) Al ₂ O ₃ ⋅ (65-75) SiO ₂ or (0.1-1.2) Na ₂ O⋅ (1-10) MO ₂ (20-24) Al ₂ O ₃ (67-74) SiO ₂ , where M is is a metal of the IVB group, selected from one or more metals from Ti, Zr, Hf and Rf.

5. A zeolite of type Y, modified by metals, according to any one of the preceding solutions, in which the metal of group IVB is Ti and / or Zr, and the zeolite of type Y, modified by metals, does not contain either a framework from Ti or a framework from Zr.

6. A zeolite of type Y, modified by metals, according to any one of the preceding decisions, in which the ratio of the content of an IVB metal on the surface of a zeolite to the content of an IVB metal inside the zeolite pores is no more than 0.2.

7. Zeolite of type Y, modified by metals, according to any one of the previous solutions, in which the content of the metal of the IVB group in the calculation of oxide is 1-10 weight. %

8. Zeolite of type Y, modified by metals, according to any one of the preceding solutions, in which the metal of group IVB is Ti and / or Zr.

9. A method of producing a zeolite of type Y, modified by metals, comprising the following steps:

(1) Y-type zeolite is in contact with an acid solution and / or an aqueous solution of EDTA (ethylenediaminetetraacetic acid); wherein said acid is an organic and / or inorganic acid;

(2) the product obtained in stage (1) is subjected to dehydration at a temperature below 400 ° C so that the water content in the zeolite is not higher than 5 weight. %;

(3) the zeolite obtained in step (2) is impregnated with a solution of a metal in an organic solvent;

(4) a zeolite of type Y, impregnated with metals, obtained in step (3), and an organic solvent is added to the reaction vessel with a weight ratio of solids / liquid of 1: 5-50, inject an inert gas into the vessel and withstand the vessel under 0- pressure 2.0 MPa, preferably 0.1-2 MPa (gauge pressure) at a temperature ranging from room temperature to 200 ° C for at least one hour and optionally filtering and / or drying.

(5) the zeolite obtained in step (4) is calcined; the calcination is carried out in an inert gas atmosphere at a calcination temperature of 300-700 ° C, the passage time is 0.5-5 hours.

10. The method according to the previous solution, in which in step (1) the zeolite of type Y is one or more zeolites of NaY, NaHY, NaNH ₄ Y, NH ₄ Y, HY, USY, DASY, zeolite of type Y, which was once subjected to ion exchange and was calcined once, zeolite of type Y, which was ion-exchanged twice and calcined twice, and zeolite of type Y, which was ion exchanged twice and calcined once.

11. A method according to any one of the preceding solutions, in which in step (1) a type Y zeolite is in contact with an acid solution with a weight ratio of solids to liquid of 1: 5-1: 20 at a temperature ranging from room temperature to 100 ° C for at least 0.5 h, then the resulting product is filtered and washed; moreover, the concentration of H ⁺ in the acid solution is 0.1-1 mol / l.

12. The method according to any one of the previous solutions, in which the contact time is 0.5-3 hours; 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 and citric acid.

13. The method according to any one of the previous solutions, in which at stage (2) dehydration occurs during the calcination process of the zeolite obtained in stage (1) at a temperature of 200-400 ° C for 2-10 hours.

14. The method according to any of the previous solutions, in which in stage (3) the metal in the solution of an organic solvent, in which the compound containing the metal of the IVB group is dissolved, is mixed with the zeolite obtained in stage (2), and the resulting mixture is aged for at least 0.5 h, while the weight ratio of the solid substances of the zeolite type Y to the liquid is 1: (0.5-5).

15. The method according to any one of the previous solutions, in which at the stage (3) the resulting mixture is aged while standing or under stirring for 0.5-12 hours.

16. The method according to any one of the preceding solutions, in which in step (3) the weight ratio of the solid substances of the Y-type zeolite to the liquid is 1: 1-2.

17. The method according to any one of the previous solutions, in which the compound containing the metal of the IVB group is a Ti-containing compound and / or a Zr-containing compound; wherein the Ti-containing compound is one or more compounds from titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate and ammonium fluorotitanate and the Zr-containing compound is one or more compounds from zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride zirconium acetate and zirconium isopropoxide.

18. A method according to any one of the preceding solutions, in which in step (4) the reaction vessel is kept for 1-48 hours.

19. The method according to any of the preceding decisions, in which at stage (4) the pressure is 0.5-1.5 MPa, the temperature ranges from room temperature to 150 ° C, the time is 4-24 hours, and the weight ratio of zeolite solids to liquid, which is an organic solvent, is 1: 5-30.

20. The method according to any one of the preceding solutions, in which in stage (5) the calcination temperature is 450-650 ° C and the calcination time is 1-4 hours.

21. The method according to any one of the previous solutions, in which the organic solvent in stages (3) and / or (4) contains water in an amount of not more than 5 weight. %

22. The method according to any of the previous solutions, in which the organic solvent in stages (3) and / or (4) contains water in an amount of not more than 3 weight. %, and the zeolite type Y, obtained in stage (2), contains water in an amount of not more than 3 weight. %

23. The method according to any one of the preceding solutions, wherein the organic solvent is one or more solvents from alkanes, aromatic hydrocarbons, alcohols, ketones, ethers, esters, and halogenated alkanes, such as chlorinated alkanes.

24. The method according to any of the previous solutions, in which the organic solvent has a boiling point under normal conditions in the range of 40-100 ° C.

25. The method according to any one of the preceding solutions, in which the organic solvent is preferably one or more solvents from n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone and trichloromethane.

26. A method for producing a metal modified Y-type zeolite, which comprises the following steps:

(1) a crude type Y zeolite is subjected to the removal of water to obtain a water content of not more than 5% by weight;

(2) the dried zeolite obtained in step (1) is contacted with a mixture of a compound containing a metal of group IVB and an organic solvent, and the resulting mixture is optionally filtered and / or dried;

(3) Y-type zeolite obtained in step (2) is calcined at a temperature of 300-700 ° C;

(4) the Y-type zeolite obtained in step (3) is contacted with an aqueous acid solution and then calcined at a temperature of 400-800 ° C to obtain a Y-type zeolite modified with metals containing group IVB metal; while the concentration of H + in the acid is 0.1-2.0 mol / l.

27. The method according to the previous solution, in which in stage (2) the weight ratio of the compound containing metal of group IVB, type Y zeolite and organic solvent when mixed is 0.01-0.15: 1: 1-50, while the weight content of compound containing the metal of the IVB group is calculated on its oxide, and the content of zeolite type Y is calculated on the dry matter.

28. The method according to any of the preceding decisions, in which in stage (2) the weight ratio of the compound containing the metal of the IVB group (calculated on its oxide) to the zeolite of type Y (calculated on the dry matter) and to the organic solvent is 0.01-0.1 : 1: 5-30, respectively.

29. The method according to any one of the preceding solutions, wherein in step (2) contacting the dried Y-type zeolite obtained in step (1) with a compound containing a metal of group IVB and an organic solvent and optionally filtering and / or drying include: mixing the compound containing metal of group IVB, organic solvent and type Y zeolite and their contacting at a temperature ranging from room temperature to 100 ° C for at least 0.5 h and then possible filtration and possible drying.

30. A method according to any one of the preceding solutions, in which in step (2) contacting the dehydrated type Y zeolite obtained in step (1) with a compound containing a metal of group IVB and an organic solvent and optionally filtering and / or drying the mixture obtained is carried out once or more than once.

31. The method according to any of the previous solutions, in which in stage (3) the calcination temperature is 350-650 ° C, the calcination time is 2-4 hours, the calcination is carried out in an atmosphere of dry air and / or inert gas.

32. The method according to any of the preceding solutions, in which in step (4) the conditions for contacting the type Y zeolite obtained in stage (3) and the aqueous acid solution include: a weight ratio (solids / liquid) of type Y zeolite obtained in stage (3), to the aqueous solution of the acid is 1: 5-20, the temperature at which the contact occurs, is in the range from room temperature to 100 ° C, the contact time is at least 0.5 h; the concentration of H + in the acid solution is 0.1-2 mol / l.

33. The method according to any of the preceding decisions, in which the concentration of H + in an aqueous acid solution is 0.5-2 mol / g.

34. The method according to any one of the preceding solutions, wherein the organic solvent is one or more solvents of alkanes, aromatic hydrocarbons, alcohols, ketones, ethers, esters, and halogenated alkanes, such as chlorinated alkanes.

35. The method according to any one of the previous solutions, in which the organic solvent is one or more solvents from n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone and trichloromethane.

36. The method according to any of the previous solutions, in which the organic solvent has a boiling point under normal conditions equal to 40-100 ° C.

37. The method according to any of the previous solutions, in which the organic solvent contains water in an amount of not more than 5 weight. %

38. The method according to any of the previous solutions, in which the organic solvent contains water in an amount of not more than 1 weight. %

39. The method according to any of the preceding solutions, in which in step (2) the temperature of contacting the dehydrated type Y zeolite obtained in step (1) and a mixture of compounds containing group IVB metal and organic solvent is the temperature at which the organic solvent is in a liquid state.

40. The method according to any one of the preceding solutions, in which the compound containing the metal of the IVB group is a Ti-containing compound and / or a Zr-containing compound.

41. A method according to any one of the preceding solutions, in which the Ti-containing compound is one or more compounds of titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate and ammonium fluorotitanate and the Zr-containing compound is one or more of zirconium tetrachloride compounds zirconium sulfate, zirconium nitrate, zirconium oxychloride, zirconium acetate and zirconium isopropoxide.

42. The method according to any one of the preceding solutions, wherein in step (1) the crude type Y zeolite is one or more zeolites selected from NaY zeolite, NaHY zeolite, NaNH ₄ Y zeolite, NH ₄ zeolite and HY zeolite.

43. The method according to any of the preceding decisions, in which at stage (1) the crude type Y zeolite after drying contains water in an amount of not more than 1 weight. %

44. The method according to any of the previous solutions, in which in stage (4), the calcination is carried out in an atmosphere containing 1-100% steam.

45. Metal modified zeolite Y according to any one of solutions 1-8, which can be obtained or obtained by the method according to any one of solutions 9-44.

46. Catalytic cracking catalyst containing, based on the total weight of this catalyst, 10-60 weight. % of zeolite type Y, modified metals, 10-60 weight. % clay and 5-50 weight. % binder, while the zeolite type Y, modified metals, is a zeolite type Y, modified metal, according to any one of solutions 1-8.

47. Catalytic cracking catalyst according to decision 46, which contains 20-55 weight. % of zeolite type Y, modified metal IVB group, 15-60 weight. % clay and 10-40 weight. % binder

48. Catalytic cracking catalyst according to solution 46, which also contains other molecular sieves commonly used in the catalytic cracking catalyst, these other molecular sieves include molecular sieves Y, molecular sieves MFI and molecular sieves SAPO (silica-alumina phosphate zeolites).

49. The catalytic cracking catalyst according to decision 46, in which the content of other molecular sieves commonly used in the catalytic cracking catalyst is not more than 40 weight. %, for example, 35 wt. %

50. A method of producing a catalytic cracking catalyst, which includes the steps of obtaining a Y-modified metal zeolite, mixing and suspending a Y-modified zeolite of a metal-modified, and clay and a binder and spray-drying the mixture, the specified Y-modified metal-modified zeolite obtained by the method of any of the solutions 9-44.

51. The method of solution 50, in which the clay is selected from one or more clays from kaolin, halloysite, rectorite, diatomite, montmorillonite, bentonite and sepiolite, and the binder is selected from one or more hydrated alumina, alumina sol, pseudo-boehmite, boehmite, aluminum oxide monohydrate, aluminum oxide trihydrate, and amorphous aluminum hydroxide.

52. The solution according to any one of the above solutions 1-51, in which a zeolite of type Y, modified by metals, essentially does not contain one or more metals from 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

Figure 1 shows the FTIR spectra of a standard zeolite of type Y (Y) and zeolites of type Y, modified by metals, obtained in Examples B. 1.1.2, B. 1.1.6 and B. 1.2.4.

Figure 2 shows the NMR ²⁷ A1 spectra of a standard zeolite of type Y (Y) and zeolites of type Y, modified by metals, obtained in Examples B. 1.1.2, B. 1.2.2 and B.1.2.5.

The implementation of the invention

Modified Zeolite

The first zeolite of type Y, modified by metals according to the present invention, is characterized in that the ratio of the content of the metal of the IVB group on the surface of the zeolite to the content of the metal of the IVB group within the pores of the zeolite is no more than 0.2, for example, 0.001-0.2 or 0.02-0.18.

The second type Y zeolite modified by metals according to the present invention is characterized in that the ratio of the content of the deformed tetrahedrally coordinated aluminum atom in the framework to the content of the tetrahedrally coordinated aluminum atom of the framework in the structure of the crystal lattice is (0.1-0.8): 1; (0.2-0.8): 1; (0.2-0.6): 1; (0.1-0.6): 1 or (0.2-0.5): 1.

The third type Y zeolite modified by the metals according to the present invention is characterized in that the ratio of the content of the metal of the IVB group on the surface of the zeolite to the content of the metal of the IVB group within the pores of the zeolite is no more than 0.2, for example, 0.001-0.2 or 0.02-0.18; and the ratio of the content of the deformed tetrahedrally coordinated aluminum atom in the framework to the content of the tetrahedrally coordinated aluminum atom of the framework in the lattice structure is (0.1–0.8): 1; (0.2-0.8): 1; (0.2-0.6): 1; (0.1-0.6): 1 or (0.2-0.5): 1.

All of the above three zeolite type Y, modified by metals, further characterized by one or more of the following characteristics:

(1) The content of metal IVB group in the form of oxide and, based on zeolite of type Y, modified by metals, is 1-15 wt. % or 1-10 weight. %;

(2) the specific surface area is 600-850 m ² / g, 600-750 m ² / g, or 630-730 m ² / g;

(3) the size of the cell parameter a0 is 2.448-2.458 nm, 2.450-2.455 nm; 2.449-2.455 nm; or 2.449-2.452 nm;

(4) the degree of crystallinity is at least 60%, for example, 60-120%, or 60-95%; and

(5) the molar ratio of SiO ₂ / Al ₂ O ₃ is 5-50, 5-20, 5-8, 5-6;

(6) the ratio of the number of secondary pores (with a pore diameter of 6-20 nm) to the total number of secondary pores (with a pore diameter of 2-100 nm) is 30-50% or 50% -65%, for example, 35%, 40%, 45%, 50%, 55%, 60%.

In accordance with the present invention, the metal of the IVB group is selected from one or more Ti, Zr, Hf and Rf, for example, one or more of Ti, Zr and Hf, preferably from Ti and / or Zr.

In accordance with this invention, a metal-modified zeolite of type Y, in an anhydrous state and based on weight by weight, has the following chemical composition: (0-2) Na ₂ O⋅ (l-15) MO ₂ (10-25) Al ₂ O ₃ ⋅ (65-75) SiO ₂ or

(0.1 -1.2) Na ₂ O⋅ (l-10) MO ₂ ⋅ (20-24) Al ₂ O ₃ (67-74) SiO ₂ ;

where M denotes a metal IVB group selected from one or more of Ti, Zr, Hf and Rf.

In a metal-modified Y zeolite according to the present invention, most of the IVB metal ions of the group are located inside the pores of the zeolite, and a small amount of these ions are on the surface of the zeolite. The ratio of the content of metals of the IVB group located on the surface of celite to the content of metals of the IVB group located in the pores of the zeolite is not more than 0.2.

According to the present invention, including the following Examples, the following methods for analyzing zeolite are used:

The content of group IVB metals located on the surface of a zeolite refers to the content of a group IVB metal, which can be measured at a depth of 2-5 nm from the surface of the zeolite using X-ray photoelectron spectroscopy (XPS). The content of group IVB metals located in the pores of the zeolite refers to the difference between the volume content of the group IVB metal in the zeolite and the content of group IVB metals located on the surface of the zeolite. The volume content of the metal of the IVB group in the zeolite is the content of the metal of the IVB group in the zeolite, which can be determined by chemical analysis.

The ratio of the content of the deformed tetrahedrally coordinated aluminum atom in the framework to the content of the tetrahedrally coordinated aluminum atom of the framework in the crystal lattice structure refers to the ratio of the area of spectral peaks during a chemical shift of 40 ppm to the area of spectral peaks at a chemical shift of 60 ppm, measured by method ²⁷ A1 NMR while rotating the sample at a magic angle.

Secondary pores are determined and measured using the standard RIPP151-90 method. Analytical methods in the petrochemical industry (RIPP Experiment Techniques) are described in Yang Cuiding et.al, Science Press, 1990.

The content of elements is determined by X-ray fluorescence spectroscopy.

The specific surface is determined by the BET method (Bruner – Emmett – Teller method).

The size of the cell parameters and the degree of crystallinity are determined by the X-ray diffraction method in accordance with the standards of RIPP145-90 and RIPP 146-90, respectively, see Analytical Methods in Petrochemical Industry (RIPP Experiment Techniques), Yang Cuiding et.al, Science Press, 1990.

The molar ratio of SiO ₂ / Al ₂ O ₃ (that is, the atomic ratio of Si / Al in the framework) is determined in accordance with the standard method SH / T0339-92.

The method of obtaining the modified zeolite

The present invention provides a method for producing a metal-modified zeolite Y, comprising:

(1) removing water from a raw type Y zeolite to achieve a water content of no more than 5% by weight of raw zeolite;

(2) contacting the dried Y-type zeolite obtained in step (1) with a mixture of a compound containing a metal of group IVB and an organic solvent and optional filtration and / or drying;

(3) calcining the type Y zeolite obtained in step (2) at a temperature of 300-700 ° C, preferably for at least 0.5 hours, for example, for 0.5-5 hours;

(4) contacting the type Y zeolite obtained in step (3) with an aqueous acid solution and then calcining at a temperature of 400-800 ° C in an atmosphere containing 1-100% steam for 0.5-5 hours to obtain a type zeolite Y, modified by metals, containing metal of group IVB; while the concentration of H ⁺ in the acid solution is 0.1-2.0 mol / l.

A metal-modified zeolite type Y, obtained by the method described above, is characterized by one or more features selected from:

(1) most of the IVB metal ions of the group are located in the pores of the zeolite, while the surface of the zeolite contains a small amount of these ions;

(2) the ratio of the metal content of the IVB group on the surface of the zeolite to the metal content of the IVB group in the pores of the zeolite is no more than 0.2;

(3) the ratio of the content of the metal of the IVB group on the surface of the zeolite to the content of the metal of the IVB group in the pores of the zeolite is 0.001-0.2;

(4) the ratio of the content of the metal of the IVB group on the surface of the zeolite to the content of the metal of the IVB group in the pores of the zeolite is 0.02-18;

(5) the ratio of the content of the deformed tetrahedrally coordinated aluminum atom in the framework to the content of the tetrahedrally coordinated aluminum atom of the framework in the structure of the crystal lattice is (0.2–0.8): 1;

(6) the ratio of the content of the deformed tetrahedrally coordinated aluminum atom in the framework to the content of the tetrahedrally coordinated aluminum atom of the framework in the lattice structure is (0.2–0.6): 1;

(7) the ratio of the content of the deformed tetrahedrally coordinated aluminum atom in the framework to the content of the tetrahedrally coordinated aluminum atom of the framework in the lattice structure is (0.1–0.6): 1; and

(8) the ratio of the content of the deformed tetrahedrally coordinated aluminum atom in the framework to the content of the tetrahedrally coordinated aluminum atom of the framework in the structure of the crystal lattice is (0.2-0.5): 1.

Stage (1): removal of water

The crude Y-type zeolite may be one or more zeolites from NaY zeolite, NH ₄ Y zeolite, HY zeolite, NaNH ₄ Y zeolite and NaHY zeolite, preferably NaY celite.

ZeYlite NaY can be obtained by crystallization. After removal of the mother liquor, the crystalline zeolite can be used according to the invention directly or after washing. NaY zeolite can be commercially available or can be obtained in a known manner, for example, by the method described in US patent No. 3,671,191.

Zeolite NaNH ₄ Y is produced by ion exchange of zeolite NaY with NH ₄ ⁺ ion to some extent.

NaHY zeolite can be obtained by calcining the zeolite NaNH4Y or by ion exchange of the zeolite NaY with the H ⁺ cation to some extent.

Removal of water is preferably carried out at a temperature not exceeding 400 ° C. Removal of water can be carried out by drying or calcining. Drying can be carried out in the usual way or under vacuum. When using calcination to remove water, the calcination temperature is preferably not more than 400 ° C, for example, 200-400 ° C, usually 250-350 ° C. The usual method of drying involves drying with heating, drying with air, instant drying or drying with spraying. Drying temperature is usually not more than 200 ° C, for example, 80-200 ° C.

Dehydrated zeolite preferably contains water in an amount of not more than 3 weight. %, preferably not more than 1 weight. %

Stage (2): Contacting - Optional Filtering - Optional Drying

In stage (2), the dehydrated type Y zeolite obtained in stage (1) is contacted with a mixture of a compound containing a metal of group IVB and an organic solvent to introduce the modifying metal into the zeolite.

The process of contacting involves mixing and suspending a mixture of a compound containing a metal of the IVB group and an organic solvent and a type Y zeolite and ion exchange at the ion exchange temperature (or at the contact temperature).

After contacting is completed, filtering is performed, but it is not mandatory. Then optionally carry out the drying.

Stage specified contacting can be performed once or more than once. The expression "more than once" means that the zeolite obtained at the stage of the previous treatment is in contact with a mixture of an organic solvent and a compound of the modifying metal; and after each contact, optionally filtering and optionally drying.

In the case of contacting more than once, it is preferable to carry out drying after the last stage of contacting. If contacting more than once, the type Y zeolite obtained after filtration can be immediately treated with a compound containing a metal of the IVB group and an organic solvent or it may be dried and / or calcined and then treated with a compound containing an IVB metal and an organic solvent.

In the ion exchange temperature range, there may be at least one point at which the solvent is in a liquid state.

At each stage of contacting, the weight ratio of the compound containing the metal of the IVB group (calculated as oxide) to the zeolite of type Y (calculated on a dry basis) is (0.01-0.15): 1: (1-50) or (0.01-0.14): 1: (5-30), or (0.02-0.11): 1: (5-25), or (0.01-0.1): 1: (5-30).

The contact time is, for example, at least 0.5 hours, for example, 0.5-5 hours or 1.5-3.5 hours.

The contact temperature may be that temperature at which the organic solvent is in a liquid state. The temperature at the stage of ion exchange may be within the temperature range at which the organic solvent is in a liquid state. Typically, the temperature at the ion exchange stage may be in the limit, the lowest value of which is less than the solidification point of the organic solvent, and the upper value less than the boiling point of the organic solvent. For example, the temperature at the ion exchange stage can range from room temperature to a temperature that is 20 ° C lower than the boiling point of an organic solvent under normal conditions; 0 to 100 ° C; from room temperature to 100 ° C; from 0 to 100 ° C, and 20 ° C lower than the boiling point of an organic solvent under normal conditions. Room temperature is considered to be in the range of 15-40 ° C. Boiling point under normal conditions means the boiling point at a pressure of 1 atm.

The temperature at the drying stage is usually not more than 200 ° C, for example, 0-200 ° C, from room temperature to 150 ° C, from room temperature to 120 ° C, from 100 to 120 ° C. Drying time can be 4-48 h, 12-48 h.

The IVB metal of the group can be one or more metals from Ti, Zr and Hf, preferably Ti and / or Zr. A compound containing a metal of the IVB group is one or more compounds from compounds containing Ti and / or Zr, for example, a Ti-containing compound, a Zr-containing compound, or Ti- and a Zr-containing compound.

A compound containing a metal of an IVB group is preferably soluble in the organic solvent used, for example, its solubility in an organic solvent is not less than 0.1 g of a compound containing a metal of the IVB group / 100 g of an organic solvent.

The Ti-containing compound may be one or more compounds of titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate and ammonium fluorotitanate, and the Zr-containing compound is one or more of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, zirconium acetate and zirconium isopropoxide.

The organic solvent contains water in an amount of not more than 5 wt. %, preferably not more than 1 weight. %, for example, not more than 0.1 weight. % or not more than 0.001 weight. % Preferably, when in an organic solvent the content of organic matter as solvent is at least 95 wt.%, Preferably at least 99 wt. % The organic solvent may be one or more solvents from alkanes, aromatic hydrocarbons, alcohols, ketones, ethers, esters, halogenated alkanes, such as chlorinated alkanes.

The boiling point of the organic solvent (at a pressure of 1 atm) is preferably 40-100 ° C, this temperature is favorable for both the dispersion of the metal component and the removal of the organic solvent. The organic solvent may be, for example, one or more solvents from n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone, and trichloromethane.

Stage (3): Calcination

The temperature of calcination can be equal to 300-700 ° C 350-650 ° C, 400-620 ° C or 450-600 ° C.

The calcination time may be, for example, 0.5-5 hours, 1-5 hours, 2-4 hours.

The calcination can be carried out, for example, in an atmosphere of dry air and / or in an atmosphere of inert gas, preferably in an atmosphere of inert gas.

The inert gas may be nitrogen and / or helium. In the case of dry air, its water content should be less than 1 vol. %, for example, less than 0.5 vol. %

Stage (4): Acid treatment - calcination

The temperature at which the aqueous solution of the acid is contacted with the type Y zeolite obtained in step (3) ranges from room temperature to 100 ° C, for example, it may be 75-95 ° C.

The contact time is at least 0.2 h, for example, 0.5–5 h. The ratio of contacting solids to liquid (weight ratio of zeolite to aqueous acid solution) is 1: 5–20, for example, 1: 6–14.

The concentration of H ⁺ in the aqueous acid solution used is 0.1–2 mol / l, 0.5–2 mol / l, 0.5–1.5 mol / l. After completion of the contacting stage, filtering is carried out. After filtration, the zeolite in contact with the acid is washed with water to remove the free acid and then dried and calcined. The calcination temperature is 400-800 ° C, 500-600 ° C. Calcination is carried out in an atmosphere containing 1-100% steam. The duration of calcination is 0.5-5 hours or 1-3 hours. The acid in step (4) is selected from one or more acids from hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, acetic acid, formic acid, preferably from one or more acids from hydrochloric acid, oxalic acid and formic acid.

According to another aspect of the invention, it provides a method for producing a zeolite of type Y, modified by metals, which includes:

(1) treating a type Y zeolite by contacting with an acid solution and / or an aqueous solution of EDTA, which acid is an organic acid and / or an inorganic acid;

(2) removal of water from the product obtained in stage (1) at a temperature below 400 ° C to obtain a water content in the zeolite of not more than 5 weight. %;

(3) impregnation of the zeolite obtained in step (2) with a metal in an organic solvent medium;

(4) adding a Y-type zeolite impregnated with metal, obtained in step (3), and an organic solvent into a vessel with a solid to liquid ratio of 1: 5-50, introducing an inert gas, such as nitrogen and / or helium, into the vessel; and holding the vessel at a pressure of 0-2.0 MPa (gauge pressure) at a temperature ranging from room temperature to 200 ° C for at least one hour, for example, within 1-48 hours; optional filtering and / or drying, it is preferable to carry out said filtration and / or drying;

(5) calcining the zeolite obtained in stage (4), this calcination is carried out in an inert gas atmosphere, the calcination temperature is 300-700 ° C, the calcination time is 0.5-5 hours or more than 0.5 hours.

Zeolite type Y, obtained by carrying out the method described above, is characterized by one or more features selected from:

(1) most of the ions of the IVB metal group are located inside the pores of the zeolite, while a small amount of ions are located on the surface of the zeolite;

(2) the ratio of the metal content of the IVB group on the surface of the zeolite to the metal content of the IVB group in the pores of the zeolite is no more than 0.2;

(3) the ratio of the content of the metal of the IVB group on the surface of the zeolite to the content of the metal of the IVB group in the pores of the zeolite is 0.001-0.2;

(4) the ratio of the content of the metal of the IVB group on the surface of the zeolite to the content of the metal of the IVB group in the pores of the zeolite is 0.02-0.18;

(5) the ratio of the content of the deformed tetrahedrally coordinated aluminum atom in the framework to the content of the tetrahedrally coordinated aluminum atom of the framework in the structure of the crystal lattice is (0.2–0.8): 1;

(6) the ratio of the deformed tetrahedrally coordinated aluminum atom in the framework to the tetrahedrally coordinated aluminum atom of the framework in the lattice structure is (0.2-0.6): 1;

(7) the ratio of the content of the deformed tetrahedrally coordinated aluminum atom in the framework to the content of the tetrahedrally coordinated aluminum atom of the framework in the lattice structure is (0.1–0.6): 1; and

(8) the ratio of the content of the deformed tetrahedrally coordinated aluminum atom in the framework to the content of the tetrahedrally coordinated aluminum atom of the framework in the structure of the crystal lattice is (0.2-0.5): 1.

Stage (1): Contacting

Y-type zeolite as a starting material may be one or more zeolites from NaY, NaHY, NaNH ₄ Y, NH ₄ Y, HY, USY, zeolite of type Y, once exchanged for ion exchange and calcined once, zeolite of DASY type, zeolite type Y, ion exchanged once and calcined once, zeolite type Y, ion exchanged two times and calcined twice and type Y zeolite twice ionized and calcined once.

Zeolite of type Y, subjected to ion exchange once and calcined once, can with zeolite of type NaY; DASY type zeolite can be, for example, type Y zeolite calcined in the presence of steam; Y-type zeolite, subjected to ion exchange two times and calcined twice, can be a Y-type zeolite obtained by ion exchange twice and calcining an NaY-type zeolite once; and at the same time, preferably, ion exchange is carried out with H ⁺ and / or NH ₄ ⁺ .

The weight ratio between the Y-type zeolite (calculated on a dry basis) and the acid solution (aqueous acid solution) or aqueous EDTA solution (solid to liquid ratio) is 1: 5-20. The temperature of the contact is in the range from room temperature to 100 ° C. The contact time is at least 0.5 hours, for example, it is 0.5-3 hours. After the contact is made, filtration and washing can be carried out.

The concentration of H ⁺ in the acid solution is 0.1-1 mol / l, 0.2-0.5 mol / l, or 0.5-1 mol / l. This acid may be an inorganic acid and / or an organic acid. The inorganic acid is selected from one or more acids from hydrochloric acid, sulfuric acid and nitric acid; the organic acid is selected from one or more acids from formic acid, acetic acid, oxalic acid, citric acid.

In step (1), washing can be performed with water, such as deionized water and distilled water, to remove acid from the zeolite. For example, the weight ratio of water to zeolite may be 5-20: 1. The treated zeolite obtained in stage (1) contains Na ₂ O in an amount of not more than 4.0 weight. % and, preferably, not more than 2.0 weight. %

Stage (2) - calcination

The treated zeolite obtained in step (1) may be calcined to remove adsorbed water. Due to calcination, the water content in the zeolite becomes no higher than 5 wt. %, for example, not higher than 3 weight. %

The temperature during calcination can be equal to 200-400 ° C, for example, 300-350 ° C.

The calcination time is 2-10 hours, for example, 2-4 hours.

The solids content in the calcined zeolite is at least 95 wt. %, not less than 97 weight. % or it is 97-99.9 weight. %

Stage (3)

Impregnation of a zeolite with a metal in an organic solvent medium involves mixing the compound containing a metal of the IVB group in an organic solvent and zeolite and holding the resulting mixture for at least 0.5 h, for example, for 0.5-12 h with stirring or without stirring (upon standing) . For example, the mixture was kept under stirring for 0.5-12 hours. Then the next stage can be carried out, for example, by performing stage (4) or repeating stage (3). The introduction of the modifying (s) metal (s) into a type Y zeolite can be carried out by one or more impregnations. The weight ratio of solids to liquid (zeolite to organic solvent) can be 1: (0.5-5), 1: (1-2), 1: (1-4) or 1: (1.1-1.6).

The temperature of impregnation is equal to the temperature at which the organic solvent is in a liquid state. Impregnation can be carried out by isometric impregnation or excess impregnation. The impregnation temperature is not particularly limited, for example, impregnation can be carried out at room temperature.

The Group IVB metal is selected from one or more metals from Ti, Zr and Hf, preferably Ti and / or Zr. A compound containing a metal of group IVB is one or more compounds from compounds containing Ti and / or Zr, for example, a Ti-containing compound, a Zr-containing compound, or Ti- and a Zr-containing compound. The compound containing the metal of the IVB group may be an inorganic salt and / or an organometallic compound of the metal of the IVB group, for example, the Ti-containing compound may be one or more compounds of titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate and ammonium fluorotitanate and The Zr-containing compound is one or more compounds of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, zirconium acetate and zirconium isopropoxide.

The organic solvent contains water in an amount of not more than 5 wt. % or not more than 3 weight. % or not more than 1 weight. % The organic solvent may be one or more solvents from alkanes, aromatic hydrocarbons, alcohols, ketones, ethers, esters, halogenated alkanes, such as chlorinated alkanes. The organic solvent has a boiling point under normal conditions equal to 40-100 ° C. The organic solvent is preferably one or more solvents from n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone and trichloromethane.

Step (4) —Inert Gas Injection — Optional Filtration — Optional Drying

The impregnated zeolite and organic solvent are placed in a reaction vessel, such as an autoclave. The weight ratio of solids (zeolite) to liquid (organic solvent) is 1: (5-50), for example, 1: (5-30) or 1: (5-10). Typically, the organic solvent used in step (4) is identical to the organic solvent used in step (3). An inert gas, such as nitrogen and helium, is injected into the reaction vessel. The pressure in the reaction vessel (gauge pressure) is 0.0-2.0 MPa or 0.5-1.5 MPa. The temperature in the reaction vessel can range from room temperature to 200 ° C, from room temperature to 150 ° C, or from room temperature to 90 ° C. Substances in the reaction vessel can be kept on standing or under agitation for at least 1 hour, usually for 1-48 hours, 2-24 hours, or 4-24 hours.

Filtration and / or drying steps can then be carried out. Filtration and drying is preferably carried out in such a way that the zeolite can be separated from the organic solvent. These filtration and / or drying steps are carried out in the usual manner. You can use an existing method of drying, such as air drying, instant drying and spray drying. The drying temperature may be, for example, 100-200 ° C. The drying time can be, for example, from 1 second to 2 days, for example, 6-24 hours.

Stage (5) - calcination

The zeolite obtained in step (4) is calcined; the calcination is carried out in an inert gas atmosphere, the calcination temperature is 300-700 ° C, the calcination time is 0.5-5 hours or more than 0.5 hours.

Calcination is carried out in an inert gas atmosphere. The calcination temperature is 300-700 ° C, 450-650 ° C or 500-600 ° C. The calcination time is 0.5-5 hours or 1-4 hours. The inert gas is one or more nitrogen and helium gases.

Catalytic Cracking Catalyst

This invention also provides a catalyst for catalytic cracking, which contains, based on the total weight of the catalyst 20-60 weight. % of zeolite type Y, modified by metals of the IVB group, according to this invention, 10-60 weight. % clay and 5-50 weight. % binder.

Method for producing catalytic cracking catalyst

The present invention also provides a method for the preparation of a catalytic cracking catalyst, which includes the steps of mixing and suspending a zeolite of type Y modified with metals according to this invention, clay and a binder and drying by spraying the resulting mixture. For example, deionized water, clay, and a binder can be mixed and suspended, and a metal-modified Y-type zeolite is added to the resulting suspension. Spray and calcination drying techniques are well known from the prior art and therefore will not be described in detail.

In accordance with the present invention, clay is selected from one or more clays from kaolin, halloysite, rectorite, diatomite, montmorillonite, bentonite and sepiolite, which are well known from the prior art.

According to this invention, a binder is a substance that can form a heat-resistant inorganic oxide after calcination. Heat-resistant inorganic oxide is one or more of oxides of aluminum oxide, silicon oxide, amorphous silicon oxide - aluminum, preferably aluminum oxide. The binder is preferably selected from hydrated alumina, alumina sol, pseudoboehmite, boehmite, alumina trihydrate, alumina monohydrate and amorphous aluminum hydroxide. These various binders can form γ-Al ₂ O ₃ after calcination. All of these binders are well known.

The type Y zeolite modified by metals of the IVB group in accordance with the present invention has a high degree of crystallinity, a large specific surface area and high thermal and hydrothermal stability.

In accordance with the present invention, a zeolite of type Y, modified by group IVB metals, rare earth metals are not used. Zeolite of type Y, modified by metals of the IVB group, has comparable or higher thermal and hydrothermal stability compared to zeolite modified by a rare-earth metal.

The modified Y-type zeolite can be used as part of a catalytic cracking catalyst to replace a rare-earth modified zeolite. The cost of such a catalyst is markedly reduced.

The catalytic cracking catalyst in accordance with the present invention has excellent properties in the cracking process, provides a high yield of gasoline and selectivity to coke.

Example

In the following examples, the room temperature was in the range of 15-40 ° C, for example, was equal to 26 ° C.

Determination of microactivity for light oil was carried out in accordance with the standard RIPP92-90, using 5 g of catalyst. The reaction temperature was 460 ° C. The feedstock was straight-run diesel fuel with a distillation temperature in the range of 235-337 ° C. The composition of the product was analyzed by gas chromatography. In accordance with the composition of the product was determined microactivity as follows:

micro-activity for light oil (MA) = (gasoline yield (<216 ° C) + gas yield + coke yield) / amount of feedstock × 100%

In the Examples and Comparative Examples, commercially available starting materials were used, their characteristics are given below.

Raw zeolites, an industrial product available from the Sinopec Catalyst Company, Qilu Division.

ReCl ₃ (mixed rare earth chloride), technical grade, available from Sinopec Catalyst Company, Qilu Division.

Other agents: chemically pure, unless otherwise noted.

The volume of the secondary pores was determined in accordance with the standard RIPP151-90.

Reference can be made to Analytical Methods in Petrochemical Industry (RIPP Experiment Techniques), Yang Cuiding et al, Science Press, 1990. The total pore volume of the zeolite was determined from the adsorption isotherm. Then, based on the adsorption isotherm, the micropore volume of the zeolite was determined according to the T-graph method. The total pore volume minus the micropore volume is the secondary pore volume and the ratio of the number of secondary pores (pores with a diameter of 6-20 nm) to the total number of secondary pores (pores with a diameter of 2-100 nm) is calculated from the distribution of the secondary pores of the zeolite.

A. 1 Modification of zeolite

Example A. 1.1.1

200 g of zeolite NaY were calcined at 300 ° C for 3 h (after calcination, the water content became 1 wt.%). After cooling to room temperature, the zeolite was placed in 2000 g of ethanol (ethanol content = 99.9 wt.%). The resulting suspension was stirred until a homogeneous state was obtained. 10.5 g of zirconium nitrate (Zr (NO ₃ ) ₄ ⋅ 5H ₂ O) was added to the suspension. Then the resulting mixture was stirred at room temperature for 2 hours and filtered. The filter residue was dried in an oven at 100 ° C for 24 hours and then calcined at 600 ° C for 2 hours.

The calcined zeolite was added to 2000 g of an aqueous solution of an inorganic acid (diluted hydrochloric acid solution) with an acid concentration of 1.0 mol / l. The resulting mixture was stirred to obtain a homogeneous product at 80 ° C for 3 h, then filtered, washed with deionized water (weight of water for washing was 15 times more dry zeolite) and filtered. The filter residue was removed and calcined in an atmosphere of 100% steam at 600 ° C for 1 h.

A zeolite modified with zirconium was obtained and was designated as Zr (2) Y, the properties of this zeolite are given in Table A1.

Example A. 1.1.2

200 g of zeolite NaY were treated under vacuum at a temperature of 200 ° C under a pressure of 0.001 Pa for 4 hours. After cooling to room temperature (water content in zeolite = 0.5 wt.%) It was placed in 1500 g of ethanol (ethanol = 99.9 weight. %). The resulting suspension was stirred until a homogeneous state was obtained. 15.7 g of zirconium oxychloride (ZrOCl ₂ · 8H ₂ O) was added to the suspension. Then the resulting mixture was stirred at room temperature for 3 hours and filtered. The filter residue was dried in a drying oven at 100 ° C for 24 hours and then calcined at 500 ° C for 3 hours.

This calcined type Y zeolite was added to an aqueous solution of oxalic acid with an acid concentration of 2.0 mol / L. The resulting mixture was stirred until a homogeneous product was obtained, then heated to 90 ° C, stirred for 1 h, then filtered and washed with deionized water (the weight of the washing water was 15 times more than the dry zeolite). The filter residue was removed and calcined in an atmosphere of 100% steam at 500 ° C for 2 hours. Zeolite modified with zirconium was obtained and was designated as Zr (4) Y, the properties of this zeolite are shown in Table A1.

Example A. 1.1.3

200 g of zeolite NaY were calcined at 300 ° C for 3 h. After cooling to room temperature (water content = 1 wt.%), It was placed in 1000 g of n-hexane (hexane content = 99.5 wt.%). The resulting suspension was stirred until a homogeneous state was obtained. 37.8 g of zirconium isopropoxide was added to the suspension. The resulting mixture was stirred at room temperature for 3 hours and filtered. The residue on the filter was dried in a drying cabinet at a temperature of 120 ° C for 48 hours and then calcined at a temperature of 500 ° C (in an atmosphere of dried air, the water content in the air was not more than 0.2% by volume) for 4 hours.

The calcined type Y zeolite described above was added to 1000 g of an aqueous solution of an inorganic acid (sulfuric acid) with a concentration of 0.5 mol / l. The resulting mixture was stirred at 80 ° C for 3 hours, then filtered and washed with deionized water (the weight of the washing water was 20 times more than the dry zeolite). The filter residue was removed and calcined at 500 ° C in an atmosphere of 100% steam for 3 hours. Zeolite modified with zirconium was obtained and its Zr (8) Y was designated, the properties of this zeolite are shown in Table A1.

Example A. 1.1.4

200 g of zeolite NaY were calcined at 300 ° C for 3 hours. After cooling to room temperature, the zeolite was placed in 1000 g of butanone (butanone content = 99.5 wt.%). The resulting suspension was stirred until a homogeneous state was obtained. 14.2 g of titanium tetrachloride was added to the suspension. The resulting mixture was stirred at room temperature for 2 hours and filtered. The filter residue was dried in a drying oven at 120 ° C for 24 hours and then calcined at 450 ° C under nitrogen for 4 hours.

The calcined type Y zeolite described above was added to 1000 g of an aqueous solution of an inorganic acid (hydrochloric acid) with a concentration of 0.5 mol / l. The resulting suspension was stirred until a homogeneous state was obtained at 80 ° C for 2 h, then filtered and washed with deionized water (the weight of the washing water was 10 times more than the dry zeolite). The filter residue was removed and calcined at 500 ° C in an atmosphere of 100% steam for 2 hours. A titanium modified zeolite was obtained and designated as Ti (4) Y, the properties of this zeolite are shown in Table A1.

Example A. 1.1.5

200 g of zeolite NaY were treated under vacuum at a temperature of 200 ° C under a pressure of 0.001 Pa for 4 hours. After cooling to room temperature, the zeolite was placed in 2000 g of cyclohexane (cyclohexane content = 99.9 wt.%). The resulting suspension was stirred until a homogeneous product was obtained. 63.9 g of tetrabutyl titanate was added to the suspension. The resulting mixture was stirred at room temperature for 3 hours and filtered. The filter residue was dried in a drying oven at 100 ° C for 48 hours and then calcined at 600 ° C under nitrogen for 2 hours.

The calcined type Y zeolite described above was added to 2000 g of an aqueous solution of oxalic acid with an acid concentration of 1.5 mol / l. The mixture was stirred until a homogeneous product was obtained at 90 ° C for 1 h, then filtered and washed with deionized water (the weight of the washing water was 20 times more than the dry zeolite). The filter residue was removed and calcined at a temperature of 600 ° C in an atmosphere of 100% steam for 2 hours. A titanium modified zeolite was obtained and denoted as Ti (10) Y, the properties of this zeolite are given in Table A1.

Example A. 1.1.6

200 g of NaY zeolite were treated under vacuum at 300 ° C under a pressure of 0.001 Pa for 4 hours. After cooling to room temperature, the zeolite was placed in 3000 g of ethanol (ethanol content = 99.9 wt.%). The resulting suspension was stirred until a homogeneous state was obtained. 3.6 g of titanium tetrachloride and 31.5 g of zirconium nitrate were added to the suspension. The resulting mixture was stirred at room temperature for 3 hours and filtered. The filter residue was dried in an oven at 100 ° C for 48 hours and then calcined at 550 ° C under nitrogen for 3 hours.

The calcined type Y zeolite described above was added to 3000 g of an inorganic acid (nitric acid) aqueous solution with an acid concentration of 1.0 mol / L. A zeolite modified with Ti and Zr was obtained, designated as Ti-Zr-Y, the properties of this zeolite are given in Table A1.

Example A. 1.1.7

The modified zeolite was prepared in accordance with Example A. 1.1.4, except that after treatment with an inorganic acid, the residue on the filter was first dried and then calcined at 500 ° C in air atmosphere to obtain a zeolite designated Ti (4) Y-l.

Example A. 1.2.1

200 g of NaY zeolite and 2000 g of deionized water were mixed and suspended. To the resulting suspension was added 45 ml of a solution of 270 g / l RECl ₃ . The pH of the resulting suspension was adjusted to a value of 3.8 using dilute hydrochloric acid and the suspension was heated to 80 ° C for 1 h to allow ion exchange. After filtration and washing, the residue obtained on the filter was calcined at 500 ° C for 3 hours. Then, the resulting type Y zeolite and 2000 g of deionized water were mixed and suspended. To the resulting suspension was added 45 g of ammonium sulfate. The pH of the resulting suspension was adjusted to a value of 4.0 with dilute hydrochloric acid and the suspension was heated to 80 ° C for 1 hour to allow ion exchange. After filtration and washing, the residue obtained on the filter was calcined at a temperature of 600 ° C in an atmosphere of 100% steam for 3 hours. A zeolite modified with a rare earth metal (RE) was obtained, designated as RE (8) Y, its properties are given in Table A1.

Example A. 1.2.2

200 g of zeolite NaY were placed in 2000 g of deionized water. The resulting suspension was stirred until a homogeneous product was obtained. 31.4 g of zirconium zirconium ZrOCl ₂ ⋅8H ₂ O was added to the suspension. The resulting mixture was heated to 90 ° C, stirred for 3 h and filtered. The filter residue was dried in an oven at 100 ° C for 12 hours and calcined at 500 ° C for 3 hours. Then, the calcined zeolite was mixed with 2000 g of deionized water and the mixture was suspended. To the resulting suspension was added 45 g of ammonium sulfate. The pH of the resulting suspension was adjusted to a value of 4.0 with diluted hydrochloric acid and the suspension was heated to 80 ° C for 1 hour to allow ion exchange. After filtration and washing, the residue obtained on the filter was calcined at a temperature of 500 ° C in an atmosphere of 100% steam for 2 hours. Zeolite modified with zirconium was obtained, designated as Zr (W) Y, its properties are given in Table A1.

Example A. 1.2.3

The modified zeolite was obtained in accordance with Example A. 1.2.2, except that instead of 31.4 g of zirconium oxychloride ZrOCl ₂ · 8H ₂ O, 14.2 g of titanium tetrachloride was used. A titanium modified zeolite was obtained, designated as Ti (W) Y, its properties are given in Table A1.

Example A. 1.2.4

Zeolite type Y, modified Zr, received in accordance with Example 1 of the application CN 101134576A. Received a zeolite of type Y, modified Zr, designated it as Zr (G) Y, its properties are shown in Table A1.

Example A. 1.2.5

200 g of NH ₄ USY (atomic ratio Si / Al = 5.2) was added to 500 g of absolute ethanol with vigorous stirring to form a slurry, to which, under vigorous stirring, 50 g / l of butyl titanate solution in absolute ethanol (based on TiO _2). The mixture was air dried overnight with stirring. The resulting sample was calcined at 500 ° C for 5 h to obtain Ti-modified zeolites with a titanium content of 2.4 wt. % and 9.1 wt. % designated as DT2 and DT9.

A.2 Stability of the modified zeolite

Modified Y-type zeolites obtained by Examples A. 1.1.1-A. 1.1.7 and A. 1.2.1-A. 1.2.5, were subjected to aging at a temperature of 800 ° C in an atmosphere of 100% steam for 8 h to determine the degree of crystallinity and specific surface and calculate the preservation of crystallinity and preserve the specific surface. The results are shown in Table A2. The resulting zeolites, subjected to aging, were tested for microactivity (MA) for light oils. The results are shown in Table A2.

Example A.2.1.8

In accordance with Example A L. 1.5, received zeolites of type Y, modified Ti, containing Ti (as TiO ₂ ) in an amount of 1 weight. %, 2 weight. %, 7 weight. %, 12 wt. %, 15 wt. % The physical and chemical properties of these zeolites are shown in Table A3. These zeolites of type Y, modified by Ti, were subjected to aging at a temperature of 800 ° C in an atmosphere of 100% steam for 8 hours and the degree of crystallinity and specific surface area were determined and the preservation of crystallinity and specific surface was calculated. Aged zeolites were tested for microactivity (MA) for light oils. The results of this test are shown in Table A3.

Example A.2.2.6

In accordance with Example A. 1.2.1, received zeolites of type Y, modified RE, containing RE in the amount of 1 weight. %, 2 weight. %, 12 wt. %, 15 wt. %

The physical and chemical properties of these zeolites are shown in Table A3. These zeolites of type Y, modified by RE, were subjected to aging at a temperature of 800 ° C in an atmosphere of 100% steam for 8 hours and then the degree of crystallinity and specific surface area were determined, as well as the preservation of crystallinity and specific surface area.

Aged zeolites were tested for microactivity (MA) for light oils. The results of this test are shown in Table A3.

A.3 Catalyst

Example A.3.1.1

A modified Y-type zeolite prepared in accordance with the present invention, Zr (8) Y, was used as an active component using a standard method for the preparation of a catalytic cracking catalyst. The method of obtaining was carried out as follows. Taking into account the ratio of zeolite (calculated on dry matter): kaolin (calculated on dry substance): pseudo-boehmite (calculated on Al ₂ O ₃ ): alumina sol (calculated on Al ₂ O ₃ ) equal to 38:34:20 : 8, kaolin and decationized water were mixed and suspended. An alumina sol was added to the resulting suspension and then pseudoboehmite was introduced with constant stirring. After 30 minutes of stirring, the mother liquor containing the zeolite was added to the colloidal liquid. The resulting mixture was stirred to obtain a homogeneous product, dried by spraying and molded to obtain the product, designated as C1.

The resulting catalyst was pretreated at 800 ° C in an atmosphere of 100% steam for 17 hours. Then, the properties of the pretreated catalyst were determined in a fluidized bed laboratory (ACE). The starting material was the oil products of the Wuhun III deposit, whose properties are shown in Table A4. Reaction temperature, catalyst: petroleum ratio, WHSV and test results are shown in Table A5, with

conversion degree = gasoline yield + liquefied gas yield + dry gas yield + coke yield;

coke selectivity = coke yield × 100 / degree of conversion

Example A.3.2.1

The catalyst was prepared according to Example A.3.1.1, except that instead of Zr (8) Y zeolite, the same amount of RE (8) Y zeolite was used and the catalyst, designated as DC1, was obtained. The properties of this catalyst were then determined by DC1, as in Example A.3.1.1. The test results are shown in Table A5.

Example A.3.2.2

The catalyst was prepared according to Example A.3.1.1, except that instead of Zr (8) Y zeolite, the same amount of Zr (W) Y zeolite was used and the catalyst, designated as DC2, was obtained. The properties of this DC2 catalyst were then determined, as in Example A.3.1.1. The test results are shown in Table A5.

Example A.3.1.2

Example A.1.1.1 was used to obtain a zeolite of type Y, modified with zirconium, denoted as Zr (6) Y, the weight ratio of the amount of zirconium nitrate used (based on ZrO ₂ ) to the amount of zeolite was 6: 100 by weight.

323 g of pseudoboehmite (with a solids content of 62% by weight) and 1343 g of deionized water were mixed. The mixture was stirred for 15 minutes until a homogeneous state of the pseudoboehmite suspension was obtained, the pH of which was adjusted to a value of 3.5 using dilute hydrochloric acid. The resulting suspension was kept at room temperature for 6 hours. 447 g of kaolin (with a solids content of 76 wt.%) And 372 g of alumina sol (with an alumina content of 21.5 wt.%) Were added to this suspension, aged. . The resulting suspension was stirred for 60 minutes. Then, a suspension obtained by suspending 380 g (calculated on a dry basis) of the above-described modified Zr (6) Y zeolite and 880 g of deionized water was added to it. The resulting mixture was stirred for 60 minutes and a catalyst slurry was obtained, which was spray dried, molded, and calcined at 550 ° C for 1 h, yielding a catalytic cracking catalyst, designated as C11. The content of ZrO ₂ in the catalyst C11, measured by the XRF method (X-ray luminescence spectroscopy) was 2.2 wt. %

Example A.3.1.3

Zeolite type Y, modified with zirconium, was obtained according to Example A.1.1.2, designated as Zr (10) Y, where the ratio ZrO ₂ : zeolite = 10: 100.

421 g of kaolin (with a solids content of 76% by weight), 465 g of alumina sol (with an alumina content of 21.5%) and 732 g of deionized water were added to the vessel and suspended, 1667 g of acidified pseudoboehmite were added (acidified with hydrochloric acid with a molar ratio of hydrochloric acid: aluminum oxide of 0.15, with a solids content of 12 wt.%). After stirring for 60 minutes, a suspension obtained by suspending 380 g (calculated on a dry basis) of the above-described modified zeolite of Zr (10) Y type and 880 g of deionized water was added to the reaction vessel. The resulting mixture was stirred for 60 minutes and a catalyst slurry was obtained, which was spray dried, molded, and calcined at 550 ° C for 1 h, yielding a catalytic cracking catalyst, designated C21. The content of ZrO ₂ in the catalyst C21, measured by XRF (X-ray luminescence spectroscopy) was 3.5 wt. %

Example A.3.1.4

447 g of kaolin, 372 g of alumina sol and 800 g of deionized water were mixed and suspended for 60 minutes. After adding 1667 g of acidified pseudoboehmite, the resulting suspension was stirred for another 60 minutes. To the resulting suspension was added a suspension obtained by suspending 380 g (calculated on a dry basis) of the above-described modified type Ti (2) Y zeolite and 880 g of deionized water. The resulting mixture was stirred for 60 minutes and a catalyst slurry was obtained, which was spray dried, molded, and calcined at 650 ° C for 2 hours to obtain a catalytic cracking catalyst, designated C31. The content of TiO ₂ in the catalyst C31, measured by the XRF method (X-ray luminescence spectroscopy) was 0.75 weight. %

Example A.3.1.5

447 g of kaolin, 372 g of alumina sol and 800 g of deionized water were mixed and suspended for 60 minutes. After adding 1667 g of acidified pseudoboehmite, the resulting suspension was stirred for another 60 minutes. To the resulting suspension was added a suspension obtained by suspending 380 g (calculated on a dry basis) of the above-described modified Ti (4) Y type zeolite and 880 g of deionized water. The resulting mixture was stirred for 60 minutes and a catalyst slurry was obtained, which was spray dried, molded, and calcined at 650 ° C for 2 h, yielding a catalytic cracking catalyst, designated C41. The content of TiO ₂ in the catalyst C41, measured by the XRF method (X-ray luminescence spectroscopy), was 1.5 wt. %

Example A.3. 1.6

The catalyst was prepared as described in Example A.3.1.5, except that instead of the Ti (4) Y zeolite, the same amount of Ti (4) Y-1 zeolite was used, a catalyst was obtained, designated C41-1.

Example A.3.1.7

The catalyst was obtained as described in Example A.3.1.5, except that the REY zeolite obtained in accordance with a known method (molar ratio SiO ₂ / Al ₂ O ₃ = 5.1, the content of rare-earth metal = 3.8 wt.%, Na content ₂ O = 0.4 wt.%), Used instead of part of the zeolite Ti (4) Y. The weight ratio of the REY zeolite obtained in accordance with the known method to the Ti (4) Y zeolite was 1: 1, a catalyst was obtained, designated as C41-2.

Example A.3.1.8

In accordance with Example A.1.1.4, a type Y zeolite, denoted as Ti (8) Y, modified by Ti was obtained using a weight ratio of titanium tetrachloride (calculated as TiO ₂ ) to zeolite equal to 8: 100.

421 g of kaolin, 698 g of alumina sol and 900 g of deionized water were mixed and stirred for 60 minutes. After adding 1250 g of acidified pseudoboehmite, the resulting suspension was stirred for another 60 minutes.

To the mixture was added a suspension obtained by suspending 380 g (calculated on a dry basis) of the above modified Ti (8) Y zeolite and 800 g of deionized water. The resulting mixture was stirred for 60 minutes and a catalyst slurry was obtained, which was spray dried, molded, and calcined at 700 ° C for 2 h, yielding a catalytic cracking catalyst, designated C51. The content of TiO ₂ in the catalyst C51, measured by the XRF method (X-ray luminescence spectroscopy), was 3.0 wt. %

Example A.3.1.9

The same starting materials were used as in Example A.3.1.2, with the exception of metal-modified zeolite Y.

355 g of pseudoboehmite and 1478 g of deionized water were mixed and stirred for 30 min to obtain a suspension of pseudoboehmite, the pH of which was set to 3.8 with diluted hydrochloric acid. The resulting suspension was kept at 60 ° C for 2 hours. The resulting mixture was stirred for 60 minutes. Then, the suspension obtained by suspending 380 g (calculated on a dry basis) of the above modified Ti-Zr-Y zeolite and 800 g of deionized water was added. The resulting mixture was stirred for 60 minutes and a catalyst slurry was obtained, which was spray dried, molded, and calcined at 600 ° C for 3 hours to obtain a catalytic cracking catalyst, designated C61.

Example A.3.2.3

The catalyst was prepared in accordance with Example A.3.1.8, except that instead of the Ti (8) Y zeolite, the same amount of RE (8) Y zeolite was used, a catalyst was obtained, designated as DC11. The content of RE ₂ O ₃ in the catalyst DC11, measured by the XRF method, was equal to 2.32 weight. %

Example A.3.2.4

The catalyst was prepared in accordance with Example A.3.1.8, except that instead of the Ti (8) Y zeolite, the same amount of Ti (W) Y type zeolite was used, a catalyst was obtained, designated as DC21. The content of TiO ₂ in the catalyst DC21, measured by the XRF method, was equal to 2.40 weight. %

Example A.3.2.5

The catalyst was obtained in accordance with Example A.3.1.2, except that instead of a zeolite of the Zr (6) Y type, the same amount of the zeolite of the Zr (W) Y type was used, a catalyst, designated as DC31, was obtained. The content of ZrO ₂ in the catalyst DC31, measured by XRF, was equal to 2.18 weight. %

The catalysts C11-C61 and DC11-DC31 were pretreated at 800 ° C in an atmosphere of 100% steam for 8 hours. Then, the properties of the pre-treated catalyst were determined in the laboratory in a fluidized bed (ACE). The starting material was Wuhun III, whose properties are shown in Table A4. Reaction temperature, catalyst: petroleum ratio, WHSV and test results are shown in Table A6, with

conversion degree = gasoline yield + liquefied gas yield + dry gas yield + coke yield.

B.1 Modification of zeolites

Example B.1.1.1

(1) At room temperature, 200 g of a zeolite of the NaY type (dry matter = 75%) and 1500 ml of hydrochloric acid solution with a molar concentration of 0.5 mol / l were mixed and stirred for 30 minutes. After filtration, the residue on the filter was washed with 15000 ml of deionized water to obtain an NaY-type zeolite treated with an acid with a Na ₂ O concentration of 3.5 wt. %

(2) Acid treated NaY zeolite was calcined at 300 ° C for 3 hours to obtain a zeolite containing 96 wt. % solids, designated 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, the ethanol content was 99.9 wt.%) To obtain a liquid for impregnation.

The impregnation liquid and the treated F1 zeolite were stirred until a homogeneous state was obtained and left to stand at room temperature for 1 hour.

(4) The product obtained in step (3) and 800 ml of ethanol were mixed and placed in an autoclave in which nitrogen was introduced. The pressure was maintained at 0.5 MPa. Then the mixture was left to stand at room temperature for 12 hours. After filtration, the resulting filter residue was dried at 100 ° C for 24 hours.

(5) The product obtained in stage (4) was calcined in a nitrogen atmosphere at 500 ° C for 4 hours, a zeolite of type Y, modified with zirconium, designated as ZrY (1), was obtained, its properties are given in Table B2.

Examples B.1.1.2-B.1.1.7

In Example B.1.1.1, the modified zeolites of the invention were obtained.

The conditions of preparation and the properties of the products obtained are shown in Table B2.

Example B.1.1.8

The modified zeolite was obtained according to Example B.1.1.1, except that at stage (4) nitrogen was introduced and the pressure (gauge pressure) was 0 MPa. The obtained modified zeolite was designated as ZrY (1) -1 the properties of which are given in Table B2.

Example B.1.1.9

The modified zeolite was obtained according to Example B.1.1.1, except that at stage (1):

(1) At room temperature, 200 g of NaY zeolite (dry matter = 75%) and 1500 ml of EDTA solution (ethylenediaminetetraacetic acid) were mixed with a molar concentration of 0.5 mol / l and the mixture was stirred for 30 minutes. After filtration, the residue on the filter was washed with 15000 ml of deionized water to obtain an NaY-type zeolite treated with an acid with a Na ₂ O concentration of 3.5 wt. %

Stages (2) - (5) were identical to the same stages in Example B.1.1.1. The obtained modified zeolite was designated as ZrY (1) -2, its properties are shown in Table B2.

Example B.1.2.1

Suspended 200 g of zeolite NaY (the same as in Example B.1.1.1) and 2000 g of deionized water. 60 g of ammonium sulfate was added to the suspension. The pH of the resulting suspension was adjusted to a value of 4.0, heated to 80 ° C for 1 h to allow ion exchange. After filtration and washing with water, the residue on the filter was calcined at a temperature of 550 ° C in an atmosphere of 100% steam for 2 hours. This stage was repeated two times to obtain a modified type Y zeolite.

Then the obtained zeolite type Y and 2000 g of deionized water were suspended. 45 ml of a solution of RECl ₃ (270 g / l) was added to the suspension. The pH of the resulting suspension was adjusted to 3.8 with diluted hydrochloric acid, heated to 80 ° C for 1 h to allow ion exchange. 45 g of ammonium sulfate was added to this mixture and the resulting product was stirred for 1 hour. After filtering and washing with water, the residue on the filter was calcined at 550 ° C in an atmosphere of 100% steam for 2 hours. REY-modified zeolite was obtained designated as REY, whose properties are listed in Table B3.

Example B.1.2.2

The modified zeolite was obtained as in Example B. 1.1.2, except that the same amount of zirconium oxychloride ZrOCl ₂ · 8H ₂ O was dissolved in 200 g of deionized water. Zirconium modified zeolite, designated as Zr (W) Y, was obtained which are shown in Table B3.

Example B.1.2.3

Suspended 200 g of zeolite NaY and 2000 g of deionized water. To the resulting suspension was added 60 g of NH ₄ Cl. The pH of the resulting suspension was adjusted to 3.8 with diluted hydrochloric acid, heated to 80 ° C for 2 h to allow ion exchange. After filtration and washing with water, the residue on the filter was calcined at a temperature of 600 ° C in an atmosphere of 100% steam for 2 hours. The calcined zeolite was suspended in 2000 g of deionized water. 45 g of NH ₄ Cl and 31.4 g of zirconium oxychloride ZrOCl ₂ · 8H ₂ O were added to the resulting suspension to conduct the second ion exchange at essentially the same temperature as the first ion exchange. After filtration and washing with water, the residue on the filter was calcined at a temperature of 600 ° C in an atmosphere of 100% steam for 2 hours. A zeolite modified with zirconium, denoted as Zr (J) Y, whose properties are shown in Table B3 was obtained.

Example B.1.2.4

Zeolite modified with Zr was prepared as described in Example 1 of the application CN 101134576 A. Zeolite modified with zirconium was obtained, designated Zr (G) Y, whose properties are shown in Table B3.

Example B.1.2.5

200 g of zeolite type DASY0.0 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 (based on TiO ₂ ) in absolute ethanol was added with vigorous stirring. The mixture was dried with stirring in air overnight. The resulting zeolite was calcined at a temperature of 500 ° C for 5 hours to obtain a Ti modified zeolite with a titanium content of 7.9 wt. % designated as Ti (D) Y.

From the Fourier transform infrared spectra of modified Y-type zeolites shown in Figure 1, it is clear that the frequency of antisymmetric stretching vibrations (1050-1150 cm ^-1 ) and the frequency of symmetrical stretching vibrations (750-820cm ^-1 ) of zeolite of type Zr (G) Y obtained in a known manner (see, for example, Example B.1.2.4) are characterized by a red shift towards a lower frequency, which indicates the presence of Zr in the skeleton of a type Y zeolite. Modified type Y zeolites obtained according to this invention (for example, ZrY zeolites and TiY) do not have a red shift, which indicates that that Zr and Ti are not contained in the skeleton of a zeolite.

From the ²⁷ A1-NMR spectra of the modified Y-type zeolites shown in Figure 2, it can be seen that the modified Y-type zeolite contains a large amount of tetrahedrally coordinated aluminum atom in the framework (chemical shift 60) and a small amount of hexahedrally coordinated aluminum atom in the framework (chemical shift 0 ). Compared to Y-type zeolite, the peak of the content of tetrahedrally coordinated aluminum atom in the skeleton of ZrY zeolite, obtained by impregnation with a solution in an organic solvent, became wider and shifted towards a lower chemical shift, which indicates that Zr got inside the pores of the zeolite, interacting with zeolite frame [AlO4]. This interaction caused the spectral peak of the tetrahedrally coordinated aluminum atom in the framework to move to a higher part of the spectrum, while the spectral peak characterizing the deformed tetrahedrally coordinated aluminum atom in the framework was very large (chemical shift 40).

The ratio of the content of the deformed tetrahedrally coordinated aluminum atom in the frame to the content of the tetrahedrally coordinated aluminum atom in the frame can be, for example, 0.1-0.6. Zeolites Zr (W) Y and Ti (D) Y, obtained according to Example B. 1.2.2 (impregnated with an aqueous solution) and Example B.1.2.5, do not show a significant change in the peak of the deformed tetrahedrally coordinated aluminum atom in the frame, which indicates that Zr or Ti interact little with the zeolite [AlO4] framework, and that the ratio of the content of the deformed tetrahedrally coordinated aluminum atom in the framework to the content of the tetrahedrally coordinated aluminum atom in the framework is less than 0.1. It can be seen that the modification method in accordance with the present invention is more favorable for the entry of metal ions into the pores of the zeolite, interaction with the skeleton of zeolite [AlO4] and leads to stabilization of the structure of the skeleton of zeolite.

B.2 Stability of the modified zeolite

The modified Y-type zeolites obtained according to Examples B.2.1.1-B.2.1.9 and B.2.2.1-B.2.2.5 were aged at 800 ° C in an atmosphere of 100% steam for 8 hours and 17 h, respectively, and determined the degree of crystallinity and specific surface area, as well as the preservation of the degree of crystallinity and specific surface area. The resulting zeolites were tested for micro-activity (MA) for light oils. The results are shown in Table B4.

Catalyst B.3

Example B.3.1.1

Modified zeolite type Zr (6) Y, obtained in accordance with this invention, was used as an active component to obtain a catalyst for catalytic cracking in a known manner. The method was carried out as follows.

From the calculation of the ratio of zeolite (on a dry basis): kaolin (on a dry basis): pseudoboehmite (calculated as Al ₂ O ₃ ): alumina sol (calculated as Al ₂ O ₃ ) equal to 38: 34: 20: 8, mixed kaolin and deionized water and suspended this mixture. An alumina sol was added to the resulting suspension and then pseudoboehmite was introduced with vigorous stirring. After 30 minutes, with stirring, the mother liquor containing the zeolite was added to the resulting colloid system. The resulting mixture was mixed to a homogeneous state, spray dried and molded, and a catalyst, designated C1, was obtained.

Evaluation of the properties of the catalyst in the cracking of heavy oils

The catalyst was pretreated at 800 ° C in an atmosphere of 100% steam for 8 hours. Then the properties of the pretreated catalyst were tested in a fluidized bed laboratory (ACE). The initial raw material was vacuum gas oil hydrocracking of oil from the ZhengHai field, mixed with the atmospheric residue of the distillation of oil from the DaQing field, whose properties are shown in Table B5. The reaction temperature was 500 ° C, WHSV = 16 h ^-1 , the ratio of catalyst: heavy oils was 45. The test results are shown in Table B6.

In this Table B6:

conversion degree + gasoline output + liquefied gas output + coke yield

coke selectivity = coke yield × 100 / degree of conversion

Example B.3.1.2

The catalyst was obtained as described in Example B.3.1.1, except that instead of zeolite ZrY (6), zeolite TiY (2) was used in the same amount, catalyst C2 was obtained. Then determined the properties of the catalyst C2 as in example B.3.1.1. The results are shown in Table B6.

Examples B.3.2.1- B.3.2.3

In accordance with Example B.3.1.1, a number of catalysts were obtained, except that instead of ZrY zeolite (6), REY zeolite, Zr (W) Y zeolite and Ti (D) Y zeolite were used in the same quantities, the DC1 catalysts were obtained DC2 and DC3. The property of the DC1-DC3 catalysts was then determined, as described in Example B.3.1.1. The results are shown in Table B6.

Example B.3.1.3

Zeolite type Y, modified with zirconium, designated as Zr (2) Y, was obtained as described in Example B.1.1.1, with a weight ratio of zirconium nitrate (based on ZrO ₂ ): type zeolite Y.

323 g of pseudoboehmite and 1343 g of deionized water were mixed and stirred for 15 min; a pseudo-boehmite suspension was obtained. The pH of the resulting suspension was adjusted with dilute hydrochloric acid (15% by weight) to 3.5 and left to stand at room temperature for 6 hours. To the resulting suspension, 421 g of kaolin and 465 g of alumina sol were added. After stirring for 60 minutes, a suspension obtained by suspending 380 g (on a dry basis) of the above modified ZrY (2) zeolite and 800 g of deionized water was added to the resulting suspension. The resulting mixture was stirred for 60 minutes, the resulting suspension of the catalyst was spray dried and molded, and then calcined at 550 ° C for 2 h, a catalytic cracking catalyst, designated as C17, was obtained. The content of The ZrO ₂ in this catalyst C17, measured by the XRF method, was 0.75%.

Example B.3.1.4

421 g of kaolin, 465 g of alumina sol and 732 g of deionized water were added to the reaction vessel, and 1667 g of acidified pseudoboehmite were added to the resulting suspension. After stirring for 60 minutes, a suspension obtained by suspending 380 g (on a dry basis) of the above modified Zr (6) Y zeolite and 800 g of deionized water was added to the suspension obtained. The resulting mixture was stirred for 60 minutes, the resulting catalyst suspension was spray dried and molded, and then calcined at 550 ° C for 1 h, a catalytic cracking catalyst, designated as C18, was obtained. The content of ZrO ₂ in this catalyst C18, measured by the XRF method, was 2.18%.

Example B.3.1.5

421 g of kaolin, 558 g of alumina sol and 800 g of deionized water were mixed, the resulting suspension was stirred for 60 minutes. After adding 1500 g of acidified pseudoboehmite, the suspension was again stirred for 60 minutes. To the resulting suspension was added a suspension obtained by suspending 380 g (on a dry basis) of the above modified ZrY zeolite (10) and 800 g of deionized water. The resulting mixture was stirred for 60 minutes, the resulting suspension of the catalyst was spray dried and molded, and then calcined at 650 ° C for 2 h, a catalytic cracking catalyst, designated as C19, was obtained. The content of ZrO ₂ in this catalyst C19, measured by the XRF method, was 3.52 wt. %

Example B.3.1.6

The titanium-modified Y-type zeolite was obtained as described in Example B.2.1.5; it was designated TiY (8), and at the impregnation stage (3), the weight ratio of titanium tetrachloride (based on TiO ₂ ): zeolite was 0.08: 1. To the resulting suspension was added a suspension obtained by suspending 380 g (on a dry basis) of the above modified TiY zeolite (8) and 800 g of deionized water.

421 g of kaolin and 380 g of deionized water were mixed and suspended for 60 minutes. After adding 1667 g of acidified pseudoboehmite, the suspension was again stirred for 30 minutes. To the resulting suspension was added a suspension obtained by suspending 380 g (on a dry basis) of the above modified TiY zeolite (8) and 800 g of deionized water. The resulting mixture was stirred for 60 minutes, 465 g of alumina sol was added. The resulting mixture was stirred for 30 minutes, then the resulting catalyst suspension was spray dried and molded, and then calcined at 700 ° C for 2 h, a catalytic cracking catalyst, designated as C20, was obtained. The content of TiO ₂ in this catalyst C20, measured by the XRF method, was 3.02 wt.%.

Example B.3.1.7

The titanium-modified Y-type zeolite was obtained as described in Example B.2.1.5; it was designated TiY (4), and at the impregnation stage (3), the weight ratio of titanium tetrachloride (based on TiO ₂ ): zeolite was 0.04: 1.

323 g of pseudoboehmite and 1478 g of deionized water were mixed. The mixture was stirred for 30 minutes to obtain a pseudoboehmite suspension, the pH of which was adjusted to 3.8 with an appropriate amount of dilute hydrochloric acid. The resulting suspension was kept at 60 ° C for 2 hours. 421 g of kaolin and 465 g of alumina sol were added to this suspension. The resulting suspension was stirred for 60 minutes. To this suspension was added a suspension obtained by suspending 380 g (on a dry basis) of the above modified TiY zeolite (800) and 800 g of deionized water. The resulting mixture was stirred for 60 minutes to obtain a catalyst slurry, this catalyst slurry was spray dried and molded, and then calcined at 600 ° C for 3 hours, a catalytic cracking catalyst was obtained, designated as C21. The content of TiO ₂ in this catalyst C21, measured by the XRF method, was 1.48 wt. %

Example B.3.1.8

Hf-type zeolite Y was obtained as described in Example B.2.1.5, it was designated HfY (6), with the weight ratio hafnium nitrate (calculated as HfO ₂ ) at the impregnation stage (3): zeolite was 0.06 :one.

421 g of kaolin and 380 g of deionized water were mixed, the mixture was stirred for 60 minutes. After adding 1667 g of acidified pseudoboehmite, the suspension was again stirred for 30 minutes. To this suspension was added a suspension obtained by suspending 380 g (on a 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 was added to the resulting suspension. The resulting mixture was stirred for 30 minutes to obtain a catalyst slurry, this catalyst slurry was spray dried and molded, and then calcined at 700 ° C for 2 h, a catalytic cracking catalyst, designated as C22, was obtained. The content of HfO ₂ in this catalyst C22, measured by the XRF method, was 2.11 wt.%.

Example B.3.1.9

421 g of kaolin and 380 g of deionized water were mixed and suspended for 60 minutes. After adding 1667 g of acidified pseudoboehmite, the resulting suspension was stirred for another 30 minutes. To this mixture was added a suspension obtained by suspending 380 g (on a dry basis) of the above modified Ti-Zr-Y zeolite and 800 g of deionized water. After stirring for 60 minutes, 465 g of alumina sol was added to the resulting suspension. The resulting mixture was stirred for 30 minutes, the resulting suspension of catalyst was spray dried and molded, and then calcined at 700 ° C for 2 h, a catalytic cracking catalyst, designated as C23, was obtained. The content of TiO ₂ and ZrO ₂ in this catalyst C23, measured by the XRF method, was 1.50 wt. % and 1.48 wt. %, respectively.

Examples B.3.1.10-B.3.1.12

A series of catalysts was prepared in accordance with Example B.3.1.3, except that instead of ZrY (2) zeolite, ZrY (1) -1 zeolites were used in the same amount, ZrY (1) -2, respectively, catalysts were obtained, designated as C24 , C25 and C26.

Example B.3.2.4

A catalyst was prepared in accordance with Example B.3.1.4, except that instead of ZrY (6) zeolite, Zr (W) Y zeolite was used in the same amount, a catalyst, designated as DC14, was obtained. The content of ZrO ₂ in the catalyst DC14, measured by the XRF method, was equal to 2.19 weight. %

Example B.3.2.5

500 g of NaY zeolite (calculated on the dry matter) and 6000 g of deionized water were mixed and suspended. To the resulting suspension was added 200 g of NH ₄ Cl. The pH of the mixture was set at 3.8 and the suspension was heated to 80 ° C for 2 h to carry out ion exchange, filtered and washed with water. This procedure was repeated three times. The residue on the filter was calcined at a temperature of 600 ° C in an atmosphere of 100% steam for 2 hours. Then, the calcined type Y zeolite and 6000 g of deionized water were mixed and suspended. To the resulting suspension was added 150 g of NH ₄ Cl and 95.1 g of titanium tetrachloride. The resulting mixture was heated to 80 ° C for 3 h for ion exchange. After filtration and washing, the resulting filter residue was calcined at a temperature of 600 ° C in an atmosphere of 100% steam for 2 hours. The resulting zeolite was designated Ti (J) Y.

A catalyst was prepared according to Example B.3.1.6, except that instead of zeolite TiY (8) the zeolite Ti (J) Y was used in the same amount, a catalyst, designated as DC15, was obtained. The content of TiO ₂ in the catalyst DC15, measured by the XRF method, was 1.72 weight. %

Example B.3.2.6

200 g of an NaY-type zeolite and 2000 g of deionized water were mixed and suspended. To the resulting suspension was added 45 ml of a solution of RECl ₃ with a concentration of 270 g / l. The pH of the mixture was set to 3.8 with dilute hydrochloric acid and the suspension was heated to 80 ° C for 1 h to allow ion exchange. After filtration and washing, the resulting filter residue was calcined at 500 ° C for 3 hours. The resulting Y-type zeolite was mixed with 2000 g of deionized water and suspended. To the resulting suspension was added 45 g of ammonium sulfate. The pH of the mixture was adjusted to 4.0 with diluted hydrochloric acid and the suspension was heated to 80 ° C for 1 h to allow ion exchange. After filtration and washing, the resulting filter residue was calcined at a temperature of 600 ° C in an atmosphere of 100% steam for 3 hours to carry out ion exchange. Received zeolite modified RE, designated it as REY (8).

Based on the weight ratio of zeolite (calculated on a dry basis): kaolin (calculated on a dry basis): pseudo-boehmite (calculated on Al ₂ O ₃ ): a sol of aluminum oxide (calculated on Al ₂ O ₃ ) equal to 38:34: 20: 8, mixed kaolin and decationized water and suspended this mixture. An alumina sol was added to the resulting suspension. Then, with continuous stirring, pseudoboehmite was added. After 30 minutes, a stock solution containing a zeolite was added to the resulting colloid. The resulting mixture was stirred until homogeneous, dried by spraying and molded to obtain a catalyst DC 16.

The C17-C26 and DC14-DC16 catalysts were pretreated at 800 ° C in an atmosphere of 100% steam for 17 hours. Then the properties of the pretreated catalysts were tested in the fluidized bed laboratory (ACE). The starting material was the oil products of the Wuhun III deposit, whose properties are listed in Table B7. The reaction temperature was 500 ° C, the catalyst: feedstock weight ratio was 5. The test results are given in Table B8.

In this table:

conversion degree + gasoline output + liquefied gas output + coke yield

coke selectivity = coke yield × 100 / degree of conversion

Claims (61)

1. Modified metal zeolite type Y for use as a catalyst for catalytic cracking, which contains 1-15 weight. % of metal IVB group in terms of oxide, while the ratio of deformed tetrahedrally coordinated frame aluminum to tetrahedrally coordinated frame aluminum in the structure of the zeolite lattice is 0.1-0.8. 2. The metal-modified Y-type zeolite according to claim 1, wherein the ratio of the deformed tetrahedrally coordinated frame aluminum to the tetrahedrally coordinated frame aluminum in the structure of the zeolite lattice is 0.2-0.8. 3. Modified metal type Y zeolite according to claim 1, which has a specific surface area of 600-850 m ² / g or 600-750 m ² / g, the unit cell size a0 equal to 2.448-2.458 nm or 2.450-2.455 nm, degree of crystallinity of at least 60% and optionally a molar ratio of SiO ₂ / Al ₂ O ₃ equal to 5-50, and the percentage ratio of the number of secondary pores (with a diameter of 6-20 nm) to the total number of secondary pores (with a diameter of 2-100 nm) equal to 30-50% or 50-65%. 4. The metal-modified Y-type zeolite according to claim 1, wherein the modifying metal is Ti and / or Zr and, compared with the unmodified Y-type zeolite, the frequency of antisymmetric stretching vibrations (1050-1150 cm ^-1 ) and the frequency of symmetrical stretching vibrations (750 -820 cm ^-1 ) in the infrared spectrum of the metal-modified zeolite type Y do not have a shift in the long wavelength region in the direction of the lower frequency. 5. A metal-modified Y-type zeolite according to claim 1 or 4, which has a chemical composition in an anhydrous state based on oxides by weight (0-2) Na ₂ O⋅ (1-15) MO ₂ (10-25) Al ₂ O ₃ ⋅ (65-75) SiO ₂ or (0.1-1.2) Na ₂ O⋅ (1-10) MO ₂ (20-24) Al ₂ O ₃ (67-74) SiO ₂ where M is an IVB metal group selected from one or more metals Ti, Zr, Hf and Rf. 6. The metal-modified Y-type zeolite according to claim 1, wherein the IVB metal is Ti and / or Zr and the metal-modified Y-type zeolite does not contain either Ti or Zr in the frame. 7. The metal-modified Y-type zeolite according to Claim 1, in which the ratio of the content of the IVB metal on the surface of the zeolite to the IVB metal content inside the pores of the zeolite does not exceed 0.2. 8. Modified metal zeolite type Y under item 1, in which the content of the metal of the IVB group in terms of oxide is 1-10 weight. % 9. The metal-modified Y-type zeolite according to Claim 1, in which the IVB metal is Ti and / or Zr. 10. The method of obtaining modified metal type zeolite Y according to any one of paragraphs. 1-9, including: (1) contacting a type Y zeolite with an acid solution and / or an EDTA solution, wherein said acid is an organic acid and / or an inorganic acid; (2) removing water from the product obtained in step (1) at a temperature below 400 ° C to obtain a water content of zeolite of not more than 5 weight. %; (3) impregnation of the zeolite obtained in step (2) with a metal in an organic solvent medium; (4) adding a type-Y zeolite impregnated with the metal in step (3) and an organic solvent into the reaction vessel with a weight ratio of solids: liquid of 1: 5-50, introducing an inert gas into the specified vessel and holding the vessel under 0- pressure 2.0 MPa (gauge pressure) at a temperature ranging from room temperature to 200 ° C for at least one hour, optionally filtering and / or drying; (5) calcining the zeolite obtained in stage (4), while the calcination is carried out in an atmosphere of inert gas at a temperature of 300-700 ° C, and the calcination time is 0.5-5 hours 11. The method according to p. 10, in which in stage (4) the reaction vessel is maintained under a pressure of 0.1-2.0 MPa (gauge pressure). 12. The method according to p. 10, in which at stage (1) zeolite type Y represents one or more zeolites from NaY, NaHY, NaNH ₄ Y, NH ₄ Y, HY, USY, DASY, zeolite type Y, subjected to a single ion an exchange and a single calcination, a Y-type zeolite subjected to double ion exchange and two-calcined, and a Y-type zeolite subjected to double ion exchange and a single calcination. 13. The method according to p. 10, in which at stage (1) the zeolite type Y is in contact with an acid solution with a weight ratio of solids: liquid, equal to 1: 5-1: 20, at a temperature ranging from room temperature to 100 ° C for at least 0.5 h, then it is filtered and washed, while the concentration of H ⁺ in the acid solution is 0.1-1 mol / l. 14. The method according to p. 13, in which the contact time is 0.5-3 hours, the acid is an inorganic acid and / or organic acid, and the organic acid is one or more formic acid, acetic acid, oxalic acid and citric acid. 15. A method according to claim 10, in which at stage (2) the removal of water is carried out by calcining the zeolite obtained in stage (1) at a temperature of 200-400 ° C for 2-10 hours 16. The method according to p. 10, in which at stage (3) the impregnation of the metal in the environment of an organic solvent involves mixing an organic solvent in which the compound containing the metal of group IVB is dissolved with the zeolite obtained in stage (2), and the mixture is incubated for at least 0.5 h, while the weight ratio of the solids of the Y-type zeolite to the organic solvent is 1: (0.5-5). 17. The method according to p. 16, in which at stage (3) the mixture is maintained at standing or with stirring for 0.5-12 hours 18. The method according to p. 16, in which in stage (3) the weight ratio of the solids of the zeolite type Y to the organic solvent is 1: 1-2. 19. A method according to claim 16, in which the compound containing the metal of the IVB group is a Ti-containing compound and / or a Zr-containing compound; The Ti-containing compound is one or more compounds from titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate and ammonium fluorotitanate, and the Zr-containing compound is one or more compounds from zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride zirconium acetate and zirconium isopropoxide. 20. The method according to p. 10, in which in stage (4) the reaction vessel is maintained for 1-48 hours 21. The method according to p. 10, in which at stage (4) the pressure is 0.5-1.5 MPa, the temperature is from room temperature to 150 ° C, the time is 4-24 hours and the weight ratio of solids of zeolite of type Y the organic solvent is 1: 5-30. 22. The method according to p. 10, in which at stage (5) the temperature of calcination is 450-650 ° C and the time of calcination is 1-4 hours 23. The method according to p. 10, in which the water content in the organic solvent is not more than 5 weight. % 24. The method according to p. 23, in which the water content in the organic solvent is not more than 3 weight. % and the water content in the zeolite type Y, obtained in stage (2), is not more than 3 weight. % 25. The method according to any one of paragraphs. 10-24, in which the organic solvent is one or more solvents from alkanes, aromatic hydrocarbons, alcohols, ketones, ethers, esters, halogenated alkanes, such as chlorinated alkanes. 26. The method according to p. 25, in which the boiling point of an organic solvent under normal conditions is 40-100 ° C. 27. The method according to p. 25, in which the organic solvent is preferably one or more solvents from n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone and trichloromethane. 28. The method of obtaining modified metal zeolite type Y according to any one of paragraphs. 1-9, which includes stages: (1) removal of water from the original type Y zeolite to obtain a water content in the original zeolite is not more than 5 weight. %; (2) contacting the dried Y type zeolite obtained in step (1) with a mixture of a compound containing a metal of group IVB and an organic solvent and optionally filtering and / or drying the resulting mixture; (3) calcining the type Y zeolite obtained in stage (2) at a temperature of 300-700 ° C; (4) contacting the type Y zeolite obtained in stage (3) with an aqueous acid solution and subsequent calcination at a temperature of 400-800 ° C to obtain a type Y metal zeolite containing an IVB metal group; the concentration of H ⁺ in the acid solution is 0.1-2.0 mol / l. 29. The method according to p. 28, in which at stage (2) by mixing, the weight ratio of the compound containing a metal of the IVB group, a type Y zeolite and an organic solvent is 0.01-0.15: 1: 1-50, and the weight compounds containing metal IVB group, calculated on its oxide, and the weight of the zeolite type Y is calculated on a dry basis. 30. The method according to p. 28, in which at stage (2) the weight ratio of the compound containing metal of the IVB group (calculated on its oxide), type Y zeolite (calculated on a dry basis) and organic solvent is 0.01-0 1: 1: 5-30. 31. The method of claim 28, wherein in step (2) the procedure for contacting the dried Y-type zeolite obtained in step (1) with a compound containing a metal of the IVB group and an organic solvent and optional filtration and / or drying involves mixing the compound containing an IVB metal group, an organic solvent and a type Y zeolite and contacting them at a temperature ranging from room temperature to 100 ° C for at least 0.5 hours, then optional filtration and then optional drying. 32. The method according to p. 28 or 31, in which at stage (2) the procedure for contacting the dehydrated zeolite type Y, obtained in stage (1), with a mixture of compounds containing metal of the IVB group, and an organic solvent and optional filtration and / or drying the resulting mixture is carried out once or more than once. 33. The method according to claim 28, wherein in the step (3) the calcination temperature is 350-650 ° C, the calcination time is 2-4 hours, the calcination is carried out in an atmosphere of dried air and / or inert gas. 34. The method of claim 28, wherein in step (4) contacting the type Y zeolite obtained in step (3) and the aqueous acid solution is carried out at a weight ratio (solid: liquid ratio) of type Y zeolite obtained in step ( 3), to the aqueous solution of the acid is 1: 5-20, the contact temperature is in the range from room temperature to 100 ° C, the contact time is at least 0.5 h; the concentration of H ⁺ in an aqueous acid solution is 0.1–2 mol / l. 35. The method according to p. 28, in which the concentration of H ⁺ in an aqueous solution of the acid is 0.5-2 mol / L. 36. The method according to p. 28, in which the organic solvent is one or more solvents from alkanes, aromatic hydrocarbons, alcohols, ketones, ethers, esters, halogenated alkanes, such as chlorinated alkanes. 37. The method according to claim 28, wherein the organic solvent is one or more solvents from n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone, and trichloromethane. 38. The method according to p. 28, in which the boiling point of an organic solvent under normal conditions is 40-100 ° C. 39. The method according to any one of paragraphs. 28-38, in which the water content in the organic solvent is not more than 5 weight. % 40. The method according to p. 28, in which the water content in the organic solvent is not more than 1 weight. % 41. The method according to any one of paragraphs. 28-38, 40, in which in stage (2) the temperature of contacting the dehydrated type Y zeolite obtained in stage (1) and a mixture of the compound containing metal of group IVB and an organic solvent is equal to the temperature at which the organic solvent is in a liquid state . 42. The method according to p. 28, in which the compound containing the metal of the IVB group is a Ti-containing compound and / or a Zr-containing compound. 43. The method of claim 42, wherein the Ti-containing compound is one or more compounds of titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate and ammonium fluorotitanate, and the Zr-containing compound is one or more tetrachloride compounds zirconium, zirconium sulfate, zirconium nitrate, zirconium oxychloride, zirconium acetate and zirconium isopropoxide. 44. The method of claim 28, wherein in step (1), the Y-type zeolite is one or more zeolites from NaY, NaHY, NaNH ₄ Y, NH ₄ Y, and HY. 45. The method of claim 28, wherein in step (1) the water content of the Y-type zeolite after dehydration is no more than 1 weight. % 46. The method of claim 28, wherein in step (4) the calcination is carried out in an atmosphere containing 1-100% steam. 47. The catalyst for catalytic cracking, which contains, based on the total weight of the catalyst 10-60 weight. % metal modified zeolite type Y, 10-60 weight. % clay and 5-50 weight. % binder, with the specified modified metal zeolite is a zeolite according to any one of paragraphs. 1-9. 48. The catalytic cracking catalyst according to claim 47, which contains 20-55 weight. % modified metal IVB group of zeolite type Y, 15-60 weight. % clay and 10-40 weight. % binder. 49. The catalytic cracking catalyst according to claim 47, which also contains Y-type molecular sieves, MFI molecular sieves and SAPO-type molecular sieves. 50. The catalytic cracking catalyst according to claim 47, wherein the content of other molecular sieves commonly used in the catalytic cracking catalyst is not more than 40 weight. %, for example 1-35 weight. % 51. A method of producing a catalytic cracking catalyst, which includes the steps of obtaining a Y-type zeolite, mixing and suspending a Y-type zeolite with a metal, clay and a binder, and spray-drying the mixture, the specified Y-modified metal-derived zeolite is prepared according to any of pp 10-46. 52. The method according to claim 51, wherein the clay is selected from one or more clays from kaolin, halloysite, rectorite, diatomite, montmorillonite, bentonite and sepiolite; and the binder is selected from one or more binders of hydrated alumina, alumina sol, pseudoboehmite, boehmite, alumina monohydrate, alumina trihydrate and amorphous aluminum hydroxide.