MX2014012902A - A metal modified y zeolite, its preparation and use. - Google Patents

A metal modified y zeolite, its preparation and use.

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Publication number
MX2014012902A
MX2014012902A MX2014012902A MX2014012902A MX2014012902A MX 2014012902 A MX2014012902 A MX 2014012902A MX 2014012902 A MX2014012902 A MX 2014012902A MX 2014012902 A MX2014012902 A MX 2014012902A MX 2014012902 A MX2014012902 A MX 2014012902A
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Mexico
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zeolite
metal
further characterized
weight
process according
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MX2014012902A
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Spanish (es)
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MX356516B (en
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Jun Long
Huiping Tian
Shanqing Yu
Zhenbo Wang
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China Petroleum & Chemical
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Publication of MX2014012902A publication Critical patent/MX2014012902A/en
Publication of MX356516B publication Critical patent/MX356516B/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/24—Type Y
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/05—Nuclear magnetic resonance [NMR]
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/10—Infrared [IR]
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
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  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

A metal modified Y zeolite contains 1-15wt% of IVB group metal, where the ratio of the zeolite surface's IVB group metal content to the zeolite interior's IVB group metal content is not higher than 0.2. Preferably, the ratio of the distorted tetrahedral-coordinated framework aluminum to the tetrahedral-coordinated framework aluminum in the Y zeolite lattice structure is 0.2-0.8. A process for preparing a metal modified Y zeolite comprises the steps of: (i) dewatering a Y zeolite raw material so that it has a water content of no more than 5%; (ii) contacting the Y zeolite obtained from (i) with a mixture of a compound containing a group IVB metal and an organic solvent; (iii) calcining the Y zeolite obtained from step (ii) with an aqueous acid solution at 400-800 ºC to produce a metal modified Y zeolite, the acid concentration being 0.1-0.2mol/L. A catalytic cracking catalyst may contain 10-60wt% of the metal modified Y zeolite, 10-60wt% clay and 5-50wt% binder.

Description

ZEOLITE AND MODIFIED WITH METAL. YOUR PREPARATION AND USE TECHNICAL FIELD The present invention relates to a metal-modified Y zeolite, its preparation and use.
BACKGROUND OF THE INVENTION Because the catalytic cracking raw material becomes heavier and heavier, it is essential for the catalytic cracking catalyst to have both higher activity and higher thermal and hydrothermal stabilities to increase the abilities of heavy conversion and contamination of anti-metal. heavy. Therefore, the main active component in the catalytic cracking catalyst, ie, Y zeolite, is required to have higher thermal and hydrothermal stabilities, and to remain an adequate contribution of active acid centers.
The rare earth modified (RE) zeolite Y has relatively high thermal and hydrothermal stabilities, and is widely used in the FCC catalyst. However, the marked rise in the price of rare earths results in the outstanding increase in the cost of the FCC catalyst. Therefore it is desired to introduce other metal ions into the Y zeolite to reduce the rare earth content in the Y zeolite and to ensure a hydrothermal stability comparable to Y zeolite with high rare earth content.
CN1350887A, CN1765492A, and US2007010698A1 propose the preparation methods for metal-modified Y zeolites. However, in comparison with the rare earth modified Y zeolite, the metal-modified Y zeolites mentioned above have poor thermal and hydrothermal stabilities.
CN101898144A and CN101134576A propose the modification of the structure of zeolites Y to increase the thermal and hydrothermal stabilities of Y zeolites. However, the non-rare earth metal-modified zeolites Y produce a low gasoline yield in catalytic cracking.
BRIEF DESCRIPTION OF THE INVENTION With reference to the problems in the prior art, the present invention proposes a metal-modified zeolite Y and its method of preparation. The metal-modified zeolite Y is modified with non-rare earth metal elements and has thermal and hydrothermal stability comparable to the Y-zeolite modified with rare earths. After being used in the catalytic cracking catalyst, the catalyst can show excellent properties in cracking activities, gasoline yield and coke selectivity.
In one aspect, the present invention provides a metal-modified zeolite Y, characterized in that: the ratio of the group IVB metal content of the surface of the zeolite to the metal content of group IVB of the interior of the zeolite is not greater than 0.2; and / or the ratio of the aluminum of distorted structure in tetrahedral coordination with the aluminum of structure in tetrahedral coordination in the lattice structure of zeolite is (0.1 -0.8): 1.
In another aspect, the present invention provides a process for preparing the metal-modified zeolite Y, which comprises: (1) a raw material of zeolite Y is subjected to dehydration so that the raw material has a water content by weight not greater than 5%; (2) the zeolite Y obtained from step (1) is contacted with a mixture of a compound containing a group IVB metal and an organic solvent, and the resulting mixture is optionally filtered and / or dried; (3) the zeolite Y obtained from step (2) is calcined at 300 to 700 ° C, preferably for at least 0.5 hours, for example, 0.5 to 5 hours; (4) The zeolite Y obtained from step (3) is contacted with an aqueous acidic solution, and then calcined at 400 to 800 ° C under a steam condition of 1 to 100% for 0.5 to 5 hours to produce the zeolite And modified with metal containing the group IVB metal; the acid concentration, such as H +, is 0.1 to 2.0 mol / L.
In another aspect, the present invention provides a process for preparing the metal-modified zeolite Y, comprising: (1) a Y zeolite is treated by contacting it with an acid solution and / or aqueous solution of EDTA; wherein said acid is an organic acid and / or an inorganic acid; (2) The product obtained from step (1) is dehydrated at a temperature below 400 ° C, so that the water content in the zeolite is not more than 5% by weight. (3) the zeolite obtained from step (2) is impregnated with a metal in an organic solvent; (4) The zeolite Y impregnated with metal obtained from step (3) and an organic solvent are added to a vessel in a weight ratio of solid with liquid of 1: (5-50) and mixed, an inert gas as one or more of nitrogen and helium is introduced into the container, and the container is maintained under a pressure of 0-2.0 MPa (gauge pressure) at a temperature in the range of room temperature to 200 ° C for at least one hour, for example , from 1 to 48 hours; Optionally filtering and / or drying are carried out, filtering and drying are preferably carried out; (5) the zeolite obtained from step (4) is calcined; the calcination is carried out in an inert gas atmosphere, the calcination temperature is 300 to 700 ° C, the calcination time is at least 0.5 hours, for example, 0.5 to 5 hours.
In another aspect, the present invention also provides a catalytic cracking catalyst containing the metal-modified zeolite Y and the method of preparing it.
Specifically, the present invention involves the following technical solutions: 1. A Y-modified zeolite with metal, which contains from 1 to 15% by weight of a metal of group IVB as oxide, wherein the metal-modified zeolite Y has an aluminum ratio of distorted structure in tetrahedral coordination with the aluminum structure in tetrahedral coordination in the lattice structure from 0.1 to 0.8, for example, from 0.2 to 0.8. 2. The metal-modified zeolite Y of any of the previous solutions, which has a surface area of 600-850 m2 / g or 600-750m2 / g, a unit cell size aO of 2,448-2,458 nm or 2,450-2,455 nm, a crystallinity of not less than 60%, and optionally a molar ratio of SÍO2 / AI2O3 (atomic ratio of Si / Al structure) of 5-50, and the percentage of secondary pores (pore diameter of 6-20 nm) with the total secondary pores (pore diameter of 2-100 nm) being 30-50% or 50% -65%. 3. The metal-modified zeolite Y of any of the previous solutions, wherein the metal modifier is Ti and / or Zr, wherein in relation to the unmodified Y zeolite, the vibration frequency of asymmetric stretching (1050-1150cm 1) and the frequency of symmetric stretching vibration (750-820cm 1) in the infrared spectrum of the metal-modified zeolite Y does not shift to red in a direction towards the lower frequency. 4. The metal-modified zeolite Y of any of the previous solutions, which has an anhydrous chemical composition, such as oxide and by weight, of (0-2) Na20 (1-15) M02 »(10-25) AI203 * (65-75) Si02 or from (0.1-1.2) Na20 »(1-10) M02« (20-24) AI203 «(67-74) Si02, where M is a metal of group IVB, selected from one or more than Ti, Zr, Hf and Rf. 5. The metal-modified zeolite Y of any of the previous solutions, wherein the group IVB metal is Ti and / or Zr, and the metal-modified zeolite Y is free of both the Ti structure and the Zr structure. 6. The metal-modified zeolite Y of any of the previous solutions, wherein the ratio of the group IVB metal content of the zeolite surface to the group IVB metal content of the interior of the zeolite is not greater than 0.2. 7. The metal-modified zeolite Y of any of the previous solutions, wherein the content of the group IVB metal as oxide is from 1 to 10% by weight. 8. The metal-modified zeolite Y of any of the previous solutions, wherein the group IVB metal comprises Ti and / or Zr. 9. A process for preparing a metal-modified zeolite Y comprising the steps of: (1) a zeolite Y is contacted with an acid solution and / or aqueous solution of EDTA; wherein said acid is an organic acid and / or a inorganic acid; (2) The product obtained from step (1) is dehydrated at a temperature below 400 ° C, so that the water content in the zeolite is not more than 5% by weight. (3) the zeolite obtained from step (2) is impregnated with a metal in an organic solvent; (4) The Y-impregnated zeolite obtained from step (3) and an organic solvent are added to a vessel in a weight ratio of solid to liquid of 1: 5-50, an inert gas is introduced into the vessel, and the container is maintained under a pressure of 0-2.0 MPa, preferably 0.1 to 2 MPa (manometric pressure) at a temperature in the range of ambient temperature to 200 ° C for at least one hour, optionally filtration is carried out and / or drying; (5) the zeolite obtained from step (4) is calcined; the calcination is carried out in an inert gas atmosphere, the calcination temperature is 300 to 700 ° C, the calcination time is at least 0.5-5 hours. 10. The process of any of the previous solutions, wherein in step (1), the Y zeolite is one or more of NaY zeolite, NaHY, NaNH4Y, NH4Y, HY, USY, DASY, Y zeolite exchanged and calcined once, zeolite And exchanged and calcined twice, and zeolite Y exchanged twice and calcined once. 11. The process of any of the previous solutions, wherein in step (1), the zeolite Y is brought into contact with the acid solution in a Weight ratio of solid with liquid of 1: 5-1: 20 at a temperature in the range of room temperature to 100 ° C for at least 0.5 hours, then filtered and washed; the acid solution has an acid concentration, such as H +, of 0.1-1mol / L. 12. The process of any of the previous solutions, where the contact time is 0.5 to 3 hours; the acid is an inorganic acid and / or an organic acid; wherein the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid; and the organic acid is one or more of formic acid, acetic acid, oxalic acid and citric acid. 13. The process of any of the previous solutions, wherein in step (2), the dehydration is for calcining the zeolite obtained from step (1) at 200 to 400 ° C for 2 to 10 hours. 14. The process of any of the previous solutions, wherein in step (3) impregnation with the metal in the organic solvent comprises the organic solvent in which a compound containing a group IVB metal is dissolved is mixed with the obtained zeolite from step (2), and the resulting mixture is maintained for at least 0.5 hours, wherein the weight ratio of solid with liquid of the zeolite Y and the organic solvent is 1: (0.5-5). 15. The process of any of the previous solutions, wherein in step (3), the resulting mixture is maintained by letting it stand or stirring for 0.5 to 12 hours. 16. The process of any of the previous solutions, wherein in step (3), the weight ratio of solid with liquid of the zeolite Y and the Organic solvent is 1: 1-2. 17. The process of any of the previous solutions, wherein the compound containing a group IVB metal is a compound containing Ti and / or a compound containing Zr; the compound containing Ti is one or more of titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate and ammonium fluotitanate, and the compound containing Zr is one or more of zirconium tetrachloride, zirconium, zirconium nitrate, zirconium oxychloride, zirconium acetate and zirconium isopropoxide. 18. The process of any of the previous solutions, wherein in step (4) the container is maintained for 1 to 48 hours. 19. The process of any of the previous solutions, where in step (4) the pressure is from 0.5 to 1.5 MPa, the temperature is from room temperature to 150 ° C, the time is from 4 to 24 hours, and the ratio in Weight of solid with liquid of the zeolite and the organic solvent is 1: 5-30. 20. The process of any of the previous solutions, wherein in step (5) the calcination temperature is from 450 to 650 ° C, and the calcination time is from 1 to 4 hours. 21. The process of any of the previous solutions, wherein the organic solvent in step (3) and / or (4) has a water content of not more than 5% by weight. 22. The process of any of the previous solutions, wherein the organic solvent in step (3) and / or (4) has a water content of no more than 3% by weight, and the zeolite Y obtained from step (2) has a water content of not more than 3%. 23. The process of any of the previous solutions, wherein the organic solvent is one or more of aleans, aromatic hydrocarbons, alcohols, ketones, ethers, asters, halogenated alkanes as chlorinated alkanes. 24. The process of any of the previous solutions, where the organic solvent has a normal boiling point of 40 to 100 ° C. 25. The process of any of the previous solutions, wherein the organic solvent is preferably one or more of n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone and trichloromethane. 26. A process for preparing a metal-modified zeolite Y comprising the steps of: (1) a raw material of zeolite Y is subjected to dehydration so that the raw material has a water content by weight not greater than 5%; (2) the dehydrated Y zeolite obtained from step (1) is contacted with a mixture of a compound containing a group IVB metal and an organic solvent, and the resulting mixture is optionally filtered and / or dried; (3) the zeolite Y obtained from step (2) is calcined at 300 to 700 ° C; (4) The zeolite Y obtained from step (3) is contacted with a aqueous acid solution, and then calcined at 400 to 800 ° C to produce the Y-modified zeolite containing the metal of group IVB; the acid concentration, such as H +, is 0.1 to 2.0 mol / L. 27. The process of any of the previous solutions, wherein in step (2) the weight ratio of the mixture of the compound containing a metal of group IVB, the zeolite Y and the organic solvent is 0.01-0.15: 1: 1- 50, wherein the weight of the compound containing a metal of group B is calculated as oxide, and the zeolite Y is calculated on a dry basis. 28. The process of any of the previous solutions, wherein in step (2), the weight ratio of the compound containing the group IVB metal (as oxide): the Y zeolite (dry basis): the organic solvent is 0.01 -0.1: 1: 5-30. 29. The process of any of the previous solutions, wherein in step (2) the method of contacting the dehydrated Y zeolite obtained from step (1) with the compound containing a group IVB metal and the organic solvent and optionally filtered and / or drying comprises: the compound containing a metal of group IVB, the organic solvent and the zeolite Y are mixed and brought into contact at a temperature in the range of room temperature to 100 ° C for at least 0.5 hours, after optionally it is filtered and then optionally dried. 30. The process of any of the previous solutions, wherein in step (2) the method of contacting the dehydrated Y zeolite obtained from step (1) with the mixture of the metal-containing compound of the Group IVB and the organic solvent and optionally filtering and / or drying the resulting mixture is carried out once or more than once. 31. The process of any of the previous solutions, wherein in step (3) the calcination temperature is 350 to 650 ° C, the calcination time is 2 to 4 hours and the calcination atmosphere is dry air and / or an inert gas. 32. The process of any of the previous solutions, wherein in step (4) the condition for contacting the Y zeolite obtained from step (3) and the aqueous acid solution comprises: the weight ratio (ratio of solid to liquid) of the zeolite Y obtained from step (3) with the aqueous acid solution is 1: 5-20, the contact temperature is in a range of room temperature to 100 ° C, the contact time is at least 0.5 hours; the aqueous acid solution has an acid concentration, such as H +, of 0.1 to 2 mol / L. 33. The process of any of the previous solutions, wherein the aqueous acid solution has an acid concentration, such as H +, of 0.5 to 2 mol / L. 34. The process of any of the previous solutions, wherein the organic solvent is one or more of aranes, aromatic hydrocarbons, alcohols, ketones, ethers, esters, halogenated alkanes such as chlorinated alkanes. 35. The process of any of the previous solutions, wherein the organic solvent is selected from one or more of n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone and trichloromethane. 36. The process of any of the previous solutions, where the organic solvent has a normal boiling point of 40 to 100 ° C. 37. The process of any of the previous solutions, wherein the organic solvent has a water content of not more than 5% by weight. 38. The process of any of the previous solutions, wherein the organic solvent has a water content of not more than 1% by weight. 39. The process of any of the previous solutions, wherein in step (2) the temperature for contacting the dehydrated Y zeolite obtained from step (1) with the mixture of the compound containing a group IVB metal and the organic solvent is a temperature such that it allows the organic solvent to be in a liquid state. 40. The process of any of the previous solutions, wherein the compound containing a group IVB metal comprises a compound containing Ti and / or a compound containing Zr. 41. The process of any of the previous solutions, wherein the compound containing Ti is one or more of titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate and ammonium fluotitanate, and the compound containing Zr. is one or more of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, zirconium acetate and zirconium isopropoxide. 42. The process of any of the previous solutions, where in step (1), the unprocessed material of zeolite Y is one or more of NaY zeolite, NaHY zeolite, NaNH Y zeolite, NH4Y zeolite, and HY zeolite 43. The process of any of the previous solutions, wherein in step (1) the unprocessed material of the zeolite Y has a water content, after dehydration, of not more than 1% by weight. 44. The process of any of the previous solutions, wherein in step (4) the calcination is carried out in a vapor atmosphere of 1 to 100%. 45. The metal-modified zeolite Y of any of the solutions 1 to 8, which can be obtained or obtained by the process of any of the solutions 9 to 44. 46. A catalytic cracking catalyst, based on the total weight of the catalyst, containing from 10 to 60% by weight of a metal-modified zeolite Y, from 10 to 60% by weight of a clay and from 5 to 50% by weight of a a binder, wherein said Y-modified zeolite is the metal-modified zeolite Y of any of Solutions 1 to 8. 47. The catalytic cracking catalyst of solution 46, wherein the catalytic cracking catalyst contains from 20 to 55% of the zeolite Y modified with a metal of group IVB, 15 to 60% by weight of the clay and 10 to 40% by weight. weight of the binder. 48. The catalytic cracking catalyst of solution 46, wherein the catalyst additionally contains other molecular sieves commonly used in the catalytic cracking catalyst, said others Molecular sieves include molecular sieves of the Y type, molecular sieves of MFI structure and SAPO molecular sieves. 49. The catalytic cracking catalyst of solution 46, wherein the content of other molecular sieves commonly used in the catalytic cracking catalyst is not more than 40% by weight, such as 1 to 35% by weight. 50. A method for preparing the catalytic cracking catalyst, comprising the steps of preparing a metal-modified Y zeolite, mixing and making an aqueous suspension with the metal-modified zeolite Y and a clay and a binder, and spray-drying the resulting mixture , wherein said Y-modified zeolite is prepared in accordance with the process of any of the solutions 9 to 44. 51. The method of solution 50, wherein the clay is selected from one or more of kaolin, halloysite, rectorite, diatomite, montmorillonite, bentonite and sepiolite; and the binder is selected from one or more of hydrated alumina, alumina sol, pseudobohemite, boehmite, alumina monohydrate, alumina trihydrate and amorphous aluminum hydroxide. 52. A solution according to any of the above solutions 1 to 51, wherein the metal-modified zeolite Y does not substantially contain one or more of V, Nb, Ta, Cr, Mo, W, Mn, Te, Re, Fe, Ru , Go, Ni, Pd, Pt, Cu, Zn, Ag, Au, Cd, Hg, Se and Y BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 deals with FT-IR spectra for a standard Y (Y) zeolite and the metal-modified Y zeolites prepared in Examples B.1.1.2, B.1.1.6 and B.1.2.4.
Figure 2 is 27AI-NMR spectra for a standard Y (Y) zeolite and the metal-modified Y zeolites prepared in Examples B.1.1.2, B.1.2.2 and B.1.2.5.
DETAILED DESCRIPTION OF THE INVENTION Modified Zeolite The first metal-modified Y zeolite according to the present invention is characterized in that the ratio of the content of the group IVB metal of the zeolite surface to the content of the group IVB metal of the interior of the zeolite is not greater than 0.2, for example, from 0.001 to 0.2 or from 0.02 to 0.18.
The second metal-modified zeolite Y according to the present invention is characterized in that the ratio of the aluminum of structure distorted in tetrahedral coordination with the aluminum of structure in tetrahedral coordination in the lattice structure of zeolite is (0.1 -0.8):; (0.2-0.8): 1; (0.2-0.6): 1; (0.1-0.6): 1; or (0.2-0.5): 1.
The third Y-modified zeolite with metal in accordance with present invention is characterized in that the ratio of the group IVB metal content of the zeolite surface to the group IVB metal content of the interior of the zeolite is not greater than 0.2; for example, from 0.001 to 0.2; or from 0.02 to 0.18; and the ratio of the aluminum of distorted structure in tetrahedral coordination with the aluminum of structure in tetrahedral coordination in the lattice structure of zeolite 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 three Y metal-modified zeolites above are additionally characterized by one or more of the following features: (1) the metal content of group IVB, as the oxide and based on the metal-modified zeolite Y: 1 to 15% by weight or 1 to 10% by weight; (2) the specific surface area: 600-850m2 / g, 600-750m2 / g, or 630-730m2 / g; (3) unit cell size (expressed as aO): 2,448-2,458nm, 2,450-2,455nm; 2.449-2.455nm; or 2.449-2.452nm; (4) the crystallinity: not less than 60%, for example, from 60 to 120% or from 60 to 95%; Y (5) the molar ratio of SÍO2 / AI2O3: 5-50, 5-20, 5-8, 5-6; (6) the percentage of secondary pores 6-20 nm) with the total secondary pores (pore diameter of 2-100 nm) is 30-50% or 50% -65%, for example, 35%, 40%, 45%, 50%, 55%, 60%.
According to the present invention, the group IVB metal is selected from one or more of Ti, Zr, Hf and Rf, for example, one or more of Ti, Zr and Hf, preferably Ti and / or Zr.
According to the present invention, as an oxide and by weight, the metal-modified zeolite Y has a formula of anhydrous chemical composition, such as oxide and by weight, of: (0-2) Na2O »(1 -15) M02 · (10-25) AI2O3 '(65-75) S0O2, or (0.1-1 2) Na20 * (1 -10) M02 «(20-24) AI2O3 * (67-74) Si02; wherein M is a metal of group IVB, selected from one or more of Ti, Zr, Hf and Rf.
In the metal-modified zeolite Y according to the present invention, most of the group IVB metal ions are located inside the zeolite, and a small amount of ions are present on the surface of the zeolite. The ratio of the group IVB metal content of the zeolite surface to the content of the group IVB metal of the interior of the zeolite is not greater than 0.2.
In the present invention, including the following Examples, the methods of analysis for the zeolite are as follows: The metal content of group IVB of the zeolite surface refers to the metal content of group IVB that can be measured in the depth of 2 to 5 nm from the surface of the zeolite using X-ray Photoelectron Spectroscopy (XPS). The metal content of group IVB of the interior of the zeolite refers to the difference between the metal content of group IVB of the zeolite mass and the metal content of group IVB of the surface of the zeolite. The metal content of group IVB of the zeolite mass is the metal content of group IVB in the zeolite that can be obtained through the chemical analysis method.
The ratio of the aluminum of distorted structure in tetrahedral coordination with the aluminum of structure in tetrahedral coordination refers to the ratio of the spectrum peak area in a chemical change of 40 up to a chemical change of 60, measured by means of 27AI MAS NMR.
Secondary pores are determined and measured in accordance with the standard method RIPP151-90. Reference can be made to Analytical Methods in Petrochemical Industry (RIPP Experiment Techniques), Yang Cuiding et.al, Science Press, 1990.
The content of elements is determined by means of X-ray fluorescence spectrometry.
The specific surface area is determined by means of the BET method.
Unitary cell size and crystallinity are determined by means of X-ray diffraction according to the standard methods RIPP145-90 and RIPP146-90, respectively. Reference can be made to Analytical Methods in Petrochemical Industry (RIPP Experiment Techniques), Yang Cuiding et.al, Science Press, 1990.
The molar ratio of Si02 / Al2O3 (ie atomic ratio of Si / Al structure) is determined in accordance with the standard method SH / T0339-92.
Process of Preparation of Modified Zeolite The present invention provides a process for preparing the metal-modified zeolite Y, which comprises: (1) a raw material of zeolite Y is subjected to dehydration so that the raw material has a water content by weight not greater than 5%; (2) the dehydrated Y zeolite obtained from step (1) is contacted with a mixture of a compound containing a group IVB metal and an organic solvent, and the resulting mixture is optionally filtered and / or dried; (3) the zeolite Y obtained from step (2) is calcined at 300 to 700 ° C, preferably for at least 0.5 hours, for example, 0.5 to 5 hours; (4) The zeolite Y obtained from step (3) is contacted with an aqueous acidic solution, and then calcined at 400 to 800 ° C in a vapor condition of 1 to 100% for 0.5 to 5 hours to produce the zeolite Y modified with metal containing the group IVB metal; the acid concentration, such as H +, is 0.1 to 2.0 mol / L.
The metal-modified Y zeolite prepared by means of the aforementioned process is characterized by one or more features selected from: (1) most of the group IVB metal ions are located inside the zeolite, while a small number of ions are present on the surface of the zeolite; (2) the ratio of the content of the group IVB metal of the zeolite surface to the content of the group IVB metal of the interior of the zeolite is not greater than 0.2; (3) the ratio of the content of the group IVB metal of the zeolite surface to the content of the group IVB metal of the interior of the zeolite is 0.001 to 0.2; (4) the ratio of the content of the group IVB metal of the zeolite surface to the content of the group IVB metal of the interior of the zeolite is 0.02 to 0.18; (5) the ratio of the aluminum of distorted structure in tetrahedral coordination with the aluminum of structure in tetrahedral coordination in the lattice structure of zeolite is (0.2-0.8): 1; (6) the relation of the aluminum of distorted structure in tetrahedral coordination with the aluminum of structure in tetrahedral coordination in the lattice structure of zeolite is (0.2-0.6): 1; (7) the ratio of the aluminum of distorted structure in tetrahedral coordination with the aluminum of structure in tetrahedral coordination in the lattice structure of zeolite is (0.1 -0.6): 1; Y (8) the ratio of the aluminum of distorted structure in tetrahedral coordination with the aluminum structure in tetrahedral coordination in the lattice structure of zeolite is (0.2-0.5): 1.
Step (1): Dehydration The raw material of zeolite Y may be one or more of NaY zeolite, NH4Y zeolite, HY zeolite, NaNH4Y zeolite and NaHY zeolite, preferably NaY zeolite.
The NaY zeolite can be synthesized by crystallization. After removing the mother liquor, the crystallized zeolite can be used in the present invention directly or after washing. The NaY zeolite may be commercially available or may be prepared in accordance with the prior art method, for example, the method disclosed in USP3671191.
The NaNH4Y zeolite is one obtained by exchanging NaY zeolite with NH4 + to a certain extent.
The NaHY zeolite can be obtained by calcining the NaNH Y zeolite or by exchanging the NaY zeolite with H + to a certain extent.
The dehydration is preferably carried out at a temperature of not more than 400 ° C. Dehydration can be done by drying or calcining. The drying may be a conventional drying method or a vacuum drying method. After using the calcination to dehydrate, the calcination temperature is preferably no more than 400 ° C, for example 200 to 400 ° C, usually 250 to 350 ° C. The conventional drying method includes heat drying, air drying, flash drying or spray drying. The drying temperature is usually no more than 200 ° C, for example, 80 to 200 ° C. The dehydrated zeolite preferably has a water content of not more than 3% by weight, preferably not more than 1% by weight.
Step (2): contact - optional filtering - optional drying In step (2), the dehydrated Y zeolite obtained from step (1) is contacted with a mixture of a compound containing a group IVB metal and an organic solvent to introduce the modifying metal into the zeolite.
The contacting process comprises mixing and making an aqueous suspension of a mixture of a compound containing a group IVB metal and an organic solvent and the Y-zeolite, and subjecting it to an ion exchange at the exchange temperature (or the contact temperature).
After the contact optionally a filtering is carried out. Then, drying is optionally carried out.
The contact can be made once or more than once. The so-called "more than once" contact means that the zeolite obtained from the pre-treatment is contacted with a mixture of an organic solvent and a metal-modifying compound; and after each contact optionally filtering is done and optionally drying is done. In the case of contact "more than once", it is preferable to dry before the last contact. In the case of contact "more than once", the Y zeolite obtained through the filtrate can be treated directly with a compound containing a group IVB metal and an organic solvent, or it can be dried and / or calcined and then treated with a compound containing a group IVB metal and an organic solvent.
There may be at least one temperature point in the exchange temperature range, at which point the solvent may be present in a liquid state.
At each contact, the weight ratio of the compound containing a group IVB metal (as oxide): Y zeolite (dry basis): the organic solvent 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, for example, is at least 0.5 hours, for example, 0.5 to 5 hours, or 1.5 to 3.5 hours.
The contact temperature can be a temperature at which the organic solvent is in a liquid state. The exchange temperature can be a temperature range such that the organic solvent is in a liquid state. Usually, the exchange temperature can be a temperature range, the lower point of which is higher than the solidification point of the organic solvent, and the upper point of which is lower than the boiling point of the organic solvent. For example, the exchange temperature is from room temperature to a temperature that is 20 ° C lower than the normal boiling point of the organic solvent; from 0 to 100 ° C; from room temperature to 100 ° C; from 0 to 100 ° C and 20 ° C lower than the normal boiling point of the organic solvent; and of room temperature at 100 ° C and 20 ° C lower than the normal boiling point of the organic solvent. The ambient temperature is 15 to 40 ° C. The point of Normal boiling means the boiling point at 1 atm.
The drying temperature is usually no more than 200 ° C, for example, from 0 to 200 ° C, from room temperature to 150 ° C, from room temperature to 120 ° C, from 100 to 120 ° C.
The drying time can be from 4 to 48 hours, from 12 to 48 hours.
The group IVB metal may be one or more of Ti, Zr and Hf, preferably Ti and / or Zr. The compound containing a group IVB metal may be one or more compounds containing Ti and / or Zr, for example, a compound containing Ti, a compound containing Zr or a compound containing Ti and Zr. The compound containing a group IVB metal is preferably soluble in the organic solvent used, for example, its solubility in the organic solvent is not less than 0.1 g of the compound containing a metal of group IVB / 100 g of the organic solvent. The Ti-containing compound can be one or more of titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate and ammonium fluotitanate, the Zr-containing compound can be one or more of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, zirconium acetate and zirconium isopropoxide.
The organic solvent has a water content of not less than 5% by weight, preferably not more than 1% by weight, not more than 0.1% by weight, not more than 0.01% by weight or not more than 0.001% by weight . Preferably, in the organic solvent, the content of organic substance as solvent is not less than 95% by weight, preferably not less than of 99% by weight. The organic solvent may be one or more of aranes, aromatic hydrocarbons, alcohols, ketones, ethers, esters, halogenated alkanes such as chlorinated alkanes. The normal boiling point of the organic solvent (1 atm) is preferably 40 to 100 ° C, which is both favorable for the dispersion of the metal component and favorable for removing the organic solvent. The organic solvent may be, for example, one or more of n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone and trichloromethane.
Step (3): Calcination The calcination temperature can be, for example, 300-700 ° C, 350-650 ° C, 400-620 ° C or 450-600 ° C.
The calcination time can be, for example, 0.5 to 5 hours, 1 to 5 hours, 2 to 4 hours.
The calcining atmosphere can be, for example, dry air and / or an inert gas atmosphere, preferably an inert gas atmosphere.
The inert gas can be nitrogen and / or helium. In the case of dry air, the water content therein is below 1% by volume, for example, below 0.5% by volume.
Step (4): Calcination of acid treatment The temperature for contacting the aqueous acid solution with the zeolite Y obtained from step (3) is in a temperature range environment at 100 ° C, for example, 75-95 ° C.
The contact time is not less than 0.2 hours, for example, from 0.5 to 5 hours.
The contact ratio of solid to liquid (the weight ratio of zeolite to the aqueous acid solution) is 1: 5-20, for example, 1: 6-14.
The concentration of the aqueous acid solution, such as H +, is 0.1-2mol / L, 0.5-2mol / L, 0.5-1.5mol / L. After the contact, filtering has already been done. After filtering, the zeolite contacted with 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. The calcination atmosphere is a vapor condition of 1 to 100%. The calcination time is 0.5 to 5 hours, or 1 to 3 hours. The acid used in step (4) is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, acetic acid, formic acid, preferably one or more of hydrochloric acid, oxalic acid and formic acid.
In another aspect, the present invention provides a process for preparing the metal-modified zeolite Y, which comprises: (1) a Y zeolite is treated by contacting it with an acid solution and / or aqueous solution of EDTA; wherein said acid is an organic acid and / or an inorganic acid; (2) The product obtained from step (1) is dehydrated at a temperature below 400 ° C, so that the water content in the zeolite is not more than 5% by weight. (3) the zeolite obtained from step (2) is impregnated with a metal in an organic solvent; (4) The Y-impregnated zeolite obtained from step (3) and an organic solvent are added to a vessel in a weight ratio of solid to liquid of 1: 5-50, an inert gas such as nitrogen and / or helium introduced into the container, and the container is maintained under a pressure of 0-2.0 MPa (manometric pressure) at a temperature in the range of room temperature to 200 ° C for at least one hour, for example, 1 to 48 hours; optionally filtering and / or drying are carried out, filtering and drying are preferably carried out; (5) the zeolite obtained from step (4) is calcined; the calcination is carried out in an inert gas atmosphere, the calcination temperature is 300 to 700 ° C, the calcination time is 0.5-5 hours, or more than 0.5 hours.
The metal-modified Y zeolite prepared by means of the aforementioned process is characterized by one or more features selected from: (1) most of the group IVB metal ions are located inside the zeolite, while a small number of ions are present on the surface of the zeolite; (2) the ratio of the content of the group IVB metal of the zeolite surface to the content of the group IVB metal of the interior of the zeolite is not greater than 0.2; (3) the ratio of the content of the group IVB metal of the zeolite surface to the content of the group IVB metal of the interior of the zeolite is 0.001 to 0.2; (4) the ratio of the content of the group IVB metal of the zeolite surface to the content of the group IVB metal of the interior of the zeolite is 0.02 to 0.18; (5) the ratio of the aluminum of distorted structure in tetrahedral coordination with the aluminum of structure in tetrahedral coordination in the lattice structure of zeolite is (0.2-0.8): 1; (6) the relation of the aluminum of distorted structure in tetrahedral coordination with the aluminum of structure in tetrahedral coordination in the lattice structure of zeolite is (0.2-0.6): 1; (7) the ratio of the aluminum of distorted structure in tetrahedral coordination with the aluminum of structure in tetrahedral coordination in the lattice structure of zeolite is (0.1 -0.6): 1; Y (8) the ratio of the aluminum of distorted structure in tetrahedral coordination with the aluminum structure in tetrahedral coordination in the lattice structure of zeolite is (0.2-0.5): 1.
Step (1): Contact The zeolite Y as starting material can be one or more of NaY zeolite, NaHY, NaNHY, NH4Y, HY, USY, exchanged and calcined once, DASY zeolite, Y zeolite exchanged and calcined twice, Y zeolite exchanged twice and burned once.
The Y zeolite exchanged and calcined once, for example, can be the zeolite Y obtained by subjecting a NaY zeolite to exchange and calcination all at once; the DASY zeolite, for example, can be the zeolite Y obtained by subjecting a zeolite Y to calcination in the presence of steam; The Y zeolite exchanged and calcined twice, for example, can be the Y zeolite obtained by subjecting a NaY zeolite to two-fold exchange and calcination; The zeolite Y exchanged twice and calcined once, for example, can be the zeolite Y obtained by subjecting a NaY zeolite to two-fold exchange and calcination at one time; and preferably the exchange is carried out with H + and / or NH4 +.
The weight ratio between the zeolite Y (dry base) and the acid solution (the acidic aqueous solution) or the aqueous solution of EDTA (the ratio of solid to liquid) is 1: 5-20. The contact temperature is in the range of ambient temperature to 100 ° C. The contact time is at least 0.5 hours, for example, from 0.5 to 3 hours. After the contact, filtering and washing can be done. The acid concentration of the acid solution, such as H +, is 0.1-1mol / L, 0.2-0.5mol / L or 0.5-1 mol / L. The acid can be an inorganic acid and / or an organic acid. The inorganic acid may be one or more of hydrochloric acid, sulfuric acid and nitric acid; The organic acid may be one or more of formic acid, acetic acid, oxalic acid and citric acid. In step (1), washing can be done with water such as deionized water and distilled water to remove the acid in the zeolite. For example, the water weight ratio with zeolite can be 5-20: 1. The treated zeolite obtained from step (1) has a Na20 content of not more than 4.0% by weight and preferably not greater than 2.0% by weight.
Step (2) -Calculation The treated zeolite obtained from step (1) can be calcined to remove adsorbed water. Through calcination, the water content in the zeolite is not greater than 5% by weight, for example, not greater than 3% by weight.
The calcination temperature can be from 200 to 400 ° C, for example, from 300 to 350 ° C.
The calcination time can be from 2 to 10 hours, for example, from 2 to 4 hours.
The solid content of the calcined zeolite is not less than 95% by weight, not less than 97% by weight or from 97 to 99.9% by weight.
Step 3) The zeolite that is impregnated with a metal in an organic solvent comprises mixing the compound containing a group IVB metal in the organic solvent and the zeolite, and maintaining the mixture for at least 0.5 hours, for example, 0.5 to 12 hours with agitation or without agitation (at rest). For example, the mixture was maintained with agitation for 0.5 to 12 hours. Then, the next step can be conducted, for example, proceeding with step (4) or repeating step (3). The introduction of modified metal (s) into the Y zeolite can be done through one or more of an impregnation. The weight ratio of solid to liquid of the zeolite Y with the organic solvent is 1: (0.5-5), 1. (1 -2), 1: (1 -4) or 1: (1.1 -1.6). The impregnation temperature is one that can cause the organic solvent to be in the liquid state. The impregnation can be done in a manner of impregnating, sommetric or excessive impregnation. The impregnation temperature is not particularly limited, for example, the impregnation can be done at room temperature.
The group IVB metal is selected from one or more of Ti, Zr, Hf and Rf, preferably Ti and / or Zr. The compound containing a group IVB metal can be one or more of a compound containing Ti, a compound containing Zr, a compound containing Hf, a compound containing Rf, for example, a compound containing Ti and / or a compound containing Zr. The compound containing a group IVB metal may be an inorganic salt and / or an organometallic compound of the group IVB metal, for example, the compound containing Ti may be one or more of titanium sulfate, titanyl sulfate, tetrachloride of titanium, titanium trichloride, tetrabutyl titanate, and ammonium fluotitanate. The Zr-containing compound may be one or more of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, zirconium acetate and zirconium isopropoxide.
The organic solvent has a water content of not more than 5% by weight, or not more than 3% by weight, or not more than 1% by weight. The organic solvent may be one or more of aléanos, aromatic hydrocarbons, alcohols, ketones, ethers, esters, halogenated alkanes as chlorinated alkanes. The organic solvent can have a normal boiling point of 40-100 ° C. Preferably the organic solvent is one or more of n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone and trichloromethane.
Step (4) Introducing an inert gas - optional filtering - optional drying The impregnated zeolite and the organic solvent are placed in a reaction vessel, such as an autoclave. The weight ratio of solid to liquid of the zeolite with the organic solvent is 1: (5-50), for example 1: (5-30) or 1: (5-10). Generally, the organic solvent that is used in step (4) is identical to that used in step (3). An inert gas, such as nitrogen and helium, can be introduced into the reaction vessel. The pressure in the reaction vessel (gauge pressure) is 0.0-2.0MPa, or 0.5-1.5MPa. The temperature in the reaction vessel is from room temperature to 200 ° C, from room temperature to 150 ° C, or from room temperature to 90 ° C. The substances that are in the reaction vessel can be kept at rest or in agitation for at least 1 hour, usually 1 to 48 hours, 2 to 24 hours, or 4 to 24 hours.
Then, filtering and / or drying can optionally be conducted. Preferably filtering and drying are carried out so that the zeolite can be separated from the organic solvent. Filtering and drying are They can drive in a conventional way. The existing drying processes can be adopted, such as air drying, instant drying and spray drying. For example, the drying temperature can be 100-200 ° C. For example, the drying time can be from 1 second to 2 days, for example, from 6 to 24 hours.
Step (51 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.
The 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 comprises one or more of nitrogen and helium.
Catalytic cracking catalyst The present invention also provides a catalytic cracking catalyst, based on the total weight of the catalyst, containing 20-60% by weight of the Y-zeolite modified with a metal of group IVB according to the present invention, of 10-60. % by weight of a clay and 5-50% by weight of a binder.
Method for preparing a catalytic cracking catalyst The present invention also provides a method for preparing the catalytic cracking catalyst, comprising the steps of mixing and forming a suspension of the metal-modified Y zeolite according to the present invention, and a clay and a binder, and spray-drying the resulting mixture. For example, a suspension can be mixed and formed with deionized water, the clay and the binder, and the modified aqueous zeolite added to the resulting aqueous suspension. The technology of spray drying and calcination is well known in the prior art, and therefore will not be discussed in detail.
In accordance with the present invention, the clay is selected from one or more of kaolin, halloysite, rectorite, diatomite, montmorillonite, bentonite, and sepiolite, which are well known in the art.
In accordance with the present invention, the binder refers to a substance, which can form a heat-resistant inorganic oxide after calcination. The heat-resistant inorganic oxide comprises one or more of alumina, silica, amorphous silica-alumina, preferably alumina. The binder is preferably selected from one or more of hydrated alumina, alumina sol, pseudobohemite, boehmite, alumina trihydrate, alumina monohydrate and amorphous alumina hydroxide. These different binders can be transferred to the Y-AI2O3 form after calcination. These binders are well known in the art.
The Y zeolite modified with IVB metal in accordance with present invention has high crystallinity, large specific surface area and high thermal and hydrothermal stability.
In accordance with the present invention, the Y zeolite is modified with the group IVB metal, without using the expensive rare earth material. And the Y zeolite modified in accordance with the present invention can provide a thermal and hydrothermal stability comparable to or better than the rare earth modified Y zeolite.
The Y zeolite modified in accordance with the present invention can be used in the catalytic cracking catalyst to replace the modified Y zeolite with rare earths. The cost of the catalyst can be reduced dramatically.
The catalytic cracking catalyst according to the present invention shows excellent performance in cracking activities, gasoline yield and coke selectivity.
EXAMPLES In the following Examples, the ambient temperature used is 15 to 40 ° C, such as 26 ° C.
The microactivity of light oil (MA) is measured in accordance with the standard method RIPP92-90, where 5 g of catalyst is used. The reaction temperature is 460 ° C. The raw material is a direct-stroke light diesel with a distillation range of 235 to 337 ° C. The The composition of the product is analyzed by means of gas chromatography. In accordance with the composition of the product, the micro-activity is calculated as follows: Light oil micro activity (MA) = (gasoline outlet (<216 ° C) + gas outlet + coke outlet) / entry of raw materialx100% In the Examples and Comparative Examples, the starting materials used are commercially available and their detailed specifications are as follows.
Raw materials of zeolite, industrial product, are available from Sinopec Catalyst Company, Qilu Division.
ReCI3 (mixed rare earth chloride), industrial grade, are available from Sinopec Catalyst Company, Qilu Division.
Other Agents: Chemically pure, unless otherwise indicated.
The secondary pore volume is measured in accordance with the standard method RIPP151-90. Reference may be made to Analytical Methods in Petrochemical Industry (RIPP Experiment Techniques), Yang Cuiding et.al, Science Press, 1990. In accordance with the adsorption isotherm, the total pore volume of the zeolite is measured. The volume of micro pore of the zeolite is then measured from the adsorption isotherm in accordance with the method of graph T. The total pore volume minus the micro-pore volume yields the secondary pore volume, and the percentage of the secondary pores (pore diameter from 6 to 20 nm) to the total secondary pores (diameter of pore from 2 to 100 nm) is calculated from the secondary pore distribution of the zeolite.
A.1 Modification of Zeolite EXAMPLE A.1.1.1 200g of NaY zeolite was calcined at 300 ° C for 3 hours (after calcination, the water content was 1% by weight). After cooling to room temperature, it was placed in 2000 g of ethanol (the ethanol content was 99.9% by weight). The resulting aqueous suspension was stirred homogeneously. To the aqueous suspension was added 10.5 g of zirconium nitrate (Zr (N03) 4 * 5H2O). Then, the resulting mixture was stirred at room temperature for 2 hours and filtered. The filtered pulp was dried in an oven at 100 ° C for 24 hours, and then calcined at 600 ° C for 2 hours.
The above calcined Y zeolite was added to 2000g of an aqueous solution of inorganic acid with an acid concentration of 1.0mol / L (a dilute solution of hydrochloric acid). The resulting mixture was mixed homogeneously, stirred at 80 ° C for 3 hours, then filtered, washed with deionized water (the weight of the wash water was 15 times greater than the weight of the dry base), and filter. The filtered pulp was stirred and calcined in a 100% steam at 600 ° C for 1 hour. Finally, the zeolite modified by Zr was obtained and Zr (2) Y was named, the properties of which are shown in Table A1.
EXAMPLE A.1.1.2 200 g of NaY zeolite were subjected to vacuum at 200 ° C under 0.001 Pa for 4 hours. After cooling to room temperature (water content was 0.5% by weight), it was placed in 1500g of ethanol (the ethanol content was 99.9% by weight). The resulting aqueous suspension was stirred homogeneously. To the aqueous suspension was added 15.7g of zirconium oxychloride (Zr0Cl2 * 8H20). Then, the resulting mixture was stirred at room temperature for 3 hours and filtered. The filtered pulp was dried in an oven at 100 ° C for 24 hours, and then calcined at 500 ° C for 3 hours.
The above calcined Y zeolite was added to 1500g of an aqueous solution of oxalic acid with an acid concentration of 2.0mol / L. The resulting mixture was mixed homogeneously, heated to 90 ° C, stirred for 1 hour, then filtered and washed with deionized water (the weight of the wash water was 15 times higher than the dry basis weight of the zeolite ). The filtered pulp was stirred and calcined in a 100% steam at 500 ° C for 2 hours. Finally, zeolite modified by Zr was obtained and named Zr (4) Y, the properties of which are shown in Table A1.
EXAMPLE A.1.1.3 200 g of NaY zeolite was calcined at 300 ° C for 3 hours. After cooling to room temperature (water content was 1% by weight), it was placed in 1000g of n-hexane (the content of n-hexane was 99.5% by weight). The resulting aqueous suspension was stirred homogeneously. 37.8g of zirconium isopropoxide was added to the aqueous suspension. The resulting mixture was stirred at room temperature for 3 hours and filtered. The filtered pulp was dried in an oven at 120 ° C for 48 hours, and then calcined at 500 ° C (in an atmosphere of dry air, the water content in the air was not greater than 0.2% by volume) for 4 hours. hours.
The above calcined Y zeolite was added to 1000g of an aqueous solution of inorganic acid (sulfuric acid) with an acid concentration of 0.5mol / L. The resulting mixture was stirred at 80 ° C for 3 hours, then filtered and washed with deionized water (the weight of the wash water was 20 times greater than the weight of the dry base of the zeolite). The filtered pulp was stirred and calcined at 500 ° C under a 100% steam atmosphere for 3 hours. Finally, zeolite modified by Zr was obtained and Zr (8) Y was named, the properties of which are shown in Table A1.
EXAMPLE A.1.1.4 200 g of NaY zeolite was calcined at 300 ° C for 3 hours.
After cooling to room temperature, it was placed in 1000g of butanone (butanone content was 99.5% by weight). The resulting aqueous suspension was stirred homogeneously. 14.2g of titanium tetrachloride was added to the aqueous suspension. The resulting mixture was stirred at room temperature for 2 hours and filtered. The filtered pulp was dried in an oven at 120 ° C for 24 hours, and then calcined at 450 ° C under a nitrogen atmosphere for 4 hours.
The above calcined Y zeolite was added to 1000g of an aqueous solution of inorganic acid (hydrochloric acid) with an acid concentration of 0.5mol / L. The mixture was mixed homogeneously, stirred at 80 ° C for 2 hours, then filtered and washed with deionized water (the weight of the wash water was 10 times greater than the weight of the dry base of the zeolite). The filtered pulp was stirred and calcined at 500 ° C in a 100% steam atmosphere for 2 hours. Finally, the zeolite modified by Ti was obtained and named as Ti (4) Y, the properties of which are shown in Table A1.
EXAMPLE A.1.1.5 200 g of NaY zeolite were subjected to vacuum at 300 ° C under 0. 001 Pa for 4 hours. After cooling to room temperature, it was placed in 2000g of cyclohexane (the content of cyclohexane was 99.9% by weight). The resulting aqueous suspension was stirred homogeneously. HE they added 63.9g of tetrabutyl titanate to the aqueous suspension. The resulting mixture was stirred at room temperature for 3 hours and filtered. The filtered pulp was dried in an oven at 100 ° C for 48 hours, and then calcined at 600 ° C under a nitrogen atmosphere for 2 hours.
The above calcined Y zeolite was added to 2000g of an aqueous solution of oxalic acid with an acid concentration of 1.5mol / L. The mixture was mixed homogeneously, stirred at 90 ° C for 1 hour, then filtered and washed with deionized water (the weight of the wash water was 20 times greater than the weight of the dry base of the zeolite). The filtered pulp was stirred and calcined at 600 ° C in a 100% steam atmosphere for 2 hours. Finally, the zeolite modified by Ti was obtained and named as Ti (10) Y, the properties of which are shown in Table A1.
EXAMPLE A.1.1.6 200 g of NaY zeolite were subjected to vacuum at 300 ° C under 0.001 Pa for 4 hours. After cooling to room temperature, it was placed in 3000g of ethanol (the ethanol content was 99.9% by weight). The resulting aqueous suspension was stirred homogeneously. 3.6 g of titanium tetrachloride and 31.5 g of zirconium nitrate were added to the aqueous suspension. The resulting mixture was stirred at room temperature for 3 hours and filtered. The filtered pulp was dried in an oven at 100 ° C for 48 hours, and then calcined at 550 ° C under a nitrogen atmosphere for 3 hours.
The above calcined Y zeolite was added to 3000 g of an aqueous solution of inorganic acid (nitric acid) with an acid concentration of 1.0 mol / L. The mixture was mixed homogeneously, stirred at 80 ° C for 2 hours, then filtered and washed with deionized water (the weight of the wash water was 20 times greater than the weight of the dry base of the zeolite). The filtered pulp was stirred and calcined at 550 ° C under a 100% steam atmosphere for 3 hours. Finally, the zeolite modified by Ti and Zr was obtained and named as Ti-Zr-Y, the properties of which are shown in Table A1.
EXAMPLE A.1.1.7 A modified zeolite was prepared according to Example A.1.1.4, except that after being treated with the inorganic acid, the filtered pulp was first dried and then dried at 500 ° C in an air atmosphere to produce the modified zeolite named Ti (4) Y-1.
EXAMPLE A.1.2.1 200 g of NaY zeolite and 2000 of deionized water were mixed and an aqueous suspension was made therewith. To the resulting aqueous suspension was added 45 mL of a 270 g / L solution of RECI3. The pH of the mixture was adjusted to 3.8 with a dilute hydrochloric acid and heated to 80 ° C at Exchange for 1 hour. After filtering and washing, the resulting filter cake was calcined at 500 ° C for 3 hours. Then, the resulting Y zeolite and 2000g of deionized water were mixed and an aqueous suspension was made therewith. 45g of ammonium sulfate was added to the aqueous suspension. The pH of the mixture was adjusted to 4.0 with a dilute hydrochloric acid and heated to 80 ° C in exchange for 1 hour. After filtering and washing, the resulting filter cake was calcined at 600 ° C under a 100% steam atmosphere for 3 hours. Finally, the zeolite modified by RE was obtained and named RE (8) Y, the properties of which are shown in Table A1.
EXAMPLE A.1.2.2 200g of NaY zeolite were placed in 2000g of deionized water. The resulting aqueous suspension was stirred homogeneously. To the aqueous suspension was added 31.4g of zirconium oxychloride Zr0Cl2 * 8H2O. The resulting mixture was heated to 90 ° C, stirred for 3 hours and filtered. The filtered pulp was dried at 100 ° C in an oven for 12 hours, and calcined at 500 ° C for 3 hours. Then, the calcined Y zeolite and 2000g of deionized water were mixed and an aqueous suspension was made. 45g of ammonium sulfate was added to the resulting aqueous suspension. The pH of the mixture was adjusted to 4.0 with a dilute hydrochloric acid and heated to 80 ° C in exchange for 1 hour. After filtering and washing, the filtered pulp was calcined at 500 ° C in a 100% steam atmosphere during 2 hours. Finally, zeolite modified by Zr was obtained and named Zr (W) Y, the properties of which are shown in Table A1.
EXAMPLE A.1.2.3 A modified zeolite was prepared according to Example A.1.2.2, except that 14.2g of titanium tetrachloride was used in place of 31.4g of zirconium oxychloride Zr0Cl2-8H2O. Finally, the zeolite modified by Ti was obtained and named as Ti (W) Y, the properties of which are shown in Table A1.
EXAMPLE A.1.2.4 A Y-zeolite modified by Zr was prepared according to Example 1 of CN101134576A. Finally, the zeolite modified by Zrse obtained and was named Zr (G) Y, the properties of which are shown in Table A1.
EXAMPLE A.1.2.5 200g of NH4USY was added (atomic ratio of Si / Al was 5. 2) to 500 g of absolute ethanol under violent agitation to form a suspension, to which 50 g / L of an ethanol solution of absolute butyl titanate (such as Ti02) was added under violent agitation. The mixture dried with low air agitation. The resulting sample was calcined at 500 ° C for 5 hours to produce Ti-modified zeolites with a titanium content of 2.4% by weight and 9.1% by weight, named as DT2 and DT9.
TABLE A1 Physical and chemical properties of zeolites Y modified by metals TABLE A1 (continuation) A.2 Stability of modified zeolite Modified Zeolites prepared according to Examples A.1.1.1 -A.1.1.7 and A.1.2.1 -A.1.2.5 were aged at 800 ° C under a 100% steam condition for 8 hours for determine the crystallinity and the specific surface area, and the retention of crystallinity and the retention of specific surface area were calculated. The results are shown in Table A2. The aged zeolites were subjected to light micro activity (MA) test. The results are shown in Table A2.
TABLE A2 Physical and chemical properties of metal-modified zeolites Y after hydrothermal aging TABLE A2 (continuation) EXAMPLE A.2.1.8 According to Example A.1.1.5, Ti-modified Y zeolites were prepared having a Ti content (such as T1O2) of 1% by weight, 2% by weight, 7% by weight, 12%, 15% by weight. weight. The physical and chemical properties are mentioned in Table A3. These Ti-modified Y zeolites were aged at 800 ° C under a 100% steam condition for 8 hours to determine the crystallinity and the specific surface area, and the retention of crystallinity and the retention of specific surface area were calculated. The aged zeolites were subjected to light micro activity (MA) test. The results are shown in Table A3.
EXAMPLE A.2.2.6 According to Example A.1.2.1, RE-modified Y zeolites were prepared having an RE content of 1% by weight, 2% by weight, 12% by weight, 15% by weight. The physical and chemical properties are mentioned in Table A3. These Y-modified Y-zeolites were aged at 800 ° C under a 100% steam condition for 8 hours to determine the crystallinity and the specific surface area, and the retention of crystallinity and the retention of specific surface area were calculated. The aged zeolites were subjected to light micro activity (MA) test.
The results are shown in Table A3.
BOX A3 A.3 Catalyst EXAMPLE A.3.1.1 The modified Y zeolite prepared according to the present invention, Zr (8) Y, was used as an active component to prepare the catalyst according to the conventional preparation method of the catalytic cracking catalyst. The preparation was prepared as follows. According to the ratio of zeolite (dry base): kaolin (dry base): pseudobohemite (as Al2O3): alumina sol (as Al203) being 38: 34: 20: 8, mixed and an aqueous suspension of kaolin was formed and decationized water. Soline alumina was added to the resulting aqueous suspension, and pseudobohemite was also added under continuous agitation. After 30 minutes of stirring, a liquor containing zeolite was added to the colloid. The resulting mixture was mixed homogeneously, spray-dried and set to produce a catalyst, called C1.
The catalyst was pretreated at 800 ° C in a 100% steam condition for 17 hours. The pretreated catalyst was then tested in a small scale fixed fluidized bed (ACE) for catalyst evaluation. The feeding material for evaluation was Wuhun III, properties of which are shown in Table A4. The reaction temperature, catalyst to oil ratio, WHSV and the evaluation result are mentioned in Table A5, where, Conversion = gas mileage + liquefied gas yield + dry gas yield + coke yield coke selectivity = coke performance c 100 / conversion EXAMPLE A.3.2.1 A catalyst was prepared according to Example A.3.1.1, except that the same amount of zeolite RE (8) Y was used in place of zeolite Zr (8) Y to produce a catalyst named as DC1. Then, the DC1 was evaluated according to example A.3.1.1. The result of the evaluation is mentioned in Table A5.
EXAMPLE A.3.2.2 A catalyst was prepared according to Example A.3.1.1, except that the same amount of Zr (W) Y zeolite was used in place of Zr (8) Y zeolite to produce a catalyst named as DC2. Then, the DC2 was evaluated according to Example A.3.1.1. The result of the evaluation is mentioned in Table A5.
BOX A4 TABLE A5 EXAMPLE A.3.1.2 According to Example A.1.1.1, the used amount of zirconium nitrate was adjusted to prepare a Y-zeolite modified by Zr, named Zr (6) Y, wherein the ratio of the amount of zirconium nitrate used ( as Zr02) to the weight amount of the zeolite was 6: 100 by weight. 323 g of pseudobohemite (with a solid content of 62% by weight) and 1343 g of deionized water were mixed. The mixture was stirred for 15 minutes and mixed homogeneously to produce an aqueous suspension of pseudobohemite, whose pH value was adjusted to 3.5 with dilute hydrochloric acid. The resulting aqueous suspension was aged at room temperature for 6 hours. 447g of kaolin (having a solid content of 76% by weight) and 372g of alumina sol (with an alumina content of 21.5% by weight) were added to the aqueous suspension. The resulting aqueous suspension was stirred for 60 minutes. To the above aqueous suspension an aqueous suspension was added by making an aqueous suspension of 380 g (dry base) of the Zr (6) Y zeolite and 880 g of deionized water. The resulting mixture was stirred for 60 minutes to produce an aqueous catalyst suspension, which was spray dried and set and calcined at 550 ° C for 1 hour to produce a catalytic cracking catalyst, named as C11. The Zr02 content of catalyst C11, as measured by XRF, was 2.2% by weight.
EXAMPLE A.3.1.3 A zeolite Y modified by Zr was prepared according to Example A.1.1.2, named as Zr (10) Y, wherein the ratio of Zr02: zeolite is equal to 10: 100. 421 g of kaolin (with a solid content of 76% by weight), 456 g of alumina sol (with an alumina content of 21.5% by weight) and 732 g of deionized water were added to and slurried in an aqueous suspension container , to which 1667g of an acidified pseudobohemite was added (acidified with hydrochloric acid, the molar ratio of hydrochloric acid / alumina was 0.15, and with a solid content of 12% by weight). After a 60 minute stirring, an aqueous suspension formed by 380g (dry base) of the above modified Zr (10) Y zeolite and 880g of deionized water was added to the aqueous suspension vessel. The resulting mixture was stirred for 60 minutes to produce an aqueous catalyst suspension, which was spray dried and set, and calcined at 550 ° C for 1 hour to produce a catalytic cracking catalyst, named C21. The Zr02 content of catalyst C21, as measured by XRF, was 3.5% by weight.
EXAMPLE A.3.1.4 447g of kaolin, 372g of alumina sol and 800g of deionized water were mixed and an aqueous suspension was made for 60 minutes. After adding 1667g of an acid pseudobohemite, the resulting aqueous suspension was stirred for another 60 minutes. To the resulting mixture was added an aqueous suspension formed by making an aqueous suspension of 380g (dry base) of the above modified Ti (2) Y zeolite and 880g of deionized water. The resulting mixture was stirred for 60 minutes to produce an aqueous catalyst suspension, which was spray dried and set, and calcined at 650 ° C for 2 hours to produce a catalytic cracking catalyst, named C31. The Ti02 content of catalyst C31, as measured by XRF, was 0.75% by weight.
EXAMPLE A.3.1.5 447g of kaolin, 372g of alumina sol and 800g of deionized water were mixed and an aqueous suspension was made for 60 minutes. After adding 1667g of an acid pseudobohemite, the resulting aqueous suspension was stirred for another 60 minutes. To the resulting mixture was added an aqueous suspension formed by making an aqueous suspension of 380g (dry base) of the above modified Ti (4) Y zeolite and 880g of deionized water. The resulting mixture was stirred for 60 minutes to produce an aqueous catalyst suspension, which was spray dried and set, and calcined at 650 ° C for 2 hours to produce a catalytic cracking catalyst, named C41. The content of Ti02 of the catalyst C41, measured by XRF, was 1.5% by weight.
EXAMPLE A.3.1.6 A catalyst was prepared according to Example A.3.1.5, except that the same amount of Ti (4) Y-1 was used in place of Ti (4) Y zeolite to produce the catalyst, named as C41- 1.
EXAMPLE A.3.1.7 A catalyst was prepared according to Example A.3.1.5, except that a REY zeolite prepared according to the above method was used (molar ratio of SÍO2 / AI2O3 equal to 5.1, rare earth content equal to 3.8% by weight, Na20 content equal to 0.4% by weight) instead of a part of the Ti (4) Y zeolite. The weight ratio of the REY zeolite prepared according to the above method to the Ti (4) Y zeolite was 1: 1 to produce a catalyst, named as C41-2.
EXAMPLE A.3.1.8 According to Example A.1.1.4, the amount of titanium tetrachloride used was adjusted to prepare a Y-modified Y zeolite, named as Ti (8) Y, wherein the ratio of the amount used of titanium tetrachloride (as Ti02) to the amount by weight of the zeolite was 8: 100 by weight. 421 g of kaolin, 698 g of alumina sol and 900 g of deionized water were mixed and an aqueous suspension was made for 60 minutes. After adding 1250 g of an acid pseudobohemite, the resulting aqueous suspension was stirred for another 60 minutes.
To the resulting mixture was added an aqueous suspension formed by making an aqueous suspension of 380g (dry base) of the above modified Ti (8) Y zeolite and 800g of deionized water. The resulting mixture was stirred for 60 minutes to produce an aqueous catalyst suspension, which was spray dried and set, and calcined at 700 ° C for 2 hours to produce a catalytic cracking catalyst, named C51. The TiO2 content of the C51 catalyst, measured by XRF, was 1.5% by weight.
EXAMPLE A.3.1.9 The same starting materials were used as those used in Example A.3.1.2, with the exception of the Y zeolite modified by metal. 355g of pseudobohemite and 1478g of deionized water were mixed and stirred for 30 minutes to produce an aqueous slurry of pseudobohemite, the pH value of which was adjusted to 3.8 with an adequate amount of dilute hydrochloric acid. The resulting aqueous suspension was aged at 60 ° C for 2 hours. The aged aqueous suspension was added 395g of kaolin and 465g of alumina sol. The resulting suspension was stirred for 60 minutes. Then, an aqueous suspension formed with 380g (dry base) of the above modified Ti-Zr-Y zeolite and 880g of deionized water was added to the above aqueous suspension. The resulting mixture was stirred for 60 minutes to produce an aqueous catalyst suspension, which was spray dried and set, and calcined at 600 ° C for 3 hours to produce a catalytic cracking catalyst, named C61.
EXAMPLE A.3.2.3 A catalyst was prepared according to Example A.3.1.8, except that the same amount of zeolite RE (8) Y was used in place of Ti (8) Y zeolite to produce a catalyst named DC11. The content of RE2O3 of the DC11 catalyst, as measured by XRF, was 2.32% by weight.
EXAMPLE A.3.2.4 A catalyst was prepared according to Example A.3.1.8, except that the same amount of Ti (W) Y zeolite was used in place of Ti (8) Y zeolite to produce a catalyst named DC21. The Ti02 content of the DC21 catalyst, as measured by XRF, was 2.40% by weight.
EXAMPLE A.3.2.5 A catalyst was prepared according to Example A.3.1.2, except that the same amount of Zr (W) Y zeolite was used in place of Zr (6) Y zeolite to produce a catalyst named as DC31. The Zr02 content of the DC31 catalyst, as measured by XRF, was 2.18% by weight.
The catalysts C11 to C61 and DC11 to DC31 were prepared at 800 ° C in a 100% vapor condition for 8 hours. The pretreated catalyst was then tested in a small scale fixed fluid bed (ACE) for the evaluation of the catalyst. The feeding material for evaluation was Wuhun III, properties of which are shown in Table A4. The reaction temperature, catalyst to oil ratio, WHSV and the evaluation result are listed in Table A6.
Where, conversion = gas mileage + liquefied gas yield + dry gas yield + coke yield TABLE A6 Evaluation result B.1 Modification of zeolite EXAMPLE B.1.1.1 (1) For 30 minutes and at room temperature, 200g of NaY zeolite (dry base, 75% by weight) and 1500ml of a hydrochloric acid solution with a molar concentration of 0.5mol / L were mixed and stirred. After filtration, the filtered pulp was washed with 1500ml of deionized water to produce an acid-treated NaY zeolite, which had a Na20 content of 3.5% by weight, (2) NaY zeolite treated with acid was calcined at 300 ° C for 3 hours to produce a zeolite having a solid content of 96% by weight, named as F1; (3) 5.23 g of zirconium nitrate ZG (N03) 4 · 5H20 were dissolved in 200g of ethanol (analytically pure, ethanol content equal to 99.9% by weight) to produce an impregnation liquor. The impregnation liquor and the F1 treated zeolite Y were mixed homogeneously and kept at room temperature for 1 hour. (4) The product of step (3) and 800 ml of ethanol were mixed and transferred to an autoclave, to which nitrogen was introduced. The pressure was maintained at 0.5MPa. Then, the mixture was kept at room temperature for 12 hours. After filtering, the filtered pulp was heat dried at 100 ° C for 24 hours. (5) The product of step (4) was calcined in a nitrogen atmosphere at 500X for 4 hours to produce a Z-modified zeolite, named ZrY (1), properties of which are shown in Table B2.
EXAMPLE B.1.1.2 a EXAMPLE B.1.1.7 With reference to Example B.1.1.1, the modified zeolites were prepared according to the process of the present invention. The operating conditions and the properties of the product are shown in the Table B2.
EXAMPLE B.1.1.8 A modified zeolite was prepared according to Example B.1.1.1, except that in step (4) nitrogen was introduced and the pressure (manometric pressure) was maintained at 0 MPa. The modified zeolite obtained was named ZrY (1) -1, properties of which are shown in Table B2.
EXAMPLE B.1.1.9 A modified zeolite was prepared according to the Example B.1.1.1, connection of step (1) (1) For 30 minutes and at room temperature, 200g of NaY zeolite (dry base, 75% by weight) and 1500ml of an EDTA solution with a molar concentration of 0.5mol / L were mixed and stirred. After filtration, the filtered pulp was washed with 1500ml of deionized water to produce an acid-treated NaY zeolite, which had a Na20 content of 3.5% by weight, Steps (2) to (5) were identical to those in Example B.1.1.1. The modified zeolite obtained was named ZrY (1) -2, properties of which are shown in Table B2.
EXAMPLE B.1.2.1 200g of NaY zeolite (the same as that in Example B.1.1.1) and 2000g of deionized water were made aqueous suspension. 60g of ammonium sulfate was added to the aqueous suspension. The pH of the resulting aqueous suspension was adjusted to 4.0 with dilute hydrochloric acid and heated to 80 ° C was exchanged for 1 hour. After filtering and washing with water, the filtered pulp was calcined at 550 ° C in a 100% steam atmosphere for 2 hours. The above procedure was repeated twice to produce a modified Y zeolite.
Then, the resulting Y zeolite and 2000g of deionized water were made an aqueous suspension. To the aqueous suspension was added 45 ml of a RECI3 solution (270 g / l). The pH of the resulting aqueous suspension was adjusted to 3.8 with dilute hydrochloric acid and heated to 80 ° C was exchanged for 1 hour. To the mixture was added 45g of ammonium sulfate and the resulting mixture was stirred for 1 hour. After filtering and washing, the filtered pulp was calcined at 550 ° C in a 100% steam atmosphere for 2 hours. Finally, a REY zeolite modified by rare earth was obtained and it was named as KING, properties of which are shown in Table B3.
EXAMPLE B.1.2.2 The modified zeolite was prepared according to B.1.1.2, except that the same amount of zirconium oxychloride Zr0Cl2 * 8H2O was dissolved in 200g of deionized water. Finally, a zeolite modified by Zr was obtained and named as Zr (W) Y, properties of which are shown in Table B3.
EXAMPLE B.1.2.3 200 g of NaY zeolite and 2000 of deionized water were made an aqueous suspension. 60g of NH 4 Cl was added to the resulting aqueous suspension. The pH of the aqueous suspension was adjusted to 3.8, heated to 80 ° C, exchanged for 2 hours. After filtering and washing with water, the filtered pulp was calcined at 600 ° C in a 100% steam condition for 2 hours. hours.
The calcined zeolite and 2000 deionized water were made an aqueous suspension. To the aqueous suspension were added 45g of NH4CI and 31.4g of zirconium oxychloride Zr0Cl2 * 8H2O to perform a second ion exchange substantially at the same temperature and for the same time as the first exchange. After filtering and washing with water, the filtered pulp was calcined at 600 ° C in a 100% steam condition for 2 hours. Finally, a zeolite modified by Zr was obtained and named as Zr (J) Y, properties of which are shown in Table B3.
EXAMPLE B.1.2.4 A Y-zeolite modified by Zr was prepared according to Example 1 of CN101134576A. Finally, zeolite modified by Zr was obtained and named as Zr (G) Y, properties of which are shown in Table B3.
EXAMPLE B.1,2.5 200g of zeolite DASYO.O zeolite was added to 500g of absolute ethanol under violent agitation to form a suspension, to which was added 50g / L of an ethanol solution of absolute butyl titanate (as Ti02) under violent agitation . The mixture was dried in the air under stirring.
The resulting sample was calcined at 500 ° C for 5 hours to produce Ti-modified zeolite with a titanium content of 7.9% by weight, named as Ti (D) Y.
From the FT-IR spectrum of modified Y zeolites it can be seen in figure 1 that the antisymmetric stretch vibration frequency (1050-1150cm 1) and the symmetric stretching vibration frequency (750-820crrf1) of the zeolite Zr ( G) And provided in the foregoing technique (e.g., Example B.1.2.4) had a redshift in the direction toward the lowest frequency, which shows that Zr entered the frame structure of zeolite Y. The modified Y zeolites provided by the present invention (e.g., ZrY and TiY) did not show redshift, which shows that Zr and Ti did not enter the framework structure of the zeolite.
From the 27AI-NMR spectrum of zeolites Y modified in figure 2 it can be seen that the zeolite Y had a lot of aluminum structure in tetrahedral coordination (chemical change 60) and little aluminum structure in hexahedral coordination (chemical change 0). In comparison with the zeolite Y, the maximum aluminum structure in tetrahedral coordination of ZrY zeolite prepared by impregnation method with organic solution became wider and moved towards the lower chemical change, which shows that the Zr enters the interior of the zeolite interacted with the structure of the zeolite [AI04] This interaction caused the maximum spectrum of aluminum structure in tetrahedral coordination to move to a higher field, while the maximum spectrum of aluminum structure in tetrahedral coordination was remarkable (chemical change 40). The ratio of the aluminum of distorted structure in tetrahedral coordination with the aluminum of structure in tetrahedral coordination can be, for example, 0.1-0.g. The zeolites Zr (W) Y and Ti (D) Y prepared according to Example B.1.2.2 (impregnation of aqueous solution) and Example B.1.2.5, did not have any notable change in the maximum aluminum structure distorted in tetrahedral coordination, which shows that Zr or Ti had little interaction with the structure of the zeolite [AI04], and the ratio of the aluminum of distorted structure in tetrahedral coordination with the aluminum structure in tetrahedral coordination was less than 0.1. It can be seen that the method of modification according to the present invention was more favorable for metal ions to enter the interior of the zeolite, interact with the structure of the zeolite [AI04], and have an effect of stabilizing the framework structure of the zeolite.
TABLE B1 PICTURE B2 PICTURE B2 (continuation) PICTURE B2 (continuation) PICTURE B2 (continuation) TABLE B3 B.2 Stability of the modified zeolite Modified Zeolites Y prepared according to example B.2.1.1 to B.2.1.9 and B.2.2.1 to B.2.2.5 were aged at 800 ° C under a 100% steam condition for 8 hours and 17 hours, respectively, to determine the crystallinity and the specific surface area, and the retention of crystallinity and the retention of specific surface area were calculated. The aged zeolites were subjected to light micro activity (MA) test. The results are listed in table B4.
TABLE B4 TABLE B4 (continued) B.3 Catalyst EXAMPLE B.3.1.1 The modified Y zeolite prepared according to the present invention, Zr (6) Y, was used as an active component to prepare the catalyst according to the conventional preparation method of the catalytic cracking catalyst. The preparation was prepared as follows.
According to the ratio of zeolite (dry base): kaolin (dry base): pseudobohemite (as Al203): alumina sol (as AI2O3) being 38: 34: 20: 8, mixed and an aqueous suspension of kaolin was formed and decationized water. Soline alumina was added to the resulting aqueous suspension, and pseudobohemite was also added under continuous agitation. After 30 minutes of stirring, a liquor containing zeolite was added to the colloid. The resulting mixture was mixed homogeneously, spray-dried and set to produce a catalyst, called C1.
Heavy oil cracking performance evaluation The catalyst was pretreated at 800 ° C in a 100% steam condition for 8 hours. The pretreated catalyst was then tested in a small scale fixed fluidized bed (ACE) for catalyst evaluation. The raw material for the evaluation was a mixed oil of ZhengHai VGO and DaQing atmospheric residue (80:20 by weight), whose properties are shown in Table B5. Temp. Reaction temperature = 500 ° C, WHSV = 16h 1, Weight ratio of catalyst to oil = 45. The result of the evaluation appears in table B6. where, Conversion = gas mileage + liquefied gas yield + dry gas yield + coke yield Coke selectivity = coke performance c 100 / conversion TABLE B5 EXAMPLE B.3.1.2 A catalyst was prepared according to Example B.3.1.1, except that the same amount of TiY (2) zeolite was used in place of ZrY (6) zeolite to produce a C2 catalyst. Then the evaluation of C2 was done according to the example B.3.1.1. The result of the evaluation appears in table B6.
EXAMPLE B.3.2.1 A EXAMPLE B.3.2.3 A series of catalysts was prepared according to example B.3.1.1, except that the same amount of zeolite REY, the same amount of zeolite Zr (W) Y, and the same amount of zeolite Ti (respectively) were used. D) And in place of the zeolite ZrY (6) to produce the catalysts DC1, DC2 and DC3. The evaluation was then made from DC1 to DC3 according to example B.3.1.1. The result of the evaluation appears in table B6.
TABLE B6 EXAMPLE B.3.1.3 A Y-modified zeolite Zr was prepared according to Example B.1.1.1, called Zr (2) Y, wherein the weight ratio of zirconium nitrate (as Zr02): Y = 0.02: 1 zeolite. 323g of pseudobohemite and 1343g of deionized water were mixed and stirred for 15 minutes to produce an aqueous suspension of pseudobohemite. The aqueous suspension was adjusted with dilute hydrochloric acid (having a concentration of 15% by weight) to a pH of 3.5, and aged at room temperature for 6 hours. To the suspension aqueous was added 421 g of kaolin and 465 g of alumina sol. After stirring for 60 minutes, to the resulting aqueous suspension was added another suspension which was formed with 380g (dry base) of the above modified ZrY (2) zeolite and 800g of deionized water. The resulting mixture was stirred for 60 minutes to produce a catalyst suspension, which was spray dried and shaped, and calcined at 550 ° C for 2 hours to produce a catalytic cracking catalyst, called C17. The Zr02 content of catalyst C17, as measured by XRF, was 0.75% by weight.
EXAMPLE B.3.1.4 421 g of kaolin, 465 g of alumina sol and 732 g of deionized water were added and an aqueous suspension was made with them in a suspension vessel, to which 1667 g of an acid pseudobohemite was added. After a 60 minute stirring, an aqueous suspension formed by 380g (dry base) of the above modified Zr (6) Y zeolite and 800g of deionized water was added to the aqueous suspension vessel. The resulting mixture was stirred for 60 minutes to produce a catalyst suspension, which was spray dried and set, and calcined at 550 ° C for 1 hour to produce a catalytic cracking catalyst, named C18. The Zr02 content of catalyst C18, as measured by XRF, was 2.18% by weight.
EXAMPLE B.3.1.5 421 g of kaolin, 558 g of alumina sol and 800 g of deionized water were mixed and an aqueous suspension was made for 60 minutes. After adding 1500g of an acid pseudobohemite, the resulting aqueous suspension was stirred for another 60 minutes. An aqueous suspension formed by making a suspension with 380 g (dry basis) of the above ZrY zeolite (10) and 800 g of deionized water was added to the resulting mixture. The resulting mixture was stirred for 60 minutes to produce a catalyst suspension, which was spray dried and set, and calcined at 650 ° C for 2 hours to produce a catalytic cracking catalyst, named C19. The Zr02 content of catalyst C19, as measured by XRF, was 3.52% by weight.
EXAMPLE B.3.1.6 According to example B.2.1.5, a Y zeolite modified with Ti was prepared and named as TYY (8), wherein during the impregnation of step (3), the weight ratio of titanium tetrachloride ( as Ti02) to zeolite was 0.08: 1. 421 g of kaolin and 380 g of deionized water were mixed and an aqueous suspension was formed for 60 minutes. After adding 1667g of an acid pseudobohemite, the resulting aqueous suspension was stirred for another 30 minutes. An aqueous suspension formed by making a suspension of 380g (dry basis) of the above modified TiY (8) zeolite and 800g of deionized water was added to the resulting mixture. After stirring for 60 minutes, 465 g of alumina sol was added to the resulting aqueous suspension. The resulting mixture was stirred for 30 minutes to produce a catalyst suspension, which was spray dried and set, and calcined at 700 ° C for 2 hours to produce a catalytic cracking catalyst, named C20. The Ti02 content of the C20 catalyst, as measured by XRF, was 3.02% by weight.
EXAMPLE B.3.1.7 According to example B.2.1.5, a Y zeolite modified with Ti was prepared and named as TiY (4), wherein during the impregnation of step (3), the weight ratio of tita tetrachloride (as Ti02) ) to zeolite was 0.04: 1. 323g of pseudobohemite and 1478g of deionized water were mixed. The mixture was stirred for 30 minutes to produce an aqueous suspension of pseudobohemite, the pH value of which was adjusted with a suitable amount of dilute hydrochloric acid to 3.8. The resulting aqueous suspension was aged at 60 ° C for 2 hours. To the aged aqueous suspension was added 421 g of kaolin and 465 g of alumina sol. The resulting aqueous suspension was stirred for 60 minutes. To the previous aqueous suspension a suspension formed with 380g (dry base) of the above modified TiY (4) zeolite and 800g of deionized water was added. The resulting mixture was stirred for 60 minutes to produce a catalyst suspension, which was spray dried and set, and calcined at 600 ° C for 3 hours to produce a catalytic cracking catalyst, named C21. The TiO2 content of catalyst C21, as measured by XRF, was 1.48% by weight.
EXAMPLE B.3.1.8 According to example B.2.1.5, a Y zeolite modified with Hf was prepared and named HfY (6), where during the impregnation of step (3), the weight ratio of haf nitrate (as Hf02) to zeolite was 0.06: 1. 421 g of kaolin and 380 g of deionized water were mixed and an aqueous suspension was formed for 60 minutes. After adding 1667 g of an acid pseudobohemite, the resulting aqueous suspension was stirred for another 30 minutes. To the resulting mixture was added an aqueous suspension formed by making a 380g suspension (dry base) of the above modified HfY (6) zeolite and 800g of deionized water. After stirring for 60 minutes, 465 g of alumina sol was added to the resulting aqueous suspension. The resulting mixture was stirred for 30 minutes to produce a catalyst suspension, which was spray dried and set, and calcined at 700 ° C for 2 hours to produce a cracking catalyst. catalytic, named C22. The Hf02 content of the C22 catalyst, as measured by XRF, was 2.11% by weight.
EXAMPLE B.3-1.9 421 g of kaolin and 380 g of deionized water were mixed and an aqueous suspension was formed for 60 minutes. After adding 1667 g of an acid pseudobohemite, the resulting aqueous suspension was stirred for another 30 minutes. To the resulting mixture was added an aqueous suspension formed by making a 380g suspension (dry base) of the above modified Ti-Zr-Y zeolite and 800g of deionized water. After stirring for 60 minutes, 465 g of alumina sol was added to the resulting aqueous suspension. The resulting mixture was stirred for 30 minutes to produce a catalyst suspension, which was spray dried and set, and calcined at 700 ° C for 2 hours to produce a catalytic cracking catalyst, named C23. The content of T02 and Zr02 of catalyst C23, measured by XRF, was 1.50% by weight and 1.48% by weight, respectively.
EXAMPLE B.3.1.10 A EXAMPLE B.3.1.12 A series of catalysts was prepared according to Example B.3.1.3, except that the same amount of ZrY (1), the same amount of ZrY (1) -1 and the same amount of ZrY (respectively) were used ( 1) -2, instead of the zeolite ZrY (2) to produce catalysts C24, C25 and C26.
EXAMPLE B.3.2.4 A catalyst was prepared according to Example B.3.1.4, except that the same amount of Zr (W) Y zeolite was used in place of zeolite ZrY (6) to produce the DC14 catalyst. The Zr02 content of the DC14 catalyst, as measured by XRF, was 2.19% by weight.
EXAMPLE B.3.2.5 500g of NaY zeolite (dry base) and 6000g of deionized water were mixed and an aqueous suspension was formed. 200g of NH 4 Cl was added to the resulting aqueous suspension. The mixture was adjusted to pH = 3.8, heated to 80 ° C for exchange for 2 hours, filtered and washed with water. The above procedure was repeated three times. The resulting filter cake was calcined at 600 ° C under a 100% steam atmosphere for 2 hours. Then, the calcined Y zeolite and 6000g of deionized water were mixed and an aqueous suspension was made. 150g of NH4CI and 95.1g of titanium tetrachloride were added to the aqueous suspension. The mixture was heated to 80 ° C for exchange for 3 hours. After filtering and washing, the resulting filter cake was calcined at 600 ° C under a 100% steam atmosphere for 2 hours. Finally, a zeolite was obtained, and it was named as the Ti (J) Y zeolite.
A catalyst was prepared according to Example B.3.1.6, except that the same amount of Ti (J) Y zeolite was used in place of TiY (8) zeolite to produce the DC15 catalyst. The Ti02 content of the DC15 catalyst, as measured by XRF, was 1.72% by weight.
EXAMPLE B.3.2.6 200 g of NaY zeolite and 2000 of deionized water were mixed and an aqueous suspension was made therewith. To the resulting aqueous suspension was added 45 ml_ of a solution of 270 g / l of RECI3. The pH of the mixture was adjusted to 3.8 with a dilute hydrochloric acid and heated to 80 ° C in exchange for 1 hour. After filtering and washing, the resulting filter cake was calcined at 500 ° C for 3 hours. Then, the resulting Y zeolite and 2000g of deionized water were mixed and an aqueous suspension was made therewith. 45g of ammonium sulfate was added to the aqueous suspension. The pH of the mixture was adjusted to 4.0 with a dilute hydrochloric acid and heated to 80 ° C in exchange for 1 hour. After filtering and washing, the resulting filter cake was calcined at 600 ° C under a 100% steam atmosphere for 3 hours. Finally, a modified zeolite with RE was obtained and it was named as KING (8).
According to the ratio of zeolite (dry base): kaolin (dry base): pseudobohemite (as Al203): alumina sol (as Al203) being 38: 34: 20: 8, mixed and an aqueous suspension of kaolin was formed and Water decationized. Soline alumina was added to the resulting aqueous suspension, and pseudobohemite was also added under continuous agitation. After about 30 minutes of stirring, a liquor containing zeolite was added to the colloid. The resulting mixture was mixed homogeneously, spray-dried and configured to produce a catalyst, which was named DC16.
The catalysts C17 to C26 and DC14 to DC16 were pre-treated at 800 ° C in a 100% vapor condition for 17 hours. Then the pretreated catalysts were tested in a fixed small-scale fluid bed (ACE) for evaluation as a catalyst. The raw material for the evaluation was Wuhun III, whose properties are shown in table B7. Reaction temperature = 500 ° C, and the ratio by weight of catalyst to oil = 5. The result of the evaluation appears in Table B8. where, conversion = gas mileage + liquefied gas yield + dry gas yield + coke yield coke selectivity = coke yield / conversion TABLE B7 Properties of the raw material TABLE B8 Evaluation result TABLE B8 Result of the evaluation (continued)

Claims (51)

NOVELTY OF THE INVENTION CLAIMS
1. - A Y-modified zeolite with metal, which contains 1 to 15% by weight of a metal of group IVB as oxide, wherein the metal-modified zeolite Y has a ratio of the aluminum of distorted structure in tetrahedral coordination with the aluminum of structure in tetrahedral coordination in the lattice structure from 0.1 to 0.8, for example, from 0.2 to 0.8.
2. - The metal-modified zeolite Y according to claim 1, further characterized in that it has a specific surface area of 600 to 850 m2 / g or 600 to 750 m2 / g, a unit cell size aO of 2,448 to 2,458 nm or 2,450 nm at 1455 nm, a crystallinity of not less than 60%, and optionally a molar ratio of SIO2 / AI2O3 from 5 to 50, and the percentage of secondary pores (pore diameter of 6 to 20 nm) with the total secondary pores ( pore diameter from 2 to 100 nm) being from 30 to 50% or from 50% to 65%.
3 - . 3 - The metal-modified zeolite Y according to claim 1, further characterized in that the metal modifier is Ti and / or Zr, wherein in relation to the unmodified Y zeolite, the vibration frequency of anti-symmetric stretching (1050) at 1150 cm 1) and the vibration frequency of symmetrical stretching (750 to 820 cm 1) in the infrared spectrum of The metal-modified zeolite Y does not shift red in a direction towards the lower frequency.
4. - The metal-modified zeolite Y according to claim 1 or 3, further characterized in that it has a formula of anhydrous chemical composition, such as oxide and by weight, of (0 to 2) Na20"(1 to 15) MO2 · (10 a 25) AI2O3 · (65 to 75) S02 or (0.1 to 1.2) Na20 * (1 to 10) M02 * (20 to 24) AI203 * (67 to 74) Si02, where M is a metal of the group IVB, selected from one or more of Ti, Zr, Hf and Rf.
5. - The metal-modified zeolite Y according to claim 1, further characterized in that the group IVB metal is Ti and / or Zr, and the metal-modified zeolite Y is free of both the Ti structure and the Zr structure.
6 -. 6 - The metal-modified zeolite Y according to claim 1, further characterized in that the ratio of the content of the group IVB metal of the zeolite surface to the content of the group IVB metal of the interior of the zeolite is not greater than 0.2 .
7. - The metal-modified zeolite Y according to claim 1, further characterized in that the content of the group IVB metal as oxide is from 1 to 10% by weight.
8. - The metal-modified zeolite Y according to claim 1, further characterized in that the group IVB metal comprises Ti and / or Zr.
9. - A process for preparing a Y-modified zeolite with metal, comprising the steps of: (1) a zeolite Y is contacted with an acid solution and / or an aqueous solution of EDTA; wherein said acid is an organic acid and / or an inorganic acid; (2) the product obtained from step (1) is dehydrated at a temperature below 400 ° C, so that the water content in the zeolite is not more than 5% by weight; (3) the zeolite obtained from step (2) is impregnated with a metal in an organic solvent; (4) The Y-impregnated zeolite obtained from step (3) and an organic solvent are added to a vessel in a weight ratio of solid with liquid of 1: 5 to 50, an inert gas is introduced into the vessel, and the container is maintained under a pressure of 0 to 2.0 MPa, preferably 0.1 to 2 MPa (gauge pressure) at a temperature in the range of room temperature to 200 ° C for at least one hour, filtration is optionally carried out and / or drying; (5) the zeolite obtained from step (4) is calcined; The calcination is carried out in an inert gas atmosphere, the calcination temperature is 300 to 700 ° C, the calcination time is at least 0.5 to 5 hours.
10. - The process according to claim 9, further characterized in that in step (1), the zeolite Y is one or more of zeolite NaY, NaHY, NaNH4Y, NH4Y, HY, USY, DASY, zeolite Y exchanged and calcined once , Y zeolite exchanged and calcined twice, and zeolite Y exchanged twice and calcined once.
11. - The process according to claim 9, further characterized in that in step (1), the zeolite Y is brought into contact with the acid solution in a weight ratio of solid with liquid of 1: 5 to 1:20 at a temperature in the range of room temperature to 100 ° C for at least 0.5 hours, then filtered and washed; the acid solution has an acid concentration, such as H +, of 0.1 to 1 / L.
12. - The process according to claim 11, further characterized in that the contact time is 0.5 to 3 hours; the acid is an inorganic acid and / or an organic acid; wherein the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid; and the organic acid is one or more of formic acid, acetic acid, oxalic acid, citric acid.
13. - The process according to claim 9, further characterized in that in step (2), dehydration is for calcining the zeolite obtained from step (1) at 200 to 400 ° C for 2 to 10 hours.
14. - The process according to claim 9, further characterized in that in step (3) the impregnation with the metal in the organic solvent comprises the organic solvent in which a compound containing a group IVB metal is dissolved, mixed with the zeolite obtained from step (2), and the resulting mixture is maintained for at least 0.5 hours, wherein the weight ratio of solid with liquid of the zeolite Y and the organic solvent is 1: (0.5 to 5).
15. - The process according to claim 14, further characterized in that in step (3), the resulting mixture is maintained by letting it stand or stirring for 0.5 to 12 hours.
16. - The process according to claim 14, further characterized in that in step (3), the weight ratio of solid with liquid of the zeolite Y and the organic solvent is from 1: 1 to 2.
17. - The process according to claim 14, further characterized in that the compound containing a group IVB metal is a compound containing Ti and / or a compound containing Zr; the compound containing Ti is one or more of titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate and ammonium fluotitanate, and the compound containing Zr is one or more of zirconium tetrachloride, sulfate of zirconium, zirconium nitrate, zirconium oxychloride, zirconium acetate and zirconium isopropoxide.
18. - The process according to claim 9, further characterized in that in step (4) the container is maintained for 1 to 48 hours.
19. - The process according to claim 9, further characterized in that in step (4) the pressure is from 0.5 to 1.5 MPa, the temperature is from room temperature to 150 ° C, the time is from 4 to 24 hours, and the Weight ratio of solid to liquid of the zeolite and the organic solvent is from 1: 5 to 30.
20. - The process according to claim 9, further characterized in that in step (5) the calcination temperature is 450 to 650 ° C, and the calcination time is 1 to 4 hours.
21. - The process according to claim 9, further characterized in that the organic solvent has a water content of not more than 5% by weight.
22 -. 22 - The process according to claim 21, further characterized in that the organic solvent has a water content of not more than 3% by weight, and the zeolite Y obtained from step (2) has a water content of no more than 3% by weight.
23. - The process according to any of claims 9 to 22, further characterized in that the organic solvent is one or more of the aleans, aromatic hydrocarbons, alcohols, ketones, ethers, ethers, halogenated alkanes such as chlorinated alkanes.
24. - The process according to claim 23, further characterized in that the organic solvent has a normal boiling point of 40 to 100 ° C.
25. - The process according to claim 23, further characterized in that the organic solvent is preferably one or more of n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone and trichloromethane.
26. A process for preparing a metal-modified zeolite Y, comprising the steps of: (1) a raw material of zeolite Y is subjected to dehydration so that the raw material has a water content by weight not greater than 5%. %; (2) the dehydrated Y zeolite obtained from step (1) is contacted with a mixture of a compound containing a group IVB metal and an organic solvent, and the resulting mixture is optionally filtered and / or dried; (3) the zeolite Y obtained from step (2) it is calcined at 300 to 700 ° C; (4) the zeolite Y obtained from step (3) is contacted with an aqueous acidic solution, and then calcined at 400 to 800 ° C to produce the Y-modified zeolite with metal containing the group IVB metal; the acid concentration, such as H +, is 0.1 to 2.0 mol / L.
27. - The process according to claim 26, further characterized in that in step (2) the weight ratio of mixture of the compound containing a metal of group IVB, the zeolite Y and the organic solvent is 0.01 to 0.15: 1: 1 to 50, wherein the weight of the compound containing a metal of group IVB is calculated as oxide, and the zeolite Y is calculated on a dry basis.
28. - The process according to claim 26, further characterized in that in step (2), the weight ratio of the compound containing the group IVB metal (as oxide): the zeolite Y (dry basis): the organic solvent is from 0.01 to 0.1: 1: 5 to 30.
29 -. 29 - The process according to claim 26, further characterized in that in step (2), the method of contacting the dehydrated Y zeolite obtained from step (1) with the compound containing a group IVB metal and the solvent organic and optionally filtered and / or dried comprises: the compound containing a group IVB metal, the organic solvent and the zeolite Y are mixed and contacted at a temperature in the range of room temperature to 100 ° C for at least 0.5 hours, then optionally filtered and then optionally dried.
30. - The process according to claim 26 or 29, further characterized in that in step (2), the method of contacting the dehydrated Y zeolite obtained from step (1) with the mixture of the compound containing a group IVB metal and the organic solvent and optionally the filtrate and / or drying of the resulting mixture is carried out once or more than once.
31. - The process according to claim 26, further characterized in that in step (3) the calcination temperature is 350 to 650 ° C, the calcination time is 2 to 4 hours and the calcination atmosphere is dry air and / or an inert gas.
32. - The process according to claim 26, further characterized in that in step (4) the condition for contacting the zeolite Y obtained from step (3) and the aqueous acid solution comprises: the weight ratio (ratio of solid to liquid) of the zeolite Y obtained from step (3) with the aqueous acid solution is from 1: 5 to 20, the contact temperature is in a range of room temperature to 100 ° C, the contact time is at least 0.5 hours; the aqueous acid solution has an acid concentration, such as H +, of 0.1 to 2 mol / L.
33 -. 33 - The process according to claim 26, further characterized in that the aqueous acid solution has an acid concentration, such as H +, of 0.5 to 2 mol / L.
34. - The process according to claim 26, further characterized in that the organic solvent is one or more of the aranes, aromatic hydrocarbons, alcohols, ketones, ethers, esters, halogenated alloys such as chlorinated alkanes.
35. - The process according to claim 26, further characterized in that the organic solvent is selected from one or more of n-hexane, cyclohexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone, trichloromethane.
36. - The process according to claim 26, further characterized in that the organic solvent has a normal boiling point of 40 to 100 ° C.
37. - The process according to any of claims 26 to 36, further characterized in that the organic solvent has a water content of not more than 5% by weight.
38. - The process according to claim 26, further characterized in that the organic solvent has a water content of not more than 1% by weight.
39. - The process according to any of claims 26 to 38, further characterized in that in step (2) the temperature for contacting the dehydrated Y zeolite obtained from step (1) with the mixture of the compound containing a metal of the group IVB and the organic solvent is such a temperature that allows the organic solvent to be in a liquid state.
40. - The process according to claim 26, further characterized in that the compound containing a group IVB metal comprises a compound containing Ti and / or a compound containing Zr.
41. - The process according to claim 40, further characterized in that the compound containing Ti is one or more of titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate, ammonium fluotitanate, and the compound containing Zr is one or more of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, zirconium acetate and zirconium isopropoxide.
42. - The process according to claim 26, further characterized in that in step (1), the unprocessed material of zeolite Y is one or more of NaY zeolite, NaHY zeolite, NaNH4Y zeolite, NH4Y zeolite and HY zeolite.
43. - The process according to claim 26, further characterized in that in step (1), the untreated material of zeolite Y has a water content, after dehydration, of not more than 1% by weight.
44. - The process according to claim 26, further characterized in that in step (4), the calcination is carried out in a vapor atmosphere of 1 to 100%.
45. - The metal-modified zeolite Y according to any of claims 1 to 8, further characterized in that it is obtainable or obtained by the process of any of claims 9 to 44.
46. - A catalytic cracking catalyst, based on weight total of the catalyst, which contains 10 to 60% by weight of a Y-modified zeolite with metal, 10 to 60% by weight of a clay and 5 to 50% by weight of a binder, wherein said Y-modified zeolite is the Metal-modified zeolite Y of any of claims 1 to 8.
47. - The catalytic cracking catalyst according to claim 46, further characterized in that the catalytic cracking catalyst contains from 20 to 55% by weight of the zeolite Y modified with a metal of group IVB, from 15 to 60% by weight of the clay and from 10 to 40% by weight of the binder.
48. - The catalytic cracking catalyst according to claim 46, further characterized in that the catalyst additionally contains other molecular sieves commonly used in the catalytic cracking catalyst, said other molecular sieves include molecular sieves of the type Y, molecular sieves of structure MFI and sieves SAPO
49. - The catalytic cracking catalyst according to claim 46, further characterized in that the content of other molecular sieves commonly used in the catalytic cracking catalyst is not more than 40% by weight, for example 1 to 35% by weight.
50. - A method for preparing the catalytic cracking catalyst, comprising the steps of preparing a metal-modified Y zeolite, mixing and making an aqueous suspension with the zeolite Y modified with metal and a clay and a binder, and spray-drying the mixture resulting, in wherein said Y-modified zeolite is prepared by the process of any of claims 9 to 44.
51. - The method according to claim 50, further characterized in that the clay is selected from one or more of kaolin, halloysite, rectorite, diatomite, montmorillonite, bentonite and sepiolite; and the binder is selected from one or more of hydrated alumina, alumina sol, pseudobohemite, boehmite, alumina monohydrate, alumina trihydrate and amorphous aluminum hydroxide.
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BR102014026338A2 (en) 2015-09-22
SG10201406881YA (en) 2015-05-28
CA2867947C (en) 2021-11-09
RU2014142572A (en) 2016-05-20
AU2014253496B2 (en) 2018-10-18
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