CN106669773A - Method for modifying Y-type molecular sieve - Google Patents
Method for modifying Y-type molecular sieve Download PDFInfo
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- CN106669773A CN106669773A CN201510761497.3A CN201510761497A CN106669773A CN 106669773 A CN106669773 A CN 106669773A CN 201510761497 A CN201510761497 A CN 201510761497A CN 106669773 A CN106669773 A CN 106669773A
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- molecular sieve
- type molecular
- roasting
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- carbon deposit
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 150000001336 alkenes Chemical class 0.000 claims abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 1
- 150000002605 large molecules Chemical class 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 24
- 239000002253 acid Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 7
- 238000004517 catalytic hydrocracking Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
- B01J29/084—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
- 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
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B01J35/617—
-
- B01J35/635—
-
- 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
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- 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
- B01J2229/14—After treatment, characterised by the effect to be obtained to alter the inside of the molecular sieve channels
-
- 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
- B01J2229/22—After treatment, characterised by the effect to be obtained to destroy the molecular sieve structure or part thereof
-
- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The invention discloses a method for modifying a Y-type molecular sieve. The method comprises the following steps of (1) performing high-temperature roasting on the Y-type molecular sieve, enabling unsaturated olefin to be in contact with the roasted Y-type molecular sieve, and performing a roasting carbon deposit reaction in an anaerobic atmosphere; and (2) under a stirring condition, adding the Y-type molecular sieve after carbon deposit into a pressure-resistant container of a sodium hydroxide solution, sealing the system, increasing the pressure to be 0.2-0.8 MPa, heating to 50-90 DEG C, performing constant-temperature treatment for 0.5-3 hours, depressurizing, performing suction filtration, drying and roasting, thereby obtaining the Y-type molecular sieve. The Y-type molecular sieve prepared by using the method has relatively large-size mesoporous distribution, relatively more reaction spaces can be provided for large molecules, and the catalysis property of the molecular sieve can be improved.
Description
Technical field
The present invention relates to a kind of method of modifying of Y type molecular sieve, there are Y type molecular sieve prepared by the method more meso-hole structures to be distributed, and be conducive to the reactant of course of reaction and the diffusion of product.
Background technology
Y type molecular sieve is mutually communicated by octahedral molecular sieve cage along three crystalline axis directions by twelve-ring and is formed, and is a kind of excellent catalyst activity component, and not only cracking activity is high, and selective good.Therefore the discovery of Y type molecular sieve and use has epoch-making meaning in catalytic field.
Due to the Y type molecular sieve of low silica-alumina ratio（Silica than aluminum oxide mol ratio between 3 ~ 4.2）Without good hydrothermal stability, therefore, extensive research and universal attention are not obtained in actual building-up process and in application.And high silica alumina ratio Y type molecular sieve（Silica than aluminum oxide mol ratio more than 4.3）Because it has good hydrothermal stability and absolute acid stability, irreplaceable effect is being played in the catalytic cracking of PETROLEUM PROCESSING and during being hydrocracked etc. as a kind of catalysis material through modified.
All the time, the modified work with regard to Y type molecular sieve has obtained the extensive concern of numerous scientific research personnel.The study on the modification of Y type molecular sieve mainly is modified to carry out desiliconization dealuminzation by conventional acid, alkali and hydro-thermal process, while producing substantial amounts of secondary mesopore structure.The a large amount of secondary pores for producing are conducive to the reaction and diffusion of macromolecular.Current modified method is mainly after the hydro-thermal process for first passing through uniform temperature carries out acid treatment, has not only carried out dealuminzation to molecular sieve, hydrothermal stability is improve, while substantial amounts of secondary pore structure can be produced.But molecular sieve secondary pore prepared by the method is concentrated mainly on surface and amount is limited, the amount for wanting to improve secondary pore is accomplished by advanced treating molecular sieve, and this can cause the acid amount reduction of the excessive dealuminzation of molecular sieve, molecular sieve to meet requirement.In recent years, huge progress is achieved by the research of aqueous slkali desiliconization, alkali process are further carried out after pickling can greatly increase the amount of secondary pore, while the acid amount of molecular sieve can also be improved, just right solves the problems, such as that the acid amount that original advanced treating is brought is not enough.Although but by first hydro-thermal process, then pickling dealuminzation, further alkali cleaning desiliconization can bring up substantial amounts of secondary pore structure, while acid amount can also meet requirement.But the aperture of secondary pore structure for preparing is concentrated mainly on 3 ~ 5nm, for the conversion of some two rings and its aromatic hydrocarbons macromolecular of the above or helpless, therefore it is a critically important direction of scientific rersearch to prepare the molecular sieve with more macroporous structure.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of method of modifying of Y type molecular sieve.Y type molecular sieve prepared by the method has larger sized mesoporous distribution, can provide more reaction compartments for macromolecular, improves the catalytic performance of molecular sieve.
The method of modifying of the Y type molecular sieve of the present invention, including following content：
（1）Y type molecular sieve is carried out into high-temperature roasting, then unsaturated olefin is contacted with the Y type molecular sieve after roasting, roasting carbon deposit reaction is carried out in an oxygen-free atmosphere；
（2）Under agitation, the Y type molecular sieve after carbon deposit is added in the pressure vessel of sodium hydroxide solution, and system is closed, 0.2 ~ 0.8MPa is boosted to, 50 ~ 90 DEG C are then heated to, constant temperature is processed 0.5 ~ 3 hour, release, suction filtration, drying and roasting, obtain Modified Zeolite Y.
In the inventive method, step（1）The Y type molecular sieve of middle addition is Hydrogen, and silica/alumina molar ratio is 10 ~ 55, preferably 18 ~ 45；Specific surface area is 650 ~ 950m2/ g, preferably 750 ~ 900m2/g；
In the inventive method, step（1）Described high-temperature roasting temperature is 350 ~ 650 DEG C, and the time is 1 ~ 12 hour.
In the inventive method, step（1）Described oxygen-free atmosphere is one or more in nitrogen or inert gas, and described inert gas is helium, neon, argon gas etc., and the temperature of roasting carbon deposit reaction is 450 ~ 650 DEG C, and the time is 1 ~ 8 hour.
In the inventive method, step（2）The addition of the Y type molecular sieve after the carbon deposit is 1 with the mass ratio of solution：5~1：20, preferably 1：7.5~15；Concentration of sodium hydroxide solution is 0.35 ~ 1.30mol/L.
In the inventive method, boosting is realized using compressed air, nitrogen or inert gas etc. is passed through in pressure vessel.
In the inventive method, step（2）Middle drying condition is：It is dried 6 ~ 24 hours under the conditions of 80 ~ 120 DEG C.
In the inventive method, step（2）Middle roasting condition is：Roasting 2 ~ 8 hours under the conditions of 450 ~ 650 DEG C.
Y type molecular sieve prepared by the inventive method, with following property：Total pore volume is 0.66 ~ 1.10ml/g, preferably 0.70 ~ 1.0ml/g；Its intermediary hole pore volume is 0.55 ~ 1.05ml/g, more preferably preferably 0.60 ~ 0.95ml/g, 0.65 ~ 0.90ml/g；Mesoporous pore volume accounts for the 55 ~ 92% of Y type molecular sieve total pore volume, and preferably 65 ~ 88%；Silica/alumina molar ratio is 8 ~ 35, preferably 10 ~ 30 in molecular sieve；Specific surface area is 680 ~ 950m2/ g, preferably 780 ~ 920m2/g。
Y type molecular sieve prepared by the inventive method can be used for preparing hydrocracking catalyst, and the hydrocracking catalyst is particularly well-suited to the conversion of condensed ring macromolecular in hydrocracking process.
The inventive method carries out under the high temperature conditions first the moisture of roasting abjection absorption to Y type molecular sieve; then it is allowed to adsorb unsaturated olefin and carbon deposit reaction is carried out under anaerobic state; charcoal will be full of in the duct of molecular sieve; then Y type molecular sieve has carried out high pressure alkali process after employing is in sodium hydroxide solution to carbon deposit; carbon deposit in Y type molecular sieve protects the microcellular structure of molecular sieve in high pressure base processing procedure; so that destruction of the alkali process process to molecular sieve structure is limited extent, the destruction of exactly this limited extent has promoted the formation of bigger mesoporous pore volume.Destroy the method limited extent original 4nm or so in molecular sieve it is mesoporous between connection hole wall so as to run through the mesoporous pore structure for defining 8nm or so.Y type molecular sieve with macropore volume structure prepared by this method can be used to prepare catalyst as acid carrier.Compare more traditional method of modifying, there is Y type molecular sieve prepared by the present invention bigger meso-hole structure to be distributed, reduce the silica alumina ratio of molecular sieve during alkali process simultaneously, substantially increase the acid amount of molecular sieve, therefore catalysis activity and diffusion that the molecular sieve that prepared by this method has had, while also having very strong anti-carbon deposition ability.
Description of the drawings
Fig. 1 is the graph of pore diameter distribution of Y type molecular sieve prepared by embodiment 1.
Fig. 2 is the XRD diffraction patterns of Y type molecular sieve prepared by embodiment 1.
Specific embodiment
The preparation process of the present invention is further illustrated with reference to embodiment, but following examples do not constitute the restriction to the inventive method.Using Hydrogen Y type molecular sieve of the addition with following property in preparation process：Y-1 silica/alumina molar ratios are 18, and specific surface area is 827m2/g；Y-2 silica/alumina molar ratios are 35, and specific surface area is 871m2/g。
Embodiment 1
（1）By Y-1 types molecular sieve under the conditions of 550 DEG C roasting 4 hours, then unsaturated olefin is contacted with the Y type molecular sieve after roasting, in nitrogen atmosphere, the roasting under the conditions of 500 DEG C carries out carbon deposit reaction in 2 hours, obtains the Y type molecular sieve after carbon deposit；
（2）Under agitation, the Y type molecular sieve after carbon deposit is added in the pressure vessel of the sodium hydroxide solution of 0.50mol/L, the addition of molecular sieve is 1 with the mass ratio of water in solution:8, and system is closed, nitrogen control system pressure is passed through for 0.4MPa, 70 DEG C are then heated to, constant temperature is processed 2 hours, and release, suction filtration to pH value are less than 9, is dried 12 hours under the conditions of 120 DEG C, finally in 550 DEG C of roastings 4 hours, obtains Modified Zeolite Y.Molecular sieve volume property is as shown in table 1.
Embodiment 2
（1）By Y-1 types molecular sieve under the conditions of 450 DEG C roasting 6 hours, then unsaturated olefin is contacted with the Y type molecular sieve after roasting, in nitrogen atmosphere, the roasting under the conditions of 550 DEG C carries out carbon deposit reaction in 2 hours, obtains the Y type molecular sieve after carbon deposit；
（2）Under agitation, the Y type molecular sieve after carbon deposit is added in the pressure vessel of the sodium hydroxide solution of 0.80mol/L, the addition of molecular sieve is 1 with the mass ratio of water in solution:15, and system is closed, air control system pressure is passed through for 0.6MPa, 80 DEG C are then heated to, constant temperature is processed 1 hour, and release, suction filtration to pH value are less than 9, is dried 18 hours under the conditions of 110 DEG C, finally in 580 DEG C of roastings 4 hours, obtains Modified Zeolite Y.Molecular sieve volume property is as shown in table 1.
Embodiment 3
（1）By Y-1 types molecular sieve under the conditions of 600 DEG C roasting 2 hours, then unsaturated olefin is contacted with the Y type molecular sieve after roasting, in nitrogen atmosphere, the roasting under the conditions of 480 DEG C carries out carbon deposit reaction in 6 hours, obtains the Y type molecular sieve after carbon deposit；
（2）Under agitation, the Y type molecular sieve after carbon deposit is added in the pressure vessel of the sodium hydroxide solution of 0.60mol/L, the addition of molecular sieve is 1 with the mass ratio of water in solution:10, and system is closed, nitrogen control system pressure is passed through for 0.2MPa, 60 DEG C are then heated to, constant temperature is processed 3 hours, and release, suction filtration to pH value are less than 9, is dried 24 hours under the conditions of 100 DEG C, finally in 520 DEG C of roastings 4 hours, obtains Modified Zeolite Y.Molecular sieve volume property is as shown in table 1.
Embodiment 4
（1）By Y-2 types molecular sieve under the conditions of 520 DEG C roasting 8 hours, then unsaturated olefin is contacted with the Y type molecular sieve after roasting, in nitrogen atmosphere, the roasting under the conditions of 600 DEG C carries out carbon deposit reaction in 1 hour, obtains the Y type molecular sieve after carbon deposit；
（2）Under agitation, the Y type molecular sieve after carbon deposit is added in the pressure vessel of the sodium hydroxide solution of 0.40mol/L, the addition of molecular sieve is 1 with the mass ratio of water in solution:5, and system is closed, air control system pressure is passed through for 0.7MPa, 65 DEG C are then heated to, constant temperature is processed 2 hours, and release, suction filtration to pH value are less than 9, is dried 18 hours under the conditions of 90 DEG C, finally in 600 DEG C of roastings 4 hours, obtains Modified Zeolite Y.Molecular sieve volume property is as shown in table 1.
Embodiment 5
（1）By Y-2 types molecular sieve under the conditions of 420 DEG C roasting 10 hours, then unsaturated olefin is contacted with the Y type molecular sieve after roasting, in nitrogen atmosphere, the roasting under the conditions of 490 DEG C carries out carbon deposit reaction in 6 hours, obtains the Y type molecular sieve after carbon deposit；
（2）Under agitation, the Y type molecular sieve after carbon deposit is added in the pressure vessel of the sodium hydroxide solution of 0.65mol/L, the addition of molecular sieve is 1 with the mass ratio of water in solution:11, and system is closed, nitrogen control system pressure is passed through for 0.8MPa, 65 DEG C are then heated to, constant temperature is processed 1.5 hours, release, suction filtration to pH value are less than 9, it is dried under the conditions of 120 DEG C 12 hours, finally in 510 DEG C of roastings 6 hours, obtains Modified Zeolite Y.Molecular sieve volume property is as shown in table 1.
Comparative example 1
With embodiment 1, simply course of reaction is carried out in atmospheric conditions.
Comparative example 2
With embodiment 1, simply directly high pressure alkali process are carried out using Y-1 molecular sieves.
The application of catalyst carrier：
Ion exchange：Molecular sieve prepared by embodiment 1 and comparative example 1 is washed to neutrality, drying, then under 80 DEG C of water bath conditions, with 1mol/L ammonium nitrate ion exchange is carried out, make sodium oxide content less than 0.5%, washing, drying, in 550 DEG C of roasting 3h, obtains hydrogen type molecular sieve.
Hydro-thermal process：By hydrogen type molecular sieve, respectively constant temperature processes 2h under the conditions of hydrothermal temperature is for 580 DEG C, obtains the molecular sieve after hydro-thermal process.
Catalyst preparation：Alumina powder, amorphous silicon aluminium, modified molecular screen powder are well mixed, acid solution is subsequently adding, aftershaping is fully rolled, are then dried 8 hours under the conditions of 100 DEG C, finally roasting 8 hours under the conditions of 600 DEG C, obtain catalyst carrier；The catalyst carrier that the metal impregnation solution impregnation of W and Ni is obtained is prepared, is then dried 6 hours under the conditions of 120 DEG C, finally roasting 6 hours under the conditions of 470 DEG C, obtain hydrocracking catalyst.Catalyst property such as table 2.
Evaluating catalyst condition：Evaluating apparatus are carried out using 200m1 small hydrogenation devices, and presulfurization is carried out to catalyst before activity rating.Evaluate the raw materials used oil nature of catalyst activity and reaction process condition is shown in Table 3 and table 4, catalyst reaction performance comparison the results are shown in Table 5.When evaluating catalyst, feedstock oil first passes through Hydrobon catalyst bed and then immediately proceeds to hydrocracking catalyst bed, and the organic nitrogen content controlled when Hydrobon catalyst bed in feedstock oil is less than 10ppm.
The physico-chemical property of the Y type molecular sieve of table 1.
The composition of the catalyst of table 2.
The process conditions of table 3.
The feedstock property of table 4.
The catalyst reaction performance of table 5.
| Catalyst | Catalyst 1 | Catalyst 2 | Catalyst 3 |
| Reaction temperature, DEG C | 383 | 376 | 379 |
| Two ring above naphthene contents, wt% | 28 | 22 | 25 |
| BMCI values | 12.5 | 9.6 | 11.2 |
Hydrocracking reaction result shows that compared with its other molecular sieve, when conversion ratio is identical, reaction temperature is low 4 ~ 7 DEG C, and the BMCI values of tail oil product and two ring above naphthene contents are lower for the molecular sieve of the present invention.Illustrate the active sites accessibility of molecular sieve prepared by the inventive method more preferably, be conducive to the hydrogenation open loop of polycyclic aromatic hydrocarbon so that naphthene content more than the BMCI values and two rings of hydrocracked product is lower.
Claims (9)
1. a kind of method of modifying of Y type molecular sieve, it is characterised in that including following content：（1）Y type molecular sieve is carried out into high-temperature roasting, then unsaturated olefin is contacted with the Y type molecular sieve after roasting, roasting carbon deposit reaction is carried out in an oxygen-free atmosphere；（2）Under agitation, the Y type molecular sieve after carbon deposit is added in the pressure vessel of sodium hydroxide solution, and system is closed, 0.2 ~ 0.8MPa is boosted to, 50 ~ 90 DEG C are then heated to, constant temperature is processed 0.5 ~ 3 hour, release, suction filtration, drying and roasting, obtain Modified Zeolite Y.
2. according to the method for modifying described in claim 1, it is characterised in that：Step（1）The Y type molecular sieve of middle addition is Hydrogen, and silica/alumina molar ratio is 10 ~ 55；Specific surface area is 650 ~ 950m2/g。
3. according to the method for modifying described in claim 1, it is characterised in that：Step（1）Described high-temperature roasting temperature is 350 ~ 650 DEG C, and the time is 1 ~ 12 hour.
4. according to the method for modifying described in claim 1, it is characterised in that：Step（1）Described oxygen-free atmosphere is one or more in nitrogen or inert gas.
5. according to the method for modifying described in claim 1, it is characterised in that：Step（1）The temperature of described roasting carbon deposit reaction is 450 ~ 650 DEG C, and the time is 1 ~ 8 hour.
6. according to the method for modifying described in claim 1, it is characterised in that：Step（1）Described step（2）The addition of the Y type molecular sieve after the carbon deposit is 1 with the mass ratio of sodium hydroxide solution:5~1：20；Concentration of sodium hydroxide solution is 0.35 ~ 1.30mol/L.
7. according to the method for modifying described in claim 1, it is characterised in that：Step（2）Middle drying condition is：It is dried 6 ~ 24 hours under the conditions of 80 ~ 120 DEG C.
8. according to the method for modifying described in claim 1, it is characterised in that：Step（2）Middle roasting condition is：Roasting 2 ~ 8 hours under the conditions of 450 ~ 650 DEG C.
9. the Y type molecular sieve for preparing according to the method described in claim 1 ~ 8 any claim, it is characterised in that：With following property：Total pore volume is 0.66 ~ 1.10ml/g, and mesoporous pore volume is 0.55 ~ 1.05ml/g, and mesoporous pore volume accounts for the 55 ~ 92% of Y type molecular sieve total pore volume, and silica/alumina molar ratio is 8 ~ 35 in molecular sieve, and specific surface area is 680 ~ 950m2/g。
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