CN108455625A - A kind of Modified Zeolite Y of high stability and preparation method thereof - Google Patents
A kind of Modified Zeolite Y of high stability and preparation method thereof Download PDFInfo
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- CN108455625A CN108455625A CN201710093436.3A CN201710093436A CN108455625A CN 108455625 A CN108455625 A CN 108455625A CN 201710093436 A CN201710093436 A CN 201710093436A CN 108455625 A CN108455625 A CN 108455625A
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910001868 water Inorganic materials 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000011148 porous material Substances 0.000 claims abstract description 27
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 14
- 238000005342 ion exchange Methods 0.000 claims abstract description 13
- 239000004411 aluminium Substances 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 7
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 97
- 239000002808 molecular sieve Substances 0.000 claims description 96
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 54
- 150000002910 rare earth metals Chemical class 0.000 claims description 31
- 230000032683 aging Effects 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 26
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- -1 rare-earth salts Chemical group 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 230000014759 maintenance of location Effects 0.000 claims description 12
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910003910 SiCl4 Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000013459 approach Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 16
- 239000000295 fuel oil Substances 0.000 abstract description 13
- 239000000571 coke Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003502 gasoline Substances 0.000 abstract description 7
- 239000010457 zeolite Substances 0.000 description 36
- 229910021536 Zeolite Inorganic materials 0.000 description 34
- 239000003054 catalyst Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 238000004523 catalytic cracking Methods 0.000 description 11
- 238000000634 powder X-ray diffraction Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 238000003483 aging Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000009834 vaporization Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000004846 x-ray emission Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910001122 Mischmetal Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 241000772415 Neovison vison Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 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
- 230000008676 import Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- HHFKUQZPNITQLU-UHFFFAOYSA-N n-(3,5-dibromo-4-hydroxyphenyl)-4-hydroxy-3,5-dimethylbenzamide Chemical compound CC1=C(O)C(C)=CC(C(=O)NC=2C=C(Br)C(O)=C(Br)C=2)=C1 HHFKUQZPNITQLU-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
- 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
- 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
-
- 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
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
-
- 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
- C01P2006/12—Surface area
-
- 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
- C01P2006/12—Surface area
- C01P2006/13—Surface area thermal stability thereof at high temperatures
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A kind of Modified Zeolite Y of high stability and preparation method thereof, the RE of the Modified Zeolite Y2O3Content is 5~12 weight %, Na2O content is 0.1~0.7 weight %, total pore volume is 0.33~0.39mL/g, the pore volume of the second hole of 2~100nm accounts for the 10~25% of total pore volume, lattice constant is 2.440~2.455nm, non-framework aluminum content accounts for total aluminium content ratio and is not higher than 20%, lattice collapse temperature is not less than 1050 DEG C, and the ratio of the B acid amount measured at 200 DEG C with pyridine adsorption infrared method and L acid amounts is not less than 2.50.The preparation method includes the steps that ion exchange, modification and is reacted with silicon tetrachloride under the conditions of certain temperature and water vapour.The Modified Zeolite Y has higher heavy oil conversion activity and lower coke selectivity, has higher yield of gasoline, yield of liquefied gas, yield of light oil and total liquid yield.
Description
Technical field
The present invention relates to a kind of Modified Zeolite Ys of high stability and preparation method thereof, are furtherly related to a kind of use
In the Y type molecular sieve of high stability and preparation method thereof of heavy oil catalytic cracking.
Background technology
Currently, industrially producing Y-type high-Si zeolite mainly uses hydro-thermal method, NaY zeolite is subjected to multiple rare earth ion friendship
It changes and is roasted with multiple high temp, the Y-type high-Si zeolite containing rare earth can be prepared, this is also that prepare Y-type high-Si zeolite the most conventional
Method, but hydro-thermal method prepares rare-earth type high-silicon gamma-zeolite and is disadvantageous in that：Due to excessively harsh hydrothermal conditions
The structure of zeolite can be destroyed, the very high y-type zeolite of silica alumina ratio cannot be obtained；Though the generation of the outer aluminium of skeleton is to the stabilization of raising zeolite
Property and form the outer aluminium of the beneficial but excessive skeleton in new acid site and reduce the selectivity of zeolite, in addition, many de- in zeolite
Aluminium hole cannot be filled by the silicon migrated out on skeleton in time, often result in the lattice defect of zeolite, the crystal retention of zeolite
Relatively low, therefore, the heat and hydrothermal stability for the Y type zeolites containing rare-earth and high content of silicon that hydro-thermal method is prepared are poor, show that its lattice collapses
Temperature of collapsing is low, its crystallinity retention rate and specific surface area retention rate are low after hydrothermal aging, and selectivity is poor.
In United States Patent (USP) US4584287 and US4429053, NaY zeolite is first then subjected to water steaming with rare earth ion exchanged
Gas disposal, the aluminium of zeolite removes relatively difficult, structure cell of the zeolite before steam treatment during the method steam treatment
Parameter increases to 2.465~2.475nm, and after handling is 2.420~2.464nm, and it is higher to reduce cell parameter required temperature
(593~733 DEG C).The heavy oil cracking activity of zeolite is not high, and coke selectivity is bad.
In the method that United States Patent (USP) US5340957 and US5206194 are provided, the SiO of raw material NaY zeolite2/Al2O3Than for
6.0, this method is also after NaY is carried out rare earth exchanged, then to carry out hydro-thermal process, equally exist aforesaid U.S. Patent
The shortcomings that US4584287 and US4429053.
Gas chemistry method is the important side of another kind for preparing silica-rich zeolite that Beyer and Mankui were reported first in 1980
Method.Gas chemistry method generally uses the SiCl under nitrogen protection4It is reacted at a certain temperature with anhydrous NaY zeolite.The U.S.
Patent US4273753, US4438178, Chinese patent CN1382525A, CN1194941A, CN1683244A disclose utilization
SiCl4The method of gas chemistry dealuminzation ultrastable.But pore structure study shows gas phase super stable molecular sieve without two
Grade hole.
Invention content
One of the technical problem to be solved in the present invention is to provide a kind of high stable suitable for mink cell focus catalyzed cracking processing
Property Y type molecular sieve (Y type molecular sieve is also referred to as y-type zeolite), which has higher heavy oil cracking activity and more
Good coke selectivity.The invention solves second technical problem be to provide a kind of preparation side of the Modified Zeolite Y
Method.
The present invention provides a kind of Modified Zeolite Y, and the rare earth oxide content of the modified molecular screen is 5~12 weight %,
Sodium oxide content is 0.1~0.7 weight %, and total pore volume is 0.33~0.39mL/g, which is 2nm
The percentage that the pore volume of the second hole of~100nm accounts for the Modified Zeolite Y total pore volume is 10%~25%, lattice constant
For 2.440nm~2.455nm, framework si-al ratio (SiO2/Al2O3Molar ratio) be：7.3~14.0, non-framework aluminum contains in molecular sieve
The percentage that amount accounts for total aluminium content is not higher than 20%, and lattice collapse temperature is not less than 1050 DEG C, also, with pyridine adsorption infrared method
B acid amount and the ratio of L acid amounts are not less than 2.50 in the Modified Zeolite Y total acid content measured at 200 DEG C.
Modified Zeolite Y provided by the invention, lattice collapse temperature are not less than 1050 DEG C, it is preferred that the molecular sieve is brilliant
1055 DEG C~1080 DEG C, for example, 1057~1075 DEG C of lattice collapse temperature.
Modified Zeolite Y provided by the invention, the modification Y types measured at 200 DEG C with pyridine adsorption infrared method point
It is, for example, 2.7~3.3 that the ratio of B acid amount and L acid amounts, which is preferably 2.6~4.0, in son sieve total acid content.
Modified Zeolite Y provided by the invention, lattice constant be 2.440nm~2.455nm be, for example, 2.442~
2.450nm。
Modified Zeolite Y provided by the invention is high-Si Y-type molecular sieve, framework si-al ratio (SiO2/Al2O3Mole
Than) it is 7.3~14.0, for example,：8.5~12.6.
Modified Zeolite Y provided by the invention, in molecular sieve non-framework aluminum content account for total aluminium content percentage it is not high
In 20%, for example, 13~19 weight %.
Modified Zeolite Y provided by the invention, aging 17 is small under 800 DEG C, normal pressure, 100 volume % water vapour atmospheres
When after crystal retention be 38% or more be, for example, 38~48% or 39~45%.The normal pressure is 1atm.
Modified Zeolite Y provided by the invention, relative crystallinity are not less than 60%, it is preferred that provided by the invention
The relative crystallinity of the Modified Zeolite Y is 60~70%, for example, 60~66%.
Modified Zeolite Y provided by the invention, a kind of embodiment, specific surface area are 620~670m2/ g is, for example,
630~660m2/g。
Modified Zeolite Y provided by the invention, it is preferred that total pore volume be 0.35~0.39mL/g be, for example, 0.36~
0.375mL/g。
Modified Zeolite Y provided by the invention, aperture (referring to diameter) are the pore volume of the second hole of 2.0nm~100nm
The percentage for accounting for total pore volume is 10%~25%, preferably 15~21%.
A kind of embodiment, the micro pore volume of Modified Zeolite Y provided by the invention be 0.25~0.35mL/g for example
For 0.26~0.32mL/g.
Modified Zeolite Y provided by the invention, containing rare earth element, with RE in the Modified Zeolite Y2O3The oxygen of meter
It is preferably 5.5~10 weight % to change content of rare earth as 5~12 weight %.
Modified Zeolite Y provided by the invention, sodium oxide content are no more than 0.7%, can be 0.3~0.7 weight %
For example, 0.35~0.60 weight % or 0.4~0.55 weight %.
The present invention provides a kind of Modified Zeolite Y preparation method, and this approach includes the following steps:
(1) NaY molecular sieve is contacted with earth solution and carries out ion-exchange reactions, be filtered, washed, obtain sodium oxide content
The Y type molecular sieve of the conventional unit cell dimension containing rare earth reduced；Wherein earth solution is also referred to as rare-earth salt solution；
(2) Y type molecular sieve for the conventional unit cell dimension containing rare earth that the sodium oxide content reduces is modified processing,
Optionally drying, obtains the Y type molecular sieve of lattice constant reduction, and the modification is dilute for containing of reducing the sodium oxide content
The Y type molecular sieve of the conventional unit cell dimension of soil is in 350~480 DEG C of temperature, the atmosphere (also referred to as 30 containing 30~90 volume % water vapours
~90 volume % water vapour atmospheres or 30~90% water vapours) under roast 4.5~7 hours；
(3) the Y type molecular sieve sample and SiCl reduced the lattice constant4The item that gas is 200~650 DEG C in temperature
Haptoreaction under part, wherein SiCl4：The weight ratio for the Y type molecular sieve that the lattice constant that the step of in terms of butt (2) obtains reduces
=0.1~0.7：1, in 10 minutes to 5 hours reaction time, then washed, filtering obtains Modified Zeolite Y.Wherein, institute
The water content for stating the Y type molecular sieve sample of lattice constant reduction is preferably more than 1 weight %；If step (2) modification obtains
To Y type molecular sieve sample in (in the Y type molecular sieve sample that roasting obtains) water content be no more than 1 weight %, can directly use
The reaction is carried out in being contacted with silicon tetrachloride, if water content is more than 1 in the Y type molecular sieve sample that step (2) roasting obtains
Weight %, the Y type molecular sieve sample that the lattice constant that step (2) roasting obtains reduces, which is dried, makes its water content be less than
1 weight %.
Modified Zeolite Y provided by the invention, heat and hydrothermal stability are high, are used for heavy oil catalytic cracking, more existing Y types
Molecular sieve have higher heavy oil conversion activity and lower coke selectivity, have higher yield of gasoline, yield of liquefied gas,
Yield of light oil and total liquid yield.
Property Modified Zeolite Y preparation method provided by the invention, can prepare high-crystallinity, high thermal stability and Gao Shui
The high-Si Y-type molecular sieve with certain two level pore structure of thermal stability, aluminium is evenly distributed in the molecular sieve, non-framework aluminum content
Few, which is used for heavy oil conversion, and coke selectivity is good, and heavy oil cracking activity is high, can improve molecular sieve and be used for
Yield of gasoline, yield of liquefied gas when heavy oil conversion and total liquid yield.
Modified Zeolite Y provided by the invention may be used as the active component of catalytic cracking catalyst, for heavy oil or
Poor oil converts；There is stronger heavy oil conversion performance by the catalytic cracking catalyst of active component of this molecular sieve, it is higher
Stability, preferable coke selectivity and higher yield of light oil and yield of gasoline.
Specific implementation mode
Modified Zeolite Y provided by the invention, a kind of embodiment, rare earth oxide content is 5~12 weight %, excellent
5.5~10 weight % are selected as, sodium oxide content is 0.1~0.7 weight %, and preferably 0.3~0.7 weight %, total pore volume is
0.33~0.39mL/g, the percentage that the pore volume of the second hole that aperture is 2nm~100nm accounts for total pore volume is 10%~
25%, preferably 15%~21%, lattice constant are 2.440nm~2.455nm, framework si-al ratio (SiO2/Al2O3Molar ratio) be：
7.3~14.0, non-framework aluminum content accounts for the percentage of total aluminium content and is not higher than 20%, preferably 13~19 in molecular sieve, relatively
Crystallinity is not less than 60%, and lattice collapse temperature is 1055 DEG C~1080 DEG C, also, with pyridine adsorption infrared method at 200 DEG C
B acid amount and the ratio of L acid amounts are not less than 2.50, preferably 2.6~4.0 in the Modified Zeolite Y total acid content measured.
Modified Zeolite Y provided by the invention, preparation process include Y type molecular sieve is contacted with silicon tetrachloride into
The step of row dealumination complement silicon reacts.
In Modified Zeolite Y preparation method provided by the invention, in step (1) by NaY molecular sieve and earth solution into
Row ion-exchange reactions, to obtain the Y type molecular sieve of the conventional unit cell dimension containing rare earth of sodium oxide content reduction.The NaY
Molecular sieve, can be commercially available or prepares, a kind of embodiment according to existing method, and the NaY molecular sieve lattice constant is 2.465
~2.472nm, framework si-al ratio (SiO2/Al2O3Molar ratio) it is 4.5~5.2, it is, for example, 85 that relative crystallinity, which is 85% or more,
~95%, sodium oxide content is 13.0~13.8 weight %.NaY molecular sieve described in step (1) carries out ion with earth solution
Exchange reaction, it is, for example, 65~95 DEG C that exchange temperature, which is preferably 15~95 DEG C, and swap time is preferably 30~120 minutes such as 45
~90 minutes.NaY molecular sieve (in terms of butt):Rare-earth salts is (with RE2O3Meter):H2O=1:0.01~0.18:5~15 weight ratios.
A kind of embodiment, the NaY molecular sieve carries out ion-exchange reactions with earth solution and includes, according to NaY molecular sieve:Rare earth
Salt:H2O=1:0.01~0.18:NaY molecular sieve (also referred to as NaY zeolite), rare-earth salts and water are formed mixing by 5~15 weight ratio
Object carries out exchanging for rare earth ions and sodium ion, institute for 30~120 minutes in 15~95 DEG C of preferred stirrings of such as 65~95 DEG C stirrings
Or mixtures thereof water stated such as decationized Y sieve water, deionized water.NaY molecular sieve, rare-earth salts and water are formed into mixture, it can be with
NaY molecular sieve and water are formed into slurries, the aqueous solution of rare-earth salts and/or rare-earth salts is then added in the slurries, it is described
Earth solution be rare-earth salts solution, the rare-earth salts is preferably rare earth chloride and/or nitric acid rare earth.The rare earth example
As one or more in La, Ce, Pr, Nd and mischmetal, it is preferred that in the mischmetal containing La, Ce, Pr and
It is one or more in Nd, or also contain at least one of the rare earth in addition to La, Ce, Pr and Nd.Washing described in step (1)
It washs, it is therefore an objective to the sodium ion being swapped out is washed away, it is, for example, possible to use deionized water or decationized Y sieve water washing.It is preferred that step
(1) content of rare earth of the Y type molecular sieve for the conventional unit cell dimension containing rare earth that the sodium oxide content obtained reduces is with RE2O3It is calculated as
5.5~14 weight % are, for example, 7~14 weight or 5.5~12 weight %, and sodium oxide content is, for example, 5.5 no more than 9 weight %
~8.5 weight % or 5.5~7.5 weight %, lattice constant are 2.465nm~2.472nm.
In Modified Zeolite Y preparation method provided by the invention, by the conventional unit cell dimension containing rare earth in step (2)
Y type molecular sieve is roasted 4.5~7 hours at 350~480 DEG C of temperature, 30~90 volume % water vapour atmospheres and is handled, preferably
, calcination temperature described in step (2) is 380~460 DEG C, and calcination atmosphere is 40~80 volume % water vapour atmospheres, when roasting
Between be 5~6 hours.Contain 30~90 volume % vapor in the water vapour atmosphere, also contains other gases, such as empty
It is one or more in gas, helium or nitrogen.The Y type molecular sieve that lattice constant described in step (2) reduces, lattice constant
For 2.450nm~2.462nm.It is preferred that also the molecular sieve that roasting obtains is dried in step (2), so that the structure cell is normal
Water content in the Y type molecular sieve that number reduces is preferably more than 1 weight %.
In Modified Zeolite Y preparation method provided by the invention, in step (3), SiCl4：Y-type zeolite (in terms of butt)
Weight ratio be preferably 0.3~0.6：1, the temperature of the reaction is preferably 350~500 DEG C, the washing methods described in step (3)
Conventional washing methods may be used, such as decationized Y sieve water or deionized water washing can be washed with water, it is therefore an objective to remove zeolite
The Na of middle remaining+, Cl-And Al3+Waiting soluble by-products, such as wash conditions can be：The weight ratio of washings and molecular sieve
Can be 5~20：1, usual molecular sieve：H2Weight ratio=1 O:6~15, pH value is preferably 2.5~5.0, wash temperature be 30~
60℃.Preferably, the washing, make to detect in the cleaning solution after washing do not go on a tour from Na+, Cl-And Al3+Plasma, usually
Na in sieve sample after washing+, Cl-And Al3+The respective content of ion is no more than 0.05 weight %.
The preparation method of Modified Zeolite Y provided by the invention, a kind of embodiment include the following steps：
(1) NaY molecular sieve (also referred to as NaY zeolite) is subjected to ion-exchange reactions with earth solution, filtered, washing obtains
The Y type molecular sieve for the conventional unit cell dimension containing rare earth that sodium oxide content reduces；The ion exchange usually stirring, temperature be
It is exchanged 30~120 minutes under conditions of 15~95 DEG C preferably 65~95 DEG C；
(2) Y type molecular sieve for the conventional unit cell dimension containing rare earth for reducing the sodium oxide content temperature 350~
480 DEG C, contains and roasted 4.5~7 hours under the atmosphere of 30~90 volume % water vapours, it is dry, water content is obtained less than 1 weight %'s
The Y type molecular sieve that lattice constant reduces；The lattice constant for the Y type molecular sieve that the lattice constant reduces be 2.450nm~
2.462nm；
(3) the Y type molecular sieve sample that the lattice constant by the water content less than 1 weight % reduces and heated vaporization
SiCl4Gas contacts, wherein SiCl4：The Y type molecular sieve (in terms of butt) that lattice constant of the water content less than 1 weight % reduces
Weight ratio=0.1~0.7：1, haptoreaction 10 minutes to 5 hours, washed and mistake under conditions of temperature is 200~650 DEG C
Filter, obtains Modified Zeolite Y provided by the invention.
The following examples will be further described the present invention, but not thereby limiting the invention.
In embodiment and in comparative example, NaY molecular sieve (also referred to as NaY zeolite) is Sinopec catalyst Co., Ltd Shandong
Branch company provides, and sodium oxide content is 13.5 weight %, framework si-al ratio (SiO2/Al2O3Molar ratio)=4.6, lattice constant is
2.470nm, relative crystallinity 90%；Rare earth chloride and the chemically pure reagent that nitric acid rare earth is Beijing Chemical Plant's production.It is quasi- thin
Diaspore is that Shandong Aluminum Plant produces industrial products, 61 weight % of solid content；Kaolin is the production of Suzhou China Kaolin Co., Ltd
The special kaolin of Cracking catalyst, 76 weight % of solid content；Aluminum sol is by asphalt in Shenli Refinery of Sinopec catalyst Co., Ltd
It provides, wherein 21 weight % of alumina content.
Analysis method：In each comparative example and embodiment, the constituent content of zeolite is by x-ray fluorescence spectrometry；Boiling
Lattice constant, the relative crystallinity of stone use the standard side RIPP145-90, RIPP146-90 by x-ray powder diffraction (XRD)
Method (see《Petrochemical analysis method》(RIPP test methods) Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes) it measures, boiling
The framework si-al ratio of stone is calculated by following formula and is obtained：SiO2/Al2O3=(2.5858-a0)×2/(a0- 2.4191)] wherein, a0For crystalline substance
Born of the same parents' constant, unit nm；Total silica alumina ratio of zeolite is calculated according to Si and the Al constituent content of x-ray fluorescence spectrometry,
The framework si-al ratio measured by XRD methods can calculate the ratio of skeleton Al and total Al with the XRF total silica alumina ratios measured, and then calculate non-
The ratio of skeleton Al and total Al.Crystal structure collapse temperature is measured by differential thermal analysis (DTA).
In each comparative example and embodiment, the acid site type and its acid amount of molecular sieve are divided using the infrared method of pyridine adsorption
Analysis measures.Laboratory apparatus：The U.S. Bruker companies IFS113V types FT-IR (fourier-transform infrared) spectrometer.Use pyridine adsorption
Infrared method measures acid amount experimental method at 200 DEG C：By sample self-supporting tabletting, it is placed in close in the pond in situ of infrared spectrometer
Envelope.400 DEG C are warming up to, and is evacuated to 10-3Pa, constant temperature 2h, the gas molecule of removing sample absorption.It is down to room temperature, imports pressure
Power is that 2.67Pa pyridine steams keep adsorption equilibrium 30min.200 DEG C are then heated to, is evacuated to 10-330min is desorbed under Pa,
It is down to room temperature and takes the photograph spectrum, scan wave-number range：1400 cm-1~1700 cm-1, it is red to obtain the pyridine adsorption that sample is desorbed through 200 DEG C
External spectrum figure.According to 1540 cm in Pyridine adsorption IR spectra figure-1With 1450 cm-1The intensity of feature adsorption peak, obtains molecule
In sieve alwaysThe relative quantity in acid site (acid sites B) and the acid sites Lewis (acid sites L).
In each comparative example and embodiment, wherein the assay method of described two level pore volume is as follows：According to RIPP151-90
Standard method《Petrochemical egineering analysis method (RIPP test methods)》(Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes) root
The total pore volume of molecular sieve is determined according to adsorption isotherm, then determines molecular sieve from adsorption isotherm according to T graphing methods
Total pore volume is subtracted micro pore volume and obtains two level pore volume by micro pore volume,
Chemical reagent used is not specifically specified in comparative example and embodiment, and specification is that chemistry is pure.
Embodiment 1
Taking 2000 grams of NaY molecular sieves to be added to stirring in 20 liters of decationized Y sieve aqueous solutions (in terms of butt) keeps its mixing equal
It is even, the RE (NO of 600ml are added3)3(earth solution concentration is with RE for solution2O3It is calculated as 319g/L), stirring is warming up to 90~95 DEG C
It is kept for 1 hour, is then filtered, washed, for filter cake in 120 DEG C of dryings, it is 2.471nm, 7.0 weight of sodium oxide content to obtain lattice constant
Measure %, with RE2O3Count the Y type molecular sieve of content of rare earth 8.8 weight %, later in 390 DEG C of temperature, containing 50 volume % water vapours and
It is roasted 6 hours under the atmosphere of 50 volume % air, obtains the Y type molecular sieve that lattice constant is 2.455nm and be dried later
Processing makes its water content be less than 1 weight %, then according to SiCl4：Y type molecular sieve (butt meter)=0.5：1 weight ratio is led to
Enter the SiCl of heated vaporization4Gas reacts 2 hours, under conditions of temperature is 400 DEG C later, with 20 liters of decationized Y sieve water
Washing, then filters, obtains Modified Zeolite Y provided by the invention, be denoted as SZ1, physico-chemical property is listed in Table 1 below, by SZ1
In naked state after 800 DEG C, 1atm, 100% vapor aging 17 hours, with point before and after the method analysis SZ1 agings of XRD
The relative crystallinity of son sieve simultaneously calculates the opposite crystal retention after aging, the results are shown in Table 2, wherein：
Embodiment 2
Taking 2000 grams of NaY molecular sieves to be added to stirring in 25 liters of decationized Y sieve aqueous solutions (in terms of butt) keeps its mixing equal
It is even, the RECl of 800ml is added3Solution is (with RE2O3The solution concentration of meter is：319g/L), it stirs, is warming up to 90~95 DEG C and keeps 1
Hour, it is then filtered, washed, filter cake obtains that lattice constant is 2.471nm, sodium oxide content is 5.5 weights in 120 DEG C of dryings
Measure %, with RE2O3The Y type molecular sieve that content of rare earth is 11.3 weight % is counted, is roasted at 450 DEG C of temperature, 80% water vapour later
It 5.5 hours, obtains the Y type molecular sieve that lattice constant is 2.461nm and processing is dried later, its water content is made to be less than 1 weight
% is measured, then according to SiCl4：Y-type zeolite=0.6：1 weight ratio is passed through the SiCl of heated vaporization4Gas is in temperature
It under conditions of 480 DEG C, reacts 1.5 hours, later, with 20 liters of decationized Y sieve water washings, then filters, obtain modified Y type molecules
Sieve, is denoted as SZ2.Its physico-chemical property is listed in Table 1 below, by SZ2 in naked state through 800 DEG C, 100% vapor aging in 17 hours
Afterwards, the crystallinity of the zeolite before and after analyzing SZ2 agings with the method for XRD simultaneously calculates the opposite crystal retention after aging,
It the results are shown in Table 2.
Embodiment 3
Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 22 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and adds
Enter the RECl of 570ml3Solution is (with RE2O3A concentration of 319g/L of earth solution of meter), stirring is warming up to 90~95 DEG C of holdings and stirs
It mixes 1 hour, is then filtered, washed, filter cake obtains that lattice constant is 2.471nm, sodium oxide content is 7.5 weights in 120 DEG C of dryings
Measure %, with RE2O3The Y type molecular sieve that content of rare earth is 8.5 weight % is counted, later at 470 DEG C of temperature, 70 volume % water vapours
Roasting 5 hours obtains the Y type molecular sieve that lattice constant is 2.458nm and processing is dried later, its water content is made to be less than 1
Weight %, then according to SiCl4：Y-type zeolite=0.4：1 weight ratio is passed through the SiCl of heated vaporization4Gas is in temperature
Under conditions of 500 DEG C, reacts 1 hour, later, with 20 liters of decationized Y sieve water washings, then filters, obtain Modified Zeolite Y,
It is denoted as SZ3.Its physico-chemical property is listed in Table 1 below, and by SZ3 in naked state through 800 DEG C, after 100% vapor aging in 17 hours, is used
The crystallinity of zeolite before and after the method analysis SZ3 agings of XRD simultaneously calculates the opposite crystal retention after aging, the results are shown in Table
2。
Comparative example 1
Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 20 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and adds
Enter 1000 grams of (NH4)2SO4, stirring, be warming up to 90~95 DEG C keep 1 hour, be then filtered, washed, filter cake in 120 DEG C it is dry it
Hydrothermal modification treatment (650 DEG C of temperature, 100% water vapour under roast 5 hours) is carried out afterwards, later, is added to 20 liters of decationized Y sieves
Stirring makes it be uniformly mixed in aqueous solution, and 1000 grams of (NH are added4)2SO4, stirring, be warming up to 90~95 DEG C keep 1 hour, then
It being filtered, washed, second of hydrothermal modification treatment is carried out after filter cake is dry in 120 DEG C, hydrothermal conditions are 650 DEG C of temperature,
It is roasted 5 hours under 100% water vapour, obtaining ion exchange twice, the super steady hydro-thermal superstable gamma-type without rare earth of hydro-thermal divides twice
Son sieve, is denoted as DZ1.Its physico-chemical property is listed in Table 1 below, by DZ1 in naked state through 800 DEG C, 100% vapor aging in 17 hours
Afterwards, the crystallinity of the zeolite before and after analyzing DZ1 agings with the method for XRD simultaneously calculates the opposite crystal retention after aging,
It the results are shown in Table 2.
Comparative example 2
Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 20 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and adds
Enter 1000 grams of (NH4)2SO4, stirring, be warming up to 90~95 DEG C keep 1 hour, be then filtered, washed, filter cake in 120 DEG C it is dry it
After carry out hydrothermal modification treatment, hydrothermal modification treatment is roasted 5 hours under 650 DEG C of temperature, 100% water vapour, later, is added to
Stirring makes it be uniformly mixed in 20 liters of decationized Y sieve aqueous solutions, and the RE (NO of 200ml are added3)3Solution is (with RE2O3Count earth solution
It is a concentration of：319g/L) and 900 grams of (NH4)2SO4, stir, be warming up to 90~95 DEG C and kept for 1 hour, is then filtered, washed, filter cake
In 120 DEG C it is dry after carry out second hydrothermal modification treatment (650 DEG C of temperature, 100% water vapour under roast 5 hours), obtain
Ion exchange super steady hydro-thermal super-stable Y molecular sieves containing rare earth of hydro-thermal twice twice, are denoted as DZ2.Its physico-chemical property is listed in table 1
In, by DZ2 in naked state through 800 DEG C, after 100% vapor aging in 17 hours, before analyzing DZ2 agings with the method for XRD
The crystallinity of zeolite afterwards simultaneously calculates the opposite crystal retention after aging, the results are shown in Table 2.
Comparative example 3
Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 20 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and adds
Enter the RE (NO of 650ml3)3Solution (319g/L), stirring are warming up to 90~95 DEG C and are kept for 1 hour, be then filtered, washed, later
The super steady modification of gas phase is carried out, molecular sieve drying process is first carried out, so that its water content is less than 1 heavy %, then according to SiCl4：Y
Type zeolite=0.4：1 weight ratio is passed through the SiCl of heated vaporization4Gas, under conditions of temperature is 580 DEG C, reaction 1.5
Hour, it later, with 20 liters of decationized Y sieve water washings, then filters, obtains the high silicon super-stable Y molecular sieves of gas phase, be denoted as DZ3.Its
Physico-chemical property is listed in Table 1 below, by DZ3 in naked state through 800 DEG C, after 100% vapor aging in 17 hours, with the method for XRD
It analyzes the crystallinity of the zeolite before and after DZ3 agings and calculates the opposite crystal retention after aging, the results are shown in Table 2.
Embodiment 4~6
Embodiment 4~6 illustrates the catalytic cracking activity and its stability of Modified Zeolite Y provided by the invention.
Modified Zeolite Y SZ1, SZ2, SZ3 prepared by Examples 1 to 3 are prepared into catalyst, catalyst number respectively
It is followed successively by：SC1, SC2 and SC3.By catalyst after 800 DEG C, 4 hours or 17 hours 100% vapor agings, catalyst is evaluated
Light oil microactivity, evaluation result is listed in Table 3 below.
Method for preparing catalyst：
By the Modified Zeolite Y, kaolin, water, boehmite adhesive and Aluminum sol urging routinely
The preparation method of fluidized cracking catalysts forms slurries, spray drying is prepared into microspherical catalyst, wherein in terms of butt, it is obtained
Contain the 30 weight % of Modified Zeolite Y, 42 weight % of kaolin, 25 weight % of boehmite, aluminium in catalyst
3 weight % of colloidal sol.
Light oil microactivity evaluation method：
Using RIPP92-90 standard method (see《Petrochemical analysis method》(RIPP test methods) Yang Cui is surely equal to be compiled,
Science Press, nineteen ninety publish) evaluation sample light oil microactivity, catalyst loading 5.0g, reaction temperature 460
DEG C, feedstock oil is 235~337 DEG C of huge port light diesel fuels of boiling range, and product composition is calculated by gas chromatographic analysis according to product composition
Light oil microactivity.
Light oil microactivity (MA)=(gasoline production+gas yield+coke output for being less than 216 DEG C in product)/charging
Total amount × 100%.
Comparative example 4~6
Comparative example 4~6 illustrate comparative example 1~3 provide method prepare super-stable Y molecular sieves catalytic cracking activity and
Its stability.
Super-stable Y molecular sieves DZ1, the DZ2 for respectively preparing comparative example 1~3 according to the method for preparing catalyst of embodiment 4
And DZ3 and boehmite, kaolin, water and Aluminum sol mixing, spray drying are prepared into microspherical catalyst, the group of each catalyst
At same embodiment 4, the content of super-stable Y molecular sieves is 30 weight % in catalyst.Catalyst number is followed successively by：DC1、DC2
And DC3.By catalyst after 800 DEG C, 4 hours or 17 hours 100% vapor agings, its light oil microactivity is evaluated.Evaluation
Method is shown in embodiment 6, and evaluation result is listed in Table 3 below.
Embodiment 7~9
Embodiment 7~9 illustrates the catalytic cracking reaction performance of Modified Zeolite Y provided by the invention.
It is anti-in small fixed flowing bed after 100% vapor aging in 17 hours by SC1, SC2, SC3 catalyst through 800 DEG C
It answers and evaluates its catalytic cracking reaction performance on device (ACE), cracked gas and product oil are not collected by gas chromatographic analysis.Catalyst
Loading amount is 9g, 500 DEG C of reaction temperature, weight (hourly) space velocity (WHSV) 16h- 1, oil ratio (weight ratio) be shown in Table 5, ACE experiment raw material oiliness
Matter is shown in Table 4, and evaluation result is shown in Table 5.
Comparative example 7~9
Comparative example 7~9 illustrates the catalytic cracking reaction of ultrastable prepared by the method that comparative example 1~3 provides
Energy.
DC1, DC2 and DC3 catalyst are anti-in small fixed flowing bed after 100% vapor aging in 17 hours through 800 DEG C
It answers and evaluates its catalytic cracking reaction performance on device (ACE), evaluation method is shown in that embodiment 7, the feedstock property of ACE experiments are shown in Table 4, comment
The results are shown in Table 5 for valence.
Table 1
By table 1 as it can be seen that the Modified Zeolite Y of high stability provided by the invention, is provided simultaneously with following advantages：Sodium oxide molybdena
Content is low, and the non-framework aluminum content when sial of molecular sieve is relatively high is less, second hole 2.0nm~100nm hole bodies in molecular sieve
Product accounts for that total pore volume percentage is relatively high, also, B acid/L acid (the ratio between total B acid acid amounts and L acid acid amounts) is higher, brilliant in molecular sieve
The crystallinity value that the smaller content of rare earth of born of the same parents' constant measures when higher is higher, has high thermal stability.
Table 2
As shown in Table 2, Modified Zeolite Y provided by the invention passes through 800 DEG C under sieve sample naked state,
After harsh conditions aging in 17 hours, sample has higher opposite crystal retention, shows modified Y types provided by the invention point
Sub- sifter device has high hydrothermal stability.
Table 3
Table 4
Table 5
| Example number | Embodiment 7 | Embodiment 8 | Embodiment 9 | Comparative example 7 | Comparative example 8 | Comparative example 9 |
| Sample number into spectrum | SC1 | SC2 | SC3 | DC1 | DC2 | DC3 |
| Molecular sieve used | SZ1 | SZ2 | SZ3 | DZ1 | DZ2 | DZ3 |
| Oil ratio | 5 | 5 | 5 | 9 | 8 | 5 |
| Product distribution/weight % | ||||||
| Dry gas | 1.35 | 1.41 | 1.35 | 1.55 | 1.48 | 1.49 |
| Liquefied gas | 16.93 | 16.71 | 17.34 | 16.86 | 15.33 | 16.21 |
| Coke | 4.72 | 4.81 | 4.45 | 8.33 | 7.61 | 6.35 |
| Gasoline | 52.83 | 53.87 | 51.95 | 38.55 | 43.91 | 50.79 |
| Diesel oil | 16.96 | 16.71 | 17.28 | 20.17 | 19.25 | 16.88 |
| Heavy oil | 7.21 | 6.49 | 7.63 | 14.54 | 12.42 | 8.28 |
| It is total | 100 | 100 | 100 | 100 | 100 | 100 |
| Conversion ratio/weight % | 75.83 | 76.8 | 75.09 | 65.29 | 68.33 | 74.84 |
| Coke selectivity/weight % | 6.22 | 6.26 | 5.93 | 12.76 | 11.14 | 8.48 |
| Yield of light oil/weight % | 69.79 | 70.58 | 69.23 | 58.72 | 63.16 | 67.67 |
| Total liquid yield/weight % | 86.72 | 87.29 | 86.57 | 75.58 | 78.49 | 83.88 |
By the result listed by table 3 and table 5 as it can be seen that the catalytic cracking prepared as active component using molecular sieve provided by the invention
Catalyst has very high hydrothermal stability, has significantly lower coke selectivity, there is considerably higher liquid to receive, light oil
Yield is considerably higher, and yield of gasoline improves, heavy oil conversion activity higher.
Claims (17)
1. a kind of Modified Zeolite Y, which is characterized in that the rare earth oxide content of the Modified Zeolite Y is 5 weight %~12
Weight %, sodium oxide content are the 0.1 weight % of weight %~0.7, and total pore volume is 0.33mL/g~0.39mL/g, modification Y
The percentage that the pore volume for the second hole that the aperture of type molecular sieve is 2nm~100nm accounts for total pore volume is 10%~25%, structure cell
Constant is 2.440nm~2.455nm, and non-framework aluminum content accounts for the percentage of total aluminium content and is not higher than in the Modified Zeolite Y
20%, lattice collapse temperature is not less than 1050 DEG C, also, the modification Y types point measured at 200 DEG C with pyridine adsorption infrared method
B acid amount and the ratio of L acid amounts are not less than 2.50 in the total acid content of son sieve.
2. Modified Zeolite Y described in accordance with the claim 1, which is characterized in that aperture is 2nm in the Modified Zeolite Y
The percentage that the pore volume of the second hole of~100nm accounts for total pore volume is 15%~21%.
3. Modified Zeolite Y described in accordance with the claim 1, which is characterized in that non-framework aluminum contains in the Modified Zeolite Y
The percentage that amount accounts for total aluminium content is 13~19%, and framework si-al ratio is with SiO2/Al2O3Molar ratio computing is 7.3~14.
4. Modified Zeolite Y described in accordance with the claim 1, which is characterized in that the Modified Zeolite Y lattice collapse temperature
1055 DEG C~1080 DEG C.
5. Modified Zeolite Y described in accordance with the claim 1, which is characterized in that surveyed at 200 DEG C with pyridine adsorption infrared method
The ratio of B acid amount and L acid amounts is 2.6~4.0 in the fixed Modified Zeolite Y total acid content.
6. Modified Zeolite Y described in accordance with the claim 1, which is characterized in that 800 DEG C, normal pressure, 100% vapor gas
After atmosphere aging in 17 hours, it is, for example, 38~48% that the opposite crystal retention of the Modified Zeolite Y, which is 38% or more,.
7. Modified Zeolite Y described in accordance with the claim 1, which is characterized in that the relative crystallinity of the Modified Zeolite Y
It is 60~70%.
8. according to any Modified Zeolite Y of claim 1~7, which is characterized in that the oxygen of the Modified Zeolite Y
Change content of rare earth be 5.5~10 weight %, sodium oxide content be 0.3~0.7 weight %, lattice constant be 2.442~
2.450nm, framework si-al ratio are 8.5~12.6.
9. a kind of preparation method of Modified Zeolite Y, this approach includes the following steps：
(1) NaY molecular sieve is contacted with rare-earth salt solution and carries out ion-exchange reactions, be filtered, washed, optionally drying obtains oxygen
Change the Y type molecular sieve for the conventional unit cell dimension containing rare earth that sodium content reduces；
(2) Y type molecular sieve for the conventional unit cell dimension containing rare earth for reducing above-mentioned sodium oxide content 350~480 DEG C of temperature,
It is roasted 4.5~7 hours under 30~90 volume % water vapour atmospheres, optionally drying, obtains the Y type molecular sieve of lattice constant reduction；
(3) according to SiCl4：Y type molecular sieve=0.1~0.7 that the lattice constant in terms of butt reduces：1 weight ratio is by institute
Y type molecular sieve and the silicon tetrachloride gas haptoreaction of lattice constant reduction are stated, reaction temperature is 200 DEG C~650 DEG C, when reaction
Between be 10 minutes to 5 hours, washing and filtering, obtain Modified Zeolite Y.
10. according to the method described in claim 9, which is characterized in that sodium oxide content described in step (1) reduce containing rare earth
The Y type molecular sieve of conventional unit cell dimension, lattice constant are 2.465~2.472nm, and sodium oxide content is no more than 9.0 weight %.
11. according to the method described in claim 9, it is characterized in that, in step (1), what the sodium oxide content reduced contains dilute
In the Y type molecular sieve of the conventional unit cell dimension of soil, content of rare earth is with RE2O3It is calculated as 5.5~14 weight %, sodium oxide content is 4~
9 weight % are, for example, 5.5~8.5 weight %, and lattice constant is 2.465nm~2.472nm.
12. according to the method described in claim 9, it is characterized in that, step (1) is described by NaY molecular sieve and rare-earth salt solution
Contact carries out ion-exchange reactions, according to NaY molecular sieve：Rare-earth salts：H2O=1：0.01~0.18：5~15 weight ratio will
NaY molecular sieve, rare-earth salts and water form mixture, stirring.
13. the method according to claim 9 or 12, which is characterized in that step (1) is described molten with rare earth by NaY molecular sieve
Liquid contact carries out ion-exchange reactions, including：NaY molecular sieve is mixed with water, rare-earth salts is added with stirring and/or rare-earth salts is molten
Liquid carries out ion-exchange reactions, filters, washing；The condition of ion-exchange reactions is：Exchange temperature is 15~95 DEG C, swap time
It it is 30~120 minutes, the rare-earth salt solution is the aqueous solution of rare-earth salts.
14. according to the method described in claim 9, it is characterized in that, the rare-earth salts is rare earth chloride or nitric acid rare earth.
15. according to the method described in claim 9, it is characterized in that, step (2) described calcination temperature be 380~460 DEG C, institute
It is 40~80% water vapour atmospheres to state calcination atmosphere, and the roasting time is 5~6 hours.
16. according to the method described in claim 9, it is characterized in that, the Y that the lattice constant obtained in step (2) reduces
The lattice constant of type molecular sieve is 2.450nm~2.462nm, the water content in the Y type molecular sieve that the lattice constant reduces
No more than 1 weight %.
17. according to the method described in claim 9, it is characterized in that, the washing methods described in step (3) is washed to be washed with water
The condition of washing is molecular sieve：H2O=1:6~15, pH value is 2.5~5.0, and wash temperature is 30~60 DEG C.
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