CN108455625B - High-stability modified Y-type molecular sieve and preparation method thereof - Google Patents
High-stability modified Y-type molecular sieve and preparation method thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 177
- 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 173
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000011148 porous material Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 23
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005342 ion exchange Methods 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 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
- 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
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 66
- 150000002910 rare earth metals Chemical class 0.000 claims description 48
- 229910001868 water Inorganic materials 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 30
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 26
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 26
- 230000032683 aging Effects 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 23
- -1 rare earth salt Chemical class 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 230000014759 maintenance of location Effects 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910003910 SiCl4 Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 16
- 239000000295 fuel oil Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 11
- 239000000571 coke Substances 0.000 abstract description 10
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000010457 zeolite Substances 0.000 description 40
- 229910021536 Zeolite Inorganic materials 0.000 description 39
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 39
- 210000004027 cell Anatomy 0.000 description 37
- 239000003054 catalyst Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 15
- 238000004523 catalytic cracking Methods 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 12
- 238000000634 powder X-ray diffraction Methods 0.000 description 9
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 8
- 239000005995 Aluminium silicate Substances 0.000 description 6
- 235000012211 aluminium silicate Nutrition 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 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 6
- 239000000047 product Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000010998 test method Methods 0.000 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 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method 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
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000009469 supplementation 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
-
- B01J35/647—
-
- 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
Abstract
High-stability modified Y-type molecular sieve and preparation method thereof, and RE of modified Y-type molecular sieve2O35 to 12% by weight of Na2The content of O is 0.1-0.7 wt%, the total pore volume is 0.33-0.39 mL/g, the pore volume of secondary pores with the diameter of 2-100 nm accounts for 10-25% of the total pore volume, the unit cell constant is 2.440-2.455 nm, the proportion of non-framework aluminum content in the total aluminum content is not higher than 20%, the lattice collapse temperature is not lower than 1050 ℃, and the ratio of B acid content to L acid content measured by a pyridine adsorption infrared method at 200 ℃ is not lower than 2.50. The preparation method comprises the steps of ion exchange, modification treatment under certain temperature and water vapor conditions and reaction with silicon tetrachloride. The modified Y-type molecular sieve has higher heavy oil conversion activity, lower coke selectivity, higher gasoline yield, liquefied gas yield, light oil yield and total liquid yield.
Description
Technical Field
The invention relates to a high-stability modified Y-type molecular sieve and a preparation method thereof, and further relates to a high-stability Y-type molecular sieve for heavy oil catalytic cracking and a preparation method thereof.
Background
At present, the industrial preparation of the high-silicon Y-type zeolite mainly adopts a hydrothermal method, and the NaY zeolite is subjected to rare earth ion exchange for many times and high-temperature roasting for many times, so that the rare earth-containing high-silicon Y-type zeolite can be prepared, which is the most conventional method for preparing the high-silicon Y-type zeolite, but the hydrothermal method for preparing the rare earth high-silicon Y-type zeolite has the defects that: because the structure of the zeolite can be damaged by too harsh hydrothermal treatment conditions, the Y-type zeolite with high silica-alumina ratio can not be obtained; although the generation of the aluminum outside the framework is beneficial to improving the stability of the zeolite and forming a new acid center, the excessive aluminum outside the framework reduces the selectivity of the zeolite, in addition, a plurality of dealuminized cavities in the zeolite cannot be timely supplemented by the silicon migrated from the framework, the lattice defect of the zeolite is often caused, and the crystallization retention degree of the zeolite is lower, so that the thermal and hydrothermal stability of the rare earth-containing high-silicon Y-type zeolite prepared by a hydrothermal method is poorer, the crystal lattice collapse temperature is lower, the crystallinity retention rate and the specific surface area retention rate are lower after hydrothermal aging, and the selectivity is poorer.
In U.S. Pat. Nos. 4,849,287 and 4,4429053, NaY zeolite is exchanged with rare earth ions and then treated with water vapor, the aluminum removal of the zeolite is difficult in the water vapor treatment process, the unit cell parameters of the zeolite before the water vapor treatment are increased to 2.465-2.475 nm, the unit cell parameters after the treatment are 2.420-2.464 nm, and the temperature required for reducing the unit cell parameters is higher (593-733 ℃). The heavy oil cracking activity of zeolite is not high and coke selectivity is not good.
In the processes provided in US5340957 and US5206194, SiO of NaY zeolite is used as the starting material2/Al2O3The ratio is 6.0, and this method also has the disadvantages of the aforementioned U.S. Pat. Nos. 4,84287 and 4429053, in which NaY is subjected to rare earth exchange and then to hydrothermal treatment.
Gas phase chemical processes are another important process for preparing high silica zeolites first reported by Beyer and Mankui in 1980. The gas phase chemical method generally adopts SiCl under the protection of nitrogen4Reacting with anhydrous NaY zeolite at a certain temperature. U.S. Pat. Nos. 4,42737,178, U.S. Pat. No. 4,4438178, Chinese patent Nos. CN1382525A, CN1194941A and CN1683244A disclose the use of SiCl4A process for preparing ultra-stable Y-type zeolite by gas-phase chemical dealumination. However, pore structure analysis shows that the gas phase ultrastable molecular sieve has no secondary pores.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a high-stability Y-type molecular sieve (Y-type molecular sieve is also called Y-type zeolite) suitable for heavy oil catalytic cracking processing, wherein the modified Y-type molecular sieve has higher heavy oil cracking activity and better coke selectivity. The second technical problem to be solved by the invention is to provide a preparation method of the modified Y-type molecular sieve.
The invention provides a modified Y-type molecular sieve, which contains 5-12 wt% of rare earth oxide and 0.1-0.7 wt% of sodium oxideThe percentage of the total pore volume is 0.33-0.39 mL/g, the pore volume of the secondary pores with the pore diameter of 2-100 nm of the modified Y-type molecular sieve accounts for 10-25 percent of the total pore volume of the modified Y-type molecular sieve, the unit cell constant is 2.440-2.455 nm, and the framework silicon-aluminum ratio (SiO)2/Al2O3Molar ratio) is: 7.3-14.0, the percentage of non-framework aluminum content in the molecular sieve to the total aluminum content is not higher than 20%, the lattice collapse temperature is not lower than 1050 ℃, and the ratio of the B acid amount to the L acid amount in the total acid amount of the modified Y-type molecular sieve measured by a pyridine adsorption infrared method at 200 ℃ is not lower than 2.50.
The modified Y-type molecular sieve provided by the invention has the lattice collapse temperature of not less than 1050 ℃, preferably, the lattice collapse temperature of the molecular sieve is 1055-1080 ℃, for example, 1057-1075 ℃.
The ratio of the amount of B acid to the amount of L acid in the total acid amount of the modified Y-type molecular sieve, which is measured at 200 ℃ by using a pyridine adsorption infrared method, is preferably 2.6-4.0, for example, 2.7-3.3.
The unit cell constant of the modified Y-type molecular sieve provided by the invention is 2.440-2.455 nm, such as 2.442-2.450 nm.
The modified Y-type molecular sieve provided by the invention is a high-silicon Y-type molecular sieve, and the framework silicon-aluminum ratio (SiO) of the high-silicon Y-type molecular sieve2/Al2O3Molar ratio) of 7.3 to 14.0, for example: 8.5 to 12.6.
According to the modified Y-type molecular sieve provided by the invention, the percentage of non-framework aluminum content in the molecular sieve in the total aluminum content is not higher than 20%, for example, 13-19 wt%.
The modified Y-type molecular sieve provided by the invention has a crystal retention of 38% or more, for example, 38-48% or 39-45% after aging for 17 hours at 800 ℃ under normal pressure and in a 100 volume% steam atmosphere. The normal pressure is 1 atm.
The relative crystallinity of the modified Y-type molecular sieve provided by the invention is not less than 60%, preferably, the relative crystallinity of the modified Y-type molecular sieve provided by the invention is 60-70%, for example, 60-66%.
The invention provides a modified Y-type molecular sieve, an embodiment, whichThe specific surface area is 620-670 m2The/g is, for example, 630 to 660m2/g。
The modified Y-type molecular sieve provided by the invention has the preferable total pore volume of 0.35-0.39 mL/g, such as 0.36-0.375 mL/g.
The modified Y-type molecular sieve provided by the invention has the pore volume of secondary pores with the pore diameter (diameter) of 2.0-100 nm accounting for 10-25% of the total pore volume, and preferably 15-21%.
In one embodiment, the modified Y-type molecular sieve provided by the invention has a micropore volume of 0.25-0.35 mL/g, for example, 0.26-0.32 mL/g.
The modified Y-type molecular sieve contains rare earth elements, and RE is used in the modified Y-type molecular sieve2O3The content of the rare earth oxide is 5 to 12 wt%, preferably 5.5 to 10 wt%.
The modified Y-type molecular sieve provided by the invention has the sodium oxide content of not more than 0.7%, and can be 0.3-0.7 wt%, such as 0.35-0.60 wt% or 0.4-0.55 wt%.
The invention provides a preparation method of a modified Y-type molecular sieve, which comprises the following steps:
(1) contacting the NaY molecular sieve with a rare earth solution to perform an ion exchange reaction, filtering and washing to obtain a Y-type molecular sieve containing rare earth with a conventional unit cell size and reduced sodium oxide content; wherein the rare earth solution is also called rare earth salt solution;
(2) modifying the rare earth-containing Y-type molecular sieve with the reduced sodium oxide content and the conventional unit cell size, and optionally drying to obtain a Y-type molecular sieve with a reduced unit cell constant, wherein the modifying is to roast the rare earth-containing Y-type molecular sieve with the reduced sodium oxide content and the conventional unit cell size at the temperature of 350-480 ℃ in an atmosphere containing 30-90 vol% of water vapor (also called 30-90 vol% of water vapor atmosphere or 30-90 vol% of water vapor) for 4.5-7 hours;
(3) mixing the Y-type molecular sieve sample with SiCl, wherein the unit cell constant is reduced4Gas is contacted and reacted at the temperature of 200-650 ℃, wherein SiCl is contained4: reduced unit cell constant on a dry basis from step (2)The weight ratio of the Y-type molecular sieve is 0.1-0.7: 1, reacting for 10 minutes to 5 hours, and then washing and filtering to obtain the modified Y-type molecular sieve. Wherein the water content of the Y-type molecular sieve sample with reduced unit cell constant is preferably not more than 1 wt%; if the water content in the Y-type molecular sieve sample obtained by modification treatment in the step (2) (in the Y-type molecular sieve sample obtained by roasting) is not more than 1 wt%, the Y-type molecular sieve sample can be directly used for contacting silicon tetrachloride to carry out the reaction, and if the water content in the Y-type molecular sieve sample obtained by roasting in the step (2) exceeds 1 wt%, the Y-type molecular sieve sample with the reduced unit cell constant obtained by roasting in the step (2) is dried to enable the water content to be lower than 1 wt%.
The modified Y-type molecular sieve provided by the invention has high thermal and hydrothermal stability, is used for heavy oil catalytic cracking, has higher heavy oil conversion activity and lower coke selectivity than the conventional Y-type molecular sieve, and has higher gasoline yield, liquefied gas yield, light oil yield and total liquid yield.
The preparation method of the sex modified Y-shaped molecular sieve provided by the invention can be used for preparing the high-silicon Y-shaped molecular sieve with a certain secondary pore structure and high crystallinity, high thermal stability and high hydrothermal stability, the molecular sieve has uniform aluminum distribution and less non-framework aluminum content, the modified Y-shaped molecular sieve is used for heavy oil conversion, the coke selectivity is good, the heavy oil cracking activity is high, and the gasoline yield, the liquefied gas yield and the total liquid yield of the molecular sieve used for heavy oil conversion can be improved.
The modified Y-type molecular sieve provided by the invention can be used as an active component of a catalytic cracking catalyst and used for converting heavy oil or poor oil; the catalytic cracking catalyst with the molecular sieve as the active component has the advantages of strong heavy oil conversion capacity, high stability, good coke selectivity, high light oil yield and high gasoline yield.
Detailed Description
The invention provides a modified Y-type molecular sieve, which comprises, by weight, 5-12% of rare earth oxide, preferably 5.5-10%, 0.1-0.7% of sodium oxide, preferably 0.3-0.7%, a total pore volume of 0.33-0.39 mL/g, and secondary pores with a pore diameter of 2-100 nmThe volume of the porous material accounts for 10-25%, preferably 15-21%, the unit cell constant is 2.440-2.455 nm, and the framework silicon-aluminum ratio (SiO)2/Al2O3Molar ratio) is: 7.3-14.0, the percentage of non-framework aluminum content in the molecular sieve in the total aluminum content is not higher than 20%, preferably 13-19, the relative crystallinity is not lower than 60%, the lattice collapse temperature is 1055-1080 ℃, and the ratio of the B acid amount to the L acid amount in the total acid amount of the modified Y-type molecular sieve measured by a pyridine adsorption infrared method at 200 ℃ is not lower than 2.50, preferably 2.6-4.0.
The preparation process of the modified Y-type molecular sieve comprises the step of contacting the Y-type molecular sieve with silicon tetrachloride to carry out dealuminization and silicon supplementation reaction.
In the preparation method of the modified Y-type molecular sieve, the NaY molecular sieve and the rare earth solution are subjected to ion exchange reaction in the step (1) to obtain the Y-type molecular sieve with the normal unit cell size and the reduced sodium oxide content and containing rare earth. The NaY molecular sieve can be purchased commercially or prepared according to the existing method, and in one embodiment, the unit cell constant of the NaY molecular sieve is 2.465-2.472 nm, and the framework silicon-aluminum ratio (SiO)2/Al2O3Molar ratio) of 4.5 to 5.2, a relative crystallinity of 85% or more, for example, 85 to 95%, and a sodium oxide content of 13.0 to 13.8% by weight. The NaY molecular sieve and the rare earth solution are subjected to ion exchange reaction, the exchange temperature is preferably 15-95 ℃, for example 65-95 ℃, and the exchange time is preferably 30-120 minutes, for example 45-90 minutes. NaY molecular sieve (dry basis) rare earth salt (RE)2O3Meter) H2O is 1:0.01 to 0.18:5 to 15 by weight. In one embodiment, the ion exchange reaction of the NaY molecular sieve and the rare earth solution comprises the following steps of mixing the NaY molecular sieve, rare earth salt and H2The method comprises the steps of mixing NaY molecular sieve (also called NaY zeolite), rare earth salt and water in a weight ratio of 1: 0.01-0.18: 5-15, stirring at 15-95 ℃, for example, 65-95 ℃, preferably for 30-120 minutes, and exchanging rare earth ions and sodium ions. The NaY molecular sieve, rare earth salt and water form a mixture, the NaY molecular sieve and the water can form slurry,then adding rare earth salt and/or rare earth salt water solution into the slurry, wherein the rare earth solution is rare earth salt solution, and the rare earth salt is preferably rare earth chloride and/or rare earth nitrate. The rare earth such as one or more of La, Ce, Pr, Nd and misch metal, preferably, the misch metal contains one or more of La, Ce, Pr and Nd, or further contains at least one of rare earth other than La, Ce, Pr and Nd. The washing in step (1) is intended to wash out exchanged sodium ions, and for example, deionized water or decationized water may be used for washing. Preferably, the rare earth content of the rare earth-containing Y-type molecular sieve with the reduced sodium oxide content obtained in step (1) and the conventional unit cell size is calculated as RE2O35.5 to 14 wt%, for example, 7 to 14 wt% or 5.5 to 12 wt%, sodium oxide content of not more than 9 wt%, for example, 5.5 to 8.5 wt% or 5.5 to 7.5 wt%, and unit cell constant of 2.465nm to 2.472 nm.
In the preparation method of the modified Y-type molecular sieve, the Y-type molecular sieve containing rare earth and having a conventional unit cell size is roasted for 4.5-7 hours at the temperature of 350-480 ℃ under the atmosphere of 30-90 vol% of water vapor in step (2), preferably, the roasting temperature in step (2) is 380-460 ℃, the roasting atmosphere is 40-80 vol% of water vapor, and the roasting time is 5-6 hours. The water vapor atmosphere contains 30-90% by volume of water vapor and other gases such as one or more of air, helium or nitrogen. The Y-type molecular sieve with the reduced unit cell constant in the step (2) has the unit cell constant of 2.450 nm-2.462 nm. Preferably, the calcined molecular sieve is also dried in step (2) so that the water content in the Y-type molecular sieve having a reduced unit cell constant is preferably not more than 1 wt%.
In the preparation method of the modified Y-type molecular sieve, SiCl is adopted in the step (3)4: the weight ratio of the Y-type zeolite (on a dry basis) is preferably 0.3-0.6: 1, the reaction temperature is preferably 350-500 ℃, and the washing method in the step (3) can adopt a conventional washing method, and can be washed by water, such as decationized water or deionized water, so as to remove Na remained in the zeolite+，Cl-And Al3+Etc. soluble by-products, for example the washing conditions may be: the weight ratio of the washing water to the molecular sieve can be 5-20: 1, typically molecular sieve: h2The weight ratio of O is 1: 6-15, the pH value is preferably 2.5-5.0, and the washing temperature is 30-60 ℃. Preferably, the washing is performed such that no free Na is detected in the washing solution after washing+，Cl-And Al3+Plasma, usually Na in washed molecular sieve samples+，Cl-And Al3+The respective contents of ions do not exceed 0.05 wt.%.
The preparation method of the modified Y-type molecular sieve provided by the invention comprises the following steps:
(1) carrying out ion exchange reaction on a NaY molecular sieve (also called NaY zeolite) and a rare earth solution, filtering and washing to obtain a Y-type molecular sieve containing rare earth and having a conventional unit cell size and reduced sodium oxide content; the ion exchange is carried out for 30-120 minutes under the conditions of stirring and the temperature of 15-95 ℃, preferably 65-95 ℃;
(2) roasting the rare earth-containing Y-type molecular sieve with the normal unit cell size and the reduced sodium oxide content for 4.5-7 hours at the temperature of 350-480 ℃ in the atmosphere containing 30-90 vol% of water vapor, and drying to obtain the Y-type molecular sieve with the reduced unit cell constant and the water content of less than 1 wt%; the unit cell constant of the Y-type molecular sieve with the reduced unit cell constant is 2.450 nm-2.462 nm;
(3) mixing the Y-type molecular sieve sample with water content lower than 1 wt% and SiCl vaporized by heating4Gas contact of SiCl4: the weight ratio of the Y-type molecular sieve with the water content lower than 1 wt% and the reduced unit cell constant (calculated by dry basis) is 0.1-0.7: 1, carrying out contact reaction for 10 minutes to 5 hours at the temperature of 200-650 ℃, and washing and filtering to obtain the modified Y-type molecular sieve provided by the invention.
The following examples further illustrate the invention but are not intended to limit the invention thereto.
In the examples and comparative examples, the NaY molecular sieve (also known as NaY zeolite) was provided by the china petrochemical catalyst company, zeugo,sodium oxide content 13.5 wt.%, framework silicon to aluminum ratio (SiO)2/Al2O3Molar ratio) of 4.6, unit cell constant of 2.470nm, relative crystallinity of 90%; the chlorinated rare earth and the nitric acid rare earth are chemical pure reagents produced by Beijing chemical plants. The pseudoboehmite is an industrial product produced by Shandong aluminum factories, and has the solid content of 61 percent by weight; the kaolin is kaolin specially used for a cracking catalyst produced by Suzhou China kaolin company, and has the solid content of 76 weight percent; the alumina sol was provided by the Qilu division of China petrochemical catalyst, Inc., in which the alumina content was 21% by weight.
The analysis method comprises the following steps: in each comparative example and example, the elemental content of the zeolite was determined by X-ray fluorescence spectroscopy; the unit cell constants and relative crystallinity of the zeolite were measured by X-ray powder diffraction (XRD) using RIPP 145-90 and RIPP146-90 standard methods (compiled by petrochemical analysis method (RIPP test method), Yankee et al, scientific Press, published in 1990), and the framework silica-alumina ratio of the zeolite was calculated from the following formula: SiO 22/Al2O3＝(2.5858-a0)×2/(a0-2.4191)]Wherein, a0Is the unit cell constant in nm; the total silicon-aluminum ratio of the zeolite is calculated according to the content of Si and Al elements measured by an X-ray fluorescence spectrometry, and the ratio of the framework Al to the total Al can be calculated by the framework silicon-aluminum ratio measured by an XRD method and the total silicon-aluminum ratio measured by an XRF method, so that the ratio of non-framework Al to the total Al can be calculated. The crystal structure collapse temperature was determined by Differential Thermal Analysis (DTA).
In each comparative example and example, the acid center type of the molecular sieve and its acid amount were determined by infrared analysis using pyridine adsorption. An experimental instrument: model Bruker IFS113V FT-IR (fourier transform infrared) spectrometer, usa. Experimental method for measuring acid content at 200 ℃ by using pyridine adsorption infrared method: and (3) carrying out self-supporting tabletting on the sample, and placing the sample in an in-situ cell of an infrared spectrometer for sealing. Heating to 400 deg.C, and vacuumizing to 10 deg.C-3And Pa, keeping the temperature for 2h, and removing gas molecules adsorbed by the sample. The temperature is reduced to room temperature, pyridine vapor with the pressure of 2.67Pa is introduced to keep the adsorption equilibrium for 30 min. Then heating to 200 ℃, and vacuumizing to 10 DEG C-3Desorbing for 30min under Pa, reducing to room temperature for spectrography, scanning wave number range: 1400 cm-1～1700 cm-1And obtaining the pyridine absorption infrared spectrogram of the sample desorbed at 200 ℃. According to pyridine absorption infrared spectrogram of 1540 cm-1And 1450 cm-1The strength of the adsorption peak is characterized to obtain the total content in the molecular sieve
Relative amount of acid center (B acid center) to Lewis acid center (L acid center).
In each of the comparative examples and examples, the secondary pore volume was determined as follows: measuring total pore volume of the molecular sieve according to adsorption isotherm, measuring micropore volume of the molecular sieve according to T mapping method from adsorption isotherm, subtracting micropore volume from total pore volume to obtain secondary pore volume,
the chemical reagents used in the comparative examples and examples are not specifically noted, and are specified to be chemically pure.
Example 1
2000 g of NaY molecular sieve (dry basis) is added into 20L of decationized aqueous solution and stirred to be mixed evenly, 600ml of RE (NO) is added3)3Solution (rare earth solution concentration in RE)2O3319g/L), stirring, heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, drying filter cake at 120 ℃, obtaining crystal cell constant of 2.471nm, sodium oxide content of 7.0 wt%, RE2O3Calculating Y-type molecular sieve with rare earth content of 8.8 wt%, calcining at 390 deg.C in atmosphere containing 50 vol% of water vapor and 50 vol% of air for 6 hr to obtain Y-type molecular sieve with unit cell constant of 2.455nm, drying to water content less than 1 wt%, and adding SiCl4: y-type molecular sieve (dry basis) ═ 0.5: 1, by weight, introducing SiCl vaporized by heating4Reacting gas at 400 ℃ for 2 hours, washing the gas with 20 liters of decationized water, and filtering the gas to obtain the modified Y-type molecular sieve which is marked as SZ1 and has the physicochemical properties shown in Table 1, wherein the exposed SZ1 is subjected to 8-step dryingAfter aging for 17 hours at 00 ℃ and 1atm with 100% water vapor, relative crystallinity of the molecular sieve before and after aging of SZ1 was analyzed by XRD and relative crystal retention after aging was calculated, and the results are shown in Table 2, in which:
example 2
2000 g of NaY molecular sieve (dry basis) is added into 25L of decationized aqueous solution and stirred to be mixed evenly, 800ml of RECl is added3Solutions (with RE)2O3The solution concentration is measured as: 319g/L), stirring, heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, drying the filter cake at 120 ℃, and obtaining the crystal cell with the constant of 2.471nm, the content of sodium oxide of 5.5 weight percent and RE2O3Calculating Y-type molecular sieve with rare earth content of 11.3 wt%, calcining at 450 deg.C under 80% water vapor for 5.5 hr to obtain Y-type molecular sieve with unit cell constant of 2.461nm, drying to water content of less than 1 wt%, and adding SiCl4: y-type zeolite 0.6: 1, by weight, introducing SiCl vaporized by heating4The gas was reacted at 480 ℃ for 1.5 hours, then washed with 20 liters of decationized water and filtered to give a modified Y molecular sieve, noted SZ 2. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of SZ2 is analyzed by XRD method after aging of SZ2 in an exposed state at 800 ℃ for 17 hours and 100% of water vapor, and the relative crystal retention after aging is calculated.
Example 3
2000 g of NaY molecular sieve (dry basis) is added into 22L of decationized aqueous solution and stirred to be mixed evenly, and 570ml of RECl is added3Solutions (with RE)2O3The calculated concentration of the rare earth solution is 319g/L), stirring, heating to 90-95 ℃, keeping stirring for 1 hour, then filtering, washing, drying a filter cake at 120 ℃, and obtaining the rare earth solution with the unit cell constant of 2.471nm, the sodium oxide content of 7.5 weight percent and the RE content2O3Y-type molecular sieve with rare earth content of 8.5 wt%,then roasting at 470 deg.C under 70 vol% water vapor for 5 hr to obtain Y-type molecular sieve with unit cell constant of 2.458nm, drying to water content of less than 1 wt%, and then drying according to SiCl4: y-type zeolite 0.4: 1, by weight, introducing SiCl vaporized by heating4The gas was reacted at a temperature of 500 ℃ for 1 hour, then washed with 20 liters of decationized water and filtered to obtain a modified Y-type molecular sieve, noted SZ 3. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of SZ3 is analyzed by XRD method after aging of SZ3 in a naked state at 800 ℃ for 17 hours and 100% of water vapor, and the relative crystal retention after aging is calculated.
Comparative example 1
2000 g of NaY molecular sieve (dry basis) is added into 20L of decationized aqueous solution, stirred to be uniformly mixed, and 1000 g of (NH) is added4)2SO4Stirring, heating to 90-95 deg.C, holding for 1 hr, filtering, washing, drying at 120 deg.C, performing hydrothermal modification treatment (at 650 deg.C, roasting with 100% water vapor for 5 hr), adding into 20L of decationized water solution, stirring, mixing, adding 1000 g (NH)4)2SO4Stirring, heating to 90-95 ℃, keeping for 1 hour, filtering, washing, drying a filter cake at 120 ℃, and then carrying out second hydrothermal modification treatment, wherein the hydrothermal treatment conditions are 650 ℃ and roasting for 5 hours under 100% of water vapor, so as to obtain the rare earth-free hydrothermal ultrastable Y-shaped molecular sieve which is subjected to twice ion exchange and twice hydrothermal ultrastable, and is marked as DZ 1. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of DZ1 is analyzed by XRD method after aging DZ1 in naked state at 800 deg.C for 17 hr with 100% water vapor, and the relative crystal retention after aging is calculated.
Comparative example 2
2000 g of NaY molecular sieve (dry basis) is added into 20L of decationized aqueous solution, stirred to be uniformly mixed, and 1000 g of (NH) is added4)2SO4Stirring, heating to 90-95 deg.C, holding for 1 hr, filtering, washing, drying at 120 deg.C, and adding waterHeat modifying treatment, calcining at 650 deg.C under 100% steam for 5 hr, adding into 20L decationized water solution, stirring, adding 200ml RE (NO)3)3Solutions (with RE)2O3The concentration of the rare earth solution is measured as follows: 319g/L) and 900 g (NH)4)2SO4Stirring, heating to 90-95 ℃, keeping for 1 hour, filtering, washing, drying a filter cake at 120 ℃, and then performing second hydrothermal modification treatment (roasting at 650 ℃ under 100% of water vapor for 5 hours) to obtain the rare earth-containing hydrothermal ultrastable Y-type molecular sieve marked as DZ2, wherein the hydrothermal ultrastable Y-type molecular sieve is hydrothermally ultrastable twice through ion exchange twice. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of DZ2 is analyzed by XRD method after aging DZ2 in naked state at 800 deg.C for 17 hr with 100% water vapor, and the relative crystal retention after aging is calculated.
Comparative example 3
2000 g NaY molecular sieve (dry basis) is added into 20L of decationized aqueous solution and stirred to be mixed evenly, 650ml of RE (NO) is added3)3Stirring the solution (319g/L), heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, then carrying out gas phase ultra-stable modification treatment, firstly carrying out molecular sieve drying treatment to ensure that the water content is lower than 1 weight percent, and then carrying out SiCl treatment4: y-type zeolite 0.4: 1, by weight, introducing SiCl vaporized by heating4The gas was reacted at 580 ℃ for 1.5 hours, then washed with 20 liters of decationized water and filtered to obtain a gas phase high silicon ultrastable Y-type molecular sieve designated as DZ 3. The physicochemical properties are shown in Table 1, and the results are shown in Table 2, wherein the crystallinity of the zeolite before and after aging of DZ3 is analyzed by XRD method after aging DZ3 in naked state at 800 deg.C for 17 hr with 100% water vapor, and the relative crystal retention after aging is calculated.
Examples 4 to 6
Examples 4-6 illustrate the catalytic cracking activity and stability of the modified Y-type molecular sieve provided by the invention.
The modified Y-type molecular sieves SZ1, SZ2 and SZ3 prepared in examples 1-3 are prepared into catalysts, and the serial numbers of the catalysts are as follows: SC1, SC2, and SC 3. The light oil micro-reactivity of the catalyst was evaluated after aging the catalyst at 800 ℃ for 4 hours or 17 hours with 100% steam, and the evaluation results are shown in table 3.
The preparation method of the catalyst comprises the following steps:
the modified Y-type molecular sieve, kaolin, water, pseudo-boehmite adhesive and alumina sol are formed into slurry according to a conventional preparation method of a catalytic cracking catalyst, and the slurry is sprayed and dried to prepare the microspherical catalyst, wherein the obtained catalyst contains 30 wt% of the modified Y-type molecular sieve, 42 wt% of the kaolin, 25 wt% of the pseudo-boehmite and 3 wt% of the alumina sol on a dry basis.
Evaluation method of light oil micro-inverse activity:
the light oil micro-reverse activity of the sample is evaluated by adopting a standard method of RIPP92-90 (see the edition of petrochemical analysis method (RIPP test method), Yangcui et al, scientific publishing company, published in 1990), the catalyst loading is 5.0g, the reaction temperature is 460 ℃, the raw oil is Hongkong light diesel oil with the distillation range of 235-337 ℃, the product composition is analyzed by gas chromatography, and the light oil micro-reverse activity is calculated according to the product composition.
Light oil Microreactivity (MA) (gasoline production at less than 216 ℃ in product + gas production + coke production)/total feed × 100%.
Comparative examples 4 to 6
Comparative examples 4-6 illustrate the catalytic cracking activity and stability of the ultrastable Y-type molecular sieves prepared by the methods provided in comparative examples 1-3.
The preparation method of the catalyst in example 4 is adopted to mix the ultrastable Y-type molecular sieves DZ1, DZ2 and DZ3 prepared in comparative examples 1-3 with pseudo-boehmite, kaolin, water and alumina sol, and spray-dry the mixture to prepare the microspherical catalyst, the composition of each catalyst is the same as that in example 4, and the content of the ultrastable Y-type molecular sieve in the catalyst is 30 wt%. The serial numbers of the catalysts are as follows: DC1, DC2, and DC 3. The light oil micro-reactivity of the catalyst was evaluated after aging at 800 ℃ for 4 hours or 17 hours with 100% water vapor. See example 6 for evaluation, and the results are shown in Table 3.
Examples 7 to 9
Examples 7-9 illustrate the catalytic cracking reaction performance of the modified Y-type molecular sieve provided by the invention.
After the catalysts SC1, SC2 and SC3 are aged by 100 percent water vapor for 17 hours at 800 ℃, the catalytic cracking reaction performance of the catalysts is evaluated on a small-sized fixed fluidized bed reactor (ACE), and cracked gas and product oil are respectively collected and analyzed by gas chromatography. The catalyst loading is 9g, the reaction temperature is 500 ℃, and the weight hourly space velocity is 16h－1The oil-to-agent ratio (weight ratio) is shown in Table 5, the properties of the raw oil in the ACE test are shown in Table 4, and the evaluation results are shown in Table 5.
Comparative examples 7 to 9
Comparative examples 7-9 illustrate the catalytic cracking reaction performance of the ultrastable Y-type zeolite prepared by the methods provided in comparative examples 1-3.
The catalytic cracking performance of the catalysts DC1, DC2 and DC3 was evaluated in a small fixed fluidized bed reactor (ACE) after aging at 800 ℃ for 17 hours with 100% steam, the evaluation method is shown in example 7, the properties of the raw materials for the ACE test are shown in Table 4, and the evaluation results are shown in Table 5.
TABLE 1
As can be seen from table 1, the high-stability modified Y-type molecular sieve provided by the present invention has the following advantages: the content of sodium oxide is low, the non-framework aluminum content is low when the silicon-aluminum content of the molecular sieve is high, the pore volume of 2.0-100 nm secondary pores in the molecular sieve accounts for the volume percentage of the total pores, the ratio of B acid/L acid (the total amount of B acid to the amount of L acid) is high, the crystallinity value measured when the content of rare earth is high when the unit cell constant of the molecular sieve is small is high, and the thermal stability is high.
TABLE 2
As can be seen from Table 2, the modified Y-type molecular sieve provided by the invention has higher relative crystal retention after being aged under the harsh conditions of 800 ℃ and 17 hours in the exposed state of the molecular sieve sample, which indicates that the modified Y-type molecular sieve provided by the invention has high hydrothermal stability.
TABLE 3
TABLE 4
TABLE 5
| Example numbering | Example 7 | Example 8 | Example 9 | Comparative example 7 | Comparative example 8 | Comparative example 9 |
| Sample numbering | SC1 | SC2 | SC3 | DC1 | DC2 | DC3 |
| The molecular sieve used | SZ1 | SZ2 | SZ3 | DZ1 | DZ2 | DZ3 |
| Ratio of agent to oil | 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 (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 |
| Total up to | 100 | 100 | 100 | 100 | 100 | 100 |
| Conversion/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/weight% | 86.72 | 87.29 | 86.57 | 75.58 | 78.49 | 83.88 |
As can be seen from the results shown in tables 3 and 5, the catalytic cracking catalyst prepared by using the molecular sieve provided by the present invention as an active component has high hydrothermal stability, significantly lower coke selectivity, significantly higher liquid yield, significantly higher light oil yield, improved gasoline yield, and higher heavy oil conversion activity.
Claims (19)
1. A modified Y-type molecular sieve is characterized in that the content of rare earth oxide of the modified Y-type molecular sieve is 5-12 wt%, the content of sodium oxide is 0.1-0.7 wt%, the total pore volume is 0.33 mL/g-0.39 mL/g, the percentage of the pore volume of secondary pores with the pore diameter of 2-100 nm in the modified Y-type molecular sieve in the total pore volume is 10-25%, the cell constant is 2.440-2.455 nm, the percentage of non-framework aluminum content in the modified Y-type molecular sieve in the total aluminum content is not higher than 20%, the lattice collapse temperature is not lower than 1050 ℃, and the ratio of the B acid amount to the L acid amount in the total acid amount of the modified Y-type molecular sieve measured by a pyridine adsorption infrared method at 200 ℃ is not lower than 2.50.
2. The modified Y-type molecular sieve of claim 1, wherein the pore volume of secondary pores with a pore diameter of 2nm to 100nm accounts for 15% to 21% of the total pore volume.
3. The modified Y-type molecular sieve of claim 1, wherein the non-framework aluminum content of the modified Y-type molecular sieve accounts for 13-19% of the total aluminum content, and the framework silica-alumina ratio is SiO2/Al2O3The molar ratio is 7.3-14.
4. The modified Y-type molecular sieve of claim 1, wherein the modified Y-type molecular sieve has a lattice collapse temperature of 1055 ℃ to 1080 ℃.
5. The modified Y-type molecular sieve of claim 1, wherein the ratio of the amount of B acid to the amount of L acid in the total acid amount of the modified Y-type molecular sieve measured at 200 ℃ by pyridine adsorption infrared is 2.6 to 4.0.
6. The modified Y-type molecular sieve of claim 1 having a relative crystal retention of 38% or more after aging at 800 ℃ under atmospheric pressure in a 100% steam atmosphere for 17 hours.
7. The modified Y-type molecular sieve of claim 1, wherein the modified Y-type molecular sieve has a relative crystallinity of 60% to 70%.
8. The modified Y-type molecular sieve of claim 1, wherein the modified Y-type molecular sieve has a relative crystal retention of 38% to 48% after aging at 800 ℃ under normal pressure in a 100% steam atmosphere for 17 hours.
9. The modified Y-type molecular sieve of any one of claims 1 to 8, wherein the modified Y-type molecular sieve has a rare earth oxide content of 5.5 to 10 wt%, a sodium oxide content of 0.3 to 0.7 wt%, a unit cell constant of 2.442 to 2.450nm, and a framework Si/Al ratio of 8.5 to 12.6.
10. A process for the preparation of a modified Y-type molecular sieve as claimed in any one of claims 1 to 9, which process comprises the steps of:
(1) contacting the NaY molecular sieve with a rare earth salt solution to perform an ion exchange reaction, filtering, washing, and optionally drying to obtain a rare earth-containing Y-type molecular sieve with a conventional unit cell size and reduced sodium oxide content;
(2) roasting the rare earth-containing Y-type molecular sieve with the conventional unit cell size and the reduced sodium oxide content for 4.5 to 7 hours at the temperature of 350 to 480 ℃ and in the atmosphere of 30 to 90 volume percent of water vapor, and optionally drying to obtain the Y-type molecular sieve with the reduced unit cell constant;
(3) according to SiCl4: the Y-type molecular sieve with reduced unit cell constant is 0.1-0.7: 1, carrying out contact reaction on the Y-shaped molecular sieve with the reduced unit cell constant and silicon tetrachloride gas at the reaction temperature of 200-650 ℃ for 10 minutes to 5 hours, washing and filtering to obtain the modified Y-shaped molecular sieve.
11. The process of claim 10, wherein the rare earth-containing Y-type molecular sieve having a conventional unit cell size and a reduced sodium oxide content in step (1) has a unit cell constant of 2.465nm to 2.472nm and a sodium oxide content of no more than 9.0 wt.%.
12. The process of claim 10, wherein in step (1), the rare earth-containing Y-type molecular sieve having a reduced sodium oxide content and a conventional unit cell size contains rare earth in an amount of RE2O35.5-14 wt%, sodium oxide content 4-9 wt%, and unit cell constant 2.465-2.472 nm.
13. The method of claim 10, wherein the step (1) of contacting the NaY molecular sieve with the rare earth salt solution to perform the ion exchange reaction is performed according to the following formula: rare earth salt: h2O is 1: 0.01-0.18: 5-15, mixing the NaY molecular sieve, the rare earth salt and water to form a mixture, and stirring.
14. The method of claim 10 or 13, wherein the step (1) of contacting the NaY molecular sieve with the rare earth solution for ion exchange reaction comprises: mixing NaY molecular sieve with water, adding rare earth salt and/or rare earth salt solution while stirring for ion exchange reaction, filtering and washing; the conditions of the ion exchange reaction are as follows: the exchange temperature is 15-95 ℃, the exchange time is 30-120 minutes, and the rare earth salt solution is a rare earth salt water solution.
15. The method of claim 10, wherein the rare earth salt is a rare earth chloride or a rare earth nitrate.
16. The method of claim 10, wherein the roasting temperature in step (2) is 380 ℃ to 460 ℃, the roasting atmosphere is 40% to 80% of steam atmosphere, and the roasting time is 5 hours to 6 hours.
17. The method according to claim 10, wherein the unit cell constant of the Y-type molecular sieve with reduced unit cell constant obtained in step (2) is 2.450nm to 2.462nm, and the water content of the Y-type molecular sieve with reduced unit cell constant is not more than 1 wt%.
18. The method according to claim 10, wherein the washing method in the step (3) is washing with water under the washing conditions that the molecular sieve: h2The weight ratio of O =1: 6-15, the pH value is 2.5-5.0, and the washing temperature is 30-60 ℃.
19. The process of claim 10, wherein in step (1), the rare earth-containing conventional unit cell size Y-type molecular sieve having a reduced sodium oxide content has a sodium oxide content of 5.5 wt.% to 8.5 wt.%.
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