CN110090660B - Composite material containing Y-type molecular sieve and preparation method thereof - Google Patents
Composite material containing Y-type molecular sieve and preparation method thereof Download PDFInfo
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- CN110090660B CN110090660B CN201810088997.9A CN201810088997A CN110090660B CN 110090660 B CN110090660 B CN 110090660B CN 201810088997 A CN201810088997 A CN 201810088997A CN 110090660 B CN110090660 B CN 110090660B
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 121
- 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 121
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title description 21
- 239000011148 porous material Substances 0.000 claims abstract description 53
- 239000013078 crystal Substances 0.000 claims abstract description 41
- 238000009826 distribution Methods 0.000 claims abstract description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 7
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 7
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 27
- 239000012065 filter cake Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 238000004537 pulping Methods 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 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 description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 25
- 239000000463 material Substances 0.000 description 22
- 238000005336 cracking Methods 0.000 description 14
- 230000005540 biological transmission Effects 0.000 description 11
- 238000004523 catalytic cracking Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 230000002902 bimodal effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 239000012229 microporous material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 carbonium ion Chemical class 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021423 nanocrystalline silicon Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229960004029 silicic acid Drugs 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A composite material containing Y-type molecular sieve is characterized in that the composite material also contains a mesoporous alumina layer with a pseudo-boehmite structure, the mesoporous alumina layer grows on the surface of the crystal grain of the Y-type molecular sieve and coats the molecular sieve crystal grain, the disordered structure of the mesoporous alumina layer extends and grows from the edge of the ordered diffraction stripe of the FAU crystal phase structure of the Y-type molecular sieve, and the two structures are built together; the chemical composition of the composite material is (4-12) Na based on the weight of the oxide2O·(20～60)SiO2·(30～75)Al2O3(ii) a The particle size parameter D (V, 0.5) of the composite material is 1.8-2.5, and the particle size parameter D (V, 0.9) is 4.0-8.0. The composite material has narrow particle size distribution, uniform particle size, smooth surface mesoporous layer pore canal and strong accessibility of an active center.
Description
Technical Field
The invention relates to a composite material containing a Y-type molecular sieve and a preparation method thereof, in particular to a composite material in which a mesoporous layer grows on the surface of a molecular sieve crystal particle and the molecular sieve is coated in the mesoporous layer and a preparation method thereof.
Background
Catalytic cracking is an important process in petroleum refining, is widely applied to the petroleum processing industry, and plays a significant role in oil refineries. In the catalytic cracking process, heavy fractions such as vacuum distillates or residues of heavier components are reacted in the presence of a catalyst to convert into gasoline, distillates and other liquid cracked products and lighter gaseous cracked products of four carbons or less. The catalytic cracking reaction process follows a carbonium ion reaction mechanism, and therefore, an acidic catalytic material, particularly a catalytic material having a strong B acid center, needs to be used. Amorphous alumino-silicate material is an acidic catalytic material, which has both B and L acid centers, is the main active component in early catalytic cracking catalysts, but is gradually replaced by crystalline molecular sieves due to its lower cracking activity and higher required reaction temperature. Crystalline molecular sieves are porous materials with a pore size of less than 2nm and a special crystalline phase structure, and materials with a pore size of less than 2nm are named as microporous materials according to the definition of IUPAC, so that crystalline molecular sieves or zeolites generally belong to microporous materials, and the microporous molecular sieve materials have stronger acidity and higher structural stability due to complete crystal structures and special framework structures, show higher catalytic activity in catalytic reactions, and are widely applied to petroleum processing and other catalytic industries.
The Y-type molecular sieve is used as a typical microporous molecular sieve material, and is applied in the fields of catalytic cracking, hydrocracking and the like on a large scale due to the regular pore channel structure, good stability and strong acidity. When the modified Y-type molecular sieve is used in a catalytic cracking catalyst, certain modification treatment is usually required to be carried out on the Y-type molecular sieve, such as skeleton dealumination inhibition through rare earth modification, the structural stability of the molecular sieve is improved, the retention degree of acid centers is increased, and the cracking activity is further improved; or the framework silicon-aluminum ratio is improved through ultra-stabilization treatment, so that the stability of the molecular sieve is improved.
Along with the increasing exhaustion of petroleum resources, the trend of crude oil heaving and deterioration is obvious, the slag blending proportion is continuously improved, and the requirement of the market for light oil products is not reduced, so that in recent years, the deep processing of heavy oil and residual oil is more and more emphasized in the petroleum processing industry, a plurality of refineries begin to blend vacuum residual oil, even normal pressure residual oil is directly used as a cracking raw material, the catalytic cracking of heavy oil gradually becomes a key technology for improving economic benefits of oil refining enterprises, and the macromolecular cracking capability of a catalyst therein is a focus of attention. The Y-type molecular sieve is the most main cracking active component in the conventional cracking catalyst, but due to the smaller pore channel structure, the Y-type molecular sieve shows a relatively obvious pore channel limiting effect in macromolecular reaction, and also shows a certain inhibiting effect on the cracking reaction of macromolecules such as heavy oil or residual oil and the like. Therefore, for catalytic cracking of heavy oil, it is necessary to use a material having a large pore size, no diffusion limitation to reactant molecules, and a high cracking activity.
According to the IUPAC definition, a material with a pore size of 2-50 nm is a mesoporous (mesoporous) material, and the size range of macromolecules such as heavy oil or residual oil is in the pore size range, so that the research of mesoporous materials, particularly mesoporous silicon-aluminum materials, has attracted great interest to researchers in the catalysis field. Mesoporous materials are firstly developed and succeeded by Mobil Corporation in 1992 (Beck J S, Vartuli J Z, Roth W J et al, J.Am.Chem.Comm.Soc., 1992, 114, 10834-containing 10843) and named as M41S series mesoporous molecular sieves, including MCM-41(Mobil Corporation Material-41) and MCM-48, etc., wherein the pore diameter of the molecular sieves can reach 1.6-10 nm, and the mesoporous materials are uniform and adjustable, have concentrated pore diameter distribution, large specific surface area and pore volume and strong adsorption capacity; however, the pore wall structure of the molecular sieve is an amorphous structure, so that the molecular sieve has poor hydrothermal stability and weak acidity, cannot meet the operation conditions of catalytic cracking, and is greatly limited in industrial application.
In order to solve the problem of poor hydrothermal stability of mesoporous molecular sieves, part of research work focuses on increasing the thickness of the pore walls of the molecular sieves, and if a neutral template agent is adopted, the molecular sieve with thicker pore walls can be obtained, but the defect of weaker acidity still exists. In CN 1349929a, a novel mesoporous molecular sieve is disclosed, in which primary and secondary structural units of zeolite are introduced into the pore walls of the molecular sieve, so that the molecular sieve has the basic structure of the conventional zeolite molecular sieve, and the mesoporous molecular sieve has strong acidity and ultrahigh hydrothermal stability. However, the molecular sieve has the defects that a template agent with high price is required to be used, the aperture is only about 2.7nm, the molecular sieve still has large steric hindrance effect on macromolecular cracking reaction, the structure is easy to collapse under the high-temperature hydrothermal condition, and the cracking activity is poor.
In the field of catalytic cracking, silicon-aluminum materials are widely used due to their strong acid centers and good cracking properties. The proposal of the mesoporous concept provides possibility for the preparation of a novel catalyst, and the current research results mostly focus on the use of expensive organic template and organic silicon source, and mostly need to be subjected to a high-temperature hydrothermal post-treatment process. In order to reduce the preparation cost and obtain a porous material in the mesoporous range, more research efforts have been focused on the development of disordered mesoporous materials. US5,051,385 discloses a monodisperse mesoporous Si-Al composite material, which is prepared by mixing acidic inorganic aluminum salt and silica sol and then adding alkali for reaction, wherein the aluminum content is 5-40 wt%, the aperture is 20-50 nm, and the specific surface area is 50-100 m2(ii) in terms of/g. US4,708,945 discloses a catalyst prepared by loading silica particles or hydrated silica on porous boehmite and hydrothermally treating the obtained composite at a temperature of more than 600 ℃ for a certain time to obtain a catalyst prepared by loading silica on the surface of the boehmite, wherein the silica is combined with hydroxyl of the transition boehmite and the surface area reaches 100-200 m2(iv) g, average pore diameter of 7 to 7.5 nm. A series of acidic cracking catalysts are disclosed in US4,440,872, some of which are supported on gamma-Al2O3Impregnating silane, and then roasting at 500 ℃ or treating with water vapor. In CN1353008A, inorganic aluminum salt and water glass are used as raw materials, stable and clear silicon-aluminum sol is formed through the processes of precipitation, washing, dispergation and the like, white gel is obtained through drying, and then the silicon-aluminum catalytic material is obtained through roasting for 1-20 hours at 350-650 ℃. CN1565733A discloses a mesoporous silicon-aluminum material which has a pseudo-boehmite structure, concentrated pore size distribution and a specific surface area of about 200-400 m2The mesoporous silicon-aluminum material has the advantages that the pore volume is 0.5-2.0 ml/g, the average pore diameter is 8-20 nm, the most probable pore diameter is 5-15 nm, an organic template agent is not needed in the preparation of the mesoporous silicon-aluminum material, the synthesis cost is low, the obtained silicon-aluminum material has high cracking activity and hydrothermal stability, and the high macromolecular cracking performance is shown in a catalytic cracking reaction.
Disclosure of Invention
Based on a large number of experiments, the inventor finds that based on the characteristics of perfect crystal structure, strong acidity, excellent structural stability, catalytic activity and the like of the microporous molecular sieve and the characteristics of pore channels and acidity of the mesoporous alumina material, the alumina mesoporous layer grows on the surface of the microporous molecular sieve, so that the effective connection of the two structures can be realized, the gradient distribution of the pore channels is built, and the respective advantages of the two structures are effectively strengthened. Based on this, the present invention was made.
One of the purposes of the invention is to provide a composite material containing a Y-type molecular sieve, wherein a mesoporous alumina layer grows on the surface of the molecular sieve, the two structures are effectively connected to form a composite structure, the pore channel distribution is in gradient distribution, the particle size distribution of the composite material is narrow, the particle size is more uniform, the pore channel of the mesoporous layer is unobstructed, and the accessibility of an acid center is strong; the invention also aims to provide a preparation method of the composite material containing the Y-type molecular sieve.
In order to realize one of the purposes of the invention, the invention provides a composite material containing a Y-type molecular sieve, which is characterized in that the composite material also contains a mesoporous alumina layer with a pseudo-boehmite structure, the mesoporous alumina layer grows on the surface of the crystal grain of the Y-type molecular sieve and uniformly coats the crystal grain of the molecular sieve, the disordered structure of the mesoporous alumina layer extends and grows from the edge of the ordered diffraction stripe of the FAU crystal phase structure of the Y-type molecular sieve, and the two structures are built together; the chemical composition of the composite material is (4-12) Na based on the weight of the oxide2O·(20～60)SiO2·(30～75)Al2O3(ii) a The particle size parameter D (V, 0.5) of the composite material is 1.8-2.5, and the particle size parameter D (V, 0.9) is 4.0-8.0.
The phase of the composite material containing the Y-type molecular sieve is characterized by adopting an X-ray diffraction method, and characteristic diffraction peaks appear at 6.2 degrees, 10.1 degrees, 11.9 degrees, 15.7 degrees, 18.7 degrees, 20.4 degrees, 23.7 degrees, 27.1 degrees, 28 degrees, 31.4 degrees, 38.5 degrees, 49 degrees and 65 degrees in an XRD spectrogram respectively, wherein the characteristic diffraction peaks at 6.2 degrees, 10.1 degrees, 11.9 degrees, 15.7 degrees, 18.7 degrees, 20.4 degrees, 23.7 degrees, 27.1 degrees and 31.4 degrees correspond to an FAU crystal phase structure of the Y-type molecular sieve, and the characteristic diffraction peaks at 28 degrees, 38.5 degrees, 49 degrees and 65 degrees correspond to a pseudo-boehmite structure of a mesoporous layer.
According to the composite material containing the Y-type molecular sieve, a Transmission Electron Microscope (TEM) picture shows that the pseudo-boehmite disordered structure of the mesoporous alumina layer extends and grows from the edge of the ordered diffraction stripe of the FAU crystal phase structure of the Y-type molecular sieve, and the two structures are built together. A Scanning Electron Microscope (SEM) shows that a fold-shaped structure is coated on the surface of the molecular sieve crystal grains, and the molecular sieve crystal grains are uniformly coated in the fold-shaped structure.
The composite material containing the Y-type molecular sieve has the characteristics that the particle size parameter measured by a laser particle sizer is 1.8-2.5 of D (V, 0.5) and 4.0-8.0 of D (V, 0.9). The measuring method using the laser particle analyzer is to mix a trace amount of the composite material of the invention with deionized water, take a small amount of slurry to add into the laser particle analyzer, record a plurality of analysis data after the analysis is stable and carry out average treatment to obtain corresponding particle size distribution data.
The Y-type molecular sieve-containing composite material has the chemical composition of (4-12) Na in terms of oxide weight2O·(20～60)SiO2·(30～75)Al2O3The total specific surface area is 380-700 m2(ii) a total pore volume of 0.32 to 0.48cm3(ii) in terms of/g. The composite material containing the Y-type molecular sieve has the characteristic of gradient pore distribution, and the BJH pore size distribution curve shows that two or more pores appear at 3-4 nm and 6-9 nm respectively.
In order to achieve the second purpose of the invention, the invention also provides a preparation method of the composite material containing the Y-type molecular sieve, which is characterized by comprising the following steps: (1) preparing raw materials capable of synthesizing a NaY molecular sieve, uniformly mixing, and then performing static crystallization at the temperature of 95-105 ℃; (2) filtering and washing the slurry after the static crystallization to obtain a NaY molecular sieve filter cake; (3) mixing the NaY molecular sieve filter cake obtained in the step (2) with deionized water, pulping and homogenizing, adding an aluminum source and an alkali solution into the mixture simultaneously in a parallel flow mode under the conditions that the temperature is between room temperature and 85 ℃ and violent stirring, and controlling the pH value of a slurry system to be 9-11 in the mixing process; (4) then the mixture is processed for 1 to 10 hours at the constant temperature of between room temperature and 90 ℃, and the product is recovered.
In the preparation process, the raw materials for synthesizing the NaY molecular sieve in the step (1) generally refer to a directing agent, water glass, sodium metaaluminate, aluminum sulfate and deionized water, and the adding proportion of the raw materials can be the charging proportion of the conventional NaY molecular sieve, such as Na2O：Al2O3：SiO2：H2O is 1.5-8: 1: 5-18: 100-500, or the feeding proportion for preparing NaY molecular sieve with special performance, such as large grain or small grain NaY molecular sieve,the charging ratio and the concentration of each raw material are not particularly limited as long as NaY molecular sieve having FAU crystal phase structure can be obtained. The guiding agent can be prepared according to the prior art (US3639099 and US3671191), and the guiding agent is prepared by mixing a silicon source, an aluminum source, alkali liquor and deionized water according to (15-18) Na2O:Al2O3:(15～17)SiO2:(280～380)H2Mixing the components according to the molar ratio of O, uniformly stirring, and standing and aging for 0.5-48 h at room temperature to 70 ℃. In the feeding proportion of the NaY molecular sieve, Al in the guiding agent2O3The content of (A) is based on the total charge Al2O33 to 15%, preferably 5 to 10% of the total amount. The static crystallization in the step (1) is carried out for 8-50 hours, preferably 10-40 hours, and more preferably 15-35 hours.
In the preparation method, the aluminum source in the step (3) is one or more selected from aluminum nitrate, aluminum sulfate and aluminum chloride; the alkali solution is selected from one or more of ammonia water, potassium hydroxide, sodium hydroxide and sodium metaaluminate, and when the sodium metaaluminate is taken as the alkali solution, the alumina content of the alkali solution is counted in the total alumina content. The sodium metaaluminate can be sodium metaaluminate with different causticity ratios and different concentrations. The caustic ratio is preferably 1.5 to 11.5, more preferably 1.65 to 2.55, and the concentration is preferably 40 to 200gAl2O3a/L, more preferably 41 to 190gAl2O3/L。
In the preparation method, the concept of the concurrent flow mode of adding the aluminum source and the alkali solution simultaneously in the step (3) refers to an operation mode of adding n +1(n is more than or equal to 1) materials (such as two materials of the aluminum source and the alkali solution) into a container simultaneously for mixing, so that each material is added at a constant speed, and the n +1 materials are added in the same time. For example, a peristaltic pump can be used in the specific operation, the flow parameters per unit time of the peristaltic pumps for respectively conveying the aluminum source and the alkali solution are controlled, and the process is performed at a constant speed so as to ensure that the aluminum source and the alkali solution are added in the same time. The temperature of the mixing process in the step (3) is between room temperature and 85 ℃, and preferably between 30 and 70 ℃.
In the preparation process, the constant temperature treatment temperature in the step (4) is room temperature to 90 ℃, preferably 40-80 ℃, and the treatment time is 1-10 hours, preferably 2-8 hours; the process for recovering the product generally comprises the steps of filtering, washing and drying the aged product, which are well known to those skilled in the art and will not be described herein.
Drawings
FIG. 1 is a SEM photograph of a sample of example 1.
FIG. 2 is a TEM image of a sample of example 1.
FIG. 3 is an X-ray diffraction pattern of the sample of example 1.
Fig. 4 is a BJH pore size distribution curve for the sample of example 1.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
The SEM was a Hitachi S4800 field emission SEM, Japan, with an accelerating voltage of 5kV, and the spectra were collected and processed with Horiba 350 software.
Transmission Electron microscope TEM test was carried out using a transmission electron microscope model of FEI Tecnai F20G2S-TWIN, operating at a voltage of 200 kV.
The phase of the sample was determined by X-ray diffraction.
The data of the specific surface, the pore volume, the pore size distribution and the like of the sample are measured by a low-temperature nitrogen adsorption-desorption method.
The particle size distribution test is carried out by mixing micro porous material with deionized water, adding a small amount of slurry into the laser particle size analyzer, recording a plurality of analysis data after stable analysis, and carrying out average treatment to obtain corresponding particle size distribution data.
In each example, Na of the sample2O、Al2O3、SiO2The content was measured by X-ray fluorescence (see "analytical methods in petrochemical industry (RIPP methods of experiments)", eds Yang Cui et al, published by scientific Press, 1990).
Example 1
This example illustrates the Y-type molecular sieve-containing composite material of the present invention and its preparation.
Mixing water glass, aluminum sulfate, sodium metaaluminate, guiding agent and deionized water according to 8.5SiO2：Al2O3：2.65Na2O：210H2Mixing the guiding agent according to a molar ratio of 5%, violently stirring to form NaY molecular sieve gel, placing the gel in a crystallization kettle for static crystallization at 100 ℃ for 34 hours, cooling after crystallization, and filtering and washing crystallized slurry to obtain a NaY molecular sieve filter cake; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, and simultaneously carrying out AlCl in a parallel flow mode at room temperature under the condition of vigorous stirring3Solution (concentration 60 gAl)2O3Adding 8 mass percent of/L) and ammonia water into the mixture, controlling the pH value of a slurry system to be 10.8 in the mixing process, mixing for a certain time, then carrying out constant temperature treatment at 50 ℃ for 5 hours, filtering, washing and drying to obtain the composite material containing the Y-type molecular sieve, which is recorded as AFCY-1.
The SEM photograph of AFCY-1 is shown in FIG. 1, and it can be seen that the molecular sieve crystal grain surface is covered with a wrinkled structure. A Transmission Electron Microscope (TEM) photograph is shown in FIG. 2, and a regular and ordered diffraction fringe and a disordered structure without fixed crystal face trend can be seen, wherein the ordered diffraction fringe represents a FAU crystal structure, the disordered structure is a pseudo-boehmite structure, the disordered structure is derived from the edge of the ordered diffraction fringe, and the two structures are built together.
The XRD spectrum of AFCY-1 is shown in fig. 3, and diffraction peaks appear at 6.2 °, 10.1 °, 11.9 °, 15.7 °, 18.7 °, 20.4 °, 23.7 °, 27.1 °, 28 °, 31.4 °, 38.5 °, 49 ° and 65 °, wherein the characteristic diffraction peak marked ^ corresponds to the FAU crystalline phase structure of the Y-type molecular sieve and the characteristic diffraction peak marked a-corresponds to the pseudo boehmite structure of the mesoporous layer.
The chemical composition of AFCY-1 is 6.5Na by weight of oxide2O·22.0SiO2·71.1Al2O3(ii) a The total specific surface area is 418m2(ii)/g, total pore volume 0.441cm3(ii)/g; the BJH pore size distribution curve is shown in FIG. 4, and bimodal distribution at about 3.8nm and 7.4nm respectively can be seen;the laser particle size analyzer measured D (V, 0.5) ═ 2.50 and D (V, 0.9) ═ 7.80.
Example 2
This example illustrates the Y-type molecular sieve-containing composite material of the present invention and its preparation.
Preparing NaY molecular sieve gel according to the molar ratio in the embodiment 1, statically crystallizing at 100 ℃ for 18 hours, cooling after crystallization, and filtering and washing crystallized slurry to obtain a NaY molecular sieve filter cake; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, heating to 50 ℃, and simultaneously carrying out AlCl in a parallel flow mode under the condition of vigorous stirring3Solution (concentration 60 gAl)2O3adding/L) and NaOH solution (with the concentration of 1M) into the mixture, controlling the pH value of a slurry system to be 9.4 in the mixing process, mixing for a certain time, then carrying out constant-temperature treatment at 70 ℃ for 6 hours, filtering, washing and drying to obtain the composite material containing the Y-type molecular sieve, which is recorded as AFCY-2.
The SEM photograph of AFCY-2 has the characteristics shown in FIG. 1, and it can be seen that the surface of the molecular sieve crystal grain is coated with a wrinkled structure. The transmission electron microscope photograph has the characteristics shown in figure 2, regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together.
The XRD spectrum of AFCY-2 has the characteristics shown in figure 3, and both FAU crystal phase structure and pseudo-boehmite structure exist; the chemical composition of the oxide-doped sodium titanate is 11.7Na by weight2O·57.6SiO2·30.1Al2O3(ii) a The total specific surface area is 651m2(ii)/g, total pore volume 0.350cm3(ii)/g; the BJH pore size distribution curve has the characteristics shown in figure 4, and bimodal distribution around 3.8nm and 6.6nm can be seen; the laser particle size analyzer measured D (V, 0.5) ═ 1.97 and D (V, 0.9) ═ 4.11.
Example 3
This example illustrates the Y-type molecular sieve-containing composite material of the present invention and its preparation.
Preparing NaY molecular sieve gel according to the molar ratio in the example 1, statically crystallizing at 100 ℃ for 45 hours, and crystallizingCooling and filtering and washing the crystallized slurry after the crystallization is finished to obtain a NaY molecular sieve filter cake; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, heating to 35 ℃, and simultaneously carrying out AlCl in a parallel flow mode under the condition of vigorous stirring3Solution (concentration 60 gAl)2O3/L) and NaAlO2Solution (concentration 180 gAl)2O3and/L) adding the components into the slurry, controlling the pH value of a slurry system in the mixing process to be 10.2, mixing for a certain time, then carrying out constant temperature treatment at 65 ℃ for 4 hours, filtering, washing and drying to obtain the composite material containing the Y-type molecular sieve, which is marked as AFCY-3.
The SEM photograph of AFCY-3 has the characteristics shown in FIG. 1, and it can be seen that the surface of the molecular sieve crystal grain is coated with a wrinkled structure. The transmission electron microscope photograph has the characteristics shown in figure 2, regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together.
The XRD spectrum of AFCY-3 has the characteristics shown in figure 3, and both FAU crystal phase structure and pseudo-boehmite structure exist; the chemical composition of the oxide-based nano-particles is 10.0Na by weight2O·48.5SiO2·41.1Al2O3(ii) a The total specific surface area thereof is 611m2(ii)/g, total pore volume of 0.397cm3(ii)/g; the BJH pore size distribution curve has the characteristics shown in figure 4, and bimodal distribution around 3.8nm and 8.1nm can be seen; the laser particle size analyzer measured D (V, 0.5) ═ 2.21 and D (V, 0.9) ═ 5.48.
Example 4
This example illustrates the Y-type molecular sieve-containing composite material of the present invention and its preparation.
Preparing NaY molecular sieve gel according to the molar ratio in the embodiment 1, statically crystallizing at 100 ℃ for 26 hours, cooling after crystallization, and filtering and washing crystallized slurry to obtain a NaY molecular sieve filter cake; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, heating to 45 ℃, and simultaneously carrying out concurrent flow on Al under vigorous stirring2(SO4)3Solution (concentration 90 gAl)2O3L) and ammonia water (mass fraction)8%) of the molecular sieve, controlling the pH value of a slurry system to be 9.8 in the mixing process, mixing for a certain time, then carrying out constant temperature treatment at 55 ℃ for 8 hours, filtering, washing and drying to obtain the Y-type molecular sieve-containing composite material, which is marked as AFCY-4.
The SEM photograph of AFCY-4 has the characteristics shown in FIG. 1, and it can be seen that the surface of the molecular sieve crystal grain is coated with a wrinkled structure. The transmission electron microscope photograph has the characteristics shown in figure 2, regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together.
The XRD spectrum of AFCY-4 has the characteristics shown in figure 3, and both FAU crystal phase structure and pseudo-boehmite structure exist; the chemical composition of the oxide-based nano-particles is 5.8Na by weight2O·31.4SiO2·62.3Al2O3(ii) a The total specific surface area is 498m2(ii)/g, total pore volume 0.432cm3(ii)/g; the BJH pore size distribution curve has the characteristics shown in figure 4, and bimodal distribution around 3.8nm and 7.4nm can be seen; the laser particle size analyzer measured D (V, 0.5) to 2.34 and D (V, 0.9) to 6.72.
Example 5
This example illustrates the Y-type molecular sieve-containing composite material of the present invention and its preparation.
According to 7.5SiO2：Al2O3：2.15Na2O：190H2Preparing NaY molecular sieve gel according to the molar ratio of O, statically crystallizing for 40 hours at the temperature of 100 ℃, cooling after crystallization, and filtering and washing crystallized slurry to obtain a NaY molecular sieve filter cake; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, heating to 55 ℃, and simultaneously carrying out Al parallel flow under vigorous stirring2(SO4)3Solution (concentration 90 gAl)2O3/L) and NaAlO2Solution (concentration 102 gAl)2O3/L) is added into the slurry, the pH value of the slurry system is controlled to be 9.0 in the mixing process, after the slurry is mixed for a certain time, the slurry is processed for 2 hours at the constant temperature of 60 ℃, and then the composite material containing the Y-shaped molecular sieve is obtained by filtering, washing and drying, and is marked as AFCY-5。
The SEM photograph of AFCY-5 has the characteristics shown in FIG. 1, and it can be seen that the surface of the molecular sieve crystal grain is coated with a wrinkled structure. The transmission electron microscope photograph has the characteristics shown in figure 2, regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together.
The XRD spectrum of AFCY-5 has the characteristics shown in figure 3, and both FAU crystal phase structure and pseudo-boehmite structure exist; the chemical composition of the oxide-doped sodium titanate is 10.8Na in terms of weight of oxide2O·53.8SiO2·35.0Al2O3(ii) a The total specific surface area of the powder is 647m2(iv)/g, total pore volume 0.377cm3(ii)/g; the BJH pore size distribution curve has the characteristics shown in figure 4, and bimodal distribution around 3.8nm and 9.0nm can be seen; d (V, 0.5) ═ 2.13 and D (V, 0.9) ═ 5.02 measured by a laser particle sizer.
Example 6
This example illustrates the Y-type molecular sieve-containing composite material of the present invention and its preparation.
Preparing NaY molecular sieve gel according to the molar ratio of the embodiment 5, statically crystallizing for 32 hours at 100 ℃, cooling after crystallization, and filtering and washing crystallized slurry to obtain a NaY molecular sieve filter cake; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, heating to 40 ℃, and simultaneously carrying out Al parallel flow under vigorous stirring2(SO4)3Solution (concentration 90 gAl)2O3and/L) and NaOH solution (with the concentration of 1M) are added into the mixture, the pH value of a slurry system is controlled to be 10.5 in the mixing process, after the mixture is mixed for a certain time, the mixture is processed for 3 hours at the constant temperature of 75 ℃, and then the composite material containing the Y-type molecular sieve is obtained by filtering, washing and drying, and is marked as AFCY-6.
The SEM photograph of AFCY-6 has the characteristics shown in FIG. 1, and it can be seen that the surface of the molecular sieve crystal grain is coated with a wrinkled structure. The transmission electron microscope photograph has the characteristics shown in figure 2, regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together.
The XRD spectrum of AFCY-6 has the characteristics shown in figure 3, and both FAU crystal phase structure and pseudo-boehmite structure exist; the chemical composition of the oxide-doped sodium titanate is 10.5Na in terms of weight of oxide2O·58.4SiO2·30.4Al2O3(ii) a The total specific surface area is 670m2(ii)/g, total pore volume 0.334cm3(ii)/g; the BJH pore size distribution curve has the characteristics shown in figure 4, and bimodal distribution around 3.8nm and 6.6nm can be seen; the laser particle size analyzer measured D (V, 0.5) ═ 1.92 and D (V, 0.9) ═ 4.01.
Example 7
This example illustrates the Y-type molecular sieve-containing composite material of the present invention and its preparation.
Preparing NaY molecular sieve gel according to the molar ratio of the embodiment 1, statically crystallizing at 100 ℃ for 20 hours, cooling after crystallization, and filtering and washing crystallized slurry to obtain a NaY molecular sieve filter cake; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, and simultaneously adding Al (NO) in a parallel flow mode at 30 ℃ under vigorous stirring3)3Solution (concentration 60 gAl)2O3/L) and NaAlO2Solution (concentration 102 gAl)2O3and/L) adding the components into the slurry, controlling the pH value of a slurry system in the mixing process to be 10.0, mixing for a certain time, then carrying out constant temperature treatment at 70 ℃ for 1 hour, filtering, washing and drying to obtain the composite material containing the Y-type molecular sieve, which is marked as AFCY-7.
The SEM photograph of AFCY-7 has the characteristics shown in FIG. 1, and it can be seen that the surface of the molecular sieve crystal grain is coated with a wrinkled structure. The transmission electron microscope photograph has the characteristics shown in figure 2, regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together.
The XRD spectrum of AFCY-7 has the characteristics shown in figure 3, and both FAU crystal phase structure and pseudo-boehmite structure exist; the chemical composition of the oxide-based nano-crystalline silicon oxide is 8.6Na by weight2O·39.4SiO2·51.5Al2O3(ii) a The total specific surface area is 558m2In terms of/g, total pore volume of0.426cm3(ii)/g; the BJH pore size distribution curve has the characteristics shown in figure 4, and bimodal distribution around 3.8nm and 7.4nm can be seen; the laser particle size analyzer measured D (V, 0.5) ═ 2.29 and D (V, 0.9) ═ 6.17.
Example 8
This example illustrates the Y-type molecular sieve-containing composite material of the present invention and its preparation.
Preparing NaY molecular sieve gel according to the molar ratio of the embodiment 1, statically crystallizing at 100 ℃ for 30 hours, cooling after crystallization, and filtering and washing crystallized slurry to obtain a NaY molecular sieve filter cake; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, and simultaneously adding Al (NO) in a parallel flow mode at 35 ℃ under vigorous stirring3)3Solution (concentration 60 gAl)2O3Adding 8 mass percent of/L) and ammonia water into the mixture, controlling the pH value of a slurry system to be 9.6 in the mixing process, mixing for a certain time, then carrying out constant temperature treatment at 60 ℃ for 7 hours, filtering, washing and drying to obtain the composite material containing the Y-type molecular sieve, which is recorded as AFCY-8.
The SEM photograph of AFCY-8 has the characteristics shown in FIG. 1, and it can be seen that the surface of the molecular sieve crystal grain is coated with a wrinkled structure. The transmission electron microscope photograph has the characteristics shown in figure 2, regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together.
The XRD spectrum of AFCY-8 has the characteristics shown in figure 3, and both FAU crystal phase structure and pseudo-boehmite structure exist; the chemical composition of the oxide-based nano-particles is 6.0Na by weight2O·25.6SiO2·67.8Al2O3(ii) a The total specific surface area thereof was 451m2In terms of/g, total pore volume of 0.428cm3(ii)/g; the BJH pore size distribution curve has the characteristics shown in figure 4, and bimodal distribution around 3.8nm and 8.1nm can be seen; the laser particle size analyzer measured D (V, 0.5) ═ 2.42 and D (V, 0.9) ═ 7.25.
Claims (9)
1. The composite material containing Y-type molecular sieve is characterized by also containingThe mesoporous alumina layer with a pseudo-boehmite structure grows on the surface of the crystal grain of the Y-type molecular sieve and coats the molecular sieve crystal grain, the disordered structure of the mesoporous alumina layer extends and grows from the edge of the ordered diffraction stripe of the FAU crystal phase structure of the Y-type molecular sieve, and the two structures are built together; the chemical composition of the composite material is (4-12) Na based on the weight of the oxide2O·(20～60)SiO2·(30～75)Al2O3(ii) a The granularity parameter D (V, 0.5) of the composite material is 1.8-2.5, and the granularity parameter D (V, 0.9) is 4.0-8.0; the composite material has the characteristic of gradient pore distribution, and can be distributed in several pores at 3-4 nm and 6-9 nm respectively.
2. Composite material according to claim 1, characterized in that its total specific surface area is 380 to 700m2/g。
3. Composite material according to claim 1, characterized in that its total pore volume is between 0.32 and 0.48cm3/g。
4. A method for preparing a composite material containing a Y-type molecular sieve according to any one of claims 1 to 3, characterized by comprising the steps of: (1) preparing raw materials capable of synthesizing a NaY molecular sieve, uniformly mixing, and then statically crystallizing at the temperature of 95-105 ℃; (2) filtering and washing the slurry after the static crystallization to obtain a NaY molecular sieve filter cake; (3) mixing the NaY molecular sieve filter cake obtained in the step (2) with deionized water, pulping and homogenizing, adding an aluminum source and an alkali solution into the mixture simultaneously in a parallel flow mode under the conditions that the temperature is between room temperature and 85 ℃ and violent stirring, and controlling the pH value of a slurry system to be 9-11 in the mixing process; (4) then the mixture is processed for 1 to 10 hours at the constant temperature of between room temperature and 90 ℃, and the product is recovered.
5. The method according to claim 4, wherein the static crystallization in the step (1) is carried out for 8 to 50 hours.
6. The production method according to claim 4, wherein the aluminum source in the step (3) is one or more selected from the group consisting of aluminum nitrate, aluminum sulfate and aluminum chloride; the alkali solution is one or more selected from ammonia water, potassium hydroxide, sodium hydroxide and sodium metaaluminate.
7. The process according to claim 4, wherein in the step (3), when sodium metaaluminate is used as the alkali solution, the alumina content is calculated to the total alumina content.
8. The method according to claim 4, wherein the temperature of the mixing process of adding the aluminum source and the alkali solution in the step (3) is 30 to 70 ℃.
9. The process according to claim 4, wherein the constant temperature treatment in the step (4) is carried out at a temperature of 40 to 80 ℃ for 2 to 8 hours.
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