CN110871104B - Porous catalytic material and preparation method thereof - Google Patents
Porous catalytic material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims description 25
- 239000011148 porous material Substances 0.000 claims abstract description 132
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 109
- 239000002808 molecular sieve Substances 0.000 claims abstract description 108
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 239000013078 crystal Substances 0.000 claims description 46
- 239000002002 slurry Substances 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 39
- 238000001914 filtration Methods 0.000 claims description 38
- 238000009826 distribution Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 35
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 30
- 239000011734 sodium Substances 0.000 claims description 25
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 24
- 238000004537 pulping Methods 0.000 claims description 24
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 23
- 235000019353 potassium silicate Nutrition 0.000 claims description 22
- 230000005540 biological transmission Effects 0.000 claims description 19
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 17
- 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 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 150000003863 ammonium salts Chemical class 0.000 claims description 13
- 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 12
- 235000019270 ammonium chloride Nutrition 0.000 claims description 12
- 239000012066 reaction slurry Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 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 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 238000001237 Raman spectrum Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 1
- 230000003595 spectral effect Effects 0.000 claims 1
- 239000000295 fuel oil Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 15
- 238000004523 catalytic cracking Methods 0.000 abstract description 13
- 238000001069 Raman spectroscopy Methods 0.000 description 29
- 239000003795 chemical substances by application Substances 0.000 description 26
- 238000005336 cracking Methods 0.000 description 23
- 238000001228 spectrum Methods 0.000 description 22
- 239000003921 oil Substances 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 7
- 239000000571 coke Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000003502 gasoline Substances 0.000 description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 7
- 229910001948 sodium oxide Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000013335 mesoporous material Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 229910001593 boehmite Inorganic materials 0.000 description 5
- 238000012921 fluorescence analysis Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 239000011268 mixed slurry Substances 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002829 reductive effect Effects 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
- 238000003917 TEM image Methods 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
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 carbonium ion Chemical class 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
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- 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
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing 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
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 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
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 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
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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
- 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
- B01J35/635—0.5-1.0 ml/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
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The porous catalytic material is characterized by simultaneously containing a microporous structure of a Y-type molecular sieve and gamma-Al 2 O 3 The mesoporous structure grows along the edge of the Y-shaped molecular sieve structure, the unit cell constant is 2.453-2.465 nm, and the chemical composition of the mesoporous structure is (0.3-1.0) Na 2 O·(30～69)SiO 2 ·(30～70)Al 2 O 3 The total specific surface area is 300-600 m 2 Per g, total pore volume of 0.5-1.0 cm 3 (ii) in terms of/g. The porous catalytic material has the structural characteristics of micropores and mesopores, and has high catalytic cracking activity and strong heavy oil conversion capability.
Description
Technical Field
The invention relates to a porous catalytic material and a preparation method thereof, and further relates to a microporous structure containing a Y-type molecular sieve and gamma-Al 2 O 3 A composite porous catalytic material with a mesoporous structure 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 to the fields of catalytic cracking, hydrocracking and the like in 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 structure, the Y-type molecular sieve shows a relatively obvious pore 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 on mesoporous materials, particularly mesoporous silicon-aluminum materials, has attracted great interest to researchers in the field of catalysis. Mesoporous materials were first developed in 1992 by the American Mobil Corporation (Beck J S, vartuli J Z, roth W J et al, J.Am.Chem.Comm.Soc.,1992, 114, 10834-10843), which is named as M41S series mesoporous molecular sieves, including MCM-41 (Mobil Corporation Material-41) and MCM-48, etc., and the pore size of the molecular sieves can reach 1.6-10 nm, and the mesoporous materials are uniform and adjustable, concentrated in pore size distribution, large in specific surface area and pore volume and strong in 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 efforts are focused on improving the thickness of the pore walls of the molecular sieves, and if a neutral template agent is adopted, a molecular sieve with a thicker pore wall can be obtained, but the defect of weaker acidity still exists. In CN 1349929A, a new type of mesoporous molecular sieve is disclosed, in which the primary and secondary structural units of zeolite are introduced into the pore wall of the molecular sieve to make it have the basic structure of conventional zeolite molecular sieve, and said mesoporous molecular sieve possesses 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, silica-alumina materials are widely used because of 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 silicon-aluminum composite material which is prepared by mixing acidic inorganic aluminum salt and silica sol and then adding alkali for reaction, wherein aluminum is5-40 wt%, 20-50 nm pore diameter, 50-100 m specific surface area 2 (iv) g. The method disclosed in US4,708,945 is that firstly, silica particles or hydrated silica are loaded on porous boehmite, and then the obtained compound is hydrothermally treated for a certain time at the temperature of more than 600 ℃ to prepare the catalyst with the silica loaded on the surface of the boehmite, wherein the silica is combined with hydroxyl of the transitional boehmite, and the surface area reaches 100-200 m 2 G, and the average pore diameter is 7-7.5 nm. A series of acidic cracking catalysts are disclosed in US4,440,872 in which some of the catalysts are supported by a catalyst supported on gamma-Al 2 O 3 Impregnating silane, and then roasting at 500 ℃ or treating with water vapor. CN1353008A uses inorganic aluminum salt and water glass as raw materials, forms stable and clear silica-alumina sol through processes of precipitation, washing, dispergation and the like, then obtains white gel through drying, and then obtains the silica-alumina catalytic material 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 m 2 The mesoporous silicon-aluminum material has the advantages of no need of using an organic template agent for preparation, low synthesis cost, high cracking activity and hydrothermal stability of the obtained silicon-aluminum material, and good macromolecule cracking performance in a catalytic cracking reaction.
Disclosure of Invention
The inventor finds out on the basis of a large number of experiments that a disordered mesoporous structure with a mesoporous scale can be extended and grown on the surface of the Y-type molecular sieve by a derivation growth method, and the two structures are organically combined together to form continuous and unobstructed gradient pore distribution and gradient acid center distribution. Based on this, the present invention was made.
One of the purposes of the invention is to provide a porous catalytic material which has the structural characteristics of micropores and mesopores, has flexible and adjustable micropore and mesopore proportion, and has higher catalytic cracking activity and heavy oil conversion capability than a mechanical mixed sample with the same proportion of the micro-mesopore material.
Another object of the present invention is to provide a method for preparing the porous catalytic material of the present invention.
In order to achieve one of the purposes of the invention, the invention provides a porous catalytic material which is characterized by simultaneously containing FAU crystal phase structure (microporous structure) of Y-type molecular sieve and gamma-Al 2 O 3 Structure (mesoporous structure), said gamma-Al 2 O 3 The mesoporous structure grows along the edge of a Y-type molecular sieve FAU crystal phase structure, and the two structures are organically connected; unit cell constant 2.453-2.465 nm, preferably 2.455-2.463 nm, relative crystallinity 25-80%, preferably 28-75%, chemical composition (0.3-1.0) Na by weight of oxide 2 O·(30～69)SiO 2 ·(30～70)Al 2 O 3 Total specific surface area of 300-600 m 2 Per g, total pore volume of 0.5-1.0 cm 3 /g。
In the porous catalytic material, the XRD spectrogram shows characteristic diffraction peaks of a Y-type molecular sieve 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, 31.4 degrees and the like, and the characteristic diffraction peaks at a wide peak between 20 and 30 degrees and about 66 degrees show that gamma-Al 2 O 3 And (5) structure.
In order to achieve the second object of the present invention, the present invention further provides a method for preparing the porous catalytic material, comprising the following steps: (1) Firstly contacting a porous material and ammonium salt according to the weight ratio of 1 (0.2-1.2) with the ammonium salt at the temperature of 40-90 ℃ for 0.5-3 hours, filtering, washing and drying; (2) Carrying out hydrothermal roasting on the mixture obtained in the step (1) at the temperature of 500-700 ℃ for 1-4 hours under the condition of 100% of water vapor; (3) And (3) adding water into the mixture obtained in the step (2) for pulping, performing second contact treatment on the mixture and ammonium salt for 0.5 to 2 hours at the temperature of between 40 and 90 ℃ according to the weight ratio of 1 (0.2 to 1.0), filtering, washing and drying to obtain the porous catalytic material.
Wherein, the porous material in the step (1) contains an FAU crystal phase structure and a pseudo-boehmite Dan Feijing phase structure in an XRD spectrogram, an ordered diffraction stripe of the FAU crystal part and a disordered structure of the pseudo-boehmite part can be simultaneously seen in a Transmission Electron Microscope (TEM), the disordered structure is derived and grown along the edge of the ordered diffraction stripe, and the two structures are effectively combinedTogether forming a microporous and mesoporous composite structure. The porous material in the step (1) has an anhydrous chemical expression of: (4 to 12) Na 2 O·(25～65)SiO 2 ·(25～70)Al 2 O 3 The specific surface area is 350 to 750m 2 Per gram, the specific surface area of the mesopores is 50 to 450m 2 The total pore volume is 0.5-1.5 ml/g, and the mesoporous pore volume is 0.2-1.2 ml/g. Raman spectroscopy (Ramam) can be used for structural analysis to determine the corresponding structure by energy-producing differences between scattered and incident photons, i.e. Raman shift, based on changes in the degree of polarization upon vibration. The porous material obtained in the step (1) has a Raman (Raman) spectrum with a/b = 1.5-10.0, wherein a represents a Raman shift of 500cm -1 B represents a Raman shift of 350cm -1 Peak intensity of the spectrum.
The porous material in the step (1) can simultaneously see the ordered diffraction stripes of the FAU crystal part and the disordered structure of the pseudo-boehmite part in a Transmission Electron Microscope (TEM), the disordered structure of the pseudo-boehmite part is derived and grown along the edges of the ordered diffraction stripes of the FAU crystal phase, the edge lines of the crystal structure disappear, and the two structures are effectively combined together to form a microporous and mesoporous composite structure. Wherein, the FAU crystal phase structure shows diffraction fringes which are orderly and regularly arranged in the transmission electron mirror. The pseudo-boehmite structure shows a disordered structure in the transmission electron mirror and has no fixed crystal face trend. SEM representation shows that the wrinkled structure and partial Y-shaped molecular sieve grains can be seen simultaneously, and most of the molecular sieve grains are coated by the wrinkled mesoporous structure grown on the surface.
The porous material in the step (1) has the gradient pore distribution characteristic formed by a microporous structure and a mesoporous structure, and obvious pore distribution is respectively generated at 3-4 nm, 8-20 nm and 18-40 nm.
Further, the porous material in step (1) can be prepared by the following process: adding water into molecular sieve dry powder with FAU crystal structure for pulping, uniformly stirring, adding an aluminum source and an alkali solution at the temperature of between room temperature and 85 ℃, and fillingSeparately mixing, controlling the pH value of a slurry system to be kept between 7 and 11, carrying out contact reaction, and then taking alumina in the aluminum source as a reference and SiO 2 :Al 2 O 3 And (1-9) adding a silicon source calculated by silicon oxide into the reaction slurry, continuously reacting for 1-10 hours at the temperature of room temperature to 90 ℃, or stirring for 1-4 hours at the constant temperature of room temperature to 90 ℃, crystallizing for 3-30 hours at the temperature of 95-105 ℃ in a closed reaction kettle, and recovering the product.
In the above process, the molecular sieve with FAU crystal structure is NaY molecular sieve. The NaY molecular sieve with different silicon-aluminum ratios, different crystallinities and different grain sizes can be adopted, and the crystallinity is preferably more than 70 percent, and more preferably more than 80 percent. For example, dry powder of NaY molecular sieve can be obtained by mixing and stirring water glass, sodium metaaluminate, aluminum sulfate, directing agent and deionized water in a certain proportion and in a certain order, crystallizing at 95-105 ℃ for a certain period of time, filtering, washing and drying. The adding proportion of the water glass, the sodium metaaluminate, the aluminum sulfate, the guiding agent and the deionized water can be the charging proportion of a conventional NaY molecular sieve, and can also be the charging proportion for preparing the NaY molecular sieve with special performance, such as the charging proportion for preparing a large-grain or small-grain NaY molecular sieve, and the like, and the charging proportion and the concentration of each raw material are not specially limited as long as the NaY molecular sieve with an FAU crystal phase structure can be obtained. The order of addition may be various, and is not particularly limited. The directing agent can be prepared by various methods, for example, according to the methods disclosed in the prior art (US 3639099 and US 3671191), and a typical directing agent is prepared by mixing a silicon source, an aluminum source, an alkali solution and deionized water according to (15-18) Na 2 O:Al 2 O 3 :(15～17)SiO 2 :(280～380)H 2 Mixing the components according to the molar ratio of O, uniformly stirring, standing and aging for 0.5-48 h at the temperature of room temperature to 70 ℃ to obtain the product. The silicon source used for preparing the guiding agent is water glass, the aluminum source is sodium metaaluminate, and the alkali liquor is sodium hydroxide solution.
In the above process, the aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate or aluminum chloride; the alkali solution is one or more selected from ammonia water, potassium hydroxide, sodium hydroxide or sodium metaaluminate, and when the sodium metaaluminate is used as the alkali solution, the alumina content is counted in the total alumina content. The contact reaction temperature is between room temperature and 85 ℃, and preferably between 30 and 70 ℃.
In the above process, the silicon source is selected from one or more of water glass, sodium silicate, tetraethoxysilane, tetramethoxysilane or silicon oxide. The temperature for continuing the reaction after adding the silicon source is between room temperature and 90 ℃, preferably between 40 and 80 ℃, and the reaction time is between 1 and 10 hours, preferably between 2 and 8 hours. The process for recovering the product generally comprises the steps of filtering, washing and drying the crystallized product, which are well known to those skilled in the art and will not be described herein.
In the preparation method of the invention, the ammonium salt in the step (1) and the step (3) can be one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium bicarbonate.
In the first contact treatment in the step (1), the ratio of the porous material to the ammonium salt is 1 (0.2-1.2), preferably 1 (0.3-1.0) in terms of weight ratio, and the exchange temperature is 40-90 ℃, preferably 50-80 ℃.
The hydrothermal calcination in the step (2) is carried out at a temperature of 500 to 700 ℃ and preferably 550 to 650 ℃ for 1 to 4 hours.
In the second contact treatment in the step (3), the ratio of the porous material to the ammonium salt is 1 (0.2-1.0), preferably 1 (0.3-0.8) in terms of weight ratio, and the contact temperature is 40-90 ℃, preferably 50-80 ℃.
The filtration, water washing and drying process is well known to those skilled in the art and will not be described herein.
The porous catalytic material provided by the invention has special structural characteristics in pore structure and acid distribution due to the organic combination of the micro-mesoporous structure and the mesoporous structure, so that the porous catalytic material has more excellent macromolecule transmission and cracking activity and more excellent reaction performance. After being aged for 17 hours at 800 ℃ and 100 percent of water vapor, the catalyst still shows higher cracking activity, the conversion rate of raw oil and the yield of gasoline are both higher, the conversion capacity of heavy oil is better, the yield of coke is relatively lower, and the distribution of products is more optimized.
Drawings
FIG. 1 is an X-ray diffraction pattern of YCMN-1, a porous material as described in example 1.
FIG. 2 is a TEM transmission electron micrograph of the porous material YCMN-1 of example 1.
FIG. 3 is the BJH pore size distribution curve of YCMN-1, the porous material in example 1.
FIG. 4 is an SEM scanning electron micrograph of the porous material YCMN-1 of example 1.
FIG. 5 is an X-ray diffraction pattern of the porous catalytic material A-1 of example 1.
FIG. 6 is the BJH pore size distribution curve of the porous material YCM-1 in example 6.
FIG. 7 is an X-ray diffraction pattern of YCM-1, a porous material in example 6.
FIG. 8 is a TEM transmission electron micrograph of the porous material YCM-1 of example 6.
FIG. 9 is an SEM scanning electron micrograph of a porous material YCM-1 in example 6.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
The preparation process of the directing agent used in the examples was: 5700g of water glass (available from Changling catalysts, inc., siO) 2 261g/L, modulus 3.31, density 1259 g/L) was placed in a beaker and 4451g of high alkali sodium metaaluminate (provided by Changling catalysts, inc., al) was added with vigorous stirring 2 O 3 39.9g/L，Na 2 O279.4g/L, density 1326 g/L) and aging at 30 ℃ for 18 hours to obtain 16.1Na with molar ratio 2 O:Al 2 O 3 :15SiO 2 :318.5H 2 A directing agent for O.
In various embodiments, na of the material 2 O、Al 2 O 3 、SiO 2 The content was measured by X-ray fluorescence (see the eds of petrochemical analysis (RIPP methods), yang Cui, published by scientific Press, 1990).
The phase, unit cell constant, crystallinity, and the like were measured by X-ray diffraction. Wherein, the crystallinity is measured according to the industry standards SH/T0340-92 and SH/T0339-92 of China general petrochemical company, and the NaY molecular sieve crystallinity standard sample is measured: naY molecular sieve (GS BG 75004-1988).
The TEM test of the transmission electron microscope adopts a transmission electron microscope of a model of Tecnai F20G2S-TWIN of FEI company, and the operating voltage is 200kV.
Scanning Electron microscope SEM test A field emission scanning electron microscope, model Hitachi S4800, japan, was used, the acceleration voltage was 5kV, and the energy spectrum was collected and processed with Horiba 350 software.
The pore parameters are measured by a low-temperature nitrogen adsorption-desorption volumetric method.
The laser Raman spectrum adopts a LabRAM HR UV-NIR type laser confocal Raman spectrometer of HORIBA company of Japan, the wavelength of an excitation light source is 325nm, an ultraviolet 15-time objective lens, a confocal pinhole is 100 mu m, and the spectrum scanning time is 100s.
Example 1
This example illustrates the porous catalytic material of the present invention and the process for its preparation.
According to 8.5SiO 2 ：Al 2 O 3 ：2.65Na 2 O：210H 2 The method comprises the steps of feeding a NaY molecular sieve gel of O in a molar ratio, sequentially mixing and stirring water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and required deionized water for 1 hour, wherein the mass ratio of the guiding agent is 5%, crystallizing the gel for 30 hours at 100 ℃, filtering and washing crystallized slurry, and drying the crystallized slurry for 10 hours at 120 ℃ in an oven to obtain the NaY molecular sieve.
Adding water again to the obtained NaY molecular sieve dry powder for pulping, uniformly stirring, heating to 50 ℃, and stirring vigorously while adding AlCl 3 Solution (concentration 60 gAl) 2 O 3 /L) and NaAlO 2 Solution (concentration 102 gAl) 2 O 3 /L) is added into the mixture in parallel, the contact reaction is carried out, the pH value of a slurry system is controlled to be 8.5, and after a certain time of reaction, the reaction is carried out according to the total Al in the used aluminum chloride solution and sodium metaaluminate solution 2 O 3 By weight, in terms of SiO 2 :Al 2 O 3 =1:8 weight ratio, tetraethoxy silicon is added to the above reaction slurryAnd then the reaction is continued for 6 hours at 80 ℃, and then the porous material YCMN-1 is obtained by filtering, washing and drying in an oven at 120 ℃.
YCMN-1 fluorescence analysis chemical composition is 9.41Na 2 O·53.6SiO 2 ·37.2Al 2 O 3 The X-ray diffraction pattern is shown in fig. 1, which shows that the material contains both FAU crystal phase structure and pseudo-boehmite structure. The TEM photograph of YCMN-1 transmission electron microscope is shown in FIG. 2, which shows that two structures exist simultaneously and are combined together, and the amorphous and amorphous structure of the pseudoboehmite grows along the edge of the FAU crystalline phase structure to form a composite structure. BJH pore size distribution curves are shown in fig. 3, showing the characteristic of having a graded pore distribution, with distinct probable pore distributions appearing at 3.8nm, 11.5nm and 19.2nm, respectively. The SEM photograph is shown in FIG. 4, and the wrinkled structure and part of the grains of the Y-type molecular sieve can be seen, and most of the grains of the molecular sieve are coated by the wrinkled mesoporous structure grown on the surface. The BET specific surface area of which was 623m 2 G, the mesoporous specific surface area is 89m 2 The volume of total pores is 0.70ml/g, and the pore volume of mesopores is 0.44ml/g; YCMN-1 with a/b =7.3, wherein a denotes a Raman shift of 500cm in the Raman (Raman) spectrum -1 B represents a Raman shift of 350cm -1 Peak intensity of the spectrum.
Contacting porous material YCMN-1 and ammonium chloride according to the weight ratio of 1:1 for 1 hour at 70 ℃, filtering, washing and drying; then carrying out hydrothermal roasting for 2 hours at the temperature of 600 ℃ under the condition of 100 percent of water vapor; and adding water again into the roasted sample, pulping, carrying out secondary contact treatment on the sample and ammonium chloride at the temperature of 70 ℃ for 1 hour according to the weight ratio of 1.3, filtering, washing with water, and drying to obtain the porous catalytic material, which is recorded as A-1.
The XRD diffraction pattern of A-1 is shown in FIG. 5, which shows the FAU crystal phase structure and gamma-Al containing both Y-type molecular sieve 2 O 3 The structure shows FAU structure characteristic peaks (corresponding to the X-signs in the figure) 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, 31.4 degrees and the like, and gamma-Al appears between 20 degrees and 30 degrees and around 66 degrees 2 O 3 Structural characteristic peak (brace pair in figure)The peak of response).
The unit cell constant of A-1 is 2.459nm, the relative crystallinity is 73%, the chemical composition is 0.65Na based on the weight of oxide 2 O·59.4SiO 2 ·39.3Al 2 O 3 Total specific surface area 579m 2 G, total pore volume 0.64cm 3 /g。
Example 2
This example illustrates the porous catalytic material of the present invention and the process for its preparation.
According to the mol ratio of gel feeding of the NaY molecular sieve in the embodiment 1, water glass, a guiding agent, aluminum sulfate, sodium metaaluminate and required deionized water are sequentially mixed and stirred for 1 hour, wherein the mass ratio of the guiding agent is 6%, the gel is crystallized at 100 ℃ for 25 hours, and then the crystallized slurry is filtered and washed, and is dried in an oven at 120 ℃ for 10 hours to obtain the NaY molecular sieve.
Adding water again to the obtained NaY molecular sieve dry powder for pulping, uniformly stirring, heating to 40 ℃, and stirring vigorously while adding Al 2 (SO 4 ) 3 Solution (concentration 50 gAl) 2 O 3 /L) and NaAlO 2 Solution (concentration 102 gAl) 2 O 3 /L) is added into the mixture in parallel, the contact reaction is carried out, the pH value of a slurry system is controlled to be 9.0, and after a certain time of reaction, the reaction is carried out according to the total Al in the used aluminum sulfate solution and sodium metaaluminate solution 2 O 3 By weight, in terms of SiO 2 :Al 2 O 3 A water glass solution (concentration 120 gSiO) in a weight ratio of 1:5 2 L) was added to the above reaction slurry and the reaction was continued at 55 ℃ for 6 hours, then filtered, washed and oven-dried at 120 ℃ to give porous material YCMN-3.
YCMN-3 has a chemical composition of 5.70Na for fluorescence analysis 2 O·34.0SiO 2 ·59.4Al 2 O 3 The X-ray diffraction spectrum has the characteristics shown in figure 1, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure. The TEM picture of the transmission electron microscope has the characteristics shown in FIG. 2, two structures exist simultaneously and are combined together, and the amorphous phase and the amorphous structure of the pseudoboehmite grow along the edge of the FAU crystalline phase structure to form a compositeAnd (5) structure. The scanning electron microscope SEM photograph has the characteristics shown in figure 4, and a wrinkled structure and a part of grains of the Y-shaped molecular sieve can be seen at the same time, and most of the grains of the molecular sieve are coated by the wrinkled mesoporous structure grown on the surface. The BET specific surface area thereof is 427m 2 (g) the mesoporous specific surface area is 241m 2 The total pore volume is 0.83ml/g, the mesoporous pore volume is 0.74ml/g, and the BJH pore size distribution curve thereof has the characteristics of the gradient pore distribution shown in figure 3. YCMN-3 with a/b =2.1 in the Raman (Raman) spectrum.
Contacting a porous material YCMN-3 with ammonium chloride according to the weight ratio of 1.6 at 50 ℃ for 2 hours, filtering, washing with water and drying; then carrying out hydrothermal roasting for 2 hours at the temperature of 650 ℃ under the condition of 100 percent of water vapor; and (2) adding water again into the roasted sample, pulping, carrying out secondary contact treatment on the sample and ammonium chloride at 50 ℃ for 1 hour according to the weight ratio of 1.
The XRD diffraction pattern of A-2 has the characteristics shown in figure 5, and shows that the FAU crystal phase structure and gamma-Al simultaneously contain the Y-type molecular sieve 2 O 3 And (5) structure.
The unit cell constant of A-2 is 2.461nm, the relative crystallinity is 29%, and the chemical composition is 0.41Na calculated by weight of oxide 2 O·37.3SiO 2 ·61.9Al 2 O 3 Total specific surface area 375m 2 G, total pore volume 0.80cm 3 /g。
Example 3
This example illustrates the porous catalytic material of the present invention and the process for its preparation.
According to 7.5SiO 2 ：Al 2 O 3 ：2.15Na 2 O：190H 2 The method comprises the steps of feeding a NaY molecular sieve gel of O in a molar ratio, sequentially mixing and stirring water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and required deionized water for 1 hour, wherein the mass ratio of the guiding agent is 5%, crystallizing the gel for 20 hours at 100 ℃, filtering and washing crystallized slurry, and drying the crystallized slurry for 10 hours at 120 ℃ in an oven to obtain the NaY molecular sieve.
Adding water again to the obtained NaY molecular sieve dry powder, pulping, and mixingAfter the mixture is uniform, alCl is added simultaneously at room temperature under the condition of vigorous stirring 3 Solution (concentration 60 gAl) 2 O 3 /L) and NaAlO 2 Solution (concentration 160 gAl) 2 O 3 /L) is added into the mixture in parallel, the contact reaction is carried out, the pH value of a slurry system is controlled to be 10.5, and after a certain time of reaction, the reaction is carried out according to the total Al in the used aluminum chloride solution and sodium metaaluminate solution 2 O 3 By weight, in terms of SiO 2 :Al 2 O 3 =1:3 weight ratio of water glass solution (concentration 120 gSiO) 2 /L) is added into the reaction slurry, the reaction is continued for 4 hours at 70 ℃, and then the porous material YCMN-4 is obtained after filtration, washing and drying in an oven at 120 ℃.
YCMN-4 has a chemical composition of 9.91Na for fluorescence analysis 2 O·54.2SiO 2 ·35.0Al 2 O 3 The X-ray diffraction spectrum has the characteristics shown in figure 1, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure. The TEM photograph of the transmission electron microscope has the characteristics shown in FIG. 2, two structures exist simultaneously and are combined together, and the amorphous and amorphous structures of the pseudo-boehmite grow along the edge of the FAU crystalline phase structure to form a composite structure. The scanning electron microscope SEM photograph has the characteristics shown in figure 4, and a wrinkled structure and a part of grains of the Y-shaped molecular sieve can be seen at the same time, and most of the grains of the molecular sieve are coated by the wrinkled mesoporous structure grown on the surface. The BET specific surface area is 624m 2 (g) the mesoporous specific surface area is 120m 2 The total pore volume is 0.56ml/g, the mesoporous pore volume is 0.32ml/g, and the BJH pore size distribution curve has the characteristics of the gradient pore distribution shown in figure 3. In the Raman (Raman) spectrum, YCMN-4 has a/b =6.7.
Contacting porous material YCMN-4 with ammonium sulfate according to the weight ratio of 1.8 at 60 ℃ for 1 hour, filtering, washing with water, and drying; then carrying out hydrothermal roasting for 4 hours at the temperature of 550 ℃ under the condition of 100 percent of water vapor; and adding water again to the roasted sample for pulping, performing secondary contact treatment on the sample and ammonium sulfate at the temperature of 60 ℃ for 1 hour according to the weight ratio of 1.5, filtering, washing with water, and drying to obtain the porous catalytic material, which is recorded as A-3.
XRD diffraction pattern of A-3Has the characteristics shown in FIG. 5, and shows that the FAU crystal phase structure and the gamma-Al simultaneously contain the Y-type molecular sieve 2 O 3 And (5) structure.
A-3 has a unit cell constant of 2.460nm and a relative crystallinity of 67%, and a chemical composition of 0.54Na in terms of oxide weight 2 O·60.2SiO 2 ·38.9Al 2 O 3 Total specific surface area 586m 2 G, total pore volume 0.53cm 3 /g。
Example 4
This example illustrates the porous catalytic material of the present invention and the process for its preparation.
NaY molecular sieve gel was prepared according to the molar ratio of the NaY molecular sieve gel charged in example 3 and the same order of addition, and crystallized at 100 ℃ for 50 hours, followed by filtering and washing the crystallized slurry and oven-drying at 120 ℃ for 10 hours to obtain NaY molecular sieve.
Adding water again to the obtained NaY molecular sieve dry powder for pulping, uniformly stirring, heating to 45 ℃, and stirring vigorously while adding Al (NO) 3 ) 3 Solution (concentration 50 gAl) 2 O 3 L) and ammonia water (mass fraction is 25 percent) are added into the mixture in parallel for contact reaction, the pH value of a slurry system is controlled to be 9.5, and after reaction for a certain time, according to Al in the used aluminum nitrate solution 2 O 3 By weight, in terms of SiO 2 :Al 2 O 3 A water glass solution (concentration 120 gSiO) in a weight ratio of 1:1 2 L) was added to the above reaction slurry and the reaction was continued at 50 ℃ for 10 hours, followed by filtration, washing and oven drying at 120 ℃ to obtain porous material YCMN-5.
YCMN-5 has a chemical composition of 11.2Na for fluorescence analysis 2 O·56.0SiO 2 ·32.5Al 2 O 3 The X-ray diffraction spectrum has the characteristics shown in figure 1, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure. The TEM photograph of the transmission electron microscope has the characteristics shown in FIG. 2, two structures exist simultaneously and are combined together, and the amorphous and amorphous structures of the pseudo-boehmite grow along the edge of the FAU crystalline phase structure to form a composite structure. SEM photograph has the characteristics shown in FIG. 4, and wrinkles are visibleThe structure of the molecular sieve is similar to that of the Y-shaped molecular sieve, and most of the molecular sieve grains are coated by the wrinkled mesoporous structure grown on the surface. Its BET specific surface area is 719m 2 Per g, the mesoporous specific surface area is 68m 2 The total pore volume is 0.52ml/g, the mesoporous pore volume is 0.21ml/g, and the BJH pore size distribution curve has the characteristics of the gradient pore distribution shown in figure 3. In the Raman (Raman) spectrum, YCMN-5 has a/b =9.6.
Contacting porous material YCMN-5 and ammonium carbonate according to the weight ratio of 1:1 at 80 ℃ for 0.5 hour, filtering, washing and drying; then carrying out hydrothermal roasting for 2 hours at the temperature of 580 ℃ under the condition of 100 percent of water vapor; and adding water again to the roasted sample, pulping, performing secondary contact treatment with ammonium carbonate at the temperature of 80 ℃ for 0.5 hour according to the weight ratio of 1.4, filtering, washing with water, and drying to obtain the porous catalytic material, which is recorded as A-4.
The XRD diffraction pattern of A-4 has the characteristics shown in figure 5, and shows that the FAU crystal phase structure and gamma-Al simultaneously contain Y-type molecular sieve 2 O 3 And (5) structure.
The unit cell constant of A-4 is 2.458nm, the relative crystallinity is 76%, and the chemical composition is 0.89Na calculated by oxide 2 O·63.7SiO 2 ·35.0Al 2 O 3 Total specific surface area 578m 2 G, total pore volume 0.50cm 3 /g。
Example 5
This example illustrates the porous catalytic material of the present invention and the process for its preparation.
Preparing the NaY molecular sieve according to the synthesis process of the NaY molecular sieve in the embodiment 2, adding water again to dry powder of the NaY molecular sieve for pulping, uniformly stirring, raising the temperature to 60 ℃, and stirring Al vigorously 2 (SO 4 ) 3 Solution (concentration 90 gAl) 2 O 3 L) and ammonia water (mass fraction is 25%) are added into the mixture in parallel for contact reaction, the pH value of a slurry system is controlled to be 9.0, and after reaction for a certain time, according to Al in the used aluminum sulfate solution 2 O 3 By weight, in terms of SiO 2 :Al 2 O 3 A water glass solution (concentration 120 gSiO) in a weight ratio of 1:9 2 /L)Adding into the above reaction slurry, reacting at 60 deg.C for 4 hr, filtering, washing, and oven drying at 120 deg.C to obtain porous material YCMN-9.
YCMN-9 fluorescence analysis chemical composition is 5.11Na 2 O·35.0SiO 2 ·59.2Al 2 O 3 The X-ray diffraction spectrum has the characteristics shown in figure 1, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure. The TEM photograph of the transmission electron microscope has the characteristics shown in FIG. 2, two structures exist simultaneously and are combined together, and the amorphous and amorphous structures of the pseudo-boehmite grow along the edge of the FAU crystalline phase structure to form a composite structure. The scanning electron microscope SEM photograph has the characteristics shown in figure 4, and a wrinkled structure and a part of grains of the Y-shaped molecular sieve can be seen at the same time, and most of the grains of the molecular sieve are coated by the wrinkled mesoporous structure grown on the surface. The BET specific surface area of the powder is 542m 2 (g) the mesoporous specific surface area is 289m 2 The total pore volume is 1.04ml/g, the mesoporous pore volume is 0.92ml/g, and the BJH pore size distribution curve has the characteristics of the gradient pore distribution shown in figure 3. In the Raman (Raman) spectrum, YCMN-9 has a/b =2.4.
The porous material YCMN-9 and ammonium chloride are contacted and treated for 0.5 hour at 60 ℃ according to the weight ratio of 1; then carrying out hydrothermal roasting for 4 hours at the temperature of 500 ℃ under the condition of 100 percent of water vapor; and adding water again to the roasted sample for pulping, performing second contact treatment on the sample and ammonium chloride at the temperature of 60 ℃ for 0.5 hour according to the weight ratio of 1.4, filtering, washing with water, and drying to obtain the porous catalytic material, which is marked as A-5.
The XRD diffraction pattern of A-5 has the characteristics shown in figure 5, and shows that the FAU crystal phase structure and the gamma-Al simultaneously contain the Y-type molecular sieve 2 O 3 And (5) structure.
The cell constant of A-5 is 2.463nm, the relative crystallinity is 35%, and the chemical composition is 0.44Na calculated by oxide weight 2 O·38.1SiO 2 ·61.2Al 2 O 3 Total specific surface area 509m 2 G, total pore volume 0.95cm 3 /g。
Example 6
This example illustrates the porous catalytic material of the present invention and its preparation.
According to the mol ratio of gel feeding of the NaY molecular sieve to 8.5SiO 2 ：Al 2 O 3 ：2.65Na 2 O：210H 2 O, mixing and uniformly stirring water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and required deionized water in sequence, wherein the mass ratio of the guiding agent is 5%, crystallizing the gel at 100 ℃ for 20 hours, filtering and washing crystallized slurry, and drying in an oven at 120 ℃ for 10 hours; adding water again to the obtained NaY molecular sieve dry powder for pulping, homogenizing, then violently stirring at room temperature, and simultaneously adding Al 2 (SO 4 ) 3 Solution (concentration 50 gAl) 2 O 3 L) and ammonia water (mass fraction 25%) were added in parallel thereto, the pH of the mixed slurry was adjusted to 9.5, the reaction slurry was collected and adjusted according to Al in the aluminum sulfate solution used 2 O 3 By weight, in terms of SiO 2 :Al 2 O 3 Ratio of 1:4, water glass solution (concentration 120 gSiO) 2 /L) adding the mixture into the slurry, stirring the mixture for 4 hours at the constant temperature of 50 ℃, then placing the slurry into a stainless steel reaction kettle, crystallizing the slurry for 10 hours at the temperature of 100 ℃ under a closed condition, filtering the crystallized slurry, washing the crystallized slurry, and drying the crystallized slurry in an oven at the temperature of 120 ℃ to obtain the porous material YCM-1.
YCM-1 contains sodium oxide 4.7 wt%, silicon oxide 27.9 wt%, aluminum oxide 66.5 wt%, and specific surface area 521m 2 G, total pore volume 1.10cm 3 The ratio of the mesopore volume to the total pore volume was 0.91. The BJH pore size distribution curve is shown in FIG. 6, and has the characteristic of gradient pore distribution, and several pore distributions appear at 3.8nm, 11nm and 32nm respectively. The XRD spectrogram is shown in figure 7, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite Dan Feijing phase structure, namely characteristic diffraction peaks of the FAU crystal phase structure appear at positions with 2 theta of 6.2 degrees, 10.1 degrees, 11.9 degrees, 15.7 degrees, 18.7 degrees, 20.4 degrees, 23.7 degrees, 27.1 degrees, 31.4 degrees and the like, and characteristic diffraction peaks of 5 pseudo-boehmite structures appear at positions with 2 theta of 14 degrees, 28 degrees, 38.5 degrees, 49 degrees and 65 degrees; the TEM photograph of the transmission electron microscope is shown in FIG. 8, and it can be seen that two structures coexist and the amorphous phase structure of the pseudo-boehmite grows along the edge of the FAU crystalline phase structure, and the two structures are organically combinedTogether; the SEM photograph is shown in FIG. 9, which shows that the pleatable boehmite with the wrinkled mesoporous structure grows on the surface of the Y-type molecular sieve grain and completely coats the Y-type molecular sieve grain. In the Raman (Raman) spectrum, YCM-1 has a/b =1.6.
The porous material YCM-1 and ammonium nitrate are contacted for treatment for 1 hour at 55 ℃ according to the weight ratio of 1; then carrying out hydrothermal roasting for 2 hours at the temperature of 600 ℃ under the condition of 100 percent of water vapor; and adding water again to the roasted sample for pulping, carrying out secondary contact treatment on the sample and ammonium nitrate at the temperature of 55 ℃ for 2 hours according to the weight ratio of 1.5, filtering, washing with water, and drying to obtain the porous catalytic material, which is recorded as A-6.
The XRD diffraction pattern of A-6 has the characteristics shown in figure 5, and shows that the FAU crystal phase structure and the gamma-Al simultaneously contain the Y-type molecular sieve 2 O 3 And (5) structure.
A-6 has a unit cell constant of 2.462nm, a relative crystallinity of 26%, and a chemical composition of 0.36Na by weight of oxide 2 O·30.2SiO 2 ·69.2Al 2 O 3 Total specific surface area 499m 2 G, total pore volume 1.0cm 3 /g。
Example 7
This example illustrates the porous catalytic material of the present invention and its preparation.
According to a conventional molar ratio of gel charge to NaY molecular sieve, e.g. 8.7SiO 2 ：Al 2 O 3 ：2.75Na 2 O：200H 2 O, mixing and uniformly stirring the water glass, the aluminum sulfate, the sodium metaaluminate, the guiding agent and the required deionized water in sequence, wherein the mass ratio of the guiding agent is 5%, crystallizing the gel at 100 ℃ for 40 hours, filtering and washing the crystallized slurry, and drying the crystallized slurry in an oven at 120 ℃ for 10 hours; adding water again to the obtained NaY molecular sieve dry powder for pulping, heating to 40 ℃ after homogenizing, and stirring vigorously while adding AlCl 3 Solution (concentration 60 gAl) 2 O 3 L) and aqueous ammonia (mass fraction 25%) were added in parallel thereto, the pH of the mixed slurry was adjusted to 8.5, the reaction slurry was collected and adjusted according to Al in the aluminum chloride solution used 2 O 3 Weight(s)Measured according to SiO 2 :Al 2 O 3 Adding tetraethoxy silicon into the slurry according to the proportion of 1:6, continuously stirring at the constant temperature of 60 ℃ for 2 hours, then placing the slurry into a stainless steel reaction kettle, crystallizing at the temperature of 100 ℃ for 5 hours, filtering the slurry after crystallization, washing, and drying in an oven at the temperature of 120 ℃ to obtain the porous material YCM-4.
YCM-4 contains 6.5 wt.% of sodium oxide, 41.9 wt.% of silicon oxide, 50.8 wt.% of aluminum oxide, and has a specific surface area of 540m 2 G, total pore volume 0.99cm 3 The ratio of the mesopore volume to the total pore volume was 0.84. The BJH pore size distribution curve has the characteristics shown in FIG. 6, and presents gradient pore distribution characteristics. The X-ray diffraction spectrum has the characteristics shown in figure 7, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite Dan Feijing phase structure; the TEM picture of the transmission electron microscope has the characteristics shown in FIG. 8, the two structures coexist, the amorphous phase structure of the pseudo-boehmite extends and grows along the edge of the FAU crystalline phase structure, and the two structures are organically combined together; the SEM photo has the characteristics shown in figure 9, and the pleatable boehmite with the wrinkled mesoporous structure grows on the surface of the Y-shaped molecular sieve crystal grains and is completely coated. In Raman (Raman) spectrum, YCM-4 a/b =3.1.
Contacting a porous material YCM-4 with ammonium sulfate according to the weight ratio of 1.3 at 65 ℃ for 1 hour, filtering, washing with water, and drying; then carrying out hydrothermal roasting for 2 hours at the temperature of 530 ℃ under the condition of 100 percent of water vapor; and (2) adding water again into the roasted sample, pulping, carrying out secondary contact treatment on the sample and ammonium sulfate at 65 ℃ for 1 hour according to the weight ratio of 1.8, filtering, washing with water, and drying to obtain the porous catalytic material, which is recorded as A-7.
The XRD diffraction pattern of A-7 has the characteristics shown in figure 5, and shows that the FAU crystal phase structure and the gamma-Al simultaneously contain the Y-type molecular sieve 2 O 3 And (5) structure.
A-7 has a unit cell constant of 2.465nm, a relative crystallinity of 43%, and a chemical composition of 0.74Na in terms of oxide weight 2 O·47.0SiO 2 ·51.9Al 2 O 3 Total specific surface area 518m 2 G, total pore volume 0.90cm 3 /g。
Example 8
This example illustrates the porous catalytic material of the present invention and its preparation.
According to the gel feed molar ratio of a conventional NaY molecular sieve, e.g. 7.5SiO 2 ：Al 2 O 3 ：2.15Na 2 O：190H 2 O, mixing and uniformly stirring water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and required deionized water in sequence, wherein the mass ratio of the guiding agent is 5%, crystallizing the gel at 100 ℃ for 15 hours, filtering and washing crystallized slurry, and drying in an oven at 120 ℃ for 10 hours; adding water again to the obtained NaY molecular sieve dry powder for pulping, heating to 35 ℃ after homogenizing, and stirring vigorously while adding Al (NO) 3 ) 3 Solution (concentration 50 gAl) 2 O 3 L) and ammonia water (mass fraction 25%) were added in parallel thereto, the pH of the mixed slurry was adjusted to 9.5, the reaction slurry was collected and adjusted according to Al in the aluminum nitrate solution used 2 O 3 By weight, in terms of SiO 2 :Al 2 O 3 According to the proportion of =1:5, tetraethoxy silicon is added into the slurry, the mixture is stirred at the constant temperature of 70 ℃ for 4 hours, then the slurry is placed into a stainless steel reaction kettle and crystallized at the temperature of 100 ℃ for 15 hours, and after crystallization, the slurry is filtered, washed and dried in an oven at the temperature of 120 ℃ to obtain the porous material YCM-6.
YCM-6 contains sodium oxide 10.8 wt%, silicon oxide 55.7 wt%, aluminum oxide 32.1 wt%, and specific surface area 620m 2 In terms of/g, total pore volume 0.59cm 3 The ratio of the mesopore volume to the total pore volume was 0.57. The BJH pore size distribution curve has the characteristics shown in FIG. 6, and presents gradient pore distribution characteristics. The X-ray diffraction spectrum has the characteristics shown in figure 7, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite Dan Feijing phase structure; the TEM picture of the transmission electron microscope has the characteristics shown in FIG. 8, the two structures coexist, the amorphous phase structure of the pseudo-boehmite extends and grows along the edge of the FAU crystalline phase structure, and the two structures are organically combined together; the SEM photograph has the characteristics shown in FIG. 9, and the wrinkled mesoporous pseudo-boehmite grows on the surface of the Y-type molecular sieve crystal grain and completely coats the Y-type molecular sieve crystal grain. YCM-6 has an a/b =7.7 in Raman (Raman) spectrum.
Contacting a porous material YCM-6 with ammonium sulfate according to the weight ratio of 1.7 at 75 ℃ for 1 hour, filtering, washing with water, and drying; then carrying out hydrothermal roasting for 3 hours at the temperature of 630 ℃ under the condition of 100 percent of water vapor; and adding water again to the roasted sample for pulping, performing secondary contact treatment on the sample and ammonium sulfate at the temperature of 70 ℃ for 0.5 hour according to the weight ratio of 1.5, filtering, washing with water, and drying to obtain the porous catalytic material, which is recorded as A-8.
The XRD diffraction pattern of A-8 has the characteristics shown in figure 5, and shows that the FAU crystal phase structure and gamma-Al simultaneously contain the Y-type molecular sieve 2 O 3 And (5) structure.
A-8 has a unit cell constant of 2.455nm and a relative crystallinity of 76% and a chemical composition of 0.98Na by weight of oxide 2 O·63.4SiO 2 ·35.0Al 2 O 3 Total specific surface area 572m 2 In terms of/g, total pore volume 0.51cm 3 /g。
Example 9
This example illustrates the porous catalytic material of the present invention and its preparation.
According to a conventional molar ratio of gel charge to NaY molecular sieve, e.g. 7.5SiO 2 ：Al 2 O 3 ：2.15Na 2 O：190H 2 O, mixing and uniformly stirring water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and required deionized water in sequence, wherein the mass ratio of the guiding agent is 5%, crystallizing the gel at 100 ℃ for 30 hours, filtering and washing crystallized slurry, and drying in an oven at 120 ℃ for 10 hours; adding water again to the NaY molecular sieve dry powder for pulping, homogenizing, and then stirring vigorously at room temperature while adding Al 2 (SO 4 ) 3 Solution (concentration 90 gAl) 2 O 3 L) and ammonia water (mass fraction 25%) were added in parallel thereto, the pH of the mixed slurry was adjusted to 8.5, the reaction slurry was collected and adjusted according to Al in the aluminum sulfate solution used 2 O 3 By weight, in terms of SiO 2 :Al 2 O 3 Ratio of = 1:7. Water glass solution (concentration 120 gSiO) 2 /L) is added to the above slurry and stirred for 1 hour at a constant temperature of 80 ℃ thenAnd then placing the slurry in a stainless steel reaction kettle, crystallizing for 28 hours at 100 ℃, filtering, washing and drying in an oven at 120 ℃ after crystallization to obtain the porous material YCM-10.
YCM-10 contains sodium oxide 5.2 wt%, silicon oxide 31.5 wt%, aluminum oxide 62.6 wt%, and specific surface area 442m 2 G, total pore volume 1.0cm 3 The ratio of the mesopore volume to the total pore volume was 0.94. The BJH pore size distribution curve has the characteristics shown in FIG. 6, and presents gradient pore distribution characteristics. The X-ray diffraction spectrogram has the characteristics shown in figure 7, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite Dan Feijing phase structure; the TEM picture of the transmission electron microscope has the characteristics shown in FIG. 8, the two structures coexist, the amorphous phase structure of the pseudo-boehmite extends and grows along the edge of the FAU crystalline phase structure, and the two structures are organically combined together; the SEM photograph has the characteristics shown in FIG. 9, and the wrinkled mesoporous pseudo-boehmite grows on the surface of the Y-type molecular sieve crystal grain and completely coats the Y-type molecular sieve crystal grain. In the Raman (Raman) spectrum, YCM-10 a/b =1.7.
Contacting a porous material YCM-10 with ammonium chloride according to the weight ratio of 1.5 at 60 ℃ for 2 hours, filtering, washing with water and drying; then carrying out hydrothermal roasting for 2 hours at the temperature of 650 ℃ under the condition of 100 percent of water vapor; and adding water again to the roasted sample for pulping, performing secondary contact treatment on the sample and ammonium chloride at the temperature of 60 ℃ for 1 hour according to the weight ratio of 1.7, filtering, washing with water, and drying to obtain the porous catalytic material, which is recorded as A-9.
The XRD diffraction pattern of A-9 has the characteristics shown in figure 5, and shows that the FAU crystal phase structure and the gamma-Al simultaneously contain the Y-type molecular sieve 2 O 3 And (5) structure.
A-9 has a unit cell constant of 2.464nm, a relative crystallinity of 28%, and a chemical composition of 0.49Na by weight of oxide 2 O·34.9SiO 2 ·64.3Al 2 O 3 Total specific surface area 419m 2 In terms of/g, total pore volume 0.89cm 3 /g。
Example 10
This example illustrates the porous catalytic material of the present invention and the process for its preparation.
Pressing to realThe method comprises the steps of feeding a gel of the NaY molecular sieve in a molar ratio in example 6, sequentially mixing and uniformly stirring water glass, a guiding agent, aluminum sulfate, sodium metaaluminate and required deionized water, wherein the mass ratio of the guiding agent is 6%, crystallizing the gel at 100 ℃ for 45 hours, filtering and washing crystallized slurry, and drying the crystallized slurry in an oven at 120 ℃ for 10 hours; adding water again to the obtained NaY molecular sieve dry powder for pulping, heating to 45 ℃ after homogenizing, and stirring vigorously while adding Al (NO) 3 ) 3 Solution (concentration 50 gAl) 2 O 3 L) and ammonia water (mass fraction 25%) were added in parallel thereto, the pH of the mixed slurry was adjusted to 10.0, the reaction slurry was collected and adjusted according to Al in the aluminum nitrate solution used 2 O 3 By weight, in terms of SiO 2 :Al 2 O 3 Ratio of = 1:9. Water glass solution (concentration 120 gSiO) 2 L) adding the mixture into the slurry, continuously stirring the mixture for 2 hours at the constant temperature of 60 ℃, then placing the slurry into a stainless steel reaction kettle, crystallizing the slurry for 25 hours at the temperature of 100 ℃, filtering the slurry after crystallization, washing the slurry and drying the slurry in an oven at the temperature of 120 ℃ to obtain the porous material YCM-5.
YCM-5 contains 8.12 wt% of sodium oxide, 47.2 wt% of silicon oxide, 44.5 wt% of aluminum oxide, and 595m of specific surface area 2 G, total pore volume 0.85cm 3 The ratio of the mesopore volume to the total pore volume was 0.74. The BJH pore size distribution curve has the characteristics shown in FIG. 6, and presents gradient pore distribution characteristics. The X-ray diffraction spectrum has the characteristics shown in figure 7, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite Dan Feijing phase structure; the TEM picture of the transmission electron microscope has the characteristics shown in FIG. 8, the two structures coexist, the amorphous phase structure of the pseudo-boehmite extends and grows along the edge of the FAU crystalline phase structure, and the two structures are organically combined together; the SEM photograph has the characteristics shown in FIG. 9, and the wrinkled mesoporous pseudo-boehmite grows on the surface of the Y-type molecular sieve crystal grain and completely coats the Y-type molecular sieve crystal grain. YCM-5 a/b =5.5 in Raman (Raman) spectra.
The porous material YCM-5 and ammonium nitrate are contacted for 1 hour at 80 ℃ according to the weight ratio of 1; then carrying out hydrothermal roasting for 2 hours at the temperature of 550 ℃ under the condition of 100 percent of water vapor; and (2) adding water again into the roasted sample, pulping, carrying out secondary contact treatment on the sample and ammonium nitrate at the temperature of 70 ℃ for 1 hour according to the weight ratio of 1.3, filtering, washing with water, and drying to obtain the porous catalytic material, which is marked as A-10.
The XRD diffraction pattern of A-10 has the characteristics shown in figure 5, and shows that the FAU crystal phase structure and gamma-Al simultaneously contain the Y-type molecular sieve 2 O 3 And (5) structure.
A-10 has a cell constant of 2.462nm, a relative crystallinity of 51%, and a chemical composition of 0.82Na by weight of oxide 2 O·52.8SiO 2 ·46.0Al 2 O 3 Total specific surface area 542m 2 G, total pore volume 0.72cm 3 /g。
Examples 11 to 20
Examples 11-20 illustrate the cracking activity of the porous catalytic materials provided by the present invention.
The porous catalytic materials a-1 to a-10 described in examples 1 to 10 were mixed with an ammonium chloride solution for exchange, the sodium oxide content of which was washed to 0.3 wt% or less, filtered and dried, then tableted and sieved into 20 to 40 mesh particles, aged at 800 ℃ under 100% steam conditions for 17 hours, and then subjected to cracking performance evaluation on a heavy oil microreaction evaluation apparatus.
Heavy oil micro-reverse evaluation conditions: the raw oil is vacuum gas oil, the sample loading is 2g, the mass ratio of the sample to the oil is 1.4, the reaction temperature is 500 ℃, and the regeneration temperature is 600 ℃.
The properties of the stock oils are shown in Table 1, and the evaluation results are shown in Table 2.
TABLE 1
Comparative examples 1 to 10
Comparative examples 1-10 illustrate comparative compositions, but using NaY molecular sieves with gamma-Al 2 O 3 Cracking activity of a comparative sample obtained by mechanically mixing the structural mesoporous material.
The same porous catalytic materials A-1 to A-10 as described in examples 1 to 10 above were usedThe composition of (1) is prepared by mixing NaY molecular sieve with gamma-Al 2 O 3 The structural mesoporous materials are mechanically mixed and are respectively subjected to twice contact treatment and hydrothermal roasting treatment with ammonium salt corresponding to the treatment methods of A-1 to A-10, so as to obtain comparison samples DB-1 to DB-10.
DB-1 ~ DB-10 and ammonium chloride solution mixed exchange again, until the sodium oxide content is washed to 0.3 wt% below, filter and dry, tablet and sieve into 20 ~ 40 mesh particles, at 800 degrees C, 100% steam conditions aging treatment for 17 hours, then in heavy oil micro-reverse evaluation device for cracking performance evaluation. The feed oil and the reaction conditions were the same as in example 11.
The evaluation results are shown in Table 3.
TABLE 2
| Sample (I) | A-1 | A-2 | A-3 | A-4 | A-5 | A-6 | A-7 | A-8 | A-9 | A-10 |
| Yield/%) | ||||||||||
| Dry gas | 1.55 | 1.79 | 1.70 | 1.65 | 1.78 | 1.70 | 1.79 | 1.90 | 1.68 | 1.76 |
| Liquefied gas | 8.96 | 9.50 | 8.85 | 7.37 | 9.47 | 9.04 | 9.42 | 9.45 | 8.56 | 9.14 |
| Gasoline (gasoline) | 42.39 | 46.01 | 43.18 | 39.96 | 44.97 | 43.91 | 44.80 | 45.81 | 40.96 | 43.98 |
| Diesel oil | 21.21 | 19.54 | 20.84 | 22.17 | 19.73 | 21.00 | 19.61 | 19.75 | 20.28 | 19.85 |
| Heavy oil | 14.44 | 11.52 | 13.58 | 17.74 | 12.81 | 13.09 | 12.63 | 12.02 | 16.70 | 13.09 |
| Coke | 11.45 | 11.64 | 11.85 | 11.11 | 11.24 | 11.26 | 11.75 | 11.07 | 11.82 | 12.18 |
| Conversion rate/%) | 64.35 | 68.94 | 66.08 | 60.09 | 67.46 | 65.91 | 67.76 | 68.23 | 63.02 | 67.06 |
| Coke/conversion ratio | 0.178 | 0.169 | 0.179 | 0.185 | 0.167 | 0.171 | 0.173 | 0.162 | 0.187 | 0.182 |
TABLE 3
| Sample (I) | DB-1 | DB-2 | DB-3 | DB-4 | DB-5 | DB-6 | DB-7 | DB-8 | DB-9 | DB-10 |
| Yield/%) | ||||||||||
| Dry gas | 1.51 | 1.79 | 1.61 | 1.53 | 1.63 | 1.53 | 1.59 | 1.71 | 1.48 | 1.62 |
| Liquefied gas | 8.54 | 8.92 | 8.89 | 7.51 | 9.02 | 8.61 | 9.11 | 8.89 | 7.82 | 8.46 |
| Gasoline (R) and its preparation method | 40.14 | 43.20 | 41.86 | 38.52 | 43.11 | 41.09 | 42.24 | 43.51 | 39.11 | 42.09 |
| Diesel oil | 21.98 | 20.46 | 21.09 | 22.88 | 20.43 | 22.15 | 20.48 | 20.89 | 22.26 | 20.44 |
| Heavy oil | 16.13 | 13.68 | 14.74 | 18.78 | 13.81 | 14.79 | 14.01 | 13.42 | 17.99 | 14.79 |
| Coke | 11.70 | 11.95 | 11.81 | 10.78 | 12.00 | 11.83 | 12.57 | 11.58 | 11.34 | 12.60 |
| Conversion rate/% | 61.89 | 65.86 | 64.17 | 58.34 | 65.76 | 63.06 | 65.51 | 65.69 | 59.75 | 64.77 |
| Coke/conversion ratio | 0.189 | 0.181 | 0.184 | 0.185 | 0.182 | 0.187 | 0.192 | 0.177 | 0.190 | 0.194 |
As can be seen from the reaction data in table 2, the porous catalytic materials a-1 to a-10 obtained in examples 1 to 10 still show higher cracking activity after aging treatment with 100% steam at 800 ℃ for 17 hours, the conversion rate reaches 60.09 to 68.94%, the gasoline yield can reach 39.96 to 46.01%, the heavy oil conversion capability is better, the heavy oil yield is between 11.52 to 17.74%, the coke yield is relatively lower, and the product distribution is more optimized.
As can be seen from the comparative example reaction data shown in Table 3, the cracking activity of comparative samples DB-1 to DB-10 after aging treatment at 800 ℃ and 100% steam for 17 hours is significantly lower than that of the example samples A-1 to A-10, the conversion rate is reduced to 58.34 to 65.86%, the gasoline yield is reduced to 38.52 to 43.51%, the heavy oil yield is increased compared with the corresponding porous catalytic material of the present invention, and the coke selectivity is deteriorated.
Therefore, the porous catalytic material has special structural characteristics in pore structure and acid distribution due to organic combination of micro-mesoporous structure and mesoporous structure, so that the porous catalytic material has more excellent macromolecule transmission and cracking activity, and has more excellent reaction performance compared with a simple mechanically mixed sample.
Claims (12)
1. A preparation method of a porous catalytic material is characterized by comprising the following steps: (1) Firstly, a porous material is contacted with ammonium salt for 0.5 to 3 hours at the temperature of between 40 and 90 ℃ according to the weight ratio of 1 to 0.2 to 1.2, and then the porous material is filtered, washed and dried; (2) Carrying out hydrothermal roasting on the mixture obtained in the step (1) for 1-4 hours at the temperature of 500-700 ℃ under the condition of 100% of water vapor; (3) Pulping the water obtained in the step (2), performing secondary contact treatment with ammonium salt for 0.5 to 2 hours at the temperature of between 40 and 90 ℃ according to the weight ratio of 1 (0.2 to 1.0), filtering, washing and drying; wherein, the porous material in the step (1) simultaneously contains an FAU crystal phase structure and a pseudo-boehmite Dan Feijing phase structure in an XRD spectrogram, and the ordered diffraction of the FAU crystal part can be simultaneously seen in a Transmission Electron Microscope (TEM)The disordered structures of the stripes and the pseudo-boehmite part are derived and grown along the edges of the ordered diffraction stripes, and the two structures are effectively combined together to form a microporous and mesoporous composite structure; in the Raman spectrum, a/b = 1.5-10, wherein a represents the shift of 500cm -1 B represents a shift of 350cm -1 Peak intensity of the spectral peak of (a); the anhydrous chemical expression is (4-12) Na 2 O·(25～65)SiO 2 ·(25～70)Al 2 O 3 The specific surface area is 350 to 750m 2 The mesoporous specific surface area is 50 to 450m 2 The total pore volume is 0.5-1.5 ml/g, the mesoporous pore volume is 0.2-1.2 ml/g, and a BJH curve shows the gradient pore distribution characteristics, and the distribution characteristics can be distributed in a plurality of pores which are respectively arranged at 3-4 nm, 8-20 nm and 18-40 nm; the porous catalytic material simultaneously contains a microporous structure of a Y-type molecular sieve and gamma-Al 2 O 3 The mesoporous structure of (1), said gamma-Al 2 O 3 The mesoporous structure grows along the edge of a Y-type molecular sieve FAU crystal phase structure, the unit cell constant is 2.453-2.465 nm, and the chemical composition of the weight of the mesoporous structure is (0.3-1.0) Na 2 O• (30～69)SiO 2 • (30～70)Al 2 O 3 The total specific surface area is 300-600 m 2 Per g, total pore volume of 0.5-1.0 cm 3 /g。
2. The method according to claim 1, wherein the porous material in the step (1) is prepared by adding water to a molecular sieve dry powder having a FAU crystal structure, pulping the molecular sieve dry powder, stirring the mixture uniformly, adding an aluminum source and an alkali solution at a temperature of between room temperature and 85 ℃, fully mixing the mixture, controlling the pH value of a slurry system to be between 7 and 11, carrying out a contact reaction, and then using SiO as a reference based on alumina in the aluminum source 2 : Al 2 O 3 According to the weight ratio of (1-9), adding a silicon source counted by silicon oxide into the reaction slurry, continuously reacting for 1-10 hours at the temperature of room temperature to 90 ℃, crystallizing for 3-30 hours at the temperature of 95-105 ℃ in a closed reaction kettle, and recovering the product.
3. The method according to claim 2, wherein said molecular sieve of FAU crystal structure is NaY molecular sieve having a crystallinity of greater than 70%.
4. The method of claim 2 wherein the aluminum source is selected from the group consisting of aluminum nitrate, aluminum sulfate and aluminum chloride.
5. The process according to claim 2, wherein the alkali solution is one or more selected from the group consisting of aqueous ammonia, a potassium hydroxide solution, a sodium hydroxide solution and a sodium metaaluminate solution, and when the sodium metaaluminate solution is used as the alkali solution, the alumina content thereof is calculated to the total alumina content.
6. The method according to claim 2, wherein the silicon source is one or more selected from water glass, tetraethoxysilane, tetramethoxysilane and silicon oxide.
7. The preparation method according to claim 1, wherein the ammonium salt in the step (1) and the step (3) is one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium bicarbonate.
8. The preparation method according to claim 1, wherein, in the first contact treatment of the porous material and the ammonium salt in the step (1), the exchange ratio is 1 (0.3-1.0) in terms of weight ratio, and the exchange temperature is 50-80 ℃.
9. The method according to claim 1, wherein the hydrothermal calcination in the step (2) is carried out at a temperature of 550 to 650 ℃ for 1 to 4 hours.
10. The preparation method according to claim 1, wherein in the second contact treatment with the ammonium salt in the step (3), the weight ratio of the porous material to the ammonium salt is 1 (0.3-0.8), and the contact temperature is 50-80 ℃.
11. The preparation method of claim 1, wherein the porous catalytic material has a unit cell constant of 2.455-2.463 nm and a relative crystallinity of 25-80%.
12. The method of claim 11, wherein the relative crystallinity of the porous catalytic material is between 28 and 75%.
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