CN111747425A - Porous catalytic material containing mesopores and micropores - Google Patents
Porous catalytic material containing mesopores and micropores Download PDFInfo
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- CN111747425A CN111747425A CN201910236269.2A CN201910236269A CN111747425A CN 111747425 A CN111747425 A CN 111747425A CN 201910236269 A CN201910236269 A CN 201910236269A CN 111747425 A CN111747425 A CN 111747425A
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- 239000000463 material Substances 0.000 title claims abstract description 62
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 43
- 239000011148 porous material Substances 0.000 claims abstract description 158
- 239000002808 molecular sieve Substances 0.000 claims abstract description 120
- 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 111
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 72
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 49
- 239000013078 crystal Substances 0.000 claims abstract description 40
- 238000011282 treatment Methods 0.000 claims abstract description 37
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 6
- 238000001237 Raman spectrum Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- 238000006243 chemical reaction Methods 0.000 claims description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- 238000005406 washing Methods 0.000 claims description 46
- 238000001914 filtration Methods 0.000 claims description 45
- 239000002002 slurry Substances 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 40
- 238000009826 distribution Methods 0.000 claims description 37
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 36
- 150000003863 ammonium salts Chemical class 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 238000004537 pulping Methods 0.000 claims description 25
- 229910052593 corundum Inorganic materials 0.000 claims description 24
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 24
- 239000011734 sodium Substances 0.000 claims description 22
- 229910052708 sodium Inorganic materials 0.000 claims description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 21
- 239000012266 salt solution Substances 0.000 claims description 20
- 230000005540 biological transmission Effects 0.000 claims description 19
- 235000019353 potassium silicate Nutrition 0.000 claims description 19
- 239000000377 silicon dioxide Substances 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
- 229910052681 coesite Inorganic materials 0.000 claims description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims description 16
- 229910052682 stishovite Inorganic materials 0.000 claims description 16
- 229910052905 tridymite Inorganic materials 0.000 claims description 16
- 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 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 13
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012066 reaction slurry Substances 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 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 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 230000003595 spectral effect Effects 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
- 239000003518 caustics Substances 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005216 hydrothermal crystallization Methods 0.000 abstract 1
- 238000001069 Raman spectroscopy Methods 0.000 description 31
- 239000003795 chemical substances by application Substances 0.000 description 27
- -1 carbonium ion Chemical class 0.000 description 23
- 238000001228 spectrum Methods 0.000 description 22
- 238000005336 cracking Methods 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 239000000295 fuel oil Substances 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 239000003921 oil Substances 0.000 description 12
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 11
- 238000004523 catalytic cracking Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 101710148027 Ribulose bisphosphate carboxylase/oxygenase activase 1, chloroplastic Proteins 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910001948 sodium oxide Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 238000012921 fluorescence analysis Methods 0.000 description 5
- 239000003502 gasoline Substances 0.000 description 5
- 239000011268 mixed slurry Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 101710201629 Ribulose bisphosphate carboxylase/oxygenase activase 2, chloroplastic Proteins 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000000643 oven drying Methods 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
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000012670 alkaline solution Substances 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
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 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
- 230000001133 acceleration Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000001212 derivatisation Methods 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
- 239000002283 diesel fuel Substances 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
- 239000012013 faujasite Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment 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
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000000449 magic angle spinning nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect 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
- 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
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052665 sodalite Inorganic materials 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
- 238000012916 structural analysis Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A porous catalytic material containing mesopores and micropores is characterized by simultaneously containing microporous structures of FAU crystal phase structures of Y-type molecular sieves and gamma-Al2O3The mesoporous structure with the structure is characterized in that the content of rare earth is 2-23 wt% calculated by rare earth oxide, and the mesoporous structure is obtained by modifying a porous material with rare earth and carrying out double-cross single baking or double-cross double baking on the porous material, wherein in a Raman spectrum of the porous material, a/b is 1.5-10, and BJH curves show that the porous material can be distributed in several pores at 3-4 nm, 8-20 nm and 18-40 nm respectively; the porous material is prepared by adding aluminum source, alkali solution and silicon source into FAU crystalline phase structure molecular sieve dry powder as a raw material, and then performing hydrothermal crystallization treatment or not.
Description
Technical Field
The invention relates to a porous catalytic material, in particular to a microporous structure containing FAU crystal phase and gamma-Al2O3Mesoporous structure of the porous catalytic material.
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. CN1436727A discloses a modified faujasite and a hydrocarbon cracking catalyst containing the zeolite, which adopts a one-exchange one-baking process, namely NaY firstly carries out a one-exchange reaction with a phosphorus compound and an ammonium compound, then a rare earth solution is added for continuous reaction, and the catalyst is obtained by filtering, washing and hydrothermal roasting.
CN1382631A discloses a high-silicon rare earth Y-type zeolite, which is prepared by gas phase reaction of rare earth Y-type zeolite and silicon tetrachloride, wherein the content of rare earth in crystal is 4-15 wt%, the cell constant is 2.450-2.458 nm, the collapse temperature is 1000-1056 ℃, the silica-alumina ratio is 8.3-8.8, and the content of sodium oxide is less than 1.0 wt%.
CN101823726A discloses a modified Y molecular sieve, which is prepared by a one-exchange one-baking process, namely NaY is firstly subjected to a one-exchange reaction with a rare earth solution, then a phosphorus compound is added for continuous reaction, and the modified Y molecular sieve is obtained by filtering, washing and hydrothermal roasting, wherein the content of rare earth is about 11-23 wt%, most of rare earth is positioned in a sodalite cage, the stability of the molecular sieve is improved, meanwhile, the acidity of the molecular sieve can be adjusted, and a catalyst containing the molecular sieve has the characteristics of strong heavy oil conversion capability and good coke selectivity.
CN100344374C discloses a rare earth Y molecular sieve and a preparation method thereof, the content of rare earth is 12-22 wt% calculated by rare earth oxide, and rare earth ions are all positioned in a molecular sieve small cage which is a small cage27In the Al MAS NMR spectrum, no peak was observed at a chemical shift of 0 ppm. The preparation method comprises the steps of adopting a one-way and one-way roasting process, adjusting the pH value of a solution to 8-11 by using an alkaline solution after one-way exchange, then filtering, washing, drying and roasting, or separating a molecular sieve filter cake after one-way exchange, collecting filtrate, adding the alkaline solution into the filtrate to adjust the pH value of the solution to 8-11, adding water into the obtained rare earth hydroxide filter cake and the molecular sieve filter cake, pulping, filtering, washing, drying and roasting. The process makes the excessive rare earth ions in the solution precipitate to avoid the rare earth loss and ensure that the rare earth ions are completely positioned in the molecular sieve small cage.
CN1317547A discloses an olefin reduction catalyst and a preparation method thereof, the catalyst mainly comprises REY molecular sieve with the rare earth content of 12-20 wt% and the crystallinity of more than 50% and a phosphorus and rare earth compound modified PREY molecular sieve with the rare earth content of 2-12 wt%, the phosphorus content of 0.2-3 wt% and the unit cell constant of 2.445-2.465 nm.
CN1506161A discloses a rare earth ultrastable Y molecular sieve, which adopts a double-cross double-baking process, namely, after a first-cross single-baking rare earth sodium Y is obtained, the first-cross single-baking rare earth sodium Y reacts with rare earth and phosphorus-containing substances step by step and is roasted for the second time to obtain a composite modified Y molecular sieve with the rare earth content of 8-25 wt%, the phosphorus content of 0.1-3.0 wt%, the crystallinity of 30-55% and the unit cell constant of 2.455-2.477 nm.
The molecular sieve prepared by adopting the double cross double roasting process also has other characteristics, for example, the molecular sieve which is disclosed in CN101537366A and can improve the coking performance and the preparation method thereof still adopt the double cross double roasting process, the phosphorus content of the molecular sieve is 0.05-5.0%, the rare earth content is less, only 0.05-4.0%, the unit cell constant is 2.430-2.440 nm, and the crystallinity is 35-55%.
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 CN1349929A, a novel mesoporous molecular sieve is disclosed, in which the 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. US5051385 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 the aluminum content is 5-40 wt%, the pore diameter is 20-50 nm, and the specific surface area is 50-100 m2(ii) in terms of/g. Method disclosed in US4708945Firstly, silica particles or hydrated silica are loaded on porous boehmite, and then the obtained compound is subjected to hydrothermal treatment at the temperature of more than 600 ℃ for a certain time 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 m2(iv) g, average pore diameter of 7 to 7.5 nm. A series of acidic cracking catalysts are disclosed in US4440872 in which some of the catalysts are supported by a catalyst 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
The inventor finds out on the basis of a large number of experiments that a porous material can be obtained by a derivatization growth method, the material is a disordered mesoporous structure with a mesoporous scale, the two structures are organically combined together to form continuous and unobstructed gradient pore distribution and gradient acid center distribution, and the material has more excellent heavy oil conversion capability after being modified by rare earth in a two-way and one-way baking or two-way and two-way baking mode. Based on this, the present invention was made.
The invention aims to provide a porous catalytic material with structural characteristics of micropores and mesopores, and the porous catalytic material has more excellent heavy oil conversion capability.
In order to achieve the aim of the invention, the invention provides a porous catalytic material, which is prepared from the following materialsCharacterized in that the microporous structure of FAU crystal phase structure containing Y-type molecular sieve and gamma-Al are simultaneously contained2O3Mesoporous structure of type structure, said gamma-Al2O3The mesoporous structure grows along the edge of a Y-shaped molecular sieve FAU crystal phase structure, the two structures are connected with each other, and the content of rare earth is 2-23 wt%, preferably 4-20 wt% calculated by rare earth oxide. The unit cell constant of the porous catalytic material is 2.450-2.472 nm, preferably 2.453-2.467 nm, the relative crystallinity is 25-65%, preferably 28-60%, and the total specific surface area is 250-600 m2(g) total pore volume of 0.3-1.0 cm3/g。
The porous catalytic material of the invention is characterized in that the porous catalytic material is prepared by a method comprising the following steps: (1) carrying out first contact treatment on a porous material and a rare earth solution and/or an ammonium salt solution, filtering, washing and drying; (2) carrying out primary roasting treatment on the obtained product in the step (1) under the condition of 0-100% of water vapor; (3) pulping the water obtained in the step (2), carrying out secondary contact treatment on the pulped water and a rare earth solution and/or an ammonium salt solution, filtering, washing and drying; or carrying out secondary roasting treatment under the condition of 0-100% of water vapor and recovering a product; the porous material in the step (1) contains an FAU crystalline phase structure and a pseudo-boehmite amorphous phase structure in an XRD spectrogram, an ordered diffraction stripe of the FAU crystalline phase part and a disordered structure of the pseudo-boehmite part can be seen in a Transmission Electron Microscope (TEM) at the same time, the disordered structure is derived and grown along the edge of the ordered diffraction stripe, and the two structures are effectively combined together to form a microporous and mesoporous composite structure; in a Raman (Raman) spectrum, a/b is 1.5-10, wherein a represents a shift of 500cm-1B represents a shift of 350cm-1Peak intensity of the spectral peak of (a); the anhydrous chemical expression is (4-12) Na2O·(25～65)SiO2·(25～70)Al2O3The specific surface area is 350-750 m2The mesoporous specific surface area is 50-450 m2The total pore volume is 0.5-1.5 ml/g, the mesoporous pore volume is 0.2-1.2 ml/g, and the BJH curve shows the gradient pore distribution characteristics, and the pores can be distributed in 3-4 nm, 8-20 nm and 18-40 nm respectively.
In the inventionThe porous material in the step (1) contains an FAU crystalline phase structure and a pseudo-boehmite amorphous phase structure in an XRD spectrogram, an ordered diffraction stripe of the FAU crystalline phase part and a disordered structure of the pseudo-boehmite crystal part can be seen in a Transmission Electron Microscope (TEM) at the same time, the disordered structure is derived and grown along the edge of the ordered diffraction stripe, and the two structures are effectively combined together to form a microporous and mesoporous composite structure. The porous material in the step (1) has an anhydrous chemical expression of: (4-12) Na2O·(25～65)SiO2·(25～70)Al2O3The specific surface area is 350 to 750m2The mesoporous specific surface area is 50-450 m2The 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, i.e., Raman shift, between scattered and incident photons by energy exchange with the incident photons based on changes in polarization upon vibration. In the porous material obtained in the step (1), in a Raman (Raman) spectrum, a/b is 1.5-10.0, wherein a represents that the Raman shift is 500cm-1B represents a Raman shift of 350cm-1Peak intensity of the spectrum.
In the invention, the porous material in the step (1) can simultaneously see the ordered diffraction stripe 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 edge of the ordered diffraction stripe of the FAU crystal phase, the edge line of the crystal structure disappears, 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.
In the invention, the porous material in the step (1) has the characteristic of gradient pore distribution formed by a microporous structure and a mesoporous structure, and obvious pore distribution can be generated at 3-4 nm, 8-20 nm and 18-40 nm respectively.
Further, in the present invention, the porous material in step (1) is prepared by the following process: adding water into molecular sieve dry powder with an FAU crystal structure, pulping, uniformly stirring, adding an aluminum source and an alkali solution at the temperature of room temperature to 85 ℃, fully mixing, controlling the pH value of a slurry system to be 7-11, carrying out contact reaction, and then taking aluminum oxide in the aluminum source as a reference and SiO2:Al2O3Adding a silicon source (calculated by silicon oxide) into the reaction slurry according to the weight ratio of (1-9), continuously reacting for 1-10 hours at the temperature of room temperature to 90 ℃, and recovering the product, or stirring for 1-4 hours at the constant temperature of room temperature to 90 ℃ after adding the silicon source, and then crystallizing for 3-30 hours at the temperature of 95-105 ℃ in a closed reaction kettle, and recovering the product.
The process for preparing a porous material as described in the step (1), wherein the molecular sieve having the FAU crystal structure is NaY molecular sieve. The NaY molecular sieve can be prepared by NaY molecular sieves with different silicon-aluminum ratios, different crystallinities and different crystal grain sizes, and the crystallinity is preferably more than 70 percent, more preferably more than 80 percent. For example, the NaY molecular sieve dry powder can be obtained by mixing and stirring water glass, sodium metaaluminate, aluminum sulfate, a directing agent and deionized water in a specific feeding sequence in proportion, crystallizing for a plurality of times at a temperature of 95-105 ℃, 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 feeding proportion of a conventional NaY molecular sieve or the feeding proportion of a NaY molecular sieve for preparing special performance, such as the feeding proportion of a large-grain or small-grain NaY molecular sieve, and the feeding 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, the directing agent can be prepared according to the methods disclosed in the prior art (US3639099 and US3671191), and the typical directing agent is prepared by mixing a silicon source, an aluminum source, an alkali solution and deionized water according to (15-18) Na2O:Al2O3:(15～17)SiO2:(280～380)H2And mixing the components according to the molar ratio of O, uniformly stirring, and standing and aging for 0.5-48 h at the temperature of room temperature to 70 ℃. 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.
The process for preparing a porous material in the step (1) as described above, wherein the aluminum source 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 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 ℃.
The process for preparing a porous material in the step (1) as described above, wherein the silicon source is one or more selected from the group consisting of water glass, sodium silicate, tetraethoxysilane, tetramethoxysilane and 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 1 to 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 invention, the porous material and the rare earth solution and/or the ammonium salt solution in the step (1) are subjected to the first contact treatment, the weight ratio of the rare earth solution to the porous material calculated by rare earth oxide is 0.02-0.14, preferably 0.03-0.13, the weight ratio of the ammonium salt to the porous material is 0.05-1.0, the contact temperature is 40-90 ℃, preferably 50-80 ℃, and the contact time is 0.5-3.0 hours, preferably 1-2 hours.
In the present invention, the first and second baking treatments in the steps (2) and (3) are performed at 500 to 700 ℃, preferably 530 to 680 ℃, and 0 to 100% steam, preferably 20 to 100% steam for 0.5 to 4.0 hours, preferably 1 to 3 hours.
In the second contact treatment in the step (3), in the contact treatment process with the rare earth solution and/or the ammonium salt solution obtained in the step (2), the weight ratio of the rare earth solution to the rare earth solution obtained in the step (2) calculated by rare earth oxide is 0.02-0.12, preferably 0.04-0.10, the weight ratio of the ammonium salt to the solution obtained in the step (2) is 0.05-0.50, preferably 0.1-0.4, the contact temperature is 40-90 ℃, preferably 50-80 ℃, and the contact time is 0.5-3.0 hours, preferably 1-2 hours.
In the present invention, the rare earth solution is well known to those skilled in the art, and may be rare earth chloride or rare earth nitrate, or rare earth chloride or rare earth nitrate composed of a single rare earth element, wherein the rare earth solution commonly includes lanthanum chloride, lanthanum nitrate, cerium chloride or cerium nitrate, etc., or may be a mixed rare earth of different rare earth element ratios, such as cerium-rich or lanthanum-rich mixed rare earth, and may be of any concentration; the mixed solution of the rare earth solution and the ammonium salt can be prepared by mixing the ammonium salt and the rare earth solution in proportion, or adding the ammonium salt and the rare earth solution one by one in proportion, wherein the ammonium salt can be one or more of ammonium chloride, ammonium nitrate, ammonium carbonate and ammonium bicarbonate.
The filtration, water washing and drying processes are well known to those skilled in the art and will not be described herein.
The porous catalytic material containing mesopores and micropores has special structural characteristics on a pore structure and acid distribution due to the organic combination of two structures of the mesopores and the micropores, and further improves the structural stability and the acid characteristics of the material by the modification effect of rare earth, so that the material has more excellent reaction performance. After aging treatment for 8 hours at 800 ℃ with 100 percent of water vapor, the cracking catalyst still shows higher cracking activity, higher conversion rate and gasoline yield, strong heavy oil conversion capability, good coke selectivity and optimized product distribution.
Drawings
FIG. 1 is an X-ray diffraction pattern of YCMN-1, a porous material 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 RA-1 obtained in 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)2261g/L, modulus 3.31, density 1259g/L) was placed in a beaker and 4451g of high alkali sodium metaaluminate (provided by Changling catalysts, Inc., Al) was added with vigorous stirring2O339.9g/L，Na2O279.4g/L, density 1326g/L) and aging at 30 ℃ for 18 hours to obtain 16.1Na with molar ratio2O:Al2O3:15SiO2:318.5H2A directing agent for O.
In various embodiments, RE of the Material2O3、Na2O、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).
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-.
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.
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 100 s.
Examples 1-10 illustrate the porous catalytic material of the present invention containing mesopores and micropores.
Example 1
According to 8.5SiO2：Al2O3：2.65Na2O：210H2The 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 AlCl3Solution (concentration 60 gAl)2O3/L) and NaAlO2Solution (concentration 102 gAl)2O3/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 solution2O3By weight, in terms of SiO2:Al2O3Tetraethoxy silicon was added to the above reaction slurry at a weight ratio of 1:8, followed by further reaction at 80 ℃ for 6 hours, followed by filtration, washing and oven-drying at 120 ℃ to obtain porous material YCMN-1.
YCMN-1 fluorescence analysis chemical composition is 9.41Na2O·53.6SiO2·37.2Al2O3The X-ray diffraction pattern is shown in fig. 1, which shows that the material contains both FAU crystal phase structure and pseudo-boehmite structure. A 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 that the pseudoboehmite is not a pseudoboehmiteThe crystalline and amorphous structure grows along the edges of the FAU crystalline 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 623m2(g) the mesoporous specific surface area is 89m2The total pore volume is 0.70ml/g, and the mesoporous pore volume is 0.44 ml/g; YCMN-1 has an a/b of 7.3, wherein a represents a Raman shift of 500cm in a Raman (Raman) spectrum-1B represents a Raman shift of 350cm-1Peak intensity of the spectrum.
The porous material YCMN-1 and the rare earth chloride solution are contacted and treated for 2 hours at 70 ℃ according to the weight ratio of the rare earth oxide to the porous material of 0.11, and then are filtered, washed and dried; then roasting for 4 hours at 500 ℃ under the condition of 100 percent of water vapor; adding water into a sample obtained by roasting, pulping, mixing with a rare earth chloride solution according to the weight ratio of 0.06 of the rare earth oxide to the sample obtained by roasting, carrying out secondary contact treatment at 60 ℃ for 2 hours, filtering, washing with water, drying, carrying out secondary roasting treatment at 550 ℃ under the condition of 100% water vapor, and carrying out treatment for 2 hours to obtain the porous catalytic material containing mesopores and micropores, which is recorded as RA-1.
The XRD diffraction pattern of RA-1 is shown in FIG. 5, which shows the FAU crystal phase structure and gamma-Al containing Y-type molecular sieve together2O3The 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 degrees2O3Structural characteristic peaks (peaks corresponding to parenthesis in the figure).
In RA-1, 16.5 percent by weight of rare earth oxide, 2.467nm of unit cell constant, 43 percent of relative crystallinity and 593m of total specific surface area2In terms of/g, total pore volume 0.67cm3/g。
Example 2
According to the molar 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 Al2(SO4)3Solution (concentration 50 gAl)2O3/L) and NaAlO2Solution (concentration 102 gAl)2O3/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 solution2O3By weight, in terms of SiO2:Al2O31:5 by weight of water glass solution (concentration 120g SiO)2L) 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 analysis2O·34.0SiO2·59.4Al2O3The 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 thereof is 427m2(g) the mesoporous specific surface area is 241m2The total pore volume is 0.83ml/g, the mesoporous pore volume is 0.74ml/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, the a/b of YCMN-3 is 2.1.
Contacting porous material YCMN-3 with rare earth chloride solution according to the weight ratio of rare earth oxide to porous material of 0.08 and ammonium salt solution according to the weight ratio of ammonium salt solution of 0.10 at 70 deg.C for 1 hr, filtering, washing with water and drying; then roasting for 2 hours at 600 ℃ under the condition of 100 percent of water vapor; adding water into a sample obtained by roasting, pulping, and mixing the materials according to a weight ratio of 1: mixing the mixture with ammonium salt solution in the proportion of 0.3, carrying out secondary contact treatment at 70 ℃ for 1 hour, filtering, washing with water, and drying to obtain the porous catalytic material containing mesopores and micropores, which is recorded as RA-2.
The XRD diffraction pattern of RA-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 sieve2O3And (5) structure.
RA-2 contains rare earth oxide 7.7 wt%, unit cell constant 2.459nm, relative crystallinity 32%, and total specific surface area 388m2In terms of/g, total pore volume 0.81cm3/g。
Example 3
According to 7.5SiO2：Al2O3：2.15Na2O：190H2The 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 for pulping, mixing uniformly, and stirring vigorously at room temperature while adding AlCl3Solution (concentration 60 gAl)2O3/L) and NaAlO2Solution (concentration 160 gAl)2O3/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 solution2O3By weight, in terms of SiO2:Al2O31:3 by weight, water glass solution (concentration 120g SiO)2/L) was added to the above reaction slurry, and the reaction was continued at 70 ℃ for 4 hours, followed by filtration, washing and oven drying at 120 ℃ to obtain a solutionDrying to obtain porous material YCMN-4.
YCMN-4 has a chemical composition of 9.91Na for fluorescence analysis2O·54.2SiO2·35.0Al2O3The 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 624m2(g) the mesoporous specific surface area is 120m2The 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 an a/b of 6.7.
Contacting porous material YCMN-4 with rare earth chloride solution according to the weight ratio of rare earth oxide to porous material of 0.06 and ammonium salt solution according to the weight ratio of ammonium salt solution of 0.15 at 80 deg.C for 1 hr, filtering, washing with water and drying; then roasting for 3 hours at 550 ℃ under the condition of 100 percent of water vapor; and adding water into the roasted sample, pulping, mixing the sample with the rare earth solution and the ammonium salt solution according to the weight ratio of the rare earth oxide to the ammonium salt of 0.04 and the weight ratio of the ammonium salt to the ammonium salt of 0.1, carrying out second contact treatment at the temperature of 80 ℃ for 1 hour, filtering, washing with water, and drying to obtain the porous catalytic material containing mesopores and micropores, wherein the mark is RA-3.
The XRD diffraction pattern of RA-3 has the characteristics shown in figure 5, and shows that the FAU crystal phase structure and gamma-Al simultaneously contain the Y-type molecular sieve2O3And (5) structure.
In RA-3, the rare earth oxide accounts for 9.6 percent by weight, the unit cell constant is 2.457nm, the relative crystallinity is 55 percent, and the total specific surface area is 580m2In terms of/g, total pore volume 0.55cm3/g。
Example 4
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)3Solution (concentration 50 gAl)2O3L) 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 solution2O3By weight, in terms of SiO2:Al2O31:1 by weight of water glass solution (concentration 120g SiO)2L) 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 analysis2O·56.0SiO2·32.5Al2O3The 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 thereof was 719m2Per g, the mesoporous specific surface area is 68m2The 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 an a/b of 9.6.
Contacting porous material YCMN-5 with rare earth chloride solution according to the weight ratio of rare earth oxide to porous material of 0.05 and ammonium salt solution according to the weight ratio of ammonium salt solution of 0.15 at 55 ℃ for 2 hours, filtering, washing and drying; then roasting for 2 hours at 650 ℃; adding water into a sample obtained by roasting, pulping, mixing with an ammonium salt solution according to the weight ratio of 0.4, carrying out secondary contact treatment for 1 hour at 55 ℃, filtering, washing with water, drying, carrying out secondary roasting treatment at 650 ℃, and carrying out treatment for 2 hours to obtain the porous catalytic material containing mesopores and micropores, which is marked as RA-4.
The XRD diffraction pattern of RA-4 has the characteristics shown in figure 5, and shows that the FAU crystal phase structure and gamma-Al simultaneously contain the Y-type molecular sieve2O3And (5) structure.
RA-4 contains rare earth oxide 4.9 wt%, unit cell constant 2.451nm, relative crystallinity 62%, and total specific surface area 587m2G, total pore volume 0.53cm3/g。
Example 5
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 vigorously2(SO4)3Solution (concentration 90 gAl)2O3L) 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 solution2O3By weight, in terms of SiO2:Al2O3Water glass solution (concentration 120 gSiO) in weight ratio 1:92L) is added into the reaction slurry, and the reaction is continued for 4 hours at 60 ℃, then the filtration, the washing and the drying in an oven at 120 ℃ are carried out, thus obtaining the porous material YCMN-9.
YCMN-9 fluorescence analysis chemical composition is 5.11Na2O·35.0SiO2·59.2Al2O3The 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 SEM photograph has the characteristics 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 grown on the surfaceAnd (4) coating the corrugated mesoporous structure. The BET specific surface area is 542m2(g) the mesoporous specific surface area is 289m2The 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, the a/b of YCMN-9 is 2.4.
Contacting porous material YCMN-9 with rare earth chloride solution at the weight ratio of rare earth oxide to porous material of 0.12 at 65 deg.C for 1 hr, filtering, washing with water, and drying; then roasting for 2 hours at 580 ℃ under the condition of 100 percent of water vapor; and adding water into the roasted sample, pulping, mixing with an ammonium salt solution according to the weight ratio of 0.3, carrying out secondary contact treatment at 65 ℃ for 1 hour, filtering, washing with water, and drying to obtain the porous catalytic material containing mesopores and micropores, wherein the mark is RA-5.
The XRD diffraction pattern of RA-5 has the characteristics shown in figure 5, and shows that the FAU crystal phase structure and gamma-Al simultaneously contain the Y-type molecular sieve2O3And (5) structure.
In RA-5, the rare earth oxide accounts for 11.8 percent by weight, the unit cell constant is 2.465nm, the relative crystallinity is 34 percent, and the total specific surface area is 520m2G, total pore volume 0.94cm3/g。
Example 6
According to the mol ratio of gel feeding of the NaY molecular sieve to 8.5SiO2：Al2O3：2.65Na2O：210H2O, 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 Al2(SO4)3Solution (concentration 50 gAl)2O3L) 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 used2O3By weight, in terms of SiO2:Al2O3Ratio of 1:4For example, a 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 521m2G, total pore volume 1.10cm3The 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 crystalline phase structure and a pseudo-boehmite amorphous phase structure, namely characteristic diffraction peaks of the FAU crystalline 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 the two structures coexist, the amorphous phase structure of the pseudo-boehmite grows along the edge of the FAU crystalline phase structure in an extending way, and the two structures are organically combined together; 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 an a/b of 1.6.
Contacting porous material YCM-1 and ammonium salt solution according to the weight ratio of 1:1 at 75 ℃ for 1 hour, filtering, washing and drying; then roasting for 4 hours at 580 ℃ under the condition of 100 percent of water vapor; and adding water into the roasted sample, pulping, mixing the sample with a rare earth chloride solution and an ammonium salt solution according to the weight ratio of the rare earth oxide to the ammonium salt of 0.04 and the weight ratio of the ammonium salt to the ammonium salt of 0.1, carrying out second contact treatment at 75 ℃ for 1 hour, filtering, washing with water, and drying to obtain the porous catalytic material containing mesopores and micropores, which is marked as RA-6.
The XRD diffraction pattern of RA-6 has the characteristics shown in figure 5, and shows that the FAU crystal phase structure and gamma-Al simultaneously contain the Y-type molecular sieve2O3And (5) structure.
RA-6 contains rare earth oxide 4.0 wt%, has unit cell constant of 2.452nm, relative crystallinity of 28%, and total specific surface area of 509m2G, total pore volume 0.98cm3/g。
Example 7
According to a conventional molar ratio of gel charge to NaY molecular sieve, e.g. 8.7SiO2：Al2O3：2.75Na2O：200H2O, 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 40 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 40 ℃ after homogenizing, and stirring vigorously while adding AlCl3Solution (concentration 60 gAl)2O3L) 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 used2O3By weight, in terms of SiO2:Al2O3Adding 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 540m2G, total pore volume 0.99cm3The 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 crystalline phase structure and a pseudo-boehmite amorphous 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 figure 9, and the wrinkled mesoporous pseudo-boehmite grows on the surface of the Y-type molecular sieve grains and is formed by growing the pseudo-boehmite on the surface of the Y-type molecular sieve grainsIt is completely encapsulated. In the Raman (Raman) spectrum, YCM-4 has an a/b of 3.1.
Contacting porous material YCM-4 and rare earth chloride solution with ammonium salt solution at a weight ratio of 0.15 to 0.08 of rare earth oxide to porous material at 85 deg.C for 1 hr, filtering, washing with water and drying; then roasting for 2 hours at the temperature of 630 ℃ under the condition of 100 percent of water vapor; adding water into a sample obtained by roasting, pulping, mixing with a rare earth solution according to the weight ratio of the rare earth oxide of 0.06, carrying out secondary contact treatment for 1 hour at 85 ℃, filtering, washing with water, drying, carrying out secondary roasting treatment at 600 ℃ under the condition of 100% water vapor for 2 hours, and obtaining the porous catalytic material containing mesopores and micropores, which is marked as RA-7.
The XRD diffraction pattern of RA-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 sieve2O3And (5) structure.
In RA-7, the rare earth oxide accounts for 13.7 percent by weight, the unit cell constant is 2.455nm, the relative crystallinity is 38 percent, and the total specific surface area is 520m2In terms of/g, total pore volume 0.87cm3/g。
Example 8
According to a conventional molar ratio of gel charge to NaY molecular sieve, e.g. 7.5SiO2：Al2O3：2.15Na2O：190H2O, 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)3Solution (concentration 50 gAl)2O3L) 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 used2O3By weight, in terms of SiO2:Al2O3Tetraethoxy silicon was added to the above slurry at a ratio of 1:5, and thenStirring at constant temperature of 70 ℃ for 4 hours, then placing the slurry in a stainless steel reaction kettle, crystallizing at 100 ℃ for 15 hours, filtering the slurry after crystallization, washing and drying in an oven at 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 620m2In terms of/g, total pore volume 0.59cm3The 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 crystalline phase structure and a pseudo-boehmite amorphous 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-6 has an a/b of 7.7.
The porous material YCM-6 and the rare earth chloride solution are contacted for 1 hour at 70 ℃ according to the weight ratio of the rare earth oxide to the porous material of 0.12, and then are filtered, washed and dried; then roasting for 4 hours at the temperature of 600 ℃ and under the condition of 100 percent of water vapor; adding water into the sample obtained by roasting, pulping, mixing with a rare earth solution according to the weight ratio of the rare earth oxide of 0.06, carrying out secondary contact treatment for 1 hour at 70 ℃, filtering, washing with water, and drying to obtain the porous catalytic material containing mesopores and micropores, which is marked as RA-8.
The XRD diffraction pattern of RA-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 sieve2O3And (5) structure.
In RA-8, the rare earth oxide accounts for 17.9 wt%, the unit cell constant is 2.470nm, the relative crystallinity is 49%, and the total specific surface area is 565m2G, total pore volume 0.53cm3/g。
Example 9
According to a conventional molar ratio of gel charge to NaY molecular sieve, e.g. 7.5SiO2：Al2O3：2.15Na2O：190H2O, 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 Al2(SO4)3Solution (concentration 90 gAl)2O3L) 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 used2O3By weight, in terms of SiO2:Al2O3Water glass solution (concentration 120 gSiO) at a ratio of 1:72/L) adding the mixture into the slurry, stirring the mixture for 1 hour at the constant temperature of 80 ℃, then placing the slurry into a stainless steel reaction kettle, crystallizing the slurry for 28 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-10.
YCM-10 contains sodium oxide 5.2 wt%, silicon oxide 31.5 wt%, aluminum oxide 62.6 wt%, and specific surface area 442m2G, total pore volume 1.0cm3The 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 spectrum has the characteristics shown in figure 7, and simultaneously contains an FAU crystalline phase structure and a pseudo-boehmite amorphous 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 has an a/b of 1.7.
The porous material YCM-10 and the rare earth chloride solution are contacted for 2 hours at 60 ℃ according to the weight ratio of the rare earth oxide to the porous material of 0.13, and then are filtered, washed and dried; then roasting for 2 hours at 600 ℃; and adding water into the sample obtained by roasting, pulping, mixing with a rare earth solution according to the weight ratio of the rare earth oxide of 0.10, carrying out secondary contact treatment at 60 ℃ for 2 hours, filtering, washing with water, and drying to obtain the porous catalytic material containing mesopores and micropores, which is marked as RA-9.
The XRD diffraction pattern of RA-9 has the characteristics shown in figure 5, and shows that the FAU crystal phase structure and gamma-Al simultaneously contain the Y-type molecular sieve2O3And (5) structure.
RA-9 contains rare earth oxide 20.1 wt%, unit cell constant 2.472nm, relative crystallinity 25%, and total specific surface area 410m2G, total pore volume 0.93cm3/g。
Example 10
According to the mol ratio of the gel of the NaY molecular sieve in the embodiment 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)3Solution (concentration 50 gAl)2O3L) 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 used2O3By weight, in terms of SiO2:Al2O3Water glass solution (concentration 120 gSiO) at a ratio of 1:92L) 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 area2G, total pore volume 0.85cm3The 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. Its X-ray diffraction spectrumThe graph has the characteristics shown in FIG. 7, and contains both FAU crystalline phase structure and pseudo-boehmite amorphous 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-5 has an a/b of 5.5.
Contacting porous material YCM-5 and rare earth chloride solution with ammonium salt solution at a weight ratio of 0.20 to 0.06 of rare earth oxide to porous material at 65 ℃ for 2 hours, filtering, washing with water and drying; then roasting for 2 hours at 550 ℃; adding water into a sample obtained by roasting, pulping, mixing with a rare earth solution according to the weight ratio of the rare earth oxide of 0.08, carrying out secondary contact treatment for 2 hours at 65 ℃, filtering, washing with water, drying, carrying out secondary roasting treatment at 550 ℃ under the condition of 100% water vapor for 2 hours, and obtaining the porous catalytic material containing mesopores and micropores, which is marked as RA-10.
The XRD diffraction pattern of RA-10 has the characteristics shown in FIG. 5, and shows that FAU crystal phase structure and gamma-Al simultaneously contain Y-type molecular sieve2O3And (5) structure.
RA-10 contains rare earth oxide 13.7 wt%, unit cell constant 2.454nm, relative crystallinity 41%, and total specific surface area 530m2G, total pore volume 0.80cm3/g。
Examples 11 to 20
Examples 11-20 are provided to illustrate the cracking activity of the mesoporous and microporous porous catalytic materials of the present invention.
The porous catalytic materials RA-1 to RA-10 containing mesopores and micropores described in the above examples 1 to 10 were mixed with an ammonium chloride solution for exchange, the sodium oxide content thereof 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 8 hours, and then cracking performance was evaluated 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 1.1, 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
TABLE 2
| Sample (I) | RA-1 | RA-2 | RA-3 | RA-4 | RA-5 | RA-6 | RA-7 | RA-8 | RA-9 | RA-10 |
| Yield/%) | ||||||||||
| Dry gas | 2.17 | 1.68 | 1.66 | 1.70 | 1.47 | 1.55 | 1.96 | 1.88 | 2.19 | 1.99 |
| Liquefied gas | 10.52 | 9.91 | 10.01 | 9.68 | 10.42 | 9.89 | 10.04 | 10.16 | 10.30 | 10.07 |
| Gasoline (gasoline) | 53.64 | 48.05 | 49.01 | 46.18 | 48.68 | 47.07 | 50.98 | 49.13 | 54.08 | 51.90 |
| Diesel oil | 17.05 | 21.03 | 20.52 | 20.80 | 20.60 | 20.95 | 18.95 | 20.78 | 17.11 | 18.13 |
| Heavy oil | 7.48 | 9.91 | 9.63 | 11.50 | 9.45 | 10.24 | 9.00 | 8.17 | 6.90 | 8.41 |
| Coke | 9.14 | 9.42 | 9.17 | 10.14 | 9.38 | 10.30 | 9.07 | 9.88 | 9.42 | 9.50 |
| Conversion rate/% | 75.47 | 69.06 | 69.85 | 67.70 | 69.95 | 68.81 | 72.05 | 71.05 | 75.99 | 73.46 |
| Coke/conversion ratio | 0.121 | 0.136 | 0.131 | 0.150 | 0.134 | 0.150 | 0.126 | 0.139 | 0.124 | 0.129 |
As can be seen from the reaction data in table 2, the porous catalytic materials RA-1 to RA-10 containing mesopores and micropores in examples 1 to 10 have high cracking activity after aging treatment with 100% steam at 800 ℃ for 8 hours, the conversion rate is 67.70% to 75.99%, the gasoline yield is 46.18% to 54.08%, the heavy oil yield is 6.90% to 11.50%, the heavy oil conversion capability is high, the coke yield is relatively low, the coke selectivity is excellent, and the product distribution is significantly optimized.
The porous catalytic material containing mesopores and micropores has more obvious characteristics on a pore structure and acid distribution due to organic combination of two structures of the mesopores and the micropores and certain rare earth modification, and is very favorable for improving macromolecule transmission and cracking activity.
Claims (10)
1. A porous catalytic material containing mesopores and micropores is characterized by simultaneously containing microporous structures of FAU crystal phase structures of Y-type molecular sieves and gamma-Al2O3Mesoporous structure of type structure, said gamma-Al2O3The mesoporous structure grows along the edge of a Y-shaped molecular sieve FAU crystal phase structure, the two structures are connected with each other, and the content of rare earth is 2-23 wt%, preferably 4-20 wt% calculated by rare earth oxide.
2. A porous catalytic material according to claim 1 characterized in that it has a unit cell constant of 2.450 to 2.472nm, preferably 2.453 to 2.467nm, a relative crystallinity of 25 to 65%, preferably 28 to 60%, and a total specific surface area of 250 to 600m2(g) total pore volume of 0.3-1.0 cm3/g。
3. The porous catalytic material according to claim 1, characterized in that it is prepared by a process comprising the steps of: (1) a plurality of holesCarrying out first contact treatment on the material and a rare earth solution and/or an ammonium salt solution, filtering, washing and drying; (2) carrying out primary roasting treatment on the obtained product in the step (1) under the condition of 0-100% of water vapor; (3) pulping the water obtained in the step (2), carrying out secondary contact treatment on the pulped water and a rare earth solution and/or an ammonium salt solution, filtering, washing and drying; or carrying out secondary roasting treatment under the condition of 0-100% of water vapor and recovering a product; the porous material in the step (1) contains an FAU crystalline phase structure and a pseudo-boehmite amorphous phase structure in an XRD spectrogram, an ordered diffraction stripe of the FAU crystalline phase part and a disordered structure of the pseudo-boehmite part can be seen in a Transmission Electron Microscope (TEM) at the same time, the disordered structure is derived and grown along the edge of the ordered diffraction stripe, and the two structures are effectively combined together to form a microporous and mesoporous composite structure; in the Raman spectrum, a/b is 1.5-10, wherein a represents a shift of 500cm-1B represents a shift of 350cm-1Peak intensity of the spectral peak of (a); the anhydrous chemical expression is (4-12) Na2O·(25～65)SiO2·(25～70)Al2O3The specific surface area is 350-750 m2The mesoporous specific surface area is 50-450 m2The total pore volume is 0.5-1.5 ml/g, the mesoporous pore volume is 0.2-1.2 ml/g, a BJH curve shows gradient pore distribution characteristics, and the pore distribution can be in a few pores at 3-4 nm, 8-20 nm and 18-40 nm respectively; and the porous material in the step (1) is prepared by adding water into molecular sieve dry powder with an FAU crystal structure, pulping, uniformly stirring, adding an aluminum source and an alkali solution at room temperature to 85 ℃, fully mixing, controlling the pH value of a slurry system to be 7-11, carrying out contact reaction, and taking alumina in the aluminum source as a reference and SiO as a reference2:Al2O3Adding a silicon source counted by silicon oxide into the reaction slurry according to the weight ratio of (1-9), continuously reacting for 1-10 hours at room temperature to 90 ℃, and recovering the product, or stirring for 1-4 hours at the constant temperature of room temperature to 90 ℃, then crystallizing for 3-30 hours at 95-105 ℃ in a closed reaction kettle, and recovering the product.
4. The porous catalytic material of claim 3 wherein said aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.
5. The porous catalytic material of claim 3 wherein said caustic solution is selected from one or more of ammonia, potassium hydroxide, sodium hydroxide or sodium metaaluminate, and when sodium metaaluminate is the caustic solution, the alumina content thereof is calculated to the total alumina content.
6. The porous catalytic material of claim 3 wherein said silicon source is selected from one or more of water glass, sodium silicate, tetraethoxysilane, tetramethoxysilane, or silica.
7. The process according to claim 3, wherein in the first contact treatment in the step (1), the weight ratio of the rare earth solution to the porous material in terms of rare earth oxide is 0.02 to 0.14, preferably 0.03 to 0.13, the weight ratio of the ammonium salt to the porous material is 0.05 to 1.0, the contact temperature is 40 to 90 ℃, preferably 50 to 80 ℃, and the contact time is 0.5 to 3.0 hours, preferably 1 to 2 hours.
8. A porous catalytic material according to claim 3, wherein the first and second calcination treatments in steps (2) and (3) are carried out at a temperature of 500 to 700 ℃, preferably 530 to 680 ℃, under the condition of 0 to 100% steam, preferably 20 to 100% steam, for 0.5 to 4.0 hours, preferably 1 to 3 hours.
9. The porous catalytic material according to claim 3, wherein in the second contact treatment in step (3), the weight ratio of the rare earth solution in terms of rare earth oxide to the weight of the rare earth solution obtained in step (2) is 0.02 to 0.12, preferably 0.04 to 0.10, the weight ratio of the ammonium salt to the weight of the rare earth oxide obtained in step (2) is 0.05 to 0.50, preferably 0.1 to 0.4, the contact temperature is 40 to 90 ℃, preferably 50 to 80 ℃, and the contact time is 0.5 to 3.0 hours, preferably 1 to 2 hours.
10. The porous catalytic material according to claim 3, wherein said ammonium salt in step (1) and step (3) is one or more of ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium bicarbonate.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173436A (en) * | 2011-01-04 | 2011-09-07 | 卓润生 | Preparation method of rare earth (RE) yttrium (Y) molecular sieve |
| CN103508467A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Rare earth Y-type molecular sieve and preparation method thereof |
| CN103657702A (en) * | 2012-09-14 | 2014-03-26 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN103657711A (en) * | 2012-09-14 | 2014-03-26 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN104014361A (en) * | 2013-02-28 | 2014-09-03 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN108927127A (en) * | 2017-05-26 | 2018-12-04 | 中国石油化工股份有限公司 | A kind of preparation method of active silica-alumina catalysis material |
| CN108927207A (en) * | 2017-05-26 | 2018-12-04 | 中国石油化工股份有限公司 | A kind of porous catalyst material and preparation method thereof of surface richness aluminium |
-
2019
- 2019-03-27 CN CN201910236269.2A patent/CN111747425B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173436A (en) * | 2011-01-04 | 2011-09-07 | 卓润生 | Preparation method of rare earth (RE) yttrium (Y) molecular sieve |
| CN103508467A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Rare earth Y-type molecular sieve and preparation method thereof |
| CN103657702A (en) * | 2012-09-14 | 2014-03-26 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN103657711A (en) * | 2012-09-14 | 2014-03-26 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN104014361A (en) * | 2013-02-28 | 2014-09-03 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN108927127A (en) * | 2017-05-26 | 2018-12-04 | 中国石油化工股份有限公司 | A kind of preparation method of active silica-alumina catalysis material |
| CN108927207A (en) * | 2017-05-26 | 2018-12-04 | 中国石油化工股份有限公司 | A kind of porous catalyst material and preparation method thereof of surface richness aluminium |
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