CN118002190A - Composite catalytic material and preparation method and application thereof - Google Patents
Composite catalytic material and preparation method and application thereof Download PDFInfo
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- CN118002190A CN118002190A CN202211330103.5A CN202211330103A CN118002190A CN 118002190 A CN118002190 A CN 118002190A CN 202211330103 A CN202211330103 A CN 202211330103A CN 118002190 A CN118002190 A CN 118002190A
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- 239000000463 material Substances 0.000 title claims abstract description 88
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000002707 nanocrystalline material Substances 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 25
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 24
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 18
- 239000003921 oil Substances 0.000 claims abstract description 11
- 238000003795 desorption Methods 0.000 claims abstract description 6
- 238000005538 encapsulation Methods 0.000 claims abstract description 5
- 238000010521 absorption reaction Methods 0.000 claims abstract description 4
- 239000012265 solid product Substances 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 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 4
- 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 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 description 20
- 239000002808 molecular sieve Substances 0.000 description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- 239000000571 coke Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229960002303 citric acid monohydrate Drugs 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002149 hierarchical pore Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- -1 ethylene, propylene, butylene Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012521 purified sample Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention relates to a composite catalytic material, a preparation method and application thereof, wherein the composite catalytic material has a structure of a hollow multistage hole ZSM-5 nanocrystalline material encapsulation reinforced heating material; wherein the hollow multistage hole ZSM-5 nanocrystalline material has a closed hollow structure, the average grain size is 0.4-3.0 mu m, the ratio of bulk phase silicon aluminum mol ratio to surface silicon aluminum mol ratio is 1.0-1.2, the total specific surface area is 340-400m 2/g, and the mesoporous specific surface area is 40-150m 2/g,N2 absorption and desorption curve presents an H4 type hysteresis ring; the reinforced heating material comprises a perovskite type heating material and sodium tungstate, wherein the perovskite type heating material contains copper-doped perovskite, and the molecular general formula of the copper-doped perovskite is ABO 3, wherein copper is doped at the B site and has a reduced valence state. The composite catalytic material has good catalytic activity and better heat release performance, and can obviously improve the yield of low-carbon olefin when being used in the catalytic cracking reaction of raw oil.
Description
Technical Field
The application relates to a composite catalytic material, a preparation method and application thereof.
Background
Catalytic cracking is the core of secondary processing in refineries, and distillate oil or residual oil obtained by atmospheric and vacuum is converted under the action of a catalyst and high temperature to produce liquefied gas, gasoline, diesel oil and other fuels or ethylene, propylene, butylene, BTX and other chemical raw materials. The catalyst is not only the reactive center of catalytic cracking reaction, but also the heat and mass transfer carrier of the catalytic cracking reaction system. The catalyst is introduced into the reactor from a high-temperature regenerator to bring in a large amount of heat, so that catalytic cracking reaction is promoted to occur, coke generated by the reaction is loaded on the surface of the catalyst, and then the catalyst is burnt with oxygen in the air to regenerate, so that a large amount of heat is generated.
Along with the heavy and poor quality of the processing raw materials and the requirement of the oil refining device for chemical transformation, the reaction conditions are more severe, more heat is required to be provided by the catalyst, however, the heat capacity of the catalyst is limited, so that the heat provided to a reaction part is limited, and the reaction temperature is difficult to further increase; in order to transfer more heat, the ratio of the agent to the oil is increased, and more side reactions are brought along.
The heat generated by the hydrocarbon conversion can be provided by utilizing the heat released by the heat generating material through the continuous oxidation-reduction reaction of the metal and the oxide thereof. However, the heating material is directly contacted with heavy oil hydrocarbon molecules, and is easy to be used as a dehydrogenation center, so that coking is obviously increased, and on the premise of ensuring the heating effect, the influence of the heating material on the reaction performance of the heating material is avoided or reduced, so that the heating material is key to industrial application.
The hollow material has special micro-environment in the capsule and unique space limiting effect, and has excellent performance in heterogeneous catalysis, biomedicine, adsorption separation, energy storage and other aspects. The hollow ZSM-5 molecular sieve has a nanoscale hierarchical pore shell and a relatively closed internal structure, has the advantages of strong acidity, excellent diffusion performance, outstanding encapsulation capacity and the like, and is a high-value material with extremely rich potential in the fields of industrial catalysis, adsorption separation and the like.
CN106082263B develops a shell layer hole-rich nano hollow ZSM-5 molecular sieve, which is prepared by mixing ethyl orthosilicate, tetrapropylammonium hydroxide, aluminum nitrate, sodium hydroxide and deionized water as raw materials, and aging, crystallizing, centrifuging, washing, drying and roasting the solution to obtain the nano ZSM-5 molecular sieve; the nanometer ZSM-5 molecular sieve is added with inorganic alkaline solution, stirred for 10 to 50 hours, separated, washed and dried to obtain the nanometer ZSM-5 with a hollow structure, the raw materials used in the preparation method are single, the size of the obtained product is 50 to 100nm, the mesopores are too large, and the hydrothermal stability and the mechanical strength are further improved.
Disclosure of Invention
The invention aims to provide a composite catalytic material, a preparation method and application thereof, and the composite catalytic material can improve the yield of low-carbon olefin, reduce the yield of byproducts and has optimized heat release performance.
In order to achieve the above object, a first aspect of the present invention provides a composite catalytic material having a structure in which a hollow multi-level pore ZSM-5 nanocrystalline material encapsulates a reinforced heating material;
The reinforced heating material comprises a perovskite heating material and sodium tungstate, wherein the perovskite heating material contains copper-doped perovskite, and the molecular general formula of the copper-doped perovskite is ABO 3, wherein copper is doped at the B site and has a reduced valence state; the average grain size of the copper-doped perovskite is 0.1 μm or less;
the hollow multistage hole ZSM-5 nanocrystalline material has a closed hollow structure, the average grain size is 0.4-3.0 mu m, the ratio of bulk phase silicon-aluminum molar ratio to surface silicon-aluminum molar ratio is 1.0-1.2, the total specific surface area is 340-400m 2/g, and the mesoporous specific surface area is 40-150m 2/g,N2 absorption and desorption curve presents an H4 type hysteresis loop.
Optionally, the copper-doped perovskite, A is a rare earth element and/or an alkaline earth element, preferably one or more of calcium, strontium, barium and lanthanum; b is copper and optionally a valence-variable metal element, wherein the valence-variable metal element is one or more selected from titanium, iron, cobalt, nickel and manganese.
Optionally, the composite catalytic material contains the hollow multistage pore ZSM-5 nanocrystalline material, the perovskite type heating material and the sodium tungstate in a molar ratio of 1: (0.01-0.1): (0.005-0.01), wherein the hollow multistage hole ZSM-5 nanocrystalline material is calculated by SiO 2, and the perovskite type heating material is calculated by CuO.
Optionally, the average grain size of the hollow multistage hole ZSM-5 nanocrystalline material is 0.4-2.5 mu m, the ratio of the bulk phase silicon aluminum molar ratio to the surface silicon aluminum molar ratio is 1.0-1.1, the total specific surface area is 360-400m 2/g, and the mesoporous specific surface area is 50-140m 2/g.
In a second aspect, the present invention provides a method of preparing the composite catalytic material provided in the first aspect of the present invention, the method comprising:
s1, mixing a silicon source, copper-doped perovskite, sodium tungstate and a first solvent at 30-50 ℃ for reaction for 0.5-5 hours, heating to 70-100 ℃ for mixing and stirring for 2-10 hours, and mixing the obtained mixed liquid with a template agent at 20-30 ℃ for 0.5-3.0 hours to obtain a first mixed product;
s2, the molar ratio is (1.5-5): (60-350): 1, a second solvent and an aluminum source calculated as Al 2O3 at 20-80 ℃ for 0.5-2 hours to obtain a second mixed product;
S3, mixing the first mixed product and the second mixed product, then carrying out dynamic crystallization, taking out the obtained solid, and carrying out first roasting to obtain a first solid product;
S4, mixing the first solid product with a solution containing alkali, and reacting for 10-90min at the reaction temperature after the temperature rises to the reaction temperature at a heating rate of 1-5 ℃/min to obtain a second solid product; wherein the reaction temperature is 60-90 ℃, and the alkali content in the alkali-containing solution is 0.45-2mol/L;
s5, carrying out ammonium exchange on the second solid product, and carrying out second roasting on the solid product obtained by the ammonium exchange to obtain the composite catalytic material.
Optionally, the molar ratio of the total amount of the copper doped perovskite, the sodium tungstate, the templating agent, the first solvent and the second solvent, the alkali metal hydroxide, and the silicon source is (0.01-0.1): (0.005-0.01): (0.06-0.55): (10-100): (0.02-1.5): 1, the molar ratio of the silicon source to the aluminum source is (20-500): 1, a step of; wherein the copper doped perovskite is calculated as CuO, the silicon source is calculated as SiO 2, the alkali metal hydroxide is calculated as alkali metal oxide, and the aluminum source is calculated as Al 2O3.
Optionally, in step S2, the molar ratio of the alkali metal hydroxide calculated as alkali metal oxide, the second solvent and the aluminum source calculated as Al 2O3 is (1.5-5): (60-500): 1, preferably (2-4.5): (80-350): 1.
Optionally, in step S4, the molar ratio of the first solid product to the amount of the alkali-containing solution is 1: (2-10), preferably 1: (4-8) the first solid product is in terms of SiO 2;
the ratio of the bulk silicon aluminum molar ratio to the surface silicon aluminum molar ratio of the first solid product is 1.2-5.0;
The conditions of the dynamic crystallization include: the temperature is 160-180 ℃ and the time is 12-60 hours;
The conditions of the first firing and the second firing each independently include: the temperature is 400-600 ℃ and the time is 2-6 hours.
Optionally, in step S5, said subjecting said second solid product to ammonium exchange comprises: the weight ratio is 1: (0.5-1.0): after mixing the second solid product of (8-10), an ammonium source and a third solvent, reacting the resulting mixture at 70-90 ℃ for 0.5-2 hours; the ammonium source is selected from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
Optionally, the template agent is selected from one or more of tetrapropylammonium bromide, tetrapropylammonium hydroxide, n-butylamine and hexamethylenediamine;
The silicon source is methyl orthosilicate and/or ethyl orthosilicate;
The aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum isopropoxide and aluminum sol;
the alkali metal hydroxide is selected from one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide;
the first solvent and the second solvent are each independently water.
The third aspect of the invention provides an application of the composite catalytic material provided by the first aspect of the invention in catalytic cracking reaction of heavy hydrocarbon oil.
The hollow multistage hole ZSM-5 nanocrystalline has proper grain size and complete hollow structure, can match a proper mesoporous structure aiming at reactants with different molecular structures, has a shell layer mainly of a microporous structure, is rich in mesoporous and macroporous structures, has large outer surface area, can provide a multidirectional diffusion path, expands a limited space, improves the diffusion performance of a molecular sieve, increases accessibility of an active center, has the potential of catalyzing cracking of macromolecular hydrocarbon, and can be applied to a high-efficiency heavy oil raw material catalytic cracking/cracking catalyst.
Through the technical scheme, the composite catalytic material disclosed by the invention contains the reinforced heating material, wherein the reinforced heating material comprises a perovskite heating material and sodium tungstate, and the perovskite heating material has good structural stability and heat release performance; the sodium tungstate can promote the oxidation-reduction reaction of the copper element to have the effect of enhancing heat, so that the content of the perovskite type heat-generating material in the composite catalytic material is reduced, the catalytic material still has good heat-generating effect, and the composite catalytic material keeps better catalytic activity and lower coke yield.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The first aspect of the invention provides a composite catalytic material, which has a structure of a hollow multistage pore ZSM-5 nanocrystalline material encapsulation reinforced heating material;
The reinforced heating material comprises a perovskite heating material and sodium tungstate, wherein the perovskite heating material contains copper-doped perovskite, and the molecular general formula of the copper-doped perovskite is ABO 3, wherein copper is doped at the B site and has a reduced valence state; the average grain size of the copper-doped perovskite is 0.1 μm or less;
the hollow multistage hole ZSM-5 nanocrystalline material has a closed hollow structure, the average grain size is 0.4-3.0 mu m, the ratio of bulk phase silicon-aluminum molar ratio to surface silicon-aluminum molar ratio is 1.0-1.2, the total specific surface area is 340-400m 2/g, and the mesoporous specific surface area is 40-150m 2/g,N2 absorption and desorption curve presents an H4 type hysteresis loop.
The hollow multi-level hole ZSM-5 nanocrystalline material encapsulation reinforced heating material means that the reinforced heating material is contained in the intra-crystal hollow structure of the hollow multi-level hole ZSM-5 nanocrystalline material, the outer surface of the reinforced heating material can be connected with the inner surface of the hollow multi-level hole ZSM-5 nanocrystalline material or not, and the composite catalytic material can also be called as having a core-shell structure when being connected together. According to the composite catalytic material, hydrocarbon molecules entering the hollow interior are screened through the hollow multi-level hole ZSM-5 nanocrystalline material, so that the phenomenon that coke generation is increased due to the fact that a perovskite type heating material is used as a dehydrogenation center to be directly contacted with heavy oil hydrocarbon molecules is avoided, copper enters a perovskite structure in a doped mode, the perovskite doped with copper has better structural stability, and the influence of the perovskite type heating material on the reaction performance of a catalytic cracking catalyst can be further reduced; the sodium tungstate contained in the catalyst can further strengthen the heating effect, so that the composite catalyst material disclosed by the invention has better heating effect and good catalytic activity, further improves the conversion rate of raw materials and the yield of low-carbon olefin, and reduces the coke yield.
In one embodiment of the present invention, the perovskite heat generating material has diffraction peaks at diffraction angles of 23±2°, 33±2°, 47±2° and 58±2° in an XRD spectrum. The perovskite heating material has the characteristics of stable structure, high temperature resistance and multiple oxygen vacancies, so that the composite catalytic material has good heating effect and catalytic activity, and the yield of the low-carbon olefin can be further improved.
In one embodiment of the invention, A is a rare earth element or an alkaline earth element, preferably one or more of calcium, strontium, barium and lanthanum; b is copper and optionally a valence-variable metal element, wherein the valence-variable metal element is one or more selected from titanium, manganese, cobalt, nickel and iron.
In one specific embodiment of the present invention, the composite catalytic material contains the hollow multistage pore ZSM-5 nanocrystalline material, the perovskite heat generating material and the sodium tungstate in a molar ratio of 1: (0.01-0.1): (0.005-0.01), preferably 1: (0.01-0.09): (0.005-0.01), wherein the hollow multistage pore ZSM-5 nanocrystalline material is calculated as SiO 2, and the perovskite type heating material is calculated as CuO.
In one embodiment of the present invention, the hollow, multi-stage pore ZSM-5 nanocrystalline material has an average crystallite size of 0.4 to 2.5. Mu.m. In the present invention, the grain size refers to the size of the widest part of the grains, which can be obtained by measuring the size of the widest part of the projection surface of the grains in an SEM or TEM image of a sample, and the average grain size is obtained by selecting any 10 molecular sieves in the SEM or TEM image and calculating the average value thereof.
In a specific embodiment of the invention, the ratio of bulk silica alumina molar ratio to surface silica alumina molar ratio of the hollow multistage hole ZSM-5 nanocrystalline material is 1.0-1.1, the total specific surface area is 360-400m 2/g, and the mesoporous specific surface area is 50-140m 2/g. Wherein, the bulk silicon-aluminum molar ratio refers to the silicon-aluminum molar ratio of the hollow multi-level pore ZSM-5 nanocrystalline material as a whole. Bulk silica to alumina molar ratio was determined by XRF method and surface silica to alumina molar ratio was determined by XPS method, specific test methods are well known to those skilled in the art and will not be described in detail herein. The total specific surface area and the mesoporous specific surface area are obtained by BET analysis.
In one embodiment of the present invention, the hollow, multi-stage pore ZSM-5 nanocrystalline material has a relative crystallinity of from 75 to 95%. In the invention, the relative crystallinity of the molecular sieve is based on an XRD standard ZSM-5 molecular sieve standard sample of the Ministry of petrochemical industry, and the crystallinity of the standard sample is regarded as 100 percent.
In a second aspect, the present invention provides a method of preparing the composite catalytic material provided in the first aspect of the present invention, the method comprising:
s1, mixing a silicon source, copper-doped perovskite, sodium tungstate and a first solvent at 30-50 ℃ for reaction for 0.5-5 hours, heating to 70-100 ℃ for mixing and stirring for 2-10 hours, and mixing the obtained mixed liquid with a template agent at 20-30 ℃ for 0.5-3.0 hours to obtain a first mixed product;
s2, the molar ratio is (1.5-5): (60-350): 1, a second solvent and an aluminum source calculated as Al 2O3 at 20-80 ℃ for 0.5-2 hours to obtain a second mixed product;
S3, mixing the first mixed product and the second mixed product, then carrying out dynamic crystallization, taking out the obtained solid, and carrying out first roasting to obtain a first solid product;
S4, mixing the first solid product with a solution containing alkali, and reacting for 10-90min at the reaction temperature after the temperature rises to the reaction temperature at a heating rate of 1-5 ℃/min to obtain a second solid product; wherein the reaction temperature is 60-90 ℃, and the alkali content in the alkali-containing solution is 0.45-2mol/L;
s5, carrying out ammonium exchange on the second solid product, and carrying out second roasting on the solid product obtained by the ammonium exchange to obtain the composite catalytic material.
According to the invention, the molar ratio of the total amount of the copper-doped perovskite, the sodium tungstate, the templating agent, the first solvent and the second solvent, the alkali metal hydroxide, and the silicon source amount is (0.01-0.1): (0.005-0.01): (0.06-0.55): (10-100): (0.02-1.5): 1, the molar ratio of the silicon source to the aluminum source is (20-500): 1, wherein the copper doped perovskite is calculated as CuO, the silicon source is calculated as SiO 2, the alkali metal hydroxide is calculated as alkali metal oxide, and the aluminum source is calculated as Al 2O3.
According to the invention, in step S2, the molar ratio of the alkali metal hydroxide calculated as alkali metal oxide, the second solvent and the aluminum source used as Al 2O3 is (1.5-5): (60-500): 1, preferably (2-4.5): (80-350): 1.
In one embodiment of the present invention, in step S3, dynamic crystallization is well known to those skilled in the art, and the conditions of the dynamic crystallization include: the temperature is 160-180 ℃ and the time is 12-60 hours.
In one embodiment of the present invention, in step S4, the molar ratio of the first solid product to the amount of the alkali-containing solution is 1: (2-10), preferably 1: (4-8) the first solid product is in terms of SiO 2; the ratio of the bulk silicon aluminum molar ratio to the surface silicon aluminum molar ratio of the first solid product is 1.2-5.0.
In one embodiment of the present invention, in step S5, said subjecting said second solid product to ammonium exchange comprises: the weight ratio is 1: (0.5-1.0): after mixing the second solid product of (8-10), an ammonium source and a third solvent, reacting the resulting mixture at 70-90 ℃ for 0.5-2 hours; the ammonium source is selected from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
In one embodiment, the first solvent, the second solvent, and the third solvent may each be independently water.
In one embodiment of the present invention, the firing may be performed in a muffle furnace, a tube furnace, or the like, as is conventional to those skilled in the art. In one embodiment, the conditions of the first firing and the second firing each independently include: the temperature is 400-600 ℃ for 2-6 hours, preferably 450-580 ℃ for 3-5 hours.
In one embodiment of the present invention, the specific surface area of the mesoporous is increased by 100-500%, the volume of the mesoporous is increased by 150-600%, and the total acid amount is increased by 50-250% compared with the first solid product. In the present invention, the mesoporous volume can be obtained by BET test, and the total acid amount can be detected by NH3-TPD method.
According to the invention, the copper-doped perovskite is prepared by one or more methods selected from a coprecipitation method, a sol-gel method and a complexation method. In a preferred embodiment of the invention, the copper-containing perovskite LaCu xMn1-xO3 is prepared by a process comprising the steps of:
(1) Dissolving a copper source, a lanthanum source and a manganese source in deionized water, and stirring at 400-700rpm; adding citric acid monohydrate, maintaining the same rotation speed, stirring at 35-55deg.C for 30-60min, and adding ethylene glycol to obtain a first mixture;
(2) Heating the first mixture to 80-100deg.C, stirring to sol state, standing for 70-100h, and drying at 90-120deg.C overnight to obtain a second mixture;
(3) And (3) heat treating the second mixture at 400-500 ℃ for 3-6 hours, and calcining the obtained substance at 750-1000 ℃ for 10-15 hours to obtain the copper-containing perovskite LaCu xMn1-xO3.
In one embodiment, the copper doped perovskite has a molecular formula LaCu xMn1-xO3 and x is 0.01 to 0.99, such as 0.2 to 0.6.
In the invention, the copper source is selected from one or more of copper sulfate, copper chloride, copper nitrate and copper carbonate, the lanthanum source is selected from one or more of lanthanum nitrate hexahydrate, lanthanum chloride, lanthanum oxide and lanthanum sulfate, and the manganese source is selected from one or more of manganese nitrate, manganese chloride, manganese nitrate and manganese sulfate.
In one embodiment of the present invention, the average grain size of the copper-doped perovskite is preferably 0.01 to 0.09 μm. In the present invention, the grain sizes of 10 copper-doped perovskites were randomly measured by SEM, and the average thereof was taken to obtain an average grain size.
In one specific embodiment of the invention, the template agent is selected from one or more of tetrapropylammonium bromide, tetrapropylammonium hydroxide, n-butylamine and hexamethylenediamine; the silicon source is methyl orthosilicate and/or ethyl orthosilicate; the aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum isopropoxide and aluminum sol; the alkali metal hydroxide is selected from one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide; the first solvent and the second solvent are each independently water.
The third aspect of the invention provides an application of the composite catalytic material provided by the first aspect of the invention in catalytic cracking of raw oil and catalytic cracking, in particular to an application in catalytic cracking reaction of heavy hydrocarbon oil.
The composite catalytic material is used in catalytic cracking and catalytic cracking reaction, and has the advantages of further improving the reaction temperature and the yield of low-carbon olefin (such as ethylene and propylene). In one embodiment of the present invention, the feedstock is contacted with a composite catalytic material to perform a catalytic cracking reaction or a catalytic cracking reaction. Preferably, the composite catalytic material is a reinforced reduced composite catalytic material.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
The raw materials used in the following examples and comparative examples are commercially available without particular description. The catalytic cracking equilibrium catalyst ECAT is purchased from the medium petrochemical catalyst company, ziluta corporation COKC-1 industrial agent.
In examples and comparative examples, the grain size of the molecular sieve was measured by SEM, 10 grain sizes were randomly measured, and the average value thereof was taken to obtain the average grain size of the molecular sieve sample.
The grain sizes of 10 copper-doped perovskites were randomly measured by SEM, and the average thereof was taken to obtain the average grain size of the copper-doped perovskite.
The bulk silica alumina molar ratio of the sample was determined by XRF method, the instrument was a ZSX Primus II (Rigaku) X-ray fluorescence spectrometer; test conditions: excitation voltage is 50kV, excitation current is 50mA, rhodium and palladium are adopted. And measuring the peak intensity of each element spectrum by using a scintillation counter and a proportional counter, and analyzing the element composition of the molecular sieve.
The silicon-aluminum molar ratio of the surface of the sample is determined by XPS method, and the instrument adopts ESCALab type X-ray photoelectron spectrometer of thermo Fisher company, test conditions: the excitation source is monochromized AlK alpha X-ray, and the excitation energy is 1496.6eV and the power is 150W. The electron binding energy was corrected for the C1s peak of the contaminating carbon (284.8 eV).
The total specific surface area and the mesoporous specific surface area of the sample are detected by adopting a BET method. Instrument: ASAP 2420 adsorbent of Micromeritics, USA. Test conditions: the samples are subjected to vacuum degassing at 100 ℃ and 300 ℃ for 0.5h and 6h respectively, N 2 adsorption and desorption tests are carried out at 77.4K, and the adsorption amount and the desorption amount of the purified samples on nitrogen under different specific pressure conditions are tested to obtain an N 2 adsorption-desorption isothermal curve. BET specific surface area is calculated by using a BET formula, micropore area is calculated by using t-plot, and aperture distribution is calculated by using BJH.
The molar quantity of the hollow hierarchical pore ZSM-5 nanocrystalline material calculated by SiO 2 in the sample, the molar quantity of the perovskite type heating material calculated by CuO and the molar quantity of sodium tungstate are detected by adopting an XRF method.
The raw materials used for ACE evaluation in examples and comparative examples are ACE standard oil, and the properties are as follows:
The following preparation example 1 is a preparation example of copper-doped perovskite.
Preparation example 1
(1) 3.94G (0.016 mol) of copper nitrate trihydrate, 17.65g (0.041 mol) of lanthanum nitrate hexahydrate and 8.75g (0.024 mol) of 50% manganese nitrate in mass fraction are dissolved in 664g of deionized water under the condition of stirring at 40 ℃ and the rotating speed is 500rpm; 34.3g (0.163 mol) of citric acid monohydrate was added thereto, and after stirring for 30 minutes at a rotation speed of 500rpm and a temperature of 40 ℃, 10.11g (0.163 mol) of ethylene glycol was added to obtain a first mixture;
(2) Heating the first mixture to 80 ℃, continuously stirring to form sol, standing for 72h, and drying overnight at 100 ℃ to obtain a second mixture;
(3) Heat-treating the second mixture in a muffle furnace at 450 ℃ for 3 hours; the resulting material was calcined at 800 ℃ for 12 hours to give copper-containing perovskite LaCu 0.4Mn0.6O3.
XRD analysis shows that the prepared copper-doped perovskite has obvious diffraction peaks at diffraction angles of 23 DEG, 33 DEG, 47 DEG and 58 DEG on an XRD spectrogram, wherein the molecular general formula of the copper-doped perovskite is ABO 3, A is lanthanum, and B is copper and manganese; the average grain size was 0.05 microns.
Example 1
S1, weighing 22.44 g of copper-doped perovskite prepared in the preparation example 1, 1g of sodium tungstate and 91.2 g of ethyl orthosilicate, adding 639.14 g of deionized water, stirring and heating for 2 hours under the water bath condition at 40 ℃, raising the water bath temperature to 70 ℃, stirring and heating for 4 hours to remove ethanol generated by hydrolysis of a silicon source, intermittently supplementing water which is evaporated simultaneously with the ethanol into a system in the process, and mixing and stirring the obtained mixed liquid with 111.65 g of tetrapropylammonium hydroxide solution (the weight percentage of tetrapropylammonium hydroxide is 25.0 percent) at 25 ℃ for 1 hour to obtain a first mixed product;
S2, adding 60.80 g of deionized water into 3.44 g of sodium hydroxide particles to completely dissolve sodium hydroxide, adding 8.16 g of aluminum nitrate nonahydrate, and stirring at room temperature for 1.0h to obtain a second mixed product (namely an aluminum source solution);
s3, slowly adding the second mixed product into the first mixed product, uniformly mixing, and stirring for 4.0h at room temperature; transferring the obtained precursor liquid into a synthesis kettle, and dynamically crystallizing at 170 ℃ for 48 hours; after crystallization, centrifugally filtering, washing and drying the obtained mixture, and roasting for 4 hours at 550 ℃ to obtain a first solid product (marked as a molecular sieve Q-M1);
S4, uniformly mixing the first solid product and a sodium hydroxide solution with the concentration of 0.65mol/L, wherein the weight ratio of the molecular sieve to the alkali solution is 1:10, heating and stirring for 30min at the temperature after the temperature rising rate of 2 ℃/min to 80 ℃, filtering, washing and drying to obtain a second solid product (named as molecular sieve Q-S1-Na);
S5, carrying out second solid product: ammonium chloride: deionized water was prepared according to 1:1:10, stirring and heating for 30min in a water bath at 80 ℃, filtering, washing, drying, and then mixing with a second solid product: ammonium chloride: deionized water is 1:0.5:10, carrying out secondary ammonium exchange, filtering, washing, drying and roasting for 2 hours at 550 ℃ to obtain the composite catalytic material (marked as Q-S1-H). The composition of the catalyst is shown in Table 1.
Example 2
A composite catalytic material Q-S2-H was prepared in the same manner as in example 1 except that in step S1, 44.88 g of the copper-doped perovskite prepared in preparation example 1 above (average crystal grain size: 0.05 μm), 2 g of sodium tungstate and 91.2 g of ethyl orthosilicate were weighed, 639.14 g of deionized water was further added, and after stirring and heating for 2 hours under a water bath condition of 40℃the water bath temperature was raised to 70℃and stirring and heating was carried out for 4 hours to remove ethanol generated by hydrolysis of a silicon source, water evaporated simultaneously with ethanol was intermittently supplemented to the system during the process, and the obtained mixed liquid was mixed and stirred with 111.65 g of tetrapropylammonium hydroxide solution (tetrapropylammonium hydroxide weight fraction: 25.0 wt%) at 25℃for 1 hour to obtain a first mixed product.
Comparative example 1
Catalysts D-S1-H were prepared in the same manner as in example 1 except that copper-doped perovskite and sodium tungstate were not added in step S1.
Comparative example 2
Catalyst D-S2-H was prepared in the same manner as in example 1 except that sodium tungstate was not added in step S1.
Comparative example 3
Catalyst D-S3-H was prepared in the same manner as in example 1, except that copper-doped perovskite was not added in step S1.
Comparative example 4
Kaolin support, alumina sol, copper doped perovskite (prepared in preparation example 1) and sodium tungstate were mixed according to the kaolin: and (2) a binder: copper doped perovskite: the weight ratio of the sodium tungstate is 50:39:10:1, mixing to prepare slurry, carrying out spray drying on the obtained slurry, and roasting a product obtained by spray drying at 550 ℃ for 3 hours to obtain the auxiliary agent G-1.
Test case
The catalysts prepared in the above examples and comparative examples were evaluated for ACE in terms of 10% by weight of a catalytic cracking Equilibrium Catalyst (ECAT) of (G-S1-H or G-S2-H or G-S3-H or G-S4-H or D-S1-H or G-1) +90% by weight, the reaction temperature was set at 530℃and the catalyst oil quality ratio was 8, and the exothermic effect was examined by recording the change in the reaction temperature. The results shown in tables 2 and 3 were obtained.
TABLE 1
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Wherein, cuO/SiO 2 in the composite catalytic material refers to the molar ratio of perovskite heating material and hollow multi-level hole ZSM-5 nanocrystalline material contained in the composite catalytic material, and Na 2WO4/SiO2 in the composite catalytic material refers to the molar ratio of sodium tungstate and hollow multi-level hole ZSM-5 nanocrystalline material contained in the composite catalytic material.
TABLE 2
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TABLE 3 Table 3
From the above, the composite catalytic material has better heat release performance and good catalytic activity, and can further improve the conversion rate of raw materials and the yield of low-carbon olefin.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (11)
1. A composite catalytic material has a structure of hollow multistage hole ZSM-5 nanocrystalline material encapsulation reinforced heating material;
The reinforced heating material comprises a perovskite heating material and sodium tungstate, wherein the perovskite heating material contains copper-doped perovskite, and the molecular general formula of the copper-doped perovskite is ABO 3, wherein copper is doped at B site; the average grain size of the copper-doped perovskite is 0.1 μm or less;
The hollow multistage hole ZSM-5 nanocrystalline material comprises: the porous material has a closed hollow structure, the average grain size is 0.4-3.0 mu m, the ratio of the silicon-aluminum molar ratio of the bulk phase to the silicon-aluminum molar ratio of the surface is 1.0-1.2, the total specific surface area is 340-400m 2/g, and the absorption and desorption curve with the mesoporous specific surface area of 40-150m 2/g,N2 presents an H4 type hysteresis ring.
2. The composite catalytic material according to claim 1, wherein the copper doped perovskite, a is a rare earth element and/or an alkaline earth element, preferably one or more of calcium, strontium, barium and lanthanum; b is copper and optionally a valence-variable metal element, wherein the valence-variable metal element is one or more selected from titanium, iron, cobalt, nickel and manganese.
3. The composite catalytic material of claim 1, wherein the composite catalytic material comprises the hollow, multi-stage pore ZSM-5 nanocrystalline material, the perovskite-type heat generating material, and the sodium tungstate in a molar ratio of 1: (0.01-0.1): (0.005-0.01), wherein the hollow multistage hole ZSM-5 nanocrystalline material is calculated by SiO 2, and the perovskite type heating material is calculated by CuO.
4. The composite catalytic material of claim 1, wherein the hollow multistage pore ZSM-5 nanocrystalline material has an average grain size of 0.4-2.5 μm, a ratio of bulk phase silica alumina molar ratio to surface silica alumina molar ratio of 1.0-1.1, a total specific surface area of 360-400m 2/g, and a mesoporous specific surface area of 50-140m 2/g.
5. A method of making the composite catalytic material of any one of claims 1-4, the method comprising:
s1, mixing a silicon source, copper-doped perovskite, sodium tungstate and a first solvent at 30-50 ℃ for reaction for 0.5-5 hours, heating to 70-100 ℃ for mixing and stirring for 2-10 hours, and mixing the obtained mixed liquid with a template agent at 20-30 ℃ for 0.5-3.0 hours to obtain a first mixed product;
s2, the molar ratio is (1.5-5): (60-350): 1, a second solvent and an aluminum source calculated as Al 2O3 at 20-80 ℃ for 0.5-2 hours to obtain a second mixed product;
S3, mixing the first mixed product and the second mixed product, then carrying out dynamic crystallization, taking out the obtained solid, and carrying out first roasting to obtain a first solid product;
S4, mixing the first solid product with a solution containing alkali, and reacting for 10-90min at the reaction temperature after the temperature rises to the reaction temperature at a heating rate of 1-5 ℃/min to obtain a second solid product; wherein the reaction temperature is 60-90 ℃, and the alkali content in the alkali-containing solution is 0.45-2mol/L;
s5, carrying out ammonium exchange on the second solid product, and carrying out second roasting on the solid product obtained by the ammonium exchange to obtain the composite catalytic material.
6. The method of claim 5, wherein the molar ratio of the total amount of copper doped perovskite, sodium tungstate, template, first solvent and second solvent, alkali metal hydroxide, and silicon source amount is (0.01-0.1): (0.005-0.01): (0.06-0.55): (10-100): (0.02-1.5): 1, the molar ratio of the silicon source to the aluminum source is (20-500): 1, a step of; wherein the copper doped perovskite is calculated as CuO, the silicon source is calculated as SiO 2, the alkali metal hydroxide is calculated as alkali metal oxide, and the aluminum source is calculated as Al 2O3.
7. The method according to claim 5, wherein in step S2, the molar ratio of the alkali metal hydroxide as alkali metal oxide, the second solvent and the aluminum source as Al 2O3 is (1.5-5): (60-500): 1, preferably (2-4.5): (80-350): 1.
8. The method of claim 5, wherein in step S4, the molar ratio of the first solid product to the amount of the alkali-containing solution is 1: (2-10), preferably 1: (4-8) the first solid product is in terms of SiO 2;
the ratio of the bulk silicon aluminum molar ratio to the surface silicon aluminum molar ratio of the first solid product is 1.2-5.0;
The conditions of the dynamic crystallization include: the temperature is 160-180 ℃ and the time is 12-60 hours;
The conditions of the first firing and the second firing each independently include: the temperature is 400-600 ℃ and the time is 2-6 hours.
9. The method of claim 5, wherein in step S5, said subjecting the second solid product to ammonium exchange comprises: the weight ratio is 1: (0.5-1.0): after mixing the second solid product of (8-10), an ammonium source and a third solvent, reacting the resulting mixture at 70-90 ℃ for 0.5-2 hours; the ammonium source is selected from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
10. The method of claim 5, wherein the template agent is selected from one or more of tetrapropylammonium bromide, tetrapropylammonium hydroxide, n-butylamine, and hexamethylenediamine;
The silicon source is methyl orthosilicate and/or ethyl orthosilicate;
The aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum isopropoxide and aluminum sol;
the alkali metal hydroxide is selected from one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide;
the first solvent and the second solvent are each independently water.
11. Use of the composite catalytic material according to any one of claims 1-4 in catalytic cracking reactions of heavy hydrocarbon oils.
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