CN107971031B - A kind of assistant for calalytic cracking and preparation method thereof improving octane number bucket - Google Patents
A kind of assistant for calalytic cracking and preparation method thereof improving octane number bucket Download PDFInfo
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- CN107971031B CN107971031B CN201610921640.5A CN201610921640A CN107971031B CN 107971031 B CN107971031 B CN 107971031B CN 201610921640 A CN201610921640 A CN 201610921640A CN 107971031 B CN107971031 B CN 107971031B
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000005336 cracking Methods 0.000 title claims abstract description 29
- 239000002808 molecular sieve Substances 0.000 claims abstract description 351
- 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 342
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 143
- 239000011574 phosphorus Substances 0.000 claims abstract description 141
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 130
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 129
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 129
- 239000004411 aluminium Substances 0.000 claims abstract description 116
- 238000000034 method Methods 0.000 claims abstract description 106
- 239000011230 binding agent Substances 0.000 claims abstract description 91
- 229910052751 metal Inorganic materials 0.000 claims abstract description 70
- 239000002184 metal Substances 0.000 claims abstract description 70
- 239000004927 clay Substances 0.000 claims abstract description 66
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 60
- 230000008569 process Effects 0.000 claims abstract description 39
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 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 claims abstract description 13
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 184
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 114
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 50
- 239000013078 crystal Substances 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 48
- 229910052593 corundum Inorganic materials 0.000 claims description 46
- 239000007787 solid Substances 0.000 claims description 46
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 46
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 41
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 40
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 39
- 229910021536 Zeolite Inorganic materials 0.000 claims description 39
- 239000010457 zeolite Substances 0.000 claims description 39
- 238000005406 washing Methods 0.000 claims description 38
- 238000012545 processing Methods 0.000 claims description 37
- 239000002002 slurry Substances 0.000 claims description 35
- 238000001354 calcination Methods 0.000 claims description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 26
- 238000007598 dipping method Methods 0.000 claims description 25
- 239000011734 sodium Substances 0.000 claims description 25
- 229910019142 PO4 Inorganic materials 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 24
- 238000005360 mashing Methods 0.000 claims description 23
- 239000000654 additive Substances 0.000 claims description 22
- 230000000996 additive effect Effects 0.000 claims description 22
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 22
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 21
- 150000007522 mineralic acids Chemical class 0.000 claims description 21
- 229910002651 NO3 Inorganic materials 0.000 claims description 20
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 20
- 230000008025 crystallization Effects 0.000 claims description 20
- 238000009826 distribution Methods 0.000 claims description 20
- 150000007524 organic acids Chemical class 0.000 claims description 19
- 239000005995 Aluminium silicate Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 235000012211 aluminium silicate Nutrition 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005259 measurement Methods 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000003292 glue Substances 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 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 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000765 intermetallic Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000004113 Sepiolite Substances 0.000 claims description 7
- 229960000892 attapulgite Drugs 0.000 claims description 7
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229910052625 palygorskite Inorganic materials 0.000 claims description 7
- 229910052624 sepiolite Inorganic materials 0.000 claims description 7
- 235000019355 sepiolite Nutrition 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 239000011135 tin Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 229960001484 edetic acid Drugs 0.000 claims description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 5
- 239000002689 soil Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 229910001648 diaspore Inorganic materials 0.000 claims description 3
- 238000001935 peptisation Methods 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 238000009331 sowing Methods 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- XPXVJLZTBUUIGC-UHFFFAOYSA-N azanium dihydrogen phosphate phosphane Chemical compound OP(O)(O)=O.N.P XPXVJLZTBUUIGC-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- 238000006263 metalation reaction Methods 0.000 claims 1
- 239000003502 gasoline Substances 0.000 abstract description 42
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 12
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- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
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- 229910018516 Al—O Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005235 decoking Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910001922 gold oxide Inorganic materials 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 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
- 238000005185 salting out Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The disclosure provides a kind of assistant for calalytic cracking and preparation method thereof for improving octane number bucket, on the basis of the dry weight of the auxiliary agent, the auxiliary agent includes the phosphorous and carried metal MFI structure molecular sieve with dry basis 10-75 weight %, with the phosphorus aluminium inorganic binder of dry basis 3-40 weight %, other inorganic binders of the weight of the 1-30 in terms of oxide %, with the metallic addition selected from least one of VIII race's metal and manganese, zinc, gallium of the second clay of dry basis 0-60 weight %, and the weight of the 0.5-15 in terms of oxide %.The auxiliary agent that the disclosure is provided is used for catalytic cracking process, by improving the content of isohydrocarbon in gasoline to improve octane number, while yield of gasoline being kept to be basically unchanged, and then improve octane number bucket.
Description
Technical field
This disclosure relates to a kind of assistant for calalytic cracking and preparation method thereof for improving octane number bucket.
Background technique
In recent years, domestic motor vehicles ownership persistently rises, and domestic gasoline terminal consumption demand is supported to keep vigorous." ten
Two or five " automobile sales volume increases by 11% every year during, drives gasoline demand to keep average annual 5% steady growth, it is contemplated that vapour in 2015
Oily Apparent con- sumption is up to 98Mt.It goes into operation as a new round specially produces propylene production capacity, the coming five years whole world propylene supply will be big
Big is more than the growth of demand.It was predicted that the coming five years whole world propylene production capacity will increase 30Mt, and demand growth is estimated only
22Mt drops since this gap between Supply and Demand may result in propylene price.In the market demand and economic benefit
Promotion under, oil refining enterprise will take voluminous gasoline to produce the production decision of liquefied gas less.For the purpose for realizing voluminous gasoline, one
Aspect can be adjusted technological parameter, on the other hand adjustable catalyst formulation.
It is required by environmental regulation and automobile industry requires tight promotion to fuel mass, in recent years global motor petrol matter
Amount promotion is very rapid, and oil quality upgrading paces in China's are also obviously accelerated, and especially face state VI and discharge the formulation newly advised, high
Octane number, low alkene arene content clean gasoline become new oil-producing scheme.External gasoline pool compositing characteristic is: catalytic cracking
Gasoline proportionality is lower, as U.S.'s FCC gasoline only accounts for 1/3 or so；Average RON higher, about 93-94；Other antiknock components
More, the development of especially other antiknock component technologies constantly promotes the raising of octane number.But China's major oil
Quality still has certain gap compared with developed countries, currently, to account for about motor petrol total for China FCC (fluid catalytic cracking) gasoline
70% or more of amount, Reformed Gasoline and other high-quality high octane gasoline component contents are too low, less than 9%, and low octane rating
Direct steaming gasoline proportion is higher, reaches about 13%.Therefore, the height of FCC gasoline octane plays octane number total level
Very important effect.The FCC gasoline octane (RON) in China is up to 90-92, minimum 87-88, average out to 89-90；
MON is up to 80.6, and minimum 78, average out to 79, there are biggish differences compared with the quality of gasoline of some other developed country
Away from therefore, raising octane number realizes that gasoline upgrading is trend of the times.In addition, during gasoline cleaning, one
A little measures such as control content of olefin in gasoline, desulfurization, result in the different degrees of loss of octane number, the contradiction of octane number shortage will more
Add protrusion.
Gasoline isomerization is to improve an effective way of octane number.Due to isomeric olefine and isomeric alkane with side chain
Hydrocarbon has a higher octane number than corresponding normal olefine, therefore the cracking additive containing high silica alumina ratio molecular sieve can be reduced suitably point
The lytic activity and hydrogen transfer activity of son sieve, while isomerization ability is improved, isomeric olefine and isoparaffin concentration increase in product
Add, so that it may while improving octane number, reduce the loss of yield of light oil.
The ZSM-5 molecular sieve of high silica alumina ratio is advantageous to improving octane number while reducing light oil loss.This is because
It is improved with silica alumina ratio, the acid site density of ZSM-5 molecular sieve can be reduced, improve acid strength, to reduce lytic activity, inhibit hydrogen
Transfer reaction enhances isomerization ability.The ZSM-5 molecular sieve of high silica alumina ratio is based on isomerization reaction, therefore octane number mentions
Height is primarily due to the increase of isomeric olefine and isoparaffin concentration in product, so yield of light oil loss is low.
Aromatic hydrocarbons is one of antiknock component important in gasoline.The arene content of current domestic FCC gasoline generally exists
20% or so, the upper limit of the arene content 35% specified in state's V gasoline standard still has certain distance.Appropriateness improves in gasoline
The content of aromatic hydrocarbons also can yet be regarded as and improve the effective means of octane number.
Although on the one hand the unique cellular structure of ZSM-5 plays preferable shape-selective effect, but then, due to its hole
Road structure is narrow, and biggish reactant molecule, which is difficult to enter in crystal duct, to be reacted, and reduces the effecting reaction of molecular sieve
Area reduces the reactivity of molecular sieve；The biggish product molecule such as isoparaffin and aromatic hydrocarbons is also not easy from molecule simultaneously
Sieve pore diffuses out inside road, causes molecular sieve to inactivate so as to cause coking.Introduced in molecular sieve it is mesoporous can be well
Solve the limitation problem in molecular sieve pore passage in macromolecular transportation and diffusion process.By upper analysis as it can be seen that high silica alumina ratio is rich simultaneously
The ZSM-5 of containing mesopore is beneficial to reduce gasoline loss in catalytic cracking process while improving octane number.
In the prior art, to improve ZSM-5 molecular sieve silica alumina ratio, Chinese patent CN 101269340A discloses a kind of high
ZSM-5 zeolite catalyst of silica alumina ratio and preparation method thereof.The catalyst is added micro using active pure silicon compound as silicon source
Aluminium, hydrothermal synthesis method are made.Zeolite skeleton silica alumina ratio reaches 1000 or more in catalyst, and the grain particles of sub-micron, duct is opened
It puts, large specific surface area, molecular diffusivity is good.
Chinese patent CN 1046922C discloses a kind of method for improving ZSM-5 molecular sieve silica alumina ratio.The molecular sieve is height
The molecular sieve of silica alumina ratio and high-crystallinity, it is made after hydro-thermal process with pressure, then with the method for acid processing, is not had in product
Or only a small amount of non-framework aluminum exists.
Chinese patent CN 103480411A discloses a kind of containing mesopore ZSM-5 molecular sieve catalyst and preparation method thereof.It should
Cheap silicon and aluminum source, sylvite and organic formwork agent are dissolved in the water by invention, using the cavitation of ultrasonic wave, to the system into
Row heating ultrasonic wave added mechanical stirring, while structure-directing effect is generated using the salting-out effect of sylvite, finally by hydro-thermal method
The containing mesopore ZSM-5 of the high silica alumina ratio with MFI structure property synthesized.
Chinese patent CN 101857243A discloses a kind of surface dealumination complement silicon and adjusts ZSM-5 molecular sieve surface apertures
Method, the invention carry out the processing means of dealumination complement silicon, realization pair using ammonium fluosilicate solution to ZSM-5 zeolite molecular sieve surface
The accurate control of its surface apertures.ZSM-5 zeolite molecular sieve is modified using ammonium fluosilicate, the Al in molecular sieve surface skeleton is same
Crystalline substance is replaced as Si, since the bond distance of Si-O is less than Al-O, so the diameter in molecular sieve surface aperture can be reduced, in molecular sieve table
Face forms the superthin layer of one layer of Silicon-rich.By finely controlling treatment conditions, the shrinkage degree in molecular sieve surface aperture can control.
Chinese patent CN 102851058A discloses a kind of method for improving catalytically cracked gasoline octane number, party's legal system
The ZSM-5 molecular sieve that standby assistant for calalytic cracking is 30-150 using framework si-al ratio, can be changed into virtue for the alkene in gasoline
Fragrant hydrocarbon reduces content of olefin in gasoline while improving octane number.
In the prior art, direct synthesizing high-silicon aluminium is needed than ZSM-5 molecular sieve using expensive template, cost
Height, production difficulty is big, and three waste discharge is high, and the usual crystal grain of ZSM-5 molecular sieve being synthesized is relatively thin (100-300nm), water
Thermal stability is poor, it is difficult to be promoted and applied in catalytic cracking catalyst.
Desiliconization processing is ZSM-5 molecular sieve can be made to generate mesoporous effective ways at present.Relevant domestic and foreign literature report
Road is more.Goen et al. is handled with ZSM-5 molecular sieve of the sodium hydroxide aqueous slkali to different silica alumina ratios, is obtained rich in mesoporous
ZSM-5 molecular sieve.In addition there are researcher use organic base or organic processing ZSM-5 molecular sieve with inorganic base compound system with
Obtain better pore-creating effect and higher crystallinity.During alkali process ZSM-5, inevitably result from amorphous
Fragment blocks duct, covers active sites, it is therefore desirable to carry out subsequent dealumination treatment to it.
Chinese patent CN103818925A and CN104229824A are disclosed a kind of coupled with soda acid and prepare grade hole ZSM-5
The method of molecular sieve, this method are that the ZSM-5 molecule with secondary pore structure first is made with inorganic alkali process ZSM-5 molecular sieve
Sieve then makes the nothing being trapped in duct by the pickling of strong acid solutions and the ion exchanges of acid ammonium salt such as hydrochloric acid, nitric acid again
Amorphous configuration dissolution to improve Kong Rong and specific surface area, while improving the outer aluminium distribution of ZSM-5 molecular sieve.
Chinese patent CN103848438A discloses a kind of modified zsm-5 zeolite for preparing high mesoporous area and its preparation
Method, this method is first swapped the molecular sieve after roasting with acid solutions such as nitric acid, hydrochloric acid and repeatedly washed, after drying
It carries out second to roast, molecular sieve desiliconization is handled with inorganic base after roasting, it is multiple with weak acid scrubbing molecular sieve after desiliconization filtering
Afterwards, drying carries out third time roasting, is repeatedly exchanged with Ammonium Salt Ionic again after roasting, and the 4th roasting is carried out after drying, obtains institute
The high mesoporous area molecular sieve stated.
Although above method can obtain the ZSM-5 molecular sieve with secondary pore, desiliconization will make the silica alumina ratio of molecular sieve
It significantly reduces, although can remove non-framework aluminum by pickling, acid pickling step is for improving the whole silica alumina ratio of molecular sieve not
Obvious effect can be generated.Therefore, mesoporous, to the molecular sieve progress desiliconization modification or progress disclosed above soda acid more for acquisition
Coupled method processing, molecular sieve silica alumina ratio will be substantially less than the silica alumina ratio of Molecular sieve raw material before modified.Thus in order to obtain high sial
The mesopore molecular sieve of ratio is needed using the higher Molecular sieve raw material of silica alumina ratio.As previously mentioned, synthesizing high-silicon aluminium than molecular sieve due to
Production cost, environmental pollution and crystal grain it is thin caused by the reasons such as hydrothermal stability difference be difficult to promote in catalytic cracking catalyst
Using.
Research shows that ZSM-5 molecular sieve phosphorus compound and it is metal-modified after, or in the catalyst use phosphorus and metal
Modified binder has positive effect for improving octane number, while can improve the active agent stability of catalyst.
Chinese patent CN 102049291A disclose it is a kind of using phosphorus aluminium glue as the high silica alumina ratio molecular sieve auxiliary agent of binder,
Intensity and activity with higher improve octane number while improving product distribution.
Chinese patent CN 1611299A discloses a kind of phosphorous and metal component MFI structure molecular sieve, anhydrous chemical
Expression formula, with the poidometer of oxide are as follows: (0-0.3) Na2O(0.5-5.5)Al2O3(1.3-10)P2O5(0.7-15)M1xOy
(0.01-5)M2mOn(70-97)SiO2, wherein M1 is selected from one of transition-metal Fe, Co and Ni, M2 be selected from metal Zn, Mn,
Any one of Ga and Sn.The molecular sieve has the performance of excellent increased low carbon olefine output and raising Aromatic Hydrocarbon in Gasoline content, can
To be applied in catalytic cracking of petroleum hydrocarbon catalyst or auxiliary agent as shape-selective active component.
Chinese patent CN 1057408A discloses a kind of catalyst for cracking containing silica-rich zeolite, and catalysis with higher is split
Solution activity, wherein the silica-rich zeolite is containing 0.01-3.0 weight % phosphorus, 0.01-1.0 weight % iron or 0.01-10 weight % aluminium
ZSM-5, β zeolite or modenite are that the Hydrogen or potassium type ZSM-5 zeolite, β zeolite or modenite by silica alumina ratio greater than 15 add
Heat was to 350-820 DEG C, with 0.1-10 hours-1Volume space velocity be passed through the halide solution of aluminium, iron halide solution or
It is obtained after saline solution of ammonium phosphate.
It is disclosed in United States Patent (USP) USP5,110,776 with the preparation method of the ZSM-5 zeolite catalyst of P Modification.It is described
P Modification process be to be dispersed in zeolite in the phosphorus-containing compound aqueous solution of pH value 2-6, then with matrix be beaten, spray drying
Molding.Gained catalyst does not increase dry gas and coke yield while improving octane number.
A kind of method for improving aperture and mesopore zeolite catalytic activity is disclosed in United States Patent (USP) USP6,080,303.The party
Method is to handle aperture and mesopore zeolite with phosphorus compound, then will be through the processed zeolite of phosphorus and AlPO4Gel Compositions.This method
The activity and hydrothermal stability of aperture and mesopore zeolite can be improved.
Summary of the invention
Purpose of this disclosure is to provide a kind of assistant for calalytic cracking and preparation method thereof for improving octane number bucket, incite somebody to action this
The open auxiliary agent provided is used for catalytic cracking process, by the content of isohydrocarbon in raising gasoline to improve octane number,
It keeps yield of gasoline to be basically unchanged simultaneously, and then improves octane number bucket.
To achieve the goals above, the disclosure provides a kind of assistant for calalytic cracking for improving octane number bucket, with described
On the basis of the dry weight of auxiliary agent, which includes with the phosphorous and carried metal MFI structure of dry basis 10-75 weight %
Molecular sieve, with the phosphorus aluminium inorganic binder of dry basis 3-40 weight %, the weight of the 1-30 in terms of oxide %'s is other inorganic
Binder, with the second clay of dry basis 0-60 weight %, and the weight of the 0.5-15 in terms of oxide % selected from VIII race gold
Belong to the metallic addition at least one of manganese, zinc, gallium；Wherein, the phosphorus aluminium inorganic binder is phosphorus aluminium glue and/or contains
The phosphorus aluminium inorganic binder of first clay, it is described on the basis of the phosphorus aluminium inorganic binder dry weight for containing the first clay
Phosphorus aluminium inorganic binder containing the first clay includes with Al2O3Count 15-40 weight % aluminium component, with P2O5Count 45-80 weight %'s
Phosphorus component and with dry basis be greater than 0 and be no more than 40 weight % the first clay, and its P/Al weight ratio be 1.0-
6.0, pH value 1-3.5, solid content are 15-60 weight %；N (the SiO of the molecular sieve2)/n(Al2O3) it is greater than 100；With P2O5
It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 0.1-5 weight %；With the oxide of carried metal
It counts and on the basis of the dry weight of molecular sieve, the carried metal content of the molecular sieve is 0.1-5 weight %；The molecular sieve
Al distribution parameter D meets: 0.6≤D≤0.85, wherein D=Al (S)/Al (C), Al (S) indicate to measure using TEM-EDS method
Zeolite crystal the inside H in crystal face edge apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C) expression is adopted
The outside H of geometric center of crystal face described in the zeolite crystal measured with TEM-EDS method is arbitrarily greater than 100 square nanometers apart from interior
The aluminium content in region, wherein the H is that the crystal face edge point arrives the 10% of the crystal face geometric center distance；The molecular sieve
Mesopore volume account for total pore volume ratio be 40-80 body %, aperture be 2 nanometers to 20 nanometers mesopore volume Zhan always in hole body
Long-pending ratio is greater than 90 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 60-80%, B acid acid amount and L acid acid
The ratio between amount is 15-80.
Preferably, the n (SiO of the molecular sieve2)/n(Al2O3) it is greater than 120；With P2O5It counts and with the dry weight of molecular sieve
On the basis of, the phosphorus content of the molecular sieve is 0.2-4 weight %；In terms of the oxide of carried metal and with the dry weight of molecular sieve
On the basis of, the carried metal content of the molecular sieve is 0.5-3 weight %；The Al distribution parameter D of the molecular sieve meets: 0.65≤
D≤0.80；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 50-70 body %, and aperture is 2 nanometers to 20 nanometers
The ratio of the total mesopore volume of mesopore volume Zhan is greater than 92 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 65-
The ratio between 75%, B acid acid amount and L acid acid amount are 20-50.
Preferably, the carried metal is selected from iron, cobalt, nickel, copper, manganese, zinc, tin, bismuth and at least one of to sow.
Preferably, first clay is selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatom
At least one of soil；Second clay is de- selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, illiteracy
At least one of stone and rectorite；Other inorganic matter binders be selected from boehmite, Aluminum sol, silicon-aluminum sol and
At least one of waterglass.
Preferably, the metallic addition introduces the auxiliary agent in the form of metallic compound, and the metallic compound is
Selected from least one of oxide, hydroxide, chloride, nitrate, sulfate, phosphate and organic compound.
Preferably, on the basis of the dry weight of the auxiliary agent, the auxiliary agent also contains with P2O5Meter is no more than 5 weight %
Phosphorus additive.
Preferably, the auxiliary agent includes the phosphorous and load of the phosphorus aluminium inorganic binder of 8-25 weight %, 20-60 weight %
Metal MFI structure molecular sieve, the second clay of 10-45 weight %, other inorganic binders of 5-25 weight %, 1.0-10 weight
Measure the metallic addition of % and the phosphorus additive of 0-3 weight %.
The disclosure also provides a kind of preparation method of assistant for calalytic cracking for improving octane number bucket, this method comprises:
Phosphorous and carried metal MFI structure molecular sieve, phosphorus aluminium inorganic binder and other inorganic binders are mixed, add or are added without the
Two clays are beaten, spray drying；Wherein, metallic addition is introduced, phosphorus additive is introduced or do not introduce；It is former with the preparation of auxiliary agent
On the basis of total dry weight of material, the raw material for preparing of the auxiliary agent includes with the phosphorous and negative of dry basis 10-75 weight %
Metal MFI structure molecular sieve is carried, with the phosphorus aluminium inorganic binder of dry basis 3-40 weight %, the weight of the 1-30 in terms of oxide
Other inorganic binders of % are measured, with the second clay of dry basis 0-60 weight %, the weight of the 0.5-15 in terms of oxide %
The metallic addition selected from least one of VIII race's metal and manganese, zinc, gallium, and including or do not include with P2O5Meter does not surpass
Cross the phosphorus additive of 5 weight %；Wherein, the phosphorus aluminium inorganic binder be phosphorus aluminium glue and/or phosphorus aluminium containing the first clay without
Machine binder, on the basis of the phosphorus aluminium inorganic binder dry weight for containing the first clay, the phosphorus aluminium for containing the first clay
Inorganic binder includes with Al2O3Count 15-40 weight % aluminium component, with P2O5Count the phosphorus component of 45-80 weight % and with butt
Poidometer be greater than 0 and be no more than 40 weight % the first clay, and its P/Al weight ratio be 1.0-6.0, pH value 1-3.5, Gu
Content is 15-60 weight %；N (the SiO of the molecular sieve2)/n(Al2O3) it is greater than 100；With P2O5It counts and with the butt of molecular sieve
On the basis of weight, the phosphorus content of the molecular sieve is 0.1-5 weight %；In terms of the oxide of carried metal and with the butt of molecular sieve
On the basis of weight, the carried metal content of the molecular sieve is 0.1-5 weight %；The Al distribution parameter D of the molecular sieve meets:
0.6≤D≤0.85, wherein D=Al (S)/Al (C), Al (S) indicate the crystalline substance of the zeolite crystal using the measurement of TEM-EDS method
Edge inside H in face indicates to measure using TEM-EDS method apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C)
Zeolite crystal described in crystal face the outside H of geometric center apart from interior any aluminium content for being greater than 100 square nanometers regions, wherein
The H is that the crystal face edge point arrives the 10% of the crystal face geometric center distance；The total hole mesopore volume Zhan of the molecular sieve
The ratio of volume is 40-80 body %, and the ratio for the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers to 20 nanometers is greater than 90
Body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 60-80%, and the ratio between B acid acid amount and L acid acid amount are 15-80.
Preferably, the phosphorous and carried metal MFI structure molecular sieve preparation step includes: a, by MFI obtained by crystallization
After structure molecular screen slurries are filtered and washed, washing molecular sieve is obtained；Wherein, in terms of sodium oxide molybdena and to wash molecular sieve
On the basis of total dry weight, the sodium content % heavy less than 3 of the washing molecular sieve；B, gained washing molecular sieve in step a is existed
Desiliconization processing is carried out in aqueous slkali, and after being filtered and washed, obtains desiliconization molecular sieve；C, by gained desiliconization point in step b
Son sieve carries out ammonium exchange processing, obtains ammonium exchange molecular sieve；Wherein, in terms of sodium oxide molybdena and with total dry basis of ammonium exchange molecular sieve
On the basis of amount, the sodium content % heavy less than 0.2 of the ammonium exchange molecular sieve；D, by step c gained ammonium exchange molecular sieve by
Dealumination treatment is carried out in the Compound-acid dealuminzation agent solution of fluosilicic acid, organic acid and inorganic acid composition, and after being filtered and washed,
Obtain dealuminzation molecular sieve；E, by dealuminzation molecular sieve obtained in step d carry out P Modification processing, the load of carried metal processing and
After calcination process, described phosphorous and carried metal MFI structure molecular sieve is obtained.
Preferably, aqueous slkali described in step b be in sodium hydroxide solution, potassium hydroxide solution and ammonium hydroxide at least
It is a kind of.
Preferably, the condition of the processing of desiliconization described in step b includes: in the molecular sieve of dry basis, aqueous slkali
The weight ratio of water in alkali and aqueous slkali is 1:(0.1-2): (5-15)；The temperature of desiliconization processing is room temperature to 100 DEG C, and the time is
0.2-4 hours.
Preferably, the condition of the processing of desiliconization described in step b includes: in the molecular sieve of dry basis, aqueous slkali
The weight ratio of water in alkali and aqueous slkali is 1:(0.2-1): (5-15).
Preferably, the step of dealumination treatment described in step d further include: organic acid is first exchanged into molecular sieve with the ammonium and is mixed
It closes, then fluosilicic acid and inorganic acid is exchanged to molecular sieve mixing with the ammonium.
Preferably, organic acid described in step d is in ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid
At least one, the inorganic acid be selected from least one of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, organic acid described in step d is oxalic acid, and the inorganic acid is hydrochloric acid.
Preferably, the condition of dealumination treatment described in step d includes: with the molecular sieve of dry basis, organic acid, inorganic
The weight ratio of acid and fluosilicic acid is 1:(0.05-0.5): (0.05-0.5): (0.02-0.5)；Treatment temperature is 25-100 DEG C,
Handling the time is 0.5-6 hours.
Preferably, the condition of dealumination treatment described in step d includes: with the molecular sieve of dry basis, organic acid, inorganic
The weight ratio of acid and fluosilicic acid is 1:(0.1-0.3): (0.1-0.3): (0.05-0.3).
Preferably, the processing of P Modification described in step e includes: that will be selected from phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid
At least one of ammonium phosphorus-containing compound carries out dipping and/or ion exchange to molecular sieve.
Preferably, carried metal described in step e load processing include: will containing selected from iron, cobalt, nickel, copper, manganese, zinc,
It tin, bismuth and at least one of sows the compound of carried metal the carried metal is loaded to by the molecular sieve by dipping method
On.
Preferably, it is air atmosphere or steam atmosphere that the condition of the calcination process, which includes: the atmosphere of calcination process,；Roasting
Burning temperature is 400-800 DEG C, and calcining time is 0.5-8 hours.
Preferably, the preparation step of the phosphorus aluminium inorganic binder for containing the first clay includes: (1), by alumina source,
One clay and water mashing are dispersed into the slurries that solid content is 8-45 weight %；The alumina source is can be by the hydrogen-oxygen of sour peptization
Change aluminium and/or aluminium oxide, with the first clay of dry basis and with Al2O3The weight ratio of the alumina source of meter is (to be greater than 0-
40):(15-40)；(2), stirring is lower is added concentrated phosphoric acid according to the weight ratio of P/Al=1-6 into the slurries that step (1) obtains；
(3), the slurries that step (2) obtains are reacted 15-90 minutes at a temperature of 50-99 DEG C.
The assistant for calalytic cracking that the disclosure provides has preferable Catalytic Cracking Performance, urges with after host agent blending for hydrocarbon ils
Change cracking reaction, catalytically cracked gasoline octane number bucket can be improved, improves the content of isohydrocarbon in gasoline significantly, and then improve vapour
Oily octane number.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Specific embodiment
The specific embodiment of the disclosure is described in detail below.It should be understood that described herein specific
Embodiment is only used for describing and explaining the disclosure, is not limited to the disclosure.
The disclosure provides a kind of assistant for calalytic cracking for improving octane number bucket, using the dry weight of the auxiliary agent as base
Standard, which includes the phosphorous and carried metal MFI structure molecular sieve with dry basis 10-75 weight %, with dry weight
Count the phosphorus aluminium inorganic binder of 3-40 weight %, other inorganic binders of the weight of the 1-30 in terms of oxide %, with dry weight
Count the second clay of 0-60 weight %, and the weight of the 0.5-15 in terms of oxide % in VIII race's metal and manganese, zinc, gallium extremely
A kind of few metallic addition；Wherein, the phosphorus aluminium inorganic binder is phosphorus aluminium glue and/or the phosphorus aluminium containing the first clay is inorganic
Binder, on the basis of the phosphorus aluminium inorganic binder dry weight for containing the first clay, the phosphorus aluminium for containing the first clay without
Machine binder includes with Al2O3Count 15-40 weight % aluminium component, with P2O5Count the phosphorus component of 45-80 weight % and with dry basis
Meter is greater than 0 and is no more than the first clay of 40 weight %, and its P/Al weight ratio is 1.0-6.0, pH value 1-3.5, admittedly contain
Amount is 15-60 weight %；N (the SiO of the molecular sieve2)/n(Al2O3) it is greater than 100；With P2O5It counts and with the dry basis of molecular sieve
On the basis of amount, the phosphorus content of the molecular sieve is 0.1-5 weight %；In terms of the oxide of carried metal and with the dry basis of molecular sieve
On the basis of amount, the carried metal content of the molecular sieve is 0.1-5 weight %；The Al distribution parameter D of the molecular sieve meets: 0.6
≤ D≤0.85, wherein D=Al (S)/Al (C), Al (S) indicate the crystal face of the zeolite crystal using the measurement of TEM-EDS method
The inside H in edge is indicated apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C) using the measurement of TEM-EDS method
The outside H of the geometric center of crystal face described in zeolite crystal is apart from interior any aluminium content for being greater than 100 square nanometers regions, wherein institute
Stating H is that the crystal face edge point arrives the 10% of the crystal face geometric center distance；The total hole body of mesopore volume Zhan of the molecular sieve
Long-pending ratio is 40-80 body %, and the ratio for the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers to 20 nanometers is greater than 90
Body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 60-80%, and the ratio between B acid acid amount and L acid acid amount are 15-80.
Preferably, the n (SiO of the molecular sieve2)/n(Al2O3) it is greater than 120；With P2O5Count and on the basis of the dry weight of molecular sieve,
The phosphorus content of the molecular sieve is 0.2-4 weight %；It is counted by the oxide of carried metal and on the basis of the dry weight of molecular sieve,
The carried metal content of the molecular sieve is 0.5-3 weight %；The Al distribution parameter D of the molecular sieve meets: 0.65≤D≤
0.80；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 50-70 body %, and aperture is in 2 nanometers to 20 nanometers
The ratio of the total mesopore volume of pore volume Zhan is greater than 92 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 65-
The ratio between 75%, B acid acid amount and L acid acid amount are 20-50.
According to the disclosure, the phosphorus aluminium inorganic binder is phosphorus aluminium inorganic binder and/or phosphorus aluminium glue containing the first clay.
A kind of specific embodiment, on the basis of the dry weight of the phosphorus aluminium inorganic binder, the phosphorus aluminium is inorganic
Binder includes with Al2O3Count 15-40 weight % aluminium component, with P2O5Count the phosphorus component of 45-80 weight % and with dry weight
The first clay of 0-40 weight % is counted, and its P/Al weight ratio is 1.0-6.0, pH value 1-3.5, solid content is 15-60 weight
Measure %；For example including with Al2O3Count 15-40 weight % aluminium component, with P2O5Count the phosphorus component of 45-80 weight % and with butt
The first clay of poidometer 1-40 weight %；It preferably comprises with Al2O3The aluminium component of 15-35 weight % is counted, with P2O5Count 50-75
The phosphorus component of weight % and with the first clay of dry basis 8-35 weight %, P/Al weight ratio is preferably 1.2-6.0,
More preferably 2.0-5.0, pH value are preferably 1.5-3.0.
Another specific embodiment, on the basis of the dry weight of the phosphorus aluminium inorganic binder, the phosphorus aluminium without
Machine binder includes with Al2O3Count 20-40 weight % aluminium component and with P2O5Count the phosphorus component of 60-80 weight %.
According to the disclosure, the carried metal refers to the metal loaded on molecular sieve by mode of loading, does not include aluminium
And the alkali metal such as sodium, potassium, it may include selected from iron, cobalt, nickel, copper, manganese, zinc, tin, bismuth and at least one of sowing, it can also be with
Including other metals, the disclosure is simultaneously not limited.
According to the disclosure, the aluminium content using TEM-EDS method measurement molecular sieve be it is well-known to those skilled in the art,
Wherein the geometric center is also well-known to those skilled in the art, can be calculated according to formula, and the disclosure is no longer superfluous
It states, the geometric center of generally symmetrical figure is the intersection point of each opposed apexes line, for example, six sides of conventional six square shape sheet ZSM-5
For the geometric center of shape crystal face in the point of intersection of three opposed apexes lines, the crystal face is a face of regular crystal grain, described
Direction inwardly or outwardly refers both to the direction inwardly or outwardly on the crystal face.
According to the disclosure, the mesopore volume of the molecular sieve accounts for the ratio of total pore volume using N2 adsorption BET specific surface area
Method measures, and the mesopore volume is that aperture is greater than 2 nanometers of pore volumes less than 100 nanometers；The strong acid of the molecular sieve
Acid amount accounts for the ratio of total acid content using NH3- TPD method measures, and the acid site of the strong acid is NH3Desorption temperature is greater than 300
Acid site corresponding to DEG C；The ratio between the B acid acid amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption.
According to the disclosure, metallic addition is added in pulping process, can be the gold in preparing molding auxiliary agent
The form for belonging to compound introduces, and is for example, selected from oxide, hydroxide, chloride, nitrate, sulfate, phosphate and has
In at least one of machine compound, preferably autoxidisable substance, orthophosphates, phosphite, subphosphate and acid phosphate
One or more forms introduce or exist.
According to the disclosure, clay is well known to those skilled in the art, first clay can for selected from kaolin,
At least one of sepiolite, attapulgite, rectorite, montmorillonite and diatomite preferably include rectorite, more preferably tired support
Soil；Second clay can be for selected from kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, rectorite, diatom
At least one of soil, galapectite, saponite, boron-moisten soil and hydrotalcite preferably are selected from kaolin, metakaolin, diatomite, Hai Pao
At least one of stone, attapulgite, montmorillonite and rectorite；Other inorganic binders can be selected from addition to the phosphorus aluminium glue
With the inorganic oxide binder for being customarily used in assistant for calalytic cracking or catalyst binder component other than phosphorus aluminium inorganic binder
One of or it is a variety of, preferably be selected from least one of boehmite, Aluminum sol, silicon-aluminum sol and waterglass, more preferably from
At least one of boehmite and Aluminum sol.
According to the disclosure, the phosphorus aluminium inorganic binder for containing the first clay is preferably comprised with Al2O3Count 15-35 weight %
Aluminium component, with P2O5Count the phosphorus component of 50-75 weight % and with the first clay of dry basis 8-35 weight %, P/
Al weight ratio is preferably 1.2-6.0, more preferably 2.0-5.0, and pH value is preferably 1.0-3.5.
According to the disclosure, on the basis of the dry weight of the auxiliary agent, the auxiliary agent can also be containing with P2O5Meter is no more than
The phosphorus additive of 5 weight %.The phosphorus additive can be selected from the compound of phosphorus, inorganic compound for example including phosphorus and have
One of machine compound is a variety of, can be soluble easily in water, is also possible to be insoluble in water or phosphorus compound not soluble in water,
Such as oxide selected from phosphorus, phosphoric acid, orthophosphates, phosphite, hypophosphites, subphosphate, acid phosphate and
One of phosphorous organic compound is a variety of.Preferred phosphorus compound is phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, phosphoric acid hydrogen
One of diammonium and aluminum phosphate are a variety of.In obtained auxiliary agent, phosphorus additive is with the phosphorus compound (oxide of such as phosphorus, just
Phosphate, phosphite, subphosphate and acid phosphate) form exist.The phosphorus additive can reside in auxiliary agent
Any position that may be present such as can reside in inside the duct of zeolite, the surface of zeolite, can reside in host material
It in (material i.e. in auxiliary agent in addition to molecular sieve), can also exist simultaneously inside the duct of zeolite, the surface of zeolite and institute
It states in host material.Do not include the phosphorus in molecular sieve in the content of phosphorus additive, does not include that the phosphorus aluminium inorganic binder draws yet
The phosphorus entered.
According to the disclosure, the auxiliary agent preferably includes the phosphorus aluminium inorganic binder of 8-25 weight %, 20-60 weight % contains
Phosphorus and carried metal MFI structure molecular sieve, the second clay of 10-45 weight %, 5-25 weight % other inorganic binders,
The metallic addition of 1.0-10 weight % and the phosphorus additive of 0-3 weight %.
The disclosure also provides a kind of preparation method of assistant for calalytic cracking for improving octane number bucket, this method comprises:
Phosphorous and carried metal MFI structure molecular sieve, phosphorus aluminium inorganic binder and other inorganic binders are mixed, add or are added without the
Two clays are beaten, spray drying；Wherein, metallic addition is introduced, phosphorus additive is introduced or do not introduce；It is former with the preparation of auxiliary agent
On the basis of total dry weight of material, the raw material for preparing of the auxiliary agent includes with the phosphorous and negative of dry basis 10-75 weight %
Metal MFI structure molecular sieve is carried, with the phosphorus aluminium inorganic binder of dry basis 3-40 weight %, the weight of the 1-30 in terms of oxide
Other inorganic binders of % are measured, with the second clay of dry basis 0-60 weight %, the weight of the 0.5-15 in terms of oxide %
The metallic addition selected from least one of VIII race's metal and manganese, zinc, gallium, and including or do not include with P2O5Meter does not surpass
Cross the phosphorus additive of 5 weight %；Wherein, the phosphorus aluminium inorganic binder be phosphorus aluminium glue and/or phosphorus aluminium containing the first clay without
Machine binder, on the basis of the phosphorus aluminium inorganic binder dry weight for containing the first clay, the phosphorus aluminium for containing the first clay
Inorganic binder includes with Al2O3Count 15-40 weight % aluminium component, with P2O5Count the phosphorus component of 45-80 weight % and with butt
Poidometer be greater than 0 and be no more than 40 weight % the first clay, and its P/Al weight ratio be 1.0-6.0, pH value 1-3.5, Gu
Content is 15-60 weight %；N (the SiO of the molecular sieve2)/n(Al2O3) it is greater than 100；With P2O5It counts and with the butt of molecular sieve
On the basis of weight, the phosphorus content of the molecular sieve is 0.1-5 weight %；In terms of the oxide of carried metal and with the butt of molecular sieve
On the basis of weight, the carried metal content of the molecular sieve is 0.1-5 weight %；The Al distribution parameter D of the molecular sieve meets:
0.6≤D≤0.85, wherein D=Al (S)/Al (C), Al (S) indicate the crystalline substance of the zeolite crystal using the measurement of TEM-EDS method
Edge inside H in face indicates to measure using TEM-EDS method apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C)
Zeolite crystal described in crystal face the outside H of geometric center apart from interior any aluminium content for being greater than 100 square nanometers regions, wherein
The H is that the crystal face edge point arrives the 10% of the crystal face geometric center distance；The total hole mesopore volume Zhan of the molecular sieve
The ratio of volume is 40-80 body %, and the ratio for the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers to 20 nanometers is greater than 90
Body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 60-80%, and the ratio between B acid acid amount and L acid acid amount are 15-80.
According to the disclosure, the phosphorous and carried metal MFI structure molecular sieve preparation step may include: a, by crystallization
After gained MFI structure molecular sieve pulp is filtered and washed, washing molecular sieve is obtained；Wherein, in terms of sodium oxide molybdena and with washing
On the basis of total dry weight of molecular sieve, the sodium content % heavy less than 3 of the washing molecular sieve；B, gained in step a is washed
Molecular sieve carries out desiliconization processing in aqueous slkali, and after being filtered and washed, obtains desiliconization molecular sieve；C, by institute in step b
It obtains desiliconization molecular sieve and carries out ammonium exchange processing, obtain ammonium exchange molecular sieve；Wherein, in terms of sodium oxide molybdena and with ammonium exchange molecular sieve
On the basis of total dry weight, the sodium content % heavy less than 0.2 of the ammonium exchange molecular sieve；D, by gained ammonium exchange point in step c
Son sieve carries out dealumination treatment in the Compound-acid dealuminzation agent solution being made of fluosilicic acid, organic acid and inorganic acid, and is filtered
After washing, dealuminzation molecular sieve is obtained；E, dealuminzation molecular sieve obtained in step d is subjected to P Modification processing, carried metal
After load processing and calcination process, described phosphorous and carried metal MFI structure molecular sieve is obtained.
According to the disclosure, MFI structure molecular sieve pulp obtained by crystallization be it is well-known to those skilled in the art, the disclosure is not
It repeats again, wherein MFI structure molecular sieve is also well-known to those skilled in the art, be can be obtained by no amine crystallization, can also be with
It is the molecular sieve prepared by template agent method, wherein the molecular sieve without amine synthesis is not required to roast, the molecular sieve prepared by template agent method
It is roasted in air after need to drying, the silica alumina ratio of ZSM-5 molecular sieve is generally less than 100.
According to the disclosure, it is well-known to those skilled in the art for being handled using aqueous slkali progress desiliconization, described in step b
Aqueous slkali can be for selected from least one of sodium hydroxide solution, potassium hydroxide solution and ammonium hydroxide, preferably sodium hydroxide be molten
The condition of liquid, the desiliconization processing may include: with the water in the alkali and aqueous slkali in the molecular sieve of dry basis, aqueous slkali
Weight ratio be 1:(0.1-2): (5-15), preferably 1:(0.2-1): (5-15)；The temperature of desiliconization processing is room temperature to 100
DEG C, the time is 0.2-4 hours.
According to the disclosure, ammonium exchange processing is well-known to those skilled in the art, for example, in step c, it can be by alkali
Desiliconization molecular sieve that treated is according to molecular sieve: ammonium salt: H2O=1:(0.1-1): the weight ratio of (5-10) is in room temperature to 100 DEG C
Lower exchange is filtered after 0.5-2 hours, makes the Na on molecular sieve2O content % heavy less than 0.2.The ammonium salt can be common
Inorganic ammonium salt, for example, selected from least one of ammonium chloride, ammonium sulfate and ammonium nitrate.
According to the disclosure, organic acid and inorganic acid are well known to the skilled person, for example, having described in step d
Machine acid can be for selected from least one of ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid, preferably oxalic acid；Nothing
Machine acid can be for selected from least one of hydrochloric acid, sulfuric acid and nitric acid, preferably hydrochloric acid.
According to the disclosure, dealumination treatment is well-known to those skilled in the art, but is not reported inorganic acid, organic acid
It is used for dealumination treatment together with fluosilicic acid.The dealumination treatment can be primary or be performed in multiple times, can be first by organic acid and institute
Ammonium exchange molecular sieve mixing is stated, then fluosilicic acid and inorganic acid are exchanged to molecular sieve mixing with the ammonium, it can will first to have
Machine acid is added in ammonium exchange molecular sieve, and then by fluosilicic acid and inorganic acid, cocurrent is added at a slow speed, or fluosilicic acid is first added and adds
Cocurrent is added at a slow speed for inorganic acid, preferably fluosilicic acid and inorganic acid.The condition of the dealumination treatment may include: with dry weight
The molecular sieve of meter, organic acid, inorganic acid and fluosilicic acid weight ratio be 1:(0.05-0.5): (0.05-0.5): (0.02-
0.5), preferably 1:(0.1-0.3): (0.1-0.3): (0.05-0.3)；Treatment temperature is 25-100 DEG C, and the processing time is 0.5-
6 hours.
According to the disclosure, P Modification processing be it is well-known to those skilled in the art, P Modification described in step e processing can
With include: will selected from least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate phosphorus-containing compound to molecular sieve into
Row dipping and/or ion exchange.
According to the disclosure, the load of carried metal processing be it is well-known to those skilled in the art, referring to will be above-mentioned negative
Carry metal loaded on the molecular sieve by mode of loading, for example, can will containing be selected from iron, cobalt, nickel, copper, manganese, zinc, tin,
Bismuth and the compound at least one of sowing carried metal are loaded to the carried metal on the molecular sieve by dipping method；
The mode of loading also may include other common metal carrying methods, and the disclosure is not restricted.
According to the disclosure, calcination process be also it is well-known to those skilled in the art, condition can be with are as follows: calcination process
Atmosphere is air atmosphere or steam atmosphere；Maturing temperature is 400-800 DEG C, and calcining time is 0.5-8 hours.
Washing described in the disclosure is well-known to those skilled in the art, and mode can be with are as follows: by 5-10 times 30-60 DEG C
Water molecular sieve after filtering is eluted.
According to the disclosure, the preparation step of the phosphorus aluminium inorganic binder for containing the first clay may include: (1), by oxygen
Change silicon source, the first clay and water mashing and is dispersed into the slurries that solid content is 8-45 weight %；The alumina source is can be sour
The aluminium hydroxide and/or aluminium oxide of peptization, with the first clay of dry basis and with Al2O3The weight ratio of the alumina source of meter
For (be greater than 0-40): (15-40)；(2), stirring is lower adds into the slurries that step (1) obtains according to the weight ratio of P/Al=1-6
Enter concentrated phosphoric acid；Wherein in the P/Al P be the phosphorus in terms of simple substance in phosphoric acid weight, Al be in alumina source in terms of simple substance
Aluminium weight；(3), the slurries that step (2) obtains are reacted 15-90 minutes at a temperature of 50-99 DEG C.
According to the disclosure, the alumina source can be for selected from ρ-aluminium oxide, χ-aluminium oxide, η-aluminium oxide, gamma oxidation
Aluminium, κ-aluminium oxide, δ-aluminium oxide, θ-aluminium oxide, gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite and quasi-
At least one of boehmite, the aluminium component in the phosphorus aluminium inorganic binder for containing the first clay are originated from the aluminium oxide
Source.First clay can be one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomite
Or a variety of, preferably rectorite.Its concentration of the concentrated phosphoric acid can be 60-98 weight %, more preferably 75-90 weight %.
The charging rate of phosphoric acid is preferably 0.01-0.10Kg phosphoric acid/minute/Kg alumina source, more preferably 0.03-0.07Kg phosphoric acid/
Minute/Kg alumina source.
According to the disclosure, the phosphorus aluminium inorganic binder for containing the first clay was not only being prepared due to the introducing of clay
Mass transfer, the heat transfer that storeroom is improved in journey avoid material and unevenly glue caused by local moment vigorous reaction heat release overtemperature
Agent solidification is tied, the adhesive property of obtained binder is suitable with the phosphorus al binder for not introducing clay mitigation preparation；And the party
Method introduces clay and improves the heavy oil conversion performance of carbon monoxide-olefin polymeric especially with the rectorite of layer structure, make to obtain
Auxiliary agent have it is more preferably selective.
The preparation method for the assistant for calalytic cracking that the disclosure provides, by phosphorous and carried metal MFI structure molecular sieve, phosphorus aluminium
Inorganic binder and the mixing of other inorganic binders, the sequence of mashing, charging do not have a particular/special requirement, for example, can by phosphorus aluminium without
Machine binder, other inorganic binders, molecular sieve, the mixing of the second clay (then can be omitted phase when being free of the second clay
The addition step of pass) mashing, it is preferred that add again after being first mixed with beating the second clay, molecular sieve and other inorganic binders
Enter the phosphorus aluminium inorganic binder, this is conducive to the activity and selectivity for improving auxiliary agent.
The assistant for calalytic cracking preparation method that the disclosure provides further includes being spray-dried the obtained slurries that are beaten
Step.The method of spray drying is known to those skilled in the art, the disclosure does not have particular/special requirement.
In the preparation method of assistant for calalytic cracking provided by the disclosure, it can be introduced by way of introducing metallic compound
The metallic addition, metallic addition can be in any steps before the spray drying forming of auxiliary agent preparation process toward slurry
Metallic compound is added in liquid and is introduced；Dipping or chemisorbed metallic can also be passed through after auxiliary agent spray drying forming
Close object after roast and introduce, including by auxiliary agent with metal-containing compound aqueous solution carry out dipping or chemisorption handle, then into
Row is separated by solid-liquid separation (if necessary), dry and roasting, wherein dry temperature can be room temperature to 400 DEG C, preferably 100-
300 DEG C, the temperature of roasting can be 400-700 DEG C, and preferably 450-650 DEG C, calcining time can be 0.5-100 hours, excellent
It is selected as 0.5-10 hours.The metallic compound is selected from one of their inorganic compound and organic compound or more
Kind, it can be soluble easily in water, be also possible to be insoluble in water or compound not soluble in water.The example of metallic compound includes gold
Oxide, hydroxide, chloride, nitrate, sulfate, phosphate, organic compound of metal of category etc..Preferred metal
Compound is selected from one of their chloride, nitrate, sulfate and phosphate or a variety of.
In assistant for calalytic cracking provided by the disclosure, the metallic addition can reside in auxiliary agent it is any there may be
Position, such as can reside in inside the duct of zeolite, the surface of zeolite, can reside in host material, can also be simultaneously
It is present in inside the duct of zeolite, in the surface of zeolite and the host material, is preferably in host material.The gold
Belonging to additive can exist in the form of their oxide, orthophosphates, phosphite, subphosphate and acid phosphate etc..
Assistant for calalytic cracking preparation method provided by the disclosure, when containing phosphorus additive in auxiliary agent, the phosphorus adds
Add agent that can introduce using the combination of one of following method or several method, but is not limited to these methods and introduces auxiliary agent
In:
1, phosphorus compound is added in slurries in going to for auxiliary agent spray drying forming；
2, through dipping or chemisorption phosphorus compound after auxiliary agent spray drying forming, through being separated by solid-liquid separation (if necessary
If), dry and roasting process introduce, the temperature of the drying can be room temperature to 400 DEG C, preferably 100-300 DEG C, roasting
Temperature can be 400-700 DEG C, and preferably 450-650 DEG C, calcining time can be 0.5-100 hours, and preferably 0.5-10 is small
When.The phosphorus compound can be selected from one of various inorganic compounds and organic compound of phosphorus or a variety of.The phosphatization
Closing object can be soluble easily in water, be also possible to be insoluble in water or phosphorus compound not soluble in water.The embodiment packet of phosphorus compound
Include oxide, phosphoric acid, orthophosphates, phosphite, hypophosphites, the phosphorous organic compound etc. of phosphorus.Preferred phosphatization is closed
Object is selected from one of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and aluminum phosphate or a variety of.
Thus, the phosphorus additive can reside in any position that may be present of auxiliary agent, as can reside in zeolite
Inside duct, the surface of zeolite, can reside in the host material, can also exist simultaneously inside the duct of zeolite,
In the surface of zeolite and the host material.The phosphorus additive is with phosphorus compound (oxide of such as phosphorus, orthophosphates, phosphorous
Hydrochlorate, subphosphate, acid phosphate) form exist.
The assistant for calalytic cracking that the disclosure provides is suitable for various hydrocarbon oil catalytic crackings.It, can when for catalytic cracking process
Individually toward adding in catalyst cracker, used after can also being mixed with catalytic cracking catalyst.Under normal circumstances, the disclosure mentions
The auxiliary agent of confession accounts for FCC catalyst and the agent mixture total amount of disclosure offer is no more than 30 weight %, preferably 1-25 weight
Measure %, more preferably 3-15 weight %, the hydrocarbon ils be selected from various petroleum distillates, as crude oil, reduced crude, decompression residuum, often
Press wax oil, decompressed wax oil, straight-run gas oil, propane it is light/one of de-oiling, wax tailings and coal liquefaction products or a variety of again.Institute
Stating hydrocarbon ils can be containing beavy metal impurities and sulphur, nitrogen impurity such as nickel, vanadium, as the content of sulphur may be up to 3.0 weight %, the content of nitrogen
The content of up to 2.0 weight %, the metal impurities such as vanadium, nickel may be up to 3000ppm.
The assistant for calalytic cracking that the disclosure provides is in catalytic cracking process, hydrocarbon oil catalytic cracking condition to be conventional urges
Change cracking conditions.In general, it is 400-600 DEG C which, which includes: reaction temperature, preferably 450-550
DEG C, weight (hourly) space velocity (WHSV) is 8-120 hours-1, preferably 8-80 hours-1, oil ratio (weight ratio) is 1-20, preferably 3-15.This public affairs
The assistant for calalytic cracking for opening offer can be used for existing various catalyst crackers, such as anti-in fixed bed reactors, fluidized bed
It answers and is carried out in device, riser reactor, multi-reaction-area reactor etc..
The disclosure will be further illustrated by embodiment below, but therefore the disclosure is not any way limited,
Instrument and reagent used by the embodiment of the present disclosure, unless otherwise instructed, be instrument commonly used by those skilled in the art and
Reagent.
The crystallinity of the disclosure is measured using the standard method of ASTM D5758-2001 (2011) e1.
N (the SiO of the disclosure2)/n(Al2O3), i.e., silica alumina ratio is calculated by the content of silica and aluminium oxide, oxidation
The content of silicon and aluminium oxide is measured using GB/T 30905-2014 standard method.
The phosphorus content of the disclosure is measured using GB/T 30905-2014 standard method, and the content of carried metal uses
GB/T 30905-2014 standard method is measured, and sodium content is measured using GB/T 30905-2014 standard method.
Research method of the TEM-EDS measuring method of the disclosure referring to solid catalyst, petrochemical industry, 29 (3), 2000:
227。
Total specific surface (S of the disclosureBET), mesoporous pore volume, total pore volume, 2-20 nanometers mesoporous pore volume use
The AS-3 of Quantachrome instrument company production, the measurement of AS-6 static state n2 absorption apparatus.Instrument parameter: sample is placed at sample
Reason system is evacuated to 1.33 × 10 at 300 DEG C-2Pa, heat-insulation pressure keeping 4h purify sample.At -196 DEG C of liquid nitrogen temperature, survey
Examination purification sample is not pressing P/P on year-on-year basis0Under the conditions of to the adsorbance and desorption rate of nitrogen, obtain N2Adsorption-desorption isothermal curve.
Then total specific surface area, micropore specific area and middle pore specific surface area are calculated using two parameter BET formula, taken than pressing P/P0=
0.98 adsorbance below is the total pore volume of sample, the pore-size distribution of hollow sections is calculated using BJH formula, and using integral
Method calculates mesoporous pore volume (2-100 nanometers) and 2-20 nanometers of mesoporous pore volume.
The strong acid acid amount and total acid content of the disclosure use II 2920 temperature programmed desorption instrument of Merck & Co., Inc, U.S. Autochem
It is measured.Test condition: weighing 0.2g sample to be tested and be packed into sample cell, is placed in conductance cell heating furnace, and He gas is carrier gas
(50mL/min) is warming up to 600 DEG C with the rate of 20 DEG C/min, and purging 60min drives away the impurity of catalyst surface absorption.Then
100 DEG C are cooled to, constant temperature 30min switches to NH3- He gaseous mixture (10.02%NH3+ 89.98%He) absorption 30min, it is further continued for
It is steady to baseline that 90min is swept with He air-blowing, the ammonia of physical absorption is desorbed.600 DEG C are warming up to 10 DEG C/min heating rate
It is desorbed, keeps 30min, desorption terminates.Using TCD detector detection gas change of component, instrument automatic integration is obtained always
Acid amount and strong acid acid amount, the acid site of strong acid are NH3Desorption temperature be greater than 300 DEG C corresponding to acid site.
The B acid acid amount of the disclosure and L acid acid amount are infrared using the FTS3000 type Fourier of U.S. BIO-RAD company production
Spectrometer is measured.Test condition: tabletted be placed in the pond in situ of infrared spectrometer of sample is sealed, at 350 DEG C
Under be evacuated to 10-3Pa keeps 1h, the gas molecule of sample surfaces is desorbed clean, is cooled to room temperature.It is imported into pond in situ
Pressure is that the pyridine steam of 2.67Pa is warming up to 200 DEG C, is evacuated to 10 again after balancing 30min-3Pa keeps 30min, cold
But to room temperature, in 1400-1700cm-1Scanning, records the infrared spectrum spectrogram of 200 DEG C of pyridine adsorptions in wave-number range.Again will
Sample in cell for infrared absorption moves to heat-treatment zone, is warming up to 350 DEG C, is evacuated to 10-3Pa keeps 30min, is cooled to room temperature,
Record the infrared spectrum of 350 DEG C of pyridine adsorptions.Instrument automatic integration obtains B acid acid amount and L acid acid amount.
The calculation method of D value is as follows: choosing a crystal grain in transmission electron microscope and some crystal face of the crystal grain is formed
One polygon, there are 10% distance H of geometric center, edge and geometric center to edge point is (different for the polygon
Edge point, H value are different), choose respectively any one piece in the inside H distance in the crystal face edge be greater than 100 square nanometers regions with
And any one piece in the outside H distance of crystal face geometric center is greater than 100 square nanometers regions, measures aluminium content, as Al (S1)
With Al (C1), and D1=Al (S1)/Al (C1) is calculated, chooses different crystal grain respectively and measure 5 times, calculating average value is D.
For the auxiliary agent of the disclosure when being used for catalytic cracking reaction performance evaluation, reaction product is by N2- 10 DEG C of liquid is brought into receive
Gas-liquid separation is carried out in bottle, gaseous product, which is collected, to be completed to be made of Agilent 6890GC (TCD detector) on-line analysis；Liquid
Weighed off line after collection of products, carries out simulation distillation respectively and gasoline detailed hydrocarbon analysis (is carried out using RIPP81-90 test method
Test), the fraction cut point of gasoline and diesel oil is respectively 221 DEG C and 343 DEG C；The regeneration of green coke catalyst on-line decoking, and according to
Flue gas flow and composition calculate coke quality；All product quality adductions calculate material balance, and octane number uses RIPP 85-90
Method measurement, gasoline PONA composition is using gasoline detailed hydrocarbon analysis measurement, octane number bucket=octane number (RON) × yield of gasoline.
For details, reference can be made to " petrochemical analysis method ", Yang Cui is surely equal to be compiled for RIPP standard method described in the disclosure, and 1990
Year version.
Part material property used in embodiment is as follows:
Boehmite is that Shandong Aluminium Industrial Corp produces industrial products, 60 weight % of solid content；Aluminum sol is that middle petrochemical industry is urged
The industrial products of agent asphalt in Shenli Refinery production, Al2O3Content is 21.5 weight %；Silica solution is middle Effect of Catalysis In Petrochemistry agent Shandong point
The industrial products of company's production, SiO2Content is 28.9 weight %, Na2O content 8.9%；Kaolin is raw for Kaolin of Suzhou company
The dedicated kaolin of the catalytic cracking catalyst of production, solid content are 78 weight %.Concentration of hydrochloric acid is 36 weight %, and rectorite is Hubei
Distinguished personages' rectorite development corporation, Ltd., Zhongxiang City product, quartz sand content < 3.5 weight %, Al2O3Content is 39.0 weight %,
Fe2O3Content is 2.0 weight %, Na2O content is 0.03 weight %, and solid content is 77 weight %；SB aluminium hydrate powder: Germany
The production of Condex company, Al2O3Content is 75 weight %；Gamma oxidation aluminium powder: German Condex company production, Al2O3Content is
95 weight %.Hydrochloric acid: chemistry is pure, and concentration is 36-38 weight %, Beijing Chemical Plant's production.
Embodiment 1-3 provides the MFI structure molecular sieve of the phosphorous and carried metal of the disclosure, and comparative example 1-13 provides comparison
Molecular sieve.
Embodiment 1
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1000g 2.0%, 65 DEG C are warming up to, after reacting 30min, after being rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 11g is added in stirring, then by 110g hydrochloric acid (mass fraction 10%) and
92g fluosilicic acid (mass fraction 3%) cocurrent is added, and time 30min is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to
Filtrate is neutral；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 1.2g H3PO4(85 weight of concentration
Measure %) and 3.3gZn (NO3)2·6H2O is uniformly mixed with dipping, drying, 550 DEG C of calcination process 2h.Obtain molecular sieve-4 A, physico-chemical property
It is listed in table 1.
Comparative example 1
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1000g 2.0%, 65 DEG C are warming up to, after reacting 30min, after being rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 27g is added in stirring；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to
Filtrate is neutral；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 1.2gH3PO4(85 weight of concentration
Measure %) and 3.3gZn (NO3)2·6H2O, uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Obtain molecular sieve DA1, object
Change property and is listed in table 1.
Comparative example 2
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1000g 2.0%, 65 DEG C are warming up to, after reacting 30min, after being rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, it takes above-mentioned molecular sieve 50g (butt) plus water is configured to the molecular sieve pulp of the weight of solid content 10 %, in stirring
It is added 215g hydrochloric acid (mass fraction 10%)；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Filter cake is added
The mashing of 1500g water, is added 80g NH4After Cl is warming up to 65 DEG C of exchange washing 40min, filtering, elution to filtrate neutrality；By filter cake
Water is added to be beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 1.2gH3PO4(85 weight % of concentration) and 3.3gZn
(NO3)2·6H2O, uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve DA2 is obtained, physico-chemical property is listed in table 1.
Comparative example 3
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1000g 2.0%, 65 DEG C are warming up to, after reacting 30min, after being rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At the molecular sieve pulp of the weight of solid content 10 %, 370g fluosilicic acid (mass fraction 3%) is added in stirring, time 30min is added；It rises
Temperature to 65 DEG C of constant temperature stir 1h, and filtering is washed to filtrate neutrality；By filter cake plus water be beaten solid content be 40 weight % molecular sieves
1.2gH is added in slurries3PO4(85 weight % of concentration) and 3.3gZn (NO3)2·6H2O is uniformly mixed with dipping, drying, 550 DEG C of roastings
Burn processing 2 hours.Molecular sieve DA3 is obtained, physico-chemical property is listed in table 1.
Comparative example 4
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1000g 2.0%, 65 DEG C are warming up to, after reacting 30min, after being rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 11g is added in stirring, then adds 110g hydrochloric acid (mass fraction 10%)
Enter, time 30min is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water are beaten to contain admittedly
Amount is the molecular sieve pulp of 40 weight %, and 1.2gH is added3PO4(85 weight % of concentration) and 3.3gZn (NO3)2·6H2O is uniformly mixed
Dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve DA4 is obtained, physico-chemical property is listed in table 1.
Comparative example 5
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1000g 2.0%, 65 DEG C are warming up to, after reacting 30min, after being rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 11g is added in stirring, it is then that 184g fluosilicic acid (mass fraction 3%) is slow
It is slow to be added, time 30min is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water are beaten
Solid content is the molecular sieve pulp of 40 weight %, and 1.2gH is added3PO4(85 weight % of concentration) and 3.3gZn (NO3)2·6H2O, uniformly
Be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve DA5 is obtained, physico-chemical property is listed in table 1.
Comparative example 6
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1000g 2.0%, 65 DEG C are warming up to, after reacting 30min, after being rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At the molecular sieve pulp of the weight of solid content 10 %, by 110g hydrochloric acid (mass fraction 10%) and 184g fluosilicic acid (quality point under stirring
Number 3%) cocurrent addition, time 30min is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus
Water is beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 1.2gH3PO4(85 weight % of concentration) and 3.3gZn (NO3)2·
6H2O, uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve DA6 is obtained, physico-chemical property is listed in table 1.
Comparative example 7
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1000g 2.0%, 65 DEG C are warming up to, after reacting 30min, after being rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At the molecular sieve pulp of the weight of solid content 10 %, 733g fluosilicic acid (mass fraction 3%) is slowly added under stirring, the time is added
30min；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；By filter cake plus water be beaten solid content be 40 heavy %
Molecular sieve pulp, be added 0.75gH3PO4(85 weight % of concentration) and 3.3gZn (NO3)2·6H2O is uniformly mixed with dipping, dries
It is dry, 550 DEG C calcination process 2 hours.Molecular sieve DA7 is obtained, physico-chemical property is listed in table 1.
Comparative example 8
By the good ZSM-5 molecular sieve of crystallization, (production of catalyst Jian Chang branch company has the synthesis of amine method, n (SiO2)/n(Al2O3)
=310) Na is washed with water to after filtering out mother liquor2O content is lower than 3.0 weight %, filters, drying, 550 DEG C in air, roasting
It burns 2h and burns up template；Above-mentioned molecular sieve 100g (butt) is taken to be added in the NaOH aqueous solution of 1500g (solution concentration 2.4%),
Stirring is warming up to 65 DEG C, after reacting 40min, is cooled to room temperature, and filters, and elution obtains filter cake to filtrate neutrality；Then it takes above-mentioned
Molecular sieve 50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, are added with stirring 220g hydrochloric acid (mass fraction
10%)；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；The mashing of 1500g water is added in filter cake, and 80g is added
NH4After Cl is warming up to 65 DEG C of exchange washing 40min, filtering, elution to filtrate neutrality；By filter cake plus water be beaten solid content be 40
The molecular sieve pulp of weight %, is added 1.0gH3PO4(85 weight % of concentration) and 3.3gZn (NO3)2·6H2O, be uniformly mixed with dipping,
Drying, 550 DEG C calcination process 2 hours.Molecular sieve DA8 is obtained, physico-chemical property is listed in table 1.
Comparative example 9
By the good ZSM-5 molecular sieve of crystallization, (production of catalyst Jian Chang branch company has the synthesis of amine method, n (SiO2)/n(Al2O3)
=72) Na is washed with water to after filtering out mother liquor2O content is lower than 3.0 weight %, filters, drying, 550 DEG C in air, roasting
2h burns up template；It takes above-mentioned molecular sieve 100g (butt) plus water is configured to the molecular sieve pulp of the weight of solid content 10 %, in stirring
It is added 670g fluosilicic acid (mass fraction 3%), time 30min is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate
It is neutral；Above-mentioned gained molecular sieve is added in the NaOH solution of 1000g 2.0%, is warming up to 65 DEG C, after reacting 30min, quickly
After being cooled to room temperature, filtering, washing to filtrate neutrality.Then with NH4The exchange of Cl solution is washed to Na2O content is lower than 0.1 weight
% is measured, is filtered, washing obtains molecular sieve filter cake；To take molecular sieve filter cake (butt 50g) plus water be beaten solid content is 40 heavy %
Molecular sieve pulp, be added 1.2gH3PO4(85 weight % of concentration) and 3.3gZn (NO3)2·6H2O, be uniformly mixed with dipping, dry,
550 DEG C calcination process 2 hours.Molecular sieve DA9 is obtained, physico-chemical property is listed in table 1.
Comparative example 10
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
Water is configured to the molecular sieve pulp of the weight of solid content 10 %, ethylenediamine tetra-acetic acid 12g is added in stirring, then by 1300g fluosilicic acid
(mass fraction 3%) cocurrent is added, and time 30min is added, is eventually adding 480g hydrochloric acid (mass fraction 10%)；It is warming up to 85 DEG C
Constant temperature stirs 6h, and filtering is washed to filtrate neutrality；It is added in the NaOH solution of 1000g 2.2%, is warming up to 60 DEG C, reaction
After 45min, after being rapidly cooled to room temperature, filtering, washing to filtrate neutrality.Then NH4The exchange of Cl solution is washed to Na2O content is low
In 0.1 weight %, molecular sieve filter cake is obtained by filtration；Take above-mentioned molecular sieve filter cake 50g (butt) plus water be beaten solid content is 40
The molecular sieve pulp of weight %, is added 1.2gH3PO4(85 weight % of concentration) and 3.3gZn (NO3)2·6H2O, be uniformly mixed with dipping,
Drying, 550 DEG C calcination process 2 hours.Molecular sieve DA10 is obtained, physico-chemical property is listed in table 1.
Comparative example 11
By the good ZSM-5 molecular sieve of crystallization, (production of catalyst Jian Chang branch company has the synthesis of amine method, n (SiO2)/n(Al2O3)
=210) NH is used after filtering out mother liquor4Cl exchange is washed to Na2O content is lower than 0.2 weight %, drying, 550 DEG C in air, roasting
It burns 2h and burns up template；Take above-mentioned molecular sieve 100g (butt) plus water be beaten solid content be 40 weight % molecular sieve pulps, add
Enter 1.6gH3PO4(concentration 85%) and 6.6gZn (NO3)2·6H2O, dipping drying；Gained sample is small in 550 DEG C of calcination process 2
When to get molecular sieve DA11.Physico-chemical property is listed in table 1.
Comparative example 12
By ZSM-5 molecular sieve (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=27) it uses
NH4The exchange of Cl solution is washed to Na2O content is lower than 0.2 weight %, filters to obtain filter cake；Take above-mentioned molecular sieve 100g (butt) plus water
It is configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 40g is added in stirring, then by 100g sulfuric acid (mass fraction
10%) it is added with 500g fluosilicic acid (mass fraction 3%) cocurrent, time 30min is added；It is warming up to 45 DEG C of constant temperature stirring 1h, mistake
Drainage is washed till filtrate neutrality；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 2.0gH3PO4(concentration
85 weight %) and 5.0 grams of Ga2(SO4)3·16H2O, uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Obtain molecular sieve
DA12, physico-chemical property are listed in table 1.
Embodiment 2
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1500g 2.4%, 60 DEG C are warming up to, after reacting 45min, after being rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At the molecular sieve pulp of the weight of solid content 10 %, citric acid 22g is added in stirring, then by 55g sulfuric acid (mass fraction 10%) and
280g fluosilicic acid (mass fraction 3%) cocurrent is added, and time 30min is added；45 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to
Filtrate is neutral；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 1.0gH3PO4(85 weight of concentration
Measure %) and 2.5 grams of Ga2(SO4)3·16H2O, uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Obtain molecular sieve B, object
Change property and is listed in table 1.
Comparative example 13
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1500g 2.4%, 60 DEG C are warming up to, after reacting 45min, after being rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 800g water is added in filter cake, 40g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At the molecular sieve pulp of the weight of solid content 10 %, citric acid 22g is added in stirring, then by 55g sulfuric acid (mass fraction 10%) and
280g fluosilicic acid (mass fraction 3%) cocurrent is added, and time 30min is added；45 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to
Filtrate is neutral；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 1.0gH3PO4(85 weight of concentration
Measure %), uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve DB1 is obtained, physico-chemical property is listed in table 1.
Embodiment 3
By the good ZSM-5 molecular sieve of crystallization (production of catalyst asphalt in Shenli Refinery, non-amine method synthesis, n (SiO2)/n(Al2O3)=
27) mother liquor is filtered out, Na is washed to2O content is lower than 3.0 weight %, filters to obtain filter cake；Above-mentioned molecular sieve 100g (butt) is taken to add
In the NaOH solution for entering 1200g 2.2%, 55 DEG C are warming up to, after reacting 60min, after being rapidly cooled to room temperature, filtering, washing is extremely
Filtrate is neutral.Then, the mashing of 1000g water is added in filter cake, 50g NH is added4Cl is warming up to 75 DEG C, after exchange handles 1h, until
Na2O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Above-mentioned molecular sieve 50g (butt) plus water is taken to prepare
At the molecular sieve pulp of the weight of solid content 10 %, ethylenediamine tetra-acetic acid 6g is added in stirring, then by 550g fluosilicic acid (mass fraction
3%) cocurrent is added, and time 30min is added, is eventually adding 220g hydrochloric acid (mass fraction 10%)；It is warming up to 85 DEG C of constant temperature stirrings
6h, filtering are washed to filtrate neutrality；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 0.8gH3PO4
(85 weight % of concentration) and 4.1gFe (NO3)3·9H2O, uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Obtain molecule
C is sieved, physico-chemical property is listed in table 1.
For the ZSM-5 molecular sieve after alkali process desiliconization it can be seen from data in table 1, using single organic acid oxalic acid
Dealuminzation (DA1) is answered using single inorganic acid HCl dealumination (DA2) and using two kinds of acid of organic acid oxalic acid and inorganic acid hydrochloric acid
Closing (DA4) all can not effectively remove the Al in molecular sieve, molecular sieve still surface richness aluminium and after only having used fluosilicic acid
Preferable dealuminzation effect could be obtained, the distribution of molecular sieve aluminium is improved.When fluosilicic acid dealuminzation is used alone (DA3 and DA7), Ke Yigai
The aluminium distribution of kind molecular sieve, but mesoporous is relatively fewer, strong acid proportion in total acid is lower, and B acid/L acid ratio is lower.Fluorine
Silicic acid composite organic acid oxalic acid dealuminzation (DA5), is equally unable to get higher mesopore proportion and preferable acid distribution.Fluosilicic acid
Composite inorganic acid HCl dealumination (DA6), although mesopore volume increased, strong acid in total acid proportion and B acid/
The molecular sieve that L acid ratio is all not so good as disclosure offer is high.To the higher ZSM-5 molecular sieve molecular sieve of silica alumina ratio, alkali process again without
Machine hydrochlorate acid is handled (DA8), although can get higher mesopore proportion, aperture is the hole of 2nm to 20nm in molecular sieve
The ratio of the total mesopore volume of volume Zhan is low, and molecular sieve bore diameter becomes larger, while the Al distribution of molecular sieve is still poor, and strong acid is less, B
Acid/L acid ratio is low, and molecular sieve stability is poor, and reactivity is low.It is higher using silica alumina ratio of the soda acid processing technique to synthesis
ZSM-5 molecular sieve is handled, although the ZSM-5 molecular sieve containing mesoporous of the silica alumina ratio range in the disclosure can be obtained meeting
(DA9), but the Al of molecular sieve distribution is poor, and strong acid is less, and B acid/L acid ratio is low.And use the technology road of first dealuminzation desiliconization again
Line, the molecular sieve that desiliconization is handled again after being improved the silica alumina ratio of ZSM-5 molecular sieve with the Compound-acid containing fluosilicic acid
(DA10), crystallinity is low, and mesopore proportion is low, and middle aperture is that the ratio of the total mesopore volume of pore volume Zhan of 2nm to 20nm is low, point
The son sieve relatively more acid distributions of outer surface Al are poor.And the high silica alumina ratio molecular sieve (DA11) and Compound-acid dealuminzation directly synthesized is mended
The molecular sieve (DA12) that silicon obtains is without secondary pore abundant.After the disclosure is using first desiliconization processing is carried out to molecular sieve, then make
It can guarantee that crystal structure of molecular sieve and mesoporous cellular structure are complete under three kinds of sour synergistic effects with compound acid system
Property under the premise of effectively improve molecular sieve silica alumina ratio, adjust aluminium distribution, improve acid distribution.
Embodiment 4-7 provides phosphorus aluminium inorganic binder used in the disclosure.
Embodiment 4
The present embodiment prepares phosphorus aluminium inorganic binder described in the disclosure.
1.91 kilograms of boehmites (are contained into Al2O31.19 kilograms), 0.56 kilogram of kaolin (0.50 kilogram of butt) with
3.27 kilograms of decationized Y sieve water are beaten 30 minutes, and stirring is lower, and 5.37 kilograms of concentrated phosphoric acids (mass concentration 85%) are added into slurries,
It is 0.04Kg phosphoric acid/minute/Kg alumina source that speed, which is added, in phosphoric acid, is warming up to 70 DEG C, is then reacted 45 minutes at this temperature,
Obtain phosphorus aluminium inorganic binder.Material proportion is shown in Table 2, obtains binder Binder1.
Embodiment 5-7
Phosphorus aluminium inorganic binder is prepared as described in Example 4, and material proportion is shown in Table 2, obtains binder Binder2-4.
Embodiment 8-13 provides the assistant for calalytic cracking of the disclosure, and comparative example 14-26 provides comparison assistant for calalytic cracking.
Embodiment 8
Molecular sieve-4 A, kaolin and boehmite are taken, decationized Y sieve water is added and Aluminum sol is beaten 120 minutes, stirring
Lower addition FeCl3·6H2Aqueous solution (the FeCl of O330 weight % of content), the slurries of 30 weight % of solid content are obtained, hydrochloric acid is added
The pH value 3.0 for adjusting slurries then proceedes to mashing 45 minutes, and phosphorus aluminium inorganic binder prepared by embodiment 4, stirring is then added
After 30 minutes, obtained slurries are spray-dried, microballoon is obtained, microballoon is roasted 1 hour at 500 DEG C, ZJ is made1, match
Than being shown in Table 3.
Embodiment 9
Molecular sieve B, kaolin and boehmite are taken, decationized Y sieve water is added and Aluminum sol is beaten 120 minutes, stirring
Lower addition FeCl3·6H2Aqueous solution (the FeCl of O330 weight % of content), the slurries of 30 weight % of solid content are obtained, hydrochloric acid is added
The pH value 3.0 for adjusting slurries then proceedes to mashing 45 minutes, and phosphorus aluminium inorganic binder prepared by embodiment 4, stirring is then added
After 30 minutes, obtained slurries are spray-dried, microballoon is obtained, microballoon is roasted 1 hour at 500 DEG C, ZJ is made2, match
Than being shown in Table 3.
Embodiment 10
Molecular sieve C, kaolin and boehmite are taken, decationized Y sieve water is added and Aluminum sol is beaten 120 minutes, stirring
Lower addition FeCl3·6H2Aqueous solution (the FeCl of O330 weight % of content), the slurries of 30 weight % of solid content are obtained, hydrochloric acid is added
The pH value 3.0 for adjusting slurries then proceedes to mashing 45 minutes, and phosphorus aluminium inorganic binder prepared by embodiment 4, stirring is then added
After 30 minutes, obtained slurries are spray-dried, microballoon is obtained, microballoon is roasted 1 hour at 500 DEG C, ZJ is made3, match
Than being shown in Table 3.
Embodiment 11
Molecular sieve-4 A, kaolin and boehmite are taken, decationized Y sieve water is added and Aluminum sol is beaten 120 minutes, obtains
The slurries of 30 weight % of solid content, are added the pH value 3.0 that hydrochloric acid adjusts slurries, then proceed to mashing 45 minutes, are then added real
Apply example 5 preparation phosphorus aluminium inorganic binder, stirring 30 minutes after, by obtained slurries be spray-dried, obtain microballoon, by microballoon in
It is roasted 1 hour at 500 DEG C.Thus obtained microsphere product is taken, ZnCl is added2Aqueous solution (30 weight % of concentration), is warming up to 60 under stirring
DEG C, it reacts at this temperature after twenty minutes, by slurries vacuum filter, drying, is then roasted 2 hours at 500 DEG C, obtain auxiliary agent
ZJ4, match and be shown in Table 3
Embodiment 12
Molecular sieve-4 A, kaolin and boehmite are taken, decationized Y sieve water is added and silica solution is beaten 120 minutes, stirring
Lower addition Co (NO3)2·6H2The aqueous solution (30 weight % of concentration) of O obtains the slurries of 30 weight % of solid content, and hydrochloric acid tune is added
The pH value 3.0 for saving slurries then proceedes to mashing 45 minutes, and phosphorus aluminium inorganic binder prepared by embodiment 6, stirring 30 is then added
After minute, obtained slurries are spray-dried, microballoon is obtained, microballoon is roasted 1 hour at 500 DEG C, ZJ is made5, proportion
It is shown in Table 3.
Embodiment 13
Molecular sieve-4 A, kaolin and boehmite are taken, decationized Y sieve water is added and Aluminum sol is beaten 120 minutes, stirring
Lower addition Ga (NO3)3Aqueous solution (30 weight % of concentration), obtain the slurries of 30 weight % of solid content, hydrochloric acid be added and adjusts slurries
PH value 2.5, then proceed to mashing 45 minutes, then be added embodiment 7 prepare phosphorus aluminium inorganic binder, stir 30 minutes
Afterwards, obtained slurries are spray-dried, obtain microballoon.The phosphoric acid hydrogen two that concentration is 7.5 weight % is added in thus obtained microsphere product
In aqueous ammonium, 60 DEG C are warming up under stirring, is reacted at this temperature after twenty minutes, by slurries vacuum filter, drying, then in
It is roasted 2 hours at 500 DEG C, auxiliary agent ZJ is made6, auxiliary agent proportion be shown in Table 3.
Comparative example 14-26
Prepare assistant for calalytic cracking by method described in embodiment 8, be a difference in that with molecular sieve DA1, DA2, DA3,
DA4, DA5, DA6, DA7, DA8, DA9, DA10, DA11, DA12, DB1 replace A respectively, and auxiliary agent DZJ is made1-DZJ13, proportion
It is shown in Table 4.
Skip test example, embodiment 14-19 are using small fixed flowing bed-tion reacting device to 100% poising agent and balance
Agent mixes auxiliary agent ZJ prepared by the embodiment of the present disclosure1-ZJ6Reactivity worth evaluation is carried out, is split with the catalysis for illustrating that the disclosure provides
Change the catalytic cracking reaction effect of auxiliary agent.
Skip test example, embodiment 14-19
Respectively by auxiliary agent ZJ1-ZJ617 hours aging processs are carried out under the conditions of 800 DEG C, 100% steam atmosphere.It takes
ZJ through aging process1-ZJ6(the industrial trade mark is the FCC equilibrium catalyst of DVR-3, micro-activity with industrial FCC equilibrium catalyst
63) to mix respectively.100% poising agent and catalyst mixture are fitted into small fixed flowing bed reactor, to shown in table 5
Feedstock oil carries out catalytic cracking, reaction condition are as follows: and 500 DEG C of reaction temperature, weight (hourly) space velocity (WHSV) 8h-1, agent oil weight ratio 6.Table 6 gives
The weight of each catalyst mixture forms and reaction result.
Comparative example 27-39 is using small fixed flowing bed-tion reacting device to prepared by poising agent incorporation disclosure comparative example
Auxiliary agent DZJ1-DZJ12The case where having carried out performance evaluation, comparison auxiliary agent used with explanation.
Comparative example 27-39
Catalytic cracking is carried out to same feedstock oil by the method in embodiment 14, the difference is that used catalyst is respectively
DZJ after aging method aging identical in embodiment 141-DZJ13With the mixture of industrial FCC equilibrium catalyst.Table 7 is given
The weight composition and reaction result of each catalyst mixture are gone out.
From table 6 and table 7 as can be seen that compared with comparing auxiliary agent, Catalytic Cracking Unit of Measure is carried out using the auxiliary agent that the disclosure provides
It should increase while guaranteeing yield of gasoline with the isomery hydrocarbon content in higher octane number, especially gasoline component,
Gasoline composition is improved well, and then improves octane number bucket.
Table 1
Table 2
Table 3
Table 4
Table 5
| Density, g/cm3(20℃) | 0.9171 |
| Viscosity (100C), mm2/s | 10.61 |
| Condensation point, DEG C | 20 |
| Carbon residue, weight % | 1.91 |
| Constituent content, weight % | |
| C | 85.96 |
| H | 12.37 |
| S | 1.0 |
| N | 0.35 |
| Tenor, μ g/g | |
| Ca | 8.3 |
| Fe | 12.3 |
| Na | 0.9 |
| Ni | 4.7 |
| V | 0.4 |
| Boiling range, DEG C | |
| Initial boiling point | 267 |
| 10% | 371 |
| 50% | 449 |
| 70% | 486 |
| 86.9% | 549 |
Table 6
Table 7
Claims (19)
1. a kind of assistant for calalytic cracking for improving octane number bucket, on the basis of the dry weight of the auxiliary agent, the auxiliary agent packet
The phosphorous and carried metal MFI structure molecular sieve with dry basis 10-75 weight % is included, with dry basis 3-40 weight %
Phosphorus aluminium inorganic binder, other inorganic binders of the weight of the 1-30 in terms of oxide %, with dry basis 0-60 weight %
The second clay, and the metal selected from least one of VIII race's metal and manganese, zinc, gallium of the weight of the 0.5-15 in terms of oxide %
Additive；Wherein,
The phosphorus aluminium inorganic binder is phosphorus aluminium glue and/or the phosphorus aluminium inorganic binder containing the first clay, contains first with described
On the basis of the phosphorus aluminium inorganic binder dry weight of clay, the phosphorus aluminium inorganic binder for containing the first clay includes with Al2O3Meter
15-40 weight % aluminium component, with P2O5It counts the phosphorus component of 45-80 weight % and is greater than 0 with dry basis and is no more than 40 weights
The first clay of % is measured, and its P/Al weight ratio is 1.0-6.0, pH value 1-3.5, solid content is 15-60 weight %；
N (the SiO of the molecular sieve2)/n(Al2O3) it is greater than 100；With P2O5Count and on the basis of the dry weight of molecular sieve, it is described
The phosphorus content of molecular sieve is 0.1-5 weight %；It is counted by the oxide of carried metal and on the basis of the dry weight of molecular sieve, institute
The carried metal content for stating molecular sieve is 0.1-5 weight %；The Al distribution parameter D of the molecular sieve meets: 0.6≤D≤0.85,
Wherein, D=Al (S)/Al (C), Al (S) indicate using TEM-EDS method measurement zeolite crystal the inside H in crystal face edge away from
From interior any aluminium content for being greater than 100 square nanometers regions, Al (C) indicates the zeolite crystal using the measurement of TEM-EDS method
The outside H of the geometric center of the crystal face is apart from interior any aluminium content for being greater than 100 square nanometers regions, wherein the H is described
Crystal face edge point arrives the 10% of the crystal face geometric center distance；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is
The ratio of 40-80%, the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers to 20 nanometers are greater than 90%；The molecular sieve
The ratio that strong acid acid amount accounts for total acid content is 60-80%, and the ratio between B acid acid amount and L acid acid amount are 15-80；The mesopore volume is hole
Diameter is greater than 2 nanometers of pore volumes less than 100 nanometers；The strong acid acid amount of the molecular sieve accounts for the ratio of total acid content using NH3-TPD
Method measures；The ratio between the B acid acid amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption.
2. auxiliary agent according to claim 1, wherein the n (SiO of the molecular sieve2)/n(Al2O3) it is greater than 120；With P2O5Meter
And on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 0.2-4 weight %；With the oxide of carried metal
It counts and on the basis of the dry weight of molecular sieve, the carried metal content of the molecular sieve is 0.5-3 weight %；The molecular sieve
Al distribution parameter D meet: 0.65≤D≤0.80；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 50-
70%, the ratio for the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers to 20 nanometers is greater than 92%；The strong acid of the molecular sieve
The ratio that acid amount accounts for total acid content is 65-75%, and the ratio between B acid acid amount and L acid acid amount are 20-50.
3. auxiliary agent according to claim 1, wherein the carried metal is selected from iron, cobalt, nickel, copper, manganese, zinc, tin, bismuth
With at least one of sow.
4. auxiliary agent according to claim 1, wherein first clay is selected from kaolin, sepiolite, concave convex rod
At least one of stone, rectorite, montmorillonite and diatomite；Second clay is selected from kaolin, metakaolin, diatom
At least one of soil, sepiolite, attapulgite, montmorillonite and rectorite；Other inorganic matter binders are thin selected from intending
At least one of diaspore, Aluminum sol, silicon-aluminum sol and waterglass.
5. auxiliary agent according to claim 1, wherein the metallic addition introduced in the form of metallic compound described in help
Agent, the metallic compound are selected from oxide, hydroxide, chloride, nitrate, sulfate, phosphate and organic compound
At least one of object.
6. auxiliary agent described in any one of -5 according to claim 1, wherein on the basis of the dry weight of the auxiliary agent, institute
Auxiliary agent is stated also to contain with P2O5Meter is no more than the phosphorus additive of 5 weight %.
7. auxiliary agent according to claim 6, wherein the auxiliary agent includes phosphorus aluminium inorganic binder, the 20- of 8-25 weight %
The phosphorous and carried metal MFI structure molecular sieve of 60 weight %, the second clay of 10-45 weight %, 5-25 weight % it is other
The phosphorus additive of inorganic binder, the metallic addition of 1.0-10 weight % and 0-3 weight %.
8. a kind of preparation method for the assistant for calalytic cracking for improving octane number bucket, this method comprises:
Phosphorous and carried metal MFI structure molecular sieve, phosphorus aluminium inorganic binder and other inorganic binders are mixed, adds or is not added
Enter the second clay, is beaten, spray drying；Wherein, metallic addition is introduced, phosphorus additive is introduced or do not introduce；
On the basis of the total dry weight for preparing raw material of auxiliary agent, the raw material for preparing of the auxiliary agent includes with dry basis 10-
The phosphorous and carried metal MFI structure molecular sieve of 75 weight %, with the phosphorus aluminium inorganic binder of dry basis 3-40 weight %,
Other inorganic binders of the weight of the 1-30 in terms of oxide %, with the second clay of dry basis 0-60 weight %, with oxidation
The metallic addition selected from least one of VIII race's metal and manganese, zinc, gallium of object meter 0.5-15 weight %, and including or not
Including with P2O5Meter is no more than the phosphorus additive of 5 weight %；Wherein,
The phosphorus aluminium inorganic binder is phosphorus aluminium glue and/or the phosphorus aluminium inorganic binder containing the first clay, contains first with described
On the basis of the phosphorus aluminium inorganic binder dry weight of clay, the phosphorus aluminium inorganic binder for containing the first clay includes with Al2O3Meter
15-40 weight % aluminium component, with P2O5It counts the phosphorus component of 45-80 weight % and is greater than 0 with dry basis and is no more than 40 weights
The first clay of % is measured, and its P/Al weight ratio is 1.0-6.0, pH value 1-3.5, solid content is 15-60 weight %；
N (the SiO of the molecular sieve2)/n(Al2O3) it is greater than 100；With P2O5Count and on the basis of the dry weight of molecular sieve, it is described
The phosphorus content of molecular sieve is 0.1-5 weight %；It is counted by the oxide of carried metal and on the basis of the dry weight of molecular sieve, institute
The carried metal content for stating molecular sieve is 0.1-5 weight %；The Al distribution parameter D of the molecular sieve meets: 0.6≤D≤0.85,
Wherein, D=Al (S)/Al (C), Al (S) indicate using TEM-EDS method measurement zeolite crystal the inside H in crystal face edge away from
From interior any aluminium content for being greater than 100 square nanometers regions, Al (C) indicates the zeolite crystal using the measurement of TEM-EDS method
The outside H of the geometric center of the crystal face is apart from interior any aluminium content for being greater than 100 square nanometers regions, wherein the H is described
Crystal face edge point arrives the 10% of the crystal face geometric center distance；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is
The ratio of 40-80%, the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers to 20 nanometers are greater than 90%；The molecular sieve
The ratio that strong acid acid amount accounts for total acid content is 60-80%, and the ratio between B acid acid amount and L acid acid amount are 15-80；The mesopore volume is hole
Diameter is greater than 2 nanometers of pore volumes less than 100 nanometers；The strong acid acid amount of the molecular sieve accounts for the ratio of total acid content using NH3-TPD
Method measures；The ratio between the B acid acid amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption.
9. preparation method according to claim 8, wherein described phosphorous and carried metal MFI structure molecular sieve preparation
Step includes:
A, after being filtered and washed MFI structure molecular sieve pulp obtained by crystallization, washing molecular sieve is obtained；Wherein, with oxidation
Sodium meter and on the basis of the total dry weight for washing molecular sieve, the sodium content of the washing molecular sieve is less than 3 weight %；
B, gained washing molecular sieve in step a is subjected in aqueous slkali desiliconization processing, and after being filtered and washed, is taken off
Si molecular sieves；Weight ratio with the water in the alkali and aqueous slkali in the molecular sieve of dry basis, aqueous slkali is 1:(0.1-2):
(5-15)；The temperature of desiliconization processing is room temperature to 100 DEG C, and the time is 0.2-4 hours；
C, gained desiliconization molecular sieve in step b is subjected to ammonium exchange processing, obtains ammonium exchange molecular sieve；Wherein, in terms of sodium oxide molybdena
And on the basis of total dry weight of ammonium exchange molecular sieve, the sodium content of the ammonium exchange molecular sieve is less than 0.2 weight %；
D, gained ammonium exchange molecular sieve in step c is molten in the Compound-acid dealumination agent being made of fluosilicic acid, organic acid and inorganic acid
Dealumination treatment is carried out in liquid, and after being filtered and washed, obtains dealuminzation molecular sieve；With the molecular sieve of dry basis, organic
The weight ratio of acid, inorganic acid and fluosilicic acid is 1:(0.05-0.5): (0.05-0.5): (0.02-0.5)；Treatment temperature is 25-
100 DEG C, the processing time is 0.5-6 hours；
E, after dealuminzation molecular sieve obtained in step d being carried out P Modification processing, the load processing of carried metal and calcination process,
Obtain described phosphorous and carried metal MFI structure molecular sieve.
10. preparation method according to claim 9, wherein aqueous slkali described in step b be selected from sodium hydroxide solution,
At least one of potassium hydroxide solution and ammonium hydroxide.
11. preparation method according to claim 9, wherein the condition of the processing of desiliconization described in step b includes: with butt
The weight ratio of the water in alkali and aqueous slkali in the molecular sieve of poidometer, aqueous slkali is 1:(0.2-1): (5-15).
12. preparation method according to claim 9, wherein the step of dealumination treatment described in step d further include: first will
Organic acid exchanges molecular sieve mixing with the ammonium, then fluosilicic acid and inorganic acid are exchanged to molecular sieve mixing with the ammonium.
13. preparation method according to claim 9, wherein organic acid described in step d be selected from ethylenediamine tetra-acetic acid,
At least one of oxalic acid, citric acid and sulfosalicylic acid, the inorganic acid are at least one in hydrochloric acid, sulfuric acid and nitric acid
Kind.
14. preparation method according to claim 9, wherein organic acid described in step d is oxalic acid, and the inorganic acid is
Hydrochloric acid.
15. preparation method according to claim 9, wherein the condition of dealumination treatment described in step d includes: with butt
The molecular sieve of poidometer, organic acid, inorganic acid and fluosilicic acid weight ratio be 1:(0.1-0.3): (0.1-0.3): (0.05-
0.3)。
16. preparation method according to claim 9, wherein P Modification described in step e processing include: will selected from phosphoric acid,
At least one of ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate phosphorus-containing compound carries out dipping to molecular sieve and/or ion is handed over
It changes.
17. preparation method according to claim 9, wherein the load of carried metal described in step e processing include: by
Containing selected from iron, cobalt, nickel, copper, manganese, zinc, tin, bismuth and at least one of sowing the compound of carried metal by dipping method for institute
Carried metal is stated to load on the molecular sieve.
18. preparation method according to claim 9, wherein the condition of the calcination process includes: the atmosphere of calcination process
For air atmosphere or steam atmosphere；Maturing temperature is 400-800 DEG C, and calcining time is 0.5-8 hours.
19. preparation method according to claim 8, wherein the preparation of the phosphorus aluminium inorganic binder for containing the first clay
Step includes:
(1), alumina source, the first clay and water mashing are dispersed into the slurries that solid content is 8-45 weight %；The oxidation
Silicon source is can be by the aluminium hydroxide and/or aluminium oxide of sour peptization, with the first clay of dry basis and with Al2O3The oxidation of meter
The weight ratio of silicon source is (being greater than 0-40): (15-40)；
(2), stirring is lower is added concentrated phosphoric acid according to the weight ratio of P/Al=1-6 into the slurries that step (1) obtains；
(3), the slurries that step (2) obtains are reacted 15-90 minutes at a temperature of 50-99 DEG C.
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