CN107970997A - A kind of assistant for calalytic cracking of propylene enhancing and preparation method thereof - Google Patents
A kind of assistant for calalytic cracking of propylene enhancing and preparation method thereof Download PDFInfo
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- CN107970997A CN107970997A CN201610920650.7A CN201610920650A CN107970997A CN 107970997 A CN107970997 A CN 107970997A CN 201610920650 A CN201610920650 A CN 201610920650A CN 107970997 A CN107970997 A CN 107970997A
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- phosphorus
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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000005336 cracking Methods 0.000 title claims abstract description 29
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 23
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 133
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 133
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 124
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 119
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 119
- 239000004411 aluminium Substances 0.000 claims abstract description 110
- 239000011230 binding agent Substances 0.000 claims abstract description 88
- 239000004927 clay Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 61
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 55
- 230000008569 process Effects 0.000 claims abstract description 27
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 7
- 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 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 215
- 239000002808 molecular sieve Substances 0.000 claims description 214
- 239000002253 acid Substances 0.000 claims description 139
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 239000013078 crystal Substances 0.000 claims description 48
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 41
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000012545 processing Methods 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 35
- 239000002002 slurry Substances 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 30
- 238000001354 calcination Methods 0.000 claims description 29
- 239000011148 porous material Substances 0.000 claims description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 28
- 229910021536 Zeolite Inorganic materials 0.000 claims description 24
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 24
- 239000010457 zeolite Substances 0.000 claims description 24
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 23
- 239000000654 additive Substances 0.000 claims description 21
- 230000000996 additive effect Effects 0.000 claims description 21
- 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 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 20
- 229910052593 corundum Inorganic materials 0.000 claims description 19
- 150000007522 mineralic acids Chemical class 0.000 claims description 19
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000005995 Aluminium silicate Substances 0.000 claims description 17
- 229910019142 PO4 Inorganic materials 0.000 claims description 17
- 235000012211 aluminium silicate Nutrition 0.000 claims description 17
- 238000005360 mashing Methods 0.000 claims description 17
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 150000007524 organic acids Chemical class 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003292 glue Substances 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
- 239000011734 sodium Substances 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 8
- 229910000765 intermetallic Inorganic materials 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 239000004113 Sepiolite Substances 0.000 claims description 7
- 239000003513 alkali 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
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- 229910052625 palygorskite Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 229910052624 sepiolite Inorganic materials 0.000 claims description 7
- 235000019355 sepiolite Nutrition 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002689 soil Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- 229960001484 edetic acid Drugs 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen 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
- 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 2
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000004523 catalytic cracking Methods 0.000 abstract description 14
- 239000012065 filter cake Substances 0.000 description 33
- 238000010792 warming Methods 0.000 description 33
- 239000003054 catalyst Substances 0.000 description 27
- 238000001914 filtration Methods 0.000 description 26
- 238000001035 drying Methods 0.000 description 25
- 235000011007 phosphoric acid Nutrition 0.000 description 19
- 239000000706 filtrate Substances 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 18
- -1 polycyclic hydro carbons Chemical class 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 12
- 241000196324 Embryophyta Species 0.000 description 11
- 229910001593 boehmite Inorganic materials 0.000 description 11
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 230000007935 neutral effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000012452 mother liquor Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000010561 standard procedure Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 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
- 239000000843 powder Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
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- 238000005507 spraying Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 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
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
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- 229920002472 Starch Polymers 0.000 description 1
- KXEOSTAFIDYVEF-UHFFFAOYSA-N [Si](O)(O)(O)O.[F] Chemical group [Si](O)(O)(O)O.[F] KXEOSTAFIDYVEF-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 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
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- 239000010426 asphalt Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 description 1
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- 238000004939 coking Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
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- 230000006837 decompression Effects 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 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
- 239000002010 green coke Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910052738 indium Inorganic materials 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
- 238000002386 leaching Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 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
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ISNYUQWBWALXEY-OMIQOYQYSA-N tsg6xhx09r Chemical compound O([C@@H](C)C=1[C@@]23CN(C)CCO[C@]3(C3=CC[C@H]4[C@]5(C)CC[C@@](C4)(O)O[C@@]53[C@H](O)C2)CC=1)C(=O)C=1C(C)=CNC=1C ISNYUQWBWALXEY-OMIQOYQYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 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
- B01J29/83—Aluminophosphates [APO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
A kind of this disclosure relates to assistant for calalytic cracking of propylene enhancing and preparation method thereof, on the basis of the butt weight of the auxiliary agent, the auxiliary agent is included with the phosphorous IMF structure molecular screens of 10 75 weight % of dry basis, with the phosphorus aluminium inorganic binder of 3 40 weight % of dry basis, other inorganic binders of in terms of oxide 1 30 weight %, with the metallic addition selected from least one of VIII race's metal and manganese, zinc, gallium of the second clay of 0 60 weight % of dry basis, and in terms of oxide 0.5 15 weight %.The auxiliary agent that the disclosure is provided is used for catalytic cracking process, can effectively improve propene yield and Propylene Selectivity.
Description
Technical field
A kind of this disclosure relates to assistant for calalytic cracking of propylene enhancing and preparation method thereof.
Background technology
For a long time, ethene, propylene and butylene are that the basic organic chemical industry of synthetic resin, synthetic fibers and synthetic rubber is former
Material, wherein propylene are a kind of important source materials for being used to manufacture petroleum chemicals for being only second to ethene.The maximum of domestic and international propylene at present
Source is the Main By product of thermal cracking production ethene, and the second largest source of propylene nearly all comes from FCC apparatus, there is provided about
30% demand, in the U.S., FCC apparatus then provides petroleum chemicals to the propylene demand of about half.
Due to increasing rapidly to polyacrylic demand, make the required propylene of petrochemical industry than ethylene requirements faster, and
The construction of ethylene plant is limited to the demand of ethene, therefore a large amount of FCC propylene that increase production are by the increase for meet demand.From previous generation
Record since the eighties, the catalyst of the ZSM-5 containing shape-selective molecular sieve starts to put into commercial Application on FCC apparatus, has reached volume increase
C3 =Purpose, but the greatest weakness of this kind of ZSM-5 molecular sieve is that activity stability is poor, in the periodic regeneration of FCC apparatus harshness
Under the conditions of easy in inactivation.
IM-5 molecular sieves are a kind of IMF structure molecular screens, are synthesized first in 1998 by Benazzi.2007 by
Baerlocher et al. completes the parsing work of structure.The molecular sieve is two-dimentional ten-ring pore passage structure, its channel diameter with
ZSM-5 molecular sieve is similar, and also there are a limited duct on third dimension direction.Since it has and ZSM-5 molecular sieve phase
Near pore passage structure, while there is the acid amount of higher and more preferable hydrothermal stability, therefore shown in many catalytic reactions
Characteristic.Corma et al. has carried out a series of researchs to the catalytic performance of IM-5 molecular sieves, finds it in terms of alkane cracking capability
Higher than ZSM-5 molecular sieve.
Although IM-5 molecular sieves can have higher alkane cracking capability, identical with other ten-ring molecular sieves, by
Narrow in its pore passage structure, larger reactant molecule such as polycyclic hydro carbons are difficult to be reacted into crystal duct, reduce
The effective affecting acreage of molecular sieve, reduces the reactivity of molecular sieve；On the other hand, isoparaffin and aromatic hydrocarbons etc. are larger
Product molecule is not easy to come out from molecular sieve pore passage diffusion inside, thus cause the secondary responses such as excessive hydrogen migration, coking and then
Molecular sieve inactivation, reaction selectivity is caused to reduce.It is divided into macromolecular restructuring in the cracking reaction of raw material, IM-5 molecular sieve pores
The defects of road aperture is narrow necessarily makes problem above more prominent.
The content of the invention
The purpose of the disclosure is to provide a kind of assistant for calalytic cracking of propylene enhancing and preparation method thereof, and the disclosure is provided
Auxiliary agent be used for catalytic cracking process, propene yield and Propylene Selectivity can be effectively improved.
To achieve these goals, the disclosure provides a kind of assistant for calalytic cracking of propylene enhancing, with the dry of the auxiliary agent
On the basis of base weight amount, which is included with the phosphorous IMF structure molecular screens of dry basis 10-75 weight %, with butt 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 butt 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
Binding agent, on the basis of the phosphorus aluminium inorganic binder butt weight for containing the first clay, the phosphorus aluminium for containing the first clay without
Machine binding agent is included with Al2O3Count 15-40 weight % aluminium component, with P2O5Count the phosphorus component of 45-80 weight % and with dry basis
Gauge is more than 0 and the first clay no more than 40 weight %, and its P/Al weight ratio is 1.0-6.0, pH value 1-3.5, admittedly contain
Measure as 15-60 weight %；The Al distributed constants D of the molecular sieve meets：0.6≤D≤0.85；Wherein, D=Al (S)/Al (C),
Al (S) represents the inside H in crystal face edge using the zeolite crystal of TEM-EDS methods measure apart from interior any more than 100 squares
The aluminium content of nano-area, Al (C) represent using TEM-EDS methods measure zeolite crystal described in crystal face geometric center to
Outer H is apart from interior any aluminium content for being more than 100 square nanometers regions, wherein the H arrives the crystal face for the crystal face edge point
The 10% of geometric center distance；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 50-80 body %, and aperture is received for 2
The ratio that the mesopore volume of -20 nanometers of rice accounts for total mesopore volume is more than 85 body %；The strong acid acid amount of the molecular sieve accounts for total acid content
Ratio be 50-80%, the ratio between B acid acid amounts and L acid acid amounts are 7-30；With P2O5Count and on the basis of the butt weight of molecular sieve,
The phosphorus content of the molecular sieve is 0.1-15 weights %.
Preferably, the Al distributed constants D of the molecular sieve meets：0.65≤D≤0.82；The mesopore volume of the molecular sieve
The ratio for accounting for total pore volume is 57-70 body %, and the ratio that the mesopore volume that aperture is 2 nanometers -20 nanometers accounts for total mesopore volume is big
In 90 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 55-70%, and the ratio between B acid acid amounts and L acid acid amounts are 8-
25；With P2O5Count and on the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 1-13 weights %.
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 binding agents 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 butt 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 IMF knots of the phosphorus aluminium inorganic binder of 8-25 weight %, 20-60 weight %
Structure molecular sieve, the second clay of 10-45 weight %, other inorganic binders of 5-25 weight %, the metal of 1.0-10 weight %
The phosphorus additive of additive and 0-3 weight %.
The disclosure also provides a kind of preparation method of the assistant for calalytic cracking of propylene enhancing, and this method includes：By phosphorous IMF
Structure molecular screen, phosphorus aluminium inorganic binder and the mixing of other inorganic binders, add or are added without the second clay, be beaten, spraying is dry
It is dry；Wherein, metallic addition is introduced, introduces or does not introduce phosphorus additive；Using total butt weight of the preparing raw material of auxiliary agent as base
Standard, the preparing raw material of the auxiliary agent is included with the phosphorous IMF structure molecular screens of dry basis 10-75 weight %, with dry basis
The phosphorus aluminium inorganic binder of gauge 3-40 weight %, other inorganic binders of the weight of the 1-30 in terms of oxide %, with dry basis
The second clay of gauge 0-60 weight %, 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, and including or do not include with P2O5Phosphorus additive of the meter no more than 5 weight %；Wherein, it is described
Phosphorus aluminium inorganic binder is phosphorus aluminium glue and/or the phosphorus aluminium inorganic binder containing the first clay, with the phosphorus aluminium for containing the first clay
On the basis of inorganic binder butt weight, the phosphorus aluminium inorganic binder for containing the first clay is included with Al2O3Count 15-40 weights
Measure % aluminium component, with P2O5Count the phosphorus component of 45-80 weight % and be more than 0 and no more than 40 weight %'s with dry basis
First clay, and its P/Al weight ratio is 1.0-6.0, pH value 1-3.5, solid content is 15-60 weight %；The molecular sieve
Al distributed constants D meets：0.6≤D≤0.85；Wherein, D=Al (S)/Al (C), Al (S) represent to measure using TEM-EDS methods
The inside H in crystal face edge of zeolite crystal represent to adopt apart from interior any aluminium content for being more than 100 square nanometers regions, Al (C)
The outside H of geometric center of crystal face is arbitrarily more than 100 square nanometers apart from interior described in the zeolite crystal measured with TEM-EDS methods
The aluminium content in region, wherein the H, which is the crystal face edge point, arrives the 10% of the crystal face geometric center distance；The molecular sieve
Mesopore volume to account for the ratio of total pore volume be 50-80 body %, aperture be 2 nanometers -20 nanometers of mesopore volume account for it is total in hole body
Long-pending ratio is more than 85 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 50-80%, B acid acid amounts and L acid acid
The ratio between amount is 7-30；With P2O5Count and on the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 0.1-15
Weight %.
Preferably, the preparation process of the phosphorous IMF structure molecular screens includes：A, sodium form IMF structure molecular screens are in alkali soluble
Desiliconization processing is carried out in liquid, obtains desiliconization molecular sieve；B, gained desiliconization molecular sieve in step a is subjected to ammonium exchange processing, obtained
Ammonium exchanges molecular sieve；Wherein, counted and on the basis of total butt weight that ammonium exchanges molecular sieve by sodium oxide molybdena, the ammonium exchanges molecule
The sodium content of sieve is less than 0.2 heavy %；C, gained ammonium in step b is exchanged into molecular sieve by fluosilicic acid, organic acid and inorganic acid group
Into Compound-acid dealuminzation agent solution in carry out dealumination treatment, and after being filtered and being washed, obtain dealuminzation molecular sieve；D, by step
After the dealuminzation molecular sieve of gained carries out P Modification processing and calcination process in c, the phosphorous IMF structure molecular screens are obtained.
Preferably, the preparation process of sodium form IMF structure molecular screens described in step a includes：To use has amine method crystallization institute
After IMF structure molecular screen slurries are filtered and are washed, obtain washing molecular sieve；Wherein, in terms of sodium oxide molybdena and with the water
Wash on the basis of total butt weight of molecular sieve, the sodium content of the washing molecular sieve is less than 3.0 heavy %；By the washing molecular sieve
It is dried and after air roasting, obtains the sodium form IMF structure molecular screens.
Preferably, aqueous slkali described in step a is selected from sodium hydrate aqueous solution, potassium hydroxide aqueous solution and ammonium hydroxide.
Preferably, the condition of the processing of desiliconization described in step a includes：With the sodium form IMF structure molecular screens of dry basis,
The weight ratio of the water in alkali and aqueous slkali in aqueous slkali is 1：(0.1-2)：(5-20), the temperature of the desiliconization processing is room temperature
To 100 DEG C, when the time is 0.2-4 small.
Preferably, the condition of the processing of desiliconization described in step a includes：With the sodium form IMF structure molecular screens of dry basis,
The weight ratio of the water in alkali and aqueous slkali in aqueous slkali is 1：(0.2-1)：(5-20).
Preferably, organic acid described in step c 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, the condition of dealumination treatment includes described in step c：Molecular sieve, organic is exchanged with the ammonium of dry basis
The weight ratio of acid, inorganic acid and fluosilicic acid is 1：(0.01-0.3)：(0.01-0.3)：(0.01-0.3)；The dealumination treatment
Temperature be 25-100 DEG C, the time for 0.5-6 it is small when.
Preferably, the condition of dealumination treatment includes described in step c：Molecular sieve, organic is exchanged with the ammonium of dry basis
The weight ratio of acid, inorganic acid and fluosilicic acid is 1：(0.02-0.2)：(0.015-0.2)：(0.015-0.2).
Preferably, the processing of P Modification described in step d includes：Phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid will be selected from
Molecular sieve is impregnated at least one of ammonium phosphorus-containing compound and/or ion exchange.
Preferably, the condition of the calcination process includes：The atmosphere of calcination process is air atmosphere or steam atmosphere；Roasting
It is 400-800 DEG C to burn temperature, when roasting time is 0.5-8 small.
Preferably, the preparation process of the phosphorus aluminium inorganic binder for containing the first clay includes：(1), by alumina source,
One clay is dispersed into the slurries that solid content is 8-45 weight % with water mashing；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 more than 0-
40):(15-40)；(2), in the lower slurries obtained toward step (1) of stirring concentrated phosphoric acid is added according to the part by weight of P/Al=1-6；
(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, is urged after being blended with host agent for hydrocarbon ils
Change cracking reaction, propene yield and Propylene Selectivity can be effectively improved.
Other feature and advantage of the disclosure will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the disclosure is described in detail below.It is it should be appreciated that described herein specific
Embodiment is only used for describing and explaining the disclosure, is not limited to the disclosure.
The present invention provides a kind of assistant for calalytic cracking of propylene enhancing, and on the basis of the butt weight of the auxiliary agent, this is helped
Agent is included with the phosphorous IMF structure molecular screens of dry basis 10-75 weight %, with the phosphorus aluminium of dry basis 3-40 weight %
Inorganic binder, other inorganic binders of the weight of the 1-30 in terms of oxide %, with the second of dry basis 0-60 weight %
Clay, and the addition of 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 %
Agent；Wherein, the phosphorus aluminium inorganic binder is phosphorus aluminium glue and/or the phosphorus aluminium inorganic binder containing the first clay, is contained with described
On the basis of the phosphorus aluminium inorganic binder butt weight of first clay, the phosphorus aluminium inorganic binder for containing the first clay include with
Al2O3Count 15-40 weight % aluminium component, with P2O5Count the phosphorus component of 45-80 weight % and be more than 0 and not with dry basis
More than the first clay of 40 weight %, and its P/Al weight ratio is 1.0-6.0, and pH value 1-3.5, solid content is 15-60 weights
Measure %；The Al distributed constants D of the molecular sieve meets：0.6≤D≤0.85；Wherein, D=Al (S)/Al (C), Al (S) represent to adopt
The inside H in crystal face edge of the zeolite crystal measured with TEM-EDS methods is apart from interior any aluminium for being more than 100 square nanometers regions
Content, Al (C) represent to appoint in the outside H distances of geometric center using crystal face described in the zeolite crystal of TEM-EDS methods measure
Meaning is more than the aluminium content in 100 square nanometers regions, wherein the H arrives the crystal face geometric center distance for the crystal face edge point
10%；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 50-80 body %, and aperture is in 2 nanometers -20 nanometers
The ratio that pore volume accounts for total mesopore volume is more than 85 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 50-
The ratio between 80%, B acid acid amount and L acid acid amounts are 7-30；With P2O5Count and on the basis of the butt weight of molecular sieve, the molecular sieve
Phosphorus content for 0.1-15 weight %.Preferably, the Al distributed constants D of the molecular sieve meets：0.65≤D≤0.82；Described point
The ratio that the mesopore volume of son sieve accounts for total pore volume is 57-70 body %, and aperture is during 2 nanometers -20 nanometers of mesopore volume accounts for always
The ratio of pore volume is more than 90 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 55-70%, B acid acid amounts and L
The ratio between sour amount is 8-25；With P2O5Count and on the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 1-13
Weight %.
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 embodiment, on the basis of the butt weight of the phosphorus aluminium inorganic binder, the phosphorus aluminium is inorganic
Binding agent is included with Al2O3Count 15-40 weight % aluminium component, with P2O5Count the phosphorus component of 45-80 weight % and with butt 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 weights
Measure %；Such as including with Al2O3Count 15-40 weight % aluminium component, with P2O5Count the phosphorus component of 45-80 weight % and with butt
The first clay of weight meter 1-40 weight %；Preferably comprise with Al2O3The aluminium component of 15-35 weight % is counted, with P2O5Count 50-75
The phosphorus component of weight % and the first clay with dry basis 8-35 weight %, its 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 embodiment, on the basis of the butt weight of the phosphorus aluminium inorganic binder, the phosphorus aluminium without
Machine binding agent is included with Al2O3Count 20-40 weight % aluminium component and with P2O5Count the phosphorus component of 60-80 weight %.
IMF structures are the topological structures of molecular sieve, such as IM-5 molecular sieves have IMF structures.
According to the disclosure, the aluminium content using TEM-EDS methods measure molecular sieve be it is well-known to those skilled in the art,
Wherein described geometric center is also well-known to those skilled in the art, can be calculated according to formula, and the present invention is no longer superfluous
State, the geometric center of generally symmetrical figure is the intersection point of each opposed apexes line, for example, conventional rectangular bulk IM-5 molecular sieves length
Point of intersection of the geometric center of square crystal face in opposed apexes line.The crystal face is a face of regular crystal grain, it is described to
Interior and outwardly direction refers both to the direction inwardly or outwardly on the crystal face.
According to the disclosure, it is 2 nanometers -20 nanometers that the mesopore volume of the molecular sieve, which accounts for the ratio of total pore volume and aperture,
The ratio that mesopore volume accounts for total mesopore volume is measured using N2 adsorption BET specific surface area method, and the mesopore volume is general
Finger-hole footpath is more than 2 nanometers of pore volumes for being less than 100 nanometers；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content uses NH3-
TPD methods measure, and the acid site of the strong acid can be NH3Desorption temperature is more than the acid site corresponding to 300 DEG C；It is described
B acid acid amount with L acid acid amount the ratio between use the infrared acid process of pyridine adsorption measure.
According to the disclosure, metallic addition adds in pulping process, it can be the gold in molding auxiliary agent is prepared
The form for belonging to compound introduces, and 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 be 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 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 except the phosphorus aluminium glue
With the inorganic oxide binder for being customarily used in assistant for calalytic cracking or catalyst binder component beyond phosphorus aluminium inorganic binder
In one or more, 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 the first clay with dry basis 8-35 weight %, its P/
Al weight ratios are 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 butt weight of the auxiliary agent, the auxiliary agent can also contain with P2O5Meter is no more than
The phosphorus additive of 5 weight %.The phosphorus additive can be selected from the compound of phosphorus, such as the inorganic compound including phosphorus and have
One or more in machine compound can be soluble easily in water or be insoluble in water or phosphorus compound not soluble in water,
Be selected from the oxide of phosphorus, phosphoric acid, orthophosphates, phosphite, hypophosphites, subphosphate, acid phosphate and
One or more in phosphorous organic compound.Preferable phosphorus compound is phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, phosphoric acid hydrogen
One or more in diammonium and aluminum phosphate.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
In (material i.e. in auxiliary agent in addition to molecular sieve), it can also be present at the same time inside the duct of zeolite, the surface of zeolite and institute
State in host material.Do not include the phosphorus in molecular sieve in the content of phosphorus additive, do not draw including the phosphorus aluminium inorganic binder 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 IMF structure molecular screens, the second clay of 10-45 weight %, other inorganic binders of 5-25 weight %, 1.0-10 weight %
Metallic addition and 0-3 weight % phosphorus additive.
The disclosure also provides a kind of preparation method of the assistant for calalytic cracking of propylene enhancing, and this method includes：By phosphorous IMF
Structure molecular screen, phosphorus aluminium inorganic binder and the mixing of other inorganic binders, add or are added without the second clay, be beaten, spraying is dry
It is dry；Wherein, metallic addition is introduced, introduces or does not introduce phosphorus additive；Using total butt weight of the preparing raw material of auxiliary agent as base
Standard, the preparing raw material of the auxiliary agent is included with the phosphorous IMF structure molecular screens of dry basis 10-75 weight %, with dry basis
The phosphorus aluminium inorganic binder of gauge 3-40 weight %, other inorganic binders of the weight of the 1-30 in terms of oxide %, with dry basis
The second clay of gauge 0-60 weight %, 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, and including or do not include with P2O5Phosphorus additive of the meter no more than 5 weight %；Wherein, it is described
Phosphorus aluminium inorganic binder is phosphorus aluminium glue and/or the phosphorus aluminium inorganic binder containing the first clay, with the phosphorus aluminium for containing the first clay
On the basis of inorganic binder butt weight, the phosphorus aluminium inorganic binder for containing the first clay is included with Al2O3Count 15-40 weights
Measure % aluminium component, with P2O5Count the phosphorus component of 45-80 weight % and be more than 0 and no more than 40 weight %'s with dry basis
First clay, and its P/Al weight ratio is 1.0-6.0, pH value 1-3.5, solid content is 15-60 weight %；The molecular sieve
Al distributed constants D meets：0.6≤D≤0.85；Wherein, D=Al (S)/Al (C), Al (S) represent to measure using TEM-EDS methods
The inside H in crystal face edge of zeolite crystal represent to adopt apart from interior any aluminium content for being more than 100 square nanometers regions, Al (C)
The outside H of geometric center of crystal face is arbitrarily more than 100 square nanometers apart from interior described in the zeolite crystal measured with TEM-EDS methods
The aluminium content in region, wherein the H, which is the crystal face edge point, arrives the 10% of the crystal face geometric center distance；The molecular sieve
Mesopore volume to account for the ratio of total pore volume be 50-80 body %, aperture be 2 nanometers -20 nanometers of mesopore volume account for it is total in hole body
Long-pending ratio is more than 85 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 50-80%, B acid acid amounts and L acid acid
The ratio between amount is 7-30；With P2O5Count and on the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 0.1-15
Weight %.
According to the disclosure, the preparation process of the phosphorous IMF structure molecular screens can include：A, sodium form IMF structural molecules
Sieve carries out desiliconization processing in aqueous slkali, obtains desiliconization molecular sieve；B, gained desiliconization molecular sieve in step a is carried out at ammonium exchange
Reason, obtains ammonium and exchanges molecular sieve；Wherein, counted and on the basis of total butt weight that ammonium exchanges molecular sieve by sodium oxide molybdena, the ammonium
The sodium content for exchanging molecular sieve is less than 0.2 heavy %；C, by step b gained ammonium exchange molecular sieve by fluosilicic acid, organic acid and
Dealumination treatment is carried out in the Compound-acid dealuminzation agent solution of inorganic acid composition, and after being filtered and being washed, obtains dealuminzation molecular sieve；
D, after the dealuminzation molecular sieve of gained in step c being carried out P Modification processing and calcination process, the phosphorous IMF structural molecules are obtained
Sieve.
According to the disclosure, sodium form IMF structure molecular screens be it is well-known to those skilled in the art, can it is commercially available can be voluntarily
Prepare, for example, the preparation process of the sodium form IMF structure molecular screens can include：To use has IMF structures obtained by amine method crystallization
After molecular sieve pulp is filtered and washed, washing molecular sieve is obtained；Wherein, in terms of sodium oxide molybdena and with the washing molecular sieve
On the basis of total butt weight, the sodium content of the washing molecular sieve is less than 3.0 heavy %；By it is described washing molecular sieve be dried and
After air roasting, the sodium form IMF structure molecular screens are obtained.It is described to there is amine method crystallization to refer to carry out hydrothermal crystallizing using template
Prepare molecular sieve, by taking the preparation of IMF molecular sieves as an example, specific document may be referred to Chinese patent CN102452667A,
CN103708491A, CN102452666A and CN103723740A.The air roasting is used to remove the mould in washing molecular sieve
Plate agent, the temperature of the air roasting can be 400-700 DEG C, when the time can be 0.5-10 small.
According to the disclosure, desiliconization processing is used for the part framework silicon atom for removing molecular sieve, and part framework silicon removes,
It is unobstructed to reach molecular sieve pore passage, produces more second hole effects, aqueous slkali described in step a can be inorganic base, be, for example,
It is preferably sodium hydrate aqueous solution selected from sodium hydrate aqueous solution, potassium hydroxide aqueous solution and ammonium hydroxide；Desiliconization described in step a
The condition of processing can include：With the water in the alkali and aqueous slkali in the sodium form IMF structure molecular screens of dry basis, aqueous slkali
Weight ratio can be 1：(0.1-2)：(5-20), is preferably 1：(0.2-1)：(5-20), the temperature of desiliconization processing can be with
Be room temperature to 100 DEG C, when the time can be 0.2-4 small.
According to the disclosure, ammonium exchange processing is well-known to those skilled in the art, and the sodium for reducing in molecular sieve contains
Amount.For example, the condition that the ammonium exchanges processing can include：According to molecular sieve：Ammonium salt：Water=1：(0.1~1)：(5~10)
Weight ratio, molecular sieve is filtered in room temperature to after when ammonium exchange 0.5~3 is small at 100 DEG C, ammonium salt used can be common nothing
Machine ammonium salt, for example, selected from least one of ammonium chloride, ammonium sulfate and ammonium nitrate, the number that ammonium exchanges can repeat 1~3 time,
Until sodium oxide content is less than 0.2 heavy % in molecular sieve.
According to the disclosure, although desiliconization processing can make molecular sieve produce second hole, in desiliconization processing procedure, point
Amorphous chips are inevitably resulted from son sieve, block molecular sieve pore passage, cover activated centre, and molecular sieve table can be made
The relatively rich aluminium in face, is unfavorable for the raising of molecular sieve reaction selectivity, it is therefore desirable to carry out follow-up dealumination treatment, dealumination treatment to it
It is well-known to those skilled in the art, but did not reported and inorganic acid, organic acid and fluosilicic acid are used for dealumination treatment together.Institute
Stating dealumination treatment can carry out once or several times, organic acid can first be exchanged to molecular sieve mixing with the ammonium, then by fluorine
Silicic acid and inorganic acid exchange molecular sieve mixing with the ammonium, you can be exchanged for organic acid first is added ammonium in molecular sieve, then
By fluosilicic acid and inorganic acid, cocurrent adds at a slow speed, or first adds fluosilicic acid and add inorganic acid, is preferably fluosilicic acid and inorganic acid
Cocurrent adds at a slow speed.For example, organic acid described in step c can be selected from ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfo group water
At least one of poplar acid, is preferably oxalic acid or citric acid, more preferably oxalic acid；The inorganic acid can be selected from salt
At least one of acid, sulfuric acid and nitric acid, are preferably hydrochloric acid or sulfuric acid, more preferably hydrochloric acid；The bar of the dealumination treatment
Part can include：The weight ratio of molecular sieve, organic acid, inorganic acid and fluosilicic acid is exchanged as 1 using the ammonium of dry basis：
(0.01-0.3)：(0.01-0.3)：(0.01-0.3), is preferably 1：(0.02-0.2)：(0.015-0.2)：(0.015-0.2)；
The temperature of the dealumination treatment can be 25-100 DEG C, when the time can be 0.5-6 small.Pass through desiliconization processing and Compound-acid dealuminzation
Agent solution dealumination treatment, which is combined, handles IMF structure molecular screens, be distributed the aluminium of molecular sieve, silica alumina ratio, Acidity and
Pore structure has carried out modulation, makes IMF structure molecular screen reamings modified, still with preferable selective activization, so that effectively
Improve the propylene, ethene and BTX yields of IMF structure molecular screens.
According to the disclosure, P Modification processing is well-known to those skilled in the art, for example, P Modification described in step d
Processing can include：At least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate phosphorus-containing compound will be selected to dividing
Son sieve is impregnated and/or ion exchange.
According to the disclosure, calcination process is well-known to those skilled in the art, for example, the condition of the calcination process can
With including：The atmosphere of calcination process is air atmosphere or steam atmosphere；Calcination temperature is 400-800 DEG C, and roasting time is
When 0.5-8 is small.
Washing is well-known to those skilled in the art described in the disclosure, refers generally to wash, it is for instance possible to use 5-10 times
The water of molecular sieve elutes molecular sieve.
According to the disclosure, the preparation process of the phosphorus aluminium inorganic binder for containing the first clay can include：(1), by oxygen
Change silicon source, the first clay and water mashing and be 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 (being more than 0-40):(15-40)；(2), add in the lower slurries obtained toward step (1) of stirring according to the part by weight of P/Al=1-6
Enter concentrated phosphoric acid；In the wherein described P/Al P be phosphoric acid in the phosphorus in terms of simple substance weight, Al be 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 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 plan
At least one of boehmite, the aluminium component in the phosphorus aluminium inorganic binder for containing the first clay are derived from the aluminium oxide
Source.First clay can be one kind in kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomite
Or it is a variety of, it is 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 sources, more preferably 0.03-0.07Kg phosphoric acid/
Minute/Kg alumina sources.
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 of storeroom are improved in journey, avoids and is glued caused by the uneven local moment vigorous reaction heat release overtemperature of material
Tie agent to cure, the adhesive property of obtained binding agent is suitable with the phosphorus al binder for not introducing clay mitigation preparation；And the party
Method introduces clay, the especially rectorite with layer structure, improves the heavy oil conversion performance of carbon monoxide-olefin polymeric, so as to get
Auxiliary agent have it is more preferably selective.
The preparation method for the assistant for calalytic cracking that the disclosure provides, by phosphorous IMF structure molecular screens, phosphorus aluminium inorganic binder
Mixed with other inorganic binders, mashing, its order to feed does not have a particular/special requirement, such as can by phosphorus aluminium inorganic binder,
Other inorganic binders, molecular sieve, the mixing of the second clay (then can be omitted relevant charging step when without the second clay
Suddenly it is beaten), it is preferred that the phosphorus aluminium is added after being first mixed with beating the second clay, molecular sieve and other inorganic binders
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 the slurries spray drying for being beaten and obtaining
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 for the assistant for calalytic cracking that the disclosure is provided, it can be introduced by introducing the form of 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
Roast and introduce after compound, including by auxiliary agent impregnated with metal-containing compound aqueous solution or chemisorbed handle, Ran Houjin
Row separation of solid and liquid (if desired), 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, be preferably 450-650 DEG C, excellent when roasting time can be 0.5-100 small
Elect as 0.5-10 it is small when.The one kind or more of the metallic compound in their inorganic compound and organic compound
Kind, it can be soluble easily in water or be insoluble in water or compound not soluble in water.The example of metallic compound includes gold
The oxide of category, hydroxide, chloride, nitrate, sulfate, phosphate, the organic compound etc. of metal.Preferable metal
One or more of the compound in their chloride, nitrate, sulfate and phosphate.
In the assistant for calalytic cracking that the disclosure is provided, 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 at the same time
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..
The assistant for calalytic cracking preparation method that the disclosure is provided, when containing phosphorus additive in auxiliary agent, the phosphorus adds
Add agent that the combination of one of following method or several method can be used to introduce, but be not limited to these methods and introduce auxiliary agent
In：
1st, phosphorus compound is added in slurries in going to for auxiliary agent spray drying forming；
2nd, after auxiliary agent spray drying forming through dipping or chemisorbed phosphorus compound, through separation of solid and liquid (if desired
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, be preferably 450-650 DEG C, be preferably 0.5-10 small when roasting time can be 0.5-100 small
When.The phosphorus compound can be selected from the one or more in the various inorganic compounds and organic compound of phosphorus.The phosphatization
Compound can be soluble easily in water or be insoluble in water or phosphorus compound not soluble in water.The embodiment bag of phosphorus compound
Include the oxide of phosphorus, phosphoric acid, orthophosphates, phosphite, hypophosphites, phosphorous organic compound etc..Preferable phosphatization is closed
One or more of the thing in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and aluminum phosphate.
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 be present at the same time 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., can during 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 carries
The auxiliary agent of confession accounts for the agent mixture total amount that FCC catalyst is provided with the disclosure and is no more than 30 weight %, is preferably 1-25 weights
%, more preferably 3-15 weight % are measured, the hydrocarbon ils be selected from various petroleum distillates, such as crude oil, reduced crude, decompression residuum, normal
Press wax oil, decompressed wax oil, straight-run gas oil, propane it is light/one or more in de-oiling, wax tailings and coal liquefaction products again.Institute
Beavy metal impurity and sulphur, the nitrogen impurities such as nickel, vanadium can be contained by stating hydrocarbon ils, as the content of sulphur may be up to 3.0 weight %, the content of nitrogen
The content of the metal impurities such as up to 2.0 weight %, vanadium, nickel may be up to 3000ppm.
The assistant for calalytic cracking that the disclosure provides is used in catalytic cracking process, and hydrocarbon oil catalytic cracking condition is urged for conventional
Change cracking conditions.In general, which includes：Reaction temperature is 400-600 DEG C, is preferably 450-550
DEG C, when weight (hourly) space velocity (WHSV) is 8-120 small-1, when being preferably 8-80 small-1, oil ratio (weight ratio) is 1-20, is 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, fluid bed
Answer and carried out in device, riser reactor, multi-reaction-area reactor etc..
The disclosure will be further illustrated by embodiment below, but the disclosure is not therefore any way limited,
Instrument and reagent used by the embodiment of the present disclosure, unless otherwise instructed, be those skilled in the art's common instrument of institute and
Reagent.
The crystallinity of the disclosure is measured using the standard method of ASTM D5758-2001 (2011) e1.
The phosphorus content of the disclosure is measured using GB/T 30905-2014 standard methods.
The TEM-EDS assay methods of the disclosure are referring to the research method of solid catalyst, petrochemical industry, 29 (3), and 2000：
227。
The disclosure always than surface (SBET), mesoporous pore volume, total pore volume, 2-20 nanometers mesoporous pore volume use
The AS-3 of Quantachrome instrument companies production, AS-6 static state n2 absorption apparatus measure.Instrument parameter：Sample is placed at sample
Reason system, 1.33 × 10 are evacuated 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 mesopore surface area are calculated using two parameter BET formula, taken than pressing P/P0=
Less than 0.98 adsorbance is the total pore volume of sample, and the pore-size distribution of mesoporous part is calculated using BJH formula, and using integration
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 of U.S. Autochem
It is measured.Test condition：Weigh 0.2g samples to be tested and load sample cell, be placed in conductance cell heating furnace, He gas is carrier gas
(50mL/min), is warming up to 600 DEG C, purging 60min drives away the impurity of catalyst surface absorption with the speed of 20 DEG C/min.Then
100 DEG C are cooled to, constant temperature 30min, switches to NH3- He gaseous mixtures (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-blowings, to be desorbed the ammonia of physical absorption.600 DEG C are warming up to 10 DEG C/min heating rates
It is desorbed, keeps 30min, desorption terminates.Using TCD detector detection gas change of component, instrument automatic integration obtains always
Acid amount and strong acid acid amount, the acid site of strong acid is NH3Desorption temperature is more than the acid site corresponding to 300 DEG C.
The B acid acid amounts of the disclosure and L acid acid amounts are infrared using the FTS3000 type Fourier of BIO-RAD companies of U.S. 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 totally, is cooled to room temperature.Imported into pond in situ
Pressure is the pyridine steam of 2.67Pa, after balancing 30min, is warming up to 200 DEG C, is evacuated to 10 again-3Pa, keeps 30min, cold
But to room temperature, in 1400-1700cm-1Scanning in wave-number range, records the infrared spectrum spectrogram of 200 DEG C of pyridine adsorptions.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 amounts and L acid acid amounts.
The sodium content of the disclosure is measured using GB/T 30905-2014 standard methods.
The computational methods of D values are as follows：A crystal grain is chosen 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 values are different), choose respectively any one piece in the inside H distances in the crystal face edge be more than 100 square nanometers regions with
And any one piece in the outside H distances of crystal face geometric center is more than 100 square nanometers regions, measures aluminium content, is Al (S1)
With Al (C1), and D1=Al (S1)/Al (C1) is calculated, choose different crystal grain respectively and measure 5 times, it is D to calculate average value.
For the auxiliary agent of the disclosure when 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 detectors) 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 methods
Test), the cut cut point of gasoline and diesel oil is respectively 221 DEG C and 343 DEG C；Green coke catalyst on-line decoking regenerates, and according to
Flue gas flow and composition calculate coke quality；All product quality adductions calculate material balance.
RIPP standard methods described in the disclosure for details, reference can be made to《Petrochemical Engineering Analysis method》, Yang Cui surely compile by grade, and 1990
Year version.
Part material property used is as follows in embodiment：
Boehmite produces industrial products, 60 weight % of solid content for Shandong Aluminium Industrial Corp；Aluminum sol is urged for sinopec
The industrial products of agent asphalt in Shenli Refinery production, Al2O3Content is 21.5 weight %；Ludox is sinopec catalyst Shandong point
The industrial products of company's production, SiO2Content is 28.9 weight %, Na2O content 8.9%；Kaolin is given birth to for Kaolin of Suzhou company
The special kaolin of 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. of 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 powders：Germany
Condex companies produce, Al2O3Content is 75 weight %；Gamma oxidation aluminium powder：German Condex companies production, Al2O3Content is
95 weight %.Hydrochloric acid：Chemistry is pure, and concentration is 36-38 weight %, and Beijing Chemical Plant produces.
Embodiment 1-2 provides the phosphorous IMF structure molecular screens of the disclosure, and comparative example 1-7 provides contrast molecular sieve.
Embodiment 1
The good IM-5 molecular sieves of crystallization (production of Chang Ling catalyst plant) are filtered out into mother liquor, washing filtering drying；Will be above-mentioned
After drying molecular sieve roasted in air 6 it is small when, 550 DEG C of calcination temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 2.4 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room
Wen Hou, filtering, is washed neutral to filtrate.Then, filter cake is added into the mashing of 800g water, adds 40gNH4Cl, is warming up to 75 DEG C, hands over
After changing processing 1h, to Na2O content is less than 0.2 weight %, filters, and washing, obtains molecular sieve filter cake；Take above-mentioned molecular sieve filter cake
50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 5g are added in stirring, then by 35g hydrochloric acid (matter
Measure fraction 10%) and the addition of 28g fluosilicic acid (mass fraction 3%) cocurrent, add time 30min；It is warming up to 65 DEG C of constant temperature stirrings
1h, filtering are washed to filtrate neutrality；By filter cake plus water be beaten solid content for 40 weight % molecular sieve pulps, add 6.3g
H3PO4(85 weight % of concentration), is uniformly mixed with dipping, dries, 550 DEG C of calcination process 2h.Molecular sieve-4 A is obtained, physico-chemical property is listed in table
1。
Comparative example 1
The good IM-5 molecular sieves of crystallization (production of Chang Ling catalyst plant) are filtered out into mother liquor, washing filtering drying；Will be above-mentioned
After drying molecular sieve roasted in air 8 it is small when, 550 DEG C of calcination temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 1000g 2.4%, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room temperature
Afterwards, filter, wash neutral to filtrate.Then, filter cake is added into the mashing of 800g water, adds 40g NH4Cl, is warming up to 75 DEG C, hands over
After changing processing 1h, to Na2O content is less than 0.2 weight %, filters, and washing, obtains molecular sieve filter cake；Take above-mentioned molecular sieve 50g
(butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, and oxalic acid 20g is added in stirring；It is warming up to 65 DEG C of constant temperature stirrings
1h, filtering are washed to filtrate neutrality；By filter cake plus water be beaten solid content for 40 weight % molecular sieve pulps, add 6.1gH3PO4
(85 weight % of concentration), when uniformly hybrid infusion, drying, 550 DEG C of calcination process 2 are small.Molecular sieve DA1 is obtained, physico-chemical property is listed in
Table 1.
Comparative example 2
The good IM-5 molecular sieves of crystallization (production of Chang Ling catalyst plant) are filtered out into mother liquor, washing filtering drying；Will be above-mentioned
After drying molecular sieve roasted in air 8 it is small when, 550 DEG C of calcination temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 2.2 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room
Wen Hou, filtering, is washed neutral to filtrate.Then obtained molecular sieve filter cake is added in HCl/water solution and is washed, specific behaviour
As taking above-mentioned molecular sieve filter cake 50g (butt) plus water to be configured to the molecular sieve pulp of the weight of solid content 10 %, added in stirring
180g 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 adds 1500g
Water is beaten, and adds 80g NH4After Cl is warming up to 65 DEG C of exchange washing 40min, filtering, elutes neutral to filtrate；By filter cake plus water
Be beaten solid content for 40 weight % molecular sieve pulps, add 6.3gH3PO4(85 weight % of concentration), is uniformly mixed with dipping, dries
It is dry, when 550 DEG C of calcination process 2 are small.Molecular sieve DA2 is obtained, physico-chemical property is listed in table 1.
Comparative example 3
The good IM-5 molecular sieves of crystallization (production of Chang Ling catalyst plant) are filtered out into mother liquor, washing filtering drying；Will be above-mentioned
After drying molecular sieve roasted in air 8 it is small when, 550 DEG C of calcination temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 2.2 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room
Wen Hou, filtering, is washed neutral to filtrate.Then, filter cake is added into the mashing of 800g water, adds 40gNH4Cl, is warming up to 75 DEG C, hands over
After changing processing 1h, to Na2O content is less than 0.2 weight %, filters, and washing, obtains molecular sieve filter cake；Take above-mentioned molecular sieve filter cake
50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, and 135g fluosilicic acid (mass fractions are added in stirring
3%) 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, which are beaten, to be consolidated
Content is the molecular sieve pulp of 40 weight %, adds 6.3gH3PO4(85 weight % of concentration), is uniformly mixed with dipping, dries, 550 DEG C of roastings
When burning processing 2 is small.Molecular sieve DA3 is obtained, physico-chemical property is listed in table 1.
Comparative example 4
The good IM-5 molecular sieves of crystallization (production of Chang Ling catalyst plant) are filtered out into mother liquor, washing filtering drying；Will be above-mentioned
After drying molecular sieve roasted in air 8 it is small when, 550 DEG C of calcination temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 1.9 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room
Wen Hou, filtering, is washed neutral to filtrate.Then, filter cake is added into the mashing of 800g water, adds 40gNH4Cl, is warming up to 75 DEG C, hands over
After changing processing 1h, to Na2O content is less than 0.2 weight %, filters, and washing, obtains molecular sieve filter cake；Take above-mentioned molecular sieve filter cake
50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 11g are added in stirring, then by 110g hydrochloric acid
(mass fraction 10%) adds, and adds time 30min；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Will filter
Cake add water be beaten solid content for 40 weight % molecular sieve pulps, add 6.3gH3PO4(85 weight % of concentration), uniformly mixing leaching
When stain, drying, 550 DEG C of calcination process 2 are small.Molecular sieve DA4 is obtained, physico-chemical property is listed in table 1.
Comparative example 5
The good IM-5 molecular sieves of crystallization (production of Chang Ling catalyst plant) are filtered out into mother liquor, washing filtering drying；Will be above-mentioned
After drying molecular sieve roasted in air 8 it is small when, 550 DEG C of calcination temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 2.0 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room
Wen Hou, filtering, is washed neutral to filtrate.Then, filter cake is added into the mashing of 800g water, adds 40gNH4Cl, is warming up to 75 DEG C, hands over
After changing processing 1h, to Na2O content is less than 0.2 weight %, filters, and washing, obtains molecular sieve filter cake；Take above-mentioned molecular sieve filter cake
50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 4g are added in stirring, then by 72g fluosilicic acid
(mass fraction 3%) is slowly added to, and adds time 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 for 40 weight % molecular sieve pulps, add 6.3gH3PO4(85 weight % of concentration), it is uniformly mixed
When conjunction dipping, drying, 550 DEG C of calcination process 2 are small.Molecular sieve DA5 is obtained, physico-chemical property is listed in table 1.
Comparative example 6
The good IM-5 molecular sieves of crystallization (production of Chang Ling catalyst plant) are filtered out into mother liquor, washing filtering drying；Will be above-mentioned
After drying molecular sieve roasted in air 8 it is small when, 550 DEG C of calcination temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 2.0 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room
Wen Hou, filtering, is washed neutral to filtrate.Then, filter cake is added into the mashing of 800g water, adds 40gNH4Cl, is warming up to 75 DEG C, hands over
After changing processing 1h, to Na2O content is less than 0.2 weight %, filters, and washing, obtains molecular sieve filter cake；Take above-mentioned molecular sieve filter cake
50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, under stirring by 42g hydrochloric acid (mass fraction 10%) and
78g fluosilicic acid (mass fraction 3%) cocurrent adds, and adds time 30min；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to
Filtrate is neutral；By filter cake plus water be beaten solid content for 40 weight % molecular sieve pulps, add 6.3gH3PO4(85 weight of concentration
Measure %), when uniformly hybrid infusion, drying, 550 DEG C of calcination process 2 are small.Molecular sieve DA6 is obtained, physico-chemical property is listed in table 1.
Comparative example 7
The good IM-5 molecular sieves of crystallization (production of Chang Ling catalyst plant) are filtered out into mother liquor, washing filtering drying；By above-mentioned baking
After dry molecular sieve roasted in air 8 it is small when, 550 DEG C of calcination temperature, to remove template therein.Take above-mentioned molecular sieve 100g
Add in the NaOH solution of 1.2 weight % of 2000g, be warming up to 65 DEG C, after reacting 30min, be quickly cooled to room temperature, filter, wash
Wash neutral to filtrate.Take above-mentioned molecular sieve filter cake 50g (butt) to add the mashing of 500g water, add 40g NH4Cl, is warming up to 75
DEG C, after exchanging processing 1h, filtering, repeated exchanged, which is washed twice to molecular sieve sodium oxide content, is less than 0.1%, and filter cake plus water are beaten
Starch solid content for 40 weight % molecular sieve pulps, add 6.3gH3PO4(85 weight % of concentration), be uniformly mixed with dipping, dry,
550 DEG C of calcination process 2 obtain molecular sieve DA7 when small, physico-chemical property is listed in table 1.
Embodiment 2
The good IM-5 molecular sieves of crystallization (production of Chang Ling catalyst plant) are filtered out into mother liquor, washing filtering drying；Will be above-mentioned
After drying molecular sieve roasted in air 8 it is small when, 550 DEG C of calcination temperature, to remove template therein；Take above-mentioned molecular sieve
100g (butt) is added in the NaOH solution of 2.3 weight % of 1500g, is warming up to 60 DEG C, after reacting 45min, is quickly cooled to room
Wen Hou, filtering, is washed neutral to filtrate.Then, filter cake is added into the mashing of 800g water, adds 40gNH4Cl, is warming up to 75 DEG C, hands over
After changing processing 1h, to Na2O content is less than 0.2 weight %, filters, and washing, obtains molecular sieve filter cake；Take above-mentioned molecular sieve filter cake
50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 4g are added in stirring, then 10g sulfuric acid (matter
Measure fraction 10%) and the addition of 45g fluosilicic acid (mass fraction 3%) cocurrent, add time 30min；It is warming up to 45 DEG C of constant temperature stirrings
1h, filtering are washed to filtrate neutrality；By filter cake plus water be beaten solid content for 40 weight % molecular sieve pulps, add 6.3gH3PO4
(85 weight % of concentration), when uniformly hybrid infusion, drying, 550 DEG C of calcination process 2 are small.Molecular sieve B is obtained, physico-chemical property is listed in table
1。
Conventional alkali process will make IM-5 molecular sieve surface richness aluminium it can be seen from data in table 1, using single organic acid
Oxalic acid dealuminzation (DA1) uses single inorganic acid HCl dealumination (DA2) and uses two kinds of organic acid oxalic acid and inorganic acid hydrochloric acid
Sour compound (DA4) effectively can not all remove the Al in molecular sieve, molecular sieve still surface richness aluminium and only used fluorine silicon
Preferable dealuminzation effect could be obtained after acid, improves the distribution of molecular sieve aluminium.When fluosilicic acid dealuminzation is used alone (DA3), Ke Yigai
The aluminium distribution of kind molecular sieve, but mesoporous is relatively fewer, strong acid proportion in total acid is relatively low, and B acid/L acid ratios are relatively low.Fluorine
Silicic acid composite organic acid oxalic acid dealuminzation (DA5), can not equally obtain 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/
L acid ratio is all be not as high as molecular sieve provided by the invention.After the present invention to molecular sieve using first desiliconization processing is carried out, reuse multiple
Acid system is closed, dealumination treatment is carried out under three kinds of sour synergistic effects, can ensure crystal structure of molecular sieve and mesopore orbit
Improve aluminium distribution and acid distribution on the premise of structural intergrity.
Embodiment 3-6 provides phosphorus aluminium inorganic binder used in the disclosure.
Embodiment 3
The present embodiment prepares the 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 adds 5.37 kilograms of concentrated phosphoric acids (mass concentration 85%) in descending toward slurries,
It is 0.04Kg phosphoric acid/minute/Kg alumina sources that phosphoric acid, which adds speed, is warming up to 70 DEG C, is then reacted 45 minutes at this temperature,
Phosphorus aluminium inorganic binder is made.Material proportion is shown in Table 2, obtains binding agent Binder1.
Embodiment 4-6
Phosphorus aluminium inorganic binder is prepared as described in Example 3, and material proportion is shown in Table 2, obtains binding agent Binder2-4.
Embodiment 7-11 provides the assistant for calalytic cracking of the disclosure, and comparative example 8-14 provides contrast assistant for calalytic cracking.
Embodiment 7
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, add hydrochloric acid
The pH value 3.0 of slurries is adjusted, then proceedes to mashing 45 minutes, then adds phosphorus aluminium inorganic binder prepared by embodiment 3, stirring
After 30 minutes, obtained slurries are spray-dried, obtain microballoon, microballoon roast at 500 DEG C 1 it is small when, obtained ZJ1, it is matched somebody with somebody
Than being shown in Table 3.
Embodiment 8
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, add hydrochloric acid
The pH value 3.0 of slurries is adjusted, then proceedes to mashing 45 minutes, then adds phosphorus aluminium inorganic binder prepared by embodiment 3, stirring
After 30 minutes, obtained slurries are spray-dried, obtain microballoon, microballoon roast at 500 DEG C 1 it is small when, obtained ZJ2, it is matched somebody with somebody
Than being shown in Table 3.
Embodiment 9
Molecular sieve-4 A, kaolin and boehmite are taken, decationized Y sieve water is added and Aluminum sol is beaten 120 minutes, obtain
The slurries of 30 weight % of solid content, add the pH value 3.0 that hydrochloric acid adjusts slurries, then proceed to mashing 45 minutes, then add real
Apply example 4 preparation phosphorus aluminium inorganic binder, stirring 30 minutes after, by obtained slurries be spray-dried, obtain microballoon, by microballoon in
When roasting 1 is small at 500 DEG C.Thus obtained microsphere product is taken, adds ZnCl2Aqueous solution (30 weight % of concentration), 60 are warming up under stirring
DEG C, react at this temperature after twenty minutes, by slurries vacuum filter, drying, when then roasting 2 is small at 500 DEG C, ZJ is made3,
Its proportioning is shown in Table 3.
Embodiment 10
Molecular sieve-4 A, kaolin and boehmite are taken, decationized Y sieve water is added and Ludox 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, adds hydrochloric acid tune
The pH value 3.0 of slurries is saved, then proceedes to mashing 45 minutes, then adds phosphorus aluminium inorganic binder prepared by embodiment 5, stirring 30
After minutes, obtained slurries are spray-dried, obtain microballoon, microballoon roast at 500 DEG C 1 it is small when, obtained ZJ4, it is matched
It is 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, stirring
Lower addition Ga (NO3)3Aqueous solution (30 weight % of concentration), obtain the slurries of 30 weight % of solid content, add hydrochloric acid and adjust slurries
PH value 2.5, then proceed to mashing 45 minutes, then add embodiment 6 prepare phosphorus aluminium inorganic binder, stir 30 minutes
Afterwards, obtained slurries are spray-dried, obtain microballoon.Thus obtained microsphere product is added into the phosphoric acid hydrogen two that concentration is 7.5 weight %
In aqueous ammonium, 60 DEG C are warming up under stirring, is reacted at this temperature after twenty minutes, by slurries vacuum filter, drying, Ran Houyu
When roasting 2 is small at 500 DEG C, auxiliary agent ZJ is made5, auxiliary agent proportioning be shown in Table 3.
Comparative example 8-14
Method as described in embodiment 7 prepares assistant for calalytic cracking, be a difference in that with molecular sieve DA1, DA2, DA3,
DA4, DA5, DA6, DA7 substitute A respectively, and auxiliary agent DZJ is made1-DZJ7, its proportioning is shown in Table 3.
Skip test example, embodiment 12-16 are using small fixed flowing bed-tion reacting device to 100% poising agent and balance
Auxiliary agent ZJ prepared by the agent incorporation embodiment of the present disclosure1-ZJ5Reactivity worth evaluation is carried out, to illustrate that the catalysis that the disclosure provides is split
Change the catalytic cracking reaction effect of auxiliary agent.
Skip test example, embodiment 12-16
Respectively by auxiliary agent ZJ1-ZJ5Burin-in process when progress 17 is small under the conditions of 800 DEG C, 100% steam atmosphere.Take
ZJ through burin-in process1-ZJ6With industrial FCC equilibrium catalysts (the industrial trade mark be DVR-3 FCC equilibrium catalysts, micro-activity
63) to mix respectively.100% poising agent and catalyst mixture are fitted into small fixed flowing bed reactor, to shown in table 4
Feedstock oil carries out catalytic cracking, and reaction condition is：500 DEG C of reaction temperature, weight (hourly) space velocity (WHSV) 8h-1, agent weight of oil is than 6.Table 5 gives
The weight composition and reaction result of each catalyst mixture.
Comparative example 15-21 is using small fixed flowing bed-tion reacting device to prepared by poising agent incorporation disclosure comparative example
Auxiliary agent DZJ1-DZJ7Performance evaluation is carried out, to illustrate the situation using contrast auxiliary agent.
Comparative example 15-21
Catalytic cracking is carried out to same feedstock oil by the method in embodiment 12, the difference is that used catalyst is respectively
Auxiliary agent DZJ after identical aging method aging in embodiment 121-DZJ7With the mixture of industrial FCC equilibrium catalysts.Table 5
Give the weight composition and reaction result of each catalyst mixture.
As can be seen from Table 5, compared with contrasting auxiliary agent, the catalyst aid of disclosure offer, can effectively increase catalysis and split
Change propylene and liquefied gas yield, while significantly increase the density of propylene in catalytic cracking liquefied gas.
Table 1
| Molecular sieve | A | DA1 | DA2 | DA3 | DA4 | DA5 | DA6 | DA7 | B |
| Crystallinity/% | 87 | 80 | 78 | 83 | 83 | 83 | 85 | 83 | 90 |
| P2O5Content/% | 7.5 | 7.2 | 7.5 | 7.5 | 7.5 | 7.5 | 7.5 | 7.5 | 7.5 |
| SBET/(m2/g) | 510 | 462 | 451 | 473 | 469 | 477 | 491 | 413 | 521 |
| (VMesoporous/VTotal hole)/% | 60.4 | 53.8 | 54.7 | 57.1 | 54.5 | 56.8 | 57.8 | 52.7 | 62.3 |
| (V2nm-20nm/VMesoporous)/% | 90 | 80 | 80 | 86 | 77 | 82 | 82 | 63 | 92 |
| (strong acid acid amount/total acid content)/% | 63 | 48 | 47 | 56 | 45 | 58 | 55 | 40 | 65 |
| The sour amount of B acid/L acid acid amounts | 13 | 4.9 | 5.0 | 8 | 5.0 | 10.1 | 9.2 | 2.3 | 14.2 |
| D (Al distributions) | 0.75 | 1.1 | 1.1 | 0.95 | 1.1 | 0.87 | 0.91 | 1.1 | 0.80 |
Table 2
Table 3
Table 4
| Project | Numerical value | Project | Numerical value |
| Density (20 DEG C)/(gcm-3) | 0.9104 | Boiling range/DEG C | |
| Refractive index (70 DEG C) | 1.4917 | Initial boiling point | 251 |
| Viscosity (80 DEG C)/(mm2·s-1) | 18.54 | 5% | 325 |
| Viscosity (100 DEG C)/(mm2·s-1) | 10.89 | 10% | 355 |
| Solidification point/DEG C | 38 | 30% | 416 |
| Carbon residue/weight % | 3.1 | 50% | 452 |
| Four component compositions/weight % | The end point of distillation | 544 | |
| Saturated hydrocarbons | 63.7 | Tenor/(μ gg-1) | |
| Aromatic hydrocarbons | 21.6 | Al | 0.6 |
| Colloid | 14.5 | Ca | 21.5 |
| Asphalitine | 0.2 | Fe | 16.4 |
| Element composition/weight % | Mg | 0.6 | |
| C | 86.12 | Na | 1.8 |
| H | 12.64 | Ni | 7.9 |
| S | 0.65 | V | 0.6 |
| N | 0.277 | Pb | 2.1 |
Table 5
Claims (18)
1. a kind of assistant for calalytic cracking of propylene enhancing, on the basis of the butt weight of the auxiliary agent, which is included with butt
The phosphorous IMF structure molecular screens of weight meter 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 second clay of dry basis 0-60 weight %, and with oxygen
The metallic addition selected from least one of VIII race's metal and manganese, zinc, gallium of compound meter 0.5-15 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 butt weight of clay, the phosphorus aluminium inorganic binder for containing the first clay is included with Al2O3Meter
15-40 weight % aluminium component, with P2O5Count the phosphorus component of 45-80 weight % and be more than 0 with dry basis and be 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 %；
The Al distributed constants D of the molecular sieve meets：0.6≤D≤0.85；Wherein, D=Al (S)/Al (C), Al (S) represent to adopt
The inside H in crystal face edge of the zeolite crystal measured with TEM-EDS methods is apart from interior any aluminium for being more than 100 square nanometers regions
Content, Al (C) represent to appoint in the outside H distances of geometric center using crystal face described in the zeolite crystal of TEM-EDS methods measure
Meaning is more than the aluminium content in 100 square nanometers regions, wherein the H arrives the crystal face geometric center distance for the crystal face edge point
10%；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 50-80 body %, and aperture is in 2 nanometers -20 nanometers
The ratio that pore volume accounts for total mesopore volume is more than 85 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 50-
The ratio between 80%, B acid acid amount and L acid acid amounts are 7-30；With P2O5Count and on the basis of the butt weight of molecular sieve, the molecular sieve
Phosphorus content for 0.1-15 weight %.
2. auxiliary agent according to claim 1, wherein, the Al distributed constants D of the molecular sieve meets：0.65≤D≤0.82；
The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 57-70 body %, and aperture is 2 nanometers -20 nanometers of mesopore volume
The ratio for accounting for total mesopore volume is more than 90 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 55-70%, and B is sour
The ratio between acid amount and L acid acid amounts are 8-25；With P2O5Count and on the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve
For 1-13 weights %.
3. 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 binding agents are thin selected from intending
At least one of diaspore, Aluminum sol, silicon-aluminum sol and waterglass.
4. 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 thing.
5. according to the auxiliary agent described in any one in claim 1-4, wherein, on the basis of the butt weight of the auxiliary agent, institute
Auxiliary agent is stated also to contain with P2O5Phosphorus additive of the meter no more than 5 weight %.
6. auxiliary agent according to claim 5, wherein, the auxiliary agent includes phosphorus aluminium inorganic binder, the 20- of 8-25 weight %
The phosphorous IMF structure molecular screens of 60 weight %, 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 %.
7. a kind of preparation method of the assistant for calalytic cracking of propylene enhancing, this method include：
Phosphorous IMF structure molecular screens, phosphorus aluminium inorganic binder and other inorganic binders are mixed, adds or is added without second and glue
Soil, is beaten, spray drying；Wherein, metallic addition is introduced, introduces or does not introduce phosphorus additive；
On the basis of total butt weight of the preparing raw material of auxiliary agent, the preparing raw material of the auxiliary agent is included with dry basis 10-
The phosphorous IMF structure molecular screens of 75 weight %, with the phosphorus aluminium inorganic binder of dry basis 3-40 weight %, in terms of oxide
Other inorganic binders of 1-30 weight %, with the second clay of dry basis 0-60 weight %, the 0.5-15 in terms of oxide
The metallic addition selected from least one of VIII race's metal and manganese, zinc, gallium of weight %, and including or do not include with P2O5
Phosphorus additive of the meter no more than 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 butt weight of clay, the phosphorus aluminium inorganic binder for containing the first clay is included with Al2O3Meter
15-40 weight % aluminium component, with P2O5Count the phosphorus component of 45-80 weight % and be more than 0 with dry basis and be 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 %；
The Al distributed constants D of the molecular sieve meets：0.6≤D≤0.85；Wherein, D=Al (S)/Al (C), Al (S) represent to adopt
The inside H in crystal face edge of the zeolite crystal measured with TEM-EDS methods is apart from interior any aluminium for being more than 100 square nanometers regions
Content, Al (C) represent to appoint in the outside H distances of geometric center using crystal face described in the zeolite crystal of TEM-EDS methods measure
Meaning is more than the aluminium content in 100 square nanometers regions, wherein the H arrives the crystal face geometric center distance for the crystal face edge point
10%；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 50-80 body %, and aperture is in 2 nanometers -20 nanometers
The ratio that pore volume accounts for total mesopore volume is more than 85 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 50-
The ratio between 80%, B acid acid amount and L acid acid amounts are 7-30；With P2O5Count and on the basis of the butt weight of molecular sieve, the molecular sieve
Phosphorus content for 0.1-15 weight %.
8. preparation method according to claim 7, wherein, the preparation process of the phosphorous IMF structure molecular screens includes：
A, sodium form IMF structure molecular screens carry out desiliconization processing in aqueous slkali, obtain desiliconization molecular sieve；
B, gained desiliconization molecular sieve in step a is subjected to ammonium exchange processing, obtains ammonium and exchange molecular sieve；Wherein, in terms of sodium oxide molybdena
And on the basis of total butt weight that ammonium exchanges molecular sieve, the sodium content that the ammonium exchanges molecular sieve is less than 0.2 heavy %；
C, it is gained ammonium exchange molecular sieve in step b 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 being washed, obtains dealuminzation molecular sieve；
D, after the dealuminzation molecular sieve of gained in step c being carried out P Modification processing and calcination process, the phosphorous IMF structures are obtained
Molecular sieve.
9. preparation method according to claim 8, wherein, the preparation process of sodium form IMF structure molecular screens described in step a
Including：
It will use after thering are IMF structure molecular screen slurries obtained by amine method crystallization to be filtered and washed, and obtain washing molecular sieve；Its
In, counted by sodium oxide molybdena and on the basis of total butt weight of the washing molecular sieve, the sodium content of the washing molecular sieve is less than
3.0 heavy %；
The washing molecular sieve is dried and after air roasting, obtains the sodium form IMF structure molecular screens.
10. preparation method according to claim 8, wherein, aqueous slkali described in step a is water-soluble selected from sodium hydroxide
Liquid, potassium hydroxide aqueous solution and ammonium hydroxide.
11. preparation method according to claim 8, wherein, the condition of the processing of desiliconization described in step a includes：With butt
The weight ratio of the water in alkali and aqueous slkali in the sodium form IMF structure molecular screens of weight meter, aqueous slkali is 1：(0.1-2)：(5-
20), the temperature of desiliconization processing is room temperature to 100 DEG C, the time for 0.2-4 it is small when.
12. preparation method according to claim 8, wherein, the condition of the processing of desiliconization described in step a includes：With butt
The weight ratio of the water in alkali and aqueous slkali in the sodium form IMF structure molecular screens of weight meter, aqueous slkali is 1：(0.2-1)：(5-
20)。
13. preparation method according to claim 8, wherein, organic acid described in step c 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 8, wherein, the condition of dealumination treatment includes described in step c：With butt
The weight ratio that the ammonium of weight meter exchanges molecular sieve, organic acid, inorganic acid and fluosilicic acid is 1：(0.01-0.3)：(0.01-
0.3)：(0.01-0.3)；The temperature of the dealumination treatment is 25-100 DEG C, when the time is 0.5-6 small.
15. preparation method according to claim 8, wherein, the condition of dealumination treatment includes described in step c：With butt
The weight ratio that the ammonium of weight meter exchanges molecular sieve, organic acid, inorganic acid and fluosilicic acid is 1：(0.02-0.2)：(0.015-
0.2)：(0.015-0.2).
16. preparation method according to claim 8, wherein, the processing of P Modification described in step d includes：Will be selected from phosphoric acid,
At least one of ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate phosphorus-containing compound impregnates molecular sieve and/or ion is handed over
Change.
17. preparation method according to claim 8, wherein, the condition of the calcination process includes：The atmosphere of calcination process
For air atmosphere or steam atmosphere；Calcination temperature is 400-800 DEG C, when roasting time is 0.5-8 small.
18. preparation method according to claim 7, 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 for can by the aluminium hydroxide and/or aluminium oxide of sour peptization, with the first clay of dry basis with Al2O3The oxidation of meter
The weight ratio of silicon source is (being more than 0-40):(15-40)；
(2), in the lower slurries obtained toward step (1) of stirring concentrated phosphoric acid is added according to the part by weight of P/Al=1-6；
(3), the slurries that step (2) obtains are reacted 15-90 minutes at a temperature of 50-99 DEG C.
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| CN103007989A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Cracking assistant for improving low-carbon olefin concentration |
| CN105732349A (en) * | 2014-12-12 | 2016-07-06 | 中国科学院大连化学物理研究所 | Method for preparing anhydrous formaldehyde through methanol dehydrogenation |
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| US20030181325A1 (en) * | 2002-03-22 | 2003-09-25 | Ou John Di-Yi | Combined oxydehydrogenation and cracking catalyst for production of olefins |
| WO2009092779A3 (en) * | 2008-01-25 | 2009-09-17 | Total Petrochemicals Research Feluy | Process for obtaining a catalyst composite |
| CN102616804A (en) * | 2011-01-27 | 2012-08-01 | 中国石油化工股份有限公司 | Copper-containing beta molecular sieve and preparation method thereof |
| CN103007989A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Cracking assistant for improving low-carbon olefin concentration |
| CN105732349A (en) * | 2014-12-12 | 2016-07-06 | 中国科学院大连化学物理研究所 | Method for preparing anhydrous formaldehyde through methanol dehydrogenation |
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