TWI400124B - 可移除金屬污染物的添加劑 - Google Patents
可移除金屬污染物的添加劑 Download PDFInfo
- Publication number
- TWI400124B TWI400124B TW094130936A TW94130936A TWI400124B TW I400124 B TWI400124 B TW I400124B TW 094130936 A TW094130936 A TW 094130936A TW 94130936 A TW94130936 A TW 94130936A TW I400124 B TWI400124 B TW I400124B
- Authority
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- Taiwan
- Prior art keywords
- catalytic cracking
- metal
- catalyst
- zeolite
- additive
- Prior art date
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- 239000000654 additive Substances 0.000 title claims description 119
- 229910052751 metal Inorganic materials 0.000 title claims description 97
- 239000002184 metal Substances 0.000 title claims description 97
- 239000000356 contaminant Substances 0.000 title description 19
- 239000003054 catalyst Substances 0.000 claims description 216
- 230000000996 additive effect Effects 0.000 claims description 105
- 238000004523 catalytic cracking Methods 0.000 claims description 96
- 239000000463 material Substances 0.000 claims description 92
- 239000010457 zeolite Substances 0.000 claims description 87
- 229910021536 Zeolite Inorganic materials 0.000 claims description 80
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 80
- 239000000203 mixture Substances 0.000 claims description 56
- 230000000694 effects Effects 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 48
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 26
- 239000011777 magnesium Substances 0.000 claims description 23
- 229910052749 magnesium Inorganic materials 0.000 claims description 20
- 238000005336 cracking Methods 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- -1 hydrotalcite compound Chemical class 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 7
- 229960001545 hydrotalcite Drugs 0.000 claims description 7
- 239000012013 faujasite Substances 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 238000003776 cleavage reaction Methods 0.000 claims description 3
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 claims description 3
- 230000007017 scission Effects 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 2
- 125000000129 anionic group Chemical group 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000000571 coke Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 12
- 229910052761 rare earth metal Inorganic materials 0.000 description 12
- 239000011701 zinc Chemical group 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 12
- 229910052746 lanthanum Inorganic materials 0.000 description 11
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- 239000000047 product Substances 0.000 description 11
- 239000006104 solid solution Substances 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 150000002910 rare earth metals Chemical class 0.000 description 10
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- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 229910052684 Cerium Inorganic materials 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
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- 230000001174 ascending effect Effects 0.000 description 8
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 229910052787 antimony Inorganic materials 0.000 description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 229910052741 iridium Inorganic materials 0.000 description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
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- 230000001965 increasing effect Effects 0.000 description 5
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 5
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- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
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- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 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 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
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- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
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- 238000002156 mixing Methods 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
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- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000002909 rare earth metal compounds Chemical class 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
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- 239000010937 tungsten Substances 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
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- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- FWKZJUMOSAVEBB-UHFFFAOYSA-I [V+5].[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12 Chemical compound [V+5].[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12 FWKZJUMOSAVEBB-UHFFFAOYSA-I 0.000 description 1
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- 230000002411 adverse Effects 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 230000002308 calcification Effects 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 description 1
- 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 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- GMDNUWQNDQDBNQ-UHFFFAOYSA-L magnesium;diformate Chemical compound [Mg+2].[O-]C=O.[O-]C=O GMDNUWQNDQDBNQ-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
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- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- WTQSPDBNCMUOKF-UHFFFAOYSA-L naphthalene-1-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 WTQSPDBNCMUOKF-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Description
本發明係關於可減輕金屬污染物對於催化性裂解之破壞性效應的方法及組合物。
催化性裂解是一種商業上經常被使用的大型石油精練過程。美國境內大部分的汽油精鍊混合池都是採用這種製程,且幾乎所有產品都是以此流體式催化性裂解(fluid catalytic cracking,FCC)製程所製作而成的。在催化性裂解製程中,重碳氫化合物部份係在高溫、有催化劑存在的情況下被轉變成較輕的產物,其中大部份的轉變或裂解係在氣相中進行。因此,此FCC碳氫化合物進料係被轉變成汽油、蒸餾物及其他液態裂解產物及較輕的氣態裂解產物(每一分子中含4個或更少的碳原子)。這些液體及氣體產物,係由飽和及不飽和碳氫化物所組成。
在FCC製程中,碳氫化合物進料係被注入一FCC反應槽的上升段中,並在其中與來自催化劑再生器中被循環回到該反應槽上升段中的催化劑接觸而裂解成有價值的、較輕的產物。隨著熱裂解反應的發生,習稱為「焦炭(coke)」的重物質會沉積在該催化劑上,因而降低了催化劑的活性,因此需要將該催化劑再次重生以恢復其催化活性。催化劑及碳氫化物蒸氣係沿著該上升段被往上帶到FCC反應槽的脫離段(disengagement section)中,而後彼此分開。接著,催化劑會流入剝除段(the stripping section)中,藉由蒸氣注射法將陷於催化劑中的碳氫化物蒸氣加以剝除。在將包陷於用過的催化劑中的碳氫化物移出之後,該經剝除處理的催化劑即流動通過一用過的催化劑管線(a spent catalyst standpipe)並進入催化劑再生器中。
一般來說,催化劑的再生係藉由引入空氣至該再生器中並將焦炭燒掉以恢復催化劑的活性。此焦炭的燃燒反應係高度放熱反應並會加熱催化劑。該高熱且再活化的催化劑會流動通過再生催化劑管線而回到該上升段以完成該催化劑的循環。焦炭燃燒後的廢氣流上升至該再生器頂部並經由該再生器廢氣管而離開再生器。該廢氣一般包含NOx
、sOx
、CO、CO2
、氨氣、氮與氧氣。
一流體催化性裂解單元的效能可藉由粗碳氫化合物進料被轉變成可用產品(例如,汽油)的比率來評估。藉由添加催化性裂解催化劑,可提高轉換率,但同時也會製造出不欲求的副產物,包括焦炭及氫氣。因此,希望在提昇一FCC單元轉換率的同時,可使焦炭及氫氣這類副產物的生成量被減至最小。
對FCC製程而言,進料中的金屬污染物是一項嚴重的問題。常見的金屬污染物為鐵、鎳、鈉及釩。這些金屬有一部份可促進裂解程中的脫氫反應,導致焦炭及較輕氣體含量增加並降低汽油製造量。某些這類金屬污染物也會對裂解產物具有不良的影響。金屬污染物會沉積在催化劑表面並影響其安定性及結晶度。在某些情況下,催化劑會因為該等金屬污染物而失活。在再生期間,催化劑中的金屬可在水熱過程中被揮發而再次沉積在催化劑表面上。
舉例來說,進料中的釩污染物可使裂解性催化劑中毒並降低其活性。此種中毒理論之一是說進料中的釩化合物會被併入在焦炭中而沉積於裂解性催化劑上,之後當焦炭於再生器中被燒掉的同時,氧化成五氧化二釩。之後,五氧化二釩遇到再生器中的水蒸氣就形成了釩酸,而與催化劑反應導致催化劑的結晶度被摧毀而活性降低。
一般來說,含有釩及其他金屬在內的化合物,無法輕易地以揮發性化合物方式由FCC單元表面被移除,通常的作法是在裂解過程於所遭遇到的條件下將這類化合物加以鈍化(passivation)。鈍化的做法可能是利用加入添加劑的方式,該添加劑可以是被併入到裂解催化劑中的形式或是單獨存在的形式來與催化劑並用。這些添加劑與金屬一起作為一種「陷阱(traps)」或「池(sink)」,以保護催化劑中的活性組成。操作期間,這些金屬污染物係與催化劑一同自系統中移出,之後再加入新鮮的金屬鈍態添加劑與補充量的催化劑至該FCC單元中,以便能於FCC操作期間連續不斷地自系統中移除該些具破壞性的金屬污染物。視進料中所含破壞性金屬含量的高低,可相對補充催化劑的量來改變添加劑的用量,以達成欲求之鈍化該等金屬的目的。
產業界持續在尋找新的、改良方法以提高一FCC單元的效能,同時使焦炭及氫氣這類副產物的生成量被減至最小。本發明即是關於此及其他重要目的所提出的解決方案。
本發明係關於一種催化性裂解添加劑,其包含一可捕捉金屬之材料;及一種高活性催化劑。本發明更係關於催化性裂解進料的方法,包含在催化性裂解條件下讓該進料與一催化劑塊(a bulk catalyst)及一催化性裂解添加劑接觸,其中該催化性裂解添加劑包含一可捕捉金屬之材料;及一種高活性催化劑。本發明也係關於在至少一種金屬存在下,用以提高一催化劑塊效能的方法,包含讓一進料與一催化性裂解添加劑接觸的步驟,其中該催化性裂解添加劑包含一可捕捉金屬之材料;及一種高活性催化劑。
本發明係關於催化性裂解添加劑,其包含一可捕捉金屬之材料;及一種高活性催化劑。本發明更係關於催化性裂解進料的方法,包含在催化性裂解條件下讓該進料與一催化劑塊(a bulk catalyst)及一催化性裂解添加劑接觸,其中該催化性裂解添加劑包含一可捕捉金屬之材料;及一種高活性催化劑。本發明也係關於在至少一種金屬存在下,用以提高一催化劑塊效能的方法,包含讓一進料與一催化性裂解添加劑接觸的步驟,其中該催化性裂解添加劑包含一可捕捉金屬之材料;及一種高活性催化劑。
「XRD」一詞在此係指X光繞射(X-ray diffraction)。
「FCC」一詞在此代表流體催化性裂解。
「Re」一詞在此代表稀土(rare earth)。
申請人意外地發現本發明催化性裂解添加劑可在不增加焦炭或氣體產量的情況下,提高催化性轉換效率(catalytic conversion)。
申請人也體認到關於進料中金屬污染物的催化性裂解乃是一種兩步驟的製程,其中(1)金屬污染物係在一FCC單元的上升段/反應器中與包括焦炭在內的其他副產物一起被沉積在催化劑顆粒上;且(2)包含金屬的催化劑顆粒被暴露在蒸氣流中以使該催化劑顆粒能被再生。
在不限於一特定理論的情況下,申請人相信應將金屬污染物自催化劑顆粒表面移除,以保存其催化能力。無論用來防止上升段/反應器內催化劑顆粒中的金屬污染物之金屬鈍化劑種類為何,都需要此種物理性移除金屬污染物的方式。申請人更相信金屬污染物乃是揮發性的,並可在有蒸氣或高溫的情況下,例如可有效將催化劑顆粒再生的反應條件下,於催化劑顆粒中或從催化劑顆粒中遷移出來。申請人相信在有蒸氣或高溫的情況下,此處所揭示的催化性裂解添加劑具有可吸附被沉積在催化劑顆粒表面之揮發性污染物的功能。
在一實施例中提供一種催化性裂解添加劑,其包含一種可捕捉金屬之材料;及一種高活性催化劑。
在一實施例中,該可捕捉金屬之材料及該高活性催化劑包含單獨的顆粒。在一實施例中,該可捕捉金屬之材料及該高活性催化劑顆粒係被同時添加到該催化性裂解單元中。
在另一實施例中,該可捕捉金屬之材料及該高活性催化劑係位在一相同顆粒中。
a)可捕捉金屬之材料(Metals Trapping Material)在一實施例中,該可捕捉金屬之材料包含一含鈣的化合物、一含鎂的化合物或其之組合。
在一實施例中,該可捕捉金屬之材料是一種低密度材料。在一實施例中,該可捕捉金屬之材料的密度介於約0.50 g/cc至約1.0 g/cc間。在另一實施例中,該密度係介於約0.70 g/cc至約0.9 g/cc間。在一實施例中,該密度係介於約0.50 g/cc至約0.7 g/cc間。在另一實施例中,該可捕捉金屬之材料的密度係少於約0.70 g/cc;少於約0.69 g/cc;少於約0.68 g/cc;少於約0.67 g/cc;少於約0.66 g/cc;少於約0.65 g/cc;少於約0.60 g/cc;或少於約0.55 g/cc。
在一實施例中,該可捕捉金屬之材料是一種多孔性材料。在一實施例中,該可捕捉金屬之材料的孔隙度(porosity)是大於約0.4 cc/g,此係以水吸收技術(a water sorption technique)所決定出來的值。在另一實施例中,該可捕捉金屬之材料的孔隙度(porosity)是大於約0.45 cc/g,大於約0.50 cc/g,大於約0.55 cc/g,或大於約0.60 cc/g。
在一實施例中,該可捕捉金屬之材料是一種低密度且高孔隙度材料。在一實施例中,該可捕捉金屬之材料的密度係少於約0.70 g/cc,且其孔隙度(porosity)是大於約0.4 cc/g。申請人深信當一可捕捉金屬之材料是一種低密度且高孔隙度材料時,其可吸附存在於蒸氣氣流中或高溫下的揮發性金屬污染物。習知技藝人士將可體認一材料的孔隙度可以是該材料之密度的函數。
在一實施例中,該可捕捉金屬之材料是一種類水滑石化合物(a hydrotalcite-like compound)、一含有矽酸鹽及鋁酸鹽的化合物、一混合金屬氧化物或其之組合。
i)類水滑石化合物
在一實施例中,該可捕捉金屬之材料是一種類水滑石化合物。類水滑石化合物的特徵是其結構中具有被結構間隙中的陰離子和/或水分子所分隔開來的正電荷層。天然的類水滑石化合物礦物包含羥鎂鋁石(meixnerite)、羥碳酸鎂鐵石(pyroaurite)、水碳鐵鎂石(sjogrenite)、水合矽酸鎂(hydrotalcite)、菱水碳鉻鎂石(stichtite)、水碳鐵鎳礦(reevesite)、鎳鋁石(eradleyite)、水碳鋁鎂石(mannaseite)、水碳鉻鎂石(barbertonite)及水鋁鈣石(hydrocalumite)。其他類水滑石化合物及其製作方法係揭示於Cavaniet al.
,Catalysis Today
,11:173-301(1991),其全文以參考文獻方式併入本文中。
在其他實施例中,該類水滑石化合物是具有式(I)、(II)、(III)和/或(IV)結構之化合物:
其中X是鎂、鈣、鋅、錳、鈷、鎳、鍶、鋇、銅或其之二或多種混合物;Y是鋁、錳、鐵、鈷、鎳、鉻、鎵、硼、鑭、鈰或其之二或多種混合物;A是CO3
、NO3
、SO4
、Cl、OH、Cr、I、SiO3
、HPO3
、MnO4
、HGaO3
、HVO4
、ClO4
、BO3
或其之二或多種混合物;a是1、2或3;b是介於0至10間的數目;且m和n是依據可使m/n的比值為約1至約10來選擇。
在一實施例中,該類水滑石化合物是水滑石,即(Mg 6 Al 2
(OH
)16
)CO 3
‧4H 2 O
。在另一實施例中,該類水滑石化合物是(Mg 6 Al 2
(OH
)18
)‧4.5H 2 O
。該類水滑石化合物、組合物和/或本發明之成型物件可以美國專利第6,028,023號所揭示的方法來製備。
在一實施例中,該類水滑石化合物是一種固溶液,其包含鎂及鋁,其比例介於約1:1至約6:1之間。
ii)含有矽酸鹽及鋁酸鹽的化合物
在一實施例中,該可捕捉金屬之材料是一種矽酸鋁材料。
在一實施例中,該矽酸鋁材料是一種結晶材料、一準結晶材料(a quasi-crystaline)、一非晶型材料或其之組合。
在另一實施例中,該矽酸鋁材料包含鈣,且該主要捕捉金屬的能力係由該鈣組成來執行。
在一實施例中,該矽酸鋁材料包含不具沸石狀的組成。
iii)混合金屬氧化物
在一實施例中,該可捕捉金屬之材料是一種混合金屬氧化物。如此所述,「混合金屬氧化物(a mixed metal oxide)」一詞代表一種由氧氣與二或多種金屬結合在一起所形成的化合物。
在一實施例中,該可捕捉金屬之材料是鋁酸鎂。
在本發明一實施例中所述的混合金屬氧化物係揭示在例如美國專利申請序號第60/527,258號及第60/576,146號中。在一實施例中,該混合金屬氧化物是一種鋁酸鎂固溶液,其包含的鋁與鎂比例介於約1:1至約6:1間,其中該鈣化之鋁酸鎂固溶液的X光繞射圖案顯示其在約43度及約62度之一2-θ波峰位置至少有一反射,且其中該混合金屬氧化物是一種含鎂及含鋁的化合物,其並非衍生自一類水滑石化合物。
在一實施例中,該混合金屬氧化物是尖晶石(spinel)。在另一實施例中,該混合金屬氧化物是一鋁酸鎂尖晶石。
在另一實施例中,該混合金屬氧化物是衍生自一類水滑石化合物,例如藉由將該類水滑石化合物崩塌後所形成的化合物。
本發明一實施例中的該混合金屬氧化物、組合物和/或成型物件可以美國專利第6,028,023號中所揭示的方法來製備。
iv)可捕捉金屬之材料的形式
在一實施例中,該可捕捉金屬之材料是以一種固溶液形式存在。在一實施例中,該可捕捉金屬之材料是可直接被用在該催化性裂解添加劑中。在一實施例中,該可捕捉金屬之材料是以一種成型物件形式(a shaped body)存在。在一實施例中,該成型物件為乾燥、鈣化或一其之混合物。
在一實施例中,該可捕捉金屬之材料可更包含一或多種其他金屬組成,例如銻、鉍、鎘、鈣、鈰、鉻、鈷、銅、鏑、鉺、銪、釓、鍺、金、鈥、銥、鐵、鑭、鉛、鎂、錳、鉬、釹、鎳、鈮、鋨、鈀、鉑、鐠、鏂、錸、銠、釕、釤、鈧、硒、矽、銀、硫、鉭、碲、鋱、錫、鈦、鎢、銩、釩、鐿、鋅、或其之二或多種的混合物。該金屬可以是元素態金屬或是金屬氧化物、金屬氫氧化物、金屬硫化物、金屬鹵化物之型態或其之二或多種混合物。某些或全部的金屬組成也可以有機或無機鹽類形式存在,包括,例如,金屬硝酸鹽和/或金屬醋酸鹽。在一實施例中,該可捕捉金屬之材料可更包含鈣(例如,CaO、Ca(OH)2
或CaCO3
)、鎂(例如,MgO、Mg(OH)2
或MgCO3
)或其之組合。以氧化物的當量來計算的話,該一或多種金屬組成(或其之氧化物、硫化物和/或鹵化物)在該可捕捉金屬之材料中的量可高達約50%(重量%);或高達約40%(重量%);高達約30%(重量%);或介於約1%(重量%)至約25%(重量%)之間;或介於約2%(重量%)至約20%(重量%)之間。該一或多種金屬組成可同時添和到該可捕捉金屬之材料中,以作為該可捕捉金屬之材料。
在另一實施例中,本發明提供成型物件,其包含可捕捉金屬之材料及一或多種金屬組成。在另一實施例中,可捕捉金屬之材料係以一種固溶液的形式存在。在一實施例中,在該金屬組成中的金屬是銻、鉍、鎘、鈣、鈰、鉻、鈷、銅、鏑、鉺、夠、釓、鍺、金、鈥、銥、鐵、鑭、鉛、鎂、錳、鉬、釹、鎳、鈮、鋨、鈀、鉑、鐠、鏂、錸、銠、釕、釤、鈧、硒、矽、銀、硫、鉭、碲、鋱、錫、鈦、鎢、銩、釩、鐿、鋅、或其之二或多種的混合物。在另一實施例中,在該金屬組成中的金屬是鈣、鎂或其之混合物。在一實施例中,該成型物件為乾燥、鈣化或一其之混合物。
在另一實施例中,本發明提供一或多成型物件,其包含可捕捉金屬之材料及一支持物。在另一實施例中,可捕捉金屬之材料係以一種固溶液的形式存在。在一實施例中,該支持物是一尖晶石、類水滑石化合物、醋酸鎂、硝酸鎂、氯化鎂、氫氧化鎂、碳酸鎂、甲酸鎂、鈦酸鋁、鈦酸鋅、鋁酸鋅、鈦酸鋅/鋁酸鋅、鋯酸鋅、氧化鈣、鋁酸鈣、水合硝基鋁(aluminum nitrohydrate)、氫氧化鋁、含鋁之金屬氧化物(例如,除了鋁或氫氧化鋁之外的化合物)、水合氯化鋁、二氧化鈦、氧化鋯、黏土(例如,多水高嶺土(halloysite)、白色矽酸鋁(rectorite)、矽酸鎂矽酸鋁黏土(hectorite)、蒙脫土(montmorillinite)、合成的蒙脫土、海泡石(sepiolite)、活化的海泡石、高嶺土(kaolin))、磷酸黏土材料、沸石、或其之二或多種的混合物。在一實施例中,該支持物為鈦酸鋅、鋁酸鋅或鈦酸鋅/鋁酸鋅。製造這類組合物的方法揭示在,例如,WO 99/42201中。在一實施例中,該成型物件為乾燥、鈣化或其之一混合物。
在另一實施例中,本發明提供包含可捕捉金屬之材料、一或多金屬組成、及一支持物在內的成型物件。在另一實施例中,可捕捉金屬之材料係以一種固溶液的形式存在。在一實施例中,該成型物件為乾燥、鈣化或其之一混合物。
在本發明揭示的某些實施例中,以氧化物的當量來計算的話,該金屬組成的用量可高達約50%(重量%);或介於約0.1%(重量)至約40%(重量%)間;或介於約1%(重量%)至約30%(重量%)之間;或介於約1%(重量%)至約25%(重量%)之間;或介於約1%(重量%)至約20%(重量%)之間;或介於約1%(重量%)至約15%(重量%)之間;或介於約1%(重量%)至約10%(重量%)之間。在一實施例中,該支持物的用量可高達約50%(重量%);或介於約1%(重量%)至約30%(重量%)之間;或介於約1%(重量%)至約20%(重量%)之間;或介於約1%(重量%)至約15%(重量%)之間;或介於約1%(重量%)至約10%(重量%)之間;或介於約1%(重量%)至約5%(重量%)之間。
該一或多種金屬組成可同時添加到該可捕捉金屬之材料中,以作為該可捕捉金屬之材料。
v)可捕捉金屬之材料的用量在一實施例中,可捕捉金屬之材料包含約2%(重量%)至約98%(重量%)之間的催化性裂解添加劑。在一實施例中,可捕捉金屬之材料約佔該催化性裂解添加劑重量之約30%(重量%)至約95%(重量%)之間。在一實施例中,可捕捉金屬之材料約佔該催化性裂解添加劑重量之約30%(重量%)至約60%(重量%)間、或約40%(重量%)至約60%(重量%)之間。在另一實施例中,可捕捉金屬之材料約佔該催化性裂解添加劑重量之約60%(重量%)至約95%(重量%)間、或約70%(重量%)至約90%(重量%)之間。
b)高活性催化劑(high Activity Catalysts)如此所述,「高活性催化劑(high Activity Catalysts)」一詞代表一種具有比催化劑塊更高百分比量的沸石和/或更高百分比之整體表面積和/或更高整體結晶度的催化劑。在一實施例中,該高活性催化劑具有較一催化劑塊之沸石百分比至少約1.5倍之沸石百分比和/或較一催化劑塊之整體表面積至少約1.5倍之整體表面積和/或較一催化劑塊之整體結晶度至少約1.5倍之整體結晶度。在另一實施例中,該高活性催化劑具有較一催化劑塊之沸石百分比至少約2.0倍之沸石百分比和/或較一催化劑塊之整體表面積至少約2.0倍之整體表面積和/或較一催化劑塊之整體結晶度至少約2.0倍之整體結晶度;或較一催化劑塊之沸石百分比至少約2.5倍之沸石百分比和/或較一催化劑塊之整體表面積至少約2.5倍之整體表面積和/或較一催化劑塊之整體結晶度至少約2.5倍之整體結晶度;較一催化劑塊之沸石百分比至少約3.0倍之沸石百分比和/或較一催化劑塊之整體表面積至少約3.0倍之整體表面積和/或較一催化劑塊之整體結晶度至少約3.0倍之整體結晶度;或較一催化劑塊之沸石百分比至少約3.5倍之沸石百分比和/或較一催化劑塊之整體表面積至少約3.5倍之整體表面積和/或較一催化劑塊之整體結晶度至少約3.5倍之整體結晶度;或較一催化劑塊之沸石百分比至少約4.0倍之沸石百分比和/或較一催化劑塊之整體表面積至少約4.0倍之整體表面積和/或較一催化劑塊之整體結晶度至少約4.0倍之整體結晶度。
第1圖示出一習知的Y型沸石催化劑塊(底部曲線)與本發明一高活性Y型沸石催化劑(上部曲線)之比較。比較該Y型沸石的XRD圖,該高活性催化劑在約6.3度處顯示出較更高的衍射強度(diffracted intensity)。更高的衍射強度代表上部曲線之高活性催化劑之結晶度更高。更高的衍射強度也代表該高活性催化劑含有更高量的沸石,且可代表該高活性催化劑後續更高的活性。
i)沸石在一實施例中,該高活性催化劑為一種沸石。在一實施例中,該高活性催化劑是一種原位合成的沸石。該沸石可以稀土金屬來使之安定,例如約0.1%至約10%(重量%)的稀土金屬。包含沸石的催化劑可含有變動量的稀土金屬化合物。這些稀土金屬化合物可在合成沸石時即已存在,或可在沸石合成後再被交換到沸石上。以稀土金屬加以穩定的沸石典型稱之為「REY(rare earth-stabilized zeolites)」。
該沸石也可以蒸氣來加以穩定,包括,例如,以蒸氣加以穩定的Y型沸石稱為「USY(steam stabilized Y zeolite)」。
在一實施例中,該沸石為X型沸石、Y型沸石、A型沸石、L型沸石、ZK-4型沸石、貝塔型沸石(beta zeolite)、八面沸石(faujasite)或其之組合。在另一實施例中,該高活性催化劑為一種大孔隙的沸石。在一實施例中,該高活性催化劑為一種貝塔型沸石、Y型沸石、八面沸石(faujasite)或其之組合。在另一實施例中,該高活性催化劑為一種以稀土金屬加以穩定的貝塔型沸石、以稀土金屬加以穩定的Y型沸石、以稀土金屬加以穩定的八面沸石(faujasite)或其之組合。
在一實施例中,該高活性催化劑的整體表面積超過約350 m2
/gr;或超過約400 m2
/gr;或超過約450 m2
/gr。在一實施例中,該高活性催化劑的整體表面積約為400 m2
/gr。
依據本發明,該高活性催化劑的實例包括,例如,Engelhard Coroporation出品的ConverterT M
。
ii)高活性催化劑用量在一實施例中,該高活性催化劑約佔該催化劑裂解添加劑重量之5%至約60%間。在一實施例中,該高活性催化劑約佔該催化劑裂解添加劑重量之約5%至約40%間;或約10%至約30%間。在一實施例中,該高活性催化劑約佔該催化劑裂解添加劑重量之約40%至約60%間。
在一實施例中,在一流體催化性裂解製程中提供一循環存量之催化劑顆粒(a circulating inventory of catalyst particles),其中約2%至約80%之該循環存量包含上述之催化性裂解添加劑。
在一實施例中,提供用以對進料進行催化性裂解的方法,包括在催化性裂解條件下讓該進料與一組合物接觸的步驟,該組合物包括一催化劑塊及一催化性裂解添加劑,其中該催化性裂解添加劑包含一可捕捉金屬之材料及一高活性催化劑。
在另一實施例中,提供用以改善一流體催化性裂解單元中FCC催化劑效能的方法,其係藉由添加上述之添加劑到該FCC單元中來達成。
在一實施例中,提供用以在至少一金屬存在下提高一催化劑塊之效能的方法,包含以一催化性裂解添加劑接觸一進料的步驟,其中該催化性裂解添加劑包含一可捕捉金屬之材料及一高活性催化劑。在另一實施例中,該催化性裂解添加劑可提高進料之催化性轉換率。在一實施例中,該催化性裂解添加劑可提高由進料中產生汽油的比例。在一實施例中,該催化性裂解添加劑可提高由進料中產生LPG的比例。在另一實施例中,該催化性裂解添加劑可提高由進料中產生LCO的比例。在一實施例中,該催化性裂解添加劑可減少進料之底部產物的量。在另一實施例中,該催化性裂解添加劑可降低由進料中產生焦炭的量。在一實施例中,該催化性裂解添加劑可減少由進料中產生氫氣的量。
在一實施例中,該催化性裂解添加劑可減輕該催化劑塊結晶度下降的情形。在一實施例中,該催化性裂解添加劑可減輕該催化劑塊在約6.3度之2-θ尖峰下降的情形。在一實施例中,該催化性裂解添加劑可減輕該催化劑塊表面積減少的情形。
a)進料可在該FCC單元中使用任一種習知的FCC進料。該進料可包括諸如石油蒸餾物或殘料,原始的或經過部分精鍊的典型進料,至諸如煤油及頁岩油之類的非典型進料。該進料可包含再生(回收)的碳氫化物,例如已經過裂解的輕或重回收油。進料的例子包括汽油、真空汽油、大氣殘渣或真空殘渣。
b)催化性裂解條件在一實施例中,該催化性裂解添加劑可被添加到一FCC單元的上升段或再生器中。在另一實施例中,該催化性裂解添加劑係被添加到一FCC單元的再生器中。在一實施例中,該催化性裂解添加劑係被添加到一含有催化劑塊的FCC單元中。
該催化性裂解添加劑及該催化劑塊可以經由袋子或鼓而被手動式地引入至該FCC單元中。該催化性裂解添加劑及該催化劑塊也可以經由自動添加系統(例如,美國專利第5,389,236號中所揭式的系統)而被自動化地引入至該FCC單元中。為了將該催化性裂解添加劑引入至該FCC單元,可事先將該催化性裂解添加劑與該催化劑塊一起混合,然後以一個系統的形式引入至該FCC單元中。或者,可經由不同的注射系統將該催化性裂解添加劑及該催化劑塊分別引入至該FCC單元中。在另一實施例中,該催化性裂解添加劑可以變動的比例被添加至FCC單元中以使該該催化性裂解添加劑的添加速率能達到最佳化。
可使用習知上升段裂解條件。典型的上升段裂解反應條件包括催化劑/油的比例在約0.5:1至約15:1之間,且催化劑接觸時間約0.1至約50秒,且上升段頂部溫度約在900℉至約1050℉間。在一實施例中,以習知技術(例如,添加大量之原子化的蒸氣流、使用多個噴嘴、使用原子化噴嘴等類似技術)來提供進料與上升段底部之催化劑間的良好混合。上升段底部可包含一上升段催化劑加速區。在一實施例中,該上升段反應器可排入一密閉氣旋系統中,用以快速且迅速地將已用過的催化劑與裂解產物加以分開來。
本發明添加劑可被添加到任一習知的反應器-再生器系統、催化劑流床系統(ebullating catalyst bed system)、及涉及在反應區及再生區等處連續傳輸或循環催化劑/添加劑的系統中。在一實施例中,該系統為一循環床系統(a circulating bed system)。典型的循環床系統為習知的移動床(moving bed)及流體床(fluidized bed)反應器-再生器系統。這兩種循環床系統均為習用於碳氫化合物裂解操作中的系統。在一實施例中,該統為一流體化催化劑床反應器-再生器系統。
可用於此處的其他特化的上升段-再生器系統包括深催化性裂解(Deep catalytic cracking,DCC)、微秒催化性裂解(Millisecond catalytic cracking,MSCC)、流體催化性裂解(resid fluid catalytic cracking,RFCC)系統。
c)催化劑塊(Bulk catalyst)如此所述,「催化劑塊(Bulk catalyst)」一詞代表任何一種可在標準催化性裂解條件(包括上述揭示的種種條件)下,用於FCC單元操作中的催化劑。
任何一種商業上販售之FCC催化劑均可作為此處的「催化劑塊」。該催化劑塊可以是100%非晶型,但在一實施例中,可包括某些存在於多孔性反射基質中的沸石,例如二氧化矽-氧化鋁、黏土或其類似物。該沸石通常佔催化劑總重的約5%至約40%,其餘重量則為基質或稀釋物。也可使用習知的沸石,例如Y型沸石,或不含鋁的這些種類的沸石,例如去鋁之Y型沸石、超安定Y型沸石及超疏水性Y型沸石等。可以稀土元素來穩定這些沸石,例如,約0.1%至約10%之稀土元素。
可用於此處的沸石可為天然來源或人工合成者。
可在本發明中使用含有相當高二氧化矽沸石的催化劑,其可忍受FCC再生器中將CO燃燒成CO2
時所必然會出現的高溫。這類催化劑包括那些含有約10%至約40%之超安定Y型沸石或稀土金屬穩定之超安定Y型沸石的催化劑。
在一實施例中,該催化劑塊的表面積低於約300 m2
/gr。在另一實施例中,該催化劑塊的表面積約為250 m2
/gr。
一適當的催化劑塊也可包括以原位合成技術合成、再與一稀釋物混合的催化劑。此包括,例如,一高活性催化劑。在一實施例中,該催化劑塊包括約5%至約70%之一高活性催化劑。在另一實施例中,該催化劑塊包括約5%至約40%之一高活性催化劑。
d)催化性裂解添加劑該催化性裂解添加劑包含一可捕捉金屬的材料及一高活性催化劑,如上述。
在一實施例中,該催化性裂解添加劑佔組合物重量約2%至約80%。在一實施例中,該催化性裂解添加劑佔組合物重量約20%至約60%。在一實施例中,該催化性裂解添加劑佔組合物重量約40%至約600%。在另一實施例中,該催化性裂解添加劑佔組合物重量約5%至約20%,或約10%。
e)其他組成除了該催化劑塊及本發明之催化性裂解添加劑之外,該催化劑存量(the catalyst inventory)也可包括一或多添加劑,其可以單獨的添加劑顆粒形式存在,或是和該裂解催化劑之每一顆粒混合。可用來提高辛烷值得添加劑包括例如中等孔隙大小的沸石,例如ZSM-5及其他具有類似結晶結構的材料。該等添加劑可用來促進CO燃燒、降低SOx排放量、降低NOx排放量和/或CO排放量、增強催化劑效能或降低汽油含硫量。
在一實施例中,本發明之催化性裂解添加劑也可用來提高辛烷值、促進CO燃燒、降低SOx排放量、降低NOx排放量和/或CO排放量、增強催化劑效能或降低汽油含硫量。
下列實施例僅係用以闡述本發明,本發明範疇並不僅限於所揭示實施例。
依照美國專利第6,028,023號所揭示的方法製備類水滑石化合物,該專利之全文以參考文獻方式併入本文中。
以約14%固體量的方式將氧化鎂粉末(表面積約為100平方公尺/克)(MAGOX®
,Premier Chemicals,Cleveland,OH)攪拌於水中。之後,在該MgO漿溶液中加入5.2%之技術級醋酸。
另外,以8%固體量的方式將氧化鋁(pseudobohemite)(Sasol Sol P2®
)攪拌於水中,以製備出氧化鋁固溶液。
將該氧化鎂漿溶液及該氧化鋁固溶液在容器中混合,使該製備中的鎂/鋁的莫耳比例為4:1。加入額外的水使混合物中的固體含量約為9%。在一段長約5小時的時間內,將該混合物加熱至約214℉。一旦加熱開始,將8份乾重之所得漿狀物與2份乾重之技術級氫氧化鈣與水一起混合,始最終固體含量為10%。在標準條件下,將該混合物漿噴霧乾燥,以製備出平均顆粒小在75-80微米的微球型顆粒。之後,該噴霧乾燥顆粒在600℃以上的溫度鈣化約1小時。進一步以水潤濕該產物,以製備出水滑石似相。所得類水滑石化合物之XRD圖案顯示其最佳可以Mg 6 Al 2
(OH
)18
.4.5H 2 O
化學式來代表,如ICDD卡35-965所繪示。此物質在此稱為『金屬陷阱A(Metals Trap A)』。之後,藉由加熱該類水滑石化合物至500℃使其崩塌,直到達到固體含量約8%為止。可獲得具有一ASTM 2小時磨損約2.1、表面塊密度約0.72 g/cc、表面積約65 m2
/g、及一孔隙體積約0.45 cc/g之耐磨損微球。
包含一氧化鈣活性組成之一可捕捉金屬的添加劑,係藉由在可點燃基礎下,混合3份氫氧化鈣、3份氧化鋁(pseudobohemite)凝膠、0.5份氧化矽凝膠及4份高嶺黏土方式來製備。並加入足夠過量的水,使最終固體含量約為20%(重量%)。將所得漿溶液噴霧乾燥成為一約100微米大小之顆粒並鈣化至最終LOI約為5%(重量%)。可獲得具有一ASTM 2小時磨損約1.2、表面塊密度約0.64 g/cc、表面積約60 m2
/g、及一孔隙體積約0.54 cc/g之耐磨損微球。此物質在此稱為『金屬陷阱A(Metals Trap B)』。
以下列方法及美國專利第6,028,023號所揭示的方法製備鋁酸鎂。
以約14%固體量的方式將氧化鎂粉末(表面積約為100平方公尺/克)(MAGOX,Premier Chemicals,Cleveland,OH)攪拌於水中。之後,在該MgO漿溶液中加入5.2%之技術級醋酸。
另外,以8%固體量的方式將氧化鋁(pseudobohemite)(Sasol Sol P2)攪拌於水中,以製備出氧化鋁固溶液。
將該氧化鎂漿溶液及該氧化鋁固溶液在容器中混合,使該製備中的鎂/鋁的莫耳比例為4:1。加入額外的水使混合物中的固體含量約為9%。在一段長約5小時的時間內,將該混合物加熱至約214℉。一旦加熱開始,將8份乾重之所得漿狀物與2份乾重之技術級氫氧化鈣與水一起混合,始最終固體含量為10%。在標準條件下,將該混合物漿噴霧乾燥,以製備出平均顆粒小在75-100微米的微球型顆粒。之後,該噴霧乾燥顆粒在600℃以上的溫度鈣化約1小時,以製備出一鎂、鈣及鋁之混合金屬氧化物。
為評估添加劑的效能,以各種催化劑塊/添加劑組合,在類似FCC反應的條件下將進料加以催化性裂解。該催化劑塊係與商業來源可買到的催化劑相當,並具有約25%烯土金屬交換的Y型沸石在一約由30%氧化鋁凝膠及氧化矽凝膠組成之活性基質中。將該催化劑漿狀物加以噴霧乾燥成微球型顆粒之後並鈣化。測量可知該催化劑表面積約為250 m2
/g且以Re2
O3
為基礎計算出來的稀土含量約微1.3%(重量%)。所使用的該高活性催化劑是一種以原位合成技術從黏土微球製備出來的Y型沸石(可購自Engelhard corporation,商品名為ConverterT M
)。其表面積約為400 m2
/g且以Re2
O3
為基礎計算出來的總稀土含量約微5%(重量%),且孔隙體積約為0.54 cc/g。
每一催化劑混合物(有或無添加劑組成)係先在732℃下鈣化1小時之後再依據實驗步驟加以去活化。以目前市面上提供的原子去活化單元(Kayser Technologies Model D-100)來將萘酸釩及萘酸鎳係被裂解至每一特定催化劑混合物上。之後在800℃下以約50%蒸氣來對該金屬污染物進行蒸氣處理約9小時。該催化劑混合物的最終釩濃度約為10,000 ppm且最終鎳濃度約為900 ppm。為比較之目的,在相同處理條件下處理一新鮮的催化劑塊。該有或無去活化之催化劑塊的XRD圖案示於第2圖中。第2圖顯示,去活化的製程對包含在該催化劑塊中的Y型沸石的結晶結構,有顯著的影響。
為測量催化效能,將已經過去活化處理的催化劑混合物裝載至一市面上販售的實驗室級FCC測試單元中(Kayser Technologies ACE Model R+)。ACE條件包括反應器溫度約為985℉,催化劑與油的比例約為7,秤重後之每小時空間速度約為8,使用一標準US海灣進料。
在測試1A中,未使用任何添加劑。測試1B到1F中使用了依據實施例1所製備而成之「金屬陷阱A」和/或高活性催化劑Y型沸石(商品名ConverterT M
)。測試1B至1F,添加劑佔總催化劑混合物重量之10%。以金屬陷阱A作為可捕捉金屬之材料的效能測試結果示於下表1。所有數據均為重量%。
在測試2A到2D中,係使用與測試1B到1F中相同的條件,除了所用催化劑混合物的最終釩濃度約為5000 ppm且最終鎳濃度約為2000 ppm,該催化劑與油的比例約為6.0,並使用一墨西哥美亞原油進料(Mexican Mayan crude feedstock)。在測試2A中,未使用添加劑。在測試2B-2D中,係使用了依據實施例1所製備而成之「金屬陷阱A」和/或高活性催化劑Y型沸石(商品名ConverterT M
)。在測試2B至2C,添加劑佔總催化劑混合物重量之25%。測試2D中,添加劑佔總催化劑混合物重量之50%。以金屬陷阱A作為可捕捉金屬之材料的效能測試結果示於下表2。所有數據均為重量%。
在測試3A到3F中,除了添加劑外,係使用與測試1B到1F中相同的條件。在測試3A中,未使用添加劑。在測試3B-3F中,係使用了依據實施例2所製備而成之「金屬陷阱B」和/或高活性催化劑Y型沸石(商品名ConverterT M
)。在測試3B至3F,添加劑佔總催化劑混合物重量之10%。以金屬陷阱B作為可捕捉金屬之材料的效能測試結果示於下表3。所有數據均為重量%。
表1、2及3的結果顯示使用包含一高活性催化劑及一可捕捉金屬之材料的添加劑具有一加乘的效果。僅單獨使用高活性催化劑作為添加劑,看不到任何明顯效果,但若在添加劑中組合使用高活性催化劑及一可捕捉金屬之材料,則其效果遠優於單獨使用可捕捉金屬之材料。此種在添加劑中組合一高活性催化劑及一可捕捉金屬之材料,可提高轉化率、增加LPG產率、提高汽油產率、降低LCO產率、降低底部物產率及降低焦炭產率並降低氫氣產率。
先從新鮮催化劑塊及實施例4所述之新鮮高活性催化劑以Cu Kα輻射測量其粉末x光繞射及表面積。結果示於下表4。
表4結果顯示一催化劑塊與本發明一高活性催化劑,兩者間有明顯差異。此XRD圖案波峰的面積乃是以公尺為單位,一般代表一催化劑的結晶程度。波峰面積愈大,代表催化劑結晶度愈高。
為進一步評估本發明的效能,先量取已經與金屬陷阱A混合之FCC催化劑的XRD及其表面積。
在測試1A中,並未使用任何催化性添加劑。在測試1D中,則使用催化性裂解添加劑金屬陷阱A與本發明之高活性催化劑。結果示於下表5。
表5結果顯示本發明可提高XRD圖案中在2-θ約6.3度處之尖峰面積。一般來說,此XRD圖案尖峰的面積係可代表該催化劑塊結晶度的一種量測。該尖峰面積愈大,表示催化劑結晶度愈高。該催化劑的實際X光繞射圖示於第3圖。在第3圖中,底部曲線顯示未經任何失活(鈍化)處理之新鮮、催化劑塊的繞射圖。在失活之後,可在中間曲線觀察到嚴重的結晶度喪失(測試1A)。在與本發明催化性裂解添加劑反應後(測試1D),可由頂部曲線看到一明顯部分的結晶度被保留了下來。
催化劑的表面積也是結晶度的另一種代表。結果顯示本發明催化性裂解添加劑可降低催劑塊表面積之減少情形。
以使用能量分散光譜的掃描式電子顯微鏡(Scanning Electron Microscopy utilizing Enegry Dispensive Spectroscopy,SEM/EDS)來分析上述實施例4中的催化性裂解添加劑。
如實施例4所述,藉由金屬化及蒸氣將FCC催化劑/催化性裂解添加劑混合物加以鈍化(失活)。已知該等添加劑顆粒中含有一或多種下列元素:釩、硫、矽、鈰。
習知技藝人士依據上述揭示內容將可輕易了解本發明還可有多種變化,這些變化仍應被視為附隨申請詹例範圍所涵蓋的範疇。
第1圖為一高活性催化劑及一催化劑塊的X-光繞射(XRD)圖。
第2圖為一新鮮且失活(鈍化)之催化劑塊的X-光繞射(XRD)圖。
第3圖為一新鮮的催化劑塊、失活之催化劑塊及在有本發明催化性裂解添加劑存在下的催化劑塊之X-光繞射(XRD)圖。
Claims (33)
- 一種催化性裂解添加劑,包含:a)一可捕捉金屬之材料;及b)含有一沸石之一高活性催化劑,其中該高活性催化劑具有大於350 m2 /g之一表面積。
- 如申請專利範圍第1項所述之催化性裂解添加劑,其中該可捕捉金屬之材料佔該催化性裂解添加劑重量之約2%至約98%。
- 如申請專利範圍第1項所述之催化性裂解添加劑,其中該可捕捉金屬之材料佔該催化性裂解添加劑重量之約30%至約95%。
- 如申請專利範圍第1項所述之催化性裂解添加劑,其中該可捕捉金屬之材料佔該催化性裂解添加劑重量之約70%至約90%。
- 如申請專利範圍第1項所述之催化性裂解添加劑,其中該高活性催化劑佔該催化性裂解添加劑重量之約5%至約60%。
- 如申請專利範圍第1項所述之催化性裂解添加劑,其中該可捕捉金屬之材料及該高活性催化劑具有個別的顆粒。
- 如申請專利範圍第1項所述之催化性裂解添加劑,其中該可捕捉金屬之材料及該高活性催化劑係在一相同顆粒中。
- 如申請專利範圍第1項所述之催化性裂解添加劑,其中該可捕捉金屬之材料包含一含鈣化合物、一含鎂化合物或其之組合。
- 如申請專利範圍第1項所述之催化性裂解添加劑,其中該可捕捉金屬之材料包含一類水滑石化合物、一含矽-及鋁-的化合物、一混合金屬之氧化物或其之組合。
- 如申請專利範圍第1項所述之催化性裂解添加劑,其中該高活性催化劑包含一沸石。
- 如申請專利範圍第1項所述之催化性裂解添加劑,其中該高活性催化劑包含一原位合成的沸石。
- 如申請專利範圍第10項所述之催化性裂解添加劑,其中該沸石為X型沸石、Y型沸石、A型沸石、L型沸石、ZK-4型沸石、貝塔型沸石(beta zeolite)、八面沸石(faujasite)或其之組合。
- 如申請專利範圍第10項所述之催化性裂解添加劑,其中該沸石是Y型沸石、貝塔型沸石(beta zeolite)、 八面沸石(faujasite)或其之組合。
- 如申請專利範圍第1項所述之催化性裂解添加劑,其中該可捕捉金屬之材料為一種可捕捉釩之材料。
- 一種催化劑顆粒於一流體催化性裂解製程中的循環存量,其中約2%至約80%之該循環存量包含如申請專利範圍第1項所述之催化性裂解添加劑。
- 一種催化性裂解進料的方法,包含在催化性裂解條件下讓該進料與一組合物接觸的步驟,該組合物包含含有一沸石之一催化劑塊(a bulk catalyst)及一催化性裂解添加劑,其中該催化劑塊具有小於約300 m2 /g之一表面積,且其中該催化性裂解添加劑包含:a)一可捕捉金屬之材料;及b)含有一沸石之一高活性催化劑,其中該高活性催化劑具有大於350 m2 /g之一表面積。
- 如申請專利範圍第16項所述之方法,其中該催化性裂解添加劑約佔該組合物重量之約2%至約80%。
- 如申請專利範圍第16項所述之方法,其中該催化性裂解添加劑約佔該組合物重量之約20%至約60%。
- 如申請專利範圍第16項所述之方法,其中該催化性裂解添加劑約佔該組合物重量之約5%至約20%。
- 如申請專利範圍第16項所述之方法,其中該可捕捉金屬之材料約佔該添加劑重量之約2%至約98%。
- 如申請專利範圍第16項所述之方法,其中該可捕捉金屬之材料約佔該添加劑重量之約60%至約95%。
- 如申請專利範圍第16項所述之方法,其中該可捕捉金屬之材料約佔該添加劑重量之約70%至約90%。
- 如申請專利範圍第16項所述之方法,其中該高活性催化劑約佔該添加劑重量之約5%至約40%。
- 如申請專利範圍第16項所述之方法,其中該可捕捉金屬之材料及該高活性催化劑具有個別的顆粒。
- 如申請專利範圍第16項所述之方法,其中該可捕捉金屬之材料及該高活性催化劑係在一相同顆粒中。
- 如申請專利範圍第16項所述之方法,其中該可捕捉金屬之材料包含一含鈣化合物、一含鎂化合物或其之組合。
- 如申請專利範圍第16項所述之方法,其中該可捕捉金屬之材料包含一非陰離子性的含鎂-與含鋁-化合物,其並非衍生自類水滑石化合物;一含矽-及鋁-的化合物或其之組合。
- 如申請專利範圍第16項所述之方法,其中該高活性催化劑包含一沸石。
- 如申請專利範圍第16項所述之方法,其中該高活性催化劑包含一原位合成的沸石。
- 如申請專利範圍第28項所述之方法,其中該沸石為X型沸石、Y型沸石、A型沸石、L型沸石、ZK-4型沸石、貝塔型沸石(beta zeolite)、ZSM-5型沸石、八面沸石(faujasite)或其之組合。
- 如申請專利範圍第28項所述之方法,其中該沸石是Y型沸石、貝塔型沸石(beta zeolite)或其之組合。
- 如申請專利範圍第16項所述之方法,其中該可捕捉金屬之材料為一種可捕捉釩之材料。
- 如申請專利範圍第16項所述之方法,其中該催化劑塊中包含約5%至約40%的沸石。
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Families Citing this family (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104117335A (zh) * | 2006-06-29 | 2014-10-29 | 雅宝荷兰有限责任公司 | 用于在烃类流化催化裂化期间除去对催化剂有毒的金属的添加剂 |
US7993623B2 (en) | 2007-06-29 | 2011-08-09 | Albemarle Netherlands B.V. | Additives for removal of metals poisonous to catalysts during fluidized catalytic cracking of hydrocarbons |
US9764314B2 (en) * | 2006-11-07 | 2017-09-19 | Saudi Arabian Oil Company | Control of fluid catalytic cracking process for minimizing additive usage in the desulfurization of petroleum feedstocks |
KR101586093B1 (ko) * | 2006-11-07 | 2016-01-15 | 사우디 아라비안 오일 컴퍼니 | 석유 공급원료의 유동 접촉 분해 방법 |
CO5930068A1 (es) * | 2006-12-06 | 2008-06-27 | Ecopetrol Sa | Proceso de produccion de trampas de vanadio por impregnacion y trampa de vanadio producida por dicho proceso |
US8309780B2 (en) * | 2007-12-21 | 2012-11-13 | Exxonmobil Research And Engineering Company | Process for making olefin oligomers and alkyl benzenes in the presence of mixed metal oxide catalysts |
CN102165044B (zh) * | 2008-07-28 | 2015-01-07 | 英特凯特公司 | 用于倾向性增加一种或多种所选烃类产物的产率的组合物和方法 |
KR101646292B1 (ko) | 2008-09-05 | 2016-08-05 | 인터캣 이큅먼트, 인코포레이티드 | 하나 이상의 유닛 내의 재료 재고를 조절하는 재료 회수 장치 및 방법 |
US8236247B2 (en) | 2008-12-23 | 2012-08-07 | Intercat Equipment, Inc. | Material withdrawal apparatus and methods of regulating material inventory in one or more units |
US20120043195A1 (en) * | 2009-04-20 | 2012-02-23 | Bo Corporation North America Inc. | Process for Regenerating Coked Particles |
US20110005968A1 (en) * | 2009-07-07 | 2011-01-13 | Bp Corporation North America Inc. | Coking Process Additives and Related Processes |
US8372269B2 (en) * | 2009-10-02 | 2013-02-12 | Basf Corporation | Heavy metals trapping co-catalyst for FCC processes |
CN102133538B (zh) * | 2010-01-27 | 2014-03-26 | 华东理工大学 | 一种可磁分离的抗重金属助剂及其制备方法和使用方法 |
CN102971399B (zh) | 2010-07-08 | 2015-04-01 | 印度石油股份有限公司 | 增值的废流化催化裂化催化剂组合物和其制备工艺 |
US8586500B2 (en) | 2010-11-11 | 2013-11-19 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US8575061B2 (en) | 2010-11-11 | 2013-11-05 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US9168519B2 (en) | 2010-11-11 | 2015-10-27 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
AU2011326682B2 (en) | 2010-11-11 | 2016-07-14 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US8658558B2 (en) | 2010-11-11 | 2014-02-25 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US8575062B2 (en) | 2010-11-11 | 2013-11-05 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US8632674B2 (en) * | 2010-11-16 | 2014-01-21 | Basf Corporation | Heavy metal passivator/trap for FCC processes |
CN102974337B (zh) * | 2011-09-06 | 2014-12-31 | 中国石油化工股份有限公司 | 一种催化裂化助剂及其制备方法 |
US20140148632A1 (en) * | 2011-11-18 | 2014-05-29 | Uop Llc | Resid catalytic cracker and catalyst for increased propylene yield |
JP6074559B2 (ja) | 2012-05-25 | 2017-02-08 | サウジ アラビアン オイル カンパニー | 流動接触分解においてプロピレンを増強させるための触媒 |
US9504993B2 (en) | 2012-09-05 | 2016-11-29 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalysts and method for making thereof |
WO2015051266A1 (en) * | 2013-10-04 | 2015-04-09 | Johnson Matthey Process Technologies, Inc. | Process for reactivating an iron-contaminated fcc catalyst |
US9796932B2 (en) | 2013-12-19 | 2017-10-24 | Basf Corporation | FCC catalyst compositions containing boron oxide and phosphorus |
US20150174559A1 (en) | 2013-12-19 | 2015-06-25 | Basf Corporation | Phosphorus-Modified FCC Catalysts |
US9895680B2 (en) | 2013-12-19 | 2018-02-20 | Basf Corporation | FCC catalyst compositions containing boron oxide |
US9441167B2 (en) | 2013-12-19 | 2016-09-13 | Basf Corporation | Boron oxide in FCC processes |
BR112019005282A2 (pt) | 2016-09-16 | 2019-06-04 | Lummus Technology Llc | processo e aparelho para a remoção melhorada de contaminantes em um processos de craqueamento catalítico fluidizado |
US11332675B2 (en) | 2017-12-11 | 2022-05-17 | Basf Corporation | Reactive silica-alumina matrix component compositions for bottoms cracking catalysts |
JP7208125B2 (ja) * | 2019-09-30 | 2023-01-18 | 日揮触媒化成株式会社 | 流動接触分解触媒用添加剤および流動接触分解触媒用添加剤の製造方法、ならびに触媒組成物 |
CN114768783A (zh) * | 2022-05-21 | 2022-07-22 | 山西腾茂科技股份有限公司 | 一种fcc废催化剂改性和再利用方法 |
CN114950574B (zh) * | 2022-07-29 | 2023-03-24 | 碳中能源科技(淄博)有限公司 | 一种fcc重金属污染元素捕集剂 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4889615A (en) * | 1988-12-06 | 1989-12-26 | Mobil Oil Corporation | Additive for vanadium capture in catalytic cracking |
US5141624A (en) * | 1989-03-30 | 1992-08-25 | Phillips Petroleum Company | Catalytic cracking process |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4259176A (en) * | 1979-09-13 | 1981-03-31 | Chevron Research Company | Restricting silica content of catalyst inventory to prevent alumina poisoning for SOx control |
US4252635A (en) * | 1980-04-11 | 1981-02-24 | Chevron Research Company | Sulfur oxides control in cracking catalyst regeneration |
MX162472A (es) * | 1981-04-10 | 1991-05-13 | Ashland Oil Inc | Catalizador para la conversion a productos mas ligeros de alimentaciones de aceites de hidrocarburo |
US4650564A (en) * | 1982-03-03 | 1987-03-17 | Gulf Research & Development Company | Process for cracking high metals content feedstocks |
US4944865A (en) * | 1982-05-06 | 1990-07-31 | Chevron Research Company | Process for cracking high metals content feedstocks |
US4465588A (en) * | 1982-05-06 | 1984-08-14 | Gulf Research & Development Company | Process for cracking high metals content feedstock |
US4493902A (en) | 1983-02-25 | 1985-01-15 | Engelhard Corporation | Fluid catalytic cracking catalyst comprising microspheres containing more than about 40 percent by weight Y-faujasite and methods for making |
ZA861527B (en) | 1985-03-01 | 1987-02-25 | Engelhard Corp | High octane,high gasoline selectivity catalyst |
US4657779A (en) * | 1986-03-19 | 1987-04-14 | Desoto, Inc. | Shrinkage-resistant ultraviolet-curing coatings |
US4708786A (en) * | 1986-03-26 | 1987-11-24 | Union Oil Company Of California | Process for the catalytic cracking of nitrogen-containing feedstocks |
ZA876932B (en) * | 1986-12-04 | 1988-05-16 | Engelhard Corporation | Catalytic cracking of metal contaminated feedstock |
US4929337A (en) * | 1988-12-30 | 1990-05-29 | Mobil Oil Corporation | Process for catalytic cracking of heavy hydrocarbon feed to lighter products |
US4988653A (en) * | 1988-12-30 | 1991-01-29 | Mobil Oil Corporation | Elutriable multi component cracking catalyst mixture and a process for catalytic cracking of heavy hydrocarbon feed to lighter products |
US5174890A (en) * | 1989-07-31 | 1992-12-29 | Union Oil Company Of California | Catalytic cracking using a metals scavenging composition |
US5260240A (en) * | 1989-12-29 | 1993-11-09 | Chevron Research And Technology Company | Process for the demetallization of FCC catalyst |
US5071807A (en) * | 1989-12-29 | 1991-12-10 | Chevron Research Company | Hydrocarbon processing composition |
US5300469A (en) * | 1992-12-08 | 1994-04-05 | Engelhard Corporation | Composition for passivating vanadium in catalytic cracking and preparation thereof |
US5559067A (en) * | 1995-03-31 | 1996-09-24 | Engelhard Corporation | Modified microsphere FCC catalysts and manufacture thereof |
US6028023A (en) * | 1997-10-20 | 2000-02-22 | Bulldog Technologies U.S.A., Inc. | Process for making, and use of, anionic clay materials |
US6372124B2 (en) | 2000-01-03 | 2002-04-16 | Saint-Gobain Norpro Corporation | Removal of impurities from hydrocarbon streams |
JP3842086B2 (ja) * | 2000-08-28 | 2006-11-08 | 財団法人石油産業活性化センター | 重質炭化水素油の流動接触分解用触媒及び流動接触分解方法 |
US6673235B2 (en) * | 2000-09-22 | 2004-01-06 | Engelhard Corporation | FCC catalysts for feeds containing nickel and vanadium |
US6656347B2 (en) * | 2000-09-22 | 2003-12-02 | Engelhard Corporation | Structurally enhanced cracking catalysts |
US20030089640A1 (en) * | 2001-10-17 | 2003-05-15 | Rostam Madon | FCC catalysts for feeds containing nickel and vanadium |
BR0100680A (pt) * | 2001-02-21 | 2002-11-05 | Petroleo Brasileiro Sa | Composições catalìticas multiparticuladas para craqueamento catalìtico fluido (fcc), processo de craqueamento catalìtico fluido (fcc) e uso das mesmas |
US6696378B2 (en) * | 2001-08-31 | 2004-02-24 | Engelhard Corporation | Fluid catalytic cracking catalyst manufacturing process |
-
2005
- 2005-09-06 US US11/220,234 patent/US20060060504A1/en not_active Abandoned
- 2005-09-07 UA UAA200703816A patent/UA95062C2/ru unknown
- 2005-09-07 SG SG200804142-8A patent/SG143282A1/en unknown
- 2005-09-07 CA CA2579299A patent/CA2579299C/en not_active Expired - Fee Related
- 2005-09-07 JP JP2007531258A patent/JP5492378B2/ja not_active Expired - Fee Related
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- 2005-09-07 KR KR1020077007932A patent/KR20070100877A/ko active Search and Examination
- 2005-09-07 EP EP05793940A patent/EP1793928A4/en not_active Withdrawn
- 2005-09-07 CN CN2005800300221A patent/CN101027128B/zh not_active Expired - Fee Related
- 2005-09-07 ZA ZA200702259A patent/ZA200702259B/en unknown
- 2005-09-07 WO PCT/US2005/031649 patent/WO2006029129A2/en active Application Filing
- 2005-09-07 AU AU2005282537A patent/AU2005282537B2/en not_active Ceased
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4889615A (en) * | 1988-12-06 | 1989-12-26 | Mobil Oil Corporation | Additive for vanadium capture in catalytic cracking |
US5141624A (en) * | 1989-03-30 | 1992-08-25 | Phillips Petroleum Company | Catalytic cracking process |
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UA95062C2 (ru) | 2011-07-11 |
AU2005282537A1 (en) | 2006-03-16 |
CN101027128B (zh) | 2011-07-06 |
CA2579299C (en) | 2013-05-07 |
TW200609038A (en) | 2006-03-16 |
SG143282A1 (en) | 2008-06-27 |
RU2007112934A (ru) | 2008-10-20 |
CA2579299A1 (en) | 2006-03-16 |
EP1793928A2 (en) | 2007-06-13 |
KR20070100877A (ko) | 2007-10-12 |
MX2007002527A (es) | 2007-05-09 |
CN101027128A (zh) | 2007-08-29 |
US20100025297A1 (en) | 2010-02-04 |
WO2006029129A2 (en) | 2006-03-16 |
AU2005282537B2 (en) | 2011-05-26 |
US20060060504A1 (en) | 2006-03-23 |
WO2006029129A3 (en) | 2007-01-11 |
US8197669B2 (en) | 2012-06-12 |
EP1793928A4 (en) | 2010-10-20 |
ZA200702259B (en) | 2008-06-25 |
JP2008512553A (ja) | 2008-04-24 |
JP5492378B2 (ja) | 2014-05-14 |
RU2376061C2 (ru) | 2009-12-20 |
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