JP6010083B2 - FCC再生器からのSOx排出を低減するための添加剤を含む陰イオン性粘土およびそれらの製造プロセス - Google Patents
FCC再生器からのSOx排出を低減するための添加剤を含む陰イオン性粘土およびそれらの製造プロセス Download PDFInfo
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- JP6010083B2 JP6010083B2 JP2014212855A JP2014212855A JP6010083B2 JP 6010083 B2 JP6010083 B2 JP 6010083B2 JP 2014212855 A JP2014212855 A JP 2014212855A JP 2014212855 A JP2014212855 A JP 2014212855A JP 6010083 B2 JP6010083 B2 JP 6010083B2
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- additive
- anionic
- anionic clay
- physical mixture
- metal compound
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- 125000000129 anionic group Chemical group 0.000 title claims description 91
- 239000000654 additive Substances 0.000 title claims description 74
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims description 76
- 239000004927 clay Substances 0.000 claims description 67
- 230000008569 process Effects 0.000 claims description 55
- 230000000996 additive effect Effects 0.000 claims description 47
- 150000002736 metal compounds Chemical class 0.000 claims description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 46
- 150000001450 anions Chemical class 0.000 claims description 44
- 239000006069 physical mixture Substances 0.000 claims description 39
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- 238000001354 calcination Methods 0.000 claims description 30
- 229910052742 iron Inorganic materials 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229910052720 vanadium Inorganic materials 0.000 claims description 17
- 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 description 16
- 239000007900 aqueous suspension Substances 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 239000010955 niobium Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052758 niobium Inorganic materials 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 10
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- 239000002019 doping agent Substances 0.000 claims description 9
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
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- 229910001412 inorganic anion Inorganic materials 0.000 claims description 5
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 150000002891 organic anions Chemical class 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 27
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 22
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- 238000006243 chemical reaction Methods 0.000 description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
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- 150000003839 salts Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000571 coke Substances 0.000 description 7
- 229910001701 hydrotalcite Inorganic materials 0.000 description 7
- 229960001545 hydrotalcite Drugs 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 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 6
- 150000004679 hydroxides Chemical class 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
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- 239000000843 powder Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
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- 239000004332 silver Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
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- 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 5
- 239000000047 product Substances 0.000 description 5
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
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- 235000012211 aluminium silicate Nutrition 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 239000000084 colloidal system Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 3
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910003120 Zn-Ce Inorganic materials 0.000 description 1
- HBDGIAVQHKWFSU-UHFFFAOYSA-K [Al](Cl)(Cl)Cl.[N+](=O)([O-])[O-].[Al+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [Al](Cl)(Cl)Cl.[N+](=O)([O-])[O-].[Al+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] HBDGIAVQHKWFSU-UHFFFAOYSA-K 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical class OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-M decanoate Chemical compound CCCCCCCCCC([O-])=O GHVNFZFCNZKVNT-UHFFFAOYSA-M 0.000 description 1
- 230000001419 dependent effect Effects 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
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 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
- GMDNUWQNDQDBNQ-UHFFFAOYSA-L magnesium;diformate Chemical compound [Mg+2].[O-]C=O.[O-]C=O GMDNUWQNDQDBNQ-UHFFFAOYSA-L 0.000 description 1
- OUHCLAKJJGMPSW-UHFFFAOYSA-L magnesium;hydrogen carbonate;hydroxide Chemical compound O.[Mg+2].[O-]C([O-])=O OUHCLAKJJGMPSW-UHFFFAOYSA-L 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- CAYKLJBSARHIDI-UHFFFAOYSA-K trichloroalumane;hydrate Chemical compound O.Cl[Al](Cl)Cl CAYKLJBSARHIDI-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/508—Sulfur oxides by treating the gases with solids
-
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
- C09C1/42—Clays
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
- C10G11/182—Regeneration
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/2047—Magnesium
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- B01D2255/2092—Aluminium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Description
が、ハイドロタルサイト(Mg6Al2(OH)16(CO3)4H2O)のパターンと類似するため、陰イオン性粘土は、「ハイドロタルサイト様化合物」と称されることも多い。
solids”(1992), 2, 108, editors: M. I. Occelli, H. E. Robson, Van Nostrand Reinhold, N.Y。
Catalytic Cracking, Petroleum Technology Quarterly, presented at the European Refining Technology Conference, Feb 2000)。
いて良好なSOx低減性能を呈する、バナジウムを含まない物質の必要性が存在する。
ある。好適な不水溶性アルミニウム化合物には、遷移アルミナ、アルミニウム三水和物(ボーキサイト鉱石の精鉱、ギブサイト、バイヤライト)およびその熱処理を施した形態(瞬間的にか焼したアルミニウム三水和物を含む)、ゾル、非晶質アルミナ、(偽)ベーマイト等の酸化アルミニウムおよび水酸化アルミニウム、カオリン、セピオライト、ベントナイト等のアルミニウムを含有する粘土、ならびにメタカオリン等の改質粘土を含む。好適な水溶性アルミニウム塩は、硝酸アルミニウム、塩化アルミニウム、塩化アルミニウム水和物(aluminium chlorohydrate)、およびアルミン酸ナトリウムである。
任意選択的に、米国特許申請番号第2003−0003035号による連続多段階操作において、実施することができる。例えば、再水和懸濁液は、フィード調製容器の中で調製され、その後、懸濁液は2つ以上の変換容器を通して連続的に汲み上げられる。必要に応じて、添加剤、酸、または塩基を、いずれかの変換容器内の懸濁液に加えてもよい。各容器は、それぞれの望ましい温度に調節することが可能である。
び再水和ステップと同じかまたは異なる条件下のいずれかで行うことができる。付加的なか焼ステップ(複数を含む)および/または再水和ステップ(複数を含む)の最中に、追加の添加剤を加えることができる。これらの追加の添加剤は、物理的混合物および/またはステップc)の水性懸濁液と同じでもまたは異なっていてもよい。
SOx添加剤の調製
添加剤の周期的な失活
SOx添加剤試験
4)N2下でサンプルを575℃まで冷却した、5)575℃の温度で5分間維持した後、サンプルをH2流(N2中の5% H2)に10分間暴露した、6)N2下でサンプルを20℃/分で725℃まで加熱した、7)ステップ2から6を繰り返す、8)ステップ2から5を繰り返す。SO2回収およびH2放出サイクルの間の重量%の変化を、TGAのためのソフトウェアを用いて決定した。Fe、CuおよびZn−Ce/HTCは、バナジウム含有物質と比較して、同等のSOxの回収量を示したが、放出量は高かった。TGA結果(重量%の変化)
物理的特性の比較
1.添加剤を含有する陰イオン性粘土の調製のためのプロセスであって、
ア 2価金属化合物と3価金属化合物との物理的混合物を粉砕するステップと、
イ 前記粉砕された物理的混合物を、約200℃〜約800℃の範囲の温度でか焼する
ステップと、
ウ 前記か焼された混合物を水性懸濁液中で再水和させて、添加剤を含有する陰イオン
性粘土を形成するステップと、を含み、
添加剤はステップ(a)の前記物理的混合物中に任意選択的に存在し、添加剤はステップ(c)の前記水性懸濁液中に存在し、前記添加剤を含有する陰イオン性粘土は、実質上バナジウムを含まない、プロセス。
2. 前記粉砕は、ボールミル、ビーズミル、サンドミル、コロイドミル、ニーダー、もしくは高剪断ミキサーにおいて、または超音波を用いて行われる、項目1に記載のプロセス。
3. 前記か焼温度は約300〜約700℃の範囲である、項目1に記載のプロセス。
4. 前記か焼温度は約350〜約600℃の範囲である、項目3に記載のプロセス。
5. 前記ステップa)の物理的混合物を熟成させるステップをさらに含む、項目1に記載のプロセス。
6. 前記熟成は、約20〜約110℃の範囲の温度で、約15分〜約6時間の範囲である、項目5に記載のプロセス。
7. 前記2価金属は、マグネシウム、亜鉛、ニッケル、銅、鉄、コバルト、マンガン、カルシウム、バリウム、ストロンチウム、およびそれらの組み合わせである、項目1に記載のプロセス。
8. 前記2価金属は、マグネシウム、マンガン、鉄、またはそれらの組み合わせである、項目7に記載のプロセス。
9. 前記3価金属は、アルミニウム、ガリウム、鉄、クロム、バナジウム、コバルト、マンガン、ニッケル、インジウム、セリウム、ニオブ、ランタン、およびそれらの組み合わせである、項目1に記載のプロセス。
10. 前記3価金属はアルミニウムである、項目9に記載のプロセス。
11. 前記添加剤は、アルカリ土類金属、IIIB族遷移金属、IVB族遷移金属、バナジウムを除くVB族遷移金属、VIB族遷移金属、VIIB族遷移金属、VIII族遷移金属、IB族遷移金属、IIB族遷移金属、IIIA族元素、IVA族元素、VA族元素、ランタニド、およびそれらの混合物からなる群から選択される元素を含む化合物であるが、ただし、前記元素は、ステップa)の前記2価および前記3価金属化合物を構成する金属とは異なる、項目1に記載のプロセス。
12. 前記添加剤は、鉄、亜鉛、ジルコニウム、ニオブ、銀、マンガン、銅、クロム、ロジウム、およびそれらの組み合わせからなる群から選択される元素を含む化合物である、項目11に記載のプロセス。
13. 前記添加剤は、酸化物、水酸化物、またはヒドロキシカーボネートである、項目12に記載のプロセス。
14. 前記形成された添加剤を含有する陰イオン性粘土を後にか焼するステップをさらに含む、項目1に記載のプロセス。
15. 前記後にか焼された添加剤を含有する陰イオン性粘土を再水和するステップをさらに含む、項目14に記載のプロセス。
16. ステップ(c)の間に陰イオン性物質が存在する、項目1に記載のプロセス。
17. 前記陰イオン性物質は、無機陰イオン、有機陰イオン、およびポリマー陰イオンからなる群から選択される陰イオンを供給する、項目16に記載のプロセス。
18. 前記供給される陰イオンはSO4 2である、項目17に記載のプロセス。
19. 前記2価金属化合物および/または前記3価金属化合物は、ドーパントを含有する金属化合物である、項目1に記載のプロセス。
20. 前記ドーパントは、アルカリ土類金属、アルカリ金属、遷移金属、アクチニド、希土類金属、貴金属、ケイ素、ガリウム、ホウ素、チタン、およびリンからなる群から選択される元素を含有する化合物である、項目19に記載のプロセス。
21. 前記ドーパントは、鉄、亜鉛、ジルコニウム、ニオブ、銀、マンガン、銅、クロム、ロジウム、およびそれらの組み合わせからなる群から選択される元素を含有する化合物である、項目20に記載のプロセス。
22. 前記ドーパントは、硝酸塩、硫酸塩、塩化物、ギ酸塩、酢酸塩、シュウ酸塩、アルコキシド、炭酸塩、またはタングステン酸塩である、項目21に記載のプロセス。
23.
ア 2価金属化合物と3価金属化合物との物理的混合物を粉砕するステップと、
イ 前記粉砕された物理的混合物を、約200℃〜約800℃の範囲の温度でか焼する
ステップと、
ウ 前記か焼された混合物を水性懸濁液中で再水和させて、添加剤を含有する陰イオン
性粘土を形成するステップと、を含むプロセスによって製造される陰イオン性粘土
であって、
添加剤はステップ(a)の前記物理的混合物中に任意選択的に存在し、添加剤はステップ(c)の前記水性懸濁液中に存在し、前記陰イオン性粘土は、実質上バナジウムを含まない、陰イオン性粘土。
24. 前記ステップa)の物理的混合物を熟成させるステップをさらに含む、項目23
に記載の陰イオン性粘土。
25. 前記熟成は、約20〜約90℃の範囲の温度で、約15分〜約6時間の範囲である、項目24に記載のプロセス。
26. 前記2価金属は、マグネシウム、マンガン、鉄、またはそれらの組み合わせである、項目23に記載の陰イオン性粘土。
27. 前記3価金属はアルミニウムである、項目23に記載の陰イオン性粘土。
28. 前記添加剤は、鉄、亜鉛、ジルコニウム、ニオブ、銀、マンガン、銅、クロム、ロジウム、およびそれらの組み合わせからなる群から選択される元素を含む化合物である、項目23に記載の陰イオン性粘土。
29. 前記2価金属化合物および/または前記3価金属化合物は、鉄、亜鉛、ジルコニウム、ニオブ、銀、マンガン、銅、クロム、ロジウム、およびそれらの組み合わせからなる群から選択される元素を含有する化合物でドープされる、項目23に記載の陰イオン性粘土。
30. 前記2価金属化合物はセリウムを含む、項目23に記載の陰イオン性粘土。
31. ステップc)の間に陰イオン性物質が存在する、項目23に記載の陰イオン性粘土。
32. 前記陰イオン性物質は、無機陰イオン、有機陰イオン、およびポリマー陰イオンからなる群から選択される陰イオンを供給する、項目31に記載の陰イオン性粘土。
33. 前記供給される陰イオンはSO4 2‐である、項目32に記載の陰イオン性粘土。34. FCC再生器からのSOx排出量を低減させるための方法であって、2価金属化合物と3価金属化合物との物理的混合物を粉砕するステップと、前記粉砕された物理的混合物を、約200℃〜約800℃の範囲の温度でか焼するステップと、前記か焼された混合物を水性懸濁液中で再水和させて、添加剤を含有する陰イオン性粘土を形成するステップと、を含むプロセスによって製造される前記陰イオン性粘土を、前記FCC再生器に加えるステップを含み、添加剤は前記物理的混合物中に任意選択的に存在し、添加剤は前記水性懸濁液中に存在し、前記陰イオン性粘土は実質上バナジウムを含まない、方法。
35. 前記物理的混合物を、約20〜約90℃の範囲の温度で、約15分〜約6時間熟成させるステップをさらに含む、項目34に記載の方法。
36. 前記2価金属は、マグネシウム、マンガン、鉄、またはそれらの組み合わせである、項目34に記載の方法。
37. 前記3価金属はアルミニウムである、項目34に記載の方法。
38. 前記添加剤は、鉄、亜鉛、ジルコニウム、ニオブ、銀、マンガン、銅、クロム、ロジウム、およびそれらの組み合わせからなる群から選択される元素を含む化合物である、項目34に記載の方法。
39. 前記2価金属化合物および/または前記3価金属化合物は、鉄、亜鉛、ジルコニウム、ニオブ、銀、マンガン、銅、クロム、ロジウム、およびそれらの組み合わせからなる群から選択される元素を含有する化合物でドープされる、項目34に記載の方法。
40. 前記2価金属化合物はセリウムを含む、項目34に記載の方法。
41. ステップc)の間に陰イオン性物質が存在する、項目34に記載の方法。
42. 前記陰イオン性物質は、無機陰イオン、有機陰イオン、およびポリマー陰イオンからなる群から選択される陰イオンを供給する、項目41に記載の陰イオン性粘土。
43. 前記供給される陰イオンはSO4 2‐である、項目42に記載の陰イオン性粘土。
Claims (13)
- 添加剤を含有する陰イオン性粘土の調製のためのプロセスであって、
(a)2価金属化合物と3価金属化合物との物理的混合物を粉砕するステップと、
(b)前記粉砕された物理的混合物を、200℃〜800℃の範囲の温度でか焼するステップと、
(c)前記か焼された混合物を水性懸濁液中で再水和させて、添加剤を含有する陰イオン性粘土を形成するステップと、を含み、
ここで、ステップ(a)において硝酸セリウムが物理的混合物に添加され、添加剤はステップ(c)の前記水性懸濁液中に存在し、前記添加剤を含有する陰イオン性粘土はバナジウムを含まず、添加剤は鉄または亜鉛から選択される元素を含む化合物である、
プロセス。 - 前記か焼温度は300〜700℃の範囲である、請求項1に記載のプロセス。
- 前記ステップ(a)の物理的混合物を熟成させるステップをさらに含む、請求項1に記載のプロセス。
- 前記2価金属は、マグネシウム、亜鉛、ニッケル、銅、鉄、コバルト、マンガン、カルシウム、バリウム、またはストロンチウムである、請求項1に記載のプロセス。
- 前記3価金属は、アルミニウム、ガリウム、鉄、クロム、コバルト、マンガン、ニッケル、インジウム、セリウム、ニオブ、またはランタンである、請求項1に記載のプロセス。
- 前記形成された添加剤を含有する陰イオン性粘土を後にか焼するステップをさらに含む、請求項1に記載のプロセス。
- 前記後にか焼された添加剤を含有する陰イオン性粘土を再水和するステップをさらに含む、請求項6に記載のプロセス。
- 前記2価金属化合物および/または前記3価金属化合物は、ドーパントを含有する金属化合物である、請求項1に記載のプロセス。
- FCC再生器からのSOx排出量を低減させるための方法であって、請求項1−8のいずれか1項記載のプロセス、または、ステップ(a)の物理的混合物を熟成させるステップを更に含む上記プロセスによって陰イオン性粘土を製造し、前記FCC再生器に加えるステップを含む方法。
- 前記物理的混合物を、20〜90℃の範囲の温度で、15分〜6時間熟成させるステップをさらに含む、請求項9に記載の方法。
- ステップ(c)の間に陰イオン性物質が存在する、請求項1記載のプロセス。
- 陰イオン性物質が、無機陰イオン、有機陰イオンおよびポリマー陰イオンからなる群から選択される陰イオンを供給する、請求項11に記載のプロセス。
- 供給される陰イオンがSO4 2-である、請求項12に記載のプロセス。
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