JP7080217B2 - 複数のシリカを有するfcc触媒、その調製及び使用 - Google Patents
複数のシリカを有するfcc触媒、その調製及び使用 Download PDFInfo
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- JP7080217B2 JP7080217B2 JP2019506090A JP2019506090A JP7080217B2 JP 7080217 B2 JP7080217 B2 JP 7080217B2 JP 2019506090 A JP2019506090 A JP 2019506090A JP 2019506090 A JP2019506090 A JP 2019506090A JP 7080217 B2 JP7080217 B2 JP 7080217B2
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- weight
- silica
- slurry
- dry base
- fcc catalyst
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- 239000003054 catalyst Substances 0.000 title claims description 109
- 238000002360 preparation method Methods 0.000 title description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 202
- 239000000377 silicon dioxide Substances 0.000 claims description 81
- 239000002002 slurry Substances 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 47
- 239000010457 zeolite Substances 0.000 claims description 41
- 239000002253 acid Substances 0.000 claims description 40
- 239000008119 colloidal silica Substances 0.000 claims description 40
- 230000008569 process Effects 0.000 claims description 36
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 33
- 229910001593 boehmite Inorganic materials 0.000 claims description 31
- 239000011734 sodium Substances 0.000 claims description 25
- 229910052708 sodium Inorganic materials 0.000 claims description 25
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 24
- 229910021536 Zeolite Inorganic materials 0.000 claims description 22
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 22
- 230000002378 acidificating effect Effects 0.000 claims description 20
- 239000004927 clay Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 230000000368 destabilizing effect Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000009849 deactivation Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 238000001694 spray drying Methods 0.000 description 9
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- -1 IVA Transition Metals Chemical class 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229910052916 barium silicate Inorganic materials 0.000 description 2
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 229960003340 calcium silicate Drugs 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000001687 destabilization Effects 0.000 description 2
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[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 PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical class [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 238000013411 master cell bank Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000036314 physical performance Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical compound [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 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
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229940094522 laponite Drugs 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- JCCNYMKQOSZNPW-UHFFFAOYSA-N loratadine Chemical compound C1CN(C(=O)OCC)CCC1=C1C2=NC=CC=C2CCC2=CC(Cl)=CC=C21 JCCNYMKQOSZNPW-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052917 strontium silicate Inorganic materials 0.000 description 1
- QSQXISIULMTHLV-UHFFFAOYSA-N strontium;dioxido(oxo)silane Chemical compound [Sr+2].[O-][Si]([O-])=O QSQXISIULMTHLV-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
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Description
、硫酸塩、及び(部分的に)ゲル化したシリカなどのゲル誘導剤の添加によって達成される。不安定化の前に、スラリー中に存在する任意の解膠性化合物を十分に解膠しなければならなかった。
(a)粘土、ベーマイト及びナトリウム安定化塩基性コロイダルシリカを添加してスラリーを形成すること;
(b)スラリーを一塩基酸で4未満のpHに消化すること;
(c)スラリーに1種以上のゼオライトを添加すること;
(d)別個に作製されインラインで添加されたポリケイ酸を添加すること;
(e)スラリーを混合し、次いでpHを4.0超に上げることによってスラリーを不安定化すること
(f)得られたFCC触媒を成形し、回収すること;
(g)続いて任意に必要に応じて過剰のナトリウムを除去するための焼成工程及び後洗浄工程、
を含む。
(a)粘土、ベーマイト、ナトリウム安定化塩基性コロイダルシリカを添加してスラリーを形成すること;
(b)スラリーを一塩基酸で4未満のpHに消化すること;
(c)スラリーに1種以上のゼオライトを添加すること;
(d)工程(a)~(c)の間または後であるが工程(e)の前の任意の時点で酸性コロイダルシリカを添加すること;
(e)スラリーを混合し、次いでpHを4.0超に上げることによってスラリーを不安定化すること;
(f)得られたFCC触媒を成形し、回収すること
を含む。
ば、改善された触媒は、改善された摩耗ならびにより高いABD及びアクセシビリティを示す。更に、改善した触媒は、失活後にゼオライト及び触媒のより高い安定性をもたらす。
a)約5~約60重量%の1種以上のゼオライト、約15~約35重量%の準結晶性ベーマイト、約0~約35重量%の微結晶性ベーマイト、約0重量%を超え約15重量%以下のナトリウム安定化塩基性コロイダルシリカからのシリカ、約0重量%を超え約30重量%以下の酸性コロイダルシリカまたはポリケイ酸からのシリカ、及び残部の粘土を含むFCC触媒組成物を提供する工程;
b)FCC触媒を前記石油留分供給原料と0.5~12秒の範囲の滞留時間で400~650℃の範囲の温度で接触させる工程、
を含む。
改善された触媒を製造するプロセスの第1の工程は、粘土源をナトリウム安定化塩基性コロイダルシリカ、及び1種以上のアルミナ(ベーマイト)源と混合することである。以下に論述するように、酸性コロイダルシリカの第2のシリカ源をこのスラリーにまたは後の工程で任意に添加することができる。粘土、ゼオライト、QCB、MCB、ナトリウム安定化塩基性コロイダルシリカ、及び任意の他の成分は、それらを乾燥固体として水に添加することによってスラリー化され得る。代替的には、個々の材料を含有するスラリーを混合して、工程a)に従ってスラリーを形成する。また、材料の一部をスラリーとして、且つ他の材料を乾燥固体として添加することも可能である。任意に、アルミニウムクロロヒドロール、硝酸アルミニウム、Al2O3、Al(OH)3、アニオン性粘土(例えば、ハイドロタルサイト)、スメクタイト、セピオライト、チタン酸バリウム、チタン酸カルシウム、カルシウム-ケイ酸塩、マグネシウム-ケイ酸塩、チタン酸マグネシウム、混合金属酸化物、層状ヒドロキシ塩、追加のゼオライト、酸化マグネシウム、塩基もしくは塩、及び/またはアルカリ土類金属(例えば、Mg、Ca、及びBa)、IIIA族遷移金属、IVA族遷移金属(例えば、Ti、Zr)、VA族遷移金属(例えば、V、Nb)、VIA族遷移金属(例えば、Cr、Mo、W)、VIIA族遷移金属(例えば、Mn)、VIIIA族遷移金属(例えば、Fe、Co、Ni、Ru、Rh、Pd、Pt)、IB族遷移金属(例えば、Cu)、IIB族遷移金属(例えば、Zn)、ランタニド(例えば、La、Ce)、またはそれらの混合物を含有する化合物などの金属添加剤などの他の成分が添加され得る。これらの化合物の任意の添加順序が使用され得る。これらの化合物を全て同時に組み合わせることも可能である。
に近いX線回折(XRD)パターンを示すアルミナ水和物を記述するために業界で使用されている。更に、ベーマイトという用語は一般に、異なる量の水和水を含有し、異なる表面積、細孔容積、比密度を有し、熱処理時に異なる熱特性を示す広い範囲のアルミナ水和物を記述するために使用される。それにもかかわらず、それらのXRDパターンは、それらが特徴的なベーマイト[AlO(OH)]ピークを示すものの、通常はそれらの幅が変化し、それらの位置もシフトし得る。XRDピークの鋭さ及びそれらの位置は、結晶化度、結晶サイズ、及び欠陥の量を示すために使用されてきた。
得るのに十分な量でスラリーに添加される。
本発明の独特の特徴は、触媒粒子内での少なくとも2つのシリカ源の使用である。添加されるシリカの総量は1.0%を超える。総シリカは約5.0%を超えることが好ましく、シリカの総量は約10.0%を超えることが最も好ましい。更に、第1のシリカ源の第2のシリカ源に対する比は、約1:1~約1:10であることが好ましい。
、ナトリウム安定化塩基性コロイダルシリカである。スラリーは、最終触媒の重量を基準として0重量%を超え約15重量%以下、より好ましくは約0.5重量%を超え約10重量%以下、最も好ましくは約1重量%を超え8重量%以下の低ナトリウムケイ素源からのシリカを更に含む。
このようにして得られた触媒は、極めて良好な摩耗抵抗性及びアクセシビリティを有する。そのため、本発明はまた、本発明によるプロセスによって得ることができる触媒に関する。触媒は一般に、約5~約60%の1種以上のゼオライト、約15~約35重量%の準結晶性ベーマイト、約0~約25重量%の微結晶性ベーマイト、約0重量%を超え約15重量%以下のナトリウム安定化塩基性コロイダルシリカからのシリカ、約0重量%を超え約30重量%以下の酸性コロイダルシリカまたはポリケイ酸からのシリカ、及び残部の粘土を含むFCC触媒である。
AAI=-d(Ct/C0)/d(t1/2)*100%
この方程式において、tは時間(分)であり、C0及びCtはそれぞれ、実験の開始時及び時間tにおける溶媒中の高分子量化合物の濃度を表す。
有量は一定のままである。
Claims (11)
- FCC触媒組成物の重量を基準として、5~60重量%の1種以上のゼオライト、15~35重量%の準結晶性ベーマイト、0~35重量%の微結晶性ベーマイト、0重量%を超え15重量%以下のナトリウム安定化塩基性コロイダルシリカからのシリカ、0重量%を超え30重量%以下の酸性コロイダルシリカまたはポリケイ酸からのシリカ、及び残部の粘土を含む、FCC触媒組成物の製造方法であって、前記方法が、
(a)15~35重量%の準結晶性ベーマイト、0~35重量%の微結晶性ベーマイト、0重量%を超え15重量%以下のシリカを含有するナトリウム安定化塩基性コロイダルシリカ、及び残部重量%の粘土(後述の工程(c)及び(d)に定義されたとおりに添加されるゼオライトポリケイ酸又は酸性コロイダルシリカの量を考慮する)を添加してスラリーを形成する工程、
(b)前記スラリーを一塩基酸で4.0未満のpHに消化する工程、
(c)前記スラリーに5~60重量%の1種以上のゼオライトを添加する工程、
(d)別個に作製されインラインで添加された0重量%を超え30重量%以下のシリカを含有するポリケイ酸を添加するか、または、
工程(a)~(c)の間もしくは後であるが工程(e)の前の任意の時点で0重量%を超え30重量%以下のシリカを含有する酸性コロイダルシリカを添加する工程、
(e)前記スラリーを混合し、次いで前記pHを4.0超に上げることによって前記スラリーを不安定化する工程、
(f)得られたFCC触媒を成形し、回収する工程、
を含み、ここで前記重量%は、特定の物質または物質の形態が構成要素または成分である最終FCC触媒の総乾燥ベース重量を基準とする、物質の特定の形態の乾燥ベース重量%である、製造方法。 - 0.5重量%を超え10重量%以下のシリカを含有するナトリウム安定化塩基性コロイダルシリカが工程(a)で添加され、ここで前記重量%は、最終FCC触媒の総乾燥ベース重量を基準とする乾燥ベース重量%である、請求項1に記載の製造方法。
- 1重量%を超え8重量%以下のシリカを含有するナトリウム安定化塩基性コロイダルシリカが工程(a)で添加され、ここで前記重量%は、最終FCC触媒の総乾燥ベース重量を基準とする乾燥ベース重量%である、請求項2に記載の製造方法。
- 1重量%を超え25重量%以下のシリカを含有する酸性コロイダルシリカまたはポリケイ酸が工程(d)で添加され、ここで前記重量%は、最終FCC触媒の総乾燥ベース重量を基準とする乾燥ベース重量%である、請求項1に記載の製造方法。
- 5重量%を超え20重量%以下のシリカを含有する酸性コロイダルシリカまたはポリケイ酸が工程(d)で添加され、ここで前記重量%は、最終FCC触媒の総乾燥ベース重量を基準とする乾燥ベース重量%である、請求項4に記載の製造方法。
- FCC触媒を製造するためのプロセスであって:
a.粘土、準結晶性ベーマイト及び任意に微結晶性ベーマイト、並びにナトリウム安定化塩基性コロイダルシリカを添加してスラリーを形成する工程;
b.前記スラリーを一塩基酸で4.0未満のpHに消化する工程;
c.前記スラリーに1種以上のゼオライトを添加する工程;
d.別個に作製されインラインで添加されたポリケイ酸を添加するか、または、
工程a~cの間または後であるが工程eの前の任意の時点で酸性コロイダルシリカを添加する工程;
e.前記スラリーを混合し、次いで前記pHを4.0超に上げることによって前記スラリーを不安定化する工程、
f.得られたFCC触媒を成形し、回収する工程、
を含む、前記プロセス。 - 5~60重量%の1種以上のゼオライトを添加することを更に含み、ここで前記重量%は、最終FCC触媒の総乾燥ベース重量を基準とする乾燥ベース重量%である、請求項6に記載のプロセス。
- 0重量%を超え15重量%以下のシリカを含有するナトリウム安定化塩基性コロイダルシリカを添加する工程を更に含み、ここで前記重量%は、最終FCC触媒の総乾燥ベース重量を基準とする乾燥ベース重量%である、請求項6に記載のプロセス。
- 0重量%を超え30重量%以下のポリケイ酸を添加する工程を更に含み、ここで前記重量%は、最終FCC触媒の総乾燥ベース重量を基準とする乾燥ベース重量%である、請求項6に記載のプロセス。
- 0重量%を超え30重量%以下の酸性コロイダルシリカを添加する工程を更に含み、ここで前記重量%は、最終FCC触媒の総乾燥ベース重量を基準とする乾燥ベース重量%である、請求項6に記載のプロセス。
- 炭化水素供給原料からより多くの液体成分を生成するためのプロセスであって、
a.請求項1に記載の製造方法により製造されたFCC触媒組成物を提供する工程と
b.前記FCC触媒組成物を前記炭化水素供給原料と0.5~12秒の範囲の滞留時間で400~650℃の範囲の1つ以上の温度で接触させる工程であって、これにより前記炭化水素供給原料の重量を基準として4~20重量%の範囲の変換効率でプロピレンが形成される、前記接触させる工程、
を含む、前記プロセス。
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