CN109641193B - 具有多于一种二氧化硅的fcc催化剂、其制备和使用 - Google Patents
具有多于一种二氧化硅的fcc催化剂、其制备和使用 Download PDFInfo
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- CN109641193B CN109641193B CN201780049265.2A CN201780049265A CN109641193B CN 109641193 B CN109641193 B CN 109641193B CN 201780049265 A CN201780049265 A CN 201780049265A CN 109641193 B CN109641193 B CN 109641193B
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- China
- Prior art keywords
- silica
- slurry
- colloidal silica
- catalyst
- boehmite
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 215
- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title description 8
- 239000002253 acid Substances 0.000 claims abstract description 47
- 239000011734 sodium Substances 0.000 claims abstract description 45
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 45
- 239000008119 colloidal silica Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 43
- 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 abstract description 42
- 239000010457 zeolite Substances 0.000 claims abstract description 40
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 39
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 38
- 239000004927 clay Substances 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 22
- 230000002378 acidificating effect Effects 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 5
- 229910052570 clay Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000000368 destabilizing effect Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000005259 measurement Methods 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
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000004231 fluid catalytic cracking Methods 0.000 description 22
- 229910021536 Zeolite Inorganic materials 0.000 description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 20
- 239000002585 base Substances 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000009849 deactivation Effects 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- -1 aluminium chloro dihydrate Chemical class 0.000 description 9
- 238000001694 spray drying Methods 0.000 description 9
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 7
- 238000007493 shaping process Methods 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 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
- 239000000463 material Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 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
- 150000007513 acids Chemical class 0.000 description 4
- 230000008901 benefit Effects 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
- 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
- 239000000654 additive Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000010979 pH adjustment Methods 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
- 239000007921 spray Substances 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000004113 Sepiolite Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 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
- 229910052918 calcium silicate Inorganic materials 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
- 230000003197 catalytic effect Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007547 defect 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
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229910000271 hectorite Inorganic materials 0.000 description 2
- 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 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 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
- 238000013411 master cell bank Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 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
- 235000012239 silicon dioxide 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
- 229910018626 Al(OH) 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
- 229910014571 C—O—Si Inorganic materials 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- ILXDAXZQNSOSAE-UHFFFAOYSA-N [AlH3].[Cl] Chemical class [AlH3].[Cl] ILXDAXZQNSOSAE-UHFFFAOYSA-N 0.000 description 1
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical compound [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229960000892 attapulgite Drugs 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
- 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
- 239000013590 bulk material Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 239000012084 conversion product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 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
- 230000029087 digestion Effects 0.000 description 1
- FSBVERYRVPGNGG-UHFFFAOYSA-N dimagnesium dioxido-bis[[oxido(oxo)silyl]oxy]silane hydrate Chemical compound O.[Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O FSBVERYRVPGNGG-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 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
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000004898 kneading 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
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 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
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate 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
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 229910052901 montmorillonite 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
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane 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
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 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
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage 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
- 238000007669 thermal treatment Methods 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
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 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
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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Abstract
本文提供了用于制备催化剂的方法和包括使用多于一种二氧化硅源的催化剂。因此,在一个实施方案中,本发明提供一种微粒FCC催化剂,其包含约5至约60重量%的一种或多种沸石、约15至约35重量%的准晶勃姆石(QCB)、约0至约35重量%的微晶勃姆石(MCB)、大于约0至约15重量%的来自钠稳定的碱性胶体二氧化硅的二氧化硅、大于约0至约30重量%的来自酸性胶体二氧化硅或聚硅酸的二氧化硅以及余量的粘土;以及用于制备所述微粒FCC催化剂的方法。这种方法产生具有良好可及性的耐磨耗催化剂。
Description
技术领域
本发明涉及一种具有更好的物理性质和性能的催化剂组合物及其在用于包含烃的进料的裂化或转化的方法中的用途,所述烃例如像从原油的加工获得的那些。
背景技术
设计和生产非均相催化剂的共同挑战是在活性位点的有效性和/或可及性与固定基质在给与催化剂颗粒足够的物理强度(即耐磨耗性)方面的有效性之间找到良好的折衷。
在若干现有技术文献中公开了耐磨耗催化剂的制备。US 4,086,187公开了一种用于通过喷雾干燥水性浆料制备耐磨耗催化剂的方法,所述水性浆料通过将(i)钠含量小于5重量%的八面沸石与(ii)高岭土、(iii)胶溶假勃姆石和(iv)聚硅酸铵混合来制备。根据US4,206,085的耐磨耗催化剂通过喷雾干燥浆料来制备,所述浆料通过混合两种类型的酸化假勃姆石、沸石、氧化铝、粘土和聚硅酸铵或二氧化硅溶胶来制备。
GB 1 315 553公开了耐磨耗烃转化催化剂的制备,所述催化剂包含沸石、粘土和氧化铝粘合剂。通过首先将沸石和粘土干燥混合、随后添加氧化铝溶胶来制备催化剂。然后将所得混合物混合至塑料稠度,这需要约20分钟的混合时间。为了形成成形颗粒,将塑料稠度造粒或挤出,或者将它与水混合并随后喷雾干燥。此英国专利说明书中公开的氧化铝溶胶包含摩尔比为4.5至7.0的氢氧化铝和三氯化铝(也称为铝氯二聚水分子)。
US 4,458,023涉及类似的制备程序,随后煅烧喷雾干燥的颗粒。在煅烧过程中,铝氯二聚水分子组分被转化成氧化铝粘合剂。WO 96/09890公开了一种用于制备耐磨耗流化催化裂化催化剂的方法。这种方法涉及硫酸铝/二氧化硅溶胶、粘土浆料、沸石浆料和氧化铝浆料的混合,随后喷雾干燥。在此过程中,将酸或碱稳定的表面活性剂添加至二氧化硅溶胶、粘土浆料、沸石浆料、氧化铝浆料和/或喷雾干燥浆料中。CN 1247885还涉及喷雾干燥的裂化催化剂的制备。这种制备使用包含铝溶胶、假勃姆石、分子筛、粘土和无机酸的浆料。在这种方法中,将铝溶胶添加至所述浆料,之后添加粘土和无机酸,并在添加无机酸之后添加分子筛浆料。根据一个实施方案,首先将假勃姆石和铝溶胶混合,随后添加无机酸。在酸化后,添加分子筛,随后添加高岭土。
WO 02/098563公开了一种用于制备具有高耐磨耗性和高可及性的FCC催化剂的方法。通过将沸石、粘土和勃姆石浆化、将浆料进料至成形设备并使混合物成形以形成颗粒来制备所述催化剂,其特征在于就在成形步骤之前使所述混合物不稳定。这种不稳定是通过例如温度升高、pH增加、pH降低或添加凝胶诱导剂如盐、磷酸盐、硫酸盐和(部分)凝胶化二氧化硅来实现。在不稳定之前,浆料中存在的任何可胶溶的化合物必须已经良好地胶溶。
WO 06/067154描述了一种FCC催化剂、其制备及其用途。它公开了一种用于制备具有高耐磨耗性和高可及性的FCC催化剂的方法。通过将粘土、沸石、无钠二氧化硅源、准晶勃姆石和微晶勃姆石浆化来制备所述催化剂,条件是所述浆料不包含胶溶的准晶勃姆石,b)向所述浆料添加单价酸,c)将所述浆料的pH调节至高于3的值,以及d)使所述浆料成形以形成颗粒。
发明内容
本发明涉及一种意在用于裂化的方法中的FCC催化剂,在特定催化剂组合物上的烃进料以产生分子量低于进料烃的转化产物烃化合物,例如包含高汽油馏分的产物。本发明的独特特征是使用多于一种二氧化硅源。
因此,在一个实施方案中,提供了一种微粒FCC催化剂,其包含约5至约60重量%的一种或多种沸石、约15至约35重量%的准晶勃姆石(QCB)、约0至约35重量%的微晶勃姆石(MCB)、大于约0至约15重量%的来自钠稳定的碱性胶体二氧化硅的二氧化硅、大于约0至约30重量%的来自酸性胶体二氧化硅或聚硅酸的二氧化硅以及余量的粘土。
在另一个实施方案中,提供了一种用于制造FCC催化剂的方法,其中所述方法包括:
(a)添加粘土、勃姆石和钠稳定的碱性胶体二氧化硅以形成浆料;
(b)用一元酸将所述浆料消化至小于4的pH;
(c)将一种或多种沸石添加至所述浆料;
(d)添加单独制备并线内添加的聚硅酸;
(e)混合所述浆料且然后通过将pH升高至超过4.0来使所述浆料不稳定
(f)成形并收集所得FCC催化剂;
(g)任选地随后进行煅烧步骤和后洗涤步骤以根据需要除去过量的钠。
在另一个实施方案中,提供了一种用于制造FCC催化剂的方法,其中所述方法包括:
(a)添加粘土、勃姆石、钠稳定的碱性胶体二氧化硅以形成浆料;
(b)用一元酸将所述浆料消化至小于4的pH;
(c)将一种或多种沸石添加至所述浆料;
(d)在步骤(a)-(c)期间或之后但在步骤(e)之前的任何时间添加酸性胶体二氧化硅;
(e)混合所述浆料且然后通过将pH升高至超过4.0来使所述浆料不稳定;
(f)成形并收集所得FCC催化剂。
所得催化剂显示出相对于本领域中已知的催化剂改进的益处。例如,改进的催化剂表现出改进的磨耗和更高的ABD和可及性。此外,改进的催化剂在失活后产生更高的沸石和催化剂稳定性。
在又一个实施方案中,提供了一种用于裂化石油馏分原料的方法,所述方法包括以下步骤:
a)提供FCC催化剂组合物,所述FCC催化剂组合物包含约5至约60重量%的一种或多种沸石、约15至约35重量%的准晶勃姆石、约0至约35重量%的微晶勃姆石、大于约0至约15重量%的来自钠稳定的碱性胶体二氧化硅的二氧化硅、大于约0至约30重量%的来自酸性胶体二氧化硅或聚硅酸的二氧化硅以及余量的粘土;
b)使所述FCC催化剂与所述石油馏分原料在400℃至650℃范围内的温度下接触,其中停留时间在0.5至12秒的范围内。
从包括所附权利要求的以下详细描述,本发明的这些和其他实施方案、优点和特征将变得更加明显。
具体实施方式
除非另外指明,否则如本文所用的重量百分比(_重量%)是基于针对其指定物质或物质形式为成分或组分的产物的总干基重量,指定形式的物质的干基重量百分比。还应该理解的是,当在本文中以某种方式将步骤或组分或要素描述为优选时,它们在本公开的初始日期是优选的,并且此类优选当然可根据给定的情况或者本领域中的未来发展而变化。
一般程序
制造改进的催化剂的方法的第一步骤是将粘土源与钠稳定的碱性胶体二氧化硅和一种或多种氧化铝(勃姆石)源混合。如将在下文论述,可任选地将酸性胶体二氧化硅的第二二氧化硅源添加至此浆料或在稍后步骤。粘土、沸石、QCB、MCB、钠稳定的碱性胶体二氧化硅和任选的其它组分可通过将它们作为干燥固体添加至水而浆化。或者,根据步骤a)将含有单独材料的浆料混合以形成浆料。还有可能添加作为浆料的一些材料,以及作为干燥固体的其他材料。任选地,可添加其他组分,如铝氯二聚水分子、硝酸铝、Al2O3、Al(OH)3、阴离子粘土(例如水滑石)、蒙脱石、海泡石、钛酸钡、钛酸钙、硅酸钙、硅酸镁、钛酸镁、混合金属氧化物、分层羟基盐、另外的沸石、氧化镁、碱或盐,和/或金属添加剂,如含有碱土金属(例如Mg、Ca和Ba)、IIIA族过渡金属、IVA族过渡金属(例如Ti、Zr)、VA族过渡金属(例如V、Nb)、VIA族过渡金属(例如Cr、Mo、W)、VIIA族过渡金属(例如Mn)、VIIIA族过渡金属(例如Fe、Co、Ni、Ru、Rh、Pd、Pt)、IB族过渡金属(例如Cu)、IIB族过渡金属(例如Zn)、镧系元素(例如La、Ce)或其混合物的化合物。可使用这些化合物的任何添加顺序。还有可能同时组合全部这些化合物。
术语“勃姆石”在工业中用于描述氧化铝水合物,其表现出接近氧化铝-氢氧化物[AlO(OH)]的X射线衍射(XRD)图案。此外,术语勃姆石通常用于描述广泛范围的氧化铝水合物,所述氧化铝水合物含有不同量的水合水,具有不同的表面积、孔体积、比密度,并且在热处理时表现出不同的热特性。然而,它们的XRD图案虽然表现出特征性勃姆石[AlO(OH)]峰,但通常在它们的宽度上变化并且还可在它们的位置上偏移。XRD峰的清晰度及其位置已用于指示结晶度、晶体尺寸和缺陷量。
从广义上讲,存在两类勃姆石氧化铝:准晶勃姆石(QCB)和微晶勃姆石(MCB)。在现有技术中,准晶勃姆石也被称为假勃姆石和凝胶状勃姆石。通常,这些QCB具有比MCB更高的表面积、更大的孔和孔体积以及更低的比密度。它们易于分散在水或酸中,具有比MCB更小的晶体尺寸,并且含有大量水合水分子。QCB的水合程度可具有广泛范围的值,例如每摩尔Al约1.4至约2摩尔的水,通常有序地或以其他方式插入八面体层之间。一些典型的可商购QCB是和产品。
微晶勃姆石与QCB的区别在于其高结晶度、相对大的晶体尺寸、非常低的表面积和高密度。与QCB相反,MCB显示具有更高的峰强度和非常窄的半宽度的XRD图案。这是由于它们的相对较少数量的插入水分子、大的晶体尺寸、本体材料的更高结晶度以及更少量的晶体缺陷。通常,插入的水分子的数量可在每摩尔Al约1至约1.4的范围内变化。典型的可商购MCB是Condea的
MCB和QCB的特征在于粉末X射线反射。ICDD含有勃姆石的条目并确认对应于(020)、(021)和(041)平面的反射将存在。对于铜辐射,此类反射将出现在14、28和38度2-θ处。反射的确切位置取决于结晶度和插入的水的量:随着插入的水的量增加,(020)反射移动至较低值,对应于较大的d-间距。尽管如此,接近上述位置的线将指示存在一种或多种类型的勃姆石相。出于本说明书的目的,将准晶勃姆石定义为具有半高全宽度(FWHH)为1.5°或大于1.5°2θ的(020)反射。具有FWHH小于1.5°2θ的(020)反射的勃姆石被认为是微晶勃姆石。基于最终催化剂,浆料优选包含约1至约50重量%、更优选约15至约35重量%的未胶溶的QCB。基于最终催化剂,所述浆料还包含约1至约50重量%、更优选约0至约35重量%的MCB。
此外,粘土优选具有低钠含量或者不含钠。合适的粘土包括高岭土、膨润土、皂石、海泡石、绿坡缕石、锂皂石(laponite)、锂蒙脱石、英国粘土、阴离子粘土如水滑石以及热处理或化学处理的粘土如偏高岭土。所述浆料优选包含约5至约70重量%、更优选约10至约60重量%且最优选约10至约50重量%的粘土。
在下一步骤中,将单价酸添加至悬浮液,从而引起消化。可使用有机和无机单价酸,或其混合物。合适的单价酸的实例是甲酸、乙酸、丙酸、硝酸和盐酸。所述酸以足以获得低于7、更优选介于1与4之间的pH的量添加至所述浆料。
在下一步骤中,添加一种或多种沸石。在根据本发明的方法中使用的沸石优选具有低钠含量(小于1.5重量%Na2O)或者不含钠。存在于步骤a)的浆料中的合适沸石包括沸石,如Y-沸石,包括HY、USY、脱铝Y、RE-Y和RE-USY-沸石β、ZSM-5、磷活化的ZSM-5、离子交换的ZSM-5、MCM-22和MCM-36、金属交换的沸石、ITQ、SAPO、ALPO和它们的混合物。基于最终催化剂,所述浆料优选包含5至60重量%的一种或多种沸石。
如下文将论述,如果第二二氧化硅源是酸性胶体二氧化硅,则可在先前任何点将所述第二二氧化硅源添加至浆料。如果第二二氧化硅源是聚硅酸,则它是线内制备的,并且就在添加沸石后并在下一步骤的混合之前添加。示例性聚硅酸是通过混合适量的硫酸和水玻璃在所述方法线内制备的钠稳定或不含钠的聚硅酸。
然后使上述浆料通过高剪切混合器,其中通过增加pH使所述浆料不稳定。随后将浆料的pH调节至高于3、更优选高于3.5、甚至更优选高于4的值。浆料的pH优选不高于7,因为具有较高pH的浆料可能难以处理。可通过向浆料中添加碱(例如NaOH或NH4OH)来调节pH。pH调节与成形步骤d)之间的时间段优选是30分钟或更短、更优选少于5分钟、最优选少于3分钟。在此步骤,浆料的固体含量优选是约10至约45重量%、更优选约15至约40重量%且最优选约25至约35重量%。
然后使浆料成形。合适的成形方法包括喷雾干燥、脉冲干燥、造粒、挤出(任选地与捏合组合)、成珠或在催化剂和吸收剂领域中使用的任何其它常规成形方法或其组合。优选的成形方法是喷雾干燥。如果催化剂通过喷雾干燥成形,则喷雾干燥器的入口温度优选在300℃至600℃的范围内,并且出口温度优选在105℃至200℃的范围内。
二氧化硅源
本发明的独特特征是在催化剂颗粒内使用至少两种二氧化硅源。添加的二氧化硅的总量大于1.0%。优选总二氧化硅大于约5.0%,并且最优选二氧化硅的总量大于约10.0%。此外,优选第一二氧化硅源与第二二氧化硅源的比率是约1∶1至约1∶10。
第一二氧化硅源通常是低钠二氧化硅源,并且被添加至初始浆料中。此类二氧化硅源的实例包括但不限于硅酸钾、硅酸钠、硅酸锂、硅酸钙、硅酸镁、硅酸钡、硅酸锶、硅酸锌、磷硅酸盐和硅酸钡。合适的有机硅酸盐的实例是硅氧烷(聚有机硅氧烷,如聚甲基苯基-硅氧烷和聚二甲基硅氧烷)以及含有Si-O-C-O-Si结构的其它化合物以及其前体,如甲基氯硅烷、二甲基氯硅烷、三甲基氯硅烷以及其混合物。优选的低钠二氧化硅源是钠稳定的碱性胶体二氧化硅。基于最终催化剂的重量,浆料还包含大于0至大约15重量%且更优选大于约0.5至约10重量%的来自低钠硅源的二氧化硅,并且最优选大于约1重量%至8重量%。
第二二氧化硅源通常是低钠或不含钠的酸性胶体二氧化硅或聚硅酸。作为第二二氧化硅源添加的合适的硅源包括(聚)硅酸、硅酸钠、不含钠的硅源和有机硅源。第二二氧化硅的一种这样的来源是通过混合适量的硫酸和水玻璃在所述方法线内制备的钠稳定或不含钠的聚硅酸。基于最终催化剂的重量,二氧化硅的这种第二次添加以大于约0至30重量%、优选大于约1重量%至约25重量%且最优选约5至约20重量%的量添加。
第二二氧化硅源的选择可影响何时将材料添加至上述浆料中。如果使用酸性胶体二氧化硅,则可在pH调节步骤之前的任何步骤添加二氧化硅。然而,如果第二二氧化硅源是钠稳定的或不含钠的聚硅酸,则应该就在pH调节步骤之前在添加沸石后添加所述二氧化硅。此外,由于聚硅酸的钠含量,可能需要洗涤最终的催化剂以除去过量的钠。可能进一步需要或希望煅烧最终催化剂。
所得催化剂
如此获得的催化剂具有特别好的耐磨耗性和可及性。因此,本发明还涉及一种通过根据本发明的方法可获得的催化剂。所述催化剂通常是FCC催化剂,其包含约5至约60%的一种或多种沸石、约15至约35重量%的准晶勃姆石、约0至约25重量%的微晶勃姆石、大于约0重量%至约15重量%的来自钠稳定的碱性胶体二氧化硅的二氧化硅、大于约0重量%至约30重量%的来自酸性胶体二氧化硅或聚硅酸的二氧化硅以及余量的粘土。
这些催化剂可用作加氢处理催化剂、烷基化催化剂、重整催化剂、气-液转化催化剂、煤转化催化剂、制氢催化剂和汽车催化剂中的FCC催化剂或FCC添加剂。因此,本发明还涉及通过本发明的方法可获得的这些催化剂作为流化催化裂化、加氢处理、烷基化、重整、气-液转化、煤转化和制氢中的催化剂或添加剂以及作为汽车催化剂的用途。
本发明的方法特别适用于流化催化裂化(FCC)。在细节通常是已知的FCC工艺中,催化剂通常作为细颗粒存在,所述细颗粒包含超过90重量%的直径在约5至约300微米范围内的颗粒。在反应器部分中,烃原料被气化并向上引导通过反应区,以使得微粒催化剂被夹带并在烃原料流中流化。来自再生器的热催化剂与烃进料反应,所述烃进料被蒸发并被催化剂裂化。通常,反应器中的温度是400-650C,并且压力可在降低的大气压或超大气压下,通常为约大气压至约5个大气压。催化过程可以是固定床、移动床或流化床,并且烃流可与催化剂流同时或逆流。本发明的方法也适用于TCC(蓄热器催化裂化)或DCC。
实施例
在任何实验室测试之前,必须使催化剂失活以模拟精炼单元中的催化剂,这通常用蒸汽进行。使这些样品通过以下失活:用Ni/V循环失活,其包括在蒸汽存在下的裂化、汽提和再生步骤,或在较高温度下使用100%蒸汽,这是工业上接受的用于FCC催化剂的失活方法。失活步骤是本领域已知的,并且对催化活性是必需的。在商业FCC设置中,失活在催化剂引入后不久发生,并且不需要作为单独的步骤进行。
可及性测量。通过将1g的催化剂添加至含有50g真空瓦斯油的搅拌容器中来测量根据以下实施例制备的催化剂的可及性。将溶液在容器与分光光度计之间循环,在所述过程中连续测量VGO浓度。催化剂对VGO的可及性通过Akzo可及性指数(AAI)量化。将溶液中VGO的相对浓度相对于时间的平方根作图。AAI被定义为此图的初始斜率:
AAI=-d(Ct/C0)/d(t1/2)*100%
在此等式中,t是时间(以分钟计),并且C0和Ct分别表示在实验开始时和时间t时溶剂中高分子量化合物的浓度。
耐磨耗性测量。通过标准磨耗测试来测量催化剂的耐磨耗性。在此测试中,催化剂床位于具有三个喷嘴的磨耗板上。磨耗板位于处于环境温度的磨耗管内。迫使空气进入喷嘴,并且所得到喷射引起催化剂颗粒的向上输送并产生细粒。在磨耗管的顶部是分离室,其中流消散,并且大于约16微米的大多数颗粒落回到磨耗管中。较小的颗粒被收集在收集袋中。此测试在600℃下煅烧催化剂样品后进行,并且首先运行5小时,并测定基于50克的假想进料收集在收集袋中的细粒的重量百分比。这是初始磨耗。然后进行测试另外15小时,并且测定在此时间段(5-20小时)内细粒的重量百分比。这是固有磨耗。磨耗指数(AI)是25小时后外推的重量%细粒。因此,催化剂的耐磨耗性越高,AI值越低。
实施例1-钠稳定的聚硅酸。使用本文描述的技术进行五个单独的实施例。将每个单独的实施例与使用单一二氧化硅源的基础案例进行比较。如在下表中所详述,每种二氧化硅的量对于每个实施例而变化。二氧化硅1是钠稳定的碱性胶体二氧化硅,并且二氧化硅2是钠稳定的聚硅酸。在喷雾干燥后,使本发明的催化剂经受洗涤过程以除去钠。从下文所示的物理性质(ABD和磨耗)数据可明显看出,本发明的所有催化剂显示出相对于具有单一二氧化硅的基础案例的改进的粘合。在这些催化剂上还注意到更高的可及性(AAI)和总表面积。在失活后,除了比现有技术催化剂高约5%表面积保留之外,本发明的催化剂的MiPV%保留高超过20%。在以下样品中,准晶勃姆石水平相同(20%),并且沸石也保持恒定。
实施例2-不含钠的聚硅酸。在此实施例中,不含钠的聚硅酸(二氧化硅3)替代来自上述实施例的钠稳定的聚硅酸(二氧化硅2)。就在喷雾干燥催化剂之前制备不含钠的聚硅酸,因为粒度随时间增长并且显示出物理和性能的负面影响,并在沸石添加步骤之后添加。由于不含钠的聚硅酸是低钠二氧化硅,因此在喷雾干燥后不必对催化剂进行后洗涤来除去钠。使用本文描述的技术制备示例催化剂。二氧化硅1是钠稳定的碱性胶体二氧化硅,并且二氧化硅3是不含钠的聚硅酸。将所述实施例与使用单一二氧化硅源的基础案例进行比较。与基础案例相比,对于此催化剂注意到磨损的约25%改进和更高的可及性。这些催化剂的循环失活表明,表面积和MiPV%保留高于基础案例催化剂,这与上述实施例中钠稳定的聚硅酸情况下的结果一致。在以下实施例中,对于所有实施例,准晶勃姆石水平相同(20%),并且沸石水平是恒定的。
催化剂描述 | 对比2-1 | 实施例2-1 |
二氧化硅-1 | 1.5 | 5 |
二氧化硅-3 | 0 | 15 |
ABD | 0.72 | 0.72 |
磨耗 | 1.57 | 1.17 |
磨耗的改进% | 25% | |
AAI | 9.2 | 11.9 |
SA BET保留% | 47% | 51% |
MiPV BET保留% | 47% | 65% |
实施例3-酸性胶体二氧化硅。当使用钠稳定的聚硅酸时,为了避免催化剂中的后生产洗涤过程以除去钠,使用了酸性胶体二氧化硅源。以下是酸性胶体二氧化硅(二氧化硅4)的实施例,其替代来自上述实施例的钠稳定的聚硅酸(二氧化硅2)。二氧化硅4是可商购的酸稳定的胶体二氧化硅,没有任何钠含量。据报道,这种二氧化硅具有1)20nm的PSD,2)2.8的pH,以及3)30重量%SiO2。这种二氧化硅完全替代第一组实施例中的钠稳定的聚硅酸(二氧化硅2),并且如下文所示,它相对于基础案例改进了催化剂ABD、表面积和磨耗。在循环失活时,具有酸性胶体二氧化硅的本发明的催化剂表现出比基础案例更好的表面积和MiPV保留。对于以下实施例中的每一个,准晶勃姆石氧化铝水平相同(20%),并且沸石含量保持恒定。
催化剂描述 | 对比3-1 | 实施例3-1 |
二氧化硅-1 | 1.5 | 5 |
二氧化硅-4 | 15 | |
ABD | 0.63 | 0.8 |
磨耗 | 2.9 | 0.85 |
磨耗的改进% | 71% | |
AAI | 12.3 | 11.2 |
SA BET保留% | 57% | 63% |
MiPV BET保留% | 51% | 63% |
实施例4-蒸汽失活:在不同的失活方案(蒸汽失活)下进一步验证这些催化剂在物理性质和表面积以及沸石保留方面的益处。制备了具有钠稳定的聚硅酸(二氧化硅2)作为第二二氧化硅源的示例性催化剂,并与用一种二氧化硅源(二氧化硅1)制备的基础案例进行比较。再次,如下表所示,对于这种催化剂注意到更好的磨耗和ABD。与基础案例相比,在蒸汽失活(788℃/20小时,使用100%蒸汽)后,对于新催化剂注意到更高的沸石保留%。
实施例5-改变二氧化硅含量:使用本文描述的技术进行十一个单独的实施例。将每个单独的实施例与使用单一二氧化硅源的基础案例进行比较。如在下表中所详述,每种二氧化硅的量对于每个实施例而变化。二氧化硅1是钠稳定的碱性胶体二氧化硅,并且二氧化硅4是酸性胶体二氧化硅。从下文所示的物理性质(ABD和磨耗)数据可明显看出,本发明的催化剂显示出相对于具有单一二氧化硅的基础案例类似或改进的粘合,除了实施例5-8外。除了增加的MiPV保留外,在这些催化剂上还注意到更高的可及性(AAI)和总表面积。对于下文的对比样品,QCB含量是30重量%,而实施例具有20重量%的QCB含量。在整个案例中总沸石是相同的。
实施例6-单一来源二氧化硅研究:使用本文描述的技术进行一种实施例。将所述实施例与使用改变量的单一二氧化硅源的若干基础案例进行比较。如在下表中所详述,每种二氧化硅的量对于每个实施例而变化。二氧化硅1是钠稳定的碱性胶体二氧化硅,并且二氧化硅-4是酸性胶体二氧化硅。数据表明,与全部其他实施例组合,使用一种或多种二氧化硅源提供与等量的单一二氧化硅源相似或改进的性能。然而,使用多于一种二氧化硅源允许制剂的更大灵活性,并且还提供在少量的二氧化硅下的益处。对于下文的每种样品,总氧化铝含量保持不变。对于所有催化剂,总沸石水平保持相同。以下实施例显示,当通过本文所述的发明制备催化剂时,相对于相同总量的单一来源二氧化硅1显示改进的物理性质,并且相对于单一来源的二氧化硅2显示类似的物理性质。然而,如在全部实施例中所示,使用至少2种二氧化硅源允许产品设计的更大灵活性,并且允许用较低量二氧化硅而具有良好物理特性。
Claims (14)
1.一种FCC催化剂组合物,其包含5至60重量%的一种或多种沸石、15至35重量%的准晶勃姆石、0至35重量%的微晶勃姆石、大于0.5重量%至10重量%的来自钠稳定的碱性胶体二氧化硅的二氧化硅、大于0重量%至30重量%的来自酸性胶体二氧化硅或聚硅酸的二氧化硅以及余量的粘土。
2.如权利要求1所述的FCC催化剂,其具有大于1重量%至8重量%的来自钠稳定的碱性胶体二氧化硅的二氧化硅。
3.如权利要求1所述的FCC催化剂,其具有大于1重量%至25重量%的来自酸性胶体二氧化硅或聚硅酸的二氧化硅。
4.如权利要求3所述的FCC催化剂,其具有大于5重量%至20重量%的来自酸性胶体二氧化硅或聚硅酸的二氧化硅。
5.如权利要求1所述的FCC催化剂,其磨耗指数测量值小于2.0。
6.一种用于制造FCC催化剂的方法,所述方法包括:
a. 添加粘土、勃姆石和钠稳定的碱性胶体二氧化硅以形成浆料;
b. 用一元酸将所述浆料消化至小于4.0的pH;
c. 将一种或多种沸石添加至所述浆料;
d. 添加单独制备并线内添加的聚硅酸;
e. 混合所述浆料且然后通过将pH升高至超过4.0来使所述浆料不稳定
f. 成形并收集所得FCC催化剂。
7.如权利要求6所述的方法,其还包括煅烧步骤和后洗涤步骤,以根据需要除去过量的钠。
8.一种用于制造FCC催化剂的方法,所述方法包括:
a. 添加粘土、勃姆石、钠稳定的碱性胶体二氧化硅以形成浆料;
b. 用一元酸将所述浆料消化至小于4的pH;
c. 将一种或多种沸石添加至所述浆料;
d. 在步骤a – c期间或之后但在步骤e之前的任何时间添加酸性胶体二氧化硅;
e. 混合所述浆料且然后通过将pH升高至超过4.0来使所述浆料不稳定;
f. 成形并收集所得FCC催化剂。
9.如权利要求6或8所述的方法,其还包括添加5至60重量%的一种或多种沸石。
10.如权利要求6或8所述的方法,其还包括添加大于0至15重量%的来自钠稳定的碱性胶体二氧化硅的二氧化硅。
11.如权利要求6所述的方法,其还包括添加大于0至30重量%的聚硅酸。
12.如权利要求8所述的方法,其还包括添加大于0至30重量%的酸性胶体二氧化硅。
13.一种由如权利要求6或8所述的方法制备的催化剂,其包含5至60重量%的一种或多种沸石、15至35重量%的准晶勃姆石、0至35重量%的微晶勃姆石、大于0至15重量%的来自钠稳定的碱性胶体二氧化硅的二氧化硅、大于0至30重量%的来自酸性胶体二氧化硅或聚硅酸的二氧化硅以及余量的粘土。
14.一种用于由烃原料生产更多液体组分的方法,所述方法包括以下步骤:
a. 提供FCC催化剂组合物,所述FCC催化剂组合物具有5至60重量%的一种或多种沸石、15至35重量%的准晶勃姆石、0至35重量%的微晶勃姆石、大于0.5至10重量%的来自钠稳定的碱性胶体二氧化硅的二氧化硅、大于0至30重量%的来自酸性胶体二氧化硅或聚硅酸的二氧化硅以及余量的粘土;
b. 使所述FCC微粒催化剂组合物与所述烃原料在400℃至650℃范围内的一个或多个温度下接触,停留时间在0.5至12秒的范围内;使得基于所述烃原料的重量,以在4至20重量%范围内的转化效率形成丙烯。
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CN101115560A (zh) * | 2004-12-21 | 2008-01-30 | 雅宝荷兰有限责任公司 | 耐磨催化剂及其制备方法和应用 |
CN101119802A (zh) * | 2004-12-21 | 2008-02-06 | 雅宝荷兰有限责任公司 | Fcc催化剂及其制备和应用 |
CN103813856A (zh) * | 2011-07-21 | 2014-05-21 | 瑞来斯实业有限公司 | 流化床催化裂化(fcc)催化剂添加剂及其制备方法 |
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WO2018027173A1 (en) | 2018-02-08 |
BR112019002111B1 (pt) | 2022-11-16 |
JP7080217B2 (ja) | 2022-06-03 |
US11926796B2 (en) | 2024-03-12 |
JP2019528163A (ja) | 2019-10-10 |
US20220348829A1 (en) | 2022-11-03 |
US11427764B2 (en) | 2022-08-30 |
BR112019002111A2 (pt) | 2019-05-07 |
CA3032811A1 (en) | 2018-02-08 |
US20190203127A1 (en) | 2019-07-04 |
EP3493903A1 (en) | 2019-06-12 |
CN109641193A (zh) | 2019-04-16 |
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