WO2005070539A2 - Catalyseur zeolithique, support a base de matrice silico-aluminique et de zeolithe, et procede d’hydrocraquage de charges hydrocarbonees - Google Patents
Catalyseur zeolithique, support a base de matrice silico-aluminique et de zeolithe, et procede d’hydrocraquage de charges hydrocarbonees Download PDFInfo
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- WO2005070539A2 WO2005070539A2 PCT/FR2004/003270 FR2004003270W WO2005070539A2 WO 2005070539 A2 WO2005070539 A2 WO 2005070539A2 FR 2004003270 W FR2004003270 W FR 2004003270W WO 2005070539 A2 WO2005070539 A2 WO 2005070539A2
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- WIPO (PCT)
- Prior art keywords
- measured
- mercury porosimetry
- pores
- zeolite
- catalyst
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 197
- 239000010457 zeolite Substances 0.000 title claims abstract description 180
- 238000000034 method Methods 0.000 title claims abstract description 142
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 141
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 80
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 13
- 229930195733 hydrocarbon Natural products 0.000 title claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 13
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 title abstract 3
- 239000011159 matrix material Substances 0.000 claims abstract description 101
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 230000000737 periodic effect Effects 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims description 345
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 257
- 229910052753 mercury Inorganic materials 0.000 claims description 257
- 238000002459 porosimetry Methods 0.000 claims description 231
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 129
- 229910052782 aluminium Inorganic materials 0.000 claims description 97
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 79
- 230000008569 process Effects 0.000 claims description 67
- 239000000203 mixture Substances 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 229910052757 nitrogen Inorganic materials 0.000 claims description 40
- 238000002441 X-ray diffraction Methods 0.000 claims description 39
- 239000000377 silicon dioxide Substances 0.000 claims description 36
- 238000010586 diagram Methods 0.000 claims description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 25
- 238000011049 filling Methods 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 230000000694 effects Effects 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 15
- 230000007704 transition Effects 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 238000001228 spectrum Methods 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 230000005587 bubbling Effects 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 9
- 238000011144 upstream manufacturing Methods 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 238000004876 x-ray fluorescence Methods 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000010687 lubricating oil Substances 0.000 claims description 4
- 229910052680 mordenite Inorganic materials 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 3
- 230000023556 desulfurization Effects 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 abstract description 9
- 239000002253 acid Substances 0.000 description 46
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 43
- 239000000243 solution Substances 0.000 description 43
- 238000001179 sorption measurement Methods 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 238000002360 preparation method Methods 0.000 description 37
- 238000011282 treatment Methods 0.000 description 34
- 239000011734 sodium Substances 0.000 description 32
- 150000001875 compounds Chemical class 0.000 description 29
- 238000007493 shaping process Methods 0.000 description 29
- 239000000725 suspension Substances 0.000 description 28
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 27
- 229910052708 sodium Inorganic materials 0.000 description 27
- 239000000499 gel Substances 0.000 description 26
- -1 silica compound Chemical class 0.000 description 24
- 229910052751 metal Inorganic materials 0.000 description 23
- 239000002184 metal Substances 0.000 description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 22
- 239000006185 dispersion Substances 0.000 description 21
- 239000000843 powder Substances 0.000 description 21
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 229910001593 boehmite Inorganic materials 0.000 description 18
- 239000002243 precursor Substances 0.000 description 18
- 239000000523 sample Substances 0.000 description 17
- 238000005470 impregnation Methods 0.000 description 16
- 238000002156 mixing Methods 0.000 description 16
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 13
- 150000002739 metals Chemical class 0.000 description 13
- 229910017604 nitric acid Inorganic materials 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 230000006870 function Effects 0.000 description 12
- 125000002091 cationic group Chemical group 0.000 description 11
- 238000000265 homogenisation Methods 0.000 description 11
- 238000009835 boiling Methods 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000010335 hydrothermal treatment Methods 0.000 description 9
- 238000004898 kneading Methods 0.000 description 9
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- 239000000084 colloidal system Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 7
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 7
- 238000007792 addition Methods 0.000 description 7
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- 239000002244 precipitate Substances 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- MHCAFGMQMCSRGH-UHFFFAOYSA-N aluminum;hydrate Chemical compound O.[Al] MHCAFGMQMCSRGH-UHFFFAOYSA-N 0.000 description 6
- 239000007900 aqueous suspension Substances 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
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- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 239000008186 active pharmaceutical agent Substances 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
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- 230000000670 limiting effect Effects 0.000 description 5
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
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- 239000000126 substance Substances 0.000 description 5
- 238000004627 transmission electron microscopy Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
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- 238000005481 NMR spectroscopy Methods 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
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- 150000003377 silicon compounds Chemical class 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 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 3
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 3
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- 101100419716 Podospora anserina RPS9 gene Proteins 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
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- 230000000875 corresponding effect Effects 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 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 3
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- 239000012808 vapor phase Substances 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
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- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
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- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 description 1
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- LMCBRBGCCDUTAB-UHFFFAOYSA-N [Mo].[Nb].[Ru] Chemical compound [Mo].[Nb].[Ru] LMCBRBGCCDUTAB-UHFFFAOYSA-N 0.000 description 1
- PCBMYXLJUKBODW-UHFFFAOYSA-N [Ru].ClOCl Chemical compound [Ru].ClOCl PCBMYXLJUKBODW-UHFFFAOYSA-N 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
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- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate 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
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
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- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
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- MPRVXUYAJZZBHG-UHFFFAOYSA-K dicarbonoperoxoyloxyalumanyl hydroxy carbonate Chemical compound [Al+3].OOC([O-])=O.OOC([O-])=O.OOC([O-])=O MPRVXUYAJZZBHG-UHFFFAOYSA-K 0.000 description 1
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
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- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical class O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
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- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
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- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- 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
- B01J23/70—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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
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- B01J35/66—Pore distribution
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- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
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- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
Definitions
- Zeolite catalyst support based on an ex-zeolite silica-aluminum matrix, and hydrocracking process for hydrocarbon feedstocks
- the present invention relates to supports based on silico-aluminum matrix and zeolite, catalysts and the hydroconversion processes using them.
- the objective of the process is essentially the production of middle distillates, that is to say sections with an initial boiling point of at least 150 ° C and a final going up to before the initial boiling point of the residue. , for example less than 340 ° C, or even less than 370 ° C.
- hydrocracking of heavy petroleum fractions is a very important refining process which makes it possible to produce, from excess heavy and little valorized charges, lighter fractions such as gasolines, jet fuels and light gas oils which the refiner seeks to adapt its production to the structure of demand.
- Certain hydrocracking processes also make it possible to obtain a highly purified residue which can provide excellent bases for oils.
- the advantage of catalytic hydrocracking is to provide middle distillates, jet fuels and diesel, of very good quality.
- the gasoline produced has a much lower octane number than that from catalytic cracking.
- Hydrocracking is a process which derives its flexibility from three main elements which are, the operating conditions used, the types of catalysts used and the fact that hydrocracking of hydrocarbon feedstocks can be carried out in one or two stages.
- the hydrocracking catalysts used in hydrocracking processes are all of the bifunctional type combining an acid function with a hydrogenating function.
- the acid function is provided by supports whose surfaces generally vary from 150 to 800 m 2 .g " 1 and having a surface acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), combinations of boron oxides and d aluminum, amorphous silica-aluminas and zeolites.
- the hydrogenating function is provided either by one or more metals from group VIII of the periodic table, or by a combination of at least one metal from group VIB of the periodic table and at least one group VIII metal.
- the balance between the two acid and hydrogenating functions is one of the parameters which govern the activity and the selectivity of the catalyst.
- a weak acid function and a strong hydrogenating function give catalysts which are not very active, working at a generally high temperature (greater than or equal to 390-400 ° C.), and at a low spatial speed of supply (the VVH expressed in volume of charge at process per unit volume of catalyst per hour is generally less than or equal to 2), but with very good selectivity in middle distillates.
- a strong acid function and a weak hydrogenating function give active catalysts, but having poorer selectivities for middle distillates (jet fuels and diesel fuels).
- One type of conventional hydrocracking catalyst is based on moderately acidic amorphous supports, such as silica-aluminas for example. These systems are used to produce good quality middle distillates, and possibly oil bases. These catalysts are for example used in two-step processes.
- the catalysts partially comprising a zeolite or a mixture of zeolites have a catalytic activity higher than those of amorphous silica-aluminas, but have selectivities for light products which are higher.
- the Applicant has demonstrated, unexpectedly, that the incorporation into a matrix, with reduced macropore content, of certain zeolites alone or in mixture has led to the preparation of catalysts having improved catalytic performance in hydrocracking processes by compared to the catalysis ⁇ rs of the prior art. More specifically, the invention relates to a hydrocracking / hydroconversion, the medium used for preparing said catalyst and the hydrocracking process the implementing.
- the term “specific surface” means the BET specific surface determined by nitrogen adsorption in accordance with standard ASTM D 3663-78 established on the basis of the BRUNAUER-EMMETT-TELLER method described in the periodical "The Journal of American Society", 60, 309, (1938).
- the term “mercury volume of the supports and catalysts” means the volume measured by intrusion with a mercury porosimeter according to the ASTM D4284- 83 at a maximum pressure of 4000 bar, using a surface tension of 484 dyne / cm and a contact angle for amorphous silica-alumina supports of 140 °.
- the mean mercury diameter is defined as being a diameter such that all the pores of size smaller than this diameter constitute 50% of the pore volume (V Hg ), in a range between 36 ⁇ and 1000 A.
- V Hg pore volume
- One of the reasons why it is preferable to use the support as a basis for defining the porous distribution lies in the fact that the contact angle of the mercury varies after impregnation of the metals and this according to the nature and the type of metals.
- the wetting angle was taken equal to 140 ° following the recommendations of the book "Engineering techniques, treatise analysis and characterization, P 1050-5, written by Jean Charpin and Bernard Rasneur".
- the value of the mercury volume in ml / g given in the following text corresponds to the value of the total mercury volume in ml / g measured on the sample minus the value of the mercury volume in ml / g measured on the same sample for a pressure corresponding to 30 psi (approximately 2 bars).
- the mean mercury diameter is also defined as being a diameter such that all the pores of size smaller than this diameter constitute 50% of the total pore volume of mercury.
- the volume V1 corresponds to the volume contained in the pores whose diameter is less than the mean diameter minus 30 A.
- the volume V2 corresponds to the volume contained in pores with a diameter greater than or equal to the average diameter minus 30 A and less than the average diameter plus 30 A.
- the volume V3 corresponds to the volume contained in the pores with a diameter greater than or equal to the average diameter plus 30 A.
- the volume V4 corresponds to the volume contained in the pores whose diameter is less than the mean diameter minus 15 A.
- the volume V5 corresponds to the volume contained in the pores of diameter greater than or equal to the mean diameter minus 15 A and less than the mean diameter plus 15 A.
- the volume V6 corresponds the volume contained in the pores with a diameter greater than or equal to the average diameter plus 15 A.
- the porous distribution measured by nitrogen adsorption has been tee determined by the Barrett-Joyner-Halenda (BJH) model.
- BJH Barrett-Joyner-Halenda
- the adsorption isotherm - nitrogen desorption according to the BJH model is described in the periodical "The Journal of American Society", 73, 373, (1951) written by EPBarrett, LGJoyner and PPHalenda.
- the mean nitrogen desorption diameter is defined as being a diameter such that all the pores smaller than this diameter constitute 50% of the pore volume (Vp) measured on the desorption branch of the nitrogen isotherm.
- adsorption surface is meant the surface measured on the branch of the adsorption isotherm. See, for example in the article by A. Lecloux “Memoirs of the Royal Society of Liège Science, 6th series, Volume I, fasc.4, pp.169-209 (1971).”
- the sodium content was measured by atomic absorption spectrometry.
- X-ray diffraction is a technique that can be used to characterize the supports and catalysts according to the invention.
- ⁇ K ⁇ 1 1.7890 A
- ⁇ lK ⁇ 1.793 A
- gamma alumina in the remainder of the text, inter alia, for example, an alumina included in the group consisting of cubic gamma, pseudo-cubic gamma, tetragonal gamma, poorly or poorly crystallized gamma, large surface gamma, low surface gamma gamma from large boehmite, gamma from crystallized boehmite, gamma from poorly or poorly crystallized boehmite, gamma from a mixture of crystallized boehmite and an amorphous gel, gamma from an amorphous gel, gamma in evolution towards delta.
- the alumina compound may contain an amorphous fraction which is difficult to detect by X-ray techniques. It will therefore be understood hereinafter that the alumina compounds used or described in the text may contain an amorphous or poorly crystallized fraction.
- the supports and catalysts according to the invention were analyzed by MAS NMR of the solid of 27 AI on a spectrometer from the firm Br ⁇ ker of the MSL 400 type, in a 4 mm probe.
- the speed of rotation of the samples is of the order of 11 kHz.
- the NMR of aluminum makes it possible to distinguish three types of aluminum whose chemical shifts are reported below:
- the aluminum atom is a quadrupole nucleus.
- the magic angle rotation NMR technique (MAS) is a quantitative technique.
- the decomposition of NMR MAS spectra allow direct access to the quantity of the different species.
- the spectrum is calibrated in chemical displacement compared to a 1M solution of aluminum nitrate.
- the aluminum signal is at zero ppm.
- the proportion of octahedral AI ⁇ is understood to mean the following ratio: area 2 / (area 1 + area 2).
- a method of characterizing the supports and catalysts according to the invention which can be used is transmission electron microscopy (TEM).
- TEM transmission electron microscopy
- an electron microscope of the Jeol 2010 or Philips Tecnai20F type, possibly with scanning
- EDS energy dispersion spectrometer
- the EDS detector must allow the detection of light elements.
- the combination of these two tools, MET and EDS makes it possible to combine imagery and local chemical analysis with good spatial resolution.
- the samples are finely dry ground in a mortar; the powder is then included in resin to make ultra-fine cuts with a thickness of around 70 nm.
- the size of the electron beam for the analysis of the zones is a maximum of 50 nm in diameter, preferably 20 nm, even more preferably 10, 5, 2 or 1 nm in diameter .
- the analyzed area will be a function of the size of the scanned area and no longer of the size of the generally reduced beam.
- the 50 nm probe is the probe used for characterizing the supports and catalysts according to the invention unless otherwise stated.
- the zeolites used for the preparation of the hydrocracking catalysts are characterized by several sizes such as their molar ratio Si0 2 / AI 2 03 of framework, their crystalline parameter, their porous distribution, their specific surface, their capacity of recovery in sodium ion, or still their water vapor adsorption capacity.
- the peak rate and the crystal fraction are important parameters to consider. Peak rates and crystal fractions are determined by X-ray diffraction from a reference zeolite, using a procedure derived from ASTM method D3906-97 "Determination of Relative X-ray Diffraction Intensifies of Faujasite-Type-Containing Materials ”.
- a diffractogram is composed of the lines characteristic of the crystallized fraction of the sample and of a background, mainly caused by the diffusion of the amorphous or microcrystalline fraction of the sample (a weak diffusion signal is linked to the apparatus, air , sample holder, etc.)
- This peak / (peak + bottom) ratio is proportional to the amount of zeolite crystallized in the material.
- the peak rate of the sample will be compared to that of a reference considered to be 100% crystallized (NaY for example).
- the peak rate of a perfectly crystallized NaY zeolite is of the order of 0.55 to 0.60.
- the packed filling density is measured, as described in the book "Applied Heterogenous Catalysis” by JF Le Page, J. Cosyns, P. Courty, E. Freund, JP. Franck, Y. Jacquin, B. Juguin, C. Marcilly, G. Martino, J. Miquel, R. Montarnal, A. Sugier, H. Van Landeghem, Technip, Paris, 1987.
- This measurement is generally carried out on 1000 cm 3 of catalyst packed in a cylinder whose height to diameter ratio is close to 5: 1.
- This measurement can, preferably, be carried out on automated devices such as Autotap® sold by Quantachrome®.
- the acidity of the matrix is measured by IR.
- the IR spectra are recorded on a Nicolet interferometer of the Nexus-670 type at a resolution of 4 cm-1 with an apodization of the Happ-Gensel type.
- the sample (20 mg) is pressed in the form of a self-supporting tablet and placed in an in-situ analysis cell (25 ° C to 550 ° C, oven remote from the IR beam, secondary vacuum of 10- 6 mbar).
- the diameter of the tablet is 16 mm.
- the sample is pretreated in the following manner in order to eliminate the physisorbed water and to partially dehydroxylate the surface of the catalyst to have a representative image of the acidity of the catalyst in operation: temperature rise from 25 ° C to 300 ° C in 3 hours 10 hour plateau at 300 ° C temperature drop from 300 ° C to 25 ° C in 3 hours
- the basic probe (pyridine) is then adsorbed at saturated pressure at 25 ° C and then thermosorbed according to the following stages:
- a spectrum is recorded at 25 ° C at the end of the pretreatment and at each desorption stage in transmission mode with an accumulation time of 100 s.
- the spectra are reduced to iso-mass (therefore assumed to iso-thickness) (exactly 20 mg).
- the number of Lewis sites is proportional to the surface of the peak, the maximum of which is around 1450 cm ⁇ 1 , all shoulders being included.
- the number of Bronsted sites is proportional to the surface of the peak, the maximum of which is around 1545 cm "1 .
- the ratio of the number of Bronsted sites / number of Lewis sites is estimated to be equal to the ratio of the areas of two peaks described above.
- the peak area is generally used at 25 ° C. This B / L ratio is generally calculated from the spectrum recorded at 25 ° C at the end of the pretreatment.
- the invention relates to a catalyst comprising at least one hydro-dehydrogenating element chosen from the group formed by the elements of group VIB and group VIII of the periodic table and a support based on at least one zeolite and based silico-aluminum matrix, said matrix containing an amount greater than 5% by weight and less than or equal to 95%) by weight of silica (Si0 2 ), said catalyst having the following characteristics: a mean porous diameter, measured by mercury porosimetry, between 20 and 140 A, a total pore volume, measured by mercury porosimetry, between 0.1 ml / g and 0.6 ml / g, a total pore volume, measured by nitrogen porosimetry, between 0.1 ml / g and 0.6 ml / g, - a BET specific surface area of between 100 and 600 m 2 / g; preferably less than 500 m 2 / g. a pore volume, measured by mercury porosimetry, included in the pores
- an X-ray diffraction diagram which contains at least the main lines characteristic of at least one of the transition aluminas included in the group composed by the aluminas alpha, rhô, chi, eta, gamma, kappa, theta and delta.
- the X-ray diffraction diagram of the catalyst also generally contains the main lines characteristic of the zeolite or zeolites chosen.
- the invention relates to a support comprising: - at least one zeolite, - a non-zeolitic matrix based on silica - alumina containing an amount greater than 5% by weight and less than or equal to 95% by weight of silica (Si0 2 ) , said support being characterized by: an average porous diameter, measured by mercury porosimetry, of between 20 and 140 A, a total pore volume, measured by mercury porosimetry, of between 0.1 ml / g and 0.6 ml / g, - a total pore volume, measured by nitrogen porosimetry, between 0.1 ml / g and 0.6 ml / g, a BET specific surface area between 100 and 650 m 2 / g, a pore volume, measured by porosimetry with mercury, included in pores with a diameter greater than 140 A less than 0.1 ml / g, - a pore volume, measured by porosimetry with mercury,
- the packed filling density of the supports is greater than 0.65 g / cm 3 , preferably greater than 0.72 g / cm 3 , and very preferably greater than 0.75 g / cm 3 and even more preferably greater at 0.78 g / cm 3 .
- a catalyst containing the above support is also included in the invention.
- the invention also relates to a hydrocracking and / or hydroconversion process, and a process for hydrotreating hydrocarbon feedstocks using said supports or catalysts.
- the catalyst according to the present invention comprises a support comprising:
- non-zeolitic matrix based on silica - alumina (that is to say comprising silica and alumina) with a mass content of silica (Si0 2 ) greater than 5% by weight and less than or equal to 95% by weight, preferably included between 10 and 80% by weight, preferably a silica content greater than 20% by weight and less than 80% by weight and even more preferably more than 25% by weight and less than 75% by weight, the silica content is advantageously included between 10 and 50% by weight, said matrix having the following characteristics: preferably a content of cationic impurities less than 0.1% by weight, preferably less than 0.05% by weight and even more preferably less than 0.025% by weight .
- the content of cationic impurities is understood to mean the total alkali content. preferably an anionic impurity content of less than 1% by weight, preferably less than 0.5% by weight and even more preferably less than 0.1% by weight.
- the silica-alumina used in the process according to the invention is preferably a homogeneous silica-alumina on the micrometer scale and in which the content of cationic impurities (for example Na + ) is less than 0.1% by weight, of preferably less than 0.05% by weight and even more preferably less than 0.025% by weight and the content of anionic impurities (for example S0 4 2 " , CI " ) is less than 1% by weight, preferably less than 0 , 5% by weight and even more preferably less than 0.1% by weight.
- any process for the synthesis of silica-alumina known to those skilled in the art leading to a homogeneous silica-alumina on the micrometer scale and in which the cationic impurities (for example Na + ) can be reduced to less than 0.1 %, preferably at a content of less than 0.05% by weight and even more preferably less than 0.025% by weight and in which the anionic impurities (for example S0 4 2 " , Cl " ) can be reduced to less than 1 % and more preferably at a content of less than 0.05% by weight is suitable for preparing the supports which are the subject of the invention, said catalyst having the following characteristics: an average porous diameter, measured by mercury porosimetry, of between 20 and 140 A, preferably between 40 and 120 A and even more preferably between 50 and 100 A, preferably a ratio between the volume V2, measured by mercury porosimetry, between average D - 30 A and average D + 30 A, over the total pore volume also measured by mercury porosimetry greater than 0.6,
- V6 included in the pores of diameters greater than average D + 15 A, measured by mercury porosimetry, less than 0.2 ml / g, preferably less than 0.1 ml / g and again more preferred less than 0.05 ml / g.
- a total pore volume, measured by mercury porosimetry of between 0.1 ml / g and 0.6 ml / g, preferably between 0.20 and 0.50 ml / g and even more preferably greater than 0.20 ml / g
- a total pore volume, measured by nitrogen porosimetry of between 0.1 ml / g and 0.6 ml / g, preferably between 0.20 and 0.50 ml / g, a surface BET specific between 100 and 600 m 2 / g, preferably between 150 and 500 m 2 / g, - preferably an adsorption surface such that the ratio between the adsorption surface and the BET surface is greater than 0.5, of more preferably greater than 0.65 and more preferably greater than 0.8.
- an X-ray diffraction diagram which contains at least the main lines characteristic of at least one of the transition aluminas included in the group composed by the aluminas rho, chi, kappa, eta, gamma, theta and delta and preferably characterized in that that it contains at least the main lines characteristic of at least one of the transition aluminas included in the group composed of alumina gamma, eta, theta and delta, and more preferably characterized in that it contains at least the main lines characteristic of gamma and eta alumina, and even more preferably characterized in that it contains the peaks at a d between 1.39 to 1.40 A and at a d between 1.97 A at 2.00 A;
- the catalyst further comprising:
- hydro-dehydrogenating element chosen. in the group formed by the elements of group VIB and group VIII of the periodic table, preferably a mass content of metal (aux) of group VIB, in metallic form or in oxide form of between 1 and 50% by weight, of preferably between 1.5 and 35%, and even more preferably between 1.5 and 30%, preferably a mass content of group VIII metals, in metallic form or in oxide form of between 0.1 and 30% by weight, preferably between 0.2 and 25% and even more preferably between 0.2 and 20%, optionally at least one doping element deposited on the catalyst and chosen from the group formed by phosphorus, boron and silicon.
- a mass content of metal (aux) of group VIB in metallic form or in oxide form of between 1 and 50% by weight, of preferably between 1.5 and 35%, and even more preferably between 1.5 and 30%, preferably a mass content of group VIII metals, in metallic form or in oxide form of between 0.1 and 30% by weight, preferably between 0.2 and 25% and even more preferably between 0.2 and 20%, optionally at least one
- the mass contents of boron, silicon, phosphorus in the form of oxides are between 0.1 and 15%, preferably between 0.1 and 10%, and even more advantageously between 0.1 and 5% by weight.
- the term “doping element” is understood to mean an element introduced after the preparation of the silico-aluminum support described above, optionally at least one element from group VIIB (manganese for example and preferably), and a weight content of between 0 and 20%, preferably between 0 and 10% of the compound in oxide or metal form, optionally at least one element of the group VB (niobium for example and preferably), and a content by weight of between 0 and 40%, preferably between 0 and 20% of the compound in oxide or metal form.
- the packed filling density of the catalysts is greater than 0.85 g / cm 3 , preferably greater than 0.95 g / cm 3 , very preferably greater than 1.025 cm 3 / g and even more preferably greater than 1.1 g / cm 3 .
- the MAS NMR spectra of the solid of 27 AI of the silico-aluminum matrix show two distinct peak masses.
- a first type of aluminum whose maximum resonates around 10 ppm ranges between -100 and 20 ppm. The position of the maximum suggests that these species are essentially of type AI V
- This massif can be broken down into at least two species. The predominant species of this massif would correspond to the atoms of AI
- the proportion of the octahedral AI V ⁇ is greater than 50%, preferably greater than 60%, and even more preferably greater than 70%.
- the catalyst contains a matrix comprising at least two silico-aluminum zones, the said zones having Si / Ai ratios lower or greater than the overall Si / Ai ratio determined by X-ray fluorescence.
- a matrix having a Si / Ai ratio equal to 0.5 comprises for example two silico-aluminum zones, one of the zones has an Si / Ai ratio determined by MET less than 0.5 and the other zone has a Si / Ai ratio determined by MET between 0.5 and 2.5.
- the catalyst contains a matrix comprising a single silico-aluminum zone, said zone having a Si / Ai ratio equal to the overall Si / Ai ratio determined by X fluorescence and less than 2.3.
- the total weight content of zeolite in the catalyst is generally between
- the catalyst of the X ray diffraction diagram contains, also generally the principal characteristic peaks of the zeolite or selected.
- the zeolite is selected from the group FAU and / or in the 'group consisting of zeolite Y and zeolite Y having undergone a secondary treatment such as in particular: USY, VUSY, SDUSY, HMUSY, DAY.
- the zeolite Y used in the catalysts according to the invention is at least partly in hydrogen or acid (H +) or ammonium (NH 4 + ) or cationic form, said cation being chosen from the group formed by groups IA, IB, liA , IIB, IIIA, IIIB (including rare earths), Sn, Pb and Si, it is preferably at least partly in H + form or it can also be used at least partly in cationic form (as defined above) above).
- the zeolite is a zeolite chosen from the group formed by the zeolites ZBM-30, ZSM-48, EU-2 and EU-11, preferably the zeolite ZBM-30, used alone or mixed with other zeolites.
- the zeolite is a zeolite chosen from the group formed by the zeolites Mordenite, Beta, NU-87, EU-1, preferably the MOR zeolite, used alone or in mixture with other zeolites.
- the catalyst according to the invention exhibits better activity without loss of selectivity for middle distillates. Without wishing to be bound by any theory, it seems that this particularly high activity without significant loss of the selectivity of the catalysts of the present invention is the synergistic effect between the zeolite and the silico-aluminum matrix.
- the catalyst thus obtained is prepared, by any technique known to a person skilled in the art, from a support which contains at least one zeolite and which contains a silico-aluminum matrix in which the mass content of silica (Si0 2 ) is greater than 5% by weight and less than or equal to 95% by weight of silica (Si0 2 )
- the mean porous diameter, measured by mercury porosimetry is between 20 and 140 A, preferably between 40 and 120 A and even more preferably between 50 and 100 A, preferably the ratio between the volume V2, measured by mercury porosimetry, encompassed between D moye n - 30 A and D mean + 30 A to the total pore volume also measured by porosimetry mercury, is greater than 0.6, more preferably greater than 0.7 and even more preferably greater than 0.8.
- the volume V3 included in the pores of diameters greater than average D + 30 A, measured by mercury porosimetry is less than 0.1 ml / g, preferably less than 0.06 ml / g and again more preferred less than 0.04 ml / g.
- the ratio between volume V5, measured by mercury porosimetry, encompassed between D mean - 15 A and D moy ⁇ n + 15 A in the volume V2, measured by mercury porosimetry, encompassed between D moye n - 30 A and the average D + 30 A is greater than 0.6, more preferably greater than 0.7 and even more preferably greater than 0.8.
- the volume V6, included in the pores of diameters greater than D moy ⁇ n + 15 A and measured by mercury porosimetry is less than 0.2 ml / g, preferably less than 0.1 ml / g and so even more preferred less than 0.05 ml / g.
- the total pore volume, measured by mercury porosimetry is between 0.1 ml / g and 0.6 ml / g, preferably between 0.20 and 0.50 ml / g and even more preferably higher at 0.20 ml / g
- the total pore volume, measured by nitrogen adsorption is between 0.1 ml / g and 0.6 ml / g, preferably between 0.20 and 0.50 ml / g
- the BET specific surface is between 100 and 650 m 2 / g, preferably between 150 and 600 m 2 / g, - preferably the adsorption surface is such that the ratio between the adsorption surface and the BET surface is greater 0.5, more preferably greater than 0.65 and even more preferably greater than 0.8.
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 140 A is less than 0.1 ml / g, preferably less than 0.05 ml / g and even more preferably less than 0, 03 ml / g.
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 160 A is less than 0.1 ml / g, preferably less than 0.05 ml / g and even more preferably less than 0.025 ml / g.
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 200 A is less than 0.1 ml / g, preferably less than 0.05 ml / g and even more preferably less than 0.025 ml / g.
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 500 A is less than 0.01 ml / g.
- the X-ray diffraction diagram contains at least the main lines characteristic of at least one of the transition aluminas included in the group composed by the aluminas alpha, rho, chi, kappa, eta, gamma, theta and delta, preferably characterized by at least what it contains the main lines characteristic of at least one of the transition aluminas included in the group made up of gamma, eta, theta and delum alumina, more preferably characterized in that it contains at least the main lines characteristic of the gamma and eta alumina and even more preferably characterized in that it contains the peaks at a d between 1.39 to 1.40 A and at a d between 1.97 A to 2.00 A.
- the X-ray diffraction diagram of the support also generally contains the main lines characteristic of the selected zeolite (s).
- the zeolite is chosen from the group of
- the Y zeolite used in the catalysts according to the invention is at least partly in hydrogen or acid (H +) or ammonium (NH + ) or cationic form, said cation being chosen from the group formed by groups IA, IB, IIA, IIB, IIIA, IIIB (including rare earths), Sn, Pb and Si, it is preferably at least partly in H + form or it can also be used at least partly in cationic form (as defined above) ).
- the zeolite is a zeolite chosen from the group formed by the zeolites ZBM-30, ZSM-48, EU-2 and EU-11, preferably the zeolite ZBM-30, used alone or mixed with other zeolites.
- the zeolite is a zeolite chosen from the group formed by the zeolites Mordenite, Beta, NU-87, EU-1, preferably the MOR zeolite, used alone or in mixture with other zeolites.
- the mass content of silica (Si0 2 ) is greater than 5% by weight and less than or equal to 95% by weight of silica (Si0 2 ), preferably between 10 and 80% by weight, preferably a silica content greater than 20% by weight and less than 80% by weight and even more preferably more than 25% by weight and less than 75% by weight, the silica content is advantageously between 10 and 50% by weight, -
- the content of cationic impurities is less than 0.1% by weight, preferably less than 0.05% by weight and even more preferably less than 0.025% by weight.
- the content of cationic impurities is understood to mean the total alkali content.
- the content of anionic impurities is less than 1% by weight, preferably less than 0.5% by weight and even more preferably less than 0.1% by weight
- the mean porous diameter, measured by mercury porosimetry is between 20 and 140 A, preferably between 40 and 120 A and even more preferably between 50 and 100 A, preferably the ratio between the volume V2, measured by mercury porosimetry, between the D moyer ⁇ - 30 A and the average D + 30 A over the total pore volume also measured by mercury porosimetry, is greater than 0.6, more preferably greater than 0.7 and even more preferably greater than 0.8.
- the volume V3 included in the pores of diameters greater than average D + 30 A, measured by mercury porosimetry is less than 0.1 ml / g, preferably less than 0.06 ml / g and again more preferred less than 0.04 ml / g.
- the ratio between volume V5, measured by mercury porosimetry, encompassed between D mean - 15 A and D moye n + 15 A in the volume V2, measured by mercury porosimetry, encompassed between D moye n - 30 A and the average D + 30 A is greater than 0.6, more preferably greater than 0.7 and even more preferably greater than 0.8.
- the volume V6, included in the pores with diameters greater than average D + 15 A and measured by mercury porosimetry is less than 0.2 ml / g, preferably less than 0.1 ml / g and so even more preferred less than 0.05 ml / g.
- the total pore volume, measured by mercury porosimetry is between 0.1 ml / g and 0.6 ml / g, preferably between 0.20 and 0.50 ml / g and even more preferably higher at 0.20 ml / g
- the total pore volume, measured by nitrogen adsorption is between 0.1 ml / g and 0.6 ml / g, preferably between 0.20 and 0.50 ml / g
- the BET specific surface is between 100 and 550 m 2 / g, preferably between 150 and 500 m 2 / g
- the adsorption surface is such that the ratio between the adsorption surface and the BET surface is greater 0.5, more preferably greater than 0.65 and even more preferably greater than 0.8.
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 140 A is less than 0.1 ml / g, preferably less than 0.05 ml / g and even more preferably • less than 0 .
- 03 ml / g. the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 160 A is less than 0.1 ml / g, preferably less than 0.05 ml / g and even more preferably less than 0.025 ml / g.
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 200 A is less than 0.1 ml / g, preferably less than 0.05 ml / g and even more preferably less than 0.025 ml / g.
- the pore volume, measured by mercury porosimetry, comprised in the pores with a diameter greater than 500 A is less than 0.01 ml / g.
- the X-ray diffraction diagram contains at least the main lines characteristic of at least one of the transition aluminas included in the group composed by the aluminas alpha, rho, chi, kappa, eta, gamma, theta and delta, preferably characterized by that it contains at least the main lines characteristic of at least one of the transition aluminas included in the group composed of alumina gamma, eta, theta and delta, more preferably characterized in that it contains at least the main lines characteristic of gamma and eta alumina and even more preferably characterized in that it contains the peaks at a d between 1.39 to 1.40 A and at a d between .97 A to 2 .00 A.
- the MAS NMR spectra of the solid of 27 AI of the matrix show two distinct peak masses.
- a first type of aluminum whose maximum resonates around 10 ppm ranges between -100 and 20 ppm. The position of the maximum suggests that these species are essentially of the AI V ⁇ (octahedral) type.
- a second type of minority aluminum the maximum of which resonates around 60 ppm, ranges between 20 and 110 ppm. This founded can be broken down into at least two species. The predominant species of this massif would correspond to the atoms of AI
- the proportion of the octahedral AI V ⁇ in the matrix is greater than 50%, preferably greater than 60%, and even more preferably greater than 70%.
- the matrix comprises at least two silico-aluminum zones having Si / Ai ratios lower or greater than the overall Si / Ai ratio determined by X-ray fluorescence.
- a matrix according to the present invention having an Si ratio / Ai overall equal to 0.5 comprises for example two silico-aluminum zones, one of the zones has an Si / Ai ratio determined by MET less than 0.5 and the other zone has a Si / Ai ratio determined by MET between 0.5 and 2.5.
- the matrix comprises a single silico-aluminum zone having a Si / Ai ratio equal to the overall Si / Ai ratio determined by X fluorescence and less than 2.3.
- the acidity of the matrix according to the invention can be advantageously, without this limiting the scope of the invention, by IR monitoring of the thermo-desorption of pyridine.
- the ratio B / L, as described above, of the matrix according to the invention is between 0.05 and 1, preferably between 0.05 and 0.7, very preferably between 0.06 and 0.3 and even more preferred between 0.075 and 0.15.
- the zeolitic supports based on silico-aluminum matrices obtained from a mixture at any stage whatsoever of an alumina compound partially soluble in acid medium with a completely soluble silica compound or with a totally soluble combination of hydrated alumina and silica, shaping followed by hydrothermal or thermal treatment in order to homogenize it on the micrometric scale, even on the nanometric scale made it possible to obtain a catalyst which is particularly active in the processes hydrocracking.
- partially soluble in acid medium the applicant understands that the contacting of the alumina compound before any addition of the totally soluble silica compound or of the combination with an acid solution for example of nitric acid or sulfuric acid causes their partial dissolution.
- the silica compounds used according to the invention may have been chosen from the group formed by silicic acid, silicic acid soils, water-soluble alkali silicates, cationic silicon salts, for example hydrated sodium metasilicate, Ludox® in ammonia or alkaline form, quaternary ammonium silicates.
- the silica sol can be prepared according to one of the methods known to those skilled in the art.
- a solution of decationized orthosilicic acid is prepared from a water-soluble alkali silicate by ion exchange on a resin.
- the totally soluble hydrated silica-aluminas used according to the invention can be prepared by true coprecipitation under controlled stationary operating conditions (pH, concentration, temperature, average residence time) by reaction of a basic solution containing the silicon, for example in the form sodium silicate, optionally aluminum for example in the form of sodium aluminate with an acid solution containing at least one aluminum salt for example aluminum sulfate. At least one carbonate or C0 2 can optionally be added to the reaction medium.
- a basic solution containing the silicon for example in the form sodium silicate, optionally aluminum for example in the form of sodium aluminate
- an acid solution containing at least one aluminum salt for example aluminum sulfate for example aluminum sulfate.
- At least one carbonate or C0 2 can optionally be added to the reaction medium.
- the applicant means a process by which at least one aluminum compound totally soluble in basic or acid medium as described below, at least one silicon compound as described below are brought into contact, simultaneously or sequentially , in the presence of at least one precipitating and / or co-precipitating compound so as to obtain a mixed phase, essentially consisting of hydrated silica-alumina which is optionally homogenized by intense stirring, shearing, colloidal grinding or even by combination of these unit operations.
- these hydrated silica-aluminas may have been prepared according to the teachings of US Patents US 2,908,635; US 3,423,332, US 3,433,747, US 3,451,947, US 3,629,152, US 3,650,988.
- the total dissolution of the silica compound or combination was approximated by the following method.
- a fixed quantity (15 g) of the silica compound or of the hydrated combination is introduced into a medium of preset pH.
- the concentration of solid reported per liter of suspension is 0.2 mole per liter.
- the pH of the dispersion solution is at least 12 and can be obtained by using an alkaline source.
- the mixture is then mechanically agitated by a turbine agitator of the deflocculating type for 30 minutes at 800 rpm. Once the stirring is complete, the mixture is centrifuged for 10 minutes at 3000 rpm. The cake is separated from the supernatant.
- alumina compounds used according to the invention are partially soluble in an acid medium. They are chosen wholly or partly from the group of alumina compounds of general formula AI2O3, nH2 ⁇ . It is possible in particular to use hydrated alumina compounds such as: hydrargillite, gibbsite, bayerite, boehmite, pseudo-boehmite and amorphous or essentially amorphous alumina gels. It is also possible to use the dehydrated forms of these compounds which consist of transition aluminas and which comprise at least one of the phases taken from the group: rho, chi, eta, gamma, kappa, theta, and delta, which essentially differentiate by the organization of their crystal structure.
- Alpha alumina commonly known as corundum can be incorporated in a small proportion in the support according to the invention.
- This partial dissolution property is a sought-after property of the invention, it applies to hydrated alumina powders, to atomized hydrated alumina powders, to hydrated alumina dispersions or suspensions or any combination thereof, before any addition of a compound containing all or part of the silicon.
- the partial dissolution of the alumina compound was evaluated approximately according to the following method. A precise quantity of the powdered or suspended alumina compound is introduced into a medium of preset pH. The mixture is then stirred mechanically. Once the stirring is complete, the mixture is left without stirring for 24 hours.
- the concentration of solid Al 2 0 3 reported per liter of suspension is 0.5 mol per liter.
- the pH of the dispersion solution is 2 and is obtained either by using HN0 3 , or HCl, or HCl 4 .
- HN0 3 it is advantageous to use HN0 3 .
- the distribution of the sedimented and dissolved fractions was followed by determination of the aluminum by UV absorption.
- the supernatants were ultrafiltered (polyethersulfone membrane, Millipore NMWL: 30,000) and digested in concentrated acid.
- the amount of aluminum in the supernatant corresponds to the non-sedimented alumina compound and the dissolved aluminum and the ultrafiltered fraction to the dissolved aluminum only.
- the quantity of sedimented particles is deduced from the theoretical concentration of aluminum in the dispersion (considering that all the solid introduced is dispersed) and from the quantities of boehmite actually dispersed and of aluminum in solution.
- alumina precursors used according to the present invention are therefore distinguished from those used in the case of true co-precipitations, which are entirely soluble in acid medium: cationic alumina salts, for example aluminum nitrate.
- the methods forming part of the invention differ from true co-precipitations because one of the elements, in this case the aluminum compound, is partially soluble.
- any alumina compound of general formula AI2O3, nH2 ⁇ can be used. Its specific surface is between 150 and 600 m ⁇ / g. It is possible in particular to use hydrated alumina compounds such as: hydrargillite, gibbsite, bayerite, boehmite, pseudoboehmite and amorphous or essentially amorphous alumina gels. It is also possible to use the dehydrated forms of these compounds which consist of transition aluminas and which comprise at least one of the phases taken from the group: rho, chi, eta, gamma, kappa, theta, delta and alpha, which are essentially differentiated by the organization of their crystal structure. During heat treatments, these different forms are liable to change with one another, according to a complex parentage which depends on the operating conditions of the treatment. It is also possible to use in measured proportions alpha alumina commonly known as corundum.
- the aluminum hydrate Al 2 0 3 , nH 2 0 used more preferably is boehmite, pseudo-boehmite and amorphous or essentially amorphous alumina gels. A mixture of these products in any combination can also be used.
- Boehmite is generally described as an aluminum monohydrate of formula AI2O3, n ⁇ O which actually encompasses a wide continuum of materials with varying degrees of hydration and organization with more or less well defined boundaries: gelatinous boehmite the more hydrated, with n possibly being greater than 2, the pseudo-boehmite or the microcrystalline boehmite with n between 1 and 2, then the crystalline boehmite and finally the boehmite well crystallized in large crystals with n close to 1.
- the morphology aluminum monohydrate can vary within wide limits between these two extreme acicular or prismatic forms. A whole set of variable shapes can be used between these two shapes: chain, boats, interlaced plates.
- the preparation and / or shaping of the aluminum hydrate can thus constitute the first step in the preparation of these catalysts.
- Numerous patents relate to the preparation and / or the shaping of supports based on transition alumina derived from aluminum monohydrate: US 3,520,654; US 3,630,670; US 3,864,461; US 4,154,812; US 4,313,923; DE 3243193; US 4,371,513.
- Relatively pure aluminum hydrates can be used in powder form, amorphous or crystallized or crystallized containing an amorphous part.
- Aluminum hydrate can also be introduced in the form of aqueous suspensions or dispersions.
- the aqueous hydrate suspensions or dispersions used according to the invention can be gelled or coagulated.
- Aqueous dispersions or suspensions can also be obtained as is well known to those skilled in the art by peptization in water or acidulated water of aluminum hydrates.
- the dispersion of aluminum hydrate can be carried out by any process known to those skilled in the art: in a batch reactor, a continuous mixer, a kneader, a colloid mill. Such mixing can also be carried out in a piston flow reactor and, in particular in a static mixer. Mention may be made of the Lightnin reactors.
- an alumina that has been subjected to a treatment capable of improving its degree of dispersion can also be used as the source of alumina.
- the dispersion of the source of alumina can be improved by a preliminary homogenization treatment.
- the aqueous dispersions or suspensions of alumina that can be used are in particular the aqueous suspensions or dispersions of fine or ultra-fine boehmites which are composed of particles having dimensions in the colloidal domain.
- the fine or ultra-fine boehmites used according to the present invention may in particular have been obtained according to French patent FR - 1,261,182 and FR - 1,381,282 or in European patent application EP 15,196. It is also possible to use aqueous suspensions or dispersions obtained from pseudo-boehmite, amorphous alumina gels, aluminum hydroxide gels or ultra-fine hydrargillite.
- Aluminum monohydrate can be purchased from a variety of commercial sources of alumina such as in particular PURAL®, CATAPAL®, DISPERAL®, DISPAL® marketed by SASOL or HIQ® marketed by ALCOA, or according to known methods skilled in the art: it can be prepared by partial dehydration of aluminum trihydrate by conventional methods or it can be prepared by precipitation. When these aluminas are in the form of a gel, they are peptized by water or an acidulated solution. In precipitation, the acid source may for example be chosen from at least one of the following compounds: aluminum chloride, aluminum sulphate, aluminum nitrate.
- the basic aluminum source can be chosen from basic aluminum salts such as sodium aluminate and potassium aluminate.
- precipitating agents sodium hydroxide, sodium carbonate, potash and ammonia can be used.
- the precipitating agents are chosen such that the source of alumina according to the present invention and these agents are precipitated together.
- the aluminum hydrate is precipitated using a base or an acid chosen, for example from hydrochloric acid, acid sulfuric, sodium hydroxide or a basic or acidic aluminum compound as mentioned above.
- the two reagents can be aluminum sulphate and sodium aluminate.
- preparation of aluminum alpha monohydrate using aluminum sulphate and sodium aluminate reference may be made in particular to US Pat. No. 4,154,812.
- the pseudo-boehmite may in particular have been prepared according to the method described in American patent US Pat. No. 3,630,670 by reaction of a solution of alkaline aluminate with a solution of a mineral acid.
- the pseudo-boehmite may in particular have been prepared according to the method described in American patent US Pat. No. 3,630,670 by reaction of a solution of alkaline aluminate with a solution of a mineral acid. It may also have been prepared as described in French patent FR 1 357 830.
- the amorphous alumina gels may in particular have been prepared according to the methods described in the article "Alcoa paper n ° 19 (1972) pages 9 to 12 "and in particular by reaction of acid aluminate or an aluminum salt or by hydrolysis of aluminum alcoholates or by hydrolysis of basic aluminum salts.
- the aluminum hydroxide gels can in particular be those which have been prepared according to the methods described in American patents US 3,268,295 and US 3,245,919.
- the aluminum hydroxide gels can in particular be those prepared according to the methods described in patent WO 00/01617, by mixing an acid source of aluminum and a base or a basic source of aluminum and of an acid so as to precipitate an alumina monohydrate, the following stages being: 2. ripening 3. filtration 4.washing, and 5. drying, processes characterized in that the mixing of stage one is carried out without back-mixing .
- the ultra-fine hydrargillite may in particular have been prepared according to the process described in US Pat. alumina counted in molecules of AI 2 0 3 0.1 monovalent acid ions. It is also possible to use aqueous suspensions or dispersions of ultra-pure boehmite or pseudo-boehmite prepared according to a process in which the reaction of an alkaline aluminate with carbon dioxide is carried out to form a precipitate of hydroxycarbonate. amorphous aluminum, the precipitate obtained is separated by filtration and then washed thereof (the process is described in particular in American patent US 3,268,295).
- the washed precipitate of amorphous aluminum hydroxycarbonate is mixed with an acid solution, a base or a salt or their mixtures; this mixing is carried out by pouring the solution onto the hydroxycarbonate, the pH of the mixture thus formed being less than
- the boehmite and pseudo-boehmite dispersions or suspensions obtained according to this process have an alkali content of less than 0.005% expressed in the form of an alkali metal oxide / Al 2 0 3 weight ratio.
- the triethylaluminum is first prepared from aluminum, hydrogen and ethylene, the reaction being carried out in two stages with partial recycling of triethylaluminium.
- Ethylene is added in the polymerization step and the product obtained is then oxidized to aluminum alcoholate, the alcohols being obtained by hydrolysis.
- the aluminum hydroxide gels can also be those which have been prepared according to the methods described in American patents US 4,676,928-A and US 6,030,599.
- the hydrated alumina obtained as a by-product of the Ziegler reaction is described in particular in a bulletin from the company CONOCO of January 19, 1971.
- the size of the alumina particles constituting the source of alumina can vary within wide limits. It is generally between 1 and 100 microns.
- a method for preparing a silica-alumina forming part of the invention consists in preparing, from a water-soluble alkali silicate, a solution of orthosilicic acid (H 2 Si0, H 2 0) decationized by ion exchange and then simultaneously adding it to a cationic aluminum salt in solution, for example nitrate and to ammonia under controlled operating conditions; or else add the orthosilicic acid solution to the cationic aluminum salt in solution and co-precipitate the solution obtained obtained with ammonia under controlled operating conditions leading to a homogeneous product.
- This silica-alumina hydrogel is mixed with powder or a suspension of aluminum hydrate.
- silica-alumina After filtration and washing, drying with shaping and then calcination preferably in air, in a rotary oven, at high temperature and for a time sufficient to promote interactions between alumina and silica, generally at least 2 hours, a matrix responding to characteristics of the invention is obtained.
- Another method of preparing silica-alumina according to the invention consists in precipitating the alumina hydrate as above, in filtering and washing it, then in mixing it with aqueous orthosilicic acid so as to obtain a suspension , which is intimately homogenized by strong agitation and shearing.
- An Ultraturrax turbine or a Staro turbine can be used, or a colloid mill for example, a Staro colloid mill.
- the homogeneous suspension is then spray-dried as above and then calcined between 500 and 1200 ° C for at least 3 hours: a silica-alumina matrix which can be used in the process according to the invention is obtained.
- Another method forming part of the invention consists in preparing as above a decationized solution of orthosilicic acid and then in adding it simultaneously or consecutively to an alumina compound, for example an aluminum hydrate in powder or in suspension tangy.
- an alumina compound for example an aluminum hydrate in powder or in suspension tangy.
- at least one basic compound can optionally be added to the reaction medium.
- the product is dried with shaping simultaneously or consecutively, then calcined as above.
- Another method also forming part of the invention consists in preparing an aqueous suspension or dispersion of alumina, for example an aluminum monohydrate and then adding it simultaneously or consecutively to a silica compound, for example a sodium silicate .
- a silica compound for example a sodium silicate .
- at least one basic compound can optionally be added to the reaction medium.
- the matrix is obtained by filtration and washing, optionally washing with an ammoniacal solution to extract the residual sodium by ion exchange, drying with shaping simultaneously or consecutively. After drying with shaping and then calcination as above, a support corresponding to the characteristics of the invention is obtained.
- the size of the alumina particles used is preferably between 1 and 100 microns to obtain good homogenization of the silica-alumina support according to the invention.
- homogenization is used to describe the re-solution of a product containing a solid fraction, for example a suspension, a powder, a filtered precipitate, then its dispersion with intense stirring.
- the homogenization of a dispersion is a process well known to those skilled in the art.
- Said-homogenization can be carried out by any process known to those skilled in the art: for example in a batch reactor, a continuous mixer, a kneader. Such a mixture can be produced in a piston flow reactor and, in particular in a static reactor. Mention may be made of the Lightnin reactors.
- An Ultraturrax® turbine or a Staro® turbine can be used, or a colloid mill for example, a Staro colloid mill. IKA® commercial colloid mills can also be used.
- the stabilizing element is preferably added in the form of a soluble salt.
- the acidity of the matrix according to the invention can be advantageously, without this restricting the scope of the invention, measured by IR monitoring of the thermo-desorption of pyridine.
- the B / L ratio of the matrix according to the invention is between 0.05 and 1, preferably between 0.05 and 0.7, very preferably between 0.06 and 0.3 and even more preferably between 0.075 and 0.15.
- Zeolites in general are beneficial for improving the performance of the catalyst in conversion. Any zeolite known for its hydrocracking and / or hydroconversion performance can be used in the supports and catalysts which are the subject of the invention.
- the zeolites Y of faujasite structure (Zeolite Molecular Sieves Structure Chemistry and Uses, DW Breck, J. WILLEY and Sons, 1973) which can be in hydrogen form or partially exchanged with metal cations, for example using cations of alkaline earth metals and / or rare earths with atomic number 57 to 71 inclusive, are used.
- Zeolites Y having undergone secondary treatment also form part of the invention.
- secondary treatment is meant in particular the treatments described in: "Hydrocracking, Science and Technology", J. Scherzer, AJGruia, 1996 or in RJBeyerlein or even in.
- Y zeolites for example are prepared according to the techniques generally used by dealumination.
- the Y zeolites generally used in hydrocracking catalysts are manufactured by modification of commercially available Na-Y zeolite. This modification leads to zeolites which are said to be stabilized, ultra-stabilized (USY), very ultra-stabilized (VUSY) or even dealuminated (SDUSY). This designation is frequent in the literature but it does not restrict the characteristics of the zeolites of the present invention to such a designation.
- This modification is carried out by combination of three types of operation known to those skilled in the art: hydrothermal treatment, ion exchange and acid attack. Hydrothermal treatment is perfectly defined by the conjunction of operating variables such as temperature, duration, total pressure and partial pressure of water vapor.
- the effect of this treatment is to extract aluminum atoms from the silico-aluminum framework of the zeolite.
- the consequence of this treatment is an increase in the SiO2 / AI203 molar frame ratio and a decrease in the parameter of the crystal lattice.
- the ion exchange generally takes place by immersion of the zeolite in an aqueous solution containing ions capable of fixing on the cation exchange sites of the zeolite. The sodium cations present in the zeolite are thus removed after crystallization.
- the acid attack operation consists in bringing the zeolite into contact with an aqueous solution of a mineral acid.
- the severity of the acid attack is adjusted by the acid concentration, the duration and the temperature. Carried out on a hydrothermally treated zeolite, this treatment has the effect of eliminating the aluminum species extracted from the frame and which block the microporosity of the solid.
- a particular hydrothermal treatment as described in patent application US Pat. No. 5,601,798 has the effect of increasing the mesoporosity of the zeolites Y, USY, VUSY and SDUSY, which zeolites are particularly advantageous in combination with the amorphous matrix described above. Different Y zeolites can be advantageously used.
- a particularly advantageous acidic zeolite HY is characterized by different specifications: an overall Si ⁇ 2 / Al2 ⁇ 3 molar ratio of between approximately 6 and 70 and preferably between approximately 12 and 50: a sodium content less than 0.15% by weight determined on the zeolite calcined at 1100 ° C; a crystalline parameter has an elementary mesh comprised between 24.58 x 10 "" O m and 24.24 x 10 "" O m and preferably between 24.38 x 10 "' ' 0 m and 24.26 x 10 "' ' ⁇ m; a CNa capacity for taking up sodium ions, expressed in grams of Na per 100 grams of modified zeolite, neutralized then calcined, greater than about 0.85; a specific surface area determined by the BET method greater than about 400 m ⁇ / g and of preferably greater than 550 m / g, a water vapor adsorption capacity at 25 ° C for a
- the zeolite has a porous distribution, determined by physisorption of nitrogen, comprising between 5 and 45% and preferably between 5 and 40% of the total pore volume of the zeolite contained in pores with a diameter between 20 x 10 ' ⁇ m and 80 x 10 ' ⁇ m, and between 5 and 45% and preferably between 5 and 40% of the total pore volume of the zeolite contained in pores with a diameter greater than 80 x 10 " ' ' ⁇ m and generally less than 1000 x 10 ' ⁇ m, the remainder of the pore volume being contained in the pores of diameter less than 20 ⁇ 10 " ' "-' m.
- a preferred catalyst using this type of zeolite contains a silico-aluminum matrix, at least one dealuminated Y zeolite and having a crystalline parameter between 2,424 nm and 2,455 nm, preferably in tre 2,426 and 2,438 nm, an overall Si ⁇ 2 / Al 2 ⁇ 3 molar ratio greater than 8, a cation content of alkaline earth or alkali metals and / or rare earth cations such as the atomic ratio (nx M n + ) / AI is less than 0.8, preferably less than 0.5 or even 0.1, a specific surface area determined by the BET method greater than 400 m 2 / g, preferably greater than 550 m 2 / g, and a capacity of adsorption of water at 25 ° C for a P / Po value of 0.2, greater than 6% by weight, said catalyst also comprising at least one hydro-dehydrogenating metal, and silicon deposited on the catalyst.
- a partially amorphous Y zeolite is used.
- the term “partially amorphous Y zeolite” means a solid having: i) a peak rate which is less than 0.40, preferably less than about 0.30; ii) a crystalline fraction expressed relative to a reference Y zeolite in sodium form
- the partially amorphous Y zeolites, solids used in the composition of the catalyst according to the invention exhibit the at least one (and preferably all) of the following other characteristics: iii) an overall Si / Ai ratio greater than 15, preferably greater than 20 and less than 150, iv) a Si / Ai lv framework ratio greater than or equal to overall Si / Ai ratio v) a pore volume at least equal to 0.20 ml / g of solid of which a fraction, between 8% and 50%, consists of pores having a diameter of at least 5 nm (nanometer) , or 50 A; vi) a specific surface of 210-800 m 2 / g, preferably 250-750 m 2 / g and advantageously
- the peak rate of a conventional USY zeolite is 0.45 to 0.55, its crystalline fraction relative to a perfectly crystallized NaY is 80 to 95%.
- the peak rate of the solid which is the subject of the present description is less than 0.4 and preferably less than 0.35. Its crystalline fraction is therefore less than 70%, preferably less than 60%.
- the partially amorphous zeolites are prepared according to the techniques generally used for dealumination, from commercially available Y zeolites, that is to say which generally have high crystallinities (at least 80%). More generally, it will be possible to start from zeolites having a crystalline fraction of at least 60%, or at least 70%.
- the Y zeolites generally used in hydrocracking catalysts are manufactured by modification of commercially available Na-Y zeolites. This modification leads to so-called stabilized, ultra-stabilized or even dealuminated zeolites. This modification is carried out by at least one of the dealumination techniques, and for example the hydrothermal treatment, the acid attack. Preferably, this modification is carried out by combination of three types of operations known to those skilled in the art: hydrothermal treatment, ion exchange and acid attack.
- Another particularly interesting zeolite is a globally non-dealuminated zeolite which is very acidic.
- globally non dealuminated zeolite is understood a Y zeolite (structural type FAU, faujasite) according to the nomenclature developed in "Atlas of zeolites structure types", WM Meier, DH Oison and Ch. Baerlocher, 4 revised Edition 1996, Elsevier.
- the crystalline parameter of this zeolite may have decreased by extraction of the aluminum from the structure or framework during the preparation, but the overall SiO 2 / AI 2 0 3 ratio has not changed since the aluminum has not been chemically extracted.
- Such a globally non dealuminated zeolite therefore has a silicon and aluminum composition expressed by the overall SiO 2 / Al 2 0 3 ratio equivalent to the starting non dealuminated zeolite Y.
- This globally non dealuminated Y zeolite can either be in the hydrogen form or be at least partially exchanged with metal cations, for example using cations of alkaline earth metals and / or rare earth metal cations of atomic number 57 to 71 inclusive.
- metal cations for example using cations of alkaline earth metals and / or rare earth metal cations of atomic number 57 to 71 inclusive.
- the non-globally dealuminated zeolite Y generally has a crystalline parameter greater than 2.438 nm, an overall Si0 2 / Al 2 0 3 ratio less than 8, a SiO2 / Al2O3 molar structure ratio less than 21 and greater than the overall SiO2 / Al2O3 ratio.
- An advantageous catalyst combines this zeolite with a matrix doped with phosphorus.
- the generally non dealuminated zeolite can be obtained by any treatment which does not extract the aluminum from the sample, such as for example the treatment with water vapor, the treatment with SiCl
- the support comprises a zeolite as described in patent application US 5, 601, 978. These zeolites are in particular described in column 30, lines 48-64. Their mesoporous volume is in particular greater than 0.202 cm 3 / g for a mesh parameter of 24.5 A and 24.6 A and greater than 0.313 cm 3 / g for a mesh parameter of between 24.3 and 24.5 A.
- a zeolite chosen from the group formed by the zeolites ZSM-48, ZBM-30, EU-2, EU-11, alone or as a mixture with another zeolite.
- zeolites ZSM-48 and ZBM-30 we consider the zeolites ZSM-48 and ZBM-30. Even more preferably, the zeolite ZBM-30 will be considered, preferably synthesized according to the procedure described in the patent (EP-A-46504).
- the zeolite is a zeolite chosen from the group formed by the zeolites Mordenite, Beta, NU-87, EU-1, preferably the MOR zeolite, used alone or in mixture with other zeolites.
- the preparation and the treatment (s) as well as the shaping of the zeolite can thus constitute a stage in the preparation of these catalysts.
- the introduction of the zeolite can be done by any technique known to those skilled in the art during the preparation of the matrix or during the shaping of the support.
- catalysts according to the invention can be prepared according to all the methods well known to those skilled in the art.
- a preferred process for preparing the catalyst according to the present invention comprises the following steps:
- the zeolite can be introduced according to any method known to those skilled in the art and this at any stage the preparation of the support or of the catalyst. According to a preferred method of preparation, the zeolite can be introduced during the synthesis of the matrix precursors.
- the zeolite can be, without being limiting, for example under powder form, ground powder, suspension, suspension having undergone a deagglomeration treatment.
- the zeolite can be placed in an acidulated suspension or not at a concentration adjusted to the final content of zeolite targeted on the support. This suspension commonly called a slip is then mixed with the precursors of the matrix at any stage of its synthesis as described above.
- the zeolite can also be introduced during the shaping of the support with the elements which constitute the matrix with optionally at least one binder.
- the zeolite can be, without being limiting, can be in the form powder, ground powder, suspension, suspension having undergone a deagglomeration treatment.
- the elements of groups VIB and / or VIII, and optionally those chosen from phosphorus, boron, silicon and optionally the elements of groups VB, and VIIB can be optionally introduced at this stage of the preparation of the catalyst by any known method of Those skilled in the art, They can also be introduced after the support has been shaped and this after or before the support is dried and calcined.
- the hydrogenating element can be introduced at any stage of the preparation, preferably during mixing, or very preferably after shaping.
- the shaping is followed by a calcination, the hydrogenating element can also be introduced before or after this calcination.
- the preparation generally ends with a calcination at a temperature of 250 to 600 ° C.
- Another preferred method according to the present invention consists in shaping the silica-alumina without binder after kneading the latter, optionally with the zeolite, then passing the dough thus obtained through a die to form extrudates of diameter between 0.4 and 4 mm.
- the hydrogenating function can then be introduced in part only (if, for example, 'of combinations of metal oxides of groups VIB and VIII) or completely ,, at the time of kneading. It can also be introduced by one or more ion exchange operations on the calcined support consisting of at least one silica-alumina, optionally shaped with a binder, using solutions containing the precursor salts of the metals chosen when these belong to group VIII.
- It can also be introduced by one or more operations of impregnating the shaped and calcined support, with a solution of the precursors of the oxides of the metals of groups VIII (in particular cobalt and nickel) when the precursors of the oxides of the metals of the group VIB (in particular molybdenum or tungsten) were previously introduced at the time of the mixing of the support.
- groups VIII in particular cobalt and nickel
- the precursors of the oxides of the metals of the group VIB in particular molybdenum or tungsten
- the calcined support consisting of at least one zeolite and at least one silica-alumina according to the invention and optionally at least one binder, by solutions containing the precursors of metal oxides of groups VI and / or VIII, the precursors of metal oxides of group VIII being preferably introduced after those of group VIB or at the same time as the latter.
- the support is impregnated with an aqueous solution.
- the impregnation of the support is preferably carried out by the so-called “dry” impregnation method well known to those skilled in the art.
- the impregnation can be carried out in a single step with a solution containing all of the components of the final catalyst.
- the catalyst of the present invention can therefore contain at least one element of group VIII such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum.
- group VIII such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum.
- group VIII it is preferred to use a metal chosen from the group formed by iron, cobalt, nickel, platinum, palladium and ruthenium.
- the catalyst according to the invention may also contain at least one element from group VIB, preferably tungsten and molybdenum.
- the preferred associations are: nickel-molybdenum, cobalt-molybdenum, cobalt-tungsten and even more advantageously platinum-palladium and nickel-tungsten.
- combinations of three metals for example nickel-cobalt-molybdenum, nickel-cobalt-tungsten.
- the following combinations of metals are used: ⁇ ickel-niobium-molybdenum, cobalt-niobium-molybdenum, iron-niobium-molybdenum, nickel-niobium-tungsten, cobalt-niobium-tungsten, iron-niobium-tungsten, preferred associations being: nickel-niobium-molybdenum, cobalt-niobium-molybdenum. It is also possible to use combinations of four metals, for example nickel-cobalt-niobium-molybdenum. One can also use combinations containing a noble metal such as ruthenium-niobium-molybdenum, or ruthenium-nickel-niobium-molybdenum.
- a noble metal such as ruthenium-niobium-molybdenum, or ruthenium-nickel-niobium-molybdenum.
- boron and / or silicon and / or phosphorus and optionally the element (s) chosen from the group (s) VIIB and VB, can be introduced into the catalyst at any level of the preparation and according to any technique known to those skilled in the art.
- a preferred method according to the invention consists in depositing the selected doping element or elements, for example the boron-silicon couple, on the precursor, calcined or not, preferably calcined.
- an aqueous solution of at least one boron salt such as ammonium biborate or ammonium pentaborate is prepared in an alkaline medium and in the presence of hydrogen peroxide and a so-called dry impregnation is carried out, in which the pore volume of the precursor is filled with the solution containing, for example, boron.
- silicon is also deposited
- the deposition of boron and silicon can also be carried out simultaneously using, for example, a solution containing a boron salt and a silicon-type silicon compound.
- a solution containing a boron salt and a silicon-type silicon compound for example in the case where the precursor is a nickel-tungsten type catalyst supported on silica-alumina, it is possible to impregnate this precursor with aqueous solution of ammonium biborate and of silicone Rhodorsil E1 P of the Rhodia company to carry out a drying for example at 120 ° C, then to impregnate with an ammonium fluoride solution, to carry out a drying for example at 120 ° C, and to carry out a calcination for example and so preferred in air in a crossed bed, for example at 500 ° C. for 4 hours.
- the doping element chosen from the group formed by silicon, boron and phosphorus as well as the elements from groups VilB, VB, can be introduced by one or more impregnation operations with excess solution on the calcined precursor.
- B and / or P and / or Si When possibly at least one doping element, B and / or P and / or Si, is introduced, its distribution and its location can be determined by techniques such as the Castaing microprobe (distribution profile of the various elements), electron microscopy by transmission coupled with an X-analysis of the components of the catalysts, or even by establishing a distribution map of the elements present in the catalyst by electronic microprobe. These techniques make it possible to demonstrate the presence of these exogenous elements added after the synthesis of the silica-alumina according to the invention.
- the boron source can be boric acid, preferably orthoboric acid H3BO3, ammonium biborate or pentaborate, boron oxide, boric esters.
- Boron can for example be introduced in the form of a mixture of boric acid, hydrogen peroxide and a basic organic compound containing nitrogen such as ammonia, primary and secondary amines, cyclic amines, compounds of the family of pyridine and quinolines and compounds of the family of pyrrole. Boron can be introduced for example by a solution of boric acid in a water / alcohol mixture.
- the preferred phosphorus source is orthophosphoric acid H3PO4, but its salts and esters such as ammonium phosphates are also suitable.
- Phosphorus can for example be introduced in the form of a mixture of phosphoric acid and a basic organic compound containing nitrogen such as ammonia, primary and secondary amines, amines cyclic, compounds of the pyridine and quinoline family and compounds of the pyrrole family.
- a basic organic compound containing nitrogen such as ammonia, primary and secondary amines, amines cyclic, compounds of the pyridine and quinoline family and compounds of the pyrrole family.
- ethyl orthosilicate Si (OEt) 4 siloxanes, polysiloxanes, silicones, silicone emulsions, halide silicates such as ammonium fluorosilicate (NH4) 2SiF6 or fluorosilicate of sodium Na2SiF ⁇ - Silicomolybdic acid and its salts, silicotungstic acid and its salts can also be advantageously used.
- Silicon can be added for example by impregnation of ethyl silicate in solution in a water / alcohol mixture. The silicon can be added for example by impregnation of a silicon compound of the silicone type or the silicic acid suspended in water.
- the metals of group VIB and group VIII of the catalyst of the present invention may be present in whole or in part in metallic form and / or oxide and / or sulphide.
- the sources of molybdenum and tungsten there can be used oxides and hydroxides, molybdic and tungstic acids and their salts, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, tungstate ammonium, phosphomolybdic acid, phosphotungstic acid and their salts, silicomolybdic acid, silicotungstic acid and their salts.
- ammonium salts such as ammonium molybdate, ammonium heptamolybdate, tungstate ammonium, phosphomolybdic acid, phosphotungstic acid and their salts, silicomolybdic acid, silicotungstic acid and their salts.
- group VIII elements which can be used are well known to those skilled in the art.
- non-noble metals nitrates, sulfates, hydroxides, phosphates, halides, for example chlorides, bromides and fluorides, carboxylates, for example acetates and carbonates, will be used.
- halides for example chlorides, nitrates, acids such as chloroplatinic acid, oxychlorides such as ammoniacal ruthenium oxychloride.
- halogens other than that introduced into the impregnation are added, this halogen preferably being chlorine.
- the support can be shaped by any technique known to those skilled in the art.
- the shaping can be carried out for example by extrusion, by tableting, by the method of coagulation in drop (oil-drop), by granulation with the turntable or by any other. method well known to those skilled in the art.
- the shaping can also be carried out in the presence of the various constituents of the catalyst and extrusion of the mineral paste obtained, by tableting, shaping in the form of beads with a rotating bezel or with a drum, drop coagulation, oil-drop, oil-up, or any other known method of agglomeration of a powder containing alumina and possibly other ingredients chosen from those mentioned above.
- the catalysts used according to the invention have the form of spheres or extrudates.
- the catalyst is in the form of extrudates with a diameter of between 0.5 and 5 mm and more particularly between 0.7 and 2.5 mm.
- the shapes are cylindrical (which can be hollow or not), twisted cylindrical, multilobed (2, 3, 4 or 5 lobes for example), rings.
- the cylindrical shape is preferably used, but any other shape can be used.
- the packed filling density of the supports, after calcination, is greater than 0.65 g / cm 3 , preferably greater than 0.72 g / cm 3 , and very preferably greater than 0.75 g / cm 3 and even more preferably greater at 0.78 g / cm 3 .
- the packed filling density of the catalysts is greater than 0.85 g / cm 3 , preferably greater than 0.95 g / cm 3 , very preferably greater than 1.025 cm 3 / g and even more preferably greater than 1.1 g / cm 3 .
- these supports used according to the present invention may have been treated as is well known to those skilled in the art with additives to facilitate shaping and / or improve the final mechanical properties of the supports.
- additives based on silico-aluminum matrices.
- additives mention may in particular be made of cellulose, carboxymethyl cellulose, carboxy ethyl cellulose, tall oil, xanthan gums, surfactants, flocculating agents such as polyacrylamides, carbon black, starches, stearic acid, polyacrylic alcohol, polyvinyl alcohol, biopolymers, glucose, polyethylene glycols, etc.
- the adjustment of the porosity characteristic of the supports of the invention is partially carried out during this step of shaping the particles of supports.
- the shaping can be carried out using the techniques for shaping the catalysts, known to a person skilled in the art, such as for example: extrusion, coating, spray drying or tabletting. Water can be added or removed to adjust the viscosity of the paste to be extruded. This step can be carried out at any stage of the kneading step. To adjust the solid content of the dough to be extruded in order to make it extrudable, it is also possible to add a predominantly solid compound and preferably an oxide or a hydrate.
- Use will preferably be made of a hydrate and even more preferably of an aluminum hydrate.
- the loss on ignition of this hydrate will be greater than 15%.
- the acid content added to the kneading before shaping is less than 30%, preferably between 0.5 and 20% by weight of the anhydrous mass of silica and alumina used in the synthesis.
- Extrusion can be carried out by any conventional tool, commercially available.
- the paste from the kneading is extruded through a die, for example using a piston or a single-screw or double extrusion screw. This extrusion step can be carried out by any method known to those skilled in the art.
- the support extrudates according to the invention generally have a crushing strength of at least 70 N / cm and preferably greater than or equal to 100 N / cm.
- the drying is carried out by any technique known to those skilled in the art.
- At least one calcination can be carried out after any of the stages of the preparation.
- This treatment for example can be carried out in a crossed bed, in a licked bed or in a static atmosphere.
- the oven used can be a rotary rotary oven or a vertical oven with radial through layers.
- the calcination conditions: temperature and duration depend mainly on the maximum temperature of use of the catalyst.
- Preferred calcination conditions are between more than one hour at 200 ° C to less than one hour at 1100 ° C. Calcination can be carried out in the presence of water vapor. The final calcination can optionally be carried out in the presence of an acidic or basic vapor. For example, calcination can be carried out under partial pressure of ammonia.
- Post-synthesis treatments can be carried out, so as to improve the properties of the support, in particular its homogeneity as defined above.
- the post-synthesis treatment is a hvdrothermal treatment.
- the hvdrothermal treatment is carried out by any technique known to those skilled in the art.
- hvdrothermal treatment is understood to mean contacting at any stage of the preparation of the mixed support with water in the vapor phase or in the liquid phase.
- hvdrothermal treatment one can hear in particular ripening, steamin ⁇ . autoclavaqe. calcination in humid air, rehvdratation. Without reducing the scope of the invention, such treatment has the effect of making the silica component mobile.
- the ripening can take place before or after the shaping.
- the hvdrothermal treatment is done by steaminq in an oven in the presence water vapor.
- the temperature during the steamino can be between 600 and 1100 ° C and preferably higher than 700 ° C for a period of time between 30 minutes and 3 hours.
- the water vapor content is greater than 20 g of water per kilo of dry air and preferably greater than 40 g of water per kg of dry air and preferably more than 100 g of water per kg dry air.
- Such a treatment can, if necessary, completely or partially replace the calcination treatment.
- the support can thus possibly be subjected to a hydrothermal treatment in a confined atmosphere.
- Hydrothermal treatment in a confined atmosphere is understood to mean treatment by autoclaving in the presence of water at a temperature above ambient temperature.
- the silica-alumina formed or the support (matrix + zeolite) formed can be treated in different ways.
- This impregnation, prior to autoclaving can be acidic or not.
- This impregnation prior to autoclaving, can be carried out dry or by immersion of the silica-alumina in an acidic aqueous solution.
- dry impregnation is understood to mean bringing the alumina into contact with a volume of solution less than or equal to the total pore volume of the treated alumina.
- the impregnation is carried out dry.
- the autoclave is preferably an autoclave with a rotating basket such as that defined in patent application EP-A-0 387 109.
- the temperature during autoclaving can be between 100 and 250 ° C. for a period of time between 30 minutes and 3 hours.
- the invention also relates to the hydrocracking processes using the hydrocracking catalysts according to the invention, said processes covering the pressure and conversion domains ranging from mild hydrocracking to high pressure hydrocracking.
- Mild hydrocracking is understood to mean hydrocracking leading to moderate conversions, generally less than 50% and preferably less than 40%, and operating at low pressure, generally between 2 MPa and 6 MPa.
- the catalysts according to the invention are used for the treatment of hydrocarbon cuts.
- the catalysts according to the invention are advantageously used for hydrocracking and / or hydroconversion of hydrocarbon fractions.
- the catalyst of the present invention can be used alone, in one or more catalytic beds in a fixed bed, in one or more reactors, in a hydrocracking scheme known as in one step, with or without liquid recycling of the unconverted fraction, optionally in combination with a hydrorefining catalyst located upstream of the catalyst of the present invention.
- the catalyst of the present invention can be used alone, in a single or more reactors in a bubbling bed, in a hydrocracking scheme called in one step, with or without liquid recycling of the unconverted fraction, optionally in combination with a catalyst.
- the bubbling bed is operated with removal of spent catalyst and daily addition of new catalyst in order to maintain a stable catalyst activity.
- the catalyst of the present invention can be used in one or in the two reactors in association or not with a catalyst hydrorefining located upstream of the catalyst of the present invention.
- Hydrocracking said in one step, first and foremost involves a thorough hydrorefining which aims to achieve a hydrodeazotation and a desulfurization of the feed before it is sent to the hydrocracking catalyst itself , in particular in the case where this comprises a zeolite.
- This advanced hydrorefining of the feed causes only a limited conversion of the feed, into lighter fractions, which remains insufficient and must therefore be completed on the more active hydrocracking catalyst.
- This version of hydrocracking also called "Once Through” has a variant which presents a recycling of the unconverted fraction to the reactor for further conversion of the feed.
- the silica contents by weight of the support used in the composition of the catalyst are between 5 and 30% and preferably between 5 and 20%.
- the silica contents by weight of the support used in the composition of the catalyst are between 20 and 80% and preferably between 30 and 60%.
- a catalyst having a low silica content by weight as defined above will advantageously be used. It can also advantageously be used in combination with a hydrorefining catalyst, the latter being located upstream of the catalyst of the present invention.
- the conversion is generally ( or preferably) less than 50% by weight and preferably less than 40%.
- Embodiment So-called one-step bubbling bed process
- the catalyst according to the invention can be used alone in one or more reactors.
- the bubbling bed reactor or reactors containing the catalyst according to the invention being preceded by one or more reactors containing at least one hydrorefining catalyst in fixed bed or bubbling bed.
- the conversion of the fraction of the charge caused by this hydrorefining catalyst is generally (or preferably) less than 30% by weight and preferably less than 25%.
- Embodiment So-called one-step process in a fixed bed with hot flash
- the catalyst according to the present invention can also be used in a so-called one-step hydrocracking process comprising a hydrorefining zone, a zone allowing the partial elimination of ammonia, for example by a hot flash, and an area comprising a hydrocracking catalyst.
- This hydrocracking process of hydrocarbon feedstocks in one step for the production of middle distillates and optionally of oil bases comprises at least a first reaction zone including a hydrorefining, and at least a second reaction zone, in which the hydrocracking of at least part of the effluent from the first reaction zone.
- This process also includes an incomplete separation of the ammonia from the effluent leaving the first zone.
- the hydrocracking carried out in the second reaction zone is carried out in the presence of ammonia in an amount less than the amount present in the feed, preferably less than 1500 ppm by weight, more preferably less than 1000 ppm by weight and even more preferably less at 800 ppm weight of nitrogen.
- the catalyst of the present invention is preferably used in the area hydrocracking reaction in combination or not with a hydrorefining catalyst located upstream of the catalyst of the present invention.
- the catalyst according to the invention can be used either in the first reaction zone in converting pretreatment, alone or in combination with a conventional hydrorefining catalyst, located upstream of the catalyst according to the invention, in one or more catalytic beds, in a or more reactors.
- a process representing a variant of the embodiments of the invention cited above comprises: a first hydrorefining reaction zone in which the feedstock is brought into contact with at least one hydrorefining catalyst having in the standard test activity a cyclohexane conversion rate of less than 10% by mass. a second hydrocracking reaction zone in which at least part of the effluent from the hydrorefining step is brought into contact with at least one zeolitic hydrocracking catalyst having in the standard activity test a conversion rate cyclohexane greater than 10% by mass, the catalyst according to the invention being present in at least one of the two reaction zones.
- the purpose of the standard activity test is to measure the activity of the catalysts in conversion of cyclohexane.
- the conversion of cyclohexane takes into account all the products different from cyclohexane. Obtaining all of these products requires the presence of a more or less strong acid function on the catalyst.
- the catalyst according to the invention can be used alone or in combination with another hydrorefining catalyst.
- the catalyst according to the invention can be used alone or in combination with another hydrocracking catalyst.
- Hydrocracking in two stages comprises a first stage which aims, as in the "one stage” process, to carry out the hydrorefining (or hydrotreatment) of the feed, but also to achieve a conversion of the latter from l generally 40 to 60%.
- the effluent from the first stage then undergoes separation (distillation), most often called intermediate separation, which aims to separate the conversion products from the unconverted fraction.
- separation distillation
- the intermediate separation of the conversion products avoids their "over-cracking" into naphtha and gas in the second step on the hydrocracking catalyst.
- the unconverted fraction of the feedstock treated in the second step generally contains very low contents of NH 3 as well as organic nitrogen compounds, in general less than 20 ppm by weight or even less than 10 ppm weight.
- the preferred catalysts according to the invention are the catalysts based on non-noble Group VIII elements, even more preferably the catalysts with base of nickel and tungsten or molybdenum, which can be doped with an element chosen from the group formed by boron, phosphorus and silicon, preferably phosphorus.
- the catalysts used in the second reaction zone of the one-step hydrocracking processes or in the second step of the two-step hydrocracking processes are preferably the catalysts based on noble elements of group VIII, even more preferably the platinum and / or palladium based catalysts.
- Very varied fillers can be treated by the hydrocracking processes according to the invention described above and generally they contain at least 20% by volume and often at least 80% by volume of compounds boiling above 340 ° C.
- the feed can be, for example, LCOs (light cycle oil), atmospheric distillates, vacuum distillates, for example gas oils obtained from the direct distillation of crude oil or from conversion units such as FCC, coker or viscoreduction, as well as feedstocks coming from aromatic extraction units from the lubricating oil bases or from solvent dewaxing of the lubricating oil bases, or else from distillates coming from desulfurization or hydroconversion processes in a fixed bed or in bubbling bed of RAT (atmospheric residues) and / or RSV (vacuum residues) and / or deasphalted oils, or the filler can be a deasphalted oil, or any mixture of the charges previously mentioned.
- LCOs light cycle oil
- atmospheric distillates for example gas oils obtained from the direct distillation of crude oil or from conversion units such as FCC, coker or viscoreduction
- feedstocks coming from aromatic extraction units from the lubricating oil bases or from solvent dewaxing of the lubricating oil bases or else from distill
- Paraffins from the Fischer-Tropsch process are excluded.
- the charges have a boiling point T5 greater than 340 ° C, and more preferably greater than 370 ° C, ie 95% of present compounds • in the feed have a boiling point above 340 ° C, and more preferably greater than 370 ° C .
- the nitrogen content of the feedstocks treated in the processes according to the invention is usually greater than 500 ppm, preferably between 500 and 5000 ppm by weight, more preferably between 700 and 4000 ppm by weight and even more preferably between 1000 and 4000 ppm, and the sulfur content between 0.01 and 5% by weight, more generally between 0.2 and 4%.
- the metal content is generally less than 2 ppm and preferably less than 1 ppm Ni + V maximum.
- the content of C7 asphaltenes is generally less than 5000 ppm, preferably less than 1000 ppm and more preferably less than 200 ppm.
- the catalysts used in the process according to the present invention are preferably subjected beforehand to a sulphurization treatment making it possible to transform, at least in part, the metallic species into sulphide before they are brought into contact with the load to be processed.
- This sulfurization activation treatment is well known to those skilled in the art and can be carried out by any method already described in the literature either in situ, that is to say in the reactor, or ex situ.
- a conventional sulfurization method well known to those skilled in the art consists in heating in the presence of hydrogen sulfide (pure or for example under a flow of a hydrogen / hydrogen sulfide mixture) to a temperature between 150 and 800 ° C., preferably between 250 and 600 ° C, generally in a reaction zone with a crossed bed.
- the hydrocracking operating conditions such as temperature, pressure, hydrogen recycling rate, hourly space velocity, can be very variable depending on the nature of the feed, the quality of the desired products and the facilities available to the refiner. .
- the hydrocracking catalyst is brought into contact, in the presence of hydrogen, with the fillers described above, at a temperature above 200 ° C, often between 250 and 480 ° C, advantageously between 320 and 450 ° C, preferably between 330 and 435 D C, under a pressure greater than 1 MPa, often between 2 and 25 MPa, preferably between 3 and 20 MPa, the space speed being between 0.1 and 20h “1 and preferably 0 , 1-6h “ , preferably 0.2-3h " 1 , and the quantity of hydrogen introduced is such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 80 and 5000I / I and more often between 100 and 2000 I / l.
- These operating conditions used in the process according to the invention make it possible to achieve conversions by pass, into products having boiling points below 340 ° C, and better still below 370 ° C, above 15% and even more more preferred between 20 and 95%.
- Example 1 Preparation and shaping of a silico-aluminum matrix MA1
- a matrix precursor MA1 is prepared in the following manner: firstly a 30% sulfuric acid solution is added to a sodium silicate solution. The quantity of H 2 S0 is defined so as to work at a fixed neutralization rate. The addition is carried out in two minutes with stirring at 600 revolutions / minute. The synthesis temperature is 60 ° C. The ripening time was set at 30 minutes. Stirring is maintained at 600 revolutions / minute, the temperature is that of the previous step. Then, AI 2 (S0) 3 (500 ml) is added, the concentration is fixed by the desired alumina content. The pH is not regulated and is fixed by the desired alumina content. The addition is done in 10 minutes.
- the gel resulting from this stage is mixed with Pural boehmite powder so that the final composition in anhydrous product is, at this stage of the synthesis, equal to 50% AI 2 Q 3 -50% Si0 2 .
- the mixing is done on a Z-arm mixer.
- the extrusion is carried out by passing the dough through a die provided with orifices with a diameter of 1.4 mm.
- the extrudates thus obtained are dried at 150 ° C, calcined at 550 ° C, then calcined at 700 ° C in the presence of steam.
- the characteristics of the matrix are as follows:
- the composition of the matrix MA1 is 50.12% Al 2 0 3 - 49.88% Si0 2 .
- the BET surface of the matrix of 254 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.43 ml / g.
- the average pore diameter, measured by mercury porosimetry, is 65 A.
- the ratio between the volume V2, measured by mercury porosimetry, between the average D n - 30 A and the Dm o y in + 30 A on the total mercury volume is 0.91.
- the volume V3, measured by mercury porosimetry, included in the pores with diameters greater than average D + 30 A is 0.03 ml / g.
- the volume V6, measured by mercury porosimetry, included in the pores with diameters greater than D mean + 15 A is 0.047 ml / g,
- the ratio between the adsorption surface and the BET surface is 0.76.
- the pore volume, measured by mercury porosimetry, included in pores with a diameter greater than 140 A is 0.015 ml / g
- the pore volume, measured by mercury porosimetry, included in pores with a diameter greater than 160 A is 0.013 ml / g
- the pore volume, measured by mercury porosimetry, included in pores with a diameter greater than 200 A is 0.011 ml / g
- the pore volume, measured by mercury porosimetry, is included in pores with a diameter greater than 500 A is 0.001 ml / g
- the X-ray diffraction diagram contains the main lines characteristic of gamma alumina and in particular it contains the peaks at a d between 1.39 to 1.40 A and at a d between 1, 97 A to 2.00 A.
- the atomic sodium content is 310 +/- 20 ppm.
- the atomic sulfur content is 1500 ppm.
- the MAS NMR spectra of the solid of 27 AI of the matrix show two distinct peak masses.
- a first type of aluminum whose maximum resonates around 10 ppm ranges between -100 and 20 ppm. The position of the maximum suggests that these species are essentially of the Alvi (octahedral) type.
- a second type of minority aluminum whose maximum resonates around 60 ppm ranges between 20 and 100 ppm. This founded can be broken down into at least two species. The predominant species of this massif would correspond to the atoms of AI
- the matrix contains two silico-aluminum zones, the said zones having Si / Ai ratios lower or greater than the overall Si / Al ratio determined by X-ray fluorescence.
- One of the zones has an Si / Ai ratio determined by TEM of 0.7 and the other zone has an Si / Ai ratio determined by MET of 0.98.
- the B / L ratio of the matrix is equal to 0.12.
- Example 2 Preparation and shaping of a silico-aluminum matrix MA2
- An alumina hydrate is prepared according to the teachings of US Pat. No. 3,124,418. After filtration, the freshly prepared precipitate is mixed with a solution of silicic acid. prepared by exchange on decationizing resin. The proportions of the two solutions are adjusted so as to achieve a composition of 70% Al 2 0 3 - 30% Si0 2 on the final support. This mixture is quickly homogenized in a commercial colloid mill in the presence of nitric acid 'so that the nitric acid content of the grinder output suspended or 8% based on the solid mixed silica-alumina. Then, the suspension is conventionally dried in an atomizer in a conventional manner.
- the powder thus prepared is shaped in a Z-shaped arm in the presence of 8% nitric acid relative to the anhydrous product.
- the extrusion is carried out by passing the dough through a die provided with orifices with a diameter of 1.4 mm.
- the extrudates thus obtained are dried at
- the characteristics of the MA2 matrix are as follows:
- the silica-alumina composition is 69.5% Al 2 0 3 and 30.5% Si0 2 .
- the BET surface area is 250 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.45 ml / g.
- the average porous diameter, measured by mercury porosimetry, is 70 A.
- the ratio between the volume V2, measured by mercury porosimetry, between the average D - 30 A and the average D + 30 A on the total mercury volume is 0.9.
- the volume V3, measured by mercury porosimetry, included in the pores with diameters greater than average D + 30 A is 0.021 ml / g.
- the volume V6, measured by mercury porosimetry, included in the pores with diameters greater than Dmoy ⁇ n + 15 A is 0.035 ml / g,
- the ratio between the adsorption surface and the BET surface is 0.82.
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 140 A is 0.015 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with diameter greater than 160 A is 0 , 01 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 200 A is 0.007 ml / g
- the pore volume, measured by mercury porosimetry, is included in the pores with a diameter greater than 500 A is 0.001 ml / g
- the X-ray diffraction diagram contains the main lines characteristic of gamma alumina and in particular it contains the peaks at a d between 1.39 to 1.40 A and at a d between 1.97 A to
- the atomic sodium content is 250 +/- 20 ppm.
- the atomic sulfur content is 2000 ppm.
- the MAS NMR spectra of the solid of 27 AI of the matrix show two distinct peak masses.
- a first type of aluminum whose maximum resonates around 10 ppm ranges between -100 and 20 ppm. The position of the maximum suggests that these species are essentially of the AI V ⁇ (octahedral) type.
- a second type of minority aluminum whose maximum resonates around 60 ppm ranges between 20 and 100 ppm. This founded can be broken down into at least two species. The predominant species of this massive would correspond to the atoms of Aliv (tetrahedral). The proportion of octahedral AI V ⁇ is 69%.
- the matrix contains a single silico-aluminum zone with an Si / Al ratio determined by TEM microprobe of 0.37.
- the B / L ratio of the matrix is equal to 0.11.
- the aluminum hydroxide powder was prepared according to the method described in patent WO 00/01617.
- the average particle size of the aluminum hydroxide particles measured by laser particle size is 40 microns.
- This powder is mixed with a silica sol prepared by exchange on decationizing resin, then filtered through porosity 2 resin.
- the concentrations of silica sol and aluminum hydroxide powder are adjusted so as to obtain a final composition of 60 % Al 2 0 3 and 40% Si0 2 .
- the shaping is carried out in the presence of 15% nitric acid relative to the anhydrous product.
- the mixing is done on a Z-arm mixer.
- the extrusion is carried out by passing the dough through a die provided with orifices with a diameter of 1.4 mm.
- the extrudates thus obtained are dried at 150 ° C, then calcined at 550 ° C, then calcined at 750 ° C in the presence of water vapor.
- composition of the silica-alumina matrix is 59.7% Al 2 0 3 and 40.3% Si0 2 .
- the BET surface area is 248 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.46 ml / g
- the mean pore diameter, measured by mercury porosimetry, is 69 A.
- the ratio between volume V2, measured by mercury porosimetry, encompassed between D moye n - 30 A and D mean + 30 A to the total mercury volume is 0.9.
- the volume V3 measured by mercury porosimetry, included in the pores with a diameter greater than
- Average + 30 A is 0.022 ml / g.
- the volume V6, measured by mercury porosimetry, included in the pores with a diameter greater than average D + 15 A is 0.031 ml / g
- the ratio between the adsorption surface and the BET surface is 0.83.
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 140 A is 0.012 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 160 A is 0.0105 ml / g
- the pore volume, measured by mercury porosimetry, included in pores with a diameter greater than 200 A is 0.0065 ml / g
- the pore volume, measured by mercury porosimetry, is included in pores with a diameter greater than 500 A is 0.001 ml / g
- the X-ray diffraction diagram contains the main lines characteristic of gamma alumina and in particular it contains the peaks at a d between 1.39 to 1.40 A and at a d between 1.97 A to 2.00 A.
- the atomic sodium content is 200 +/- 20 ppm.
- the atomic sulfur content is 800 ppm.
- the MAS NMR spectra of the solid of 27 AI of the matrix show two distinct peak masses.
- a first type of aluminum whose maximum resonates around 10 ppm ranges between -100 and 20 ppm. The position of the maximum suggests that these species are essentially of the AI V ⁇ (octahedral) type.
- a second type of minority aluminum whose maximum resonates around 60 ppm ranges between 20 and 100 ppm. This massif can be broken down into at least two species. The predominant species of this massif would correspond to the atoms of AI
- the matrix contains two silico-aluminum zones, the said zones having Si / AI ratios lower or greater than the overall Si / AI ratio determined by X-ray fluorescence.
- One of the zones has an Si / AI ratio determined by TEM of 0.22 and l the other zone has an Si / AI ratio determined by MET of 0.85.
- the B / L ratio of the matrix is equal to 0.12.
- the MA4 matrix is obtained in the following manner.
- Silica-alumina gels are prepared by mixing sodium silicate and water, sending this mixture over an ion exchange resin. A solution of aluminum chloride hexahydrate in water is added to the decationized silica sol. In order to obtain a gel, ammonia is added, the precipitate is then filtered and washing is carried out with a solution of concentrated ammonia and water until the conductivity of the washing water is constant. The gel from this step is mixed with Pural boehmite powder so that the final composition of the mixed support in anhydrous product is, at this stage of the synthesis, equal to 60% AI 2 O 3 -40% Si0 2 . This suspension is passed through a colloid mill in the presence of nitric acid.
- the content of added nitric acid is adjusted so that the percentage at the outlet of the nitric acid mill is 8% relative to the mass of solid mixed oxide. This mixture is then filtered to reduce the amount of water in the mixed cake. Then, the cake is kneaded in the presence of 10% nitric acid and then extruded. Mixing was' fits on a mixer arm Z. The extrusion is carried out by passing the dough through a die with 1.4 mm diameter orifices. The extrudates thus obtained are dried at 150 ° C, then calcined at 550 ° C, then calcined at 700 ° C in the presence of water vapor.
- the characteristics of the MA4 matrix are as follows: The composition of the silica-alumina matrix is 60.7% Al 2 0 3 and 39.3% Si0 2 .
- the BET surface area is 258 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.47 mi / g
- the average pore diameter, measured by mercury porosimetry, is 69 A.
- the ratio between the volume V2, measured by mercury porosimetry, between the average D - 30 A and the average D + 30 A on the total mercury volume is 0.89.
- the volume V3, measured by mercury porosimetry, included in the pores of diameters greater than average D + 30 A is 0.032 ml / g.
- the volume V6, measured by mercury porosimetry, included in the pores of diameters greater than Dm 0y in + 15 A is 0.041 ml / g,
- the ratio between the adsorption surface and the BET surface is 0.83.
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 140 A is 0.012 ml / g
- the pore volume, measured by mercury porosimetry, included in pores with a diameter greater than 160 A is 0.0082 ml / g
- the pore volume, measured by mercury porosimetry, included in pores with a diameter greater than 200 A is 0.0063 ml / g
- the pore volume, measured by mercury porosimetry, is included in the pores with a diameter greater than 500 A is 0.001 ml / g
- the X-ray diffraction diagram contains the main lines characteristic of gamma alumina and in particular it contains the peaks at a d between 1.39 to 1.40 A and at a d between 1.97 A to
- the atomic sodium content is 200 +/- 20 ppm.
- the atomic sulfur content is 800 ppm.
- the MAS NMR spectra of the solid of 27 AI of the matrix show two distinct peak masses.
- a first type of aluminum whose maximum resonates around 10 ppm ranges between -100 and 20 ppm. The position of the maximum suggests that these species are essentially of the AI V ⁇ (octahedral) type.
- a second type of minority aluminum whose maximum resonates around 60 ppm ranges between 20 and 100 ppm. This founded can be broken down into at least two species. The predominant species of this massif would correspond to the atoms of AI
- the matrix contains a single silico-aluminum zone with an Si / Al ratio determined by TEM microprobe of 0.63.
- the B / L ratio of the matrix is equal to 0.11.
- the supports SU5 to SU8 are thus obtained containing 5% of zeolite Z1 added in anhydrous mass.
- the composition of the support matrix is 50.1% Al 2 0 3 - 49.9% Si0 2 .
- the total pore volume, measured by nitrogen adsorption, is 0.418 ml / g.
- the ratio between the volume V2, measured by mercury porosimetry, between the average D - 30 A and ' the average D + 30 A on the total mercury volume is 0.91.
- the volume V3, measured by mercury porosimetry, included in the pores with diameters greater than average D + 30 A is 0.03 ml / g.
- the volume V6, measured by mercury porosimetry, included in the pores with diameters greater than average D + 15 A is 0.047 ml / g,
- the ratio between the adsorption surface and the BET surface is 0.76.
- the pore volume, measured by mercury porosimetry, included in pores with a diameter greater than 140 A is 0.014 ml / g
- the pore volume, measured by mercury porosimetry, included in pores with a diameter greater than 160 A is 0.012 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 200 A is 0.010 ml / g
- the pore volume, measured by mercury porosimetry, is included in the pores with a diameter greater than 500 A is 0.001 ml / g
- the packed filling density of the support is 0.795 g / cm 3
- the X-ray diffraction diagram contains:
- the atomic sodium content is 290 +/- 20 ppm.
- the atomic sulfur content is 1500 ppm.
- the characteristics of the supports are as follows: the composition of silica-alumina in the matrix of the support is 69.5% Al 2 0 3 and 30.5% Si0 2 .
- the BET surface area is 279 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.437 ml / g.
- the average pore diameter, measured by mercury porosimetry, is 69 A.
- the ratio between the volume V2, measured by mercury porosimetry, between the average D - 30 A and the D m0 y in + 30 A on the total mercury volume is 0.9.
- the volume V3, measured by mercury porosimetry, included in the pores with diameters greater than average D + 30 A is 0.020 ml / g.
- the volume V6, measured by mercury porosimetry, included in the pores with diameters greater than D mean + 15 A is 0.034 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 140 A is 0.015 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with diameter greater than 160 A is 0 , 01 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 200 A is 0.068 ml / g
- the pore volume, measured by mercury porosimetry, is included in the pores with a diameter greater than 500 A is 0.001 ml / g
- the packed filling density of the support is 0.797 g / cm 3 .
- the X-ray diffraction diagram contains:
- the atomic sodium content is 240 +/- 20 ppm.
- the atomic sulfur content is 1900 ppm.
- the characteristics of the support SU 7 are as follows: The composition of the silica-alumina matrix is 59.7% Al 2 0 3 and 40.3% Si0 2 .
- the BET surface area is 283 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.45 ml / g.
- the average pore diameter, measured by mercury porosimetry, is 68 A.
- the ratio between the volume V2, measured by mercury porosimetry, included between the average D - 30 A and the average D + 30 A on the total mercury volume is 0.9.
- the volume V3, measured by mercury porosimetry, included in the pores with a diameter greater than D m ⁇ yen + 30 A is 0.021 ml / g.
- the volume V6, measured by mercury porosimetry, included in the pores with a diameter greater than D mean + 15 A is 0.030 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 140 A is 0.012 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 160 A is 0.010 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with diameter greater than 200 A is 0.063 ml / g
- the pore volume, measured by mercury porosimetry, is included in the pores with a diameter greater than 500 A is 0.001 ml / g
- the X-ray diffraction diagram contains:
- the atomic sodium content is 190 +/- 20 ppm.
- the atomic sulfur content is 800 ppm.
- the packed filling density of the support is 0.79 g / cm 3 .
- the characteristics of the SU8 support are as follows: The composition of the matrix of the silica-alumina support is 60.7% Al 2 0 3 and 39.3% Si0 2 .
- the BET surface area is 287 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.46 ml / g
- the average pore diameter, measured by mercury porosimetry, is 68 A.
- the ratio between the volume V2, measured by mercury porosimetry, between the average D - 30 A and the average D + 30 A on the total mercury volume is 0.89.
- the volume V3, measured by mercury porosimetry, included in the pores of diameters greater than average D + 30 A is 0.031 ml / g.
- the volume V6, measured by mercury porosimetry, included in the pores with diameters greater than Dmoyen + 15 A is 0.040 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with diameter greater than 140 A is 0.012 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 160 A is 0.008 ml / g
- the pore volume, measured by mercury porosimetry, included in pores with a diameter greater than 200 A is 0.006 ml / g
- the pore volume, measured by mercury porosimetry, is included in pores with a diameter greater than 500 A is 0.001 ml / g
- the packed filling density of the support is 0.795 g / cm 3 .
- the X-ray diffraction diagram contains:
- the atomic sodium content is 200 +/- 20 ppm.
- the atomic sulfur content is 800 ppm.
- a Z2 zeolite with an Si / AI ratio measured by FX of 73, a sodium content of 102 ppm, a mesh parameter a 24.15 A, a crystallinity rate of 44% and a BET surface area of 783 m 2 / is used.
- the composition of the matrix of the support is 50.1% Al 2 0 3 - 49.9% Si0 2 .
- the BET surface of the support of 283 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.418 ml / g.
- the average pore diameter, measured by mercury porosimetry, is 64 A.
- the ratio between volume V2, measured by mercury porosimetry, encompassed between D moye n - 30 A and D mean + 30 A to the total mercury volume is 0.91.
- the volume V3, measured by mercury porosimetry, encompassed in the pores with diameters greater than D m edium + 30 A is 0.03 ml / g.
- the volume V6, measured by mercury porosimetry, included in the pores with diameters greater than D m0 yen + 15 A is 0.047 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with diameter greater than 140 A is 0.014 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 160 A is 0.012 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 200 A is 0.010 ml / g
- the pore volume, measured by mercury porosimetry, is included in the pores with a diameter greater than 500 A is 0.001 ml / g
- the packed filling density of the support is 0.795 g / cm 3
- the X-ray diffraction diagram contains: - the main lines characteristic of gamma alumina and in particular it contains the peaks at a d between 1.39 to 1.40 A and at a d between 1.97 A at 2.00 AT
- the atomic sodium content is 290 +/- 20 ppm.
- the atomic sulfur content is 1500 ppm.
- the characteristics of the supports are as follows: the silica-alumina composition of the matrix of the support is 69.5% Al 2 0 3 and 30.5% Si0 2 .
- the BET surface area is 279 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.438 ml / g.
- the average porous diameter, measured by mercury porosimetry, is 69 A.
- the ratio between the volume V2, measured by mercury porosimetry, between the average D - 30 A and the average D + 30 A on the total mercury volume is 0.9.
- the volume V3, measured by mercury porosimetry, included in the pores with diameters greater than D mean + 30 A is 0.020 ml / g.
- the volume V6, measured by mercury porosimetry, included in the pores with diameters greater than average D + 15 A is 0.034 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 140 A is 0.015 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 160 A is 0.013 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with diameter greater than 200 A is 0, 0068ml / g
- the pore volume, measured by mercury porosimetry, is included in the pores with a diameter greater than 500 A is 0.001 ml / g.
- the packed filling density of the support is 0.79 g / cm 3 .
- the X-ray diffraction diagram contains:
- the atomic sodium content is 240 +/- 20 ppm.
- the atomic sulfur content is 1900 ppm.
- the characteristics of the SU 11 support are as follows:
- composition of the silica-alumina matrix is 59.7% Al 2 0 3 and 40.3% Si0 2 .
- the BET surface area is 275 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.45 ml / g
- the average pore diameter, measured by mercury porosimetry, is 68 A.
- the ratio between the volume V2, measured by mercury porosimetry, between the average D - 30 A and the Dm o y in + 30 A on the total mercury volume is 0.9.
- the volume V3 measured by mercury porosimetry, included in the pores with a diameter greater than
- Average + 30 A is 0.021 ml / g.
- Average + 15 A is 0.030 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 140 A is 0.012 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 160 A is 0.010 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 200 A is 0.006 ml / g
- the pore volume, measured by mercury porosimetry, is included in the pores with a diameter greater than 500 A is 0.001 ml / g.
- the packed filling density of the support is 0.795 g / cm 3 .
- the X-ray diffraction diagram contains:
- the atomic sodium content is 190 +/- 20 ppm.
- the atomic sulfur content is 800 ppm.
- the characteristics of the SU12 support are as follows:
- composition of the matrix of the silica-alumina support is 60.7% Al 2 0 3. And 39.3% Si0 2 .
- the BET surface area is 284 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.46 ml / g
- the average pore diameter, measured by mercury porosimetry, is 68 A.
- the ratio between the volume V2, measured by mercury porosimetry, between the D mean - 30 A and the Dm o y e n + 30 A on the total mercury volume is 0.89.
- the volume V3, measured by mercury porosimetry, encompassed in the pores with diameters greater than D m edium + 30 A is 0.031 ml / g.
- the volume V6, measured by mercury porosimetry, included in the pores with diameters greater than D mean + 15 A is 0.040 ml / g,
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 140 A is 0.012 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 160 A is 0.008 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 200 A is 0.006 ml / g
- the pore volume, measured by mercury porosimetry, is included in the pores with a diameter greater than 500 A is 0.001 ml / g.
- the packed filling density of the support is 0.79 g / cm 3 .
- the X-ray diffraction diagram contains:
- the atomic sodium content is 200 +/- 20 ppm.
- the atomic sulfur content is 800 ppm.
- Example 7 Preparation of the hydrocracking catalyst supports according to the invention (SU13 to
- a Z3 zeolite is used as described in the patent application US Pat. No. 5,601,798. This zeolite is prepared according to the method described in Example 52 in Table 16. The mesoporous volume obtained is 0.36 cm 3 / g. The mesh parameter a is 24.34 ⁇ and the crystallinity rate of 75%. 5 g of zeolite Z3 described above and 95 g of the precursor matrices of the supports MA1 to MA4 added in solid material are then mixed as described above. This mixing takes place before introduction into the extruder. The zeolite powder is previously wetted and added to the matrix suspension in the presence of 66% nitric acid (7% weight of acid per gram of dry gel) then kneaded for 15 minutes.
- the dough obtained is passed through a die having cylindrical orifices with a diameter of 1.4 mm.
- the extrudates are then dried overnight at 120 ° C in air and then calcined at 550 ° C in air, then calcined at 700 ° C in the presence of water vapor.
- the supports SU 13 to SU 16 are thus obtained.
- the characteristics of the supports according to the invention are:
- the composition of the support matrix is 50.1% Al 2 0 3 - 49.9% Si0 2 .
- the BET surface of the support is 280 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.425 ml / g.
- the ratio between the volume V2, measured by mercury porosimetry, between the D m0 y in - 30 A and the Dmoy e n + 30 A on the total mercury volume is 0.91.
- the volume V3 measured by mercury porosimetry, included in the pores with a diameter greater than
- D m edium + 30 A is 0.03 ml / g.
- Average + 15 A is 0.047 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 140 A is 0.015 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 160 A is 0.013 ml / g
- the pore volume, measured by. mercury porosimetry, included in pores with a diameter greater than 200 A is 0.011 ml / g
- the pore volume, measured by mercury porosimetry, is included in the pores with a diameter greater than 500 A is 0.001 ml / g.
- the packed filling density of the support is 0.79 g / cm 3 .
- the X-ray diffraction diagram contains:
- the atomic sodium content is 290 +/- 20 ppm.
- the atomic sulfur content is 1500 ppm.
- the characteristics of the supports are as follows: the silica-luminous composition of the matrix of the support is 69.5% Al 2 0 3 and 30.5% Si0 2 .
- the BET surface area is 276 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.438 ml / g.
- the average pore diameter, measured by mercury porosimetry, is 69 A.
- the ratio between the volume V2, measured by mercury porosimetry, between D mean 0 - 30 A and Dm ow n + 30 A on the total mercury volume is 0.9.
- the volume V3, measured by mercury porosimetry, included in the pores with diameters greater than D mean + 30 A is 0.020 ml / g.
- the volume V6, measured by mercury porosimetry, included in the pores with diameters greater than D mean + 15 A is 0.034 ml / g,
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 140 A is 0.012 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 160 A is 0.010 ml / g
- the pore volume, measured by mercury porosimetry, included in pores with a diameter greater than 200 A is 0.006 ml / g
- the pore volume, measured by mercury porosimetry, is included in pores with a diameter greater than 500 A is 0.001 ml / g
- the packed filling density of the support is 0.79 g / cm 3 .
- the X-ray diffraction diagram contains:
- the atomic sodium content is 240 +/- 20 ppm.
- the atomic sulfur content is 1900 ppm.
- the characteristics of the SU 15 support are as follows:
- the composition of the silica-alumina matrix is 59.7% Al 2 0 3 and 40.3% Si0 2 .
- the BET surface area is 275 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.455 ml / g
- the average pore diameter, measured by mercury porosimetry, is 68 A.
- the ratio between the volume V2, measured by mercury porosimetry, between the average D - 30 A and the Dm o y e n + 30 A on the total mercury volume is 0.9.
- Average + 30 A is 0.021 ml / g.
- the volume V6 measured by mercury porosimetry, included in the pores with a diameter greater than
- Dmo in + 15 A is 0.030 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 140 A is 0.012 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 160 A is 0.010 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with diameter greater than 200 A is 0.006 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores of diameter greater than 500 A is 0.001 ml / g
- the packed filling density of the support is 0.795 g / cm 3 .
- the X-ray diffraction diagram contains: - the main lines characteristic of gamma alumina and in particular it contains the peaks at a d between 1.39 to 1.40 A and at a d between 1.97 A at 2.00 A, - the main lines characteristic of the zeolite Z3.
- the atomic sodium content is 190 +/- 20 ppm.
- the atomic sulfur content is 800 ppm.
- the characteristics of the SU 16 support are as follows: The composition of the matrix of the silica-alumina support is 60.7% Al 2 0 3 and 39.3% Si0 2 .
- the BET surface area is 284 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.46 ml / g
- the average pore diameter, measured by mercury porosimetry, is 68 A.
- the ratio between the volume V2, measured by mercury porosimetry, included between the D m0 y in - 30 A and the Dm o y e n + 30 A on the total mercury volume is 0.89.
- the volume V3, measured by mercury porosimetry, included in the pores with diameters greater than D mean + 30 A is 0.031 ml / g.
- the volume V6, measured by mercury porosimetry, included in the pores with diameters greater than D mean + 15 A is 0.040 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with diameter • greater than 140 A is 0.012 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 160 A is 0.008 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 200 A is 0.006 ml / g
- the pore volume, measured by mercury porosimetry, is included in the pores with a diameter greater than 500 A is 0.001 ml / g
- the packed filling density of the support is 0.79 g / cm 3 .
- the X-ray diffraction diagram contains: - the main lines characteristic of gamma alumina and in particular it contains the peaks at a d between 1.39 to 1.40 A and at a d between 1.97 A at 2.00 AT , - the main lines characteristic of the Z3 zeolite
- the atomic sodium content is 200 +/- 20 ppm.
- the atomic sulfur content is 800 ppm.
- Example 8 Preparation of the hydrocracking catalyst supports according to the invention (SU 16 to SU20)
- zeolite ZBM-30 is synthesized according to BASF patent EP-A-46504 with the organic structuring agent triethylenetetramine. Then it is subjected to calcination at 550 ° C under dry air flow for 12 hours.
- the H-ZBM-30 zeolite (acid form) thus obtained has an Si / Al ratio of 45 and an Na / Al ratio less than 0.001.
- the zeolite powder is previously wetted and added to the matrix suspension in the presence of 66% nitric acid (7% weight of acid per gram of dry gel) then kneaded for 15 minutes. At the end of this kneading, the dough obtained is passed through a die having cylindrical orifices with a diameter equal to 1.4 mm. The extrudates are then dried overnight at 120 ° C in air and then calcined at 550 ° C in air, then calcined at 700 ° C in the presence of steam.
- the supports SU 17 to SU20 are thus obtained.
- the composition of the support matrix is 50.1% Al 2 0 3 - 49.9% Si0 2 .
- the BET surface of the support of 280 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.445 ml / g.
- the average pore diameter, measured by mercury porosimetry, is 64 A.
- the ratio between the volume V2, measured by mercury porosimetry, between the average D n - 30 A and the average D n + 30 A on the total mercury volume is 0.91.
- the volume V3, measured by mercury porosimetry, included in the pores with a diameter greater than D mo y e n + 30 A is 0.03 ml / g.
- the volume V6 measured by mercury porosimetry, included in the pores with a diameter greater than
- Average + 15 A is 0.047 ml / g
- the pore volume, measured by mercury porosimetry, included in pores with a diameter greater than 140 A is 0.015 ml / g
- the pore volume, measured by mercury porosimetry, included in pores with a diameter greater than 160 A is 0.012 ml / g
- the pore volume, measured by mercury porosimetry, included in pores with a diameter greater than 200 A is 0.010 ml / g
- the pore volume, measured by mercury porosimetry, is included in pores with a diameter greater than 500 A is 0.001 ml / g
- the packed filling density of the support is 0.795 g / cm 3
- the X-ray diffraction diagram contains:
- the atomic sodium content is 290 +/- 20 ppm.
- the atomic sulfur content is 1500 ppm.
- the characteristics of the supports are as follows: the silica-alumina composition of the matrix of the support is 69.5% Al 2 0 3 and 30.5% Si0 2 .
- the BET surface area is 276 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.43 ml / g.
- the average pore diameter, measured by mercury porosimetry, is 69 A.
- the ratio between the volume V2, measured by mercury porosimetry, between the D m0 y e n - 30 A and the Dm o y in + 30 A on the total mercury volume is 0.9.
- the volume V3, measured by mercury porosimetry, included in the pores with diameters greater than D mean + 30 A is 0.020 ml / g.
- the volume V6, measured by mercury porosimetry, included in the pores with diameters greater than D mean + 15 A is 0.034 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores of diameter greater than 140 A is 0.011 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores. diameter greater than 160 A is 0.010 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 200 A is 0.006 ml / g
- the pore volume, measured by mercury porosimetry, is included in the pores with a diameter greater than 500 A is 0.001 ml / g
- the packed filling density of the support is 0.795 g / cm 3 .
- the X-ray diffraction diagram contains:
- the atomic sodium content is 230 +/- 20 ppm.
- the atomic sulfur content is 1900 ppm.
- the characteristics of the support SU 19 are as follows: The composition of the silica-alumina matrix is 59.7% Al 2 0 3 and 40.3% Si0 2 .
- the BET surface area is 275 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.435 ml / g
- the average pore diameter, measured by mercury porosimetry, is 68 A.
- the ratio between the volume V2, measured by mercury porosimetry, between the D m0 ye n - 30 A and the Dm o y in + 30 A on the total mercury volume is 0.9.
- the volume V3 measured by mercury porosimetry, included in the pores with a diameter greater than
- Average + 30 A is 0.021 ml / g.
- the volume V6 measured by mercury porosimetry, included in the pores with a diameter greater than
- Average + 15 A is 0.030 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 140 A is 0.011 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 160 A is 0.010 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with a diameter greater than 200 A is 0.006 ml / g
- the pore volume, measured by mercury porosimetry, is included in the pores with a diameter greater than 500 A is 0.001 ml / g
- the X-ray diffraction diagram contains:
- the atomic sodium content is 190 +/- 20 ppm.
- the atomic sulfur content is 800 ppm.
- the packed filling density of the support is 0.795 g / cm 3 .
- the characteristics of the SU20 support are as follows:
- composition of the matrix of the silica-alumina support is 60.7% Al 2 0 3 and 39.3% Si0 2 .
- the BET surface area is 284 m 2 / g.
- the total pore volume, measured by nitrogen adsorption, is 0.435 ml / g
- the average porous diameter, measured by mercury porosimetry, is 68 A.
- the ratio between the volume V2, measured by mercury porosimetry, between D m0 y e n - 30 A and Dmoy in + 30 A on the volume total mercury is 0.89.
- the volume V3, measured by mercury porosimetry, included in the pores of diameters greater than D mean + 30 A is -0.031 ml / g.
- the volume V6, measured by mercury porosimetry, included in the pores with diameters greater than Dmoyen + 15 A is 0.040 ml / g
- the pore volume, measured by mercury porosimetry, included in the pores with diameter greater than 140 A is 0.011 ml / g
- the pore volume, measured by mercury porosimetry, included in pores with a diameter greater than 160 A is 0.006 ml / g
- the pore volume, measured by mercury porosimetry, included in pores with a larger diameter at 200 A is 0.006 ml / g
- the packed filling density of the support is 0.79 g / cm 3 .
- the X-ray diffraction diagram contains: - the main lines characteristic of gamma alumina and in particular it contains the peaks at a d between 1.39 to 1.40 A and at a d between 1.97 A at 2.00 A, - the main lines characteristic of the ZBM30 zeolite.
- the atomic sodium content is 190 +/- 20 ppm.
- the atomic sulfur content is 800 ppm.
- the catalysts C1 to C20 are obtained by dry impregnation of an aqueous solution containing tungsten and nickel salts, respectively, of the supports SU1 to SU20 under form of extrudates and the preparations of which were respectively described in Examples 1 to 7.
- the tungsten salt is ammonium metatungstate (NH 4 ) 6 H 2 W ⁇ 2 O 40 * 4H 2 O and that of nickel is nickel nitrate Ni (N0 3 ) 2 * 6H 2 0.
- the impregnated extrudates are dried at 120 ° C overnight then calcined at 500 ° C in dry air.
- Table 1 Weight contents of W0 3 and NiO of catalysts C1 to C8
- Example 10 The catalysts C21 and C22 are obtained by dry impregnation of the supports SU3 and SU 10 (in the form of extrudates), prepared in Examples 1 and 5 by a dry impregnation of a solution of hexachloroplatinic acid H 2 PtCI 6 . The impregnated extrudates are then calcined at 550 ° C. in dry air. The platinum content is 0.49% by weight.
- Example 11 - Evaluation of Catalysts C1 to C20 in Hydrograining of a Vacuum Distillate in a High Pressure Stage
- the catalysts C1 to C20 are used to carry out the hydrocracking of a distillate under vacuum, the main characteristics of which are given below:
- the catalysts Prior to the hydrocracking test, the catalysts are sulfurized at 120 bars, at 350 ° C. by means of a direct distillation gas oil added with 2% by weight of DMDS.
- VVH space velocity
- the catalytic performances are expressed by the net conversion into products having a boiling point below 370 ° C., by the net selectivity in medium distillate cuts 150-370 ° C. and the ratio of gas oil yield / kerosene yield in the middle distillate fraction. They are expressed from the results of simulated distillation.
- the net CN conversion is taken equal to:
- feed mass content of compounds having boiling points below 370 ° C in the feed.
- the gross selectivity for middle distillate SB is taken equal to:
- SB definition [(fraction in 150 - 370 eff iuents) j / [(% of 370 ° C " effluents)]
- Example 11 Evaluation of the catalyst C21 and C22 under conditions simulating the operation of the second reactor of a so-called two-stage hydro-crawling process
- the charge of the second stage is produced by hydrotreating a distillate under vacuum on a hydrorefining catalyst marketed by Axens in the presence of hydrogen, at a temperature of 395 ° C and at an hourly space speed of 0.55h-1 .
- the conversion to 380 ° C products is approximately 50% by weight.
- the 380 ° C + fraction is collected and will serve as a feed for the second step.
- Table 3 Table 5: characteristics of the second stage load
- This charge is injected into the hydrocracking test unit 2 nd step which comprises a fixed bed reactor, with upward circulation of the charge (“up-flow”), into which is introduced the catalyst C9 prepared in the example. 9. Before injection of the charge, the catalyst is reduced under pure hydrogen at 450 ° C for 2 hours.
- the operating conditions of the test unit are as follows:
- Examples 10 and 11 therefore show the advantage of using a catalyst according to the invention for carrying out the hydrocracking of hydrocarbon feedstocks. Indeed, they make it possible to obtain high conversions of the charge and selectivities into interesting middle distillates.
- Example 12 Evaluation of the catalysts C5 and C9 in hydrocracking of a distillate under vacuum in a step at moderate pressure (mild hydrocrououage)
- the catalysts C5 and C9, the preparation of which is described in Example 9, are used to carry out the hydrocracking of the distillate under vacuum, described in Example 11.
- the catalysts C5 and C9 were used according to the method of the invention using a pilot unit comprising 1 reactor with a fixed bed crossed, the fluids circulating from bottom to top (up-flow).
- the catalysts Prior to the hydrocracking test, the catalysts are sulfurized at 120 bars, at 350 ° C. by means of a direct distillation gas oil added with 2% by weight of DMDS.
- VVH space velocity
- the catalytic performances are expressed by the net conversion into products having a boiling point below 370 ° C., by the net selectivity in medium distillate cuts 150-370 ° C. and the ratio of gas oil yield / kerosene yield in the middle distillate fraction. They are expressed from the results of simulated distillation and the definitions are identical to those given in Example 10.
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Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/584,144 US7790019B2 (en) | 2003-12-23 | 2004-12-16 | Zeolitic catalyst, substrate based on a silica-alumina matrix and zeolite, and hydrocracking process for hydrocarbon feedstocks |
EP04816406A EP1711260A2 (fr) | 2003-12-23 | 2004-12-16 | Catalyseur zeolithique, support a base de matrice silico-aluminique et de zeolithe, et procede d'hydrocraquage de charges hydrocarbonees |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0315210A FR2863913B1 (fr) | 2003-12-23 | 2003-12-23 | Catalyseur zeolithique,support a base de matrice silico-aluminique et de zeolithe, et procede d'hydrocraquage de charges hydrocarbonees |
FR0315210 | 2003-12-23 |
Publications (2)
Publication Number | Publication Date |
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WO2005070539A2 true WO2005070539A2 (fr) | 2005-08-04 |
WO2005070539A3 WO2005070539A3 (fr) | 2005-10-13 |
Family
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PCT/FR2004/003270 WO2005070539A2 (fr) | 2003-12-23 | 2004-12-16 | Catalyseur zeolithique, support a base de matrice silico-aluminique et de zeolithe, et procede d’hydrocraquage de charges hydrocarbonees |
Country Status (4)
Country | Link |
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US (1) | US7790019B2 (fr) |
EP (1) | EP1711260A2 (fr) |
FR (1) | FR2863913B1 (fr) |
WO (1) | WO2005070539A2 (fr) |
Families Citing this family (30)
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BRPI0508276A (pt) * | 2004-03-03 | 2007-08-07 | Shell Int Research | suporte catalìtico conformado, processo para a preparação de um suporte catalìtico, composição catalìtica, processos para a preparação de uma composição catalìtica e de hidrocraqueamento, e, uso de uma composição catalìtica |
ITMI20041289A1 (it) * | 2004-06-25 | 2004-09-25 | Enitecnologie Spa | Catalizzatore e processo per la preparazione di idrocarburi aromatici alchilati |
ATE515324T1 (de) * | 2004-12-23 | 2011-07-15 | Inst Francais Du Petrole | Zeolithkatalysator mit kontrolliertem gehalt eines dotierungselements und verbessertes verfahren zur behandlung von kohlenwasserstoffeinsätzen |
MX2007009504A (es) | 2007-08-07 | 2009-02-06 | Mexicano Inst Petrol | Catalizador para la primera etapa de hidrodesmetalizacion en un sistema de hidro procesamiento con reactores multiples para el mejoramiento de crudos pesados y extra-pesados. |
US8030240B2 (en) * | 2007-12-28 | 2011-10-04 | Exxonmobil Research And Engineering Company | Multiple molecular sieve catalyst for sour service dewaxing |
FR2926028B1 (fr) * | 2008-01-04 | 2010-02-12 | Inst Francais Du Petrole | Catalyseur comprenant au moins une zeolithe particuliere et au moins une silice-alumine et procede d'hydrocraquage de charges hydrocarbonees utilisant un tel catalyseur |
US20090211453A1 (en) * | 2008-02-26 | 2009-08-27 | Nassivera Terry W | Filtration Media for the Removal of Basic Molecular Contaminants for Use in a Clean Environment |
MX2008006050A (es) * | 2008-05-09 | 2009-11-09 | Mexicano Inst Petrol | Catalizador con acidez moderada para hidroprocesamiento de crudo pesado y residuo, y su procedimiento de sintesis. |
US7687423B2 (en) * | 2008-06-26 | 2010-03-30 | Uop Llc | Selective catalyst for aromatics conversion |
US7922997B2 (en) | 2008-09-30 | 2011-04-12 | Uop Llc | UZM-35 aluminosilicate zeolite, method of preparation and processes using UZM-35 |
US8048403B2 (en) * | 2008-12-16 | 2011-11-01 | Uop Llc | UZM-26 family of crystalline aluminosilicate compositions and method of preparing the compositions |
US7575737B1 (en) * | 2008-12-18 | 2009-08-18 | Uop Llc | UZM-27 family of crystalline aluminosilicate compositions and a method of preparing the compositions |
US20100160464A1 (en) * | 2008-12-24 | 2010-06-24 | Chevron U.S.A. Inc. | Zeolite Supported Cobalt Hybrid Fischer-Tropsch Catalyst |
US8377286B2 (en) * | 2008-12-31 | 2013-02-19 | Exxonmobil Research And Engineering Company | Sour service hydroprocessing for diesel fuel production |
EP2462060A2 (fr) * | 2009-08-04 | 2012-06-13 | Uop Llc | Famille uzm-29 de compositions zéolithiques cristallines et procédé de préparation des compositions |
MY164575A (en) | 2010-09-14 | 2018-01-15 | Ifp Energies Now | Methods of upgrading biooil to transportation grade hydrocarbon fuels |
US8586501B2 (en) * | 2010-10-04 | 2013-11-19 | General Electric Company | Catalyst and method of manufacture |
FR2987842B1 (fr) | 2012-03-12 | 2015-02-27 | IFP Energies Nouvelles | Procede optimise pour la valorisation de bio-huiles en carburants hydrocarbones |
WO2016005277A1 (fr) * | 2014-07-11 | 2016-01-14 | Total Research & Technology Feluy | Procédé de préparation de matériaux cristallins microporeux mésoporeux impliquant un agent de modélisation de mésopores recyclable |
FR3043399B1 (fr) * | 2015-11-09 | 2018-01-05 | Eco'ring | Procede de production de laine de roche et de fonte valorisable |
US10603657B2 (en) | 2016-04-11 | 2020-03-31 | Saudi Arabian Oil Company | Nano-sized zeolite supported catalysts and methods for their production |
US11084992B2 (en) * | 2016-06-02 | 2021-08-10 | Saudi Arabian Oil Company | Systems and methods for upgrading heavy oils |
US10689587B2 (en) | 2017-04-26 | 2020-06-23 | Saudi Arabian Oil Company | Systems and processes for conversion of crude oil |
JP2020527632A (ja) | 2017-07-17 | 2020-09-10 | サウジ アラビアン オイル カンパニーSaudi Arabian Oil Company | 重質油を処理するためのシステムおよび方法 |
CN111097491B (zh) * | 2018-10-26 | 2021-05-14 | 中国石油化工股份有限公司 | 含高硅分子筛的加氢裂化催化剂及其制备方法和应用 |
CN113546669B (zh) * | 2020-04-24 | 2023-11-14 | 中国石油化工股份有限公司 | 含有磷钨酸改性高比表面积介孔材料的催化裂化助剂及其制备方法和应用 |
US11577235B1 (en) * | 2021-08-13 | 2023-02-14 | Chevron U.S.A. Inc. | Layered catalyst reactor systems and processes for hydrotreatment of hydrocarbon feedstocks |
FR3130640B1 (fr) | 2021-12-21 | 2024-09-13 | Ifp Energies Now | Catalyseur comprenant un support à base de matrice silico-aluminique et de zéolithe, sa préparation et procédé d’hydrocraquage de charges hydrocarbonées |
CN115155552B (zh) * | 2022-07-13 | 2024-03-12 | 黄骏 | 一种五配位铝富集无定型硅铝材料及其合成方法 |
FR3143622A1 (fr) | 2022-12-16 | 2024-06-21 | Axens | Procédé de traitement d’une charge issue de source renouvelable pour la production d’oléfines biosourcées |
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EP0686687A1 (fr) * | 1992-05-29 | 1995-12-13 | Texaco Development Corporation | Hydrocraquage doux de charges d'hydrocarbonées lourdes avec des catalyseurs silice-alumine |
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US6045687A (en) * | 1996-10-22 | 2000-04-04 | Institut Francais Du Petrole | Catalyst containing at least two dealuminated Y zeolites and a conventional hydroconversion process for petroleum cuts using this catalyst |
US6174429B1 (en) * | 1997-10-20 | 2001-01-16 | Institut Francais Du Petrole | Catalyst and process for hydrocracking fractions that contain hydrocarbon |
US20020160906A1 (en) * | 1998-11-13 | 2002-10-31 | China Petrochemical Corporation | Amorphous silica-alumina, a carrier combination and a hydrocracking catalyst containing the same, and processes for the preparation thereof |
US20020160911A1 (en) * | 2001-01-15 | 2002-10-31 | Institut Francais Du Petrole | Catalyst that comprises a silica-alumina and its use in hydrocracking of hydrocarbon feedstocks |
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FR2812302B1 (fr) * | 2000-07-31 | 2003-09-05 | Inst Francais Du Petrole | Procede d'hydrocraquage en 2 etapes de charges hydrocarbonees |
FR2846574B1 (fr) * | 2002-10-30 | 2006-05-26 | Inst Francais Du Petrole | Catalyseur et procede d'hydrocraquage de charges hydrocarbonees |
-
2003
- 2003-12-23 FR FR0315210A patent/FR2863913B1/fr not_active Expired - Lifetime
-
2004
- 2004-12-16 WO PCT/FR2004/003270 patent/WO2005070539A2/fr active Application Filing
- 2004-12-16 US US10/584,144 patent/US7790019B2/en active Active
- 2004-12-16 EP EP04816406A patent/EP1711260A2/fr not_active Ceased
Patent Citations (8)
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US4500645A (en) * | 1981-06-13 | 1985-02-19 | Catalysts & Chemicals Industries Co., Ltd. | Hydrocracking catalyst composition and method of making same |
US4738941A (en) * | 1984-04-26 | 1988-04-19 | Societe Francaise Des Produits Pour Catalyse Pro-Catalyse | Hydrocracking catalyst for the production of middle distillates |
EP0686687A1 (fr) * | 1992-05-29 | 1995-12-13 | Texaco Development Corporation | Hydrocraquage doux de charges d'hydrocarbonées lourdes avec des catalyseurs silice-alumine |
US5500109A (en) * | 1993-06-03 | 1996-03-19 | Mobil Oil Corp. | Method for preparing catalysts comprising zeolites extruded with an alumina binder |
US6045687A (en) * | 1996-10-22 | 2000-04-04 | Institut Francais Du Petrole | Catalyst containing at least two dealuminated Y zeolites and a conventional hydroconversion process for petroleum cuts using this catalyst |
US6174429B1 (en) * | 1997-10-20 | 2001-01-16 | Institut Francais Du Petrole | Catalyst and process for hydrocracking fractions that contain hydrocarbon |
US20020160906A1 (en) * | 1998-11-13 | 2002-10-31 | China Petrochemical Corporation | Amorphous silica-alumina, a carrier combination and a hydrocracking catalyst containing the same, and processes for the preparation thereof |
US20020160911A1 (en) * | 2001-01-15 | 2002-10-31 | Institut Francais Du Petrole | Catalyst that comprises a silica-alumina and its use in hydrocracking of hydrocarbon feedstocks |
Also Published As
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US20070209968A1 (en) | 2007-09-13 |
US7790019B2 (en) | 2010-09-07 |
WO2005070539A3 (fr) | 2005-10-13 |
EP1711260A2 (fr) | 2006-10-18 |
FR2863913B1 (fr) | 2006-12-29 |
FR2863913A1 (fr) | 2005-06-24 |
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