WO2020002139A1 - Catalyseur additivé au lactate d'alkyle, sa préparation et son utilisation dans un procédé d'hydrotraitement et/ou d'hydrocraquage - Google Patents
Catalyseur additivé au lactate d'alkyle, sa préparation et son utilisation dans un procédé d'hydrotraitement et/ou d'hydrocraquage Download PDFInfo
- Publication number
- WO2020002139A1 WO2020002139A1 PCT/EP2019/066437 EP2019066437W WO2020002139A1 WO 2020002139 A1 WO2020002139 A1 WO 2020002139A1 EP 2019066437 W EP2019066437 W EP 2019066437W WO 2020002139 A1 WO2020002139 A1 WO 2020002139A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- catalyst
- formula
- alumina
- silica
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 215
- 238000000034 method Methods 0.000 title claims description 66
- 230000008569 process Effects 0.000 title claims description 51
- 238000004517 catalytic hydrocracking Methods 0.000 title claims description 34
- 238000002360 preparation method Methods 0.000 title claims description 33
- -1 alkyl lactate Chemical compound 0.000 title claims description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 63
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 40
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 37
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 36
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 19
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 8
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 194
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 48
- 239000011574 phosphorus Substances 0.000 claims description 48
- 229910052698 phosphorus Inorganic materials 0.000 claims description 48
- 239000007787 solid Substances 0.000 claims description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 34
- 239000011593 sulfur Substances 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 239000012018 catalyst precursor Substances 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims description 20
- 229920006395 saturated elastomer Polymers 0.000 claims description 19
- 125000004122 cyclic group Chemical group 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 14
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- SPRJWMSXOLZOIO-UHFFFAOYSA-N 2-hydroxypropanoyl octanoate Chemical compound CCCCCCCC(=O)OC(=O)C(C)O SPRJWMSXOLZOIO-UHFFFAOYSA-N 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 11
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 claims description 11
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 8
- SEQKRHFRPICQDD-UHFFFAOYSA-N N-tris(hydroxymethyl)methylglycine Chemical compound OCC(CO)(CO)[NH2+]CC([O-])=O SEQKRHFRPICQDD-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- OMSUIQOIVADKIM-UHFFFAOYSA-N ethyl 3-hydroxybutyrate Chemical compound CCOC(=O)CC(C)O OMSUIQOIVADKIM-UHFFFAOYSA-N 0.000 claims description 8
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- 150000003568 thioethers Chemical class 0.000 claims description 5
- 150000003573 thiols Chemical class 0.000 claims description 5
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 4
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 4
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 claims description 4
- TWYIPMITVXPNEM-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidine-2,5-dione Chemical compound OCCN1C(=O)CCC1=O TWYIPMITVXPNEM-UHFFFAOYSA-N 0.000 claims description 4
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical compound CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 claims description 4
- IEMMBWWQXVXBEU-UHFFFAOYSA-N 2-acetylfuran Chemical compound CC(=O)C1=CC=CO1 IEMMBWWQXVXBEU-UHFFFAOYSA-N 0.000 claims description 4
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- PLHCSZRZWOWUBW-UHFFFAOYSA-N 2-methoxyethyl 3-oxobutanoate Chemical compound COCCOC(=O)CC(C)=O PLHCSZRZWOWUBW-UHFFFAOYSA-N 0.000 claims description 4
- OMQHDIHZSDEIFH-UHFFFAOYSA-N 3-Acetyldihydro-2(3H)-furanone Chemical compound CC(=O)C1CCOC1=O OMQHDIHZSDEIFH-UHFFFAOYSA-N 0.000 claims description 4
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims description 4
- OUDFNZMQXZILJD-UHFFFAOYSA-N 5-methyl-2-furaldehyde Chemical compound CC1=CC=C(C=O)O1 OUDFNZMQXZILJD-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 4
- 229930091371 Fructose Natural products 0.000 claims description 4
- 239000005715 Fructose Substances 0.000 claims description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 4
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 4
- UZMAPBJVXOGOFT-UHFFFAOYSA-N Syringetin Natural products COC1=C(O)C(OC)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)O)=C1 UZMAPBJVXOGOFT-UHFFFAOYSA-N 0.000 claims description 4
- 239000007997 Tricine buffer Substances 0.000 claims description 4
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 4
- QOTQFLOTGBBMEX-UHFFFAOYSA-N alpha-angelica lactone Chemical compound CC1=CCC(=O)O1 QOTQFLOTGBBMEX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 239000007998 bicine buffer Substances 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- KCFYHBSOLOXZIF-UHFFFAOYSA-N dihydrochrysin Natural products COC1=C(O)C(OC)=CC(C2OC3=CC(O)=CC(O)=C3C(=O)C2)=C1 KCFYHBSOLOXZIF-UHFFFAOYSA-N 0.000 claims description 4
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 claims description 4
- 229960003692 gamma aminobutyric acid Drugs 0.000 claims description 4
- 239000000174 gluconic acid Substances 0.000 claims description 4
- 235000012208 gluconic acid Nutrition 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 4
- 150000002923 oximes Chemical class 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 235000000346 sugar Nutrition 0.000 claims description 4
- 150000008163 sugars Chemical class 0.000 claims description 4
- 150000003457 sulfones Chemical class 0.000 claims description 4
- 150000003462 sulfoxides Chemical class 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000811 xylitol Substances 0.000 claims description 4
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 4
- 229960002675 xylitol Drugs 0.000 claims description 4
- 235000010447 xylitol Nutrition 0.000 claims description 4
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 3
- WBPAQKQBUKYCJS-UHFFFAOYSA-N 2-methylpropyl 2-hydroxypropanoate Chemical compound CC(C)COC(=O)C(C)O WBPAQKQBUKYCJS-UHFFFAOYSA-N 0.000 claims description 3
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims description 3
- LXXNWCFBZHKFPT-UHFFFAOYSA-N Ethyl 2-mercaptopropionate Chemical compound CCOC(=O)C(C)S LXXNWCFBZHKFPT-UHFFFAOYSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- UJNOLBSYLSYIBM-WISYIIOYSA-N [(1r,2s,5r)-5-methyl-2-propan-2-ylcyclohexyl] (2r)-2-hydroxypropanoate Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1OC(=O)[C@@H](C)O UJNOLBSYLSYIBM-WISYIIOYSA-N 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- VFGRALUHHHDIQI-UHFFFAOYSA-N butyl 2-hydroxyacetate Chemical compound CCCCOC(=O)CO VFGRALUHHHDIQI-UHFFFAOYSA-N 0.000 claims description 3
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 3
- CKSRFHWWBKRUKA-UHFFFAOYSA-N ethyl 2-ethoxyacetate Chemical compound CCOCC(=O)OCC CKSRFHWWBKRUKA-UHFFFAOYSA-N 0.000 claims description 3
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 claims description 3
- MRYSSTRVUMCKKB-UHFFFAOYSA-N ethyl 2-hydroxyhexanoate Chemical compound CCCCC(O)C(=O)OCC MRYSSTRVUMCKKB-UHFFFAOYSA-N 0.000 claims description 3
- MQGTZMCASHTGBJ-UHFFFAOYSA-N ethyl 2-hydroxypentanoate Chemical compound CCCC(O)C(=O)OCC MQGTZMCASHTGBJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940116333 ethyl lactate Drugs 0.000 claims description 3
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 3
- 229940057867 methyl lactate Drugs 0.000 claims description 3
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002211 L-ascorbic acid Substances 0.000 claims 1
- 235000000069 L-ascorbic acid Nutrition 0.000 claims 1
- NNLLMULULOBXBY-PLNGDYQASA-N cis-3-Hexenyl lactate Chemical compound CC\C=C/CCOC(=O)C(C)O NNLLMULULOBXBY-PLNGDYQASA-N 0.000 claims 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 claims 1
- 238000005470 impregnation Methods 0.000 description 75
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- 238000006243 chemical reaction Methods 0.000 description 14
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- 230000003197 catalytic effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 11
- 229910052796 boron Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000011737 fluorine Substances 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 10
- 229910052750 molybdenum Inorganic materials 0.000 description 10
- 239000011733 molybdenum Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
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- 239000002019 doping agent Substances 0.000 description 8
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- 239000003921 oil Substances 0.000 description 8
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 7
- 230000003716 rejuvenation Effects 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 238000004523 catalytic cracking Methods 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 239000003502 gasoline Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 238000007493 shaping process Methods 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229910021472 group 8 element Inorganic materials 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
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- 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/283—Porous sorbents based on silica
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/284—Porous sorbents based on alumina
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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
- 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
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0209—Esters of carboxylic or carbonic acids
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
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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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- 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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- 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
- 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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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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
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
Definitions
- the invention relates to a catalyst additive using an organic compound, its preparation method and its use in the field of hydrotreating and / or hydrocracking.
- a hydrotreating catalyst for hydrocarbon fractions is to eliminate the sulfur or nitrogen compounds contained therein in order, for example, to produce a petroleum product with the required specifications (sulfur content, aromatic content, etc.) for a given application (automotive fuel, petrol or diesel, heating oil, jet fuel).
- Conventional hydrotreatment catalysts generally comprise an oxide support and an active phase based on metals of groups VIB and VIII in their oxide forms as well as phosphorus.
- the preparation of these catalysts generally comprises a step of impregnating the metals and phosphorus on the support, followed by drying and calcination which makes it possible to obtain the active phase in their oxide forms.
- these catalysts are generally subjected to sulfurization in order to form the active species.
- the invention relates to a catalyst comprising a support based on alumina or silica or silica-alumina, at least one element of group VIII, at least one element of group VIB and at least one compound of formula (I)
- Ri is a hydrocarbon radical comprising from 1 to 12 carbon atoms, saturated or not, linear, branched or cyclic
- R 2 and R 3 are chosen from a hydrogen atom and a hydrocarbon radical comprising from 1 to 12 carbon atoms, saturated or not, linear, branched or cyclic
- X is chosen from an oxygen atom or a sulfur atom, except when R 2 and R 3 represent a hydrogen atom, X is then an oxygen atom
- Y is chosen from a hydrogen atom, a hydrocarbon radical comprising from 1 to 12 carbon atoms, saturated or not, linear, branched or cyclic or a -C (0) R 4 unit , R 4 being chosen from an atom of hydrogen and a hydrocarbon radical comprising from 1 to 12 carbon atoms, saturated or not, linear, branched or cyclic.
- the catalyst according to the invention shows an increased activity compared to the non-additive catalysts and to the known dry additive catalysts.
- the temperature necessary to reach a desired sulfur or nitrogen content for example 10 ppm of sulfur in the case of a diesel charge, in ULSD or Ultra Low Sulfur Diesel mode depending on the Anglo-Saxon terminology
- stability is increased as the cycle time is extended by the necessary temperature reduction.
- the compound of formula (I) is chosen from methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, isopentyl lactate, lactate of cis-3-hexenyl, L-menthyl lactate, butyl butyryllactate, ethyl 2-mercaptopropanoate, methyl glycolate, ethyl glycolate, butyl glycolate, ethyl ethoxyacetate, ethyl a-hydroxyisobutanoate, tert-butyl a-hydroxyisobutanoate, ethyl 2-hydroxycaproate and ethyl 2-hydroxyvalerate.
- R 2 represents a methyl radical and R 3 represents a hydrogen atom.
- the compound of formula (I) is chosen from butyl lactate and butyl butyryllactate.
- the content of element of group VIB is between 5 and 40% by weight expressed as metal oxide of group VIB relative to the total weight of the catalyst and the content of element of group VIII is between 1 and 10% by weight expressed as group VIII metal oxide relative to the total weight of the catalyst.
- the molar ratio element of group VIII to element of group VIB in the catalyst is between 0.1 and 0.8.
- the catalyst also contains phosphorus, the phosphorus content being between 0.1 and 20% by weight expressed as P 2 0 5 relative to the total weight of the catalyst and the phosphorus molar ratio to the group element VIB in the catalyst is greater than or equal to 0.05.
- the content of compound of formula (I) is between 1 and 45% by weight relative to the total weight of the catalyst.
- the catalyst further contains an organic compound other than the compound of formula (I) containing oxygen and / or nitrogen and / or sulfur.
- the organic compound (s) is (are) chosen from a compound comprising one or more chemical functions chosen from a carboxylic, alcohol, thiol, thioether, sulfone, sulfoxide function, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea, amide or the compounds including a furan cycle or sugars.
- the organic compound other than the compound of formula (I) is chosen from g-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetraacetic acid (EDTA), l maleic acid, malonic acid, citric acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, g-ketovaleric acid, dimethylformamide, 1-methyl-2 -pyrrolidinone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, bicine, tricine, 2-furaldehyde (also known as furfural), 5-hydroxymethylfurfural (also known as 5- (hydroxymethyl) -2-furaldehyde or 5-HMF), 2-acetylfuran, 5-methyl-2-furaldehyde, ascorbic acid , ethyl 3-hydroxybutanoate, ethyl 3-
- the catalyst is at least partially sulfurized.
- the invention also relates to processes for preparing the catalyst according to the invention as described in the claims.
- the invention also relates to the use of the catalyst according to the invention in a hydrotreatment and / or hydrocracking process of hydrocarbon fractions.
- group VIII according to the CAS classification corresponds to the metals in columns 8, 9 and 10 according to the new IUPAC classification.
- hydrotreatment means reactions including in particular hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and the hydrogenation of aromatics (HDA).
- HDS hydrodesulfurization
- HDN hydrodenitrogenation
- HDA hydrogenation of aromatics
- the invention relates to a catalyst comprising a support based on alumina or silica or silica-alumina, at least one element of group VIII, at least one element of group VIB and at least one organic compound of formula (I) such as described below.
- the catalyst according to the invention can be a fresh catalyst, that is to say a catalyst which has not been used as a catalyst before in a catalytic unit and in particular in hydrotreating and / or hydrocracking.
- the catalyst according to the invention can also be a rejuvenated catalyst.
- a rejuvenated catalyst is meant a catalyst which has been used as a catalyst in a catalytic unit and in particular in hydrotreating and / or hydrocracking and which has been subjected to at least one step of partial or total elimination of coke for example by calcination (regeneration). This regenerated catalyst is then added with at least one compound of formula (I) to obtain the rejuvenated catalyst.
- This rejuvenated catalyst can contain one or more other organic additive (s) which can be added before, after or at the same time as the compound of formula (I).
- the hydrogenating function of said catalyst also called active phase, is provided by at least one element from group VIB and by at least one element from group VIII.
- the preferred group VIB elements are molybdenum and tungsten.
- the preferred group VIII elements are non-noble elements and in particular cobalt and nickel.
- the hydrogenating function is chosen from the group formed by the combinations of the elements cobalt-molybdenum, nickel-molybdenum, nickel-tungsten or nickel-cobalt-molybdenum, or nickel-molybdenum-tungsten.
- the hydrogenating function is advantageously ensured by the association of nickel and molybdenum; a combination of nickel and tungsten in the presence of molybdenum may also be advantageous.
- combinations of the cobalt-nickel-molybdenum type can be advantageously used.
- the total content of elements of group VIB and of group VIII is advantageously greater than 6% by weight expressed as oxide relative to the total weight of the catalyst.
- the content of group VIB element is between 5 and 40% by weight, preferably between 8 and 35% by weight, and more preferably between 10 and 30% by weight expressed as metal oxide of group VIB relative to the total weight of the catalyst.
- the content of group VIII element is between 1 and 10% by weight, preferably between 1, 5 and 9% by weight, and more preferably between 2 and 8% by weight expressed as metal oxide of group VIII relative to the weight total catalyst.
- the molar ratio of group VIII element to group VIB element in the catalyst is preferably between 0.1 and 0.8, preferably between 0.15 and 0.6 and even more preferably between 0.2 and 0.5.
- the catalyst according to the invention advantageously also comprises phosphorus as a dopant.
- the dopant is an added element which in itself has no catalytic character but which increases the catalytic activity of the active phase.
- the phosphorus content in said catalyst is preferably between 0.1 and 20% by weight expressed in P 2 0 5 relative to the total weight of the catalyst, preferably between 0.2 and 15% by weight expressed in P 2 0 5 , and very preferably between 0.3 and 1 1% by weight expressed as P 2 0 5 .
- the phosphorus molar ratio on the element of group VIB in the catalyst is greater than or equal to 0.05, preferably greater than or equal to 0.07, preferably between 0.08 and 1, preferably between 0.1 and 0.9 and very preferably between 0.15 and 0.8.
- the catalyst according to the invention can advantageously also contain at least one dopant chosen from boron, fluorine and a mixture of boron and fluorine.
- the content of boron or fluorine or a mixture of the two is preferably between 0.1 and 10% by weight expressed as boron oxide and / or in fluorine relative to the total weight of the catalyst, preferably between 0.2 and 7% by weight, and very preferably between 0.2 and 5% by weight.
- the catalyst according to the invention comprises a support based on alumina or silica or silica-alumina.
- the support for said catalyst is based on alumina, it contains more than 50% by weight of alumina relative to the total weight of the support and, in general, it contains only alumina or silica-alumina such as defined below.
- the support comprises alumina, and preferably extruded alumina.
- the alumina is gamma alumina.
- the alumina support advantageously has a total pore volume of between 0.1 and 1.5 cm 3 .g 1 , preferably between 0.4 and 1.1 cm 3 . g 1 .
- the total pore volume is measured by mercury porosimetry according to standard ASTM D4284 with a wetting angle of 140 °, as described in the work Rouquerol F.; Rouquerol J.; Singh K. "Adsorption by Powders & Porous Solids: Principle, methodology and applications", Academy Press, 1999, for example using an Autopore III TM model device from the Micromeritics TM brand.
- the specific surface of the alumina support is advantageously between 5 and 400 m 2 .g 1 , preferably between 10 and 350 m 2 .g 1 , more preferably between 40 and 350 m 2 .g 1 .
- the specific surface is determined in the present invention by the BET method according to standard ASTM D3663, method described in the same work cited above.
- the support for said catalyst is a silica-alumina containing at least 50% by weight of alumina relative to the total weight of the support.
- the silica content in the support is at most 50% by weight relative to the total weight of the support, most often less than or equal to 45% by weight, preferably less than or equal to 40%.
- Sources of silicon are well known to those skilled in the art.
- silica When the support of said catalyst is based on silica, it contains more than 50% by weight of silica relative to the total weight of the support and, in general, it contains only silica.
- the support consists of alumina, silica or silica-alumina.
- the support can also advantageously also contain from 0.1 to 50% by weight of zeolite relative to the total weight of the support.
- zeolite is chosen from the group FAU, BEA, ISV, IWR, IWW, MEI, UWY and, preferably, the zeolite is chosen from the group FAU and BEA, such as the zeolite Y and / or beta, and particularly preferably such as the USY and / or beta zeolite.
- the support can also contain at least part of metal (metals) VIB and VIII, and / or at least part of dopant (s) including phosphorus and / or at least part of (s) organic compound (s) containing oxygen (the compound of formula (I) or other) and / or nitrogen and / or sulfur which have been introduced outside of the impregnations (introduced for example during support preparation).
- metal metal
- VIB and VIII metal
- dopant including phosphorus and / or at least part of (s) organic compound (s) containing oxygen (the compound of formula (I) or other) and / or nitrogen and / or sulfur which have been introduced outside of the impregnations (introduced for example during support preparation).
- the support is advantageously in the form of balls, extrudates, pellets or irregular and non-spherical agglomerates whose specific shape can result from a crushing step.
- the catalyst according to the invention also comprises at least one compound of formula (I)
- Ri is a hydrocarbon radical comprising from 1 to 12 carbon atoms, saturated or not, linear, branched or cyclic
- R 2 and R 3 are chosen from a hydrogen atom and a hydrocarbon radical comprising from 1 to 12 carbon atoms, saturated or not, linear, branched or cyclic
- X is chosen from an oxygen atom or a sulfur atom, except when R 2 and R 3 represent a hydrogen atom, X is then an oxygen atom
- Y is chosen from a hydrogen atom, a hydrocarbon radical comprising from 1 to 12 carbon atoms, saturated or not, linear, branched or cyclic or a -C (0) R 4 unit , R 4 being chosen from an atom of hydrogen and a hydrocarbon radical comprising from 1 to 12 carbon atoms, saturated or not, linear, branched or cyclic.
- Ri is a hydrocarbon radical comprising from 1 to 4 carbon atoms, saturated or not, linear, branched or cyclic.
- R 2 and R 3 are chosen from a hydrogen atom and a hydrocarbon radical comprising from 1 to 4 carbon atoms, saturated or not, linear, branched or cyclic.
- Y is chosen from a hydrogen atom, a hydrocarbon radical comprising from 1 to 4 carbon atoms, saturated or not, linear, branched or cyclic or a unit -C (O) R 4 , R 4 being chosen from a hydrogen atom and a hydrocarbon radical comprising from 1 to 4 carbon atoms, saturated or not, linear, branched or cyclic.
- the compound of formula (I) is chosen from methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, isopentyl lactate, lactate of cis-3-hexenyl, L-menthyl lactate, butyl butyryllactate, ethyl 2-mercaptopropanoate, methyl glycolate, ethyl glycolate, butyl glycolate, ethyl ethoxyacetate, ethyl ⁇ -hydroxyisobutanoate, tert-butyl ⁇ -hydroxyisobutanoate, ethyl 2-hydroxycaproate and ethyl 2-hydroxyvalerate.
- R 2 represents a methyl radical and R 3 represents a hydrogen atom.
- the compound of formula (I) is chosen from butyl lactate and butyl butyryllactate which correspond respectively to the following formulas (a) and (b):
- the presence of at least one compound of formula (I) on the catalyst makes it possible to observe an increased activity compared to the non-additive catalysts and to the known dry additive catalysts.
- the catalyst can comprise one or more compounds of formula (I), in particular two compounds of formula (I).
- the content of compound (s) of formula (I) on the catalyst according to the invention is between 1 and 45% by weight, preferably between 2 and 30% by weight, and more preferably between 3 and 25% by weight relative to the total weight of the catalyst.
- the drying step or steps following the introduction of the compound of formula (I) is (are) carried out at a temperature below 200 ° C. so as to preserve preferably at least 30%, preferably at least 50%, and very preferably at least 70% of the amount of the compound of formula (I) introduced calculated on the basis of the carbon remaining on the catalyst.
- the compound of formula (I) can be obtained from the traditional chemical industry with generally high purities.
- the catalyst according to the invention can comprise, in addition to the compound of formula (I), another organic compound or a group of organic compounds known for their role as additives.
- the function of additives is to increase the catalytic activity compared to non-additive catalysts.
- the catalyst according to the invention can also comprise one or more organic compounds containing oxygen other than the compound of formula (I) and / or one or more organic compounds containing nitrogen and / or one or more organic compounds containing sulfur.
- the catalyst according to the invention can also comprise one or more organic compounds containing oxygen other than the compound of formula (I) and / or one or more organic compounds containing nitrogen.
- the organic compound contains at least 2 carbon atoms and at least one oxygen and / or nitrogen atom.
- the organic compound is chosen from a compound comprising one or more chemical functions chosen from a carboxylic function, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea and amide or the compounds including a furan cycle or sugars.
- the organic compound containing oxygen can be one or more chosen from compounds comprising one or more chemical functions chosen from a carboxylic, alcohol, ether, aldehyde, ketone, ester or carbonate function or alternatively compounds including a furanic cycle or sugars.
- the organic compound containing oxygen can be one or more chosen from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, a polyethylene glycol (with a molecular weight of between 200 and 1500 g / mol), propylene glycol, 2-butoxyethanol, 2- (2-butoxyethoxy) ethanol, 2- (2-methoxyethoxy) ethanol, triethylene glycoldimethyl ether, glycerol, acetophenone, 2,4-pentanedione, pentanone, acetic acid, maleic acid, malic acid, malonic acid, oxalic acid, gluconic acid, tartaric acid, citric acid, g-ketovaleric acid, a succinate of C1-C4 dialkyl and more particularly dimethyl succinate, methyl acetoacetate, ethyl acetoacetate, 2-methoxyethyl 3-oxobutanoate, 2-methacryloyloxyethyl
- the organic nitrogen-containing compound may be one or more chosen from compounds comprising one or more chemical functions chosen from an amine or nitrile function.
- the organic compound containing nitrogen can be one or more chosen from the group consisting of ethylenediamine, diethylenetriamine, hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylene hexane, acetonitrile , octylamine, guanidine or a carbazole.
- the organic compound containing oxygen and nitrogen may be one or more chosen from compounds comprising one or more chemical functions chosen from a carboxylic acid, alcohol, ether, aldehyde, ketone, ester, carbonate, amine function , nitrile, imide, amide, urea or oxime.
- the organic compound containing oxygen and nitrogen may be one or more chosen from the group consisting of 1,2-cyclohexanediaminetetraacetic acid, monoethanolamine (MEA), 1 - methyl-2-pyrrolidinone, dimethylformamide, ethylenediaminetetraacetic acid (EDTA), alanine, glycine, nitrilotriacetic acid (NTA), N- (2-hydroxyethyl) ethylenediamine-N, N ', N '-triacetic (HEDTA), diethylene triaminepentaacetic acid (DTPA), tetramethylurea, glutamic acid, dimethylglyoxime, bicine, tricine, 2-methoxyethyl cyanoacetate, 1-ethyl-2-pyrrolidinone, 1-vinyl-2-pyrrolidinone, 1, 3-dimethyl-2-imidazolidinone, 1 - (2-hydroxyethyl) -2-pyrrolidinone, 1
- the organic sulfur-containing compound may be one or more chosen from compounds comprising one or more chemical functions chosen from a thiol, thioether, sulfone or sulfoxide function.
- the organic sulfur-containing compound may be one or more chosen from the group consisting of thioglycolic acid, 2,2'-thiodiethanol, 2-hydroxy-4-methylthiobutanoic acid, a sulfonated derivative of a benzothiophene or a sulfoxidated derivative of a benzothiophene, methyl 3- (methylthio) propanoate and ethyl 3- (methylthio) propanoate.
- the organic compound contains oxygen, preferably it is chosen from g-valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediaminetetra-acetic acid (EDTA), l maleic acid, malonic acid, citric acid, gluconic acid, glucose, fructose, sucrose, sorbitol, xylitol, g-ketovaleric acid, dimethylformamide, 1-methyl-2 -pyrrolidinone, propylene carbonate, 2-methoxyethyl 3-oxobutanoate, bicine, tricine, 2-furaldehyde (also known as furfural), 5-hydroxymethylfurfural (also known as 5- (hydroxymethyl ) -2-furaldehyde or 5-HMF), 2-acetylfuran, 5-methyl-2-furaldehyde, ascorbic acid, ethyl 3-hydroxybutanoate, ethyl 3-ethoxy
- the content of organic compound (s) with additive function (s) containing oxygen (other than the compound of formula (I)) and / or nitrogen and / or sulfur on the catalyst according to the invention is between 1 and 30% by weight, preferably between 1, 5 and 25% by weight, and more preferably between 2 and 20% by weight relative to the total weight of the catalyst.
- the catalyst according to the invention can be prepared according to any method of preparation of a supported catalyst additive with an organic compound known to those skilled in the art.
- the catalyst according to the invention can be prepared by implementing a step of impregnating said compound of formula (I), advantageously using a solution containing a solvent in which the compound of formula (I).
- the process for the preparation of said catalyst implements a step of adding said compound of formula (I) by the liquid phase. After impregnation, a drying step is then necessary to remove the solvent and / or the excess of the compound of formula (I) and thus release the porosity necessary for the use of the catalyst.
- the catalyst according to the invention can be prepared by implementing a step of adding said compound of formula (I) by the gas phase.
- the catalyst according to the invention can be prepared according to a preparation process comprising the following steps:
- step b) said catalyst precursor from step a) is dried at a temperature below 200 ° C., without calcining it subsequently.
- the method for preparing a fresh catalyst will first be described, then the method for preparing a rejuvenated catalyst subsequently.
- Step a) of contacting comprises several modes of implementation which are distinguished in particular by the time of introduction of the compound of formula (I) which can be carried out either at the same time as the impregnation of metals (co impregnation), either after the impregnation of metals (post-impregnation), or finally before the impregnation of metals (pre-impregnation).
- the contacting step can combine at least two modes of implementation, for example co-impregnation and post-impregnation. These different modes of implementation will be described later. Each mode, taken alone or in combination, can take place in one or more stages.
- the catalyst according to the invention during its preparation process does not undergo calcination after the introduction of the compound of formula (I) or any other organic compound containing oxygen and / or l nitrogen and / or sulfur in order to preserve at least in part the compound of formula (I) or any other organic compound in the catalyst.
- calcination is meant here a heat treatment under a gas containing air or oxygen at a temperature greater than or equal to 200 ° C.
- the catalyst precursor can undergo a calcination step before the introduction of the compound of formula (I) or of any other organic compound containing oxygen and / or nitrogen and / or sulfur, in particular after l 'impregnation of elements of group VIB and VIII (post-impregnation) possibly in the presence of phosphorus and / or another dopant or during the regeneration of a catalyst already used.
- the hydrogenating function comprising the elements of group VIB and group VIII of the catalyst according to the invention, also called active phase, is then found in an oxide form.
- the catalyst precursor does not undergo a calcination step after the impregnation of the elements of group VIB and VIII (post- impregnation), it is simply dried.
- the hydrogenating function comprising the elements of group VIB and group VIII of the catalyst according to the invention, also called active phase, is therefore not in an oxide form.
- step a) of contacting generally comprises at least one impregnation step, preferably a dry impregnation step, in which the support is impregnated with a solution of impregnation comprising at least one element from group VIB, at least one element from group VIII, and optionally phosphorus.
- this impregnation solution also comprises at least one compound of formula (I).
- the elements of group VIB and of group VIII are generally introduced by impregnation, preferably by dry impregnation or by impregnation in excess of solution.
- all the elements of group VIB and of group VIII are introduced by impregnation, preferably by dry impregnation and this whatever the mode of implementation.
- the elements of group VIB and of group VIII can also be introduced in part during the shaping of said support at the time of mixing with at least one alumina gel chosen as matrix, the rest of the hydrogenating elements then being introduced subsequently by impregnation .
- the proportion of element of group VIB introduced during this stage is less than 5% by weight of the total amount of element of group VIB introduced on the final catalyst.
- the element of group VIB is introduced at the same time as the element of group VIII, whatever the mode of introduction.
- the molybdenum precursors which can be used are well known to those skilled in the art.
- the sources of molybdenum it is possible to use oxides and hydroxides, molybdic acids and their salts, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, phosphomolybdic acid (H 3 PMoi 2 O 40 ) and their salts, and optionally silicomolybdic acid (H 4 SiMoi 2 O 40 ) and its salts.
- the sources of molybdenum can also be heteropoly compounds of the Keggin, Lacunary Keggin, Substituted Keggin, Dawson, Anderson, Strandberg type, for example.
- molybdenum trioxide and heteropolyanions of the Strandberg, Keggin, lacunary Keggin or substituted Keggin type are used.
- the tungsten precursors which can be used are also well known to those skilled in the art.
- oxides and hydroxides tungstic acids and their salts, in particular ammonium salts such as ammonium tungstate, ammonium metatungstate, phosphotungstic acid and their salts, and optionally silicotungstic acid (H 4 SiW 12 O 40 ) and its salts.
- the sources of tungsten can also be heteropoly compounds of the Keggin, Kungin Gap, Substituted Keggin, Dawson type, for example.
- oxides and ammonium salts such as ammonium metatungstate or heteropolyanions of Keggin, Keggin lacunar or substituted Keggin type.
- the precursors of group VIII elements which can be used are advantageously chosen from the oxides, hydroxides, hydroxycarbonates, carbonates and nitrates of group VIII elements, for example, nickel hydroxycarbonate, carbonate or hydroxide cobalt are preferably used.
- Phosphorus when present, can be introduced in whole or in part by impregnation. Preferably, it is introduced by impregnation, preferably dry, using a solution containing the precursors of the elements of group VIB and of group VIII.
- Said phosphorus can advantageously be introduced alone or as a mixture with at least one of the elements of group VIB and of group VIII, and this during any of the steps for impregnating the hydrogenating function if the latter is introduced several times.
- Said phosphorus can also be introduced, in whole or in part, during the impregnation of the compound of formula (I) if it is introduced separately from the hydrogenating function (case of the post- and pre-impregnation described later) and this in the presence or absence of an organic compound other than the compound of formula (I) containing oxygen and / or nitrogen and / or sulfur. It can also be introduced from the synthesis of the support, at any stage of the synthesis thereof. It can thus be introduced before, during or after the kneading of the chosen alumina gel matrix, such as for example and preferably aluminum oxyhydroxide (boehmite) precursor of alumina.
- the chosen alumina gel matrix such as for example and preferably aluminum oxyhydroxide (boe
- the preferred phosphorus precursor is orthophosphoric acid H 3 P0 4 , but its salts and esters such as ammonium phosphates are also suitable.
- the phosphorus can also be introduced at the same time as the element (s) of group VIB in the form of heteropolyanions of Keggin, Keggin lacunar, substituted Keggin or of Strandberg type.
- the compound of formula (I) is advantageously introduced into an impregnation solution which, depending on the method of preparation, can be the same solution or a solution different from that containing the elements of group VIB and VIII, in a corresponding amount:
- a molar ratio of the compound of formula (I) per element (s) of group VIB of the catalyst precursor of between 0.01 to 5 mol / mol, preferably between 0.05 to 3 mol / mol, so preferred between 0.05 and 1.5 mol / mol and very preferably, between 0.1 and 1 mol / mol, calculated on the basis of the components introduced into the impregnation solution (s), and
- a molar ratio of the compound of formula (I) per element (s) of group VIII of the catalyst precursor of between 0.02 to 17 mol / mol, preferably between 0.1 to 10 mol / mol, so preferred between 0.15 and 5 mol / mol and very preferably, between 0.2 and 3.5 mol / mol, calculated on the basis of the components introduced into the impregnation solution (s).
- the different molar ratios apply for each of the compounds of formula (I) present.
- any impregnation solution described in the present invention can comprise any polar solvent known to a person skilled in the art.
- Said polar solvent used is advantageously chosen from the group formed by methanol, ethanol, water, phenol, cyclohexanol, taken alone or as a mixture.
- Said polar solvent can also be advantageously chosen from the group formed by propylene carbonate, DMSO (dimethylsulfoxide), N-methylpyrrolidone (NMP) or sulfolane, taken alone or as a mixture.
- DMSO dimethylsulfoxide
- NMP N-methylpyrrolidone
- sulfolane sulfolane
- the solvent used is water or ethanol, and particularly preferably, the solvent is water.
- the solvent can be absent in the impregnation solution, in particular during a preparation in pre- or post-impregnation.
- the introduction of this (these) dopant (s) can be carried out in the same way as the introduction of the phosphorus described above at various stages of preparation and in various ways.
- the boron precursors can be boric acid, orthoboric acid H 3 B0 3 , ammonium biborate or pentaborate, boron oxide, boric esters.
- Boron can be introduced for example by a solution of boric acid in a water / alcohol mixture or also in a water / ethanolamine mixture.
- the boron precursor, if boron is introduced, is orthoboric acid.
- the fluoride anions can be introduced in the form of hydrofluoric acid or its salts. These salts are formed with alkali metals, ammonium or an organic compound. In the latter case, the salt is advantageously formed in the reaction mixture by reaction between the organic compound and hydrofluoric acid.
- Fluorine can be introduced, for example, by impregnating an aqueous solution of hydrofluoric acid, or ammonium fluoride or alternatively ammonium bifluoride.
- the catalyst also comprises an additional additive (in addition to the compound of formula (I)) or a group of additional additives chosen from an organic compound other than the compound of formula (I) containing oxygen and / or nitrogen and / or sulfur, this can be introduced into the impregnation solution of step a).
- an additional additive in addition to the compound of formula (I)
- the molar ratio of organic compound (s) containing oxygen and / or nitrogen and / or sulfur per element (s) of group VIB on the catalyst is between 0.05 to 5 mol / mol, preferably between 0.1 to 4 mol / mol, preferably between 0.2 and 3 mol / mol, calculated on the basis of the components introduced into the impregnation solution (s).
- the molar ratio of organic compound (s) containing oxygen and / or nitrogen and / or sulfur per compound of formula (I) is between 0.05 and 5 mol / mol, preferably between 0.1 and 4 mol / mol, preferably between 0.2 and 3 mol / mol, calculated on the basis of the components introduced into the impregnation solution (s).
- the impregnated support is left to mature.
- the maturation allows the impregnation solution to disperse homogeneously within the support.
- Any maturation step described in the present invention is advantageously carried out at atmospheric pressure, in an atmosphere saturated with water and at a temperature between 17 ° C and 50 ° C, and preferably at room temperature. Generally a ripening period of between ten minutes and forty-eight hours and preferably between thirty minutes and five hours is sufficient. Longer durations are not excluded, but do not necessarily bring improvement.
- step b) of the preparation process according to the invention the catalyst precursor obtained in step a) optionally matured is subjected to a drying step at a temperature below 200 ° C without subsequent calcination step.
- Any drying step subsequent to the introduction of the compound of formula (I) described in the present invention is carried out at a temperature below 200 ° C, preferably between 50 and 180 ° C, preferably between 70 and 150 ° C and very preferably between 75 and 130 ° C.
- the drying step is advantageously carried out by any technique known to those skilled in the art. It is advantageously carried out at atmospheric pressure or at reduced pressure, and preferably at atmospheric pressure. It is advantageously carried out in a crossed bed using air or any other hot gas.
- the gas used is either air, or an inert gas such as argon or nitrogen.
- the drying is carried out in a crossed bed in the presence of nitrogen and / or air.
- the drying step has a short duration of between 5 minutes and 4 hours, preferably between 30 minutes and 4 hours and very preferably between 1 hour and 3 hours.
- the drying is then carried out so as to preferably retain at least 30% of the compound of formula (I) introduced during an impregnation step, preferably this amount is greater than 50% and even more preferably, greater than 70 %, calculated on the basis of the carbon remaining on the catalyst.
- the drying step is carried out so as to preferably preserve at least 30 %, preferably at least 50%, and very preferably at least 70% of the amount introduced calculated on the basis of the carbon remaining on the catalyst.
- a dried catalyst is obtained, which is not subjected to any subsequent calcination step.
- step a) of the process for preparing the catalyst (fresh) the said compounds are deposited comprising the elements of group VIB, of group VIII, of the compound of formula (I) and optionally phosphorus on said support, by one or more co-impregnation steps, that is to say that said compounds comprising the elements of group VIB, of group VIII, the compound of formula (I) and optionally phosphorus are introduced simultaneously in said support (“co-impregnation”).
- step a) of the process for preparing the catalyst (fresh) according to the invention at least one compound of formula (I) is brought into contact with a dried and optionally calcined impregnated support comprising at least one element from group VIB, at least one element from group VIII and optionally phosphorus, said support being based on alumina or silica or silica-alumina, so as to obtain a catalyst precursor.
- This second embodiment is a preparation by "post-impregnation" of the compound of formula (I).
- the introduction of elements from group VIB and group VIII and optionally phosphorus onto the support can advantageously be carried out by one or more impregnations in excess of solution on the support, or preferably by one or more dry impregnations, and, preferably, by a single dry impregnation of said support, using solution (s), preferably aqueous (s), containing the metal precursor (s) and preferably the phosphorus precursor.
- each impregnation step is preferably followed by an intermediate drying step at a temperature below 200 ° C.
- Each intermediate drying step, prior to the introduction of the compound of formula (I) can be followed by a calcination step.
- the calcination is generally carried out at a temperature between 200 ° C and 900 ° C, preferably between 250 ° C and 750 ° C.
- the calcination time is generally between 0.5 hour and 16 hours, preferably between 1 hour and 5 hours. It is generally carried out in air. Calcination makes it possible to transform the precursors of the metals of group VIB and VIII into oxides.
- the compound of formula (I) can then advantageously be deposited in one or more stages either by excess impregnation, or by dry impregnation, or by any other means known to those skilled in the art.
- the compound of formula (I) is introduced in dry impregnation, in the presence or absence of a solvent as described above.
- the solvent in the impregnation solution is water, which facilitates implementation on an industrial scale.
- the catalyst precursor which has been optionally matured is then subjected to a drying step at a temperature below 200 ° C. without a subsequent calcination step, as described above.
- step a) of the process for the preparation of the catalyst (fresh) according to the invention at least one compound comprising an element from group VIB is brought into contact, at least one compound comprising an element of group VIII, optionally phosphorus with the support based on alumina or silica or silica-alumina which contains at least one compound of formula (I) so as to obtain a catalyst precursor.
- This third mode of implementation is a preparation by "pre-impregnation" of the compound of formula (I).
- the compound of formula (I) can be introduced at any time during the preparation of the support, and preferably during the shaping or by impregnation on an already formed support. If the introduction of the compound of formula (I) is chosen on the support previously formed, then this can be carried out as indicated for the post-impregnation.
- said shaping is carried out by kneading extrusion, by tableting, by the method of drop coagulation (oil-drop according to English terminology), by granulation on the turntable or by any other method well known to those skilled in the art.
- said shaping is carried out by extrusion kneading, the compound of formula (I) can be introduced at any time during extrusion kneading.
- the formed material obtained at the end of the shaping step then advantageously undergoes a heat treatment step at a temperature such that at least part of the compound of formula (I) remains present, preferably at a lower temperature. at 200 ° C.
- the contacting according to step a) combines at least two contacting methods, for example the co-impregnation of the elements of group VIB and of group VIII and optionally phosphorus with a compound organic, followed by drying at a temperature below 200 ° C, then by post-impregnation of an organic compound which may be the same or different from that used for co-impregnation, given that at least one organic compound is a compound of formula (I).
- the catalyst according to the invention can be a rejuvenated catalyst. Its preparation process comprises the following steps: a) contacting a regenerated catalyst containing a support based on alumina or silica or silica-alumina, at least one element from group VIB, at least one element from group VIII and optionally phosphorus, with at least one compound of formula (I) so as to obtain a catalyst precursor, b) said catalyst precursor resulting from stage a) is dried at a temperature below 200 ° C., without the calcine later.
- the regenerated catalyst is a catalyst which has been used as a catalyst in a catalytic unit and in particular in hydrotreating and / or hydrocracking and which has been subjected to at least one step of partial or total elimination of coke for example by calcination (regeneration ).
- Regeneration can be carried out by any means known to those skilled in the art. Regeneration is generally carried out by calcination at temperatures between 350 and 550 ° C, and most often between 400 and 520 ° C, or between 420 and 520 ° C, or even between 450 and 520 ° C, lower temperatures at 500 ° C being often advantageous.
- the regenerated catalyst contains a support based on alumina or silica or silica-alumina, at least one element from group VIB, at least one element from group VIII and optionally phosphorus in the respective proportions indicated above.
- the hydrogenating function comprising the elements of group VIB and group VIII of the regenerated catalyst is in an oxide form. It can also contain dopants other than phosphorus, as described above.
- the contacting of step a) is carried out by impregnation of the regenerated catalyst with an impregnation solution comprising at least one compound of formula (I) so as to obtain a catalyst precursor.
- the compound of formula (I) can advantageously be deposited in one or more stages either by excess impregnation, or by dry impregnation, or by any other means known to a person skilled in the art in the same way as described above and with the molar ratios by element of group VIB or group VIII described above.
- the fresh catalyst according to the invention can be prepared by using a step of adding said compound of formula (I) by the gas phase as described in the French applications filed under national numbers 17 / 53.921 and 17 / 53,922.
- the process for the preparation of said catalyst does not involve a conventional step of impregnating said compound of formula (I). Consequently, it is not necessary to carry out a drying step after introduction of the compound of formula (I).
- the process for preparing the catalyst according to the invention comprises the following steps:
- At least one compound of formula (I) is deposited on a support based on alumina or silica or silica-alumina by implementing a step in which said support and the compound of formula ( I) in the liquid state and without physical contact between the support and the compound of formula (I) in the liquid state, at a temperature below the boiling point of the compound of formula (I) and under conditions of pressure and duration such that a fraction of said compound of formula (I) is transferred in the gaseous state to the support,
- step ii) at least one compound comprising an element from group VIB, at least one compound comprising an element from group VIII, and optionally phosphorus are brought into contact with the support based on alumina or silica or silica-alumina, iii) the solid obtained at the end of step ii) is dried,
- step i) being carried out before or after steps ii) and iii) or during step iii).
- This variant is characterized in that the addition of the compound of formula (I) to the support is carried out without physical contact with the compound of formula (I) in the liquid state, that is to say without impregnation of the liquid support.
- the process is based on the principle of the existence of a vapor pressure of the compound of formula (I) which is generated by its liquid phase at a given temperature and pressure.
- a part of the molecules of compound of formula (I) in the liquid state passes to the gaseous state (vaporization) and is then transferred (by gaseous route) to the support.
- This step i) of bringing together is carried out for a sufficient time to reach the targeted content of compound of formula (I) in the support.
- step i) is carried out at an absolute pressure of between 0 and 1 MPa.
- the processing temperature of step i) is less than 200 ° C, preferably between 10 ° C and 150 ° C, more preferably between 25 ° C and 120 ° C.
- the process for preparing the catalyst according to the invention comprises the following steps:
- At least one compound of formula (I) is deposited on a support based on alumina or on silica or on silica-alumina by implementing a step in which is placed in a closed or open enclosure, the support with a porous solid containing at least one compound of formula (I), this step being carried out under temperature, pressure and duration conditions such that a fraction of said compound of formula (I) is transferred by gas from the solid porous to the support,
- At least one compound comprising an element from group VIB, at least one compound comprising an element from group VIII, and optionally phosphorus are brought into contact with the support based on alumina or silica or silica-alumina,
- step iii) the solid obtained at the end of step ii) is dried
- step i ') being carried out separately before or after steps ii) and iii).
- the addition of the compound of formula (I) consists in bringing into contact, in an open or closed enclosure, a first batch of porous solids rich in a compound of formula (I) which has been previously deposited on said solid in the liquid state, with a support (second batch of porous solid poor in said compound of formula (I)).
- the objective of this bringing together of porous solids is to allow a gaseous transfer of a part of the compound of formula (I) contained in the first batch of porous solids in the second batch of porous solids.
- the term "poor in compound of formula (I)" covers in particular the case where the second batch of porous solids is free of said compound of formula (I).
- This second variant is also based on the principle of the existence of a vapor pressure of the compound of formula (I) at a given temperature and pressure.
- part of the molecules of compound of formula (I) of the batch of porous solids rich in compound of formula (I) passes in gaseous form (vaporization) and is then transferred (by gaseous route) to the support (solid poor in compound of formula (I)).
- the porous solid rich in compound of formula (I) plays the role of source in compound of formula (I) to enrich in compound of formula (I) the support (porous solid poor in compound of formula (I) ).
- the porous solid rich in compound of formula (I) is advantageously a porous support, preferably a support based on alumina or silica or silica-alumina which can contain at least one element of group VIB, at least one element of group VIII, and possibly phosphorus.
- the mass ratio (first batch of solids rich in compound of formula (I)) / (support or second batch of solids poor in compound of formula (I)) depends on the porous distribution of the solids and the objective in terms of target quantity of compound of formula (I) on the solids from step i ') of bringing together.
- This mass ratio is generally less than or equal to 10, preferably less than 2 and even more preferably between 0.05 and 1, limits included.
- the step of bringing lots of porous solids together is preferably carried out under controlled temperature and pressure conditions and so that the temperature is lower than the boiling temperature of said compound of formula (I) to be transferred by way of gas.
- the processing temperature is less than 150 ° C and the absolute pressure is generally between 0 and 1 MPa, preferably between 0 and 0.5 MPa and more preferably between 0 and 0.2 MPa. It will thus be possible to operate the step of bringing into presence in an open or closed enclosure, with possibly a control of the composition of the gas present in the enclosure.
- the step of bringing porous solids together takes place in an open enclosure, it will be ensured that the entrainment of the compound of formula (I) outside the enclosure is limited as much as possible.
- the step of bringing porous solids into contact can be carried out in a closed enclosure, for example in a container for storing or transporting the solid which is impermeable to gas exchange with the external environment.
- the term "rich in compound of formula (I)” translates the fact that the solid contains more than 50% of the total amount of said compound of formula (I) used in step i '), preferably at least 60 %, preferably at least 80%, preferably at least 90% and preferably 100%.
- the porous solid rich in compound of formula (I) contains 100% of the total amount involved in step i') and the support (second batch of solids poor in compound of formula (I)) therefore contains 0% of the total amount of said compound of formula (I).
- the two variants of catalyst preparation (fresh) by gas phase can be carried out according to two embodiments.
- the active phase is first introduced comprising at least one compound comprising an element from group VIB, at least one compound comprising an element from group VIII and optionally phosphorus on a porous support (step ii), then dried (step iii), then the dried support containing the active metallic phase and optionally phosphorus is treated according to step i) or i ') of bringing into contact with at least one compound of formula (I) in the liquid state or a porous solid containing at least one compound of formula (I) so as to provide a catalyst additive to said compound of formula (I).
- step i) is carried out at the same time as step iii).
- the support is first subjected to a step of adding the compound of formula (I) so as to provide a catalyst support additivated with the organic compound (step i) or i ')), which after an optional maturation phase, is sent to the impregnation step of the active phase (step ii) and then to drying (step iii).
- the porous support may in particular already contain an additional organic compound different from the compound of formula (I).
- this additional organic compound can be introduced with the solution containing the active phase of the metals and optionally the phosphorus.
- the step of adding said compound of formula (I) by the gas phase can also be carried out on a regenerated catalyst.
- the process for preparing the catalyst according to the invention comprises the following steps:
- At least one compound of formula (I) is deposited on a regenerated catalyst containing a support based on alumina or silica or silica-alumina, at least one element of group VIB, at least one element of group VIII and optionally phosphorus, by implementing a step in which said regenerated catalyst and at least one compound of formula (I) are brought into contact simultaneously in the liquid state and without physical contact between the regenerated catalyst and the compound of formula ( I) in the liquid state, at a temperature below the boiling point of the compound of formula (I) and under pressure and duration conditions such that a fraction of said compound of formula (I) is transferred to l 'gaseous state with regenerated catalyst, or
- At least one compound of formula (I) is deposited on a regenerated catalyst containing a support based on alumina or silica or silica-alumina, at least one element of group VIB, at least one element of group VIII and optionally phosphorus, by implementing a step in which the regenerated catalyst is brought into contact, in a closed or open enclosure, with a porous solid containing at least one compound of formula (I), this step being carried out under conditions of temperature, pressure and duration such that a fraction of said compound of formula (I) is transferred by gas from the porous solid to the regenerated catalyst.
- the fresh or rejuvenated additive catalyst obtained by the introduction of the compound of formula (I) by gas phase as described above can also be treated by one or more subsequent stages in order to incorporate one or more other additional organic compounds different from the one used in step i) i '), i ”) or i” ”).
- the incorporation of one or more other different additional organic compounds can be carried out by means of the gas phase addition processes or by any other method known to those skilled in the art, for example by impregnating a solution containing the compound. additional organic.
- step b) At the end of step b) according to the different methods of preparing the process according to the invention, said catalyst obtained is therefore advantageously subjected to a sulphurization step, without an intermediate calcination step.
- Said dried catalyst is advantageously sulfurized ex situ or in situ.
- Sulfurizing agents are H 2 S gas, elemental sulfur, CS 2 , mercaptans, sulfides and / or polysulfides, hydrocarbon fractions with a boiling point below 400 ° C containing sulfur compounds or any other compound containing sulfur used for the activation of hydrocarbon charges in order to sulfurize the catalyst.
- Said sulfur-containing compounds are advantageously chosen from alkyl disulfides such as for example dimethyl disulfide (DMDS), alkyl sulfides, such as for example dimethyl sulfide, thiols such as for example n- butylmercaptan (or 1 -butanethiol) and tertiononylpolysulfide-type polysulfide compounds.
- the catalyst can also be sulfurized by the sulfur contained in the feed to be desulphurized.
- the catalyst is sulfurized in situ in the presence of a sulfurizing agent and a hydrocarbon feed.
- the catalyst is sulfurized in situ in the presence of a hydrocarbon feed additive with dimethyl disulfide.
- Another subject of the invention is the use of the catalyst according to the invention or prepared according to the preparation process according to the invention in hydrotreatment and / or hydrocracking processes of hydrocarbon fractions.
- the catalyst according to the invention and having preferably previously undergone a sulfurization step is advantageously used for hydrotreatment and / or hydrocracking reactions of hydrocarbon feedstocks such as petroleum cuts, cuts derived from coal or hydrocarbons produced at from natural gas, optionally in mixtures or from a hydrocarbon fraction obtained from biomass and more particularly for the hydrogenation, hydrodenitrogenation, hydrodesaromatization, hydrodesulfurization, hydrodeoxygenation, hydrodemetallization reactions or hydroconversion of hydrocarbon feedstocks.
- hydrocarbon feedstocks such as petroleum cuts, cuts derived from coal or hydrocarbons produced at from natural gas, optionally in mixtures or from a hydrocarbon fraction obtained from biomass and more particularly for the hydrogenation, hydrodenitrogenation, hydrodesaromatization, hydrodesulfurization, hydrodeoxygenation, hydrodemetallization reactions or hydroconversion of hydrocarbon feedstocks.
- the catalyst according to the invention and having preferably previously undergone a sulfurization step has an improved activity compared to the catalysts of the prior art.
- This catalyst can also advantageously be used during the pretreatment of catalytic cracking or hydrocracking charges, or the hydrodesulfurization of residues or the advanced hydrodesulfurization of gas oils (ULSD Ultra Low Sulfur Diesel according to English terminology).
- the fillers used in the hydrotreating process are for example gasolines, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuels, oils, waxes and paraffins, used oils, deasphalted residues or crudes, fillers from thermal or catalytic conversion processes, lignocellulosic fillers or more generally fillers from biomass, taken alone or as a mixture.
- the charges which are treated, and in particular those mentioned above, generally contain heteroatoms such as sulfur, oxygen and nitrogen and, for heavy charges, they most often also contain metals.
- the operating conditions used in the processes implementing the hydrotreatment reactions of hydrocarbon feedstocks described above are generally the following: the temperature is advantageously between 180 and 450 ° C, and preferably between 250 and 440 ° C, the pressure is advantageously between 0.5 and 30 MPa, and preferably between 1 and 18 MPa, the hourly space velocity is advantageously between 0.1 and 20 h 1 and preferably between 0.2 and 5 h 1 , and the hydrogen / charge ratio expressed in volume of hydrogen, measured under normal temperature and pressure conditions, per volume of liquid charge is advantageously between 50 l / l to 5000 l / l and preferably 80 to 2000 l / l.
- said hydrotreatment process according to the invention is a hydrotreatment process, and in particular hydrodesulfurization (HDS) of a diesel cut carried out in the presence of at least one catalyst according to the invention .
- Said hydrotreatment process according to the invention aims to eliminate the sulfur compounds present in said diesel cut so as to achieve the environmental standards in force, namely an authorized sulfur content up to 10 ppm. It also makes it possible to reduce the aromatic and nitrogen contents of the diesel cut to be hydrotreated.
- Said diesel cut to be hydrotreated according to the process of the invention contains from 0.02 to 5.0% by weight of sulfur. It is advantageously obtained from direct distillation (or straight run diesel according to Anglo-Saxon terminology), a coking unit (coking according to Anglo-Saxon terminology), a visbreaking unit (visbreaking according to Anglo-Saxon terminology), a steam cracking unit ( steam cracking according to Anglo-Saxon terminology), a hydrotreating and / or hydrocracking unit for heavier charges and / or a catalytic cracking unit (Fluid Catalytic Cracking according to Anglo-Saxon terminology).
- Said gas oil cut preferably has at least 90% of the compounds whose boiling temperature is between 250 ° C and 400 ° C at atmospheric pressure.
- the hydrotreatment process of said diesel cut according to the invention is carried out under the following operating conditions: a temperature between 200 and 400 ° C, preferably between 300 and 380 ° C, a total pressure between 2 MPa and 10 MPa and more preferably between 3 MPa and 8 MPa with a volume ratio of hydrogen per volume of hydrocarbon feedstock, expressed in volume of hydrogen, measured under normal conditions of temperature and pressure, per volume of liquid feedstock, between 100 and 600 liters per liter and more preferably between 200 and 400 liters per liter and an hourly volume speed (WH) of between 1 and 10 h 1 , preferably between 2 and 8 h 1 .
- WH hourly volume speed
- the WH corresponds to the inverse of the contact time expressed in hours and is defined by the ratio of the volume flow rate of liquid hydrocarbon feedstock to the volume of catalyst loaded into the reaction unit implementing the hydrotreatment process according to the invention .
- the reaction unit implementing the hydrotreatment process of said diesel cut according to the invention is preferably operated in a fixed bed, in a moving bed or in a bubbling bed, preferably in a fixed bed.
- said hydrotreatment and / or hydrocracking process according to the invention is a hydrotreatment process (in particular hydrodesulfurization, hydrodeazoation, hydrogenation of aromatics) and / or hydrocracking of a cut of vacuum distillate produced in the presence of at least one catalyst according to the invention.
- Said hydrotreating and / or hydrocracking process, otherwise called hydrocracking pretreatment process or hydrocracking according to the invention aims, depending on the case, to remove the sulfur, nitrogen or aromatic compounds present in said distillate cut so as to carry out a pretreatment before conversion in catalytic cracking or hydroconversion processes, or to hydrocrack the distillate cut which may have been pretreated before if necessary.
- fillers can be treated by the hydrotreatment and / or hydrocracking processes of vacuum distillates described above. Generally they contain at least 20% volume and often at least 80% volume of compounds boiling above 340 ° C at atmospheric pressure.
- the feed can be, for example, vacuum distillates as well as feeds from aromatic extraction units from the lubricating oil bases or from solvent dewaxing of the lubricating oil bases, and / or deasphalted oils , or the filler can be a deasphalted oil or paraffins from the Fischer-Tropsch process or any mixture of the aforementioned fillers.
- the charges have a boiling point T5 greater than 340 ° C at atmospheric pressure, and better still greater than 370 ° C at atmospheric pressure, that is to say that 95% of the compounds present in the charge have a point boiling above 340 ° C, and better still above 370 ° C.
- the nitrogen content of the feeds treated in the processes according to the invention is usually greater than 200 ppm by weight, preferably between 500 and 10 000 ppm by weight.
- the sulfur content of the feeds treated in the processes according to the invention is usually between 0.01 and 5.0% by weight.
- the feed can optionally contain metals (for example nickel and vanadium).
- the asphaltenes content is generally less than 3000 ppm by weight.
- the hydrotreating and / or hydrocracking catalyst is generally brought into contact, in the presence of hydrogen, with the feeds described above, at a temperature above 200 ° C., often between 250 ° C. and 480 ° C., advantageously. between 320 ° C and 450 ° C, preferably between 330 ° C and 435 ° C, under a pressure greater than 1 MPa, often between 2 and 25 MPa, preferably between 3 and 20 MPa, the volume speed being between 0.1 and 20.0 h 1 and preferably 0.1 -6.0 h 1 , preferably 0, 2-3.0 h 1 , and the quantity of hydrogen introduced is such that the volume ratio of liter of hydrogen / liter of hydrocarbon, expressed in volume of hydrogen, measured under normal conditions of temperature and pressure, per volume of liquid charge, is between 80 and 5000 l / l and most often between 100 and 2000 l / l.
- the hydrotreatment and / or hydrocracking processes of vacuum distillates using the catalysts according to the invention cover 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 40%, and operating at low pressure, generally between 2 MPa and 6 MPa.
- the catalyst according to the 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 one step, with or without liquid recycling of the unconverted fraction, or also in a hydrocracking scheme known as two stages, optionally in combination with a hydrorefining catalyst located upstream of the catalyst of the present invention.
- said hydrotreatment and / or hydrocracking process according to the invention is advantageously used as pretreatment in a catalytic cracking process in a fluidized bed (or FCC process for Fluid Catalytic Cracking according to the terminology Anglo-Saxon).
- the operating conditions of the pretreatment in terms of temperature range, pressure, hydrogen recycling rate, hourly volume speed are generally identical to those described above for the hydrotreatment and / or hydrocracking processes of vacuum distillates.
- the FCC process can be carried out in a conventional manner known to those skilled in the art under the appropriate cracking conditions in view to produce lower molecular weight hydrocarbon products.
- a summary description of catalytic cracking can be found in ULLMANS ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY VOLUME A 18, 1991, pages 61 to 64.
- said hydrotreatment and / or hydrocracking process according to the invention is a hydrotreatment process (in particular hydrodesulfurization) of a gasoline fraction in the presence of at least one catalyst according to the invention. 'invention.
- the hydrotreatment (in particular hydrodesulfurization) of gasolines must make it possible to respond to a double antagonistic constraint: ensuring deep hydrodesulfurization of gasolines and limiting the hydrogenation of the unsaturated compounds present in order to limit loss of octane number.
- the feed is generally a cut of hydrocarbons having a distillation range between 30 and 260 ° C.
- this cut of hydrocarbons is a cut of the gasoline type.
- the gasoline cut is an olefinic gasoline cut, for example from a catalytic cracking unit (Fluid Catalytic Cracking according to English terminology).
- the hydrotreatment process consists in bringing the fraction of hydrocarbons into contact with the catalyst according to the invention and hydrogen under the following conditions: at a temperature between 200 and 400 ° C, preferably between 230 and 330 ° C, at a total pressure between 1 and 3 MPa, preferably between 1, 5 and 2.5 MPa, at an Hourly Volume Velocity (WH), defined as being the volume flow rate of feed relative to the volume of catalyst, between 1 and 10 h 1 , preferably between 2 and 6 h 1 and at a hydrogen / gasoline volume ratio between 100 and 600 N l / l, preferably between 200 and 400 N l / l.
- WH Hourly Volume Velocity
- the gasoline hydrotreatment process can be carried out in one or more reactors in series of the fixed bed type or of the bubbling bed type. If the process is implemented works by means of at least two reactors in series, it is possible to provide a device for removing H 2 S from the effluent from the first hydrodesulfurization reactor before treating said effluent in the second reactor hydrodesulfurization.
- Example 1 Preparation of CoMoP catalysts on alumina without organic compound C1 and C2 (not in accordance with the invention).
- alumina support having a BET surface area of 230 m 2 / g, a pore volume measured by mercury porosimetry of 0.78 ml / g and an average pore diameter of 11.5 nm defined as the median diameter in volume by mercury porosimetry and which is in the “extruded” form, cobalt, molybdenum and phosphorus are added.
- the impregnation solution is prepared by dissolving molybdenum oxide (21.1 g) and cobalt hydroxide (5.04 g) in 11.8 g of an aqueous solution at 90 ° C. 85% by weight phosphoric acid.
- the extrudates are left to mature in a water saturated atmosphere for 24 h at room temperature, then they are dried at 90 ° C for 16 hours.
- the dried catalyst precursor thus obtained is denoted C1.
- the calcination of the catalyst precursor C1 at 450 ° C for 2 hours leads to the calcined catalyst C2.
- Example 2 Preparation of the CoMoP catalyst on C3 alumina (not in accordance with the invention) by introduction of an organic compound (citric acid) by co-
- Cobalt, molybdenum and phosphorus are added to the alumina support described above in example 1 and which is in the "extruded" form.
- the impregnation solution is prepared by dissolving molybdenum oxide (28.28 g) and cobalt hydroxide (6.57 g) in 15.85 g of an aqueous acid solution at 90 ° C. 85% phosphoric and water. After homogenization of the above mixture, 38 g of citric acid were added before adjusting the volume of solution to the pore volume of the support by adding water.
- the molar ratio (citric acid) / Mo is equal to 1 mol / mol and that (citric acid) / Co is equal to 2.7 mol / mol.
- the extrudates After dry impregnation, the extrudates are left to mature in a water saturated atmosphere for 24 h at room temperature, then they are dried at 120 ° C for 16 hours.
- the dried catalyst with citric acid additive thus obtained is denoted C3.
- Example 3 Preparation of the CoMoP catalyst on C4 alumina (according to the invention) by introduction of an organic compound (butveal lactate) in the vapor phase after the impregnation of the metals.
- organic compound butveal lactate
- Example 4 Preparation of the CoMoP catalyst on C5 alumina (according to the invention) by introduction of an organic compound (butyl butyryllactate) in the vapor phase after the impregnation of the metals.
- organic compound butyl butyryllactate
- the amount of butyl butyryllactate thus transferred to the catalyst is such that the butyl butyryllactate / Mo molar ratio is 0.8 moles per mole of molybdenum (corresponding to 2.2 moles per mole of cobalt).
- the catalyst precursors are previously sulfurized in situ at 350 ° C. in the reactor under pressure using diesel fuel from the test to which 2% by weight of dimethyldisulphide is added.
- the hydrodesulfurization tests were carried out under the following operating conditions: a total pressure of 7 MPa, a volume of catalyst of 30 cm 3 , a temperature of 330 to 360 ° C, with a hydrogen flow rate of 24 l / h and with a charge rate of 60 cm 3 / h.
- the catalytic performances of the catalysts tested are given in Table 1. They are expressed in degrees Celsius relative to the catalyst C2 (comparative) chosen as reference: they correspond to the temperature difference to be applied to reach 50 ppm of sulfur in the effluent. A negative value means that the sulfur content target is reached for a lower temperature and that there is therefore a gain in activity. A positive value means that the sulfur content target is reached for a higher temperature and therefore there is a loss of activity.
- Table 1 clearly shows the gain on the catalytic effect provided by the organic compounds according to the invention. Indeed, the catalysts C4 and C5 (according to the invention) exhibit activities higher than those obtained for all the other catalysts evaluated.
- the advantage of the catalysts according to the invention is significant when they have a lower proportion of organic compound than the catalyst C3, with thus an intrinsic efficiency higher than that of the other compounds for which it is necessary to introduce a greater proportion of compound to observe a significant catalytic effect.
- Table 1 Activities relating to iso-volume in hydrodesulfurization of diesel fuel of catalysts C1 and C3 (not in accordance with the invention) and C4 and C5 (in accordance with the invention) compared to catalyst C2 (not in conformity).
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Abstract
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Priority Applications (4)
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JP2020573020A JP7394080B2 (ja) | 2018-06-27 | 2019-06-21 | 乳酸アルキルを添加された触媒、その調製および水素化処理および/または水素化分解の方法におけるその使用 |
EP19732027.8A EP3814006A1 (fr) | 2018-06-27 | 2019-06-21 | Catalyseur additivé au lactate d'alkyle, sa préparation et son utilisation dans un procédé d'hydrotraitement et/ou d'hydrocraquage |
US17/255,801 US11534742B2 (en) | 2018-06-27 | 2019-06-21 | Catalyst additivated with alkyl lactate, preparation thereof and use thereof in a hydrotreating and/or hydrocracking process |
CN201980043099.4A CN112543676B (zh) | 2018-06-27 | 2019-06-21 | 添加了乳酸烷基酯的催化剂、其制备及其在加氢处理和/或加氢裂化方法中的用途 |
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FR1855773A FR3083130B1 (fr) | 2018-06-27 | 2018-06-27 | Catalyseur a base d'un lactate d'alkyle et son utilisation dans un procede d'hydrotraitement et/ou d'hydrocraquage |
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CN112543676B (zh) | 2024-03-01 |
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EP3814006A1 (fr) | 2021-05-05 |
JP7394080B2 (ja) | 2023-12-07 |
US20210229082A1 (en) | 2021-07-29 |
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CN112543676A (zh) | 2021-03-23 |
FR3083130A1 (fr) | 2020-01-03 |
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