EP3154680A1 - Catalyseur a porosite bimodal, son procede de preparation par comalaxage de la phase active et son utilisation en hydrotraitement de residus d'hydrocarbures - Google Patents
Catalyseur a porosite bimodal, son procede de preparation par comalaxage de la phase active et son utilisation en hydrotraitement de residus d'hydrocarburesInfo
- Publication number
- EP3154680A1 EP3154680A1 EP15729134.5A EP15729134A EP3154680A1 EP 3154680 A1 EP3154680 A1 EP 3154680A1 EP 15729134 A EP15729134 A EP 15729134A EP 3154680 A1 EP3154680 A1 EP 3154680A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- volume
- aluminum
- active phase
- alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 222
- 238000000034 method Methods 0.000 title claims abstract description 79
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 25
- 229930195733 hydrocarbon Natural products 0.000 title claims description 24
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 21
- 230000002902 bimodal effect Effects 0.000 title abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052751 metal Inorganic materials 0.000 claims abstract description 80
- 239000002184 metal Substances 0.000 claims abstract description 80
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 230000000737 periodic effect Effects 0.000 claims abstract description 12
- 238000002459 porosimetry Methods 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims description 56
- 239000002243 precursor Substances 0.000 claims description 55
- 230000008569 process Effects 0.000 claims description 43
- 238000002360 preparation method Methods 0.000 claims description 36
- 239000000725 suspension Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 22
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 238000000975 co-precipitation Methods 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 230000005587 bubbling Effects 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 9
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 claims description 9
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000006259 organic additive Substances 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000012431 aqueous reaction media Substances 0.000 claims description 2
- 230000004907 flux Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 26
- 150000002739 metals Chemical class 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 17
- 238000005470 impregnation Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910001593 boehmite Inorganic materials 0.000 description 12
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000003245 coal Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000007493 shaping process Methods 0.000 description 7
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000010979 pH adjustment Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005987 sulfurization reaction Methods 0.000 description 5
- IFTRQJLVEBNKJK-UHFFFAOYSA-N Ethylcyclopentane Chemical compound CCC1CCCC1 IFTRQJLVEBNKJK-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- YTAHJIFKAKIKAV-XNMGPUDCSA-N [(1R)-3-morpholin-4-yl-1-phenylpropyl] N-[(3S)-2-oxo-5-phenyl-1,3-dihydro-1,4-benzodiazepin-3-yl]carbamate Chemical compound O=C1[C@H](N=C(C2=C(N1)C=CC=C2)C1=CC=CC=C1)NC(O[C@H](CCN1CCOCC1)C1=CC=CC=C1)=O YTAHJIFKAKIKAV-XNMGPUDCSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011066 ex-situ storage Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910015338 MoNi Inorganic materials 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000010730 cutting oil Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910021472 group 8 element Inorganic materials 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- -1 hydroxycarbonates Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000010025 steaming Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 230000001131 transforming effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- QWHNJUXXYKPLQM-UHFFFAOYSA-N 1,1-dimethylcyclopentane Chemical class CC1(C)CCCC1 QWHNJUXXYKPLQM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 241000370685 Arge Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910000154 gallium phosphate Inorganic materials 0.000 description 1
- LWFNJDOYCSNXDO-UHFFFAOYSA-K gallium;phosphate Chemical compound [Ga+3].[O-]P([O-])([O-])=O LWFNJDOYCSNXDO-UHFFFAOYSA-K 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003476 subbituminous coal Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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Definitions
- the invention relates to hydrotreatment catalysts, especially residues, and relates to the preparation of comalaxed active phase hydrotreating catalysts having a texture and a formulation that are favorable for the hydrotreatment of residues, in particular for hydrodemetallization.
- the preparation process according to the invention also makes it possible to avoid the impregnation step usually carried out on a previously shaped support.
- the invention consists in the use of catalysts comprising at least one alumina oxide matrix, at least one group VI B element, optionally at least one group VIII element, and optionally the phosphorus element.
- the fixed bed residue hydrotreating processes (commonly called "Residual Desulfurization” unit or RDS) lead to high refining performance: typically they can produce a boiling temperature cut above 370 ° C. containing less than 0 ° C. , 5% by weight of sulfur and less than 20 ppm of metals from fillers containing up to 5% by weight of sulfur and up to 250 ppm of metals (Ni + V).
- the different effluents thus obtained can serve as a basis for the production of good quality heavy fuel oils and / or pretreated feedstocks for other units such as cracking.
- catalytic Fluid Catalytic Cracking
- the hydroconversion of the residue into slices lighter than the atmospheric residue is generally low, typically of the order of 10-20% by weight.
- the feed, premixed with hydrogen circulates through a plurality of fixed bed reactors arranged in series and filled with catalysts.
- the total pressure is typically between 100 and 200 bar and the temperatures between 340 and 420 ° C.
- the effluents withdrawn from the last reactor are sent to a fractionation section.
- the fixed bed hydrotreating process consists of at least two steps (or sections).
- the first so-called hydrodemetallation (HDM) stage is mainly aimed at eliminating the majority of metals from the feedstock by using one or more hydrodemetallization catalysts.
- This stage mainly includes vanadium and nickel removal operations and, to a lesser extent, iron.
- the second step, or so-called hydrodesulfurization (HDS) section consists in passing the product of the first step over one or more hydrodesulfurization catalysts, which are more active in terms of hydrodesulphurization and hydrogenation of the feedstock, but less tolerant to metals.
- 6,780,817 teaches that it is necessary to use a catalyst support that has at least 0.32 ml / g macroporous volume for stable fixed bed operation.
- a catalyst further has a median diameter in the mesopores of 8 to 13 nm and a high specific surface area of at least 180 m 2 / g.
- US Pat. No. 6,919,294 also describes the use of so-called bimodal, therefore mesoporous and macroporous support, with the use of high macroporous volumes, but with a mesoporous volume limited to no more than 0.4 ml / g.
- US Pat. No. 7,169,294 describes a heavy-weight hydroconversion catalyst comprising between 7 and 20% of Group VI metal and between 0.5 and 6% by weight of Group VIII metal on an aluminum support.
- the catalyst has a specific surface area of between 100 and 180 m 2 / g, a total pore volume greater than or equal to 0.55 ml / g, and at least 50% of the total pore volume is included in pores larger than 20 nm.
- At least 5% of the total pore volume is comprised in pores larger than 100 nm, at least 85% of the total pore volume being included in pores between 10 and 120 nm in size, less than 2% of pore volume total being contained in the pores of diameter greater than 400 nm, and less than 1% of the total pore volume being contained in pores with a diameter greater than 1000 nm.
- Numerous developments include the optimization of the porous distribution of the catalyst or catalyst mixtures by optimizing the catalyst support.
- US Pat. No. 6,589,908 describes, for example, a process for preparing an alumina characterized by the absence of macropores, less than 5% of the total pore volume constituted by pores with a diameter of greater than 35 nm, and a high pore volume greater than 0.8 ml / g, and a bimodal mesopore distribution in which the two modes are separated by 1 to 20 nm and the primary porous mode being larger than the porous median diameter.
- the method of preparation described implements two stages of precipitation of alumina precursors under well-controlled conditions of temperature, pH and flow rates. The first step operates at a temperature between 25 and 60 ° C, a pH between 3 and 10.
- the suspension is then heated to a temperature between 50 and 90 ° C.
- Reagents are again added to the slurry, which is then washed, dried, shaped and calcined to form a catalyst support.
- Said support is then impregnated with an active phase solution to obtain a hydrotreatment catalyst; a catalyst for hydrotreating residues on a mesoporous monomodal support of porous median diameter around 20 nm is described.
- the patent application WO 2004/052534 A1 describes the use in hydrotreatment of heavy hydrocarbon feeds of a mixture of two catalysts with supports having different porous characteristics, the first catalyst having more than half the pore volume in the pores of diameter greater than 20 nm, 10 to 30% of the pore volume being contained in the pores of diameter greater than 200 nm, the total pore volume being greater than 0.55 ml / g, the second having more than 75% of the pore volume content in pores with a diameter of between 10 and 120 nm, less than 2% in pores with a diameter greater than 400 nm and 0 to 1% in pores with a diameter greater than 1000 nm.
- the preparation method described for the preparation of these catalysts implements a step of co-precipitating aluminum sulphate with sodium aluminate, the gel obtained is then dried, extruded and calcined. It is possible to add silica during or after precipitation. Adjusting the layout provides the characteristics of the media.
- Group VIB, VII, IA or V metals may be incorporated in the support, by impregnation and / or by incorporation into the support before it is shaped into particles. Impregnation is preferred.
- patent application WO 2012/021386 discloses hydrotreatment catalysts comprising a porous refractory oxide support shaped from alumina powder and from 5% to 45% by weight of catalyst fines.
- the support comprising the fines is then dried, calcined.
- the support obtained has a specific surface area of between 50 m 2 / g and 450 m 2 / g, a median pore diameter of between 50 and 200 A, and a total pore volume exceeding 0.55 cm 3 / g.
- the support thus comprises metal incorporated thanks to the metals contained in the catalyst fines.
- the resulting support can be treated with a chelating agent.
- the pore volume may be partially filled by means of a polar additive, and may be impregnated with a metal impregnating solution.
- a catalyst prepared from an alumina resulting from the calcination of a specific alumina gel having a targeted alumina content by comalaxing a hydro-dehydrogenating active phase with the calcined alumina exhibited a porous structure of particular interest for the hydrotreatment of heavy loads, while having a suitable active phase content.
- the invention relates to a hydroconversion / hydrotreating residue catalyst having an optimized porous distribution and an active phase comalaxed in a calcined aluminic matrix.
- the invention also relates to a catalyst preparation process suitable for the hydroconversion / hydrotreatment of residues by comalaxing the active phase with a particular alumina.
- the invention finally relates to the use of the catalyst in hydrotreating processes, in particular the hydrotreatment of heavy feedstocks.
- the invention relates to a process for the preparation of a comalaxed active phase catalyst, comprising at least one metal of group VI B of the periodic table of elements, optionally at least one metal of group VIII of the periodic table of elements, optionally of phosphorus and a predominantly calcined aluminum oxide matrix, comprising the following steps: a) a step of dissolving an aluminum acid precursor chosen from aluminum sulphate, aluminum chloride and aluminum nitrate in the water, at a temperature between 20 and 90 ° C, at a pH between 0.5 and 5, for a period of between 2 and 60 minutes; b) A step of adjusting the pH by adding to the suspension obtained in step a) at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, hydroxide and the like.
- step b) a step of co-precipitation of the suspension obtained at the end of step b) by adding to the suspension at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid, at least one of the basic or acidic precursors comprising aluminum, the relative flow rate of the acidic and basic precursors being chosen so as to obtain a pH of the reaction medium of between 7 and 10 and the flow rate of the aluminum-containing acidic and basic precursors being adjusted so as to obtain a final alumina concentration in the suspension of between 10 and 38 g / L;
- step d) a step of drying said alumina gel obtained in step d) to obtain a powder
- step f) a step of heat treatment of the powder obtained at the end of step e) at a temperature of between 500 and 1000 ° C., for a duration of between 2 and 10 h, in the presence or absence of a flux air containing up to 60% water volume to obtain a calcined aluminous porous oxide;
- the alumina concentration of the alumina gel suspension obtained in step c) is preferably between 13 and 35 g / l, very preferably between 15 and 33 g / l, inclusive.
- the acidic precursor is advantageously chosen from aluminum sulphate, aluminum chloride and aluminum nitrate, preferably aluminum sulphate.
- the basic precursor is advantageously chosen from sodium aluminate and potassium aluminate, preferably sodium aluminate.
- the aqueous reaction medium is water and said steps operate with stirring, in the absence of organic additive.
- the invention also relates to a bimodal porous structure hydroconversion catalyst comprising:
- hydro-dehydrogenating active phase comprising at least one Group VIB metal of the periodic table of the elements, optionally at least one metal of group VIII of the periodic table of the elements, optionally phosphorus, said active phase being at least partially comalaxed; in said matrix oxide predominantly aluminized calcined,
- said catalyst having a surface area Sbet greater than 100 m 2 / g, a mesoporous median diameter by volume between 12 and 25 nm, limits included, a median macroporous volume diameter between 250 and 1500 nm, limits included, a mesoporous volume such as as measured by mercury porosimeter intrusion greater than or equal to 0.55 ml / g and a total pore volume measured by mercury porosimetry greater than or equal to 0.70 ml / g.
- the median mesoporous median diameter determined by intrusion into the mercury porosimeter is between 13 and 17 nm, inclusive.
- the macroporous volume is between 10 and 40% of the total pore volume.
- the mesoporous volume is greater than 0.70 ml / g.
- the hydroconversion catalyst does not have micropores.
- the group VI B metal content is between 2 and 10% by weight of trioxide of at least Group VI B metal relative to the total mass of the product.
- the group VIII metal content is between 0.0 and 3.6% by weight of the oxide of at least the group VIII metal relative to the total mass of the catalyst
- the phosphorus element content is between 0 and 5% by weight of phosphorus pentoxide relative to the total mass of the catalyst.
- the hydro-dehydrogenating active phase may be composed of molybdenum or nickel and molybdenum or cobalt and molybdenum.
- the hydrodehydrogenating active phase may also include phosphorus.
- the hydro-dehydrogenating active phase is fully comalaxed.
- Part of the hydro-dehydrogenating active phase may be impregnated on the calcined aluminum oxide matrix.
- the invention also relates to a process for the hydrotreatment of a heavy hydrocarbon feedstock chosen from atmospheric residues, vacuum residues resulting from direct distillation, deasphalted oils, residues resulting from conversion processes such as, for example, those originating from coking, hydroconversion fixed bed, ebullated bed or moving bed, taken alone or in a mixture comprising contacting said feedstock with hydrogen and a catalyst that can be prepared according to the process of l invention or a catalyst as described above.
- a heavy hydrocarbon feedstock chosen from atmospheric residues, vacuum residues resulting from direct distillation, deasphalted oils, residues resulting from conversion processes such as, for example, those originating from coking, hydroconversion fixed bed, ebullated bed or moving bed, taken alone or in a mixture
- a catalyst that can be prepared according to the process of l invention or a catalyst as described above.
- the process may be carried out partly in a bubbling bed at a temperature of between 320 ° and 450 ° C., under a hydrogen partial pressure of between 3 MPa and 30 MPa, at a space velocity advantageously between 0.1 and 10 vol. charge per volume of catalyst per hour, and with a hydrogen gas ratio on a hydrocarbon liquid charge advantageously between 100 and 3000 normal cubic meters per cubic meter.
- the process may be carried out at least in part in a fixed bed at a temperature of between 320 ° C. and 450 ° C., at a hydrogen partial pressure of between 3 MPa and 30 MPa, at a space velocity of between 0.05 and 5. volume of charge per volume of catalyst and per hour, and with a hydrogen gas ratio on a hydrocarbon liquid charge of between 200 and 5000 normal cubic meters per cubic meter.
- the process may be a heavy hydrocarbon feedstock hydrotreatment process of the fixed bed residues type comprising at least:
- a catalyst which simultaneously has a high pore volume (greater than or equal to 0.70 ml / g), a median diameter of the mesopores corresponding to pores with a diameter of between 2 and 50 nm , high (between 12 and 25 nm) and the presence of a proportion of macropores, corresponding to pores with a diameter greater than 50 nm, high (advantageously a macroporous volume between 10 and 40% of the total pore volume), but also active phase characteristics favorable to hydrotreatment.
- the advantage of a comparison compared to an impregnation is that there is no risk of partial blockage of the porosity of the support during the deposition of the active phase and therefore the appearance of limitation problems.
- the catalyst used in the present invention has a specific porous distribution, where the macroporous and mesoporous volumes are measured by mercury intrusion and the microporous volume is measured by nitrogen adsorption.
- Macropores means pores whose opening is greater than 50 nm.
- pores is meant pores whose opening is between 2 nm and 50 nm, limits included.
- micropores pores whose opening is less than 2 nm.
- specific surface means the specific surface B.E.T. determined by nitrogen adsorption according to ASTM D 3663-78 established from the BRUNAUER-EMMETT-TELLER method described in the journal "The Journal of the American Society", 60, 309, (1938).
- total pore volume of the alumina or the predominantly aluminum matrix or catalyst means the volume measured by mercury porosimeter intrusion according to ASTM D4284-83 at a pressure of maximum of 4000 bar, using a surface tension of 484 dyne / cm and a contact angle of 140 °. The angle of wetting was taken equal to 140 ° following the recommendations of the book "Techniques of the engineer, treated analysis and characterization, P 1050-5, written by Jean Charpin and Bernard Rasneur”.
- the value of the total pore volume in ml / g given in the following text corresponds to the value of the total mercury volume (total pore volume measured by mercury porosimeter intrusion) in ml / g measured on the sample minus the mercury volume value in ml / g measured on the same sample for a pressure corresponding to 30 psi (approximately 0.2 MPa).
- the volume of macropores and mesopores of the catalyst is measured by mercury intrusion porosimetry according to ASTM D4284-83 at a maximum pressure of 4000 bar, using a surface tension of 484 dyne / cm and a contact angle of 140 °. .
- the value at which mercury fills all the intergranular voids is fixed at 0.2 MPa, and it is considered that beyond this the mercury enters the pores of the sample.
- the macroporous volume of the catalyst is defined as the cumulative volume of mercury introduced at a pressure of between 0.2 MPa and 30 MPa, corresponding to the volume contained in the pores with an apparent diameter greater than 50 nm.
- the mesoporous volume of the catalyst is defined as the cumulative volume of mercury introduced at a pressure of between 30 MPa and 400 MPa, corresponding to the volume contained in the pores with an apparent diameter of between 2 and 50 nm.
- the micropore volume is measured by nitrogen porosimetry.
- the quantitative analysis of the microporosity is carried out using the "t" method (Lippens-De Boer method, 1965) which corresponds to a transformation of the starting adsorption isotherm as described in the book “Adsorption by powders and porous solids. Principles, methodology and applications "written by F. Rouquérol, J. Rouquérol and K. Sing, Académie Press, 1999.
- the mesoporous median diameter (meso Dp in nm) is also defined as a diameter such that all smaller pores at this diameter constitute 50% of the total mesoporous volume determined by mercury porosimeter intrusion.
- Macroporous median diameter is also defined as a diameter such that all pores smaller than this diameter constitute 50% of the total macroporous volume determined by mercury porosimeter intrusion.
- group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
- the invention relates to a hydrolysis / hydroconversion catalyst of residues with a comalaxed active phase, comprising at least one metal of group VI B of the periodic table, optionally at least one metal of group VIII of the periodic table of elements, optionally phosphorus and an aluminum oxide support, its method of preparation and its use in a hydrotreatment process of heavy hydrocarbon feedstocks such as petroleum residues (atmospheric or vacuum).
- the catalyst according to the invention is in the form of a matrix comprising for the most part a calcined porous refractory oxide in which the metals of the active phase are distributed.
- the invention also relates to the process for preparing the catalyst which is carried out by comalaxing a particular alumina with a metal solution of formulation adapted to the target metal target for the final catalyst.
- the Group VI B metals are advantageously selected from molybdenum and tungsten, and preferably said Group VI B metal is molybdenum.
- Group VIII metals are preferably selected from iron, nickel or cobalt and nickel or cobalt, or a combination of both, is preferred.
- the respective quantities of group VI B metal and of group VIII metal are advantageously such that the atomic ratio metal (aux) of group VIII on group VI B (VIII: VI B) metal (s) is between 0.0: 1 and 0.7: 1, preferably between 0.05: 1 and 0.6: 1 and more preferably between 0.2: 1 and 0.5: 1. This ratio can in particular be adjusted according to the type of load and the process used.
- the respective quantities of group VI B metal and phosphorus are advantageously such that the atomic phosphorus to metal (A) group VI (P / VI B) atomic ratio is between 0.2: 1 and 1.0: 1, preferably between 0.4: 1 and 0.9: 1 and even more preferably between 0.5: 1.0 and 0.85: 1.
- the metal content of group VI B is advantageously between 2 and 10% by weight of group VI B metal trioxide relative to the total mass of the catalyst, preferably between 3 and 8%, and even more preferably between 4 and 8%. and 7% weight.
- the group VIII metal content when at least one Group VIII metal is present, is advantageously between 0.0 and 3.6% by weight of the Group VIII metal oxide relative to the total mass of the group VIII metal.
- catalyst preferably between 0.4 and 2.5% and even more preferably between 0.7 and 1.8% by weight.
- the content of phosphorus element when it is present, is advantageously between 0.0 and 5% by weight of phosphorus pentoxide relative to the total mass of the catalyst, preferably between 0.6 and 3.5% by weight and even more preferably between 1.0 and 3.0% by weight.
- the predominantly calcined aluminum matrix of said catalyst according to the invention comprises an alumina content greater than or equal to 90% and a silica content of at most 10% by weight of SiO 2 equivalent relative to the final oxide, preferably a content silica less than 5% by weight, very preferably less than 2% by weight.
- the silica may be introduced, by any technique known to those skilled in the art, during the synthesis of the alumina gel or during the comalaxing.
- the aluminic matrix contains nothing other than alumina.
- the said co-axial phase active catalyst according to the invention is generally presented in all the forms known to those skilled in the art.
- it consists of extrudates of diameter generally between 0.5 and 10 mm, preferably between 0.8 and 3.2 mm and very preferably between 1.0 and 2.5 mm.
- This one can be advantageously presented in the form of cylindrical, trilobed or quadrilobed extrudates.
- Preferably its shape will be trilobed or quadrilobed.
- the shape of the lobes can be adjusted according to all known methods of the prior art.
- the comalaxed catalyst according to the invention has particular textural properties.
- the catalyst according to the invention has a total pore volume (VPT) of at least 0.70 ml / g and preferably at least 0.80 ml / g. In a preferred embodiment, the catalyst has a total pore volume of from 0.80 to 1.00 ml / g.
- VPT total pore volume
- the catalyst used according to the invention advantageously has a macroporous volume, Vmacro or V 50 nm, defined as the volume of pores with a diameter greater than 50 nm, representing between 10 and 40% of the total pore volume, and preferably between 20 and 35. % of the total pore volume.
- the macroporous volume represents between 25 and 35% of the total pore volume.
- the mesoporous volume (V meso ) of the catalyst is at least 0.55 ml / g, preferably at least 0.60 ml / g. In a preferred embodiment, the mesoporous volume of the catalyst is between 0.60 ml / g and 0.80 ml / g.
- the median mesoporous diameter is between 12 nm and 25 nm, inclusive, and preferably between 12 and 18 nm, limits included. Very preferably, the average mesoporous diameter is between 13 and 17 nm.
- the catalyst has a macroporous median diameter of between 250 and 1500 nm, preferably between 500 and 1000 nm, even more preferably between 600 and 800 nm.
- the catalyst according to the present invention has a BET (S B ET) specific surface area of at least 100 m 2 / g, preferably at least 120 m 2 / g and even more preferably between 150 and 250 m 2 /boy Wut.
- the catalyst has a low microporosity, very preferably no microporosity is detectable in nitrogen porosimetry. If necessary, it is possible to increase the metal content by introducing a second part of the active phase by impregnation on the catalyst already comalaxed with a first part of the active phase. It is important to emphasize that the catalyst according to the invention differs structurally from a catalyst obtained by simply impregnating a precursor on an alumina support in which the alumina forms the support and the active phase is introduced into the pores of this support.
- the catalyst according to the invention is prepared by co-mixing a porous aluminum oxide obtained from a specific alumina gel and the precursor (s) of metals.
- the process for preparing the catalyst according to the invention comprises the following steps: Steps a) to e): Synthesis of the precursor gel of the porous oxide
- step j) Possible heat treatment (preferably under dry air).
- the solid obtained at the end of steps a) to f) undergoes a g / comalaxing step. It is then shaped in a step h), then can then simply be dried at a temperature of less than or equal to 200 ° C (step i) or dried, and then subjected to a new calcination heat treatment in a step j) optional.
- the catalyst Prior to its use in a hydrotreatment process, the catalyst is usually subjected to a final sulfurization step. This step consists in activating the catalyst by transforming, at least in part, the oxide phase in a sulpho-reducing medium.
- a conventional sulphurization method well known to those skilled in the art consists in heating the mixture of solids under a stream of a mixture of hydrogen and hydrogen sulphide or under a stream of a mixture of hydrogen and of hydrocarbons containing sulfur-containing molecules at a temperature of temperature between 150 and 800 ° C, preferably between 250 and 600 ° C, generally in a crossed-bed reaction zone.
- the comalaxed active phase catalyst according to the invention is prepared from a specific alumina gel, which is dried and undergoes a heat treatment, before comalaxing with the active phase, and then shaped.
- the preparation of said alumina gel comprises three successive stages: a) step of dissolving an aluminum acid precursor, b) step of adjusting the pH of the suspension using a basic precursor, and c) step of co-precipitation of at least one acidic precursor and at least one basic precursor, at least one of which contains aluminum.
- the final alumina concentration in the alumina gel suspension must be between 10 and 38 g. / L, preferably between 13 and 35 g / l and more preferably between 15 and 33 g / l.
- Step a) is a step of dissolving an aluminum acid precursor in water, carried out at a temperature of between 20 and 80 ° C, preferably between 20 and 75 ° C and more preferred between 30 and 70 ° C.
- the acid precursor of aluminum is chosen from aluminum sulphate, aluminum chloride and aluminum nitrate, preferably aluminum sulphate.
- the pH of the suspension obtained is between 0.5 and 5, preferably between 1 and 4, preferably between 1.5 and 3.5.
- This step advantageously contributes to an amount of alumina introduced relative to the final alumina of between 0.5 and 4%, preferably between 1 and 3%, very preferably between 1.5 and 2.5%.
- the suspension is left stirring for a period of between 2 and 60 minutes, and preferably 5 to 30 minutes.
- pH adjustment step is a step of dissolving an aluminum acid precursor in water, carried out at a temperature of between 20 and 80 ° C, preferably between 20 and 75 ° C and more preferred between 30 and 70 ° C.
- the acid precursor of aluminum is chosen
- the step of adjusting the pH b) consists in adding to the suspension obtained in step a) at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide.
- the basic precursor is an aluminum precursor chosen from sodium aluminate and potassium aluminate.
- the basic precursor is sodium aluminate.
- the basic precursor (s) and acid (s) are added in said step of adjusting the pH in aqueous solution.
- Step b) is carried out at a temperature between 20 and 90 ° C, preferably between 20 and 80 ° C, and more preferably between 30 and 70 ° C and at a pH between 7 and 10, preferably between 8 and 10, preferably between 8.5 and 10 and most preferably between 8.7 and 9.9.
- the duration of step b) of pH adjustment is between 5 and 30 minutes, preferably between 8 and 25 minutes, and very preferably between 10 and 20 minutes.
- Step c) is a step of precipitating the suspension obtained after step b) by adding to the suspension at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid, at least one of the basic precursors or acid comprising aluminum, said precursors being chosen identical or not to the precursors introduced in steps a) and b).
- at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid and nitric acid, at least one of the basic precursors or acid comprising aluminum, said precursors being chosen identical or not to the precursors introduced in steps a) and b).
- the relative flow rate of the acidic and basic precursors is chosen so as to obtain a pH of the reaction medium of between 7 and 10 and the flow rate of the acidic and basic precursor (s) containing aluminum is adjusted so as to obtain a final alumina concentration. in the suspension of between 10 and 38 g / l, preferably between 13 and 35 g / l and more preferably between 15 and 33 g / l.
- the basic precursor (s) and acid (s) are added in said co-precipitation step in aqueous solution.
- the co-precipitation step is conducted at a temperature between 20 and 90 ° C, and more preferably between 30 and 70 ° C.
- the co-precipitation step c) is carried out at a pH of between 7 and 10, preferably between 8 and 10, preferably between 8.5 and 10 and very preferably between 8.7 and 9.9.
- the co-precipitation step c) is preferably carried out for a period of between 1 and 60 minutes, and preferably of 5 to 45 minutes.
- said steps a), b) and c) are carried out in the absence of organic additive.
- the synthesis of the alumina gel (steps a), b) and c)) is carried out with stirring, d) Filtration step
- the process for preparing the alumina according to the invention also comprises a step of filtration of the suspension obtained at the end of step c).
- Said filtration step is carried out according to the methods known to those skilled in the art. Said filtration step is advantageously followed by at least one washing step, with an aqueous solution, preferably with water, and preferably from one to three washing steps, with a quantity of water equal to the quantity filtered precipitate. e) Drying step
- the alumina gel obtained at the end of the precipitation step c), followed by a filtration step d), is dried in a drying step e) to obtain a powder, said drying step being carried out advantageously at a temperature greater than or equal to 120 ° C or by atomization or by any other drying technique known to those skilled in the art.
- said drying step d) may advantageously be carried out in a closed and ventilated oven.
- said drying step operates at a temperature between 120 and 300 ° C, very preferably at a temperature between 150 and 250 ° C.
- said drying step e) is carried out by atomization
- the cake obtained at the end of the second precipitation step, followed by a filtration step is resuspended.
- Said suspension is then sprayed in fine droplets, in a vertical cylindrical chamber in contact with a stream of hot air to evaporate the water according to the principle well known to those skilled in the art.
- the powder obtained is driven by the heat flow to a cyclone or a bag filter that will separate the air from the powder.
- drying step e) is carried out by atomization
- the atomization is carried out according to the operating protocol described in the publication Asep Bayu Dani Nandiyanto, Kikuo Okuyama, Advanced Powder Technology, 22, 1-19 , 201 1. f) Heat treatment step
- the raw material obtained at the end of the drying step e) is then subjected to a heat treatment step f) at a temperature of between 500 and 1000 ° C. for a period of between 2 and 10 hours. h, with or without a flow of air containing up to 60% water volume.
- said heat treatment is carried out in the presence of an air flow containing water.
- said heat treatment step f) operates at a temperature of between 540 ° C. and 850 ° C.
- Said f) heat treatment step allows the transition of the boehmite to the final alumina.
- the heat treatment step may be preceded by drying at a temperature between 50 ° C and 120 ° C, according to any technique known to those skilled in the art.
- the powder obtained after drying step e), after heat treatment in a step f), is comalaxed with the metal precursor (s) of the active phase, in a step g) comalaxing allowing the contact or solutions containing the active phase to come into contact with the powder, and then shaping the resulting material to obtain the catalyst in a step h).
- the active phase is provided by one or more solutions containing at least one Group VIB metal, optionally at least one Group VIII metal and optionally the phosphorus element.
- the said solution (s) may be aqueous, consisting of an organic solvent or a mixture of water and at least one organic solvent (for example ethanol or toluene).
- the solution is aquo-organic and even more preferably aqueous-alcoholic.
- the pH of this solution may be modified by the possible addition of an acid.
- the compounds which can be introduced into the solution as sources of group VIII elements advantageously are: citrates, oxalates, carbonates, hydroxycarbonates, hydroxides, phosphates, sulphates, aluminates, molybdates, tungstates, oxides, nitrates, halides for example, chlorides, fluorides, bromides, acetates, or any mixture of the compounds set forth herein.
- the sources of the group VIB element which are well known to those skilled in the art, there are advantageously, for example, for molybdenum and tungsten: oxides, hydroxides, molybdic and tungstic acids and their salts, in particular sodium salts.
- ammonium, ammonium heptamolybdate, ammonium tungstate, phosphomolybdic acid, phosphotungstic acid and their salts Oxides or ammonium salts such as ammonium molybdate, ammonium heptamolybdate or ammonium tungstate are preferably used.
- the preferred phosphorus source is orthophosphoric acid, but its salts and esters such as alkaline phosphates, ammonium phosphate, gallium phosphate or alkyl phosphates are also suitable.
- Phosphorous acids for example hypophosphorous acid, phosphomolybdic acid and its salts, phosphotungstic acid and its salts can be advantageously used.
- An additive for example a chelating agent of organic nature, may advantageously be introduced into the solution if the person skilled in the art deems it necessary.
- Any other element for example silica in the form of a solution or emulsion of silicic precursor, can be introduced into the mixing tank at the time of this step.
- a kneader for example a "Brabender" kneader, well known to those skilled in the art.
- the calcined alumina powder obtained in step f) and one or more additives or possible elements are placed in the tank of the kneader.
- the solution of metal precursors, for example nickel and molybdenum, and optionally deionized water are added to the syringe for a period of a few minutes, typically about 2 minutes at a given kneading speed.
- the kneading can be maintained for a few minutes, for example about 15 minutes at 50 rpm.
- the paste obtained at the end of the comalaxing step g) is then shaped according to any technique known to those skilled in the art, for example the methods of forming by extrusion, by pelletizing, by the oil drop method, or by rotating plate granulation.
- said support used according to the invention is shaped by extrusion in the form of extrudates of diameter generally between 0.5 and 10 mm and preferably 0.8 and 3.2 mm. In a preferred embodiment, it will be composed of trilobed or quadrilobed extrudates of size between 1.0 and 2.5 mm in diameter.
- said comalling step g) and said shaping step h) are combined in a single kneading-extruding step.
- the paste obtained after mixing can be introduced into a capillary MTS rheometer through a die having the desired diameter, typically between 0.5 and 10 mm.
- the catalyst obtained at the end of step g) of comalaxing and shaping h) undergoes drying i) at a temperature of less than or equal to 200 ° C., preferably less than 150 ° C. C, according to any technique known to those skilled in the art, for a period advantageously between 2 and 12 hours.
- the catalyst thus dried can then undergo a complementary heat treatment or hydrothermal step j) at a temperature of between 200 and 1000 ° C., preferably between 300 and 800 ° C. and even more preferably between 350 and 550 ° C., while a duration of between 2 and 10 h, in the presence or absence of a flow of air containing up to 60% by volume of water.
- a complementary heat treatment or hydrothermal step j) at a temperature of between 200 and 1000 ° C., preferably between 300 and 800 ° C. and even more preferably between 350 and 550 ° C., while a duration of between 2 and 10 h, in the presence or absence of a flow of air containing up to 60% by volume of water.
- Several combined cycles of thermal or hydrothermal treatments can be carried out.
- the catalyst is only advantageously dried in step i).
- the contact with the steam can take place at atmospheric pressure (steaming) or autogenous pressure (autoclaving).
- steaming the water content is preferably between 150 and 900 grams per kilogram of dry air, and even more preferably between 250 and 650 grams per kilogram of dry air. According to the invention, it is possible to envisage introducing all or part of the metals mentioned during the comalaxing of the metal solution (s) with the porous aluminum oxide.
- a part of the metals remains introduced by impregnating said catalyst from step g / or h /, according to any method known to man of the trade, the most common being that of dry impregnation.
- all of the metal phase is introduced during the preparation by comalaxing the porous aluminum oxide and no additional impregnation step is therefore necessary.
- the active phase of the catalyst is fully comalaxed within the calcined porous aluminum oxide.
- the catalyst according to the invention can be used in hydrotreatment processes making it possible to convert heavy hydrocarbon feeds containing sulfur impurities and metallic impurities.
- One objective sought by the use of the catalysts of the present invention relates to an improvement of the performances, in particular in hydrodemetallation and hydrodesulphurization, while improving the ease of preparation with respect to the catalysts known from the prior art.
- the catalyst according to the invention makes it possible to improve the performances in hydrodemetallation and in hydrodesulphalate with respect to conventional catalysts, while having a high stability over time.
- the hydrotreatment processes for converting heavy hydrocarbon feeds, containing sulfur impurities and metal impurities operate at a temperature of between 320 and 450 ° C. under a hydrogen partial pressure of between 3 MPa and 30 MPa, at a space velocity advantageously between 0.05 and 10 volumes of filler per volume of catalyst and per hour, and with a hydrogen gas ratio on hydrocarbon liquid feed advantageously between 100 and 5000 normal cubic meters per cubic meter.
- the feedstocks treated in the process according to the invention are advantageously chosen from atmospheric residues, vacuum residues resulting from direct distillation, deasphalted oils, residues resulting from conversion processes such as, for example, those originating from coking, from a hydroconversion in a fixed bed, in a bubbling bed, or in a moving bed, taken alone or as a mixture.
- These fillers can advantageously be used as they are or else diluted by a hydrocarbon fraction or a mixture of hydrocarbon fractions which may be chosen from the products of the FCC process, a light cutting oil (LCO according to the initials of the English name of Light Cycle Oil), a heavy cutting oil (HCO according to the initials of the English name of Heavy Cycle Oil), a decanted oil (OD according to the initials of the English name of Decanted Oil), a slurry, or From the distillation, gas oil fractions including those obtained by vacuum distillation called according to the English terminology VGO (Vacuum Gas Oil).
- the heavy charges can thus advantageously comprise cuts resulting from the process of liquefying coal, aromatic extracts, or any other hydrocarbon cut.
- Said heavy charges generally have more than 1% by weight of molecules having a boiling point greater than 500 ° C., a metal content (Ni + V) of greater than 1 ppm by weight, preferably greater than 20 ppm by weight, so very preferred greater than 50 ppm by weight, an asphaltene content, precipitated in heptane, greater than 0.05% by weight, preferably greater than 1% by weight, very preferably greater than 2%.
- the heavy fillers can advantageously also be mixed with coal in the form of powder, this mixture being generally called slurry. These fillers can advantageously be by-products from the conversion of the coal and mixed again with fresh coal.
- the coal content in the heavy load is generally and preferably a 1 ⁇ 4 (Oil / Coal) ratio and may advantageously vary widely between 0.1 and 1.
- the coal may contain lignite, be a sub-bituminous coal (according to the English terminology), or bituminous. Any other type of coal is suitable for use of the invention, both in fixed bed reactors or in bubbling bed reactors.
- the comalaxed active phase catalyst is preferably used in the first catalytic beds of a process successively comprising at least one hydrodemetallization step and at least one hydrodesulfurization step.
- the process according to the invention is advantageously carried out in one to ten successive reactors, the catalyst (s) according to the invention can advantageously be charged in one or more reactors and / or in all or some of the reactors. .
- reactive reactors ie reactors operating alternately, in which hydrodemetallation catalysts according to the invention can preferably be implemented, can be used upstream of the unit.
- the reactive reactors are then followed by reactors in series, in which hydrodesulphurization catalysts are used which can be prepared according to any method known to those skilled in the art.
- two permutable reactors are used upstream of the unit, preferably for the hydrodemetallation and containing one or more catalysts according to the invention. They are advantageously monitored by one to four reactors in series, advantageously used for hydrodesulfurization.
- the method according to the invention can advantageously be implemented in a fixed bed with the objective of eliminating metals and sulfur and lowering the average boiling point of the hydrocarbons.
- the operating temperature is advantageously between 320 ° C. and 450 ° C., preferably 350 ° C. to 410 ° C., under a partial pressure.
- in hydrogen advantageously between 3 MPa and 30 MPa, preferably between 10 and 20 MPa, at a space velocity advantageously between 0.05 and 5 volume of charge per volume of catalyst per hour, and with a gaseous hydrogen gas on charge ratio hydrocarbon liquid advantageously between 200 and 5000 normal cubic meters per cubic meter, preferably 500 to 1500 normal cubic meters per cubic meter.
- the process according to the invention can also advantageously be implemented partly in bubbling bed on the same charges.
- the catalyst is advantageously used at a temperature of between 320 and 450 ° C. under a hydrogen partial pressure of advantageously between 3 MPa and 30.degree. MPa, preferably between 10 and 20 MPa, at a space velocity advantageously between 0.1 and 10 volumes of filler per volume of catalyst and per hour, preferably between 0.5 and 2 volumes of filler by volume of catalyst and by hour, and with a gaseous hydrogen gas on hydrocarbon liquid charge advantageously between 100 and 3000 normal cubic meters per cubic meter, preferably between 200 to 1200 normal cubic meters per cubic meter.
- the method according to the invention is implemented in a fixed bed.
- the catalysts of the present invention are preferably subjected to a sulphurization treatment making it possible, at least in part, to convert the metallic species into sulphides before they come into contact with the charge. treat.
- This activation treatment by sulphurisation is well known to those skilled in the art and can be performed by any previously known method already described in the literature.
- a conventional sulphurization method well known to those skilled in the art consists of heating the mixture of solids under a stream of a mixture of hydrogen and hydrogen sulphide or under a stream of a mixture of hydrogen and of hydrocarbons containing sulfur-containing molecules at a temperature of temperature between 150 and 800 ° C, preferably between 250 and 600 ° C, generally in a crossed-bed reaction zone.
- the sulfurization treatment can be carried out ex situ (before the introduction of the catalyst into the hydrotreatment / hydroconversion reactor) or in situ by means of an organosulfur precursor agent of H 2 S, for example DMDS (dimethyl disulphide).
- organosulfur precursor agent of H 2 S for example DMDS (dimethyl disulphide).
- Solutions A, B, C and D used for the preparation of catalysts A1, A2, A3, B1, C1, D1, D3 were prepared by dissolving in water the precursors of the following phases MoO 3 , Ni (OH) 2 , and optionally H 3 P0 4 . All of these precursors come from Sigma-Aldrich. The concentration of elements of the various solutions is indicated in the following table.
- a laboratory reactor with a capacity of about 7000 ml is used.
- Table 2 Characteristics of the gel used for the preparation of alumina.
- Alumina AI (A1) serving as matrix for the catalyst A1 is obtained.
- Alumina Al (B1) serving as a matrix for catalyst B1 is prepared in exactly the same manner as the alumina described above.
- the impregnation solutions A and B were respectively kneaded in the presence of the Al (A1) and Al (B1) aluminas as described below to obtain the catalysts A1 and B1.
- the comalaxing takes place in a "Brabender" mixer with a tank of 80 cm 3 and a mixing speed of 30 rpm.
- the calcined powder is placed in the bowl of the kneader.
- solution A or B MoNi (P)
- the kneading is maintained 15 minutes after obtaining a paste.
- the calcined catalysts A1 and B1 have the characteristics reported in Table 4 below.
- Catalyst E is a catalyst prepared by boehmite extrusion-mixing, followed in the order of calcination and hydrothermal treatment to form an S (E) support before dry impregnation of an aqueous solution so that the metal content is the same as that introduced by the comalaxing on the catalyst A1.
- aqueous precursor solutions of sodium aluminate and aluminum sulfate are prepared from stock solution.
- a laboratory reactor with a capacity of about 7000 ml is used.
- the synthesis is carried out at 70 ° C. and with stirring. We have a foot of water of 1679 ml.
- the pH of co-precipitation is maintained between 7 and 10.
- the suspension is filtered and washed several times.
- the cake is over-dried in an oven for at least one night at 200 ° C.
- the powder to be shaped is obtained.
- the shaping is carried out on a Brabender kneader with an acid level (total, expressed relative to dry alumina) of 1%, a neutralization rate of 20% and acid and basic fire losses respectively of 62 and 64%.
- the extrusion is carried out on a piston extruder through a trilobal die diameter 2.1 mm.
- the support S (E) is then impregnated with a NiMoP metal phase by the so-called dry method using the same precursors as in Example 1, ie MoO 3 , Ni (OH) 2 , H 3 PO 4 .
- the concentration of the metals in solution sets the content, which has been chosen to be compared with that of the catalyst A1.
- the impregnated support undergoes a maturing stage of 24 hours in a saturated water atmosphere before being dried for 12 hours at 80 ° C. in air and then calcined under air at 400 ° C. for 2 hours.
- Catalyst E is obtained.
- the metal contents have been checked and are reported in Table 4.
- Example 4 (Comparative) Preparation of an Incomplete Comalaxed Catalyst A2
- the solution A is kneaded in the presence of an alumina AI (A2) prepared in a non-compliant manner, in that the concentration of final alumina in the suspension of step c) is not in accordance with the invention (60 g / 1).
- aqueous precursor solutions of sodium aluminate and aluminum sulfate are prepared from stock solution.
- a laboratory reactor with a capacity of about 7000 ml is used.
- the synthesis is carried out at 70 ° C. and with stirring. We have a foot of water of 1679 ml.
- a solution of 60 g / l of final alumina and with a contribution rate of the first step of 2.1% is prepared.
- the suspension is filtered and washed several times.
- the cake is over-dried in an oven for at least one night at 200 ° C.
- the powder obtained is then calcined at 800 ° C. for 2 hours.
- Comalaxing takes place in a "Brabender" mixer with an 80 cm 3 tank and a mixing speed of 50 rpm.
- the calcined powder is placed in the bowl of the kneader.
- solution A MoNi (P) is added at a speed of 15 rpm.
- the kneading is maintained 15 minutes after obtaining a paste.
- the paste thus obtained is introduced into a piston extruder through a 2.1 mm die.
- the extrudates thus obtained are then dried overnight in an oven at 80 ° C and then calcined at 400 ° C, 2h in air (1 l / h / g).
- the catalyst A2 obtained has the characteristics reported in Table 4.
- Alumina preparation A1 (A1), but no heat treatment step f) is involved.
- a laboratory reactor with a capacity of about 7000 ml is used.
- the synthesis is carried out at 70 ° C. and with stirring. We have a foot of water of 1679 ml.
- the pH of co-precipitation is maintained between 7 and 10.
- the suspension is filtered and washed several times (step d)).
- the cake is dried (step e)) in an oven for at least one night at 200 ° C.
- the powder B (A3) is obtained which must be shaped. No calcination of the powder occurs at this stage.
- Solution A is then kneaded in the presence of the alumina precursor powder B (A3) (in the form AIOOH) prepared above until the drying step e).
- the powder is not calcined, so it is a boehmite powder.
- the mixing-extrusion conditions used are strictly the same as those described above (Example 4).
- the extrudates thus obtained are then dried overnight in an oven at 80 ° C and then calcined at 400 ° C, 2h in air (1 l / h / g).
- the catalyst A3 has the characteristics reported in Table 4. Compared to the catalyst A2, the macroporous volume is lower, but it remains high, to the detriment of a very low mesoporous volume. The median mesoporous diameter (Dpmeso) is unchanged relative to the catalyst A2, so low (less than 8 nm).
- the hydro-dehydrogenating function plays a critical role in view of the high content of aromatic compounds in these feeds.
- the hydrogenation test of toluene was therefore used to know the interest of catalysts for applications such as those targeted here, in particular the hydrotreatment of residues.
- the catalysts previously described in Examples 2 to 5 are in-situ sulfide-dynamic in the fixed-bed tubular reactor passed through a Microcat-type pilot unit (manufacturer: Vinci Company), the fluids flowing from top to bottom.
- the measurements of hydrogenating activity are carried out immediately after sulphurization under pressure and without re-airing with the hydrocarbon feedstock which was used to sulphurize the catalysts.
- the sulfurization and test load is composed of 5.8% dimethyl disulphide (DMDS), 20% toluene and 74.2% cyclohexane (by weight).
- DMDS dimethyl disulphide
- the sulfurization and test load is composed of 5.8% dimethyl disulphide (DMDS), 20% toluene and 74.2% cyclohexane (by weight).
- the stabilized catalytic activities of equal volumes of catalysts are thus measured in the hydrogenation reaction of toluene.
- Catalyst volume 4 cm 3 (extruded length between 2 and 4 mm)
- Table 5 Comparison of the hydrogenation performance of toluene catalysts according to the invention (A1, B1) and comparison with non-compliant catalysts
- catalytic results show the particular effect of the comalaxing of a metal solution with an alumina according to the preparation method according to the invention, namely a hydrogenation activity at least maintained, with respect to a reference catalyst impregnated with a phase content. equivalent (catalyst E), and much better than for catalysts comalaxed from calcined alumina from non-conformably prepared alumina gel (catalyst A2) or from boehmite (catalyst A3), with a cost less manufacturing and improved ease of preparation.
- Catalyst A2 non-conformably prepared alumina gel
- boehmite catalyst A3
- HDS ((% wt S) load - (% wt S) re this) / (% wt S) load x 100
- the HDM rate is defined as follows:
- HDM (%) ((ppm wt Ni + V) cha rge- (ppm wt Ni + V) reCet ) / (ppm wt Ni + V) cha rge x 100
- Table 8 HDS, HDM performance of catalysts according to the invention (A1, B1) and comparison with non-compliant catalysts A2, A3 and E
- the catalysts A1 and B1 prepared according to the invention were compared in a petroleum residue hydrotreatment test with, in comparison, the performances of the catalyst E.
- the charge consists of a mixture of an atmospheric residue (RA) of Middle East origin (Arabian medium) and a vacuum residue (Arabian Light).
- the corresponding charge is characterized by high contents of Conradson Carbon (14.4% by weight) and Asphaltenes (6.1% by weight) and a high amount of nickel (25 ppm by weight), vanadium (79 ppm by weight). and sulfur (3.90% by weight).
- the full characteristics of these loads are reported in Table 9.
- Table 9 Characteristics of RA AM / RSV AL Loads Used for Testing
- the mixture of RA AM / RSV AL feeds is injected and then the temperature of the test is raised. After a stabilization period of 300 hours, the hydrodesulfurization (HDS) and hydrodemetallation (HDM) performances are recorded.
- HDS hydrodesulfurization
- HDM hydrodemetallation
- Example 7 The performances obtained (Table 1 1) confirm the results of Example 7, that is to say the good performance of the catalysts comalaxés according to the invention compared to reference catalyst, prepared according to dry impregnation methods. However, a gain in preparation cost and greater ease of it is presented by the preparation route according to the invention.
- Table 1 1 HDS, HDM performances of catalysts A1 and B1 compared to
- the impregnation solutions C and D as prepared in Example 1 are kneaded in the presence of the first alumina AI (A1) used for the synthesis of the catalyst A1, according to the protocol described in Example 2, to respectively obtain the catalysts C1 and D1.
- A1 first alumina AI
- Catalysts C1 and D1 have the characteristics reported in Table 12 below.
- the boehmite B powder (A3) prepared in Example 5 is comalaxed with the solution D according to the protocol described in Example 5 to obtain the catalyst D3.
- the reactor is cooled and after a triple stripping of the atmosphere under nitrogen (10 minutes at 1 MPa), the effluent is collected and analyzed by fluorescence X-rays (sulfur and metals) and by simulated distillation (ASTM D7169).
- the HDS ratio is defined as follows:
- HDS (%) ((% wt S) c arge - (wt% S) Rec etie) / (wt% S) cha rge X 100
- the HDM rate is defined as follows:
- HDM (%) ((ppm wt Ni + V) feed - (ppm wt Ni + V) recipe ) / (ppm wt Ni + V) feed x 100
- conversion rate of the 540 ° C + fraction is defined by the following relation:
- HDX 5 4o + (%) ((X540 +) charge- (X540 +) effluent) / (X540 +) load X 100
- Table 15 HDS, HDM performances of the catalysts according to the invention (C1, D1) and comparison with the non-D3-compliant catalyst
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Abstract
Description
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FR1455416A FR3022157B1 (fr) | 2014-06-13 | 2014-06-13 | Catalyseur bimodal a phase active comalaxee, son procede de preparation et son utilisation en hydrotraitement de residus |
PCT/EP2015/062822 WO2015189196A1 (fr) | 2014-06-13 | 2015-06-09 | Catalyseur a porosite bimodal, son procede de preparation par comalaxage de la phase active et son utilisation en hydrotraitement de residus d'hydrocarbures |
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EP15729134.5A Withdrawn EP3154680A1 (fr) | 2014-06-13 | 2015-06-09 | Catalyseur a porosite bimodal, son procede de preparation par comalaxage de la phase active et son utilisation en hydrotraitement de residus d'hydrocarbures |
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US (1) | US20170120229A1 (fr) |
EP (1) | EP3154680A1 (fr) |
CN (1) | CN106922134B (fr) |
FR (1) | FR3022157B1 (fr) |
RU (1) | RU2687084C2 (fr) |
WO (1) | WO2015189196A1 (fr) |
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US10604709B2 (en) | 2017-02-12 | 2020-03-31 | Magēmā Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials |
US20190233741A1 (en) | 2017-02-12 | 2019-08-01 | Magēmā Technology, LLC | Multi-Stage Process and Device for Reducing Environmental Contaminates in Heavy Marine Fuel Oil |
US11788017B2 (en) | 2017-02-12 | 2023-10-17 | Magëmã Technology LLC | Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil |
US20220410124A1 (en) * | 2019-11-29 | 2022-12-29 | Rhodia Operations | Alumina with a particular pore profile |
CN112892612B (zh) * | 2019-12-03 | 2023-01-17 | 中国石化集团金陵石油化工有限责任公司 | 一种用于烃类转化反应的催化剂 |
CN113559889B (zh) * | 2020-04-28 | 2023-09-05 | 中国石油化工股份有限公司 | 改性含磷拟薄水铝石及其制备方法和改性含磷氧化铝及加氢催化剂 |
CN113559875B (zh) * | 2020-04-28 | 2023-09-05 | 中国石油化工股份有限公司 | 加氢催化剂及其制备方法和应用 |
CN113562749B (zh) * | 2020-04-28 | 2023-05-05 | 中国石油化工股份有限公司 | 一种具有双峰孔结构的含磷氧化铝及其制备方法和应用 |
CN111604074B (zh) * | 2020-06-29 | 2022-12-13 | 煤炭科学技术研究院有限公司 | 一种煤焦油双峰孔结构加氢预处理催化剂及其制备方法 |
CN114425383B (zh) * | 2020-10-29 | 2023-08-08 | 中国石油化工股份有限公司 | 含第vb族金属的重油加氢脱金属催化剂及其制备方法和重油加氢处理方法 |
CN114425324B (zh) * | 2020-10-29 | 2023-08-08 | 中国石油化工股份有限公司 | 一种重油加氢脱金属催化剂及应用 |
CN114425352B (zh) * | 2020-10-29 | 2023-08-08 | 中国石油化工股份有限公司 | 一种含卤素的重油加氢催化剂及其制备方法和重油加氢处理方法 |
CN116020498A (zh) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | 加氢催化剂的制备方法、由该方法制备的催化剂及应用 |
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DE4310971A1 (de) * | 1993-04-03 | 1994-10-06 | Huels Chemische Werke Ag | Nickel/Aluminiumoxid-Katalysator, Verfahren zu seiner Herstellung, seine Verwendung sowie Verfahren zur Hydrierung von aromatischen Kohlenwasserstoffen mit Hilfe des Katalysators |
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JP3838660B2 (ja) * | 1994-07-29 | 2006-10-25 | シェブロン ユー.エス.エー. インコーポレイテッド | 低マクロ細孔率の残油転化触媒 |
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2014
- 2014-06-13 FR FR1455416A patent/FR3022157B1/fr not_active Expired - Fee Related
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- 2015-06-09 CN CN201580043355.1A patent/CN106922134B/zh active Active
- 2015-06-09 RU RU2017100960A patent/RU2687084C2/ru active
- 2015-06-09 US US15/318,561 patent/US20170120229A1/en not_active Abandoned
- 2015-06-09 WO PCT/EP2015/062822 patent/WO2015189196A1/fr active Application Filing
- 2015-06-09 EP EP15729134.5A patent/EP3154680A1/fr not_active Withdrawn
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RU2017100960A3 (fr) | 2018-12-21 |
FR3022157B1 (fr) | 2017-09-01 |
CN106922134A (zh) | 2017-07-04 |
FR3022157A1 (fr) | 2015-12-18 |
US20170120229A1 (en) | 2017-05-04 |
CN106922134B (zh) | 2020-05-05 |
WO2015189196A1 (fr) | 2015-12-17 |
RU2017100960A (ru) | 2018-07-16 |
RU2687084C2 (ru) | 2019-05-07 |
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