EP3898899A1 - Procede d'hydrodesulfuration de coupes essence olefinique contenant du soufre mettant en ouvre un catalyseur regenere - Google Patents
Procede d'hydrodesulfuration de coupes essence olefinique contenant du soufre mettant en ouvre un catalyseur regenereInfo
- Publication number
- EP3898899A1 EP3898899A1 EP19813884.4A EP19813884A EP3898899A1 EP 3898899 A1 EP3898899 A1 EP 3898899A1 EP 19813884 A EP19813884 A EP 19813884A EP 3898899 A1 EP3898899 A1 EP 3898899A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- regenerated catalyst
- weight
- hydrodesulfurization
- metal
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 260
- 238000000034 method Methods 0.000 title claims abstract description 80
- 230000008569 process Effects 0.000 title claims abstract description 60
- 239000003502 gasoline Substances 0.000 title claims abstract description 59
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 50
- 239000011593 sulfur Substances 0.000 title claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 67
- 239000002184 metal Substances 0.000 claims abstract description 67
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims description 29
- 230000008929 regeneration Effects 0.000 claims description 28
- 238000011069 regeneration method Methods 0.000 claims description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims description 21
- 239000011574 phosphorus Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 230000003716 rejuvenation Effects 0.000 claims description 20
- 150000001336 alkenes Chemical class 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- 238000005987 sulfurization reaction Methods 0.000 claims description 11
- 238000004523 catalytic cracking Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 235000012245 magnesium oxide Nutrition 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 24
- 230000000694 effects Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000008186 active pharmaceutical agent Substances 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000571 coke Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000000686 essence Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical compound CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 4
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- -1 heterocyclic sulfur compounds Chemical class 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000004230 steam cracking Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- QCDFBFJGMNKBDO-UHFFFAOYSA-N Clioquinol Chemical compound C1=CN=C2C(O)=C(I)C=C(Cl)C2=C1 QCDFBFJGMNKBDO-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229910052804 chromium Inorganic materials 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J35/613—10-100 m2/g
-
- 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
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- 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
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4081—Recycling aspects
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/701—Use of spent catalysts
Definitions
- the present invention relates to a process for hydrodesulfurization of a gasoline cut using a regenerated catalyst.
- Sulfur is a naturally occurring element in crude oil and is therefore present in gasoline and diesel if it is not removed during refining.
- Sulfur in gasoline affects the efficiency of emission reduction systems (catalytic converters) and contributes to air pollution.
- emission reduction systems catalytic converters
- all countries are gradually adopting strict sulfur specifications, the specifications being, for example, 10 ppm (weight) of sulfur in commercial species in Europe, China, United States and in Japan.
- the problem of reducing sulfur contents essentially focuses on gasolines obtained by cracking, whether it is catalytic (FCC Fluid Catalytic Cracking according to English terminology) or non-catalytic (coking, visbreaking, steam cracking), main sulfur precursors in petrol pools.
- a solution, well known to those skilled in the art, for reducing the sulfur content consists in carrying out a hydrotreatment (or hydrodesulfurization) of the hydrocarbon cuts (and in particular essences of catalytic cracking) in the presence of hydrogen and a heterogeneous catalyst .
- this process has the major drawback of causing a very significant drop in the octane number if the catalyst used is not selective enough. This reduction in the octane number is notably linked to the hydrogenation of olefins present in this type of gasoline concomitantly with hydrodesulfurization.
- the hydrodesulfurization of gasolines must therefore make it possible to respond to a double antagonistic constraint: ensuring deep hydrodesulfurization of gasolines and limiting the hydrogenation of the unsaturated compounds present.
- the catalysts used for this type of application are sulfide type catalysts containing an element of group VI B (Cr, Mo, W) and an element of group VIII (Fe, Ru, Os, Co, Rh, Ir, Pd, Ni, Pt).
- a hydrotreatment catalyst When it is used for the hydrotreatment of an oil cut, a hydrotreatment catalyst sees its activity decrease due to the deposition of coke and / or sulfur-containing compounds or containing other heteroelements. Beyond a certain period, its replacement is therefore necessary. In particular, the severity of the sulfur specifications of fuels induces an increase in the frequency of replacement of the catalyst, which leads to an increase in the cost associated with the catalyst and to an increase in the quantity of spent catalyst. To combat these drawbacks, the regeneration (gentle calcination) of hydrodesulfurization catalysts for middle distillates (diesel) or used residues is an economically and ecologically advantageous process because it allows these catalysts to be used again in industrial units rather than to landfill or recycle them (recovery of metals).
- patent application US201 1/0079542 indicates that after regeneration, a typical distillate hydrotreatment catalyst, commercially available, can have a reactivity of about 75% to about 90% of the activity of the fresh catalyst. corresponding.
- the gasoline selective hydrodesulfurization catalysts present different regeneration problems from the diesel hydrotreatment catalysts, in particular because of the need to maintain the selective nature of the catalyst with respect to hydrodesulfurization and hydrogenation reactions. olefins. Indeed, an increase in the selectivity is generally more sought after than an increase or maintenance of activity in the field of species.
- the selective hydrodesulfurization of gasolines if conventional regeneration is possible, the skilled person expects, taking into account what has been demonstrated for hydrotreatment catalysts for middle distillates, that the catalyst has a significantly lower activity than that of fresh catalyst and with a potentially reduced selectivity, due to the changes in structure of the active phase supported on the catalyst during regeneration.
- the invention therefore relates to a process for hydrodesulfurization of an olefinic gasoline cut containing sulfur in which said gasoline cut, hydrogen and a regenerated catalyst are brought into contact, said process being carried out at a temperature between 200 and 400 ° C, a total pressure between 1 and 3 MPa, an hourly volume speed, defined as the volume flow rate of feed relative to the catalyst volume, between 1 and 10 h 1 ; and a hydrogen / gasoline volume ratio of between 100 and 1200 NL / L, said regenerated catalyst being obtained from an at least partially used catalyst resulting from a hydrodesulfurization process of an olefinic gasoline fraction containing sulfur, said catalyst regenerated comprises at least one group VIII metal, at least one group VI B metal and an oxide support.
- the regenerated catalyst has a group VI B metal content of between 1 and 20% by weight of oxide of said group VI B metal relative to the total weight of the regenerated catalyst and a group VIII metal content of between 0.1 and 10% by weight of oxide of said group VIII metal relative to the total weight of the regenerated catalyst.
- the regenerated catalyst also contains phosphorus, the phosphorus content being between 0.3 and 10% by weight expressed as P2O5 relative to the total weight of the regenerated catalyst and the phosphorus / (metal from group VI B) molar ratio. ) in the regenerated catalyst is between 0.1 and 0.7.
- the metal from group VI B is chosen from tungsten and molybdenum and the metal from group VIII is chosen from nickel and cobalt in the regenerated catalyst.
- the regenerated catalyst is characterized by a specific surface of between 20 and 200 m 2 / g, preferably between 30 and 180 m 2 / g.
- the oxide support of the regenerated catalyst is chosen from aluminas, silica, alumina silicas or alternatively titanium or magnesium oxides used alone or in mixture with alumina or silica alumina.
- the regenerated catalyst contains residual carbon at a content of less than 2% by weight relative to the total weight of the regenerated catalyst.
- the regenerated catalyst contains sulfur at a content of less than 5% by weight relative to the total weight of the regenerated catalyst.
- the regenerated catalyst is subjected to a sulfurization step before or during the hydrodesulfurization process.
- the gasoline cut is a gasoline from a catalytic cracking unit.
- the regenerated catalyst comes from a regeneration stage carried out in a flow of gas containing oxygen carried out at a temperature between 350 ° C and 550 ° C.
- the regeneration step is preceded by a deoiling step which comprises bringing into contact an at least partially used catalyst resulting from a hydrodesulfurization process of an olefinic gasoline cut containing sulfur with a stream of inert gas at a temperature between 300 ° C and 400 ° C.
- the regenerated catalyst does not undergo the addition of metals from groups VI B and / or VIII, phosphorus and / or organic compound after the regeneration step.
- the process is carried out in a catalytic bed of a reactor of the fixed bed type containing several catalytic beds, at least one other catalytic bed upstream or downstream of the catalytic bed containing the catalyst regenerated in the direction of circulation of the charge contains at least partly a fresh catalyst and / or a rejuvenated catalyst.
- the process is carried out in at least two reactors in series of the fixed bed type or of the bubbling bed type, at least one of the reactors contains a regenerated catalyst while another reactor contains a fresh catalyst or a rejuvenated catalyst, or a mixture of a regenerated catalyst and a fresh and / or rejuvenated catalyst, and this in any order, with or without removal of at least part of the h ⁇ S from the effluent from the first reactor before treating said effluent in the second reactor.
- the invention therefore relates to a process for hydrodesulfurization of an olefinic gasoline cut containing sulfur in which said gasoline cut, hydrogen and a regenerated catalyst are brought into contact, said process being carried out at a temperature between 200 and 400 ° C, a total pressure between 1 and 3 MPa, an hourly volume velocity, defined as being the volume flow rate of feed relative to the volume of catalyst, between 1 and 10 fr 1 ; and a hydrogen / gasoline volume ratio of between 100 and 1200 NL / L, said regenerated catalyst being obtained from an at least partially used catalyst resulting from a hydrodesulfurization process of an olefinic gasoline fraction containing sulfur, said catalyst regenerated comprises at least one group VIII metal, at least one group VI B metal and an oxide support.
- the hydrodesulfurization process according to the invention makes it possible to transform the organo-sulfur compounds of a gasoline fraction into hydrogen sulfide (H2S) while limiting as much as possible the hydrogenation of the olefins present in said fraction. Load to be processed
- the method according to the invention makes it possible to treat any type of olefinic gasoline cut containing sulfur, such as for example a cut resulting from a coking unit (coking according to English terminology), visbreaking (visbreaking according to English terminology -saxonne), steam cracking (steam cracking according to Anglo-Saxon terminology) or catalytic cracking (FCC, Fluid Catalytic Cracking according to Anglo-Saxon terminology).
- This gasoline can optionally be composed of a significant fraction of gasoline from other production processes such as atmospheric distillation (gasoline from direct distillation (or straight run gasoline according to English terminology) or from conversion (coking or steam cracking gasoline)
- the said charge preferably consists of a gasoline cut coming from a catalytic cracking unit.
- the feedstock is an olefinic petroleum cut containing sulfur, the range of boiling points typically extending from the boiling points of hydrocarbons with 2 or 3 carbon atoms (C2 or C3) up to 260 ° C, preferably from the boiling points of hydrocarbons with 2 or 3 carbon atoms (C2 or C3) up to 220 ° C, more preferably the boiling points of hydrocarbons with 5 carbon atoms up to 220 ° C .
- the method according to the invention can also treat loads having end points lower than those mentioned above, such as for example a C5-180 ° C cut.
- the sulfur content of gasoline cuts produced by catalytic cracking depends on the sulfur content of the feed treated by the FCC, on the presence or not of a pretreatment of the feed of the FCC, as well as on the end point of the chopped off.
- the sulfur contents of an entire gasoline cut in particular those originating from the FCC, are greater than 100 ppm by weight and most of the time greater than 500 ppm by weight.
- the sulfur contents are often greater than 1000 ppm by weight, they can even in certain cases reach values of the order of 4000 to 5000 ppm by weight.
- gasolines from catalytic cracking units contain, on average, between 0.5% and 5% by weight of diolefins, between 20% and 50% by weight of olefins, between 10 ppm and 0.5% weight of sulfur of which generally less than 300 ppm of mercaptans.
- Mercaptans are generally concentrated in the light fractions of petrol and more precisely in the fraction whose boiling temperature is below 120 ° C.
- sulfur compounds present in gasoline can also include heterocyclic sulfur compounds, such as for example thiophenes, alkylthiophenes or benzothiophenes. These heterocyclic compounds, unlike mercaptans, cannot be removed by the extractive processes. These sulfur compounds are therefore removed by hydrotreatment, which leads to their transformation into hydrocarbons and H2S.
- the gasoline treated by the process according to the invention is a heavy gasoline (or HCN for Heavy Cracked Naphtha according to English terminology) resulting from a distillation step aiming to separate a wide section from the gasoline obtained a cracking process (or FRCN for Full Range Cracked Naphtha according to English terminology) into a light essence (LCN for Light Cracked Naphtha according to Anglo-Saxon terminology) and a heavy essence FICN.
- the cutting point of light petrol and heavy petrol is determined in order to limit the sulfur content of the light petrol and to allow its use in the petrol pool preferably without additional post-treatment.
- the large cut FRCN is subjected to a selective hydrogenation step described below before the distillation step.
- the regenerated catalyst used in the process according to the invention comes from an at least partially used catalyst, itself coming from a fresh catalyst, which has been used in a hydrodesulfurization process of an olefin gasoline fraction. containing sulfur under the conditions as described below for a certain period of time and has a significantly lower activity than the fresh catalyst which requires its replacement.
- the fresh catalyst comprises at least one group VIII metal, at least one group VI B metal, an oxide support and optionally phosphorus.
- the fresh catalyst can also further comprise at least one organic compound containing oxygen and / or nitrogen and / or sulfur before sulfurization.
- the fresh catalyst does not comprise phosphorus.
- the preparation of the fresh catalyst is known and generally comprises a step of impregnating the metals of group VIII and group VIB and optionally phosphorus and / or the organic compound on the oxide support, followed by drying, then optional calcination to obtain the active phase in their oxide forms.
- the fresh catalyst is generally subjected to sulfurization in order to form the active species as described below.
- the fresh catalyst has not undergone calcination during its preparation, that is to say that the impregnated catalytic precursor has not been subjected to a heat treatment step at a temperature above 200 ° C under an inert atmosphere or under an oxygen-containing atmosphere, in the presence of water or not.
- the fresh catalyst has undergone a calcination step during its preparation, that is to say that the impregnated catalytic precursor has been subjected to a heat treatment step at a temperature comprised between 200 and 1000 ° C and preferably between 350 and 750 ° C, for a period typically between
- An at least partially used catalyst is understood to mean a catalyst which leaves a hydrodesulfurization process of the olefinic gasoline fraction containing sulfur carried out under the conditions as described below and which has not undergone heat treatment under a gas containing air or oxygen at a temperature above 200 ° C. It may have been deoiled.
- the term "coke” or "carbon” in the present application designates a hydrocarbon-based substance deposited on the surface of the catalyst during its use, strongly cyclized and condensed and having an appearance similar to graphite.
- the at least partially used catalyst contains in particular carbon at a content generally greater than or equal to 2% by weight, preferably between 2 and 10% by weight, and even more preferably between 2.2 and 6% by weight relative to the total weight of at least partially spent catalyst.
- the process for regenerating the at least partially spent catalyst used to generate the regenerated catalyst used in the process according to the invention comprises a step of removing coke and sulfur (regeneration step), generally preceded by a step of oil removal.
- the regeneration is preferably not carried out by keeping the catalyst loaded in the hydrodesulfurization reactor (in situ regeneration).
- the at least partially used catalyst is therefore extracted from the reactor and sent to a regeneration installation in order to perform the regeneration in said installation (ex-situ regeneration).
- the deoiling step generally comprises bringing the at least partially spent catalyst into contact with a stream of inert gas (that is to say essentially free of oxygen), for example in a nitrogen atmosphere or the like. a temperature between 300 ° C and 400 ° C, preferably between 300 ° C and 350 ° C.
- the flow rate of inert gas in terms of flow rate per unit volume of the catalyst is 5 to 150 NL.L Lh 1 for 3 to 7 hours.
- the deoiling step can be carried out using light hydrocarbons, by steam treatment or any other similar process.
- the regeneration step is generally carried out in a flow of gas containing oxygen, generally air.
- the water content is generally between 0 and 50% by weight.
- the gas flow rate in terms of flow rate per unit volume of spent catalyst is preferably from 20 to 2000 NL.L Lh 1 , more preferably from 30 to 1000 NL.L Lh 1 , and in a particularly preferred manner from 40 to 500 NL .L Lh 1 .
- the duration of the regeneration is preferably 2 hours or more, more preferably 2.5 hours or more, and so particularly preferred 3 hours or more.
- the regeneration of the at least partially spent catalyst is generally carried out at a temperature between 350 ° C and 550 ° C, preferably between 360 ° C and 500 ° C.
- the regenerated catalyst obtained in the regeneration step contains residual carbon at a content preferably less than 2% by weight, preferably between 0.1% and 1.9% by weight relative to the total weight of the regenerated catalyst, preferably included between 0.1% and 1.5% by weight and particularly preferably between 0.1% and 1.0% by weight.
- the regenerated catalyst may also not contain residual carbon.
- residual carbon in the present application means carbon (coke) remaining in the regenerated catalyst after regeneration of the at least partially spent catalyst. This residual carbon content in the regenerated catalyst is measured by elemental analysis according to ASTM D5373.
- the regenerated catalyst obtained in the regeneration stage contains residual sulfur (before optional sulfurization) at a content of less than 5% by weight, preferably between 0.1% and 4.9% by weight relative to the total weight of the catalyst regenerated, preferably between 0.1% and 2.0% by weight and particularly preferably between 0.2% and 0.8% by weight.
- the regenerated catalyst may also not contain residual sulfur. This residual sulfur content in the regenerated catalyst is measured by elemental analysis according to ASTM D5373.
- the regenerated catalyst of the process according to the invention is generally composed of the oxide support, of the active phase formed of at least one metal from group VI B and at least one metal from group VIII and optionally phosphorus from the fresh catalyst. .
- the contents of group VI B metal, of group VIII metal and of phosphorus in the fresh, at least partially spent or regenerated catalyst are expressed as oxides after correction of the loss on ignition of the catalyst sample at 550 ° C. for two hours in a muffle oven. Loss on ignition is due to loss of moisture, carbon, sulfur and / or other contaminants. It is determined according to ASTM D7348.
- the contents of group VIB metal, of group VIII metal and optionally of phosphorus in the regenerated catalyst are substantially identical to the contents of the at least partially spent catalyst from which it comes.
- the contents of group VIB metal, group VIII metal and optionally phosphorus in the at least partially spent catalyst are substantially identical to the contents of the fresh catalyst from which it is derived.
- the regenerated catalyst used in the hydrodesulfurization process according to the invention is in particular non-additive, that is to say that it does not contain any organic compound introduced after its regeneration.
- no addition of metals from groups VIB and / or VIII or phosphorus is made after the regeneration step.
- the group VIB metal present in the active phase of the regenerated catalyst is preferably chosen from molybdenum and tungsten.
- the group VIII metal present in the active phase of the regenerated catalyst is preferably chosen from cobalt, nickel and the mixture of these two elements.
- the active phase of the regenerated catalyst is preferably chosen from the group formed by the combination of the elements nickel-molybdenum, cobalt-molybdenum and nickel-cobalt-molybdenum, and very preferably the active phase consists of cobalt and molybdenum.
- the content of group VIII metal is between 0.1 and 10% by weight of oxide of group VIII metal relative to the total weight of the regenerated catalyst, preferably between 0.6 and 8% by weight, preferably between 2 and 7%, very preferably between 2 and 6% by weight and even more preferably between 2.5 and 6% by weight.
- the group VIB metal content is between 1 and 20% by weight of group VIB metal oxide relative to the total weight of the regenerated catalyst, preferably between 2 and 18% by weight, very preferably between 3 and 10% oxide weight.
- the group VIII metal to group VIB metal molar ratio of the regenerated catalyst is generally between 0.15 and 1.15, preferably between 0.19 and 0.8.
- the regenerated catalyst has a density of group VIB metal, expressed in number of atoms of said metal per unit area of catalyst, which is between 0.5 and 30 atoms of group VIB metal per nm 2 of catalyst. , preferably between 2 and 25, even more preferably between 3 and 15.
- the density of group VIB metal expressed as the number of group VIB metal atoms per unit area of the catalyst (number of metal atoms of group VIB per nm 2 of catalyst) is calculated for example from the following relationship:
- N A Number of Avogadro equal to 6,022.10 23 ;
- M M molar mass of the group VIB metal (for example 95.94 g / mol for molybdenum).
- M M molar mass of the group VIB metal (for example 95.94 g / mol for molybdenum).
- the catalyst contains 20% by weight of molybdenum oxide M0O3 (i.e. 13.33% by weight of Mo) and has a specific surface of 100 m 2 / g, the density d (Mo) is equal to :
- the regenerated catalyst of the process according to the invention may also have a phosphorus content generally between 0.3 and 10% by weight of P2O5 relative to the total weight of catalyst, preferably between 0.5 and 5% by weight , very preferably between 1 and 3% by weight.
- the phosphorus / (group VIB metal) molar ratio is generally between 0.1 and 0.7, preferably between 0.2 and 0.6, when the phosphorus is present.
- the regenerated catalyst of the process according to the invention may have, in addition to coke and sulfur, also a low content of contaminants originating from the feed treated by the fresh catalyst from which it originates, such as silicon, arsenic or chlorine.
- the silicon content (in addition to that possibly present on the fresh catalyst) is less than 2% by weight and very preferably less than 1% by weight relative to the total weight of the regenerated catalyst.
- the arsenic content is less than 2000 ppm by weight and very preferably less than 500 ppm by weight relative to the total weight of the regenerated catalyst.
- the chlorine content is less than 2000 ppm by weight and very preferably less than 500 ppm by weight relative to the total weight of the regenerated catalyst.
- the regenerated catalyst is not contaminated, that is to say contains a content of less than 100 ppm by weight of silicon (in addition to that possibly present on the fresh catalyst), less than 50 ppm by weight of arsenic , and less than 50 ppm by weight of chlorine relative to the total weight of the regenerated catalyst.
- the regenerated catalyst of the process according to the invention in oxide form, is characterized by a specific surface of between 5 and 400 m 2 / g, preferably between 10 and 250 m 2 / g, preferably between 20 and 200 m 2 / g, very preferably between 30 and 180 m 2 / g.
- the specific surface is determined in the present invention by the BET method according to standard ASTM D3663, as described in the work Rouquerol F .; Rouquerol J .; Singh K. “Adsorption by Powders & Porous So / ids; Princip / e, methodology and applications ”, Academy Press, 1999, for example using an Autopore III TM model device from the Microméritics TM brand.
- the pore volume of the regenerated catalyst is generally between 0.4 cm 3 / g and 1.3 cm 3 / g, preferably between 0.6 cm 3 / g and 1.1 cm 3 / g.
- the total pore volume is measured by mercury porosimetry according to standard ASTM D4284 with a wetting angle of 140 °, as described in the same work.
- the packed filling density (DRT) of the regenerated catalyst is generally between 0.4 and 0.7 g / ml, preferably between 0.45 and 0.69 g / ml.
- the measurement of DRT consists in introducing the catalyst into a test tube whose volume has previously been determined and then, by vibration, packing it until a constant volume is obtained.
- the apparent density of the packed product is calculated by comparing the mass introduced and the volume occupied after packing.
- This catalyst can be in the form of small diameter, cylindrical or multi-lobed extrudates (three-lobed, four-lobed, etc.), or spheres.
- the oxide support of the regenerated catalyst is usually a porous solid chosen from the group consisting of: aluminas, silica, silica alumina or alternatively titanium or magnesium oxides used alone or as a mixture with alumina or silica alumina. It is preferably chosen from the group consisting of silica, the family of transition aluminas and alumina silicas, very preferably, the oxide support consists essentially of at least one transition alumina, that is to say saying that it comprises at least 51% by weight, preferably at least 60% by weight, very preferably at least 80% by weight, or even at least 90% by weight of transition alumina. It preferably consists only of a transition alumina.
- the oxide support of the regenerated catalyst of the process according to the invention is a “high temperature” transition alumina, that is to say which contains aluminas of theta, delta, kappa or alpha phase, alone or as a mixture and an amount of less than 20% of alumina of gamma, chi or eta phase.
- the hydrodesulfurization process according to the invention consists in bringing the olefinic gasoline fraction containing sulfur into contact with the regenerated catalyst and hydrogen under the following conditions:
- - 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
- WH hourly volume speed
- the hydrodesulfurization 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 using at least two reactors in series, it is possible to provide a device for removing H2S from the effluent from the first hydrodesulfurization reactor before treating said effluent in the second hydrodesulfurization reactor.
- the hydrodesulfurization process according to the invention is carried out in the presence of a regenerated catalyst. It can also be carried out in the presence of a mixture of a regenerated catalyst and a fresh catalyst or a rejuvenated catalyst.
- a fresh or rejuvenated catalyst when present, it comprises at least one group VIII metal, at least one group VI B metal and an oxide support, and optionally phosphorus and / or an organic compound as described above .
- the active phase and the support of the fresh or rejuvenated catalyst may or may not be identical to the active phase and the support of the regenerated catalyst.
- the active phase and the support of the fresh catalyst may or may not be identical to the active phase and the support of the rejuvenated catalyst.
- the hydrodesulfurization process When the hydrodesulfurization process is carried out in the presence of a regenerated catalyst and a fresh or rejuvenated catalyst, it can be carried out in a reactor of the fixed bed type containing several catalytic beds. In this case, and according to a first variant, a catalytic bed containing the fresh or rejuvenated catalyst can precede a catalytic bed containing the regenerated catalyst in the direction of the charge circulation.
- a catalytic bed containing the regenerated catalyst can precede a catalytic bed containing the fresh or rejuvenated catalyst in the direction of the charge circulation.
- a catalytic bed can contain a mixture of a regenerated catalyst and a fresh catalyst and / or a rejuvenated catalyst.
- the operating conditions are those described above. They are generally identical in the various catalytic beds except for the temperature which generally increases in a catalytic bed following the exothermic hydrodesulfurization reactions.
- one reactor may comprise a regenerated catalyst while another reactor can comprise a fresh or rejuvenated catalyst, or a mixture of a regenerated catalyst and a fresh and / or rejuvenated catalyst, and this in any order.
- One can provide a device for removing the hhS from the effluent from the first hydrodesulfurization reactor before treating said effluent in the second reactor.
- gasoline cut is subjected to a selective hydrogenation step before the hydrodesulfurization process according to the invention.
- the gasoline treated by the hydrodesulfurization process according to the invention is a heavy gasoline resulting from a distillation step aiming to separate a wide cut from the gasoline resulting from a cracking process (or FRCN for Full Range Cracked Naphtha according to Anglo-Saxon terminology) in a light essence and a heavy essence.
- the large cut FRCN is subjected to a selective hydrogenation step described below before the distillation step.
- Said FRCN cut is previously treated in the presence of hydrogen and of a selective hydrogenation catalyst so as to at least partially hydrogenate the diolefins and carry out a weighting reaction for part of the mercaptan compounds (RSH) present in the feed. as thioethers, by reaction with olefins.
- RSH mercaptan compounds
- the large cut FRCN is sent to a selective hydrogenation catalytic reactor containing at least one fixed or mobile bed of catalyst for the selective hydrogenation of diolefins and the weighting of mercaptans.
- the reaction for the selective hydrogenation of diolefins and the weighting down of mercaptans is preferably carried out on a sulfur catalyst comprising at least one group VIII metal and optionally at least one group VI B metal and an oxide support.
- the group VIII metal is preferably chosen from nickel and cobalt and in particular nickel.
- the group VIB metal when it is present, is preferably chosen from molybdenum and tungsten and very preferably molybdenum.
- the catalyst oxide support is preferably chosen from alumina, nickel aluminate, silica, silicon carbide, or a mixture of these oxides.
- Alumina is preferably used and even more preferably high-purity alumina.
- the selective hydrogenation catalyst contains nickel at a content by weight of nickel oxide (in NiO form) of between 1 and 12%, and molybdenum at a content by weight of molybdenum oxide. (in M0O3 form) of between 6% and 18% relative to the total weight of the catalyst and a nickel / molybdenum molar ratio of between 0.3 and 2.5, the metals being deposited on a support consisting of alumina and the sulfurization rate of the metals constituting the catalyst being greater than 50%.
- the gasoline is brought into contact with the catalyst at a temperature between 50 ° C and 250 ° C, and preferably between 80 ° C and 220 ° C, and even more preferably between 90 ° C and 200 ° C, with a liquid space speed (LHSV) of between 0.5 h 1 and 20 h 1 , the unit of liquid space speed being the liter load per liter of catalyst per hour (L / L. h).
- the pressure is between 0.4 MPa and 5 MPa, preferably between 0.6 and 4 MPa and even more preferably between 1 and 2 MPa.
- the optional selective hydrogenation stage is typically carried out with a gasoline hV charge ratio of between 2 and 100 Nm 3 of hydrogen per m 3 of charge, preferably between 3 and 30 Nm 3 of hydrogen per m 3 of charge.
- the regenerated catalyst of the process according to the invention Before the contact with the feed to be treated, the regenerated catalyst of the process according to the invention generally undergoes a sulfurization step.
- the sulfurization is preferably carried out in a sulforeductive medium, that is to say in the presence of hhS and of hydrogen, in order to transform the metal oxides into sulphides such as, for example, SO 2 and CogSs.
- Sulfurization is carried out by injecting a flux containing hhS and hydrogen onto the catalyst, or else a sulfur-containing compound capable of decomposing into H2S in the presence of the catalyst and hydrogen.
- Polysulfides such as dimethyldisulfide (DM DS) are hhS precursors commonly used to sulfurize catalysts. Sulfur can also come from the feed.
- DM DS dimethyldisulfide
- the temperature is adjusted so that the hhS reacts with the metal oxides to form metal sulfides.
- This sulphurization can be carried out in situ or ex situ (inside or outside the reactor) of the reactor of the process according to the invention at temperatures between 200 and 600 ° C, and more preferably between 300 ° C and 500 ° C. Examples
- the support for catalyst A is a transition alumina with a specific surface of 140 m 2 / g and a pore volume of 1.0 cm 3 / g.
- Catalyst A is prepared by dry impregnation of the support with an aqueous solution of ammonium heptamolybdate and cobalt nitrate, the volume of the solution containing the metal precursors being strictly equal to the pore volume of the mass of support. The concentration of metal precursors in aqueous solution is adjusted so as to obtain the desired weight percentage of molybdenum, cobalt and phosphorus on the final catalyst. After dry impregnation on the support, the catalyst is left to mature for 1 h 30 in an enclosure saturated with water, air dried in an oven at 90 ° C for 12 hours and then calcined in air at 450 ° C for 2 hours.
- the catalyst A obtained after calcination has a content of 15.5% by weight of molybdenum (equivalent MOO3) and 3.4% by weight of cobalt (equivalent CoO). This catalyst has a Co / Mo atomic ratio of 0.42.
- Catalyst A is used to desulfurize a catalytic cracking gasoline (FCC), the characteristics of which are collated in Table 1.
- FCC catalytic cracking gasoline
- the catalyst is treated beforehand at 350 ° C. with a feed containing 4% by weight of sulfur in the form of DM DS (dimethyldisulfide) to ensure the sulfurization of the oxide phases.
- DM DS dimethyldisulfide
- the spent catalyst A is taken from the reactor after the hydrodesulfurization of a catalytic cracking gasoline (FCC) described above.
- FCC catalytic cracking gasoline
- the spent catalyst A is then washed with toluene in a Soxhlet for 7 hours at 250 ° C. (deoiling).
- a model charge representative of a catalytic cracking gasoline (FCC) containing 10% by weight of 2,3-dimethylbut-2-ene and 0.33% by weight of 3-methylthiophene (i.e. 1000 ppm by weight of sulfur in the charge) is used for the evaluation of the catalytic performances of the various catalysts.
- the solvent used is heptane.
- the catalyst Prior to the HDS reaction, the catalyst is sulfurized in situ at 350 ° C for 2 hours under a stream of hydrogen containing 15 mol% of H2S at atmospheric pressure. Each of the catalysts is placed successively in said reactor. Samples are taken at different time intervals and are analyzed by gas chromatography in order to observe the disappearance of the reagents and the formation of the products.
- the catalytic performances of the catalysts are evaluated in terms of catalytic activity and selectivity.
- the hydrodesulfurization activity (H DS) is expressed from the rate constant for the HDS reaction of 3-methylthiophene (kHDS), normalized by the volume of catalyst introduced and assuming order 1 kinetics with respect to to the sulfur compound.
- the olefin hydrogenation activity (HydO) is expressed from the rate constant of the hydrogenation reaction of 2,3-dimethylbut-2-ene, normalized by the volume of catalyst introduced and assuming kinetics of order 1 compared to the olefin.
- the selectivity of the catalyst is expressed by the normalized ratio of the rate constants kHDS / kHydO.
- the kHDS / kHydO ratio will be higher the more selective the catalyst.
- the values obtained are normalized by taking catalyst A as a reference (relative H DS activity and relative selectivity equal to 100). The performances are therefore the relative H DS activity and the relative selectivity (Table 2).
- the regenerated catalyst B has an activity similar to fresh catalyst A and an improved selectivity in hydrodesulfurization compared to the hydrogenation of olefins compared to comparative catalyst A (fresh calcined).
- This improvement in the selectivity of the catalysts is particularly advantageous in the case of implementation in a process for the hydrodesulfurization of gasoline containing olefins for which it is sought to limit as much as possible the loss of octane due to the hydrogenation of the olefins.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1873238A FR3090005B1 (fr) | 2018-12-18 | 2018-12-18 | Procédé d’hydrodésulfuration de coupes essence oléfinique contenant du soufre mettant en œuvre un catalyseur régénéré. |
PCT/EP2019/084438 WO2020126677A1 (fr) | 2018-12-18 | 2019-12-10 | Procede d'hydrodesulfuration de coupes essence olefinique contenant du soufre mettant en œuvre un catalyseur regenere |
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Publication Number | Publication Date |
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EP3898899A1 true EP3898899A1 (fr) | 2021-10-27 |
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ID=66530249
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EP19813884.4A Pending EP3898899A1 (fr) | 2018-12-18 | 2019-12-10 | Procede d'hydrodesulfuration de coupes essence olefinique contenant du soufre mettant en ouvre un catalyseur regenere |
Country Status (9)
Country | Link |
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US (1) | US11795405B2 (fr) |
EP (1) | EP3898899A1 (fr) |
JP (1) | JP7510936B2 (fr) |
KR (1) | KR20210102256A (fr) |
CN (1) | CN113383056A (fr) |
BR (1) | BR112021008475A2 (fr) |
FR (1) | FR3090005B1 (fr) |
MX (1) | MX2021005795A (fr) |
WO (1) | WO2020126677A1 (fr) |
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FR3090005B1 (fr) | 2018-12-18 | 2021-07-30 | Ifp Energies Now | Procédé d’hydrodésulfuration de coupes essence oléfinique contenant du soufre mettant en œuvre un catalyseur régénéré. |
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AU513580B2 (en) | 1976-03-04 | 1980-12-11 | Amoco Corporation | The selective desulfurization of cracked naphthas |
US4774220A (en) | 1987-03-02 | 1988-09-27 | Texaco, Inc. | Lithium-doped gamma-alumina supported cobalt-molybdenum catalyst |
JP3802106B2 (ja) * | 1995-06-08 | 2006-07-26 | 日本ケッチェン株式会社 | 炭化水素油の水素化処理触媒とその製造方法およびその活性化方法 |
US5985136A (en) | 1998-06-18 | 1999-11-16 | Exxon Research And Engineering Co. | Two stage hydrodesulfurization process |
US6236723B1 (en) | 1998-06-29 | 2001-05-22 | Aspect Communications | Computer/telephony integration logging application |
FR2797639B1 (fr) | 1999-08-19 | 2001-09-21 | Inst Francais Du Petrole | Procede de production d'essences a faible teneur en soufre |
FR2811328B1 (fr) | 2000-07-06 | 2002-08-23 | Inst Francais Du Petrole | Procede comprenant deux etapes d'hydrodesulfuration d'essence et une elimination intermediaire de l'h2s forme au cours de la premiere etape |
DE60134140D1 (de) * | 2000-07-12 | 2008-07-03 | Albemarle Netherlands Bv | Verfahren zur herstellung eines ein additiv enthaltenden mischmetallkatalysators |
US7105140B2 (en) | 2002-03-04 | 2006-09-12 | Conocophillips Company | Desulfurization compositions |
FR2850299B1 (fr) | 2003-01-29 | 2006-12-01 | Inst Francais Du Petrole | Catalyseurs partiellement cokes utilisables dans l'hydrotraitement des coupes contenant des composes soufres et des olefines |
BRPI0414865B1 (pt) * | 2003-10-03 | 2014-07-08 | Albemarle Netherlands Bv | Processo para ativação de um catalisador de hidrotratamento |
US7820579B2 (en) * | 2004-01-20 | 2010-10-26 | Shell Oil Company | Method of restoring catalytic activity to a spent hydrotreating catalyst, the resulting restored catalyst, and a method of hydroprocessing |
CN101374598B (zh) | 2006-01-17 | 2014-05-28 | 埃克森美孚研究工程公司 | 用于石脑油加氢脱硫的具有高温氧化铝载体的选择性催化剂 |
JP5674276B2 (ja) | 2006-01-17 | 2015-02-25 | エクソンモービル リサーチ アンド エンジニアリング カンパニーExxon Research And Engineering Company | ナフサ水素化脱硫のための選択的触媒 |
FR2904242B1 (fr) | 2006-07-28 | 2012-09-28 | Inst Francais Du Petrole | Procede d'hydrodesulfuration de coupes contenant des composes soufres et des olefines en presence d'un catalyseur supporte comprenant des elements des groupes viii et vib |
US7906447B2 (en) * | 2008-04-11 | 2011-03-15 | Exxonmobil Research And Engineering Company | Regeneration and rejuvenation of supported hydroprocessing catalysts |
JP4610664B1 (ja) | 2009-07-09 | 2011-01-12 | Jx日鉱日石エネルギー株式会社 | 再生水素化処理用触媒の製造方法及び石油製品の製造方法 |
WO2011043936A2 (fr) | 2009-10-05 | 2011-04-14 | Exxonmobil Research And Engineering Company | Empilement d'un catalyseur de faible activité ou régénéré sur un catalyseur d'activité plus élevée |
CN102463127B (zh) | 2010-11-04 | 2014-05-21 | 中国石油化工股份有限公司 | 一种催化剂再生活化方法 |
FR2994864B1 (fr) * | 2012-09-05 | 2015-08-21 | IFP Energies Nouvelles | Procede de sulfuration d'un catalyseur d'hydrodesulfuration |
CN103920541A (zh) * | 2013-01-16 | 2014-07-16 | 中国石油化工集团公司 | 一种沸腾床加氢催化剂脱油***及其方法 |
FR3035600B1 (fr) | 2015-04-30 | 2017-04-21 | Ifp Energies Now | Catalyseur a base d'acide y-cetovalerique et son utilisation dans un procede d'hydrotraitement et/ou d'hydrocraquage |
FR3049475B1 (fr) | 2016-03-30 | 2018-04-06 | IFP Energies Nouvelles | Catalyseur a base de catecholamine et son utilisation dans un procede d'hydrotraitement et/ou d'hydrocraquage |
EP3315195A1 (fr) * | 2016-10-28 | 2018-05-02 | Repsol, S.A. | Procédés d'activation d'un catalyseur d'hydrotraitement |
FR3061038B1 (fr) * | 2016-12-22 | 2021-05-21 | Ifp Energies Now | Procede de sulfuration d'un catalyseur a partir d'une coupe d'hydrocarbures prealablement hydrotraitee et d'un compose soufre. |
FR3090005B1 (fr) | 2018-12-18 | 2021-07-30 | Ifp Energies Now | Procédé d’hydrodésulfuration de coupes essence oléfinique contenant du soufre mettant en œuvre un catalyseur régénéré. |
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2018
- 2018-12-18 FR FR1873238A patent/FR3090005B1/fr active Active
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- 2019-12-10 BR BR112021008475-4A patent/BR112021008475A2/pt active Search and Examination
- 2019-12-10 MX MX2021005795A patent/MX2021005795A/es unknown
- 2019-12-10 US US17/414,437 patent/US11795405B2/en active Active
- 2019-12-10 JP JP2021534668A patent/JP7510936B2/ja active Active
- 2019-12-10 CN CN201980084701.9A patent/CN113383056A/zh active Pending
- 2019-12-10 KR KR1020217017927A patent/KR20210102256A/ko unknown
- 2019-12-10 EP EP19813884.4A patent/EP3898899A1/fr active Pending
- 2019-12-10 WO PCT/EP2019/084438 patent/WO2020126677A1/fr unknown
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MX2021005795A (es) | 2021-06-30 |
JP7510936B2 (ja) | 2024-07-04 |
JP2022513952A (ja) | 2022-02-09 |
KR20210102256A (ko) | 2021-08-19 |
FR3090005A1 (fr) | 2020-06-19 |
US20220081627A1 (en) | 2022-03-17 |
FR3090005B1 (fr) | 2021-07-30 |
WO2020126677A1 (fr) | 2020-06-25 |
CN113383056A (zh) | 2021-09-10 |
US11795405B2 (en) | 2023-10-24 |
BR112021008475A2 (pt) | 2021-08-03 |
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