EP3583192B1 - Désulfuration oxydative de fractions d'huiles et gestion des sulfones à l'aide d'un craquage catalytique fluide - Google Patents
Désulfuration oxydative de fractions d'huiles et gestion des sulfones à l'aide d'un craquage catalytique fluide Download PDFInfo
- Publication number
- EP3583192B1 EP3583192B1 EP18708818.2A EP18708818A EP3583192B1 EP 3583192 B1 EP3583192 B1 EP 3583192B1 EP 18708818 A EP18708818 A EP 18708818A EP 3583192 B1 EP3583192 B1 EP 3583192B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stream
- oxidized
- compounds
- hydrocarbon
- sulfur
- 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.)
- Active
Links
- 230000001590 oxidative effect Effects 0.000 title claims description 21
- 238000006477 desulfuration reaction Methods 0.000 title description 8
- 230000023556 desulfurization Effects 0.000 title description 8
- 150000003457 sulfones Chemical class 0.000 title description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 137
- 150000002430 hydrocarbons Chemical class 0.000 claims description 134
- 239000004215 Carbon black (E152) Substances 0.000 claims description 102
- 239000003054 catalyst Substances 0.000 claims description 65
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 62
- 229910052717 sulfur Inorganic materials 0.000 claims description 60
- 239000011593 sulfur Substances 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 58
- 239000003921 oil Substances 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 238000007254 oxidation reaction Methods 0.000 claims description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 40
- 230000003647 oxidation Effects 0.000 claims description 40
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 39
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 39
- 150000003464 sulfur compounds Chemical class 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 28
- 238000000605 extraction Methods 0.000 claims description 28
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000002798 polar solvent Substances 0.000 claims description 21
- 239000012263 liquid product Substances 0.000 claims description 20
- 239000007800 oxidant agent Substances 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 18
- 238000001179 sorption measurement Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 239000003463 adsorbent Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 238000000638 solvent extraction Methods 0.000 claims description 6
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002432 hydroperoxides Chemical class 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 229910016287 MxOy Inorganic materials 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000010426 asphalt Substances 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 150000002019 disulfides Chemical class 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000003079 shale oil Substances 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical class O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- 238000005336 cracking Methods 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 32
- 238000009835 boiling Methods 0.000 description 19
- 239000010779 crude oil Substances 0.000 description 18
- 239000000446 fuel Substances 0.000 description 16
- -1 aromatic sulfur compounds Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003502 gasoline Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000000571 coke Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000003915 liquefied petroleum gas Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000003209 petroleum derivative Substances 0.000 description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 125000001741 organic sulfur group Chemical group 0.000 description 3
- 229910052815 sulfur oxide Inorganic materials 0.000 description 3
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 2
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 229910020350 Na2WO4 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000004967 organic peroxy acids Chemical class 0.000 description 2
- 239000013520 petroleum-based product Substances 0.000 description 2
- 229920006112 polar polymer Polymers 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical class C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZDGGJQMSELMHLK-UHFFFAOYSA-N m-Trifluoromethylhippuric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC(C(F)(F)F)=C1 ZDGGJQMSELMHLK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 239000004058 oil shale Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003716 rejuvenation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/16—Oxygen-containing compounds
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/20—Nitrogen-containing compounds
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/22—Compounds containing sulfur, selenium, or tellurium
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/27—Organic compounds not provided for in a single one of groups C10G21/14 - C10G21/26
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/28—Recovery of used solvent
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
-
- 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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
-
- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/44—Solvents
Definitions
- Crude oil is the world's main source of hydrocarbons used as fuel and petrochemical feedstock.
- petroleum and petroleum-based products are also a major source for air and water pollution today.
- the exact compositions of natural petroleum or crude oils vary significantly, all crude oils contain some measurable amount of sulfur compounds and most crude oils also contain some measurable amount of nitrogen compounds.
- crude oils may also contain oxygen, but the oxygen content of most crude is low.
- sulfur concentrations in crude oils are less than about 5 percent by weight (wt%), with most crude oils having sulfur concentrations in the range from about 0.5 to about 1.5 wt%.
- Nitrogen concentrations of most crude oils are usually less than 0.2 wt%, but can be as high as 1.6 wt%.
- motor gasoline fuel is regulated to have a maximum total sulfur content of less than 10 parts per million weight (ppmw) sulfur.
- Crude oils are refined in oil refineries to produce transportation fuels and petrochemical feedstocks.
- fuels for transportation are produced by processing and blending of distilled fractions from the crude oil to meet the particular end use specifications. Because most of the crudes generally available today have high concentrations of sulfur, the distilled fractions typically require desulfurization to yield products, which meet various performance specifications, environmental standards, or both.
- the sulfur-containing organic compounds present in crude oils and resulting refined fuels can be a major source of environmental pollution.
- the sulfur compounds are typically converted to sulfur oxides during the combustion process, which in turn can produce sulfur oxyacids and contribute to particulate emissions.
- One method for reducing particulate emissions includes the addition of various oxygenated fuel blending compounds, compounds that contain few or no carbon-to-carbon chemical bonds, such as methanol and dimethyl ether, or both. Most of these compounds, however, suffer in that they can have high vapor pressures, are nearly insoluble in diesel fuel, or have poor ignition quality, as indicated by their cetane numbers, or combinations thereof.
- Diesel fuels that have been treated by chemical hydrotreating or hydrogenation to reduce their sulfur and aromatics contents can have a reduced fuel lubricity, which in turn can cause excessive wear of fuel pumps, injectors, and other moving parts that come in contact with the fuel under high pressures.
- middle distillates that is, a distillate fraction that nominally boils in the range of about 180-370°C
- the middle distillate fraction typically includes between about 1 and 3 wt% sulfur. Allowable sulfur concentration in middle distillate fractions were reduced to 5-50 ppmw levels from 3000 ppmw level since 1993 in Europe and United States.
- refiners In order to comply with the increasingly stringent regulations for ultra-low sulfur content fuels, refiners must make fuels having even lower sulfur levels at the refinery gate so that they can meet the specifications after blending.
- Low pressure conventional hydrodesulfurization (HDS) processes can be used to remove a major portion of the sulfur from petroleum distillates for the blending of refinery transportation fuels. These units, however, are not efficient to remove sulfur from compounds at mild conditions (that is, up to about 30 bar pressure), when the sulfur atom is sterically hindered as in multi-ring aromatic sulfur compounds. This is particularly true where the sulfur heteroatom is hindered by two alkyl groups (for example, 4,6-dimethyldibenzothiophene). Because of the difficulty in the removal, the hindered dibenzothiophenes predominate at low sulfur levels, such as 50 ppmw to 100 ppmw.
- Severe operating conditions for example, high hydrogen partial pressure, high temperature, or high catalyst volume
- Increasing the hydrogen partial pressure can only be achieved by increasing the recycle gas purity, or new grassroots units must be designed, which can be a very a costly option.
- the use of severe operating conditions typically results in decreased yield, lower catalyst life cycle, and product quality deterioration (for example, color), and therefore are typically sought to be avoided.
- US 2012/055844 A1 discloses a method and apparatus for recovering components from a hydrocarbon feedstock.
- the method includes the steps of (a) supplying a hydrocarbon feedstock to an oxidation reactor, wherein the hydrocarbon feedstock is oxidized in the presence of a catalyst under conditions sufficient to selectively oxidize sulfur compounds and nitrogen compounds present in the hydrocarbon feedstock; (b) separating the hydrocarbons, the oxidized sulfur compounds, and the oxidized nitrogen compounds by solvent extraction; (c) collecting a residue stream that includes the oxidized sulfur compounds and the oxidized nitrogen compounds; and (d) supplying the residue stream to a fluid catalytic cracking unit.
- a method of recovering components from a hydrocarbon feedstock includes supplying the hydrocarbon feedstock to an oxidation reactor, wherein the hydrocarbon feedstock includes sulfur compounds and nitrogen compounds, and contacting the hydrocarbon feedstock with an oxidizing agent in the oxidation reactor under conditions sufficient to selectively oxidize sulfur compounds and nitrogen compounds present in the hydrocarbon feedstock to produce an oxidized hydrocarbon stream that includes hydrocarbons, oxidized sulfur compounds, and oxidized nitrogen compounds.
- the method further includes separating the hydrocarbons, the oxidized sulfur compounds, and the oxidized nitrogen compounds in the oxidized hydrocarbon stream by solvent extraction with a polar solvent to produce an extracted hydrocarbon stream and a mixed stream, the mixed stream including the polar solvent, the oxidized sulfur compounds, and the oxidized nitrogen compounds, wherein the extracted hydrocarbon stream has a lower concentration of sulfur compounds and nitrogen compounds than the hydrocarbon feedstock.
- the method further includes separating the mixed stream using a distillation column into a first recovered polar solvent stream and a first residue stream, wherein the first residue stream including the oxidized sulfur compounds and the oxidized nitrogen compounds, and supplying the first residue stream to a fluid catalytic cracking unit.
- the method further includes feeding the first residue stream through a hydrotreater prior to supplying the first residue stream to the fluid catalytic cracking unit.
- the fluid catalytic cracking unit is operative to catalytically crack the oxidized sulfur and the oxidized nitrogen to produce regenerated catalyst and gaseous and liquid products and allow for recovery of hydrocarbons from the first residue stream.
- the method further includes recycling at least a portion of the liquid products to the oxidation reactor to selectively oxidize sulfur compounds in the liquid products, the portion of the liquid products comprising at least one of light cycle oils and heavy cycle oils.
- the method further includes supplying the extracted hydrocarbon stream to a stripper to produce a second recovered polar solvent stream and a stripped hydrocarbon stream, and recycling the first recovered polar solvent stream and the second polar solvent stream to an extraction vessel for the separating the hydrocarbons, the oxidized sulfur compounds, and the oxidized nitrogen compounds in the oxidized hydrocarbon stream.
- the method further includes recycling a portion of the regenerated catalyst with a fluid catalytic cracking feedstream to the fluid catalytic cracking unit, wherein the recycling further includes catalytically cracking the fluid catalytic cracking feedstream with the portion of the regenerated catalyst to recover the hydrocarbons from the first residue stream.
- the oxidant is selected from the group consisting of air, oxygen, peroxides, hydroperoxides, ozone, nitrogen oxides compounds, and combinations thereof.
- the contacting the hydrocarbon feedstock with an oxidizing agent occurs in the presence of a catalyst including a metal oxide having the formula M x O y , wherein M is an element selected from Groups IVB, VB, and VIB of the periodic table.
- the sulfur compounds include sulfides, disulfides, mercaptans, thiophene, benzothiophene, dibenzothiophene, alkyl derivatives of dibenzothiophene, or combinations thereof.
- the oxidation reactor is maintained at a temperature of between about 20 and about 350°C and at a pressure of between about 1 and about 10 bars.
- the ratio of the oxidant to sulfur compounds present in the hydrocarbon feedstock is between about 4:1 and about 10:1.
- the polar solvent has a Hildebrandt value of greater than about 19.
- the polar solvent is selected from the group consisting of acetone, carbon disulfide, pyridine, dimethyl sulfoxide, n-propanol, ethanol, n-butanol, propylene glycol, ethylene glycol, dimethlyformamide, acetonitrile, methanol and combinations thereof.
- the polar solvent is acetonitrile.
- the polar solvent is methanol.
- the solvent extraction is conducted at a temperature of between about 20°C and about 60°C and at a pressure of between about 1 and about 10 bars.
- the method further includes supplying the extracted hydrocarbon stream to an adsorption column, wherein the adsorption column is charged with an adsorbent suitable for the removal of oxidized compounds present in the extracted hydrocarbon stream, the adsorption column producing a high purity hydrocarbon product stream and a second residue stream, the second residue stream including a portion of the oxidized compounds.
- the method further includes supplying the second residue stream to the fluid catalytic cracking unit.
- the adsorbent is selected from the group consisting of activated carbon, silica gel, alumina, natural clays, silica-alumina, zeolites, and combinations of the same.
- the adsorbent is a polymer coated support, wherein the support has a high surface area and is selected from the group consisting of silica gel, alumina, silica-alumina, zeolites, and activated carbon, and the polymer is selected from the group consisting of polysulfone, polyacrylonitrile, polystyrene, polyester terephthalate, polyurethane, and combinations of the same.
- the supplying the first residue stream to the fluid catalytic cracking unit further includes contacting the first residue stream with a fluid catalytic cracking feedstream in the presence of a catalyst to catalytically crack the fluid catalytic cracking feedstream to recover hydrocarbons from the first residue stream.
- the fluid catalytic cracking feedstream includes vacuum gas oil (VGO), reduced crude, demetalized oil, whole crude, cracked shale oil, liquefied coal, cracked bitumen, heavy coker gas oils, light cycle oils, heavy cycle oils, clarified slurry oils, or combinations thereof.
- VGO vacuum gas oil
- Embodiments address known problems associated with conventional methods of upgrading and recovering compounds from a hydrocarbon feedstock, particularly the desulfurization, denitrogenation, or both, of hydrocarbon feedstocks, and the subsequent removal and recovery of usable hydrocarbons. According to at least one embodiment, there is provided a method for the removal of sulfur and nitrogen compounds from a hydrocarbon feedstock and the use of oxidized sulfur species and oxidized nitrogen species in a FCC process.
- upgrading or “upgraded,” with respect to petroleum or hydrocarbons refers to a petroleum or hydrocarbon product that is lighter (that is, has fewer carbon atoms, such as methane, ethane, and propane), has at least one of a higher API gravity, higher middle distillate yield, lower sulfur content, lower nitrogen content, or lower metal content, than does the original petroleum or hydrocarbon feedstock.
- FIG. 1 provides one embodiment for the recovery of hydrocarbons not according to the invention and present for illustration purposes only.
- Hydrocarbon recovery system 100 includes oxidation reactor 104, extraction vessel 112, solvent regeneration column 116, stripper 120, and FCC unit 130.
- a method for the recovery of components from a hydrocarbon feedstock particularly a hydrocarbon feedstock that includes sulfur- and nitrogen-containing compounds.
- the method includes supplying hydrocarbon feedstock 102 to oxidation reactor 104, where the hydrocarbon feedstock is contacted with an oxidant and a catalyst.
- the oxidant can be supplied to oxidation reactor 104 via oxidant feed line 106 and fresh catalyst can be supplied to the reactor via catalyst feed line 108.
- Hydrocarbon feedstock 102 can be any petroleum based hydrocarbon, and can include various impurities, such as elemental sulfur, compounds that include sulfur or nitrogen, or both.Hydrocarbon feedstock 102 can be a diesel oil having a boiling point between about 150°C and about 400°C. Alternatively, hydrocarbon feedstock 102 can have a boiling point up to about 450°C, alternatively up to about 500°C. Alternatively, hydrocarbon feedstock 102 can have a boiling point between about 100°C and about 500°C. Optionally, hydrocarbon feedstock 102 can have a boiling point up to about 600°C, alternatively up to about 700°C, or, in certain embodiments, greater than about 700°C. The feedstock can exist in a solid state after distillation called residue.
- Hydrocarbon feedstock 102 can include heavy hydrocarbons.
- heavy hydrocarbons refer to hydrocarbons having a boiling point of greater than about 360°C, and can include aromatic hydrocarbons, as well as alkanes and alkenes.
- Hydrocarbon feedstock 102 can be selected from whole range crude oil, topped crude oil, product streams from oil refineries, product streams from refinery steam cracking processes, liquefied coals, liquid products recovered from oil or tar sand, bitumen, oil shale, asphaltene, hydrocarbon fractions such as diesel and VGO boiling in the range of about 180 to about 370°C and about 370 to about 520°C, respectively, and the like, and mixtures thereof.
- Sulfur compounds present in hydrocarbon feedstock 102 can include sulfides, disulfides, and mercaptans, as well as aromatic molecules such as thiophenes, benzothiophenes, dibenzothiophenes, and alkyl dibenzothiophenes, such as 4,6-dimethyl-dibenzothiophene.
- Aromatic compounds are typically more abundant in higher boiling fractions, than is typically found in the lower boiling fractions.
- Nitrogen-containing compounds present in hydrocarbon feedstock 102 can include compounds having the following structures: Please note that the sulfur oxidation is the limiting targeted reaction, during which nitrogen oxidation occurs. Two types could be considered basic and neutral nitrogen.
- Oxidation reactor 104 can be operated at mild conditions. More specifically, oxidation reactor 104 can be maintained at a temperature of between about 30°C and about 350°C, or alternatively, between about 45°C and about 60°C. The operating pressure of oxidation reactor 104 can be between about 1 bar and about 30 bars, alternatively between about 1 bar and about 15 bars, alternatively between about 1 bar and about 10 bars, or alternatively between about 2 bars and about 3 bars.
- the residence time of the hydrocarbon feedstock within oxidation rector 104 can be between about 1 minutes and about 120 minutes, alternatively between about 15 minutes and about 90 minutes, alternatively between about 5 minutes and about 90 minutes, alternatively between about 5 minutes and about 30 minutes, alternatively between about 30 minutes and about 60 minutes, and is preferably for a sufficient amount of time for the oxidation of any sulfur or nitrogen compounds present in the hydrocarbon feedstock.
- the residence time of the hydrocarbon feedstock within oxidation rector 104 can be between about 15 minutes and about 90 minutes.
- Oxidation reactor 104 can be any reactor suitably configured to ensure sufficient contacting between hydrocarbon feedstock 102 and the oxidant, in the presence of a catalyst, for the oxidation of the sulfur- and nitrogen-containing compounds.
- Sulfur and nitrogen compounds present in hydrocarbon feedstock 102 are oxidized in oxidation reactor 104 to sulfones, sulfoxides, and oxidized nitrogen compounds, which can be subsequently removed by extraction or adsorption.
- Various types of reactors can be used.
- the reactor can be a batch reactor, a fixed bed reactor, an ebullated bed reactor, lifted reactor, a fluidized bed reactor, a slurry bed reactor, or combinations thereof.
- Suitable reactors that can be used will be apparent to those of skill in the art and are to be considered within the scope of various embodiments.
- suitable oxidized nitrogen compounds can include pyridine-based compounds and pyrrole-based compounds. It is believed that the nitrogen atom is not directly oxidized, rather it is the carbon atom(s) next to the nitrogen that is actually oxidized.
- a few examples of oxidized nitrogen compounds can include the following compounds: or combinations thereof.
- the oxidant can be supplied to oxidation reactor 104 via oxidant feed stream 106.
- Suitable oxidants can include air, oxygen, hydrogen peroxide, organic peroxides, hydroperoxides, organic peracids, peroxo acids, oxides of nitrogen, ozone, and the like, and combinations thereof.
- Peroxides can be selected from hydrogen peroxide and the like.
- Hydroperoxides can be selected from t-butyl hydroperoxide and the like.
- Organic peracids can be selected from peracetic acid and the like.
- the mole ratio of oxidant to sulfur present in the hydrocarbon feedstock can be from about 1:1 to about 50:1, preferably between about 2:1 and about 20:1, more preferably between about 4:1 and about 10:1.
- the molar feed ratio of oxidant to sulfur can range from about 1:1 to about 30:1.
- the molar feed ratio of oxidant to nitrogen compounds can be from about 4:1 to about 10:1.
- the feedstock can contain more nitrogen compounds than sulfur, such as, for instance, South American Crude oils, Africa crude oils, Russian crude oils, China crude oils, or intermediate refinery streams, such as coker, thermal cracking, visbreaking, gas oils, FCC cycle oils, and the like.
- the catalyst can be supplied to oxidation reactor 104 via catalyst feed stream 108.
- the catalyst can be a homogeneous catalyst.
- the catalyst can include at least one metal oxide having the chemical formula M x O y , where M is a metal selected from groups IVB, VB, or VIB of the periodic table.
- Metals can include titanium, vanadium, chromium, molybdenum, and tungsten. Molybdenum and tungsten are two particularly effective catalysts that can be used in various embodiments.
- the spent catalyst can be rejected from the system with the aqueous phase (for example, when using an aqueous oxidant) after the oxidation vessel.
- the ratio of catalyst to oil is between about 0.1 wt% and about 10 wt%, preferably between about 0.5 wt% and about 5 wt%. In certain embodiments, the ratio is between about 0.5 wt% and about 2.5 wt%. Alternatively, the ratio is between about 2.5 wt% and about 5 wt%. Other suitable weight ratios of catalyst to oil will be apparent to those of skill in the art and are to be considered within the scope of the various embodiments.
- Catalyst present in oxidation reactor 104 can increase the rate of oxidation of the various sulfur- and nitrogen-containing compounds in hydrocarbon feedstock 102, reduce the amount of oxidant necessary for the oxidation reaction, or both.
- the catalyst can be selective toward the oxidation of sulfur species.
- the catalyst can be selective toward the oxidation of nitrogen species.
- Oxidation reactor 104 produces oxidized hydrocarbon stream 110, which can include hydrocarbons and oxidized sulfur- and oxidized nitrogen-containing species.
- Oxidized hydrocarbon stream 110 is supplied to extraction vessel 112 where the oxidized hydrocarbon stream and oxidized sulfur- and oxidized nitrogen-containing species are contacted with extraction solvent stream 137.
- Extraction solvent 137 can be a polar solvent, and can have a Hildebrandt solubility value of greater than about 19.When selecting the particular polar solvent for use in extracting oxidized sulfur- and oxidized nitrogen-containing species, selection can be based upon, in part, solvent density, boiling point, freezing point, viscosity, and surface tension, as non-limiting examples.
- Polar solvents suitable for use in the extraction step can include acetone (Hildebrand value of 19.7), carbon disulfide (20.5), pyridine (21.7), dimethyl sulfoxide (DMSO) (26.4), n-propanol (24.9), ethanol (26.2), n-butyl alcohol (28.7), propylene glycol (30.7), ethylene glycol (34.9), dimethylformamide (DMF) (24.7), acetonitrile (30), methanol (29.7), and like compositions or compositions having similar physical and chemical properties. Acetonitrile and methanol, due to their low cost, volatility, and polarity, are preferred. Methanol is a particularly suitable solvent. Solvents that include sulfur, nitrogen, or phosphorous, preferably have a relatively high volatility to ensure adequate stripping of the solvent from the hydrocarbon feedstock.
- the extraction solvent can be non-acidic.
- acids are typically avoided due to the corrosive nature of acids, and the requirement that all equipment be specifically designed for a corrosive environment.
- acids such as acetic acid, can present difficulties in separation due to the formation of emulsions.
- Extraction vessel 112 can be operated at a temperature of between about 20°C and about 60°C, preferably between about 25°C and about 45°C, even more preferably between about 25°C and about 35°C. Extraction vessel 112 can operate at a pressure of between about 1 and about 10 bars, preferably between about 1 and about 5 bars, more preferably between about 1 and about 2 bars. Extraction vessel 112 can operate at a pressure of between about 2 and about 6 bars.
- the ratio of the extraction solvent to hydrocarbon feedstock can be between about 1:3 and about 3:1, preferably between about 1:2 and about 2:1, more preferably about 1:1.
- Contact time between the extraction solvent and oxidized hydrocarbon stream 110 can be between about 1 second and about 60 minutes, preferably between about 1 second and about 10 minutes.
- the contact time between the extraction solvent and oxidized hydrocarbon stream 110 can be less than about 15 minutes.
- Extraction vessel 112 can include various means for increasing the contact time between the extraction solvent and oxidized sulfur- and oxidized nitrogen-containing hydrocarbon stream 110, or for increasing the degree of mixing of the two solvents. Means for mixing can include mechanical stirrers or agitators, trays, or like means.
- Extraction vessel 112 can produce mixed stream 114 that can include extraction solvent, oxidized species (for example, the oxidized sulfur and nitrogen species that were originally present in hydrocarbon feedstock 102), and traces of hydrocarbon feedstock 102, and extracted hydrocarbon stream 118, which can include the hydrocarbon feedstock having a reduced sulfur and low nitrogen content, relative to hydrocarbon feedstock 102.
- oxidized species for example, the oxidized sulfur and nitrogen species that were originally present in hydrocarbon feedstock 102
- traces of hydrocarbon feedstock 102 and extracted hydrocarbon stream 118, which can include the hydrocarbon feedstock having a reduced sulfur and low nitrogen content, relative to hydrocarbon feedstock 102.
- Mixed stream 114 is supplied to solvent regeneration column 116 where extraction solvent can be recovered as first recovered solvent stream 117 and separated from first residue stream 123, which includes oxidized sulfur and oxidized nitrogen compounds.
- mixed stream 114 can be separated in solvent regeneration column 116 into a recovered hydrocarbon stream 124, which can include hydrocarbons present in mixed stream 114 from hydrocarbon feedstock 102.
- Solvent regeneration column 116 can be a distillation column that is configured to separate mixed stream 114 into first recovered solvent stream 117, first residue stream 123, and recovered hydrocarbon stream 124.
- Extracted hydrocarbon stream 118 can be supplied to stripper 120, which can be a distillation column or like vessel designed to separate a hydrocarbon product stream from residual extraction solvent.
- a portion of mixed stream 114 can be supplied to stripper 120 via line 122, and may optionally be combined with extracted hydrocarbon stream 118.
- Solvent regeneration column 116 can produce recovered hydrocarbon stream 124, which can be supplied to stripper 120, where recovered hydrocarbon stream 124 can optionally be contacted with extracted hydrocarbon stream 118 or a portion of mixed stream 114, which can be supplied to stripper 120 via line 122.
- Stripper 120 separates the various streams supplied thereto into stripped oil stream 126, which has a reduced sulfur and nitrogen content relative to hydrocarbon feedstock 102, and second recovered solvent stream 128.
- First recovered solvent stream 117 can be combined with second recovered solvent stream 128 and recycled to extraction vessel 112.
- make-up solvent stream 132 which can include fresh solvent, can be combined with first recovered solvent stream 117, second recovered solvent stream 128, or both, and supplied to extraction vessel 112.
- First residue stream 123 which includes oxidized compounds, such as oxidized sulfur and nitrogen compounds, and which can also include low concentrations of hydrocarbonaceous material, can be supplied to FCC unit 130 where liquid products (including hydrocarbons) 136 are recovered.
- Oxidized sulfur compounds, such as sulfones, and oxidized nitrogen compounds are embedded in heavy hydrocarbons, such as hydrocarbons having a boiling point in a range of about 343°C to about 524°C; or alternatively, in a range of about 360°C to about 550°C.
- first residue stream 123 is contacted with FCC feedstream 134 in the presence of a catalyst to catalytically crack FCC feedstream 134 to recover liquid products 136 from first residue stream 123.
- the catalyst can include hot solid zeolitic active catalyst particles.
- the weight ratio of catalyst to FCC feedstream 134 can be within a range of between about 1 and about 15 with a pressure ranging from about 1 barg (gauge pressure) to about 200 barg to form a suspension. Other suitable ratios of catalyst and FCC feedstream 134 and operating conditions will be apparent to those of skill in the art and are to be considered within the scope of the various embodiments.
- the suspension can then be passed through a riser reaction zone or downer at a temperature (not shown) between about 300 °C and less than about 650 °C to catalytically crack the FCC feedstream 134, while avoiding thermal conversion of said feedstream 134 and providing a hydrocarbon residence time between about 0.1 second and about 10 minutes.
- the lower boiling components and the solid catalyst particles can then be separated and recovered. At least a portion of the separated solid catalyst particles is regenerated with a water-free oxygen-containing gas in a fluidized bed operated at conditions to produce regenerated catalyst 140 and gaseous products 138 consisting essentially of carbon monoxide and carbon dioxide and liquid products 136. At least a portion of the regenerated catalyst is returned and combined with FCC feedstream 134 (not shown).
- FCC feedstream 134 can vary.
- FCC feedstream 134 can include VGO, reduced crude, demetalized oil, whole crude, cracked shale oil, liquefied coal, cracked bitumens, heavy coker gas oils, and FCC heavy products, such as LCO, HCO and CSO, as non-limiting examples.
- Table 1 shows the typical yield from a FCC unit.
- FCC feedstream 134 sent to the FCC unit 130 can have the properties shown in Table 2.
- Other suitable compounds that can be used in FCC feedstream 134 being sent to the FCC unit 130 will be apparent to those of skill in the art and are to be considered within the scope of the various embodiments.
- FCC catalyst particles include a zeolitic matrix with metals selected from Groups IVB, VI, VII, VIIIB, IB, IIB, or a compound thereof, and with catalyst particles less than 200 microns in nominal diameter.
- Other suitable types of catalysts that can be used in FCC unit 130 will be apparent to those of skill in the art and are to be considered within the scope of the various embodiments.
- the operating parameters for FCC unit 130 can be varied depending upon the type of FCC feedstream 134 that is sent to FCC unit 130.
- FCC unit 130 is conducted in the temperature range of about 400°C to about 850 °C.FCC unit 130 can be operated at a pressure ranging from about 1 barg to about 200 barg. FCC unit 130 can be operated for a residence time ranging from about 0.1 second to about 3600 seconds. Other suitable operating parameters for FCC unit 130 will be apparent to those of skill in the art and are to be considered within the scope of the various embodiments.
- the properties of the components recovered from FCC unit 130 will vary depending upon the composition of the hydrocarbon FCC feedstream 134.
- FIG. 2 provides one embodiment for the recovery of hydrocarbons from a feedstream.
- Hydrocarbon recovery system 200 includes oxidation reactor 104, extraction vessel 112, solvent regeneration column 116, stripper 120, FCC unit 130, and hydrotreater 202.
- first residue stream 123 which includes oxidized compounds, such as oxidized sulfur and nitrogen compounds, and which can also include low concentrations of hydrocarbonaceous material, can be supplied to FCC unit 130 where liquid products (including hydrocarbons) 136 are recovered.
- oxidized sulfur compounds, such as sulfones, and oxidized nitrogen compounds are embedded in heavy hydrocarbons, such as hydrocarbons having a boiling point in a range of about 343°C to about 524°C; or alternatively, in a range of about 360°C to about 550°C.
- first residue stream 123 is contacted with FCC feedstream 134 and subsequently fed through hydrotreater 202 to hydrotreat the mixture for reducing sulfur, nitrogen, and aromatics.
- Resultant stream 204 exits hydrotreater 202 and is fed to FCC unit 130 in the presence of a catalyst to catalytically crack resultant stream 204 to recover liquid products 136 from first residue stream 123 and resultant stream 204.
- the catalyst can include hot solid zeolitic active catalyst particles.
- the weight ratio of catalyst to resultant stream 204 is within a range of between about 1 and about 15 with a pressure ranging from about 1 barg to about 200 barg to form a suspension. Other suitable ratios of catalyst and resultant stream 204 and operating conditions will be apparent to those of skill in the art and are to be considered within the scope of the various embodiments.
- the suspension is then passed through a riser reaction zone or downer at a temperature (not shown) between about 300 °C and less than about 650 °C to catalytically crack the FCC feedstream 134, while avoiding thermal conversion of said feedstream 134 and providing a hydrocarbon residence time between about 0.1 second and about 10 minutes.
- the lower boiling components and the solid catalyst particles are then separated and recovered. At least a portion of the separated solid catalyst particles is regenerated with a water-free oxygen-containing gas in a fluidized bed operated at conditions to produce regenerated catalyst 140 and gaseous products 138 consisting essentially of carbon monoxide and carbon dioxide and liquid products 136. At least a portion of the regenerated catalyst is returned and combined with FCC feedstream 134 (not shown).
- liquid products 136 is recycled via line 206 back to oxidation reactor 104, where liquid products 136 contains at least one of light cycle oils and heavy cycle oils.
- Liquid products 136 are sulfur rich and can be desulfurized in the oxidative desulfurized process occurring in oxidation reactor 104.
- FCC catalyst particles include a zeolitic matrix with metals selected from Groups IVB, VI, VII, VIIIB, IB, IIB, or a compound thereof, and with catalyst particles less than 200 microns in nominal diameter.
- Other suitable types of catalysts that can be used in FCC unit 130 will be apparent to those of skill in the art and are to be considered within the scope of the various embodiments.
- FIG. 3 provides one embodiment for the recovery of hydrocarbons from a feedstream.
- Hydrocarbon recovery system 300 includes oxidation reactor 104, extraction vessel 112, solvent regeneration column 116, stripper 120, FCC unit 130, hydrotreater 302, and adsorption column 306.
- stripped oil stream 126 can be supplied to adsorption column 306, where stripped oil stream 126 can be contacted with one or more adsorbents designed to remove one or more various impurities, such as sulfur-containing compounds, oxidized sulfur compounds, nitrogen-containing compounds, oxidized nitrogen compounds, and metals remaining in the hydrocarbon product stream after oxidation and solvent extraction steps.
- adsorption column 306 where stripped oil stream 126 can be contacted with one or more adsorbents designed to remove one or more various impurities, such as sulfur-containing compounds, oxidized sulfur compounds, nitrogen-containing compounds, oxidized nitrogen compounds, and metals remaining in the hydrocarbon product stream after oxidation and solvent extraction steps.
- the one or more adsorbents can include activated carbon; silica gel; alumina; natural clays; silica-alumina; zeolites; and fresh, used, regenerated or rejuvenated catalysts having affinity to remove oxidized sulfur and nitrogen compounds and other inorganic adsorbents.
- the adsorbent can include polar polymers that have been applied to or that coat various high surface area support materials, such as silica gel, alumina, and activated carbon.
- Example polar polymers for use in coating various support materials can include polysulfones, polyacrylonitrile, polystyrene, polyester terephthalate, polyurethane, other like polymer species that exhibit an affinity for oxidized sulfur species, and combinations thereof.
- adsorption column 306 can be operated at a temperature of between about 20°C and about 60°C, preferably between about 25°C and about 40°C, even more preferably between about 25°C and about 35°C. In certain embodiments, the adsorption column can be operated at a temperature of between about 10°C and about 40°C. In certain embodiments, the adsorption column can be operated at temperatures of greater than about 20°C, or alternatively at temperatures less than about 60°C. Adsorption column 306 can be operated at a pressure of up to about 15 bars, preferably up to about 10 bars, even more preferably between about 1 and about 2 bars.
- adsorption column 306 can be operated at a pressure of between about 2 and about 5 bar. In accordance with at least one embodiment, the adsorption column can be operated at a temperature of between about 25°C and about 35°C and a pressure of between about 1 and about 2 bars.
- the weight ratio of the stripped oil stream to the adsorbent is between about 1:1 to about 20:1; or alternatively, about 10:1.
- Adsorption column 306 separates the feed into extracted hydrocarbon product stream 308 having very low sulfur content (for example, less than 15 ppmw of sulfur) and very low nitrogen content (for example, less than 10 ppmw of nitrogen), and second residue stream 310.
- Second residue stream 310 includes oxidized sulfur- and oxidized nitrogen-containing compounds, and as shown in FIG. 3 is directed to FCC unit 130.
- stream 310 can be combined with first residue stream 123 and supplied to FCC unit 130 and processed as noted previously.
- first residue stream 123 is contacted with FCC feedstream 134 and subsequently fed through hydrotreater 202 to hydrotreat the mixture for reducing sulfur, nitrogen, and aromatics.
- Resultant stream 204 exits hydrotreater 202 and is fed to FCC unit 130 in the presence of a catalyst to catalytically crack resultant stream 204 to recover liquid products 136 from first residue stream 123 and resultant stream 204.
- the adsorbent can be regenerated by contacting spent adsorbent with a polar solvent, such as methanol or acetonitrile, to desorb the adsorbed oxidized compounds from the adsorbent.
- a polar solvent such as methanol or acetonitrile
- heat, stripping gas, or both can also be employed to facilitate the removal of the adsorbed compounds.
- Other suitable methods for removing the absorbed compounds will be apparent to those of skill in the art and are to be considered within the scope of the various embodiments.
- FIG. 4 shows the process flow diagram for the oxidative desulfurization (oxidation and extraction steps) and FCC unit.
- Vessels 10, 16, 20 and 25 are oxidation, extraction, solvent recovery, and FCC vessels, respectively.
- a hydrotreated straight run diesel containing 500 ppmw of elemental sulfur, 0.28 wt% of organic sulfur, density of 0.85 kilogram per liter (Kg/l) was oxidatively desulfurized.
- the reaction conditions were as follows:
- the FCC unit was operated at 518 °C with a catalyst to oil ratio of 5, which resulted in 67 wt% conversion of the feedstock.
- straight run VGO derived from Arabian crude oils was used as a blending component.
- the feedstock contained 2.65 wt% sulfur and 0.13 wt% of micro carbon residue.
- the mid and 95 wt% boiling points for the feedstocks were 408 °C and 455 °C, respectively.
- the catalyst used was an equilibrium catalyst and used as is without any treatment.
- the catalyst has 131 meter squared per gram (m 2 /g) surface area and 0.1878 centimeter squared per gram (cm 3 /g) pore volume.
- the nickel and vanadium contents are 96 and 407 ppmw, respectively.
- the FCC process yielded the following products and deposited coke on the catalysts.
- the coke produced in the FCC process was 2.5 wt% of the feedstock processed.
- the product yields are given in Table 5: Table 5 - FCC Step Material Balance Stream # 22 23 24 26 27 28 29 Stream Name Sulfones VGO FCC Feedstock Gases Gasoline LCO HCO Kg/h Kg/h Kg/h Kg/h Kg/h Kg/h Kg/h Kg/h Kg/h Kg/h Stream Type Feed Feed Feed Oil Oil Oil Oil Oil Phase Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Sulfur, wt% 0.05 2.67 2.5 0.27 2.65 4.70 VGO 10,000 10,000 Total Gas 771 Sulfones 771 1,822 Gasoline 4,957 LCO 1,707 HCO 1,764 Total 771 10,000 10,771 1,822 4,957 1,707 1,764
- VGO was hydrodesulfurized over Co-Mo/Alumina catalyst to obtain a final product with 500 ppmw of sulfur.
- Table 6 Operating Conditions for Hydrotreater Item Units Reactor LHSV Hr -1 0.6 Hydrogen Partial Pressure Kg/cm 2 (g) 60.0 Temperature °C 385.0 Hydrogen to Oil Ratio Sm 3 /m 3 566
- FIG. 5 shows an effect of hydrotreating on FCC performance.
- FIG. 5 illustrates that hydrotreating may substantially impact gasoline quality (that is, the impact of hydrodesulfurization (HDS) level on gasoline and SOx emissions).
- gasoline quality that is, the impact of hydrodesulfurization (HDS) level on gasoline and SOx emissions.
- HDS hydrodesulfurization
- the gasoline sulfur content can be reduced to less than 100 ppmw levels.
- the SOx emissions from the FCC can also be reduced to less than 500 ppmw levels.
- Table 8 The operating conditions of the hydrotreater according to various embodiments are shown in Table 8.
- Table 8 Hydrotreater Operating Conditions Variable Range Unit Value Temperature Broad °C 300-450 Temperature Preferred °C 350-420 Pressure Broad Bar 50-200 Pressure Preferred Bar 60-80 LHSV Broad Hours 0.2-5.0 LHSV Preferred Hours 0.5-2.0 Hydrogen Oil Broad L/L 300-1500 Hydrogen Oil Preferred L/L 500-1000
- Embodiments provide a way of disposing of the oxidized sulfur and nitrogen compounds without having to dispose of the compounds.
- Optional or optionally means that the subsequently described event or circumstances may or may not occur.
- the description includes instances where the event or circumstance occurs and instances where it does not occur.
- Ranges may be expressed as from about one particular value to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value or to the other particular value, along with all combinations within said range.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Extraction Or Liquid Replacement (AREA)
- Catalysts (AREA)
- Fats And Perfumes (AREA)
Claims (15)
- Procédé de récupération de composants d'une charge d'hydrocarbures, le procédé caractérisé par les étapes de:alimentation de la charge d'hydrocarbures à un réacteur d'oxydation, la charge d'hydrocarbures comprenant des composés de soufre et des composés d'azote;mise en contact de la charge d'hydrocarbures avec un agent oxydant dans le réacteur d'oxydation sous des conditions suffisantes pour oxyder sélectivement les composés de soufre et les composés d'azote présents dans la charge d'hydrocarbures pour produire un écoulement d'hydrocarbures oxydé qui comprend des hydrocarbures, des composés de soufre oxydés, et des composés d'azote oxydés;séparation des hydrocarbures, des composés de soufre oxydés, et des composés d'azote oxydés dans l'écoulement d'hydrocarbures oxydé par extraction au solvant avec un solvant polaire pour produire un écoulement d'hydrocarbures extrait et un écoulement mixte, l'écoulement mixte comprenant le solvant polaire, les composés de soufre oxydés, et les composés d'azote oxydés, l'écoulement d'hydrocarbures extrait ayant une concentration inférieure des composés de soufre et des composés d'azote par rapport à la charge d'hydrocarbures;séparation de l'écoulement mixte en utilisant une colonne de distillation dans un premier écoulement de solvant polaire récupéré et un premier écoulement résiduel, le premier écoulement résiduel comprenant les composés de soufre oxydés et les composés d'azote oxydés;alimentation du premier écoulement résiduel à une unité de craquage catalytique de fluide, l'alimentation comprenant en outre l'alimentation du premier écoulement résiduel à travers un dispositif d'hydrotraitement avant l'alimentation du premier écoulement résiduel à l'unité de craquage catalytique de fluide, l'unité de craquage catalytique de fluide étant fonctionnelle pour craquer catalytiquement le soufre oxydé et l'azote oxydé pour produire un catalyseur régénéré et des produits gazeux et liquides et de permettre la récupération des hydrocarbures du premier écoulement résiduel; etrecyclage d'au moins une portion des produits liquides vers le réacteur d'oxydation pour oxyder sélectivement les composés de soufre dans les produits liquides, la portion des produits liquides comprenant au moins l'une d'huiles légères de recyclage et d'huiles lourdes de recyclage.
- Procédé selon la revendication 1, caractérisé en outre par l'étape de:alimentation de l'écoulement d'hydrocarbures extrait à un épurateur pour produire un second écoulement de solvant polaire récupéré et un écoulement d'hydrocarbures purifié; etrecyclage du premier écoulement de solvant polaire récupéré et du second écoulement de solvant polaire vers un récipient d'extraction pour la séparation des hydrocarbures, des composés de soufre oxydés, et des composés d'azote oxydés dans l'écoulement d'hydrocarbures oxydé.
- Procédé selon la revendication 1 ou la revendication 2, caractérisé en outre par l'étape de: recyclage d'une portion du catalyseur régénéré avec un écoulement d'alimentation de craquage catalytique de fluide vers l'unité de craquage catalytique de fluide, le recyclage comprenant en outre le craquage catalytiquement de l'écoulement d'alimentation de craquage catalytique de fluide avec la portion du catalyseur régénéré pour récupérer les hydrocarbures du premier écoulement résiduel.
- Procédé selon l'une quelconque des revendications précédentes, l'oxydant étant sélectionné dans le groupe constitué de l'air, de l'oxygène, des peroxydes, des hydroperoxydes, de l'ozone, des composés oxydes d'azote, et des combinaisons de ceux-ci.
- Procédé selon l'une quelconque des revendications précédentes, la mise en contact de la charge d'hydrocarbures avec un agent oxydant se produit en présence d'un catalyseur comprenant un oxyde métallique ayant la formule MxOy, M étant un élément sélectionné parmi les Groupes IVB, VB, et VIB du tableau périodique.
- Procédé selon l'une quelconque des revendications précédentes, les composés de soufre comprenant des sulfures, des disulfures, des mercaptanes, du thiophène, du benzothiophène, du dibenzothiophène, des dérivés alkyliques de dibenzothiophène, ou des combinaisons de ceux-ci.
- Procédé selon l'une quelconque des revendications précédentes, le réacteur d'oxydation étant maintenu à une température comprise entre environ 20 et environ 350°C et à une pression comprise entre environ 1 et environ 10 bars.
- Procédé selon l'une quelconque des revendications précédentes, le rapport de l'oxydant aux composés de soufre présents dans la charge d'hydrocarbures étant compris entre environ 4:1 et environ 10:1.
- Procédé selon l'une quelconque des revendications précédentes, le solvant polaire:(i) ayant une valeur d'Hildebrandt supérieure à environ 19; et/ou(ii) étant sélectionné dans le groupe constitué de l'acétone, du disulfure de carbone, de la pyridine, du sulfoxyde de diméthyle, du n-propanol, de l'éthanol, du n-butanol, du propylène glycol, de l'éthylène glycol, du diméthlylformamide, de l'acétonitrile, du méthanol et des combinaisons de ceux-ci; et/ou(iii) étant l'acétonitrile; et/ou(iv) étant le méthanol.
- Procédé selon l'une quelconque des revendications précédentes, l'extraction au solvant étant conduite à une température comprise entre environ 20°C et environ 60°C et à une pression comprise entre environ 1 et environ 10 bars.
- Procédé selon l'une quelconque des revendications précédentes, caractérisé en outre par l'étape de:
alimentation de l'écoulement d'hydrocarbures extrait à une colonne d'adsorption, la colonne d'adsorption étant chargée avec un adsorbant convenant à l'élimination des composés oxydés présents dans l'écoulement d'hydrocarbures extrait, la colonne d'adsorption produisant un écoulement de produit d'hydrocarbures de pureté élevée et un second écoulement résiduel, le second écoulement résiduel comprenant une portion des composés oxydés. - Procédé selon la revendication 11, le procédé étant en outre caractérisé par l'étape d'alimentation du second écoulement résiduel à l'unité de craquage catalytique de fluide.
- Procédé selon la revendication 11:(i) l'adsorbant étant sélectionné dans le groupe constitué du charbon actif, du gel de silice, de l'alumine, des argiles d'origine naturelle, de la silice-alumine, des zéolites, et des combinaisons de ceux-ci; ou(ii) l'adsorbant étant un support revêtu d'un polymère, le support ayant une surface active élevée et étant sélectionné dans le groupe constitué du gel de silice, de l'alumine, de la silice-alumine, des zéolites, et du charbon actif, et le polymère étant sélectionné dans le groupe constitué de la polysulfone, du polyacrylonitrile, du polystyrène, du téréphtalate de polyester, du polyuréthane, et des combinaisons de ceux-ci.
- Procédé selon l'une quelconque des revendications précédentes, l'alimentation du premier écoulement résiduel à l'unité de craquage catalytique de fluide comprenant en outre la mise en contact du premier écoulement résiduel avec un écoulement d'alimentation de craquage catalytique de fluide en la présence d'un catalyseur pour craquer catalytiquement l'écoulement d'alimentation de craquage catalytique de fluide pour récupérer les hydrocarbures du premier écoulement résiduel.
- Procédé selon la revendication 14, l'écoulement d'alimentation de craquage catalytique de fluide comprenant du gasoil sous vide, du brut réduit, du brut démétallisé, du brut complet, de l'huile de schiste craquée, du charbon liquéfié, du bitume craqué, des gasoils de coke lourds, des huiles légères de recyclage, des huiles lourdes de recyclage, des huiles en suspension clarifiées, ou des combinaisons de ceux-ci.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/437,276 US10093872B2 (en) | 2010-09-07 | 2017-02-20 | Oxidative desulfurization of oil fractions and sulfone management using an FCC |
PCT/US2018/018789 WO2018152521A1 (fr) | 2017-02-20 | 2018-02-20 | Désulfuration oxydative de fractions d'huiles et gestion des sulfones à l'aide d'un craquage catalytique fluide |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3583192A1 EP3583192A1 (fr) | 2019-12-25 |
EP3583192B1 true EP3583192B1 (fr) | 2022-01-05 |
Family
ID=61563497
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP18708818.2A Active EP3583192B1 (fr) | 2017-02-20 | 2018-02-20 | Désulfuration oxydative de fractions d'huiles et gestion des sulfones à l'aide d'un craquage catalytique fluide |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP3583192B1 (fr) |
JP (1) | JP2020510719A (fr) |
KR (1) | KR20190116466A (fr) |
CN (1) | CN110337487A (fr) |
SG (1) | SG11201907206YA (fr) |
WO (1) | WO2018152521A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11571672B2 (en) * | 2019-11-25 | 2023-02-07 | Saudi Arabian Oil Company | Method of providing catalysts for a fluidized bed reactor |
CN114133954B (zh) * | 2020-09-03 | 2024-08-09 | 中国石油化工股份有限公司 | 一种加工渣油制低硫石油焦的方法和装置 |
CN114733512B (zh) * | 2021-10-18 | 2023-09-05 | 华北电力大学(保定) | 新型钼钨氧化物催化剂、使用其降解二甲基亚砜的装置及方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4388176A (en) * | 1981-11-19 | 1983-06-14 | Texaco Inc. | Hydrocarbon conversion process |
US6843906B1 (en) * | 2000-09-08 | 2005-01-18 | Uop Llc | Integrated hydrotreating process for the dual production of FCC treated feed and an ultra low sulfur diesel stream |
US7153413B2 (en) * | 2001-07-10 | 2006-12-26 | W.R. Grace &Co.-Conn. | Gasoline sulfur reduction in fluid catalytic cracking |
US20070151901A1 (en) * | 2005-07-20 | 2007-07-05 | Council Of Scientific And Industrial Research | Process for desulphurisation of liquid hydrocarbon fuels |
US9574144B2 (en) * | 2010-09-07 | 2017-02-21 | Saudi Arabian Oil Company | Process for oxidative desulfurization and denitrogenation using a fluid catalytic cracking (FCC) unit |
US9574143B2 (en) * | 2010-09-07 | 2017-02-21 | Saudi Arabian Oil Company | Desulfurization and sulfone removal using a coker |
US9598647B2 (en) * | 2010-09-07 | 2017-03-21 | Saudi Arabian Oil Company | Process for oxidative desulfurization and sulfone disposal using solvent deasphalting |
-
2018
- 2018-02-20 EP EP18708818.2A patent/EP3583192B1/fr active Active
- 2018-02-20 WO PCT/US2018/018789 patent/WO2018152521A1/fr active Application Filing
- 2018-02-20 KR KR1020197027338A patent/KR20190116466A/ko not_active Application Discontinuation
- 2018-02-20 CN CN201880012412.3A patent/CN110337487A/zh active Pending
- 2018-02-20 SG SG11201907206YA patent/SG11201907206YA/en unknown
- 2018-02-20 JP JP2019544875A patent/JP2020510719A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
CN110337487A (zh) | 2019-10-15 |
EP3583192A1 (fr) | 2019-12-25 |
SG11201907206YA (en) | 2019-09-27 |
WO2018152521A1 (fr) | 2018-08-23 |
KR20190116466A (ko) | 2019-10-14 |
JP2020510719A (ja) | 2020-04-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9574144B2 (en) | Process for oxidative desulfurization and denitrogenation using a fluid catalytic cracking (FCC) unit | |
US9598647B2 (en) | Process for oxidative desulfurization and sulfone disposal using solvent deasphalting | |
US9574143B2 (en) | Desulfurization and sulfone removal using a coker | |
EP2732009B1 (fr) | Procédé pour la conversion de sulfone par des super-donneurs d'électrons | |
US20120055849A1 (en) | Process for Oxidative Desulfurization and Sulfone Management by Gasification | |
US10081770B2 (en) | Process for oxidative desulfurization and sulfone disposal using solvent deasphalting | |
EP3583191B1 (fr) | Désulfuration et élimination des sulfones à l'aide d'une unité de cokéfaction | |
EP3583192B1 (fr) | Désulfuration oxydative de fractions d'huiles et gestion des sulfones à l'aide d'un craquage catalytique fluide | |
CN110446772B (zh) | 使用溶剂脱沥青的氧化脱硫和砜处理方法 | |
CN110312779B (zh) | 使用焦化器脱硫和除砜 | |
JP6937832B2 (ja) | Fccを用いた油分の酸化的脱硫およびスルホンの管理 | |
US10093871B2 (en) | Desulfurization and sulfone removal using a coker | |
US10093872B2 (en) | Oxidative desulfurization of oil fractions and sulfone management using an FCC | |
US10087377B2 (en) | Oxidative desulfurization of oil fractions and sulfone management using an FCC | |
US10093870B2 (en) | Desulfurization and sulfone removal using a coker | |
EP3870673A1 (fr) | Démétallisation par cokéfaction retardée et désulfuration oxydative en phase gazeuse d'huile résiduelle démétallisée | |
WO2009070251A1 (fr) | Désulfuration de courants de pétrole à l'aide d'un complexe de métal alcalin aromatique à plusieurs cycles |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20190912 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20200716 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20210927 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1460595 Country of ref document: AT Kind code of ref document: T Effective date: 20220115 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602018029086 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1460595 Country of ref document: AT Kind code of ref document: T Effective date: 20220105 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220505 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220405 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220405 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220406 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220505 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602018029086 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20220228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220220 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 |
|
26N | No opposition filed |
Effective date: 20221006 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20220405 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220228 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220220 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220405 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220228 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230526 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20240123 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220105 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240123 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20180220 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20240123 Year of fee payment: 7 |