EP4055121A1 - Procede de production d'olefines comprenant un desasphaltage, un hydrocraquage et un vapocraquage - Google Patents
Procede de production d'olefines comprenant un desasphaltage, un hydrocraquage et un vapocraquageInfo
- Publication number
- EP4055121A1 EP4055121A1 EP20797148.2A EP20797148A EP4055121A1 EP 4055121 A1 EP4055121 A1 EP 4055121A1 EP 20797148 A EP20797148 A EP 20797148A EP 4055121 A1 EP4055121 A1 EP 4055121A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fraction
- compounds
- separation
- hydrocracking
- stage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 60
- 230000008569 process Effects 0.000 title claims abstract description 46
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 25
- 238000004517 catalytic hydrocracking Methods 0.000 title claims description 68
- 238000004230 steam cracking Methods 0.000 title claims description 42
- 238000002360 preparation method Methods 0.000 title abstract 2
- 238000009835 boiling Methods 0.000 claims abstract description 62
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 36
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 36
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 28
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims description 73
- 239000003054 catalyst Substances 0.000 claims description 65
- 239000002904 solvent Substances 0.000 claims description 62
- 150000001875 compounds Chemical class 0.000 claims description 55
- 239000007788 liquid Substances 0.000 claims description 41
- 238000000197 pyrolysis Methods 0.000 claims description 35
- 238000000605 extraction Methods 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 27
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 23
- 238000004821 distillation Methods 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- 238000011144 upstream manufacturing Methods 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000010426 asphalt Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000005292 vacuum distillation Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 239000003502 gasoline Substances 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 239000003921 oil Substances 0.000 description 35
- 229910052751 metal Inorganic materials 0.000 description 24
- 239000002184 metal Substances 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 150000002431 hydrogen Chemical class 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 150000002739 metals Chemical class 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 230000003716 rejuvenation Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000000622 liquid--liquid extraction Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 235000015076 Shorea robusta Nutrition 0.000 description 1
- 244000166071 Shorea robusta Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005235 decoking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
-
- 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
- C10G21/003—Solvent de-asphalting
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/002—Apparatus for fixed bed hydrotreatment processes
-
- 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
- C10G7/00—Distillation of hydrocarbon oils
- C10G7/06—Vacuum distillation
-
- 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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
- C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4025—Yield
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
Definitions
- the present invention relates to a process for the production of olefins from heavy fractions of hydrocarbons containing inter alia sulfur impurities, metals and asphaltenes.
- ethylene and propylene are highly desirable olefins, because they are essential intermediates for many petrochemicals such as polyethylene and polypropylene.
- refining sites and existing petrochemical sites in remodeling the refining sites, so as to produce at least part of petrochemical bases, or to design new integrated refining-petrochemical schemes, or even to design sites where most or all of the crude is converted into petrochemical bases.
- the main process for converting heavy hydrocarbon fractions into high yield olefins is steam cracking.
- the production of the desired olefins is accompanied by co-products, in particular aromatic compounds and pyrolysis oil which require purification steps.
- the selectivity for the desired olefins is highly dependent on the quality of the feeds introduced in the steam cracking step. There is therefore an interest in identifying new processes allowing the production of olefins from heavy hydrocarbon fractions in a more efficient, profitable and independent manner from the heavy hydrocarbon fraction treated.
- the process according to the invention makes it possible to optimize the properties of the fractions which will be introduced in the steam cracking stage and thus to maximize the yields of olefins of interest during the steam cracking stage.
- the hydrotreatment of the residue in a fixed bed makes it possible to remove some of the contaminants from the feed, in particular metals, sulfur and asphaltenes.
- Deasphalting separates an asphalt fraction rich in asphaltenes called pitch according to English terminology from a deasphalted oil fraction, called DAO for “DeAsphalted OU” according to English terminology, with a greatly reduced asphaltene content, thus facilitating its upgrading by catalytic cracking or hydrocracking.
- the conversion products and more particularly the heavy cuts resulting from the conversion processes such as deasphalted oils and vacuum distillates are difficult to treat directly in a steam cracking step.
- the presence of high contents of naphthenic and aromatic compounds leads to a sharp drop in the yields of olefins of interest, to an increase in the yield of pyrolysis oil and to increased coking of the tubes of the steam cracking furnaces, which affects the operability. . It is therefore necessary to improve the operability of the steam cracking step in order to produce olefins with good yield.
- the present invention aims to overcome the problems set out above, and in particular to provide a process allowing flexible and optimized production of olefins from heavy hydrocarbon feedstocks, so as to improve the profitability of the olefin production process.
- the Applicant has developed a new process for the production of olefins comprising a deasphalting step to produce a DAO fraction and an asphalt fraction, a step of hydroconversion of the DAO fraction in an ebullating bed, a hydrocracking step in fixed bed, an extraction step to produce a raffinate and a fraction rich in aromatics and a steam cracking step of said raffinate.
- the object of the present invention relates to a process for the production of olefins from a hydrocarbon feedstock 1 having a sulfur content of at least 0.1% by weight, an initial boiling point of at least 180 °. C and a final boiling temperature of at least 600 ° C, said process comprising the following steps: a) a step a) of deasphalting by extraction of said heavy hydrocarbon feed 1 by means of a solvent 2 or of a mixture of solvents making it possible to obtain on the one hand a fraction comprising asphalt, and on the other hand a deasphalted oil fraction (denoted DAO) 3, b) a stage b) of hydroconversion carried out in an ebullated bed reactor in which fraction 3 DAO in the presence of hydrogen 4 is brought into contact in the presence of a hydroconversion catalyst, said step making it possible to obtain an effluent 5, c) a step c) of separation of the effluent 5 from step b) of hydroconversion into at least one gas fraction 6, a fraction
- step a) of deasphalting is carried out under specific conditions making it possible to obtain, on the one hand, a DAO 3 with a high yield, preferably greater than 60% by weight relative to the quantity of compounds having a boiling point greater than 540 ° C at the inlet of deasphalting step a), and on the other hand a fraction comprising asphalt having a softening point greater than 100 ° C.
- the solvent 2 used in step a) is an apolar solvent composed of at least 80% by volume of saturated hydrocarbon (s) comprising a number of carbons between 3 and 5.
- the separation step c) comprises a vacuum distillation allowing a vacuum distillate fraction and a vacuum residue fraction to be obtained.
- the separation step c) comprises, upstream of the vacuum distillation, atmospheric distillation making it possible to obtain at least one atmospheric distillate fraction and at least one atmospheric residue fraction, said atmospheric residue fraction being sent to said distillation. under vacuum making it possible to obtain at least one distillate fraction under vacuum and at least one residue fraction under vacuum.
- the polar solvent used in step d) for extracting the aromatics is chosen from furfural, N-methyl-2-pyrrolidone (NMP), sulfolane, dimethylformamide (DMF) , dimethylsulfoxide (DMSO), phenol, or a mixture of these solvents.
- hydrocracking step e) is carried out at a temperature of between 340 and 480 ° C. and at an absolute pressure of between 5 and 25 MPa. In a preferred embodiment, hydrocracking step e) is carried out so as to obtain a yield of liquid compounds having a boiling point of less than 180 ° C. greater than 50% by weight of the feed at the inlet of the hydrocracking step e).
- the separation step f) comprises at least one atmospheric distillation making it possible to obtain at least one liquid fraction 14 comprising compounds having a boiling point of less than 350 ° C. and a liquid fraction. comprising vacuum distillate comprising compounds having a boiling point greater than 350 ° C.
- the liquid fraction 14 and the fraction comprising vacuum distillate are sent to step g) of steam cracking.
- part of a fraction 8 comprising compounds having a boiling point of less than 180 ° C from step c) of separation is introduced in step g) of steam cracking.
- step g) of steam cracking is carried out in at least one pyrolysis furnace at a temperature between 700 and 900 ° C, at a pressure between 0.05 and 0.3 MPa for a period of time. of stay less than or equal to 1.0 seconds.
- the cuts rich in saturated compounds obtained from the light gases or from the pyrolysis gasoline obtained from stage h) of separation are recycled to stage g) of steam cracking.
- the pyrolysis oil fraction 20 is subjected to an additional separation step so as to obtain a light pyrolysis oil comprising compounds having a boiling point of less than 350 ° C and a heavy pyrolysis oil. comprising compounds having a boiling point greater than 350 ° C, said light pyrolysis oil is injected upstream of hydrocracking step e), and said heavy pyrolysis oil is injected upstream of step b) of hydroconversion and / or of step a) of deasphalting.
- FIG. 1 represents a sequence of the steps of the method according to the invention. Description of the embodiments
- FIG. 1 illustrates an example of implementation of the process for producing olefins from heavy hydrocarbon feedstocks according to the invention.
- FIG. 1 illustrates an example of implementation of the process for producing olefins from heavy hydrocarbon feedstocks according to the invention.
- the mention of the elements referenced in Figure 1 in the remainder of the description allows a better understanding of the invention, without it being limited to the particular example illustrated in Figure 1.
- the method according to the invention comprises the following steps:
- DAO deasphalted oil
- step d) of extracting at least part of fraction 7 from step c) of separation with a solvent or a combination of solvents 11, makes it possible to obtain at least one fraction 10 rich in saturated compounds (raffinate), and a fraction 9 rich in aromatic compounds (extract),
- a hydrocracking step e) in the presence of a hydrogen-rich gas 12 and at least part of the fraction 9 rich in aromatics from the extraction step d), carried out in at least one reactor in fixed bed comprising a hydrocracking catalyst, a step f) of separating the effluent 13 from hydrocracking step e) making it possible to obtain at least one gaseous fraction 15 comprising hydrogen, and a liquid fraction 14 comprising compounds having a temperature of d '' boiling below 350 ° C,
- Figure 1 is an exemplary embodiment of the invention which does not limit the invention in any way. Only the main stages are shown in said figures, it is understood that all the equipment necessary for operation is present (tanks, pumps, exchangers, furnaces, columns, etc.). Only the main streams containing hydrocarbons are shown, but it is understood that streams of gas rich in hydrogen (make-up or recycle) can be injected at the inlet of each reactor or catalytic bed or between two reactors or two catalytic beds. Means well known to those skilled in the art of purifying and recycling hydrogen are also used. The hydrogen produced during the steam cracking step is advantageously used in addition to steps b) hydroconversion and / or d) hydrocracking.
- At least part of the pyrolysis oil fraction 20 resulting from separation step h) can be injected upstream of deasphalting step a) and / or of step b) of hydroconversion.
- this variant makes it possible to partially eliminate the asphaltenes contained in the pyrolysis oil and thus to maximize the production of olefins.
- the pyrolysis oil fraction resulting from separation step h) can be separated into at least two fractions, for example into a light pyrolysis oil fraction which is sent at least in part to step e) hydrocracking, and a heavy pyrolysis oil fraction which is sent at least in part to step b) hydroconversion and / or step a) of deasphalting.
- this variant still makes it possible to maximize the production of olefins.
- step c) of separating the effluent from hydroconversion step b) also makes it possible to obtain an atmospheric distillate fraction comprising compounds having a boiling point between 180 and 350 ° C. which can be introduced at least in part in stage d) for extracting the aromatics.
- the heavy hydrocarbon feed 1 treated in the process according to the invention is advantageously a hydrocarbon feed containing asphaltenes, and in particular having a C7 asphaltenes content of at least 1.0% by weight, preferably of at least 2.0%. weight in relation to the weight of the load.
- Charge 1 has an initial boiling temperature of at least 180 ° C, preferably at least 350 ° C and more preferably at least 540 ° C and a final boiling temperature of at least 600 ° C.
- the hydrocarbon feedstock 1 according to the invention can be chosen from atmospheric residues, vacuum residues resulting from direct distillation or resulting from other conversion processes, crude oils, topped crude oils, bituminous sands or their derivatives, Oil shales or their derivatives, mother rock oils or their derivatives, taken alone or in mixture.
- the feeds treated are preferably atmospheric residues or vacuum residues, or mixtures of these residues, and more preferably vacuum residues.
- the heavy hydrocarbon feed treated in the process may contain, among other things, sulfur impurities.
- the sulfur content can be at least 0.1% by weight, at least 0.5% by weight, preferably at least 1.0% by weight, more preferably at least 2.0%. by weight relative to the weight of the load.
- the heavy hydrocarbon feed treated in the process may contain, inter alia, metals.
- the nickel and vanadium content may be at least 20 ppm, preferably at least 50 ppm, based on the weight of the feed.
- the heavy hydrocarbon feed treated in the process may contain, inter alia, Conradson carbon.
- Conradson carbon content can be at least 2.0% by weight, preferably at least 5.0% by weight based on the weight of the filler.
- fillers can advantageously be used as they are.
- said charges can be mixed with at least one co-charge.
- co-fillers can be used at different stages of the process according to the invention in order to modulate the viscosity of the filler introduced at each of the stages.
- a co-charge can be introduced upstream of at least one reactor of stage b) of hydroconversion.
- This co-feed can be a hydrocarbon fraction or a mixture of lighter hydrocarbon fractions, which can preferably be chosen from the products resulting from a process of catalytic cracking in a fluid bed (FCC or “Fluid Catalytic Cracking” according to the English terminology).
- This co-charge can also be an atmospheric gas oil fraction or a vacuum gas oil fraction obtained by atmospheric or vacuum distillation of a crude oil or of an effluent from a conversion process such as coking or visbreaking or be obtained from stages c) and / or f) of separation. This co-charge does not represent more than 20% by weight of the heavy hydrocarbon feed 1.
- the process comprises a step a) of deasphalting by liquid-liquid extraction of the heavy hydrocarbon feed 1 or of the feed mixture c).
- Said step a) is carried out by liquid-liquid extraction using a solvent or a mixture of solvents 2 making it possible to obtain, on the one hand, a pitch fraction comprising asphalt, and on the other hand a deasphalted oil fraction (DAO) 3.
- DAO deasphalted oil fraction
- Step a) of deasphalting is preferably carried out under specific conditions making it possible to obtain, on the one hand, a DAO 3 fraction with a high yield, preferably greater than 60% by mass than the amount of compounds having a temperature of boiling greater than 540 ° C at the inlet of deasphalting step a), and on the other hand a pitch fraction comprising relatively soft asphalt, that is to say having a softening point greater than 100 ° C, preferably less than 120 ° C.
- Step a) of deasphalting is preferably carried out in a single step using an apolar solvent or a mixture of apolar solvents.
- Step a) can be carried out in an extraction column or extractor, or in a mixer-settler.
- Step a) is preferably carried out in an extraction column containing liquid-liquid contactors (packing elements and / or trays, etc.) placed in one or more zones.
- the solvent or the mixture of solvents 2 is introduced into the extraction column at two different levels.
- the deasphalting charge is introduced into an extraction column at a single introduction level, generally mixed with at least part of the solvent or of the mixture of solvents 2 and generally below a first zone of contactors. liquid-liquid.
- the other part of the solvent or mixture of solvents 2 is injected lower than the deasphalting charge, generally below a second zone of liquid-liquid contactors, the deasphalting charge being injected above this second. contactors area.
- Step a) is carried out under subcritical conditions, that is to say below the critical point, for said solvent or mixture of solvents 2.
- Step a) is carried out at a temperature advantageously between 50 and 350 ° C, preferably between 80 and 320 ° C, more preferably between 120 and 310 ° C, even more preferably between 150 and 300 ° C, and at a pressure advantageously between 0.1 and 6 MPa, preferably between 1 and 6 MPa, more preferably between 2 and 5 MPa.
- the volume ratio of the solvent or of the mixture of solvents 2 to the volume of charge 1 is generally between 1/1 and 12/1, preferably between 2/1 and 9/1 expressed in liters per liter. This ratio includes all of the solvent or mixture of solvents which can be divided into several injection points.
- the apolar solvent used is preferably a solvent composed of saturated hydrocarbon (s) comprising a number of carbons greater than or equal to 3, preferably between 4 and 5.
- These solvents can be for example propane, butane. or pentane. These solvents are used pure or as a mixture. He
- the solvent 2 used in step a) is an apolar solvent composed of at least 80% by volume of saturated hydrocarbon (s) comprising a number of carbons between 4 and 5, this so maximizing the yield of the DAO fraction intended to be treated during hydroconversion step b).
- Step a) can make it possible, thanks to these specific deasphalting conditions, to precipitate in the fraction comprising asphalt a limited quantity of polar structures of heavy resin and asphaltene type, which makes it possible to obtain a DAO 3 with a improved yield, generally greater than 60%, or even greater than 65% relative to the quantity of compounds having a boiling point greater than 540 ° C. at the inlet of deasphalting stage a).
- the DAO 3 fraction obtained comprises less than 1500 ppm of C7 asphaltenes, generally less than 1000 ppm of C7 asphaltenes.
- a fraction is recovered which comprises the DAO 3 fraction and a part of the solvent or mixture of solvents.
- a fraction is recovered which comprises asphalt and part of the solvent or mixture of solvents.
- the solvent or mixture of solvents 2 can be made up of a make-up and / or a part recycled during separation steps. These additions advantageously make it possible to compensate for the losses of solvent in the fraction comprising asphalt and / or in the DAO 3 fraction, due to the separation steps.
- Step a) of deasphalting comprises an integrated sub-step of separation of fraction 3 comprising the DAO and the solvent or mixture of solvents.
- the solvent or the mixture of solvents recovered can be recycled in step a) of deasphalting.
- This integrated separation sub-step making it possible to separate the DAO 3 and the solvent or the mixture of solvents can use all the necessary equipment known to those skilled in the art (separator flasks, distillation or stripping columns, heat exchangers , furnaces, pumps, compressors, etc.). At least part, and preferably all, of the DAO 3 fraction is sent to stage b) of ebullated bed hydroconversion.
- At least part, and preferably all, of the pitch fraction comprising asphalt 4 is sent to an optional conditioning step.
- an ebullating bed hydroconversion step b) is carried out in a boiling bed reactor in which the DAO 3 fraction resulting from deasphalting step a), in the presence of hydrogen 4, are brought into contact. with a hydroconversion catalyst.
- the DAO 3 fraction is introduced in step b) in the presence of a co-load.
- hydroconversion we mean all the reactions used to reduce the size of molecules, mainly by cleavage of carbon-carbon bonds, by the action of hydrogen 4 in the presence of a catalyst. During the hydroconversion step, hydrotreatment and hydrocracking reactions occur in particular.
- hydroconversion step b) comprises one or more three-phase reactors with an upward flow of liquid and gas containing at least one hydroconversion catalyst, the ebullating bed reactors possibly being arranged in series and / or in parallel, typically operating using the technology and under the conditions of the H-Oil TM process as described for example in US Patents 4,521, 295 or US 4,495,060 or US 4,457,831 or US 4,354,852, or in the article AlChE, March 19 -23, 1995, Houston, Texas, paper number 46d, "Second generation ebullated bed technology", or in chapter 3.5 "Hydroprocessing and Hydroconversion of Residue Fractions" of the book “Catalysis by Transition Métal Sulphides", edited by Éditions Technip in 2013.
- Each reactor advantageously comprises a recirculation pump allowing the catalyst to be maintained in an ebullating bed by continuous recycling of at least part of a liquid fraction advantageously withdrawn from the head of the reactor.
- the hydroconversion step b) is carried out under conditions making it possible to obtain a liquid effluent with a reduced content of sulfur, Conradson carbon, metals, and nitrogen.
- step b) is preferably carried out at an absolute pressure of between 5 MPa and 35 MPa, more preferably between 8 MPa and 25 MPa and so even more preferred, between 10 MPa and 20 MPa, at a temperature between 300 ° C and 550 ° C, more preferably between 350 ° C and 500 ° C and more preferably between 370 ° C and 450 ° C .
- the hourly space velocity (WH) relative to the volume of each three-phase reactor is preferably between 0.05 h 1 and 10 h 1 .
- the WH is between 0.1 h 1 and 10 h 1 , more preferably between 0.1 h 1 and 5.0 h 1 and even more preferably between 0.15 h 1 and 2.0 hrs 1 .
- the quantity of hydrogen 4 mixed with the feed is preferably between 50 and 5000 normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of liquid feed, preferably between 100 and 2000 Nm 3 / m 3 and very preferably between 200 and 1000 Nm 3 / m 3 .
- the hydroconversion catalyst used in hydroconversion step b) of the process according to the invention may contain one or more elements from groups 4 to 12 of the periodic table of the elements, which may or may not be deposited on a support.
- a catalyst comprising a support, preferably amorphous, such as silica, alumina, silica-alumina, titanium dioxide or combinations of these structures, and very preferably alumina.
- the catalyst may contain at least one metal from non-noble group VIIIB chosen from nickel and cobalt, and preferably nickel, said element from group VIIIB being preferably used in combination with at least one metal from group VIB chosen from among molybdenum and tungsten, and preferably the Group VIB metal is molybdenum.
- group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
- the hydroconversion catalyst used in hydroconversion step b) comprises an alumina support and at least one metal from group VIII chosen from nickel and cobalt, preferably nickel, and at least one metal from group VIB chosen from molybdenum and tungsten, preferably molybdenum.
- the hydroconversion catalyst comprises nickel as a group VIII element and molybdenum as a group VIB element.
- the non-noble group VIII metal content, in particular nickel is advantageously between 0.5% to 10.0% expressed by weight of metal oxide (in particular of NiO), and preferably between 1, 0% to 6.0% by weight, and the content of metal from group VIB, in particular molybdenum, is advantageously between 1.0% and 30% expressed by weight of oxide of the metal (in particular of molybdenum trioxide Mo0 3 ), and preferably between 4% and 20% by weight.
- the metal contents are expressed as a percentage by weight of metal oxide relative to the weight of the catalyst.
- This catalyst is advantageously used in the form of extrudates or beads.
- the balls have, for example, a diameter of between 0.4 mm and 4.0 mm.
- the extrudates have, for example, a cylindrical shape with a diameter of between 0.5 and 4.0 mm and a length of between 1.0 and 5.0 mm.
- the extrudates can also be objects of a different shape such as trilobes, regular or irregular tetralobes, or other multilobes. Catalysts of other forms can also be used, for example in the form of pellets ("pellets").
- the size of these different forms of catalyst can be characterized using the equivalent diameter.
- the equivalent diameter is defined by 6 times the ratio between the volume of the particle and the outer surface of the particle.
- the catalyst used in the form of extrudates, beads or other shapes therefore has an equivalent diameter of between 0.4 mm and 4.4 mm. These catalysts are well known to those skilled in the art.
- a different hydroconversion catalyst is used in each reactor of this initial hydroconversion stage (ai), the catalyst used in each reactor being adapted to the charge sent to this. reactor.
- each reactor contains one or more catalysts suitable for ebullating bed operation.
- the hydroconversion catalyst when it is used, can be partly replaced by fresh catalyst, and / or used catalyst but with catalytic activity. greater than the used catalyst to be replaced, and / or the regenerated catalyst, and / or the rejuvenated catalyst (catalyst from a rejuvenation zone in which most of the deposited metals are removed, before sending the spent and rejuvenated catalyst to a regeneration zone in which the carbon and sulfur it contains are removed, thus increasing the activity of the catalyst) , by withdrawing the used catalyst, preferably at the bottom of the reactor, and by introducing the replacement catalyst either at the top or at the bottom of the reactor.
- This replacement of used catalyst is preferably carried out at regular time intervals, and preferably in a puff or almost continuously.
- the replacement of spent catalyst can be done in whole or in part with used and / or regenerated and / or rejuvenated catalyst obtained from the same reactor and / or from another reactor of any hydroconversion stage.
- the catalyst can be added with the metals in the form of metal oxides, with the metals in the form of metal sulfides, or after preconditioning.
- the rate of replacement of the spent hydroconversion catalyst with fresh catalyst is advantageously between 0.01 kg and 10 kg per cubic meter of feed treated, and preferably between 0.1 kg and 3 kg per cubic meter. load processed. This withdrawal and this replacement are carried out using devices advantageously allowing the continuous operation of this hydroconversion step.
- the replacement at least in part, with regenerated catalyst, it is possible to send the spent catalyst withdrawn from the reactor to a regeneration zone in which the carbon and sulfur it contains are removed and then returned to this catalyst. regenerated in the hydroconversion step.
- the replacement at least in part by rejuvenated catalyst it is possible to send the spent catalyst withdrawn from the reactor to a rejuvenation zone in which most of the deposited metals are removed, before sending the spent catalyst. and rejuvenated in a regeneration zone in which the carbon and sulfur which it contains are removed, and then this regenerated catalyst is returned to hydroconversion stage b).
- Hydroconversion step b) is characterized by a degree of conversion of compounds boiling above 540 ° C greater than 50% by mass, preferably greater than 70% by mass.
- the effluent 5 obtained at the end of hydroconversion step b) comprises at least a liquid fraction 7 and a gas fraction 6 containing the gases, in particular H 2 , H 2 S, NH 3 , and hydrocarbons in CC 4 (i.e. comprising from 1 to 4 carbon atoms).
- the method comprises a step c) of separating the effluent 5 from hydroconversion step b) into at least one gaseous fraction 6, a fraction 7 comprising compounds having a boiling point between 180 and 540 ° and a fraction 8 comprising compounds having a boiling point of less than 180 ° C.
- the gas fraction 6, the fraction 7 and the fraction 8 can be separated from the effluent 5 using separation devices well known to those skilled in the art, in particular using one or more separator flasks which can operate at different pressures and temperatures, optionally associated with a means of stripping with steam or hydrogen and with one or more distillation columns. After possible cooling, the gas fraction 6 is preferably treated in a means for purifying hydrogen so as to recover the hydrogen not consumed during the hydroconversion reactions.
- the purified hydrogen can then advantageously be recycled in the process according to the invention.
- the hydrogen can be recycled to the inlet and / or to different places of stage b) of hydroconversion and / or of stage e) of hydrocracking.
- the separation step c) comprises a vacuum distillation in which at least part of the effluent 5 from step b) can undergo treatments using well-known separation devices, then be fractionated by distillation. under vacuum to at least one vacuum distillate fraction and at least one vacuum residue fraction.
- the vacuum distillate fraction comprises vacuum gas oil-type fractions, that is, compounds having a boiling point between 350 and 540 ° C.
- the vacuum residue fraction is preferably a liquid hydrocarbon fraction containing at least 80% of compounds having a boiling point greater than or equal to 540 ° C.
- the separation step c) comprises atmospheric distillation, upstream of the vacuum distillation, in which the liquid hydrocarbon fraction (s) obtained after separation is (are) ) fractionated by atmospheric distillation into at least one atmospheric distillate fraction and at least one atmospheric residue fraction, then vacuum distillation in which the atmospheric residue fraction obtained after atmospheric distillation is fractionated by vacuum distillation into at least one distillate fraction under vacuum and at least a residue fraction under vacuum.
- the separation step c) further comprises at least one atmospheric distillation upstream of the vacuum distillation, in which at least part of the effluent from step b) is fractionated by atmospheric distillation in at least one.
- at least one fraction 8 comprising compounds having a boiling point of less than 180 ° C, and a distillate fraction containing diesel, that is to say comprising compounds having a boiling point of between 180 and 350 ° C .
- fraction 8 comprising compounds having a boiling point of less than 180 ° C is at least partly and preferably entirely sent to step g) of steam cracking.
- the distillate fraction containing diesel can be at least in part and preferably in full sent to the extraction step d).
- At least part, and preferably all of fraction 7 comprising at least part, preferably all, of a vacuum distillate fraction and of a diesel-containing distillate fraction is sent to step d) extraction of aromatics.
- the vacuum residue fraction can optionally be sent to stage d) of extraction and / or e) of hydrocracking.
- the separation step c) comprises atmospheric distillation and the atmospheric residue obtained is sent to the extraction step d).
- the process comprises a step d) of extracting the aromatics from at least part of fraction 7 from step c). Said stage d) of extracting the aromatics makes it possible to obtain an extract fraction 9 and a raffinate fraction 10.
- Fraction 7 resulting from step c) comprises at least one part, preferably all, of a vacuum distillate fraction comprising compounds having a boiling point of between 350 and 540 ° C and at least one part, preferably all of a distillate fraction comprising compounds having a boiling point of between 180 and 350 ° C resulting from step c) of separation.
- stage d) of extracting the aromatics is to extract at least part of the aromatic compounds as well as the resins by liquid-liquid extraction using a polar solvent 11.
- the compounds extracted during step d) preferably have a boiling point greater than the boiling point of the solvent, which advantageously makes it possible to maximize the yield during the separation of the solvent from the raffinate after the extraction. In addition, the recovery of the solvent is also more efficient and economical.
- solvent furfural, N-methyl-2-pyrrolidone (NMP), sulfolane, dimethylformamide (DMF), dimethylsulfoxide (DMSO), phenol, or a mixture of these solvents in equal proportions or different.
- NMP N-methyl-2-pyrrolidone
- sulfolane dimethylformamide
- DMF dimethylformamide
- DMSO dimethylsulfoxide
- phenol phenol
- the solvent is furfuraldehyde.
- the operating conditions are generally a solvent / feed ratio of step d) of 1/2 to 6/1, preferably from 1/1 to 4/1, a temperature profile between room temperature and 150 ° C, preferably between 50 and 150 ° C.
- the pressure is between atmospheric pressure and 2.0 MPa, preferably between 0.1 and 1.0 MPa.
- the liquid / liquid extraction can generally be carried out in a mixer-settler or in an extraction column operating in countercurrent.
- the extraction is carried out in an extraction column.
- the chosen solvent has a sufficiently high boiling point to be able to fluidify the charge of step d) without vaporizing.
- step d After contact with the solvent, with the effluent introduced in step d), two fractions are obtained at the end of step d), an extract fraction 9, consisting of parts of the heavy fraction not soluble in the solvent ( and highly concentrated in aromatics) and a raffinate fraction 10, consisting of the solvent and the soluble parts of the heavy fraction.
- the solvent is distilled off from the soluble parts and recycled internally to the liquid / liquid extraction process.
- the separation of the extract and the raffinate and the recovery of the solvent are carried out in a separation sub-step integrated in step d) of extracting the aromatics.
- the process comprises a stage e) of hydrocracking in a fixed bed of at least part of the extracted fraction 9 resulting from the extraction stage d) in the presence of a hydrocracking catalyst.
- Hydrogen 12 can also be injected upstream of the various catalytic beds contained in the hydrocracking reactor (s).
- any type of hydrotreatment reaction also occurs (HDM, HDS, HDN, etc.)
- Hydrocracking reactions leading to the formation of atmospheric distillates take place with a degree of conversion of the vacuum distillate to atmospheric distillate which is generally greater than 30%, typically between 30 and 50% for mild hydrocracking and greater than 80% for extensive hydrocracking.
- Specific conditions, in particular temperature, and / or the use of one or more specific catalysts, make it possible to promote the desired hydrocracking reactions.
- Hydrocracking step e) is carried out under hydrocracking conditions. It can advantageously be carried out at a temperature between 340 and 480 ° C, preferably between 350 and 430 ° C and at an absolute pressure between 5 and 25 MPa, preferably between 8 and 20 MPa, preferably between 10 and 18 MPa. The temperature is usually adjusted depending on the desired level of hydrotreatment and the duration of the intended treatment. Most often, the space velocity of the hydrocarbon feed, commonly called WH, and which is defined as being the volumetric flow rate of the feed divided by the total volume of the catalyst, can be in a range from 0.1 to 3, 0 h 1 , preferably from 0.2 to 2.0 h 1 , and more preferably from 0.25 to 1.0 h 1 .
- the quantity of hydrogen mixed with the feed can be between 100 and 5000 normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of liquid feed, preferably between 200 and 2000 Nm 3 / m 3 , and more preferably between 300 and 1500 Nm 3 / m 3 .
- Hydrocracking stage e) can be carried out industrially in at least one reactor with a downward flow of liquid.
- Hydrocracking step e) preferably comprises two catalytic sections in series, with an upstream hydrotreating catalytic section so as to limit the deactivation of the downstream hydrocracking catalytic section.
- This hydrotreatment section aims in particular to significantly reduce the nitrogen content of the feed, nitrogen being an inhibitor of the acid function of the bifunctional catalysts of the hydrocracking catalytic section.
- Hydrocracking step e) can also comprise a second hydrocracking catalytic section treating at least one heavy cut obtained from the first hydrocracking catalytic section previously separated in a separation step.
- Hydrocracking step e) can comprise the recycling of a heavy cut obtained from the first hydrocracking catalytic section previously separated in a separation step.
- the catalysts in hydrocracking step e) used can be hydrotreatment and hydrocracking catalysts.
- the hydrotreatment catalysts used can be hydrotreatment catalysts consisting of a support of inorganic oxide type (preferably an alumina) and of an active phase comprising chemical elements chosen from group VIII (Ni, Co, etc. ) and group VI (Mo, etc.).
- the hydrocracking catalysts can advantageously be bifunctional catalysts, having a hydrogenating phase in order to be able to hydrogenate the aromatics and to achieve the equilibrium between the saturated compounds and the corresponding olefins and an acid phase which makes it possible to promote the hydroisomerization reactions. and hydrocracking.
- the acid function is advantageously provided by supports with large surfaces (generally 100 to 800 m 2 .g 1 ) having a surface acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), combinations of oxides of boron and of. aluminum, amorphous silica-aluminas and zeolites.
- the hydrogenating function is advantageously provided either by one or more metals from group VIII of the periodic table of the elements, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum , or by a combination of at least one metal from group VIB of the periodic table, such as molybdenum and tungsten, and at least one non-noble metal from group VIII (such as nickel and cobalt).
- the bifunctional catalyst used comprises at least one metal chosen from the group formed by the metals of groups VIII and VIB, taken alone or as a mixture, and a support comprising 10 to 90% by weight of a zeolite and 90 to 10%. weight of inorganic oxides.
- the group VIB metal used is preferably chosen from tungsten and molybdenum and the group VIII metal is preferably chosen from nickel and cobalt.
- monofunctional catalysts and bifunctional catalysts of the alumina, silica-amorphous or zeolitic alumina type can be used as a mixture or in successive layers.
- the catalytic volume used during the second hydrocracking stage e) consists of at least 30% of hydrocracking catalysts of the bifunctional type.
- a co-feed (not shown) can be injected upstream of any catalytic bed of hydrocracking section e).
- This co-charge is typically a vacuum distillate resulting from direct distillation or resulting from a conversion process, or a deasphalted oil.
- hydrocracking step e) is carried out in “maxi naphtha” mode, that is to say it makes it possible to obtain a yield of liquid compounds having a boiling point of less than 180 ° C. greater than 50% by weight of the feedstock entering hydrocracking stage e).
- step f The effluent 13 from step e) of fixed bed hydrocracking is sent to a separation step f).
- Step f separation of the hydrocraquaqe effluent in a fixed bed
- the method further comprises a step f) of separating the effluent 13 from step e) of fixed bed hydrocracking into at least one gas fraction 15 and at least one liquid fraction 14.
- Said effluent 13 is advantageously separated in at least one separator flask into at least one gaseous fraction 15 and at least one liquid fraction 14.
- the step of separating said effluent 13 can be carried out using any known separation devices in the field. a person skilled in the art, such as one or more separator flasks which can operate at different pressures and temperatures, optionally associated with a means for stripping with steam or with hydrogen and with one or more distillation columns.
- These separators can for example be high pressure high temperature separators (HPHT) and / or high pressure low temperature separators (HPBT).
- the gaseous fraction 15 obtained at the end of stage e) of separation comprises gases, such as H 2 , H 2 S, NH 3 , and C1-C4 hydrocarbons (such as methane, ethane, propane, etc. butane).
- the hydrogen contained in the gaseous fraction 15 is purified and recycled in any one of stages b) of ebullating bed hydroconversion and / or e) of fixed bed hydrocracking.
- the purification of the hydrogen contained in the gas fraction 15 can be carried out simultaneously with the treatments of the gas fractions resulting from the separation of the effluents from stages b) of hydroconversion in an ebullating bed and e) of hydrocracking. in a fixed bed.
- the purification of hydrogen can be carried out by amine wash, a membrane, a system of PSA type (Pressure Swing Adsorption according to the English terminology), or several of these means arranged in series.
- the separation step f) further comprises gas-liquid separation or the succession of separation devices, at least one atmospheric distillation, in which the hydrocarbon fraction (s) ) liquid (s) obtained after separation is (are) fractionated by atmospheric distillation into at least one atmospheric distillate fraction 14 comprising compounds having a boiling point below 350 ° C and optionally a liquid fraction comprising vacuum distillate comprising compounds having a boiling point greater than 350 ° C.
- At least part, and preferably all, of the atmospheric distillate fraction 14 and optionally of the fraction comprising vacuum distillate is advantageously sent to step g) of steam cracking.
- At least part of the vacuum distillate type fraction is recycled to hydrocracking step e), and according to this variant it may be necessary to perform a purge consisting of unconverted fractions of vacuum distillate type from so as to deconcentrate the polyaromatic species and to limit the deactivation of the hydrocracking catalyst of step e).
- a purge consisting of unconverted fractions of vacuum distillate type from so as to deconcentrate the polyaromatic species and to limit the deactivation of the hydrocracking catalyst of step e).
- it may be advantageous to optionally carry out this purge by sending at least part of the unconverted fraction of vacuum distillate type at the input of step a) of deasphalting of so as to at least partially eliminate the polyaromatic species in the fraction comprising asphalt.
- the compounds boiling above 180 ° C. are at least partly and preferably completely recycled to step e) in a manner to increase the yield of compounds boiling below 180 ° C in the atmospheric distillate cut 14.
- the process comprises a step g) of steam cracking at least the raffinate fraction 10 resulting from the extraction step d), the fraction 8 resulting from the separation step c) and the liquid fraction 14 resulting from separation step f) comprising compounds having a boiling point of less than 350 ° C, and optionally a fraction comprising compounds having a boiling point greater than 350 ° C. resulting from stage f) of separation.
- the light hydrocarbons of 2 to 4 carbon atoms resulting from stages c) and f) of separation are sent to the steam cracking stage.
- Step g) of steam cracking is advantageously carried out in at least one pyrolysis furnace at a temperature between 700 and 900 ° C, preferably between 750 and 850 ° C, and at a pressure between 0.05 and 0.3 Relative MPa.
- the residence time of the hydrocarbons is generally less than or equal to 1.0 seconds (denoted s), preferably between 0.1 and 0.5 s.
- water vapor is introduced upstream of steam cracking step g).
- the quantity of water introduced is between 0.3 and 3.0 kg of water per kg of hydrocarbons at the inlet of step g).
- step g) is carried out in several pyrolysis ovens in parallel so as to adapt the operating conditions to the different flows feeding step g) and resulting from steps c), d), f) and h), and also to manage the decoking times of the tubes.
- a furnace comprises one or more tubes arranged in parallel.
- a furnace can also refer to a group of furnaces operating in parallel. For example, one furnace can be dedicated to cracking fractions rich in ethane, another furnace dedicated to cuts rich in propane and butane, another furnace dedicated to cuts comprising compounds having a boiling point between 80 and 180 ° C. , and another oven dedicated to cuts comprising compounds having a boiling point between 180 and 350 ° C.
- the method comprises a step h) of separating the effluent 16 from steam cracking step g) making it possible to obtain at least one fraction 17 comprising, preferably consisting of, hydrogen, a fraction 18 comprising, preferably consisting of ethylene, a fraction 19 comprising, preferably consisting of, propylene and a fraction 20 comprising, preferably consisting, and pyrolysis oil.
- step h) of separation also makes it possible to recover a fraction comprising, preferably consisting of, butenes and a fraction comprising, preferably consisting of, pyrolysis gasoline.
- the cuts rich in saturated compounds resulting from the light gases or from the pyrolysis gasoline resulting from the separation stage h) can be recycled to the stage g) of steam cracking, in particular ethane and propane, so as to increase the yield of ethylene and propylene.
- the pyrolysis oil fraction 20 can optionally be subjected to an additional separation step so as to obtain several fractions, for example a light pyrolysis oil comprising compounds having a boiling point of less than 350 ° C and a heavy pyrolysis oil. comprising compounds having a boiling point greater than 350 ° C.
- the light pyrolysis oil can advantageously be injected upstream of step d) of hydrocracking.
- the heavy pyrolysis oil can advantageously be injected upstream of step b) of hydroconversion and / or of step a) of deasphalting.
- the separation of fraction 20 into two fractions and their recycling in one of steps b), a), or e) of the process makes it possible to maximize the formation of olefins from heavy hydrocarbon feedstocks.
- the heavy hydrocarbon feed 1 treated in the process is a vacuum residue of Safaniyah origin and having the properties indicated in Table 1.
- Table 1 Properties of the charge Charge 1 is subjected to a deasphalting step a) carried out in an extraction column operating continuously under the conditions presented in Table 2:
- step a) of deasphalting a 3 DAO fraction is obtained with a yield of 68% and a pitch fraction comprising asphalt is obtained with a yield of 32%; these yields are related to the charge of deasphalting step a).
- the DAO fraction 3 resulting from deasphalting step a) is subjected to a hydroconversion step b) in two ebullating bed reactors in series and in the presence of hydrogen 4 and a boiling bed hydroconversion catalyst of NiMo type on alumina under the conditions indicated in Table 3.
- the effluent 5 resulting from the ebullating bed hydroconversion stage b) is subjected to a separation stage c) comprising separator flasks as well as an atmospheric distillation column and a vacuum distillation column.
- the yields of the different Fractions obtained after separation are shown in Table 4 (% mass relative to the feedstock upstream of stage b) of ebullating bed hydroconversion, noted% m / m):
- Table 4 yields of hydroconversion step b) after separation in step c)
- the fraction (180-350 ° C) and the fraction (350-540 ° C) obtained from step c) of separation are sent to a stage d) for extracting the aromatics carried out in a mixer-settler, the conditions of which are presented in Table 5:
- the effluent 13 resulting from the fixed bed hydrocracking stage e) is subjected to a separation stage comprising separator flasks as well as an atmospheric distillation column.
- the yields of the different fractions obtained after separation are shown in Table 7 (% by mass relative to the feedstock upstream of stage e) of fixed bed hydrocracking, noted% m / m):
- Table 7 Yields of fixed bed hydrocracking step e) after separation in step f).
- the liquid fractions ( ⁇ 220 ° C), (220-350 ° C) and (350 ° C +) resulting from stage f) of separation of the effluent from the fixed bed hydrocracking stage, fraction 8 ( ⁇ 180 ° C) from step c) of separation and the raffinate fraction from step d) of extraction of the aromatics are sent to a step g) of steam cracking where each of the liquid fraction is cracked in different conditions (Table 8).
- Table 8 conditions of the steam cracking step
- the effluents from the various steam cracking furnaces are subjected to a separation stage h) making it possible to recycle the saturated compounds and to obtain the yields presented in Table 9 (% by mass relative to the total load upstream of stage g) steam cracking, noted% m / m).
- Table 9 shows the yields of steam cracking products. Compared to the vacuum residue type feedstock 1 introduced in deasphalting step a), the process according to the invention makes it possible to achieve mass yields of ethylene and propylene of 15.6% and 8.5% respectively. . In addition, the specific sequence of steps upstream of the steam cracking step makes it possible to limit the formation of coke.
- the fraction (540 ° C +) of the vacuum residue type resulting from stage c) of separation of the effluent from stage b) from hydroconversion in an ebullating bed and the pyrolysis oil fraction resulting from stage h) for separating the effluent from steam cracking step g) are upgraded as fuel bases and in particular as heavy fuel oil after other fuel bases from other processes.
- the pitch fraction comprising asphalt from deasphalting step a) is characterized by a softening point of 140 ° C and is sent to a conditioning step to recover the pitch fraction in the form of divided solids.
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Abstract
Description
Claims
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Application Number | Priority Date | Filing Date | Title |
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FR1912442A FR3102772B1 (fr) | 2019-11-06 | 2019-11-06 | Procede de production d’olefines comprenant un desasphaltage, un hydrocraquage et un vapocraquage |
PCT/EP2020/080670 WO2021089477A1 (fr) | 2019-11-06 | 2020-11-02 | Procede de production d'olefines comprenant un desasphaltage, un hydrocraquage et un vapocraquage |
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EP4055121A1 true EP4055121A1 (fr) | 2022-09-14 |
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EP20797148.2A Pending EP4055121A1 (fr) | 2019-11-06 | 2020-11-02 | Procede de production d'olefines comprenant un desasphaltage, un hydrocraquage et un vapocraquage |
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US (1) | US20220372384A1 (fr) |
EP (1) | EP4055121A1 (fr) |
CN (1) | CN114599768B (fr) |
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WO (1) | WO2021089477A1 (fr) |
Family Cites Families (23)
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GB1400884A (en) * | 1972-03-13 | 1975-07-16 | Ici Ltd | Treatment of the feedstock for a aromatic hydrocarbon extraction process |
US4354852A (en) | 1981-04-24 | 1982-10-19 | Hydrocarbon Research, Inc. | Phase separation of hydrocarbon liquids using liquid vortex |
US4457831A (en) | 1982-08-18 | 1984-07-03 | Hri, Inc. | Two-stage catalytic hydroconversion of hydrocarbon feedstocks using resid recycle |
US4495060A (en) | 1982-12-27 | 1985-01-22 | Hri, Inc. | Quenching hydrocarbon effluent from catalytic reactor to avoid precipitation of asphaltene compounds |
US4521295A (en) | 1982-12-27 | 1985-06-04 | Hri, Inc. | Sustained high hydroconversion of petroleum residua feedstocks |
WO1992008367A1 (fr) * | 1990-11-16 | 1992-05-29 | The Procter & Gamble Company | Compositions contenant du psyllium |
CN1043051C (zh) * | 1994-07-22 | 1999-04-21 | 国际壳牌研究有限公司 | 制备氢化石蜡的方法 |
KR101147469B1 (ko) * | 2004-03-08 | 2012-05-21 | 리서치 인스티튜트 오브 페트롤리움 프로세싱 시노펙 | 경질 올레핀 및 방향족 화합물의 제조 방법 |
WO2006063201A1 (fr) * | 2004-12-10 | 2006-06-15 | Bhirud Vasant L | Craquage a la vapeur avec desaromatisation de naphtha |
US20090156876A1 (en) * | 2007-12-18 | 2009-06-18 | Ou John D Y | Apparatus and Process for Cracking Hydrocarbonaceous Feed Treated to Adsorb Paraffin-Insoluble Compounds |
FR2958656B1 (fr) * | 2010-04-13 | 2012-05-11 | Inst Francais Du Petrole | Procede d'hydroconversion de charges petrolieres via une technologie en slurry permettant la recuperation des metaux du catalyseur et de la charge mettant en oeuvre une etape d'extraction. |
US9284502B2 (en) * | 2012-01-27 | 2016-03-15 | Saudi Arabian Oil Company | Integrated solvent deasphalting, hydrotreating and steam pyrolysis process for direct processing of a crude oil |
SG11201509166QA (en) * | 2013-07-02 | 2016-01-28 | Saudi Basic Ind Corp | Method of producing aromatics and light olefins from a hydrocarbon feedstock |
FR3014897B1 (fr) * | 2013-12-17 | 2017-04-07 | Ifp Energies Now | Nouveau procede integre de traitement de charges petrolieres pour la production de fiouls a basse teneur en soufre et en sediments |
FR3033797B1 (fr) | 2015-03-16 | 2018-12-07 | IFP Energies Nouvelles | Procede ameliore de conversion de charges hydrocarbonees lourdes |
JP6965245B2 (ja) * | 2015-11-30 | 2021-11-10 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | 蒸気分解処理のための高品質フィードストックを作り出すための方法 |
FR3053047B1 (fr) * | 2016-06-23 | 2018-07-27 | Axens | Procede ameliore d'hydroconversion profonde au moyen d'une extraction des aromatiques et resines avec valorisation de l'extrait a l'hydroconversion et du raffinat aux unites aval. |
FR3054453B1 (fr) * | 2016-07-28 | 2020-11-20 | Ifp Energies Now | Procede de production d'une fraction hydrocarbonee lourde a basse teneur en soufre comportant une section de demettalation et d'hydrocraquage avec des reacteurs echangeables entre les deux sections. |
US10619112B2 (en) * | 2016-11-21 | 2020-04-14 | Saudi Arabian Oil Company | Process and system for conversion of crude oil to petrochemicals and fuel products integrating vacuum gas oil hydrotreating and steam cracking |
AR110493A1 (es) * | 2016-12-08 | 2019-04-03 | Shell Int Research | Un método para pretratar y convertir hidrocarburos |
US10513664B1 (en) * | 2018-12-17 | 2019-12-24 | Saudi Arabian Oil Company | Integrated aromatic separation process with selective hydrocracking and steam pyrolysis processes |
FR3098824B1 (fr) * | 2019-07-17 | 2021-09-03 | Ifp Energies Now | Procede de production d’olefines comprenant un hydrotraitement, un desasphaltage, un hydrocraquage et un vapocraquage |
FR3101637B1 (fr) * | 2019-10-07 | 2021-10-22 | Ifp Energies Now | Procede de production d’olefines comprenant un desasphaltage, une hydroconversion, un hydrocraquage et un vapocraquage |
-
2019
- 2019-11-06 FR FR1912442A patent/FR3102772B1/fr active Active
-
2020
- 2020-11-02 WO PCT/EP2020/080670 patent/WO2021089477A1/fr unknown
- 2020-11-02 EP EP20797148.2A patent/EP4055121A1/fr active Pending
- 2020-11-02 CN CN202080077328.7A patent/CN114599768B/zh active Active
- 2020-11-02 US US17/772,602 patent/US20220372384A1/en active Pending
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CN114599768A (zh) | 2022-06-07 |
CN114599768B (zh) | 2023-11-07 |
US20220372384A1 (en) | 2022-11-24 |
WO2021089477A1 (fr) | 2021-05-14 |
FR3102772A1 (fr) | 2021-05-07 |
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