EP1474499B1 - Procede integre de desulfuration d un effluent de craquage o u de vapocraquage d hydrocarbures - Google Patents
Procede integre de desulfuration d un effluent de craquage o u de vapocraquage d hydrocarbures Download PDFInfo
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- EP1474499B1 EP1474499B1 EP03709894A EP03709894A EP1474499B1 EP 1474499 B1 EP1474499 B1 EP 1474499B1 EP 03709894 A EP03709894 A EP 03709894A EP 03709894 A EP03709894 A EP 03709894A EP 1474499 B1 EP1474499 B1 EP 1474499B1
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- European Patent Office
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- alkylation
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- compounds
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 9
- 238000004230 steam cracking Methods 0.000 title claims abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 8
- 238000005336 cracking Methods 0.000 title abstract description 5
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 59
- 230000029936 alkylation Effects 0.000 claims abstract description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 31
- 238000004821 distillation Methods 0.000 claims abstract description 23
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 6
- 230000023556 desulfurization Effects 0.000 claims abstract description 6
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 5
- 230000008030 elimination Effects 0.000 claims abstract description 5
- 238000003379 elimination reaction Methods 0.000 claims abstract description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 50
- 150000001336 alkenes Chemical class 0.000 claims description 38
- 229930192474 thiophene Natural products 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 22
- 238000009835 boiling Methods 0.000 claims description 21
- 229910052717 sulfur Inorganic materials 0.000 claims description 20
- 239000011593 sulfur Substances 0.000 claims description 20
- 239000003377 acid catalyst Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- -1 alkyl thiophenes Chemical class 0.000 claims description 10
- 150000001993 dienes Chemical class 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims 9
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 238000011144 upstream manufacturing Methods 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 18
- 229910017464 nitrogen compound Inorganic materials 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 150000002830 nitrogen compounds Chemical class 0.000 description 12
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 9
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 150000003577 thiophenes Chemical class 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 150000003464 sulfur compounds Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000006471 dimerization reaction Methods 0.000 description 3
- 238000007327 hydrogenolysis reaction Methods 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 241000894007 species Species 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 241001080024 Telles Species 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000006069 physical mixture Substances 0.000 description 2
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 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
- 238000005406 washing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical class CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G69/12—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 polymerisation or alkylation 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
- C10G69/12—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 polymerisation or alkylation step
- C10G69/123—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 polymerisation or alkylation step alkylation
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
Definitions
- WO-A-0 196 498, US-A-5 599 441 and US-A-6 024 865 relate to the desulfurization of gasolines.
- the present invention relates to a process for desulfurizing hydrocarbon cuts containing olefins and sulfur at least partly in the form of thiophene compounds or benzothiophene.
- the olefin content of the hydrocarbon cuts that are desulfurize is at least 3% by weight and the contents of these cuts in compounds thiophenics or benzothiophenics of at least 5 ppm and up to 3% by weight sulfur weight.
- the final boiling point of the hydrocarbon cut that is usually treated in the context of the present invention is generally less than or equal to 350 ° C.
- This cup may contain benzene. It is therefore most often a petrol cut either wholly or partly (preferably at least 10% by weight), of any hydrocarbon conversion process known from the skilled person.
- the charge is generally selected from the group consisting of the effluents of a unit of catalytic cracking, steam cracking or coke production (coking according to the Anglo-Saxon terminology).
- the gasolines originating from cracking processes are treated in particular (the most often a catalytic cracking process) which usually constitute in France approximately 40% by weight of the gasoline mixture stored in the refinery "pool according to the English terminology". They are particularly interesting because they have significant contents unsaturated hydrocarbons of the olefinic type. These olefins give these species high octane. However, they sometimes have a high sulfur content between 0.05% and 1% by weight. In the European specifications, the sulfur content in the species for marketing must not exceed 50 ppm by weight or even 10 ppm in weight in the near future.
- the method of the present invention comprises a step for the purpose of selectively sulfur compounds contained in these species thus making it possible to separate them from olefins by distillation. It then remains only to treat with a gas containing hydrogen a cut enriched in sulfur and depleted in olefins. The other cut (lighter) depleted in sulfur and containing olefins does not undergo hydrogenation and thus retains its anti-knocking properties.
- the present invention may make it possible not to carry out the prior elimination of the compounds nitrogen, generally basic, present in the feeds to be treated, by an acid wash or by use of a guard bed.
- the presence of such compounds required either to use a completely different type sequences, especially in the case where it is desired to eliminate thiophene or thiophene compounds, to get rid of these basic nitrogen compounds, by an acid wash or by use of a guard bed usually containing a specific adsorbent.
- the gasoline (or ⁇ ) that may contain diolefins is injected via line 1 into a unit (A) hydrogenation of diolefins.
- This step a), as well as step c) described below are steps optional if the feed is free of diolefins.
- Hydrogen is injected via line 2.
- the charge and hydrogen are contacted with a hydrogenation catalyst.
- This step Hydrogenation of diolefins is known to those skilled in the art.
- this step a) it is Often produces at least partial elimination of light sulfur compounds such as mercaptans, having a lower boiling point than thiophene, by adding these compounds on olefinic compounds present in the feed to be treated.
- Said fraction 6 containing olefins may, for example, according to the invention be used as charge or as a complement to the charge in the e) alkylation step described in the following description.
- the light section 9 (or ⁇ ) whose boiling points are usually between 60 ° C. and 180 ° C (or 150 ° C or 115 ° C) is sent, possibly after mixing with some of the olefins from line 10 in an alkylation unit E (step e)).
- Olefins can be introduced if necessary by line 20 into the unit E of alkylation.
- Said olefins include generally from 2 to 10 carbon atoms, often from 3 to 7 and preferentially from 3 to 5 atoms of carbon.
- the thiophenic compounds and mercaptans contained in the 60 ° C-180 ° C or 60 ° C-150 ° C or 60 ° C-115 ° C section will react at least in part and often in the majority, generally at more than 50% and even more than 95% with olefins to form thiophene alkyls and sulfides according to the following reaction for thiophene:
- This e) alkylation step is carried out in the presence of an acid catalyst.
- This catalyst can be indifferently a resin, a silica-alumina, a zeolite, a clay or any silico-aluminate having any acidity (possibly provided by the absorption of acids on this support).
- the hourly volume velocity: charge volume injected per hour over the catalyst volume is preferably from about 0.1 to about 10 h -1 (liter / liter / hour) and very preferably from about 0.5 to about 4 h -1 .
- this alkylation step is usually carried out in the presence of at least one acid catalyst chosen from the group formed by silica-aluminas, silicoaluminates, titanosilicates, mixed titanium alumina, clays, resins and mixed oxides.
- at least one acid catalyst chosen from the group formed by silica-aluminas, silicoaluminates, titanosilicates, mixed titanium alumina, clays, resins and mixed oxides.
- organo-metallic organosoluble or water-soluble compound most often chosen from the group formed by the alkyls and / or alkoxy metals of at least one element of Groups IVA, IVB, VA, such as titanium, zirconium silicon, germanium, tin, tantalum, niobium
- at least one mineral oxide such as alumina (gamma, delta, eta, alone or as a mixture), silica, silica-aluminas, titanium silicas, zirconia silicas or any other solid having any acidity.
- a particular embodiment of the invention may consist in using a physical mixture of at least two catalysts such as those mentioned above in proportions by volume ranging from 95/5 to 5/95, preferably 85/15 to 15/85 and very preferably 70/30 to 30/70. It is also possible to use supported sulfuric acid or phosphoric acid. In this case the support is usually a mineral carrier such as for example one of those mentioned above and more particularly silica, alumina or a silica-alumina.
- the temperature for this step is usually from about 30 ° C to about 250 ° C, and the most often from about 50 ° C to about 220 ° C, or even about 50 ° C to about 190 ° C and even 50 ° C to 180 ° C depending on the type of catalyst and / or the strength of the acidity of the catalyst. So for a resin ion exchange type organic acid, the temperature is from about 50 ° C to about 150 ° C preferably from about 50 ° C to about 120 ° C, or even from about 50 ° C to about 110 ° C.
- the alkylation step is generally carried out at a temperature of between about 50 ° C and about 200 ° C, preferably between about 50 ° C and about 180 ° C, and more preferably between 80 ° C and 150 ° C.
- the molar ratio olefins on the sum (thiophene + thiophene compounds) present in the cut is from about 0.1 to about 2000 mole / mole preferably from about 0.5 to about 1000 mole / mole.
- the section •, arriving via line 13, will be mixed with hydrogen introduced via line 14.
- This mixture enters the hydrocracking unit G which contains an acid catalyst.
- This catalyst can be indifferently a resin, a zeolite, a clay, a silica-alumina or any silico-aluminate.
- the hourly volume velocity: charge volume injected per hour over the catalyst volume is preferably from about 0.1 to about 10 h -1 (liter / liter / hour) and more preferably from about 0.5 to about 4 h -1 .
- this hydrocracking step g) is usually carried out in the presence of at least one acid catalyst chosen from the group formed by silica-aluminas, silicoaluminates, titanosilicates, mixed titanium alumina, clays, resins, mixed oxides obtained by grafting at least one organo-metallic organosoluble or water-soluble compound (most often chosen from the group formed by the alkyls and / or alkoxy metals of at least one element of groups IVA, IVB, VA, such as titanium , zirconium silicon, germanium, tin, tantalum, niobium) on at least one mineral oxide such as alumina (gamma, delta, eta, alone or as a mixture), silica, silica-aluminas, titanium silicas, zirconia silicas or any other acidic solid.
- at least one acid catalyst chosen from the group formed by silica-aluminas, silicoaluminates, titanosilicates, mixed titanium alumina, clay
- the catalyst which is employed may also contain metals generally in the form of sulphides such as, for example, non-noble Group VIII metals and / or Group VIB metals. Among these metals the most commonly used are nickel, cobalt, molybdenum and tungsten.
- a particular embodiment of the invention may consist in using a physical mixture of at least two catalysts such as those mentioned above in volume proportions ranging from 95/5 to 5/95, preferably 85/15 to 15/85. and very preferably 70/30 to 30/70. It is also possible to use supported sulfuric acid or phosphoric acid. In this case the support is usually a mineral carrier such as for example one of those cited above and more particularly silica, alumina or a silica-alumina.
- the temperature for this step is from about 30 ° C to about 500 ° C, often from about 60 ° C to about 400 ° C and most often from about 100 ° C to about 400 ° C, or about 200 ° C to about 400 ° C depending on the type of catalyst or the strength of the catalyst acidity. So for a zeolite Y, the temperature is from about 80 ° C to about 400 ° C, preferably from about 100 ° C to about 380 ° C, or about 130 ° C to about 360 ° C or even 200 ° C to 350 ° C.
- the temperature is generally between about 200 ° C and about 400 ° C, preferably between about 220 ° C and about 400 ° C, more preferably between about 240 ° C and about 390 ° C.
- the hydrocracking temperature is generally between about 200 ° C and about 400 ° C, preferably between about 220 ° C and about 390 ° C and more preferably between about 220 ° C and 380 ° C.
- the hydrocracking is carried out at a temperature greater than 200 ° C., whatever the acidic solid used, while the alkylation step is carried out at a temperature preferably less than 200 ° C and more preferably less than 190 ° C or even 180 ° C whatever the nature of the acid solid.
- This hydrocracking unit will transform the di-alkyl thiophenes, previously formed in the alkylation unit E of step e) in thiophene and light isoparaffins or isomerize the di-alkyls thiophene. Indeed, these di-alkyl thiophene compounds are very congested compounds sterically and where sulfur is insensitive to hydrogenolysis. After hydrocracking or isomerization the thiophene formed is then easily hydrogenolyzed by means of a hydrotreatment conventional known to those skilled in the art during the subsequent step h).
- Step h) Hydroprocessing is usually carried out in the presence of a conventional hydrotreatment catalyst preferably chosen from group formed by catalysts comprising a mineral carrier (such as, for example, silica, alumina or a silica-alumina) and comprising at least one preferably non-noble metal of group VIII (for example nickel, cobalt) and / or at least one group VIB metal (for example molybdenum, tungsten).
- a conventional hydrotreatment catalyst preferably chosen from group formed by catalysts comprising a mineral carrier (such as, for example, silica, alumina or a silica-alumina) and comprising at least one preferably non-noble metal of group VIII (for example nickel, cobalt) and / or at least one group VIB metal (for example molybdenum, tungsten).
- the catalyst will comprise a support based on alumina, at least one non-noble metal of group VIII and at least of group VIB.
- a catalyst comprising on a support of alumina, cobalt and molybdenum.
- step d) is adapted according to the content of basic nitrogen compounds on the acid catalyst of step e). These nitrogen compounds basic are thus found in the heavy fraction leaving the separation zone D of step d) line 8.
- the heavier nitrogen compounds the lightest of which is pyridine, have a boiling point above 110 ° C. They are therefore removed for example by distillation (step d), line 8). They found at the bottom of the column and are sent directly to the hydrotreatment (step h)).
- the charge ⁇ which is then sent to the alkylation (preferentially a 60 ° C.-180 ° C. or 60 ° C.-150 ° C. C or 60 ° C-115 ° C) is then freed, almost entirely, of the nitrogenous compounds basic, preferably without the need for an acid wash or a bed of keep.
- the first embodiment (I), not in accordance with the present invention does not include the step hydrocracking.
- the effluent leaving the alkylation zone (step e) is sent to a separation zone (step f) from which a light fraction and a fraction are recovered. which is sent directly to a hydrotreating step (step h).
- the second embodiment (II) comprises a step hydrocracking.
- the effluent leaving the alkylation zone (step e) is sent to a separation zone (step f) from which a light fraction and a fraction are recovered. heavy which is sent in a hydrocracking step (step g).
- the effluent from the stage hydrocracking is then sent to the hydrotreatment zone (step h).
- the feed used was first hydrogenated (step a) and then distilled into three cuts (steps b and d).
- the core section is then alkylated (step e) and then fractionated (step f).
- the heavy fraction resulting from step f is mixed with the heavy fraction from step d then the entire stream obtained is hydrotreated.
- the heavy fraction resulting from step f is firstly hydrocracked before being mixed with the heavy fraction from step d then the entire flow obtained is hydrotreated. For each stage, the characteristics of the charges, effluents and that the operating conditions applied are described below. Numbering of the sections correspond to those mentioned in Figure 1.
- This step eliminates diolefins to prevent clogging of the unit and to preserve downstream catalysts. It also makes it possible to weigh down light mercaptans.
- step a The effluent from step a is distilled into three sections, the characteristics of which are shown in Table 2.
- the light cut (cut ⁇ or section 4 according to Figure 1) contains almost no sulfur and does not contains more mercaptans. It can then be directly integrated into the gasoline pool.
- the cup intermediate (cut ⁇ or cut 9) is sent to the alkylation step (step e) and the heavy cut (cut ⁇ or section 8) is sent in the hydrotreating step (step h).
- section ⁇ (or section 9), the characteristics of which are given in Table 3, was treated with an Amberlyst ion exchange resin catalyst at 20 bar of total pressure, with a VHV of 1 hour. -1 and a temperature of 110 ° C.
- the characteristics of the effluent (section 11) obtained are also shown in Table 3.
- the main reaction is the alkylation of thiophene-type compounds and methylthiophenes. Hydrocarbon alkylation reactions lead to changing the distillation range of the charge.
- step e The effluent of step e is distilled into two sections, the characteristics of which are shown in Table 4.
- the sulfur content of the light fraction ( ⁇ cut or 12 cut) is sufficiently low for this cup is directly integrated into the gasoline pool.
- the heavy fraction ( ⁇ section or 13 section) requires hydrotreatment.
- this section ⁇ is mixed with the section ⁇ (section 8) from step d) before being hydrotreated.
- the section ⁇ or section 13 is hydrocracked before being mixed with the cup ⁇ , then hydrotreated.
- Step g (conforming case)
- the ⁇ section was treated with an acid catalyst composed of 10% zeolite Y and 90% alumina, under a pressure of 20 bar, a temperature of 350 ° C. a ratio of hydrogen / charge rates of 150 liter / liter, and a VVH of 1h -1 . Under these conditions, the main reactions observed are isomerization and cracking reactions of heavy alkylthiophenes.
- the characteristics of the effluent (section 15) obtained are also shown in Table-5.
- step h the sulfur compounds with high boiling point resulting from the alkylation of thiophenic compounds in step e are isomerized and slightly cracked which facilitates their hydrogenolysis during the hydrotreating step (step h).
- the section ⁇ (from step d, section 8) is directly mixed with the section ⁇ (from step f, section 13) in the embodiment not according to the present invention and to the section hydrocracked (from step g, section 15) in the embodiment according to the present invention.
- the fraction ⁇ represents 67% and the hydrocracked section (section 15, Figure 1) or not represents 33%.
- the charge I is not in accordance with the invention, ie it has not undergone the hydrocracking step g).
- Charge II is in accordance with the invention, ie it has undergone hydrocracking step g)
- the catalyst used during the hydrotreatment step is a catalyst based on cobalt sulphide and molybdenum deposited on alumina.
- the operating conditions applied during the hydrotreatment according to the charges as well as the characteristics of the effluents obtained are summarized in Table 7.
- the desulfurization overall is around 96%.
- the alkylation catalyst is an acid catalyst selected from the group consisting of phosphoric or sulfuric acids supported by zeolites, silica-aluminas and ion exchange resins.
- the distillation is carried out after the alkylation, but also the distillation can be carried out at the same time as the alkylation in a catalytic column. Can also carry out a distillation before the alkylation step, which then allows the content to be considerably reduced nitrogen compound of the charge which is introduced into the alkylation unit.
- the hydrotreatment unit may be located after at least one distillation step and before at least one a hydrocracking step.
- thiophene and / or thiophene compounds are alkylated on a catalyst in the presence of olefins having at least 2 carbon atoms and preferably at most 10 carbon atoms; the olefin molar ratio on thiophene sum + thiophene compounds generally ranging from 0.1 to 2000 moles per mole and preferably 0.5 to 1000 moles / mole, the pressure of the alkylation unit being more particularly at least 0.5 MPa. Often the pressure of this step is from about 0.5 MPa to about 10 MPa and most often about 1 MPa at about 5 MPa.
- the hydrocracking catalyst is an acid catalyst selected from the group consisting of by zeolites, silica-aluminas, clays and acid resins.
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- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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FR0201531A FR2835530B1 (fr) | 2002-02-07 | 2002-02-07 | Procede integre de desulfuration d'un effluent de craquage ou de vapocraquage d'hydrocarbures |
FR0201531 | 2002-02-07 | ||
PCT/FR2003/000203 WO2003066778A1 (fr) | 2002-02-07 | 2003-01-22 | Procede integre de desulfuration d'un effluent de craquage ou de vapocraquage d'hydrocarbures |
Publications (2)
Publication Number | Publication Date |
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EP1474499A1 EP1474499A1 (fr) | 2004-11-10 |
EP1474499B1 true EP1474499B1 (fr) | 2005-08-17 |
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EP03709894A Expired - Lifetime EP1474499B1 (fr) | 2002-02-07 | 2003-01-22 | Procede integre de desulfuration d un effluent de craquage o u de vapocraquage d hydrocarbures |
Country Status (12)
Country | Link |
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US (1) | US7344635B2 (ja) |
EP (1) | EP1474499B1 (ja) |
JP (1) | JP4366583B2 (ja) |
KR (1) | KR100958363B1 (ja) |
AT (1) | ATE302256T1 (ja) |
AU (1) | AU2003214328A1 (ja) |
BR (1) | BR0307481B1 (ja) |
CA (1) | CA2474525C (ja) |
DE (1) | DE60301333T2 (ja) |
ES (1) | ES2248734T3 (ja) |
FR (1) | FR2835530B1 (ja) |
WO (1) | WO2003066778A1 (ja) |
Families Citing this family (12)
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FR2884521B1 (fr) * | 2005-04-19 | 2009-08-21 | Inst Francais Du Petrole | Nouveau procede de desulfuration des essences par alourdissement des composes soufres |
US20080093265A1 (en) * | 2006-10-18 | 2008-04-24 | Exxonmobil Research And Engineering Company | Process for selective sulfur removal from FCC naphthas using zeolite catalysts |
FR2913692B1 (fr) * | 2007-03-14 | 2010-10-15 | Inst Francais Du Petrole | Procede de desulfuration de fractions hydrocarbonees issues d'effluents de vapocraquage |
US8343336B2 (en) * | 2007-10-30 | 2013-01-01 | Saudi Arabian Oil Company | Desulfurization of whole crude oil by solvent extraction and hydrotreating |
US20100197977A1 (en) * | 2009-02-05 | 2010-08-05 | Harris Stephen H | Allyl diacetate decomposition |
US8309758B2 (en) | 2009-12-17 | 2012-11-13 | Lyondell Chemical Technology, L.P. | Allyl acetate purification |
US10087377B2 (en) | 2010-09-07 | 2018-10-02 | Saudi Arabian Oil Company | Oxidative desulfurization of oil fractions and sulfone management using an FCC |
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 |
US10093872B2 (en) | 2010-09-07 | 2018-10-09 | Saudi Arabian Oil Company | Oxidative desulfurization of oil fractions and sulfone management using an FCC |
CN102211042B (zh) * | 2011-03-25 | 2012-08-08 | 西南石油大学 | 一种催化汽油烷基化脱硫络合物催化剂的制备方法 |
EP2888341B1 (en) * | 2012-08-21 | 2019-12-18 | Catalytic Distillation Technologies | Selective hydrodesulfurization of fcc gasoline to below 10 ppm sulfur |
CN106753524B (zh) * | 2016-11-21 | 2020-11-20 | 山东昌邑石化有限公司 | 一种汽油加氢工艺 |
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US5599441A (en) * | 1995-05-31 | 1997-02-04 | Mobil Oil Corporation | Alkylation process for desulfurization of gasoline |
US5863419A (en) * | 1997-01-14 | 1999-01-26 | Amoco Corporation | Sulfur removal by catalytic distillation |
US6024865A (en) * | 1998-09-09 | 2000-02-15 | Bp Amoco Corporation | Sulfur removal process |
FR2797639B1 (fr) * | 1999-08-19 | 2001-09-21 | Inst Francais Du Petrole | Procede de production d'essences a faible teneur en soufre |
DE19944003C1 (de) | 1999-09-14 | 2001-03-22 | Baumeister & Ostler Gmbh Co | Faltbare Trenneinrichtung |
WO2001096498A1 (fr) * | 2000-06-13 | 2001-12-20 | Institut Francais Du Petrole | Procede de desulfuration d'un effluent de craquage ou vapocraquage |
-
2002
- 2002-02-07 FR FR0201531A patent/FR2835530B1/fr not_active Expired - Fee Related
-
2003
- 2003-01-22 EP EP03709894A patent/EP1474499B1/fr not_active Expired - Lifetime
- 2003-01-22 KR KR1020047012134A patent/KR100958363B1/ko not_active IP Right Cessation
- 2003-01-22 ES ES03709894T patent/ES2248734T3/es not_active Expired - Lifetime
- 2003-01-22 CA CA2474525A patent/CA2474525C/fr not_active Expired - Fee Related
- 2003-01-22 AU AU2003214328A patent/AU2003214328A1/en not_active Abandoned
- 2003-01-22 AT AT03709894T patent/ATE302256T1/de not_active IP Right Cessation
- 2003-01-22 WO PCT/FR2003/000203 patent/WO2003066778A1/fr active IP Right Grant
- 2003-01-22 DE DE60301333T patent/DE60301333T2/de not_active Expired - Lifetime
- 2003-01-22 BR BRPI0307481-1B1A patent/BR0307481B1/pt not_active IP Right Cessation
- 2003-01-22 US US10/503,807 patent/US7344635B2/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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ATE302256T1 (de) | 2005-09-15 |
AU2003214328A1 (en) | 2003-09-02 |
CA2474525A1 (fr) | 2003-08-14 |
WO2003066778A1 (fr) | 2003-08-14 |
BR0307481A (pt) | 2004-12-07 |
DE60301333D1 (de) | 2005-09-22 |
EP1474499A1 (fr) | 2004-11-10 |
DE60301333T2 (de) | 2006-06-01 |
KR100958363B1 (ko) | 2010-05-17 |
JP4366583B2 (ja) | 2009-11-18 |
KR20040086351A (ko) | 2004-10-08 |
CA2474525C (fr) | 2010-12-14 |
FR2835530B1 (fr) | 2004-04-09 |
US20050230286A1 (en) | 2005-10-20 |
ES2248734T3 (es) | 2006-03-16 |
FR2835530A1 (fr) | 2003-08-08 |
JP2005522530A (ja) | 2005-07-28 |
US7344635B2 (en) | 2008-03-18 |
BR0307481B1 (pt) | 2013-07-16 |
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