EP1433835A1 - Verfahren zur Umwandlung von Kohlenwasserstoffen in eine Fraktion mit verbesserter Oktanzahl und eine Fraktion mit hoher Cetanzahl - Google Patents
Verfahren zur Umwandlung von Kohlenwasserstoffen in eine Fraktion mit verbesserter Oktanzahl und eine Fraktion mit hoher Cetanzahl Download PDFInfo
- Publication number
- EP1433835A1 EP1433835A1 EP03293026A EP03293026A EP1433835A1 EP 1433835 A1 EP1433835 A1 EP 1433835A1 EP 03293026 A EP03293026 A EP 03293026A EP 03293026 A EP03293026 A EP 03293026A EP 1433835 A1 EP1433835 A1 EP 1433835A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- effluent
- ethers
- cut
- fraction
- hydrocarbons
- 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.)
- Granted
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 33
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims description 41
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title claims description 27
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 title claims description 13
- 230000009466 transformation Effects 0.000 title abstract description 3
- 150000001336 alkenes Chemical class 0.000 claims abstract description 46
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 23
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 17
- 238000006266 etherification reaction Methods 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims description 31
- 150000002170 ethers Chemical class 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005336 cracking Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000004523 catalytic cracking Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 3
- 238000001833 catalytic reforming Methods 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 239000006069 physical mixture Substances 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- HIGRAKVNKLCVCA-UHFFFAOYSA-N alumine Chemical compound C1=CC=[Al]C=C1 HIGRAKVNKLCVCA-UHFFFAOYSA-N 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- -1 clays Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- SIWVGXQOXWGJCI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;2-ethenylbenzenesulfonic acid Chemical compound C=CC1=CC=CC=C1C=C.OS(=O)(=O)C1=CC=CC=C1C=C SIWVGXQOXWGJCI-UHFFFAOYSA-N 0.000 description 1
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction 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
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
-
- 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
- C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
- C10G57/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process with polymerisation
-
- 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
- C10G69/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural parallel stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
Definitions
- the present invention relates to a method allowing a simple and economical way of modulate the respective productions of gasoline and diesel for example within the refinery. More precisely, according to the method that is the subject of the present invention, it is possible to transforming an initial charge of hydrocarbons comprising from 4 to 15 carbon atoms, included terminals, preferably from 4 to 11 carbon atoms, inclusive, or even from 4 to 10 carbon atoms, limits included, in at least one hydrocarbon fraction having a improved octane number and a hydrocarbon fraction with a high cetane number.
- the processes for adding to isobutane (branched alkane) alkenes having between 2 and 5 carbon atoms make it possible to produce highly branched molecules having between 6 and 9 carbon atoms and generally characterized by high octane numbers.
- Other possible transformations using methods for etherification of branched olefins, such as for example described in US Pat. No. 5,633,416 and EP-A-0451989, are known.
- oligomerization processes based essentially on the dimerization and trimerization of light olefins resulting from catalytic cracking process and having between 2 and 4 carbon atoms, allow the production of gasoline cuts or distillates.
- a method is for example described in the patent application EP-A-0734766.
- the effluents resulting from the processes of conversion of more or less heavy residues resulting from the atmospheric or vacuum distillation of the crude oil within the refinery contain an olefin content between 10 and 80%.
- These effluents are used in the composition of commercial species at a rate of 20 to 40% depending on the geographical origin (about 27% in Western Europe and about 36% in the USA). This content varies mainly depending on the final boiling point of the petrol cut and the refinery. It is likely that in the context of environmental protection, the standards for commercial species will be oriented in the coming years towards a reduction of the olefin content allowed in these species.
- One of the aims of the present invention is to separate linear olefins from branched olefins from an initial gasoline feedstock.
- Another goal of the The present invention is to provide an alternative allowing increased flexibility of management products from the refinery. More specifically, the process according to the present invention advantageously makes it possible to modulate the gasoline / diesel proportions obtained at the output of refinery according to the needs of the market.
- step a) of the process according to the invention at least 50% of the branched olefins, preferably at least 70% and very preferably at least 90% of said olefins are etherified.
- the final boiling point of the ⁇ -cut most often corresponds to the initial boiling point of the ⁇ cut.
- the totality of the effluent resulting from step a) is treated in step b) and the ⁇ -cut comprises the ethers formed during step a).
- the method further comprises a step for separating the ethers from the remainder of the effluent resulting from stage a), said effluent freed from said ethers is treated according to step b) and said ethers are treated with the ⁇ cut according to step d).
- All the ethers included in the ⁇ -cut can be cracked during step d).
- the experimental conditions are selected in such a way that a variable part of the ethers included in the ⁇ section can be cracked during step d).
- said portion can be between 85 and 99.9% molar, even between 90 and 99.9 mol%.
- said oligomerization is carried out at a pressure of between 0.2 and 10. MPa, a charge rate ratio on catalyst volume of between 0.05 and 50 l / l / h and a temperature of between 15 and 300 ° C.
- said oligomerization can be carried out in the presence of a catalyst comprising at least one Group VIB metal of the Periodic Table.
- said etherification is carried out at a pressure of between 0.2 and 10 MPa, a charge flow rate on catalyst volume of between 0.05 and 50 l / l / h and a temperature of between 15 and 300 ° C.
- the present method may further include a step of removing at least a portion nitrogen or basic impurities contained in the initial charge of hydrocarbons.
- the initial hydrocarbon feedstock treated by the present process may be a process for catalytic cracking, catalytic reforming or dehydrogenation of paraffins.
- the initial hydrocarbon feedstock is conveyed by line 1 to a unit A.
- This unit A eliminates a large part, that is at least 90% by weight, of nitrogen and / or basic compounds contained in the feedstock. This elimination, although optional, is necessary when the load includes a high rate, that is at least 5 ppm, said nitrogen compounds and / or basic because they constitute a poison for catalysts of the following steps of the process according to the invention. Said compounds can be removed by adsorption on an acidic solid.
- This solid can be chosen from the group formed by zeolites, silicoaluminates, titanosilicates, mixed oxides alumina-oxide titanium, clays, resins, mixed oxides obtained by grafting at least one compound organometallic, organosoluble or water-soluble, and comprising at least one element selected from the group consisting of titanium, zirconium, silicon, germanium, tin, tantalum and niobium on at least one oxide support such as alumina (forms gamma, delta, eta, alone or in admixture), silica, silica-aluminas, silica-oxides, titanium, zirconia silicas, ion exchange resins, for example styrene-divinylbenzene resins sulfonated resins such as Amberlyst® type resins or any other acidic resin.
- a particular embodiment of the invention may consist in implementing a physical mixture of minus two of the previously described solids.
- the pressure is between atmospheric pressure and 10 MPa, preferably between atmospheric pressure and 5 MPa, and a pressure under which the charge is in the liquid state.
- the ratio of the charge rate to the volume of solid catalytic is most often between 0.05 l / l / h and 50 l / l / h and preferably included between 0.1 l / l / h and 20 l / l / h, or even between 0.2 and 10 l / l / h.
- the temperature is between 15 and 300 ° C, preferably between 15 and 150 ° C and very preferably between 15 ° C and 60 ° C.
- the elimination of nitrogen and / or basic compounds contained in the feed can also be carried out by washing with an acidic aqueous solution, or by any equivalent means known to those skilled in the art.
- the purified feed is conveyed via line 2 to an etherifying unit B corresponding to step a) of the process according to the invention.
- etherifying unit B corresponding to step a) of the process according to the invention.
- olefins preferentially react with an alcohol to form an ether.
- Alcohol is preferably methanol or ethanol and can be added via line 3 to the feedstock.
- of hydrocarbons in an alcohol / olefins molar ratio generally between 0.5 and 3 and preferably about 1.
- the pressure of the unit is such that in the temperature conditions of the catalyst used in said step a) of the process according to the invention, the charge is in the liquid state, i.e. the pressure is generally between 0.2 MPa and 10 MPa, preferably between 0.3 and 6 MPa or between 0.3 and 4 MPa.
- the ratio of the charge rate to the volume of catalyst is generally between 0.05 l / l / h and 50 l / l / h, preferably between 0.1 l / l / h and 20 l / l / h or between 0.2 and 10 l / l / h.
- the temperature is between 15 and 300 ° C, preferably between 30 and 150 ° C and very often between 30 ° C and 100 ° C.
- the etherifying unit B advantageously contains an acid catalyst.
- the acid catalyst may be a catalyst of the same nature as those conventionally used for the production of MTBE, ETBE or TAME.
- it may be chosen from the group consisting of zeolites, silicoaluminates, titanosilicates, mixed alumina-titanium oxide oxides, clays, resins and mixed oxides obtained by grafting and comprising at least one element selected from the group consisting of group consisting of titanium, zirconium, silicon, germanium, tin, tantalum and niobium on at least one oxide support such as alumina (gamma, delta, eta, alone or as a mixture), the silica, alumina silicas, titanium dioxide silicas, zirconia silicas, Amberlyst type ion exchange resins or any other acidic resin.
- a particular embodiment of the invention may consist in using a physical mixture of at least two of the previously described catalysts.
- the effluent from the etherification unit B is then optionally treated under conditions of elimination of at least a portion of the excess alcohol contained in the mixture obtained. This elimination can be done conventionally by washing with water or by any equivalent means known to those skilled in the art.
- all of the effluent from the etherification unit B is sent to an oligomerization unit C corresponding to step b) of the process according to the invention, without intermediate separation of the ethers.
- linear olefins present in the initial hydrocarbon feedstock and unreacted during the previous etherification step will undergo moderate oligomerization reactions, that is to say in general dimerizations or trimerizations, the conditions of said reaction being optimized for the production of a majority of hydrocarbons whose carbon number is between 9 and 25, preferably between 10 and 20.
- the catalyst of the oligomerization unit C can be chosen in the group formed by zeolites, silicoaluminates, titanosilicates, mixed oxides alumina-titanium oxides, clays, resins, mixed oxides obtained by grafting at least one organo-metallic organosoluble or water-soluble compound and comprising at least one element selected from the group consisting of titanium, zirconium, silicon, germanium, tin, tantalum and niobium on at least one oxide support and alumina (gamma, delta, eta, alone or as a mixture), silica, silica aluminas, silica-titanium oxides, zirconia silicas or any other solid having any acidity.
- the catalyst used to carry out said oligomerization comprises at least one Group VIB metal of the periodic classification and advantageously an oxide of said metal.
- This catalyst may furthermore comprise an oxide support selected from the group of aluminas, titanates, silicas, zirconiums, aluminosilicates.
- a particular embodiment of the invention may consist in using a physical mixture of at least two of the catalysts mentioned above. It has surprisingly been found that the experimental conditions used in the oligomerization unit C have a very significant influence not only on the final yield of the various products of the oligomerization reaction but also on the quality of said products. in particular on the cetane number of the gasoil section and on the octane number of the gasoline section finally obtained.
- the RON octane number of the petrol fraction finally obtained is advantageously at least 93, preferably at least 95.
- the cetane number of the gasoil fraction is advantageously at least 40, preferably at least 50 and most preferably at least 55.
- the pressure of the oligomerization unit C is most often selected so that the charge is in a liquid form. This pressure is in principle between 0.2 MPa and 10 MPa, preferably between 0.3 and 6 MPa, and still between 0.3 and 4 MPa.
- the ratio of the feed rate to the volume of catalyst can be between 0.05 l / l / h and 50 l / l / h, preferably between 0.1 l / l / h and 20 l / l / h and even more preferably between 0.2 and 10 l / l / h. It was found by the applicant that, under the prevailing pressure and VVH conditions, the oligomerization reaction temperature should be between 15 and 300 ° C, preferably between 60 and 250 ° C and more particularly between 100 and 200 ° C to optimize the quality of the products finally obtained.
- the heavy cut ⁇ is a cut whose initial boiling point corresponds to a cut diesel.
- This cup can be mixed with hydrogen, conveyed by line 8, to be hydrogenated in a hydrogenation unit E of conventional structure in the presence of a catalyst and under operating conditions known to those skilled in the art.
- the effluent hydrocarbon recovered by line 9 is an improved cetane number gas oil, that is to say having a cetane number of at least 40, preferably at least 50 and preferably at least 55.
- the light cut ⁇ is a gasoline cut and is conveyed via line 6 to a cracking unit F corresponding to step d) of the process according to the invention.
- the conditions are selected such that all the ethers present in the ⁇ -section are cracked to a hydrocarbon fraction comprising olefins, mainly branched olefins. , and a fraction comprising the initial alcohol.
- the cracking conditions can be adjusted in such a way that only a part of said ethers is cracked. This mode advantageously makes it possible to further improve the octane number of the gasoline fraction finally obtained, but is however limited by the current legislation of many countries concerning the content of oxygenated compounds in gasolines.
- said portion may be between 85 and 99.9 mol%, or even between 90 and 99.9 mol%.
- the pressure of the cracking unit F is between 0.2 and 10 MPa, preferably between 0.3 and 6 MPa, or even between 0.3 and 4 MPa.
- the ratio of the feed rate to the catalyst volume is between 0.05 l / l / h and 50 l / l / h, preferably between 0.1 l / l / h and 20 l / l / h and again between 0.2 and 10 l / l / h.
- the temperature is generally above 15 ° C, and most often between 15 ° C and 350 ° C, preferably between 100 ° C and 350 ° C.
- the catalyst used in the cracking unit F may be an acid catalyst chosen from the group formed by zeolites, silicoaluminates, titanosilicates, mixed oxides alumina-titanium oxides, clays, resins, mixed oxides obtained by grafting of least an organometallic, organosoluble or water-soluble compound, and comprising at least an element selected from the group consisting of titanium, zirconium, silicon, germanium, tin, tantalum and niobium on at least one oxide such as alumina (forms gamma, delta, eta, alone or in admixture), silica, silica aluminas, silica-oxides titanium, zirconia silicas, Amberlyst type ion exchange resins or any other solid having any acidity.
- a particular embodiment of the invention may consist of a physical mixture of at least two of the previously described catalysts is used.
- the effluent from the cracking unit F is conveyed via line 11 to a unit G allowing separate the alcohols from the hydrocarbons and uncracked ethers during the previous step.
- This unit G may be a distillation column, a thermal diffusion column or a known means of washing with water or any other means known to those skilled in the art for the separation of alcohols and hydrocarbons.
- Alcohol can be recycled through line 13 to the inlet of the etherification unit B or sent to a storage tank via the line 12.
- the hydrocarbon effluent recovered by line 14 is an improved octane gasoline whose olefin content is lower than that of the initial hydrocarbon feedstock. Content in olefins is advantageously reduced by at least 40% by weight, very advantageously at least 50% by weight.
- the ethers contained in the effluent from the etherification unit B can be separated from the hydrocarbon fraction.
- Units C and D then treat in this mode an effluent freed of substantially all the ethers.
- the gasoline obtained in this case at the outlet of the unit D can be mixed with the ethers in the case where the ethers have been removed after the etherification unit B. This section can then be sent to the cracking unit F and then to the separation unit G.
- the initial charge I is a boiling point FCC gasoline between 40 ° C and 150 ° C. This essence contains 10 ppm of basic nitrogen.
- This feed is sent to a reactor A containing a solid consisting of a mixture of 20% alumina and 80% by weight of zeolite of the mordenite type.
- the zeolite used in the present example has a silicon / aluminum ratio of 45.
- the pressure of the unit is 0.2 MPa, the ratio of the liquid flow rate of the feedstock to the volume of acidic solid is 1 liter / liter / hour.
- the temperature of the reactor is 20 ° C. Table 1 gives the composition of the initial charge I and that of the effluent A from unit A. composition of the feedstock and the effluent of step A.
- the effluent A is then sent to an etherification reactor B containing an Amberlyst 15 ion exchange resin sold by Rohm & Haas. To this product is added methanol in a ratio of 1 mole of methanol per mole of olefin.
- the pressure of unit B is 3 MPa.
- the ratio of the feed rate to the catalyst volume is 1 liter / liter / hour.
- the temperature is 90 ° C.
- Table 2 gives the composition of effluent B from unit B relative to that of effluent A. composition of effluents A and B.
- the effluent B is injected into an oligomerization reactor C containing a catalyst consisting of a mixture of 50% by weight of zirconia and 50% by weight of H 3 PW 12 O 40 .
- the pressure of the unit is 2 MPa, the ratio of the feed rate on the catalyst volume is equal to 1.5 liter / liter / hour.
- the temperature is set at 170 ° C.
- An effluent C is obtained at the outlet of unit C.
- the respective olefin contents of effluents A, B and C as a function of the number of carbon atoms are given in Table 3. olefin content of effluents A, B, C.
- Figure 2 shows the comparison of simulated distillations of the initial charge (round black) and effluent C (white squares). It is observed that 24% by weight of the effluent boils at a temperature above 150 ° C, end point of distillation of the initial charge.
- the light fraction ⁇ distillation interval 40 ° C-200 ° C and from the unit D is injected into a cracking reactor F containing Deloxan marketed by the company Degussa.
- This catalyst is a polysiloxane grafted with alkylsulphonic acid groups (of the -CH2-CH2-CH2-SO3H type).
- the pressure of the unit is 3 MPa.
- the ratio of the feed rate to the catalyst volume is 3 liters / liter.
- the temperature is 200 ° C.
- the characteristics of the gasoline cut G, resulting from the unit F and after separation of the methanol by extraction with water, can be compared with those of the initial charge I with reference to Table 5.
- the present process makes it possible to obtain from a petrol cut in a manner simple and economical, that is to say by the use of conventional and inexpensive technologies a gasoline cut (G effluent) with a low olefin content and an octane number improved and a diesel cut (effluent E) with a high cetane number; compatible with a marketing.
- G effluent gasoline cut
- effluent E diesel cut
- the same initial charge I is processed by the units A and B in identical conditions to those of Example 1.
- the effluent B obtained is introduced into the reactor C comprising the same catalyst and under the same conditions as for Example 1 to difference that the temperature in said reactor C is this time raised to 350 ° C.
- Figure 3 shows the comparison of simulated distillations of the initial charge (round black) and effluent C '(white squares). This time, it is observed that 32% by weight of the effluent C ' end at a temperature above 150 ° C, end point of distillation of the initial charge.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Liquid Carbonaceous Fuels (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0216474 | 2002-12-23 | ||
FR0216474A FR2849051B1 (fr) | 2002-12-23 | 2002-12-23 | Procede de transformation d'hydrocarbures en une fraction presentant un indice d'octane ameliore et une fraction a fort indice de cetane |
Publications (2)
Publication Number | Publication Date |
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EP1433835A1 true EP1433835A1 (de) | 2004-06-30 |
EP1433835B1 EP1433835B1 (de) | 2009-09-02 |
Family
ID=32406360
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Application Number | Title | Priority Date | Filing Date |
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EP03293026A Expired - Lifetime EP1433835B1 (de) | 2002-12-23 | 2003-12-03 | Verfahren zur Umwandlung von Kohlenwasserstoffen in eine Fraktion mit verbesserter Oktanzahl und eine Fraktion mit hoher Cetanzahl |
Country Status (6)
Country | Link |
---|---|
US (1) | US7329787B2 (de) |
EP (1) | EP1433835B1 (de) |
DE (1) | DE60329065D1 (de) |
ES (1) | ES2330513T3 (de) |
FR (1) | FR2849051B1 (de) |
RU (1) | RU2317317C2 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2404980A1 (de) | 2010-07-08 | 2012-01-11 | Total Raffinage Marketing | Erhöhung des durchschnittlichen Molekulargewichts von Kohlenwasserstoffeinsätzen |
WO2012089716A1 (en) | 2010-12-28 | 2012-07-05 | Total Raffinage Marketing | Nitrile containing hydrocarbon feedstock, process for making the same and use thereof |
FR2975103A1 (fr) * | 2011-05-12 | 2012-11-16 | IFP Energies Nouvelles | Procede de production de coupes kerosene ou gazole a partir d'une charge olefinique ayant majoritairement de 4 a 6 atomes de carbone |
WO2013104614A1 (en) | 2012-01-09 | 2013-07-18 | Total Raffinage Marketing | Method for the conversion of low boiling point olefin containing hydrocarbon feedstock |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101245259B (zh) * | 2007-02-14 | 2011-01-19 | 中国石油化工股份有限公司石油化工科学研究院 | 一种与催化裂化吸收稳定系统组合的烃类醚化方法 |
FR2944028B1 (fr) * | 2009-04-03 | 2011-05-06 | Inst Francais Du Petrole | Procede de production de distillats moyens par hydroisomerisation et hydrocraquage d'une fraction lourde issue d'un effluent fischer-tropsch mettant en oeuvre une resine |
FR2944027B1 (fr) * | 2009-04-03 | 2011-05-06 | Inst Francais Du Petrole | Procede de production de distillats moyens par hydroisomerisation et hydrocraquage d'une fraction lourde issue d'un effluent fischer-tropsch |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4528411A (en) * | 1982-09-24 | 1985-07-09 | Phillips Petroleum Company | Diesel fuel and gasoline production |
EP0237372A1 (de) * | 1986-02-13 | 1987-09-16 | Institut Français du Pétrole | Verfahren zur Herstellung von MTBE Superbenzin und Düsentreibstoff aus Butanen und/oder C4-Fraktionen einer Spaltung oder einer katalytischen Reformierung |
EP0332243A1 (de) * | 1988-02-22 | 1989-09-13 | Shell Internationale Researchmaatschappij B.V. | Verfahren zur Herstellung von normalerweise flüssigen Kohlenwasserstoffen aus einer Kohlenwasserstoffcharge, die geradkettige und verzweigte Olefine enthält |
US5382705A (en) * | 1989-03-20 | 1995-01-17 | Mobil Oil Corporation | Production of tertiary alkyl ethers and tertiary alkyl alcohols |
EP0659723A1 (de) * | 1993-12-20 | 1995-06-28 | Bayer Ag | Verfahren zur Herstellung von Alkyl-tert.-alkyl-ether enthaltenden Kohlenwasserstoffgemischen |
US6028239A (en) * | 1996-04-09 | 2000-02-22 | Institut Francais Du Petrole | Process for the production of tertiary olefin(s) by decomposition of the corresponding ether using a particular catalyst |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2925379A (en) * | 1956-11-13 | 1960-02-16 | Union Oil Co | Hydrocarbon denitrogenation |
FR2760006B1 (fr) * | 1997-02-21 | 1999-04-16 | Inst Francais Du Petrole | Procede de production d'olefine tertiaire par decomposition d'ether alkylique tertiaire |
-
2002
- 2002-12-23 FR FR0216474A patent/FR2849051B1/fr not_active Expired - Fee Related
-
2003
- 2003-12-03 ES ES03293026T patent/ES2330513T3/es not_active Expired - Lifetime
- 2003-12-03 DE DE60329065T patent/DE60329065D1/de not_active Expired - Lifetime
- 2003-12-03 EP EP03293026A patent/EP1433835B1/de not_active Expired - Lifetime
- 2003-12-22 US US10/740,685 patent/US7329787B2/en not_active Expired - Fee Related
- 2003-12-22 RU RU2003136849/04A patent/RU2317317C2/ru not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4528411A (en) * | 1982-09-24 | 1985-07-09 | Phillips Petroleum Company | Diesel fuel and gasoline production |
EP0237372A1 (de) * | 1986-02-13 | 1987-09-16 | Institut Français du Pétrole | Verfahren zur Herstellung von MTBE Superbenzin und Düsentreibstoff aus Butanen und/oder C4-Fraktionen einer Spaltung oder einer katalytischen Reformierung |
EP0332243A1 (de) * | 1988-02-22 | 1989-09-13 | Shell Internationale Researchmaatschappij B.V. | Verfahren zur Herstellung von normalerweise flüssigen Kohlenwasserstoffen aus einer Kohlenwasserstoffcharge, die geradkettige und verzweigte Olefine enthält |
US5382705A (en) * | 1989-03-20 | 1995-01-17 | Mobil Oil Corporation | Production of tertiary alkyl ethers and tertiary alkyl alcohols |
EP0659723A1 (de) * | 1993-12-20 | 1995-06-28 | Bayer Ag | Verfahren zur Herstellung von Alkyl-tert.-alkyl-ether enthaltenden Kohlenwasserstoffgemischen |
US6028239A (en) * | 1996-04-09 | 2000-02-22 | Institut Francais Du Petrole | Process for the production of tertiary olefin(s) by decomposition of the corresponding ether using a particular catalyst |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2404980A1 (de) | 2010-07-08 | 2012-01-11 | Total Raffinage Marketing | Erhöhung des durchschnittlichen Molekulargewichts von Kohlenwasserstoffeinsätzen |
WO2012004328A1 (en) | 2010-07-08 | 2012-01-12 | Total Raffinage Marketing | Hydrocarbon feedstock average molecular weight increase. |
WO2012089716A1 (en) | 2010-12-28 | 2012-07-05 | Total Raffinage Marketing | Nitrile containing hydrocarbon feedstock, process for making the same and use thereof |
FR2975103A1 (fr) * | 2011-05-12 | 2012-11-16 | IFP Energies Nouvelles | Procede de production de coupes kerosene ou gazole a partir d'une charge olefinique ayant majoritairement de 4 a 6 atomes de carbone |
WO2012153011A3 (fr) * | 2011-05-12 | 2013-01-03 | IFP Energies Nouvelles | Procede de production de coupes kerosene ou gazole a partir d'une charge olefinique ayant majoritairement de 4 a 6 atomes de carbone |
WO2012153010A3 (fr) * | 2011-05-12 | 2013-01-03 | IFP Energies Nouvelles | Procédé production de coupes kérosène ou gazole a partir d'un charge oléfinique ayant majoritairement de 4 a 6 atomes de carbone faisant appel a deux unités d'oligomérisation |
WO2013104614A1 (en) | 2012-01-09 | 2013-07-18 | Total Raffinage Marketing | Method for the conversion of low boiling point olefin containing hydrocarbon feedstock |
Also Published As
Publication number | Publication date |
---|---|
FR2849051B1 (fr) | 2005-02-04 |
US7329787B2 (en) | 2008-02-12 |
RU2003136849A (ru) | 2005-06-10 |
FR2849051A1 (fr) | 2004-06-25 |
RU2317317C2 (ru) | 2008-02-20 |
DE60329065D1 (de) | 2009-10-15 |
EP1433835B1 (de) | 2009-09-02 |
ES2330513T3 (es) | 2009-12-11 |
US20040186331A1 (en) | 2004-09-23 |
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