EP1640435B1 - Verfahren zur Isomerisierung von einer C7-Fraktion mit Koproduktion von einer aromatischen Toluenreichen Fraktion - Google Patents

Verfahren zur Isomerisierung von einer C7-Fraktion mit Koproduktion von einer aromatischen Toluenreichen Fraktion Download PDF

Info

Publication number
EP1640435B1
EP1640435B1 EP05291857A EP05291857A EP1640435B1 EP 1640435 B1 EP1640435 B1 EP 1640435B1 EP 05291857 A EP05291857 A EP 05291857A EP 05291857 A EP05291857 A EP 05291857A EP 1640435 B1 EP1640435 B1 EP 1640435B1
Authority
EP
European Patent Office
Prior art keywords
unit
hand
aromatic compounds
isomerization
process according
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.)
Expired - Lifetime
Application number
EP05291857A
Other languages
English (en)
French (fr)
Other versions
EP1640435A1 (de
Inventor
Paul Broutin
Dominique Casanave
Jean-Francois Joly
Elsa Jolimaitre
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Publication of EP1640435A1 publication Critical patent/EP1640435A1/de
Application granted granted Critical
Publication of EP1640435B1 publication Critical patent/EP1640435B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

Definitions

  • the product of the isomerization (or isomerate) is free of aromatic compounds in contrast to the refonnat which usually contains a significant amount due to dehydrocyclization reactions of paraffins and dehydrogenation of naphthenes.
  • Isomerate and reformate are usually sent to the gasoline pool in which other bases such as gasoline resulting from fluidized catalytic cracking (FCC) or additives such as methyl tertiary butyl ether (MTBE) can also be used.
  • FCC fluidized catalytic cracking
  • MTBE methyl tertiary butyl ether
  • Aromatics have high octane numbers favorable for their use in spark ignition engines, but for environmental reasons, their total content in gasoline is increasingly limited.
  • the present invention relates more particularly to the isomerization of the C 7 -rich fraction derived from atmospheric distillation naphtha.
  • Table 1 below gives the research octane number (RON) and the boiling points of the main hydrocarbon compounds present in the C7 cut obtained from atmospheric distillation naphtha: ⁇ U> Table 1 ⁇ / u> RON Teb (° C) trimethyl 2-2-3 butane 112.1 80.8 dimethyl 2-2 pentane 92.8 79.2 dimethyl 2-4 pentane 83.1 80.5 dimethyl 3-3 pentane 80.8 86 dimethyl 2-3 pentane 91.1 89.7 2-methyl hexane 42.4 90 3-methyl hexane 52 91.9 ethyl-3 pentane 65 93.4 n-heptane 0 98.4 1,1-dimethylcyclopentane 92.3 87.8 cis-dimethyl-1,3 cyclopentane 79.2 90.8 1,3-trans-1,3-dimethylcyclopentane 80.6 91.7 1,2-trans-1,2-dimethylcyclopentane 80.6 91.8 methyl-cyclohe
  • isomers with only one branch or mono-branched have insufficient octane numbers (42 for 2-methylhexane, 52 for 3-methylhexane) to be mixed with the gasoline pool.
  • nC7 in the isomerate Up to 1 wt.% Of nC7 in the isomerate and, if possible, less than 0.5 wt.% Can be tolerated.
  • the toluene present in the fresh feedstock can be totally hydrogenated to methylcyclohexane (MCH), either in a specific hydrogenation unit, or in the paraffin isomerization unit which has a hydrogenating function.
  • MCH methylcyclohexane
  • toluene has an excellent RON unlike that of MCH, and it may therefore be interesting to isolate it either for use as a solvent or as a petrochemical base, or with a view to reintroducing it into the gasoline pool as an octane enhancer at a level permitted by the specifications.
  • MCH methyl-cyclohexane
  • the C 7 feed may contain up to 30% by weight of methyl cyclohexane, a compound whose RON is less than 75, which significantly increases the RON of the C 7 isomerate obtained.
  • the problem that the present invention seeks to solve is that of the production of gasoline bases from a C 7 fraction which have a search octane number (RON) of at least 80, with a content limited aromatic compounds, which makes it possible to anticipate the new regulations on the specifications of the gasoline pool.
  • RON search octane number
  • the isomerization unit produces predominantly paraffinic effluents, and it is possible to treat them in a separation unit of normal and mono-branched paraffins on the one hand and di- and tri-branched paraffins on the other hand, so as to recycle until the normal paraffins and mono branched at the top of the isomerization unit are exhausted.
  • the amount of naphthenic that can be admitted into the feed at the inlet of the isomerization is limited only by the RON of the product isomerate.
  • the naphthenic content in the feedstock at the isomerization is around 20% by weight for most of the C7 feedstock from an atmospheric distillation naphtha.
  • One of the advantages of the invention is precisely by using the adapted variant, to be able to treat a C7 charge having any distribution in paraffins, naphthenes and aromatics.
  • the invention thus makes it possible to obtain an isomerate containing a majority of branched di- and tri-branched paraffins whose RON can easily reach 80 or more.
  • the separation between aromatics and paraffins can be done either by extraction with solvent or by extractive distillation.
  • Zeolite membranes of the faujasite structural type also have a good selectivity with respect to aromatic molecules, as described in the articles of Nair et al. in Microporous and Mesoporous Materials, 48, pp 219-228, 2001 and of Jeong et al. in Separation Science and Technology, 37 (6), pp 1225-1239, 2002 .
  • Liquid membranes can also be used as described by AL GOSWAMI and B. RAWAT in Journal of Membrane Science No. 24, 145 of 1985 .
  • US Patent 6,069,289 discloses a multi-branched paraffin separation process, optionally coupled to isomerization, but the treated feedstock does not contain naphthenic and aromatic compounds.
  • the US Patent 6,338,791 discloses a separation process coupled to an isomerization reactor.
  • the separation process makes it possible to produce a cut rich in multibranched paraffins and optionally saturated or unsaturated cyclic compounds. This method makes it possible to produce a single slice because the naphthenes and aromatics of the filler are not separated from the paraffins, and are introduced in admixture with the paraffins in the isomerization reactor.
  • the present invention must be placed in the more general context of the treatment of the naphtha fraction resulting from the atmospheric distillation of the crude.
  • the whole of the paraffins therefore represents 55 to 90% by weight of the cut, methylcyclohexane of 5 to 30% by weight and toluene of 4 to 15% by weight.
  • the present invention is therefore defined as a process for producing an RON isomerate at least equal to 80, and for coproduction of an aromatic cut consisting predominantly of toluene, from a 7-atom hydrocarbon fraction. carbon containing paraffins, naphthenes and aromatics in any proportion, said process using at least one aromatic extraction unit contained in the feed, at least one isomerization unit, and at least one separation unit of the linear and mono-branched paraffins on the one hand, and branched di- and tri-branched paraffins, on the other hand, characterized in that the isomerate produced contains less than 1% by weight of aromatics and preferably less than 0.5% by weight of aromatics.
  • the fresh feedstock (1) is introduced into an aromatics extraction unit (EA) which makes it possible firstly to produce an aromatic cut predominantly containing toluene (3), and secondly, a deflavored C7 cut (2) which is sent as feedstock from an isomerization unit (IS) whose effluent is after stabilization (5), introduced into a separation unit (SP) from which on the one hand linear and mono-branched paraffins (8) which are recycled to the input of the isomerization unit (IS) mixed with the effluent (2) from the aromatics extraction unit (EA), and on the other hand, a stream (9) rich in di- and tri-branched paraffins which constitutes the isomerate produced.
  • EA aromatics extraction unit
  • the process according to the invention comprises a distillation column
  • the top stream (13) of the distillation column (CD) is sent to a separation unit (SP) of the normal and mono branched paraffins.
  • SP separation unit
  • the normal and mono-branched paraffins (21) being reintroduced into the isomerization unit (IS), and the branched di- and tri-paraffins (20) constituting the isomerate.
  • the bottom stream (15) of the distillation column (CD) is sent to an opening unit of the naphthenic rings (OC) from which an effluent (16) is extracted which is sent at the isomerization unit (IS).
  • the bottom stream (15) of the distillation column (CD) is sent to an opening unit of the naphthenic rings (OC) from which an effluent is extracted (16). which is sent to the feed of the column (CD) mixed with the flow (12).
  • the distillation column (CD) may advantageously be of the column type with an inner wall.
  • the separation unit of linear and mono-branched paraffins on the one hand, and branched di- and tri-branched paraffins, on the other hand, can be carried out by a PSA-type adsorption process.
  • the separation of linear and mono-branched paraffins on the one hand, and di- and tri-branched paraffins on the other hand may be carried out by a simulated counter-current type (CCS) adsorption method.
  • CCS counter-current type
  • the extraction of aromatics (EA) may be carried out using a solvent.
  • the aromatics extraction unit (EA) may be carried out by extractive distillation.
  • the aromatics extraction unit (EA) may be carried out by adsorption or by use of a membrane.
  • the C7 feedstock may be introduced into a naphthene-specific dehydrogenation unit upstream of the aromatics extraction unit.
  • CD bottom flow of the column
  • IS isomerization unit
  • the fresh feedstock (1) is introduced into an aromatics extraction unit (EA) from which a flow (3) containing a majority of of aromatic compounds and especially toluene and a stream (2) containing a majority of paraffinic and naphthenic compounds which is sent to the isomerization unit (IS).
  • EA aromatics extraction unit
  • IS isomerization unit
  • the effluent (5) of the isomerization unit is sent to a stabilization column (ST) which makes it possible to release a stream (6) consisting of light gases at the top
  • the effluent (7) of the stabilization column (ST) containing branched di- and tri-branched paraffins, naphthenic rings, but also linear and mono-branched paraffins is sent to a separation unit (SP) of the linear and mono-branched paraffins. on the one hand and paraffins di and tri branched on the other.
  • the effluent (9) of the separation unit (SP) composed of a majority of di- and tri-branched paraffins is the isomerate, while the effluent (8) of the separation unit (SP) consists of a majority of linear and mono branched paraffins is returned to the isomerization unit in admixture with the stream (2).
  • the flow (4) consists of hydrogen for the needs of the isomerization unit which works under partial pressure of hydrogen.
  • the aromatics extraction unit (EA) may use any technique known to those skilled in the art. It is possible, for example, to employ either a solvent extraction technique such as DMSO or sulfolane, or an extractive distillation technique using a solvent such as N-methylpyrrolidone, or dimethylformamide or tetraethylene glycol. With these processes, it is possible to extract a cut having an aromatic content of at least 99.0 wt%.
  • a solvent extraction technique such as DMSO or sulfolane
  • an extractive distillation technique using a solvent such as N-methylpyrrolidone, or dimethylformamide or tetraethylene glycol.
  • the isomerization unit transforms normal and mono branched paraffins into multi-branched paraffins.
  • the isomerization catalyst used in said unit will be included in the group consisting of supported catalysts containing at least one halogen and at least one Group VIII metal, zeolitic catalysts containing at least one Group VIIII metal, Friedel catalysts and Krafts, super acid catalysts of type HPA on zirconia, WOx on zirconia, or sulphated zirconia.
  • the total pressure in the isomerization reaction zone is from about 10 to 50 10 5 Pascals relative, the hourly space velocity being from about 0.2 to 10 hours -1.
  • the hydrogen / hydrocarbon molar ratio is between 0.06 and 30 mol / mol and preferably between 0.1 and 0.5 mol / mol.
  • the temperature in the reaction zone is between 50 and 150 ° C, and preferably between 60 and 100 ° C.
  • the separation unit (SP) of the linear and mono-branched paraffins on the one hand and the di- and tri-branched paraffins on the other hand may use any technique known to those skilled in the art. Among these, there may be mentioned the pressure swing adsorption process known by the abbreviation PSA or the simulated countercurrent separation (CCS) method. In the case where the separation (SP) is carried out by an adsorption unit, any adsorbent or adsorbent mixture having a selectivity in favor of linear and mono-branched paraffins may be used, in particular the MFI, FER type zeolite adsorbents.
  • the adsorptive separation (SP) can be carried out in the gas phase by a PSA or CCS type process.
  • the operating temperature of the unit is between 150 and 400 ° C.
  • the pressure of the column during the adsorption phase is between 2 and 30 5 Pascals, and during the desorption phase between 0.5 and 5 10 5 Pa.
  • the desorbent used may be an inert gas, such as hydrogen or nitrogen, or a hydrocarbon, such as C3-C6 paraffins. Hydrogen is also a desorbent particularly well suited for this separation, since it can be directly recycled to the isomerization reactor with the desorbate (effluent from the desorption unit rich in normal and branched paraffins).
  • Such a separation unit (SP) in the gas phase makes it possible to produce an isomer of RON at least equal to 80.
  • the adsorption separation can be carried out in the liquid phase by a CCS type process.
  • the operating temperature of the unit is between 100 and 250 ° C.
  • the pressure in the unit is between 2 and 20 10 5 Pa.
  • the desorbent used is preferably a hydrocarbon, and may be in particular C3-C6 paraffins.
  • Such a separation unit by CCS in the liquid phase also makes it possible to produce an isomer of RON at least equal to 80.
  • the fresh feedstock (11) is introduced into the aromatics extraction unit (EA), from which a stream (23) rich in aromatics and containing predominantly toluene, and a stream ( 12) rich in paraffinic compounds and naphthenic which is sent in a distillation column (CD).
  • the aromatics extraction unit may use any technique known to those skilled in the art, such as those proposed in the description of FIG. The values given below are typical values which in no way limit the invention.
  • the distillation column (CD) has about 100 trays and the supply is made in the vicinity of the tray 50 (numbered with respect to the column head). ). The temperature at the top of the column is close to 95 ° C.
  • a bottom stream (15) is withdrawn from the column (CD) which optionally can supply the aromatics extraction unit (EA) when the latter is not directly fed by the fresh feed (11).
  • the effluents from the aromatics extraction unit are then sent to the isomerization unit (IS), optionally mixed with a side stream (14).
  • the aromatics extraction unit is fed with the fresh feed (11)
  • the bottom stream (15) is sent directly to the isomerization unit (IS).
  • a side stream (14) containing paraffinic and naphthenic compounds which is mixed with the bottom stream (15) in the isomerization unit (IS) can be withdrawn laterally at the plateau 44.
  • the latter is operated under the same conditions as those provided in the description of FIG.
  • the effluent (17) of the isomerization unit containing a stream enriched in branched mono, di and tri paraffins is sent to the stabilization column (ST) from which a gas-rich fraction (19) is discharged at the top and a stabilized effluent (18), ie free of overhead gases, which is recycled to the distillation column (CD) at a level above the extraction level of the lateral flow (14).
  • This stream (18) containing linear paraffins, mono di and tri branched will benefit from the separation effect of the column (CD) insofar as branched di paraffins and branched with a boiling point generally lower than that of linear or mono branched paraffins, will be found preferentially at the head of the column (CD) to constitute the flow of head (13).
  • FIG. 3 the diagram of FIG. 2 is repeated, to which is added on the bottom flow (15) of the column (CD) a unit for opening naphthenic rings (OC). which will produce a paraffin-enriched stream (16) which is mixed with the side stream (14) to the isomerization unit (IS).
  • This flow (16) may in another variant be returned to the supply of the column (CD) in mixture with the flow (12).
  • the opening unit of the naphthenic rings (OC) makes it possible to transform naphthenes into linear and branched paraffins.
  • the catalyst used in said unit may be any catalyst for converting by ring opening at least 5% by weight of methylcyclohexane present in the mixture to be treated.
  • the hydrocarbon is between 0.5 and 10 moles / mole
  • the temperature in the reaction zone is between 200 and 400 ° C, and preferably between 250 and 350 ° C. It is also possible to add to the diagram illustrated in FIG.
  • IS hydroisomerisation unit
  • Example 1 illustrates the preferred variant in accordance with FIG. 3, and uses in addition aromatic aromatics (EA) and isomerization (IS) base units, a naphthenic ring opening unit (OC) fed by the feed stream. bottom of the distillation column.
  • the feed to be treated (11) is introduced into an aromatics extraction unit (EA) which carries out an extractive distillation with N-methylpyrrolidone.
  • EA aromatics extraction unit
  • the fresh batch (11) has in the example considered the following composition (in% by weight) and a mass flow rate given below: dimethyl 2-3 butane 0.01 2-methyl pentane 0.13 methyl-3 pentane 0.17 n-hexane 1.41 methyl-cyclopentane 0.60 cyclohexane 1.73 benzene 0.33 trimethyl 2-2-3 butane 0.08 dimethyl 2-2 pentane 0.20 dimethyl 2-3 pentane 3.56 dimethyl 2-4 pentane 0.49 dimethyl 3-3 pentane 0.25 2-methyl hexane 8.99 3-methyl hexane 12.24 ethyl-3 pentane 1.14 n-heptane 31,45 1,1-dimethylcyclopentane 0.82 cis-dimethyl-1,3 cyclopentane 2.29 1,3-trans-1,3-dimethylcyclopentane 2.21 1,2-trans-1,2-dimethylcyclopentane 4.19 methyl-cyclohexane 12.97 eth
  • the rich aromatic section (23) has in the example considered the following composition (in% by weight) and a mass flow rate given below: benzene 2.37 toluene 97.03 Other compounds 0.60 total flow (kg / hour) 1527
  • the flow (12) rich in paraffinic and naphthenic compounds from the aromatics extraction unit is fed into a distillation column (CD) comprising 88 actual trays at the tray 50.
  • the weight composition and the flow rate the mass of this flux (12) are as follows: dimethyl 2-3 butane 0.02 2-methyl pentane 0.14 methyl-3 pentane 0.18 n-hexane 1.63 methyl-cyclopentane 0.70 cyclohexane 2.01 benzene 0.00 trimethyl 2-2-3 butane 0.09 dimethyl 2-2 pentane 0.24 dimethyl 2-3 pentane 4.13 dimethyl 2-4 pentane 0.57 dimethyl 3-3 pentane 0.29 2-methyl hexane 10.42 3-methyl hexane 14.19 ethyl-3 pentane 1.31 n-heptane 36.42 1,1-dimethylcyclopentane 0.95 cis-dimethyl-1,3 cyclopentane 2.66 1,3-trans-1,3-dimethyl
  • a stream (13) is produced which corresponds to the isomerate produced when an additional unit for separating the normal and monobranched paraffins is not added on the one hand and the paraffins on the other hand.
  • the weight composition and the mass flow rate of this stream 13 are as follows: isopentane 3.15 dimethyl 2-2 butane 0.20 dimethyl 2-3 butane 0.17 2-methyl pentane 0.81 methyl-3 pentane 0.53 n-hexane 2.19 methyl-cyclopentane 1.13 cyclohexane 2.07 benzene 0.00 trimethyl 2-2-3 butane 7.15 dimethyl 2-2 pentane 21.94 dimethyl 2-3 pentane 1.19 dimethyl 2-4 pentane 45.79 dimethyl 3-3 pentane 3.64 2-methyl hexane 6.14 3-methyl hexane 2.58 ethyl-3 pentane 0.08 n-heptane 0.50 1,1-dimethylcyclopentane 0.24 cis
  • the RON of this isomerate (stream 13) is 82.8 and its aromatic content is less than 0.01 wt%.
  • a stream (14) containing a majority (at least 60%) of normal-heptane and paraffins C 7 mono-branched.
  • a stream (15) rich in methylcyclohexane and n-heptane.
  • This stream (15) is sent to a ring opening unit (OC) which produces an effluent (16) mainly containing a mixture of paraffins resulting in part from the opening of the rings, as well as unconverted methylcyclohexane.
  • the ring opening unit uses an iridium catalyst deposited on alumina or silica-alumina, such as that described in the application WO 02/07881 .
  • the weight composition and the mass flow rate (excluding hydrogen) of the stream (16) corresponding to the effluent of the ring opening unit are as follows: C 5 - 1.83 C 5 paraffins 3.71 paraffins C 6 1.72 methyl-cyclopentane 0.00 cyclohexane 0.00 benzene 0.00 paraffins C 7 78.32 1,1-dimethylcyclopentane 0.39 cis-dimethyl-1,3 cyclopentane 0.37 1,3-trans-1,3-dimethylcyclopentane 0.40 1,2-trans-1,2-dimethylcyclopentane 0.40 methyl-cyclohexane 11.51 ethyl-cyclopentane 0.39 toluene 0.18 C 8 + 0.78 total flow (kg / hour) 6891
  • the stream (16) is mixed with the stream (14) to give a stream (22) which is introduced into an isomerization unit (IS) using a platinum catalyst on chlorinated alumina as described in the application patent US20020002319 A1 .
  • the weight composition and the mass flow rate (excluding hydrogen) of the stream (17) corresponding to the effluent of the isomerization unit are as follows: C 5 - 2.48 isopentane 0.37 dimethyl 2-2 butane 0.02 dimethyl 2-3 butane 0.02 2-methyl pentane 0.08 methyl-3 pentane 0.04 n-hexane 0.10 methyl-cyclopentane 0.07 cyclohexane 0.18 benzene 0.00 trimethyl 2-2-3 butane 1.66 dimethyl 2-2 pentane 3.32 dimethyl 2-3 pentane 4.15 dimethyl 2-4 pentane 8.30 dimethyl 3-3 pentane 4.15 2-methyl hexane 22.40 3-methyl hexane 16.59 ethyl-3 pentane 0.83 n-heptane 21.57 1,1-dimethylcyclopentane 0.30 cis-dimethyl-1,3 cyclopentane 0.29 1,3-trans-1,3-dimethylcyclopentane
  • the effluent (17) of the isomerization unit is sent to a stabilization column (ST) from which a flow (19) comprising the light gases resulting from the reactions of cracking within the isomerization unit (C 5- cut) and bottom a flow (18) whose composition is very close to that of the stream (17) and which is reintroduced at the top of the column (CD) at plateau level 12.
  • the mass flow (excluding hydrogen) of the flow (19) is 1658 kg / h. It can be verified that the mass flow rate of the flow (11) is equal to the sum of the mass flow rates (excluding hydrogen) of the flows (23), (13), (19).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (16)

  1. Verfahren zur Herstellung eines RON Isomerats, das mindestens gleich 80 ist und zur Koproduktion einer aromatischen Fraktion, die sich hauptsächlich aus Toluol zusammensetzt, aus einer Fraktion, die sich aus Kohlenwasserstoffen mit 7 Kohlenstoffatomen zusammensetzt, welche Paraffine, Naphthene und aromatische Verbindungen in beliebigen Anteilen enthält, wobei das Verfahren mindestens eine Einheit zur Extraktion von in der Charge enthaltenen aromatischen Verbindungen, mindestens eine Isomerisierungseinheit und mindestens eine Einheit zur Trennung linearer und einfach verzweigter Paraffine einerseits und zweifach und dreifach verzweigter Paraffine andererseits umfasst, dadurch gekennzeichnet, dass das hergestellte Isomerat weniger als 1 Gewichtsprozent aromatische Verbindungen und vorzugsweise weniger als 0,5 Gewichtsprozent aromatische Verbindungen enthält.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die frische Charge (1) in eine Einheit zur Extraktion von aromatischen Verbindungen (EA) eingeführt wird, die es einerseits gestattet, eine aromatische Fraktion herzustellen, welche hauptsächlich Toluol (3) enthält und andererseits eine dearomatisierte C7-Fraktion (2), die als Charge in eine Isomerisierungseinheit (IS) geschickt wird, deren Abfluss nach Stabilisierung (5) in eine Trenneinheit (SP) eingeführt wird, aus der einerseits lineare und einfach verzweigte Paraffine (8) extrahiert werden, welche beim Eintritt in die Isomerisierungseinheit (IS) im Gemisch mit dem aus der Einheit zur Extraktion aromatischer Verbindungen stammenden Abfluss (2) wieder aufbereitet werden und andererseits ein Fluss (9), der reich an zweifach und dreifach verzweigten Paraffinen ist, welcher das hergestellte Isomerat bildet.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die frische Charge (11) in eine Einheit zur Trennung aromatischer Verbindungen (EA) eingeführt wird, die es gestattet einerseits eine aromatische Fraktion (23) herzustellen, die hauptsächlich Toluol enthält und andererseits eine dearomatisierte C7-Fraktion (12), welche in eine Destillationskolonne (CD) eingeführt wird, aus der extrahiert wird:
    ein oberer Fluss (13), der das hergestellte Isomerat bildet,
    ein unterer Fluss (15), der die Isomerisierungseinheit (IS) speist,
    wobei der Abfluss (18) der Isomerisierungseinheit nach der Stabilisierung zur Destillationskolonne (CD) auf einer Ebene zurückgeführt wird, welche sich oberhalb der Ebene der Speisung der Kolonne befindet.
  4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die frische Charge (11) in eine Einheit zur Trennung aromatischer Verbindungen (EA) eingeführt wird, die es gestattet einerseits eine aromatische Fraktion (23) herzustellen, die hauptsächlich Toluol enthält und andererseits eine dearomatisierte C7-Fraktion (12), welche in eine Destillationskolonne (CD) eingeführt wird, aus der extrahiert wird:
    a) ein oberer Fluss (13), der das hergestellte Isomerat bildet,
    b) ein seitlicher Fluss (14), der die Isomerisierungseinheit (IS) speist,
    c) ein unterer Fluss (15), der die lsomerisierungseinheit (IS) im Gemisch mit dem seitlichen Fluss (14) speist,
    wobei der Abfluss (18) der Isomerisierungseinheit nach der Stabilisierung zur Destillationskolonne (CD) auf einer Ebene zurückgeführt wird, welche sich oberhalb der Ebene des Ausgangs des seitlichen Flusses (14) befindet.
  5. Verfahren nach Anspruch 1, wobei die frische Charge in eine Destillationskolonne (CD) eingeführt wird, aus welcher extrahiert wird:
    a) ein oberer Fluss (13), der das hergestellte Isomerat bildet,
    b) ein unterer Fluss (15), der eine Einheit zur Extraktion von aromatischen Verbindungen (EA) speist, was die Bildung einer Fraktion (25), welche hauptsächlich aromatische Verbindungen enthält, einerseits und eines Abflusses (26), der in die Isomerisierungseinheit (IS) eingeführt wird, andererseits gestattet,
    wobei der Abfluss (18) der Isomerisierungseinheit nach der Stabilisierung in die Destillationskolonne (CD) auf einer Ebene zurückgeführt wird, die sich oberhalb der Ebene der Speisung der Kolonne befindet.
  6. Verfahren nach Anspruch 1, wobei die frische Charge in eine Destillationskolonne (CD) eingeführt wird, aus welcher extrahiert wird:
    a) ein oberer Fluss (13), der das hergestellte lsomerat bildet,
    b) ein seitlicher Fluss (14), der die Isomerisierungseinheit (IS) speist,
    c) ein unterer Fluss (15), der eine Einheit zur Extraktion von aromatischen Verbindungen (EA) speist, was die Bildung einer Fraktion (25), welche hauptsächlich aromatische Verbindungen enthält, einerseits und eines Abflusses (26), der im Gemisch mit dem Abfluss (14) in die Isomerisierungseinheit (IS) eingeführt wird, andererseits gestattet,
    wobei der Abfluss (18) der Isomerisierungseinheit nach der Stabilisierung in die Destillationskolonne (CD) auf einer Ebene zurückgeführt wird, die sich oberhalb der Ebene des Ausgangs des seitlichen Flusses (14) befindet.
  7. Verfahren nach einem der Ansprüche 3 und 4, dadurch gekennzeichnet, dass der untere Fluss (15) der Destillationskolonne (CD) in eine Einheit zur Öffnung naphthenischer Ringstrukturen (OC) geschickt wird, aus der ein Abfluss (16) extrahiert wird, der zur Isomerisierungseinheit (IS) geschickt wird.
  8. Verfahren nach einem der Ansprüche 3 und 4, dadurch gekennzeichnet, dass der untere Fluss (15) der Destillationskolonne (CD) in eine Einheit zur Öffnung naphthenischer Ringstrukturen (OC) geschickt wird, aus der ein Abfluss (16) extrahiert wird, der im Gemisch mit dem Fluss (12) zur Speisung der Kolonne (CD) geschickt wird.
  9. Verfahren nach einem der Ansprüche 3 bis 8, dadurch gekennzeichnet, dass der obere Fluss (13) der Destillationskolonne in eine Einheit zur Trennung (SP) normaler und einfach verzweigter Paraffine einerseits und zweifach und dreifach verzweigter Paraffine andererseits geschickt wird, wobei die normalen und einfach verzweigten Paraffine (21) wieder in die Isomerisierungseinheit (IS) eingeführt werden und die zweifach und dreifach verzweigten Paraffine (20) das Isomerat bilden.
  10. Verfahren nach einem der Ansprüche 3 bis 9, wobei die Destillationskolonne (CD) vom Typ einer Kolonne mit Innenwand ist.
  11. Verfahren nach einem der Ansprüche 9 und 10, wobei die Trennung der linearen und einfach verzweigten Paraffine einerseits und der zweifach und dreifach verzweigten Paraffine andererseits durch ein Adsorptionsverfahren des Typs PSA erzielt wird.
  12. Verfahren nach einem der Ansprüche 9 und 10, wobei die Trennung der linearen und einfach verzweigten Paraffine einerseits und der zweifach und dreifach verzweigten Paraffine andererseits durch ein Adsorptionsverfahren vom Typ eines simulierten Gegenstromverfahrens (CCS) erzielt wird.
  13. Verfahren nach einem der Ansprüche 1 bis 12, wobei die Extraktion der aromatischen Verbindungen (EA) mit Hilfe eines Lösemittels erzielt wird.
  14. Verfahren nach einem der Ansprüche 1 bis 12, wobei die Extraktion der aromatischen Verbindungen (EA) durch extraktive Destillation erzielt wird.
  15. Verfahren nach einem der Ansprüche 1 bis 12, wobei die Extraktion der aromatischen Verbindungen (EA) durch Adsorption oder durch Verwendung einer Membran erzielt wird.
  16. Verfahren nach einem der Ansprüche 1 bis 6 und 9 bis 15, wobei die C7 Charge in eine Einheit zur spezifischen Dehydrogenierung von Naphthenen stromaufwärts der Einheit zur Extraktion aromatischer Verbindungen eingeführt wird.
EP05291857A 2004-09-22 2005-09-07 Verfahren zur Isomerisierung von einer C7-Fraktion mit Koproduktion von einer aromatischen Toluenreichen Fraktion Expired - Lifetime EP1640435B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR0409999A FR2875508B1 (fr) 2004-09-22 2004-09-22 Procede ameliore d'isomerisation d'une coupe c7 avec coproduction d'une coupe riche en molecules aromatiques

Publications (2)

Publication Number Publication Date
EP1640435A1 EP1640435A1 (de) 2006-03-29
EP1640435B1 true EP1640435B1 (de) 2007-10-03

Family

ID=34950864

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05291857A Expired - Lifetime EP1640435B1 (de) 2004-09-22 2005-09-07 Verfahren zur Isomerisierung von einer C7-Fraktion mit Koproduktion von einer aromatischen Toluenreichen Fraktion

Country Status (4)

Country Link
US (1) US7612246B2 (de)
EP (1) EP1640435B1 (de)
DE (1) DE602005002709T2 (de)
FR (1) FR2875508B1 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1954786A1 (de) * 2005-11-22 2008-08-13 Haldor Topsoe A/S C7-isomerisierung mit reaktiver destillation
US7777089B2 (en) * 2006-12-06 2010-08-17 Haldor Topsøe A/S Hydrocarbon separation
FR3034764B1 (fr) * 2015-04-13 2017-04-28 Ifp Energies Now Procede d'isomerisation d'une charge d'hydrocarbures en c7 a c11.
US11220648B2 (en) * 2016-11-15 2022-01-11 Exxonmobil Research And Engineering Company Fuel compositions for controlling combustion in engines
US10851315B1 (en) * 2019-06-27 2020-12-01 Uop Llc Processes for increasing an octane value of a gasoline component
US11066345B2 (en) * 2019-06-27 2021-07-20 Uop Llc Processes for increasing an octane value of a gasoline component
US10829702B1 (en) * 2019-06-27 2020-11-10 Uop Llc Dehydrogenation process for gasoline production
US10941352B2 (en) 2019-06-27 2021-03-09 Uop Llc Processes for increasing an octane value of a gasoline component

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US462673A (en) * 1891-11-03 russell
FR2383148A2 (fr) * 1977-03-08 1978-10-06 Inst Francais Du Petrole Procede de purification de benzene et de toluene par distillation azeotropique-extractive
US4982048A (en) * 1989-02-24 1991-01-01 Shell Oil Company Isomerization process with preliminary normal paraffin and mono-methyl paraffin feed capture step
GB9013566D0 (en) * 1990-06-18 1990-08-08 Shell Int Research Process for producing gasoline components
US5643442A (en) * 1994-07-19 1997-07-01 Exxon Research And Engineering Company Membrane process for enhanced distillate or hydrotreated distillate aromatics reduction
FR2771419B1 (fr) * 1997-11-25 1999-12-31 Inst Francais Du Petrole Essences a haut indice d'octane et leur production par un procede associant hydro-isomerisation et separation
US6069289A (en) * 1998-08-31 2000-05-30 Uop Llc Process for separating and recovering multimethyl-branched alkanes
US6683020B2 (en) * 2000-07-21 2004-01-27 Exxonmobil Research And Engineering Company Naphthene ring opening over an iridium ring opening catalyst
FR2813304B1 (fr) * 2000-08-23 2002-11-29 Inst Francais Du Petrole Procede de deshydrogenation de composes organiques en presence d'un catalyseur bimetallique supporte comportant une forte interaction entre un metal du groupe viii et de l'etain

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
US20060106266A1 (en) 2006-05-18
DE602005002709D1 (de) 2007-11-15
FR2875508A1 (fr) 2006-03-24
EP1640435A1 (de) 2006-03-29
DE602005002709T2 (de) 2008-01-24
US7612246B2 (en) 2009-11-03
FR2875508B1 (fr) 2006-11-03

Similar Documents

Publication Publication Date Title
EP2321385B1 (de) Verfahren zur umwandlung einer schweren ladung in benzin und propylen mit einer struktur für variablen ertrag
EP1931751B1 (de) Verfahren zur entschwefelung von benzinen durch adsorption einer leichtfraktion und durch hydroentschwefelung einer schwerfraktion
WO2003078364A1 (fr) Procede de conversion en plusieurs etapes d'une charge comprenant des olefines a quatre, cinq atomes de carbone ou plus, en vue de produire du propylene
WO2003078547A2 (fr) Procede de production conjointe de propylene et d'essence a partir d'une charge relativement lourde
FR2925065A1 (fr) Nouveau schema permettant d'optimiser la production d'essence a haut indice d'octane et la coproduction de bases aromatiques
CA2730515C (fr) Procede d'hydrogenation du benzene
EP1640436B1 (de) Verfahren zur Isomerisierung von einer C7-Fraktion mit Koproduktion von einer cyclischen Methylcyclohexan-reichen Fraktion
EP2636661A1 (de) Umwandlungsverfahren einer schweren Ladung durch Einsatz einer Katkrackeinheit und einer selektiven Hydrierphase des aus dem Katkrackverfahren entstandenen Kraftstoffs
FR2862311A1 (fr) Procede de production d'essences a haut indice d'octane a partir d'une coupe c5/c6 utilisant une unite de separation par menbrane
EP1640435B1 (de) Verfahren zur Isomerisierung von einer C7-Fraktion mit Koproduktion von einer aromatischen Toluenreichen Fraktion
EP0559518A1 (de) Verfahren zur Isomerisierung von n-C5/C6-Paraffinen mit Recyclierung von n-Paraffinen und Methylpentanen
FR2847260A1 (fr) Procede de desulfuration comprenant une etape d'hydrogenation selective des diolefines et une etape d'extraction des composes soufres
CA2074140C (fr) Procede d'isomerisation de paraffines normales en c5/c6 avec recyclage de paraffines normales
FR2795405A1 (fr) Production d'un isomere du xylene en trois etapes: separation, isomerisation avec un catalyseur a base de zeolithe euo et transalkylation avec recyclage des aromatiques en c10
CA2738541A1 (fr) Procede ameliore de reduction selective de la teneur en benzene et en composes insatures legers de differentes coupes hydrocarbures
CA2266003C (fr) Procede de conversion d'hydrocarbures par traitement dans une zone de distillation associee a une zone reactionnelle et son utilisation en hydrogenation du benzene
FR2857973A1 (fr) Procede de desulfuration des essences par adsorption
WO2012175823A1 (fr) Nouveau solide hybride organique-inorganique im-22 et son utilisation dans la separation de paraffines multibranchees des paraffines lineaires et mono-branchees
EP1496099B1 (de) Verbessertes Isomerisierungsverfahren eines C7-Schnitts mit Öffnung der Naphtenringe
CA2265991C (fr) Procede de conversion d'hydrocarbures par traitement dans une zone de distillation associee a une zone reactionnelle, et son utilisation en hydrogenation du benzene
EP1110931B1 (de) Verfahren und Vorrichtung zur Alkylierung von Isobutan mittels leichten Olefinen
FR2968656A1 (fr) Procede de separation de paraffines multibranchees utilisant un adsorbant de la famille des zif de type structural sod
FR2787117A1 (fr) Procede de conversion d'hydrocarbures par traitement dans une zone de distillation associee a une zone reactionnelle comprenant le recontactage du distillat vapeur avec la charge, et son utilisation en hydrogenation du benzene
EP0980909A1 (de) Kohlenwasserstoff-Umwandlungsverfahren und seine Verwendung in der Hydrierung von Benzol
WO2013098523A1 (fr) Procédé pour maximiser la production de composés aromatiques

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

17P Request for examination filed

Effective date: 20060929

AKX Designation fees paid

Designated state(s): BE DE GB IT NL

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE GB IT NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REF Corresponds to:

Ref document number: 602005002709

Country of ref document: DE

Date of ref document: 20071115

Kind code of ref document: P

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20071031

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20080704

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602005002709

Country of ref document: DE

Owner name: IFP ENERGIES NOUVELLES, FR

Free format text: FORMER OWNER: INSTITUT FRANCAIS DU PETROLE, RUEIL MALMAISON, FR

Effective date: 20110331

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20200925

Year of fee payment: 16

Ref country code: GB

Payment date: 20200925

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20200923

Year of fee payment: 16

Ref country code: BE

Payment date: 20200925

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20201127

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602005002709

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20211001

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20210930

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20210907

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210907

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220401

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210907