EP2454218B1 - Procédé et installation de production de carburants synthétiques - Google Patents

Procédé et installation de production de carburants synthétiques Download PDF

Info

Publication number
EP2454218B1
EP2454218B1 EP10737757.4A EP10737757A EP2454218B1 EP 2454218 B1 EP2454218 B1 EP 2454218B1 EP 10737757 A EP10737757 A EP 10737757A EP 2454218 B1 EP2454218 B1 EP 2454218B1
Authority
EP
European Patent Office
Prior art keywords
fraction
etherification
reactor
methanol
pentene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP10737757.4A
Other languages
German (de)
English (en)
Other versions
EP2454218A1 (fr
Inventor
Martin Rothaemel
Theis Ohlhaver
Peter Trabold
Andreas Ochs
Harald KÖMPEL
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.)
Air Liquide Global E&C Solutions Germany GmbH
Original Assignee
Air Liquide Global E&C Solutions Germany GmbH
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 Air Liquide Global E&C Solutions Germany GmbH filed Critical Air Liquide Global E&C Solutions Germany GmbH
Publication of EP2454218A1 publication Critical patent/EP2454218A1/fr
Application granted granted Critical
Publication of EP2454218B1 publication Critical patent/EP2454218B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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
    • C10G2400/22—Higher olefins
    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
    • 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
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/543—Distillation, fractionation or rectification for separating fractions, components or impurities during preparation or upgrading of a fuel
    • 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
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/58—Control or regulation of the fuel preparation of upgrading process
    • 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
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/60—Measuring or analysing fractions, components or impurities or process conditions during preparation or upgrading of a fuel
    • 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
    • C10L2300/00—Mixture of two or more additives covered by the same group of C10L1/00 - C10L1/308
    • C10L2300/30—Mixture of three components

Definitions

  • the invention relates to a process and a plant for the production of synthetic fuels from a water vapor and oxygenates, such as methanol and / or dimethyl ether (DME), containing educt mixture.
  • a water vapor and oxygenates such as methanol and / or dimethyl ether (DME), containing educt mixture.
  • DME dimethyl ether
  • C 2 -C 4 -olefins in particular propylene
  • MTP methanol to propylene
  • a variety of methods are known in the art, which usually on the implementation of a steam and methanol and / or or Dimethyletherdampf-containing educt mixture based on a shape-selective zeolite catalyst. Such methods are, for example, in the DE 100 27 159 A1 or the EP 0 882 692 B1 described.
  • methanol is placed in an adiabatically operated prereactor where it is converted to dimethyl ether (DME) and water (H 2 O) using a highly active and highly selective Al 2 O 3 catalyst.
  • DME dimethyl ether
  • H 2 O water
  • the methanol / water / DME stream is passed to the first of several reactor stages, in which the resulting vapor is supplied.
  • This reactor stage there is an almost complete reaction of both methanol and dimethyl ether, wherein as a hydrocarbon product mainly produces propylene. Further reactions can be achieved in subsequent reactor stages.
  • the process conditions are chosen in all stages to ensure similar reaction conditions and maximum propylene yield. This results in a yield of propylene of over 60%, in addition to other olefin fractions, but also a gasoline fraction.
  • a separation of the olefins, z As an extraction, is technically very complicated and is less selective, which in addition to the olefins and the non-interfering combintanigen aromatics are removed from the final product. Furthermore, the hydrogenation of the olefins to paraffins would be a fundamental possibility for lowering the olefin content, which is also technically easy to implement. Due to the increased paraffin content, however, the octane number drops by 5-7 points, so that even the limit value of normal gasoline (RON> 91) can no longer be met.
  • the high octane number of synthetic crude gas can be achieved by alkylation, for example of i-butane with butenes.
  • the olefin content decreases with simultaneous formation of high-octane paraffinic adducts.
  • the high-acid catalyst eg sulfuric acid, hydrogen fluoride
  • the reaction would therefore require a complex and unprofitable separation of the fraction to be alkylated, such as the C 4 fraction.
  • pamphlets such as the EP 0 320 180 B1 or the EP 0 432 163 A1
  • methods for the combination of a methanol-to-olefin process with a subsequent etherification of the olefins but here always connects the oxygenate conversion to the etherification. This leads to additional by-products during oxygenation, which must then be removed from the process.
  • the EP 0 320 158 describes an integrated process for the conversion of methanol to high octane gasoline and distillate in which methanol is converted to olefins and the resulting olefin stream is split into various fractions.
  • C 3 olefin stream As well as the C 6 and C 7 olefin streams, C 5+ gasoline is produced. Unreacted methanol and C 4 and C 5 hydrocarbons and a high ether content stream may also be added to the oligomerization.
  • the EP 0 254 496 teaches a process for converting methanol to liquid hydrocarbons wherein the methanol-containing stream is also first converted to olefins and then separated into individual fractions. Isoalkenes undergo etherification, while butene is at least partially converted into an alkylate petrol together with isobutane.
  • the US 5,130,101 describes the conversion of methanol or other alcohols to higher octane moieties wherein the olefins generated from the oxygenates are converted to tertiary alkyl ethers. These ethers can then be admixed with a gasoline stream, for example the C 6+ stream obtained from the oxygenate-to-olefin preparation.
  • the DE 103 46 532 describes a process for preparing aliphatic olefins, amines, aldehydes and alcohols in which butenes are added to other dienes, the resulting dienes are isomerized and then individual fractions are separated. Thereafter, the resulting dienes can be selectively hydrogenated to olefins or converted to amines, aldehydes or alcohols.
  • the object of the invention is therefore to achieve a reduction of the olefin content in synthetic fuels and thus to produce a salable product.
  • the development of environmentally problematic by-products should be reduced, whereby additional and non-process-related substances should be avoided.
  • a starting material mixture containing water vapor and oxygenates such as methanol and / or dimethyl ether
  • this olefin mixture is converted into a C 1 -C 4 hydrocarbons rich stream and a split rich in C 5 + hydrocarbons stream rich in C 5 + hydrocarbons stream is in an at C 5 - and C 6 - hydrocarbons (pentene, hexene) rich stream and a C 7 to + hydrocarbons divided rich stream of C 5 - and C 6 - rich hydrocarbon stream is at least partially subjected to etherification with methanol and ether thus formed are rich in C 7+ hydrocarbons gasoline product stream admixed while a partial flow of the C 5 - and C 6 - fraction passed through the etherification and directly to the fractions with seven and more coals mixed atoms.
  • the C 5 and C 6 olefins contained in the gasoline fraction have octane numbers from 110-145, paraffins, which may also be produced by additional hydrogenation, lead to octane numbers of 85 - 100 and the By the etherification resulting methyl ethers have octane numbers of 115-125, these octane numbers must be understood in each case as a mixture octane numbers, so-called. BONs (blending octane numbers).
  • a partial stream of C 5 and C 6 hydrocarbons is passed past the etherification and mixed directly into the gasoline product stream rich in C 7+ hydrocarbons.
  • the C 4 fraction is separated off from the stream rich in C 1 -C 4 -hydrocarbons and at least partially subjected to etherification with methanol.
  • etherification with methanol.
  • the amount of the valuable product can be further increased in compliance with the specifications.
  • MTBE Methyl tertiary butyl ether
  • Another embodiment of the invention involves returning at least parts of the pentene and hexene fractions to the reactor of the first process stage, which additionally increases the flexibility of the process with respect to the product spectrum.
  • the invention further relates to a plant for the production of synthetic fuels, which is suitable for carrying out the method according to the invention with the features of claim 1.
  • This plant comprises a reactor for the catalytic conversion of a water vapor and oxygenates, such as methanol and / or dimethyl ether, containing educt mixture Olefins, a first separation device for dividing the olefin mixture in a current rich in C 1 -C 4 hydrocarbons and a stream of C 5+ hydrocarbons stream, another separator for diversion of a stream of C 5 - and C 6 - rich hydrocarbons the stream rich in C 5+ hydrocarbons and a reactor for etherifying the C 5 fraction and the C 6 fraction with methanol,
  • a reactor for the catalytic conversion of a water vapor and oxygenates such as methanol and / or dimethyl ether, containing educt mixture Olefins
  • a first separation device for dividing the olefin mixture in a current rich in C 1
  • the system includes a bypass line (39) through which a partial stream of C 5 - passed fraction of the reactor (36) for the etherification and into the conduit (40) of the fraction having seven or more carbon atoms is carried out - and C. 6
  • butene is additionally fed to the etherification reactor via a feed line.
  • the olefin content of the resulting gasoline can be further reduced and the butene can be used to increase value.
  • a further embodiment of the system according to the invention provides a line for at least partial recycling of the pentene and hexene fraction from the further separation device to the olefin-producing reactor. This further increases the flexibility with regard to the product range generated by this system.
  • a reactor for selective hydrogenation of these compounds is provided, which is connected upstream of the reactor for etherification.
  • the etherification reactor is an ion exchanger, whereby an established and thus risk-minimized component is used
  • a cooler is preferably used, whereby, unlike a chemical separation method, the introduction of additional substances is dispensed with.
  • the single figure shows schematically a plant for carrying out the method according to the invention.
  • methanol methanol is fed as starting material through line 1 into a DME reactor 2 and there, for example.
  • a DME reactor 2 At an Al 2 O 3 catalyst at least partially converted to dimethyl ether.
  • the methanol / DME mixture is then passed through lines 3 and 4, mixed with the steam coming from line 14 and finally fed via line 5 into the reactor 6 where it is catalytically converted to hydrocarbons, in particular to propylene (MTP ).
  • Line 7 leads the product mixture into a cooler 8 designed as the first separation device, in which the olefin fractions are divided into a stream which is rich in C 1 -C 4 -hydrocarbons and a stream which is rich in C 5+ -hydrocarbons. Furthermore, there is water as by-product of the reaction.
  • the cooler 8 is thus a three-phase separator (liquid / liquid / gaseous).
  • the C 1 -C 4 fractions are fed via line 16 into the compressor 17 and through line 18 to a second separator 19, which consists of at least one distillation column.
  • a propylene-rich stream is fed to a further separating device 50, in which a propane-rich stream is separated off.
  • the propylene-rich stream is discharged via line 20a.
  • the separated C 4 fraction leaves the separator 19.
  • a portion of the stream via line 21 a is discharged together with the propane from line 20 b as liquid gas (LPG).
  • LPG liquid gas
  • This mainly consisting of propane and butane LPG with only low olefin content can be used for example as LPG.
  • the main part of the stream 21 is transferred via the line 21b and 24 in line 26, in the with Line 22 and the preferably withdrawn via the top of the separator 19 ethylene-rich fraction is transferred.
  • the stream can then be returned to the line 4 in front of the reactor 6.
  • the C 5+ stream passes via line 15 into a further, third separating device 28, in which a stream rich in C 7+ hydrocarbons is separated and withdrawn from the process through lines 38, 40 and 41.
  • the C 5 -fraction and the C 6 -fraction are withdrawn via line 29 from the third separator 28.
  • this fraction can be at least partially fed into line 26 and combined with the ethylene and the butylene fraction to the reactor 6 recycled.
  • At least a subset of the C 5 / C 6 fraction from line 29 is transferred to line 30. From there, the further divided stream wholly or partially mixed through line 39 the higher olefins from line 38 and are withdrawn from the process whereby the ratio of the flow rates in line 39 to that in line 30 can be between 0 and 100%.
  • the remaining part-stream (100-0%) of the C 5 / C 6 fraction is passed via lines 33 and 35 into an etherification reactor 36 formed, for example, as an ion exchanger.
  • an etherification reactor 36 formed, for example, as an ion exchanger.
  • methanol which has been diverted, for example, before the DME reactor 2 from the supply line 1.
  • the olefins are etherified to methyl-amyl-ether or methyl-hexyl-ether.
  • these ethers can then be added to the fractions having seven or more carbon atoms from line 40 and the thus upgraded gasoline product can be withdrawn via line 41.
  • Through line 23 butene can also be supplied from the second separator 19 of the etherification.
  • the etherification reactor 36 may be preceded by a selective hydrogenation in order to remove interfering compounds, such as dienes.
  • the division of the pentene and hexene fraction on lines 32 and 39 is controlled as a function of the olefin content of the gasoline product in line 41.
  • the olefin content of the streams 38 and 30 changes, for example as a result of aging of the catalyst or altered reaction conditions, a new operating point for the etherification fraction is obtained.
  • the olefin content in the effluent streams has decreased so that the operator of a plant can reduce the etherification fraction to 33% and still not exceed 18% in the gasoline product 41.

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)

Claims (14)

  1. Procédé de fabrication de carburants de synthèse, consistant à
    faire réagir sur un catalyseur, dans une première étape de procédé, un mélange de réactifs contenant de la vapeur d'eau et des produits oxygénés tels que le méthanol et/ou l'éther diméthylique, pour obtenir des oléfines,
    diviser, dans un dispositif de séparation, ce mélange d'oléfines de manière à obtenir une fraction C1 - C4 et une fraction C5+.
    diviser la fraction C5+ de manière à obtenir une fraction de pentène et d'hexène et une fraction dont le nombre d'atomes de carbone est supérieur ou égal à sept,
    soumettre la fraction de pentène et d'hexène au moins partiellement à une éthérification au méthanol, et
    réaliser un mélange en ajoutant les éthers, ainsi obtenus, aux fractions dont le nombre d'atomes de carbone est supérieur ou égal à sept,
    caractérisé en ce qu'un débit partiel de la fraction de C5 et de C6 est amené à contourner l'éthérification pour être ajouté directement, en mélangeant, aux fractions dont le nombre fractions dont le nombre d'atomes de carbone est supérieur ou égal à sept,
  2. Procédé selon la revendication 1 ou 2, caractérisé en ce que la proportion de la fraction de C5/C6 laquelle est acheminée vers l'éthérification et la proportion de la fraction C5/C6 laquelle est amenée à contourner l'éthérification, sont réglées en fonction de la teneur globale en oléfines d'un produit d'essence que l'on obtient.
  3. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'on sépare, à partir de la fraction C1 à C4, la fraction C4 pour la soumettre, au moins partiellement, à l'éthérification au méthanol.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'on ajoute, en mélangeant, une fraction C4 aux fractions dont le nombre d'atomes de carbone est supérieur ou égal à sept.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que la fraction de pentène et d'hexène est partiellement recyclée vers la première étape de procédé.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'on met en oeuvre, en amont de ladite éthérification, une hydrogénation sélective.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'on met en oeuvre ladite éthérification au moyen d'un échangeur d'ions.
  8. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'on met en oeuvre ladite éthérification à une température comprise entre 50 et 90 °C et à une pression comprise entre 1 et 1,5 MPa.
  9. Installation qui permet de fabriquer des carburants de synthèse, et notamment de mettre en oeuvre un procédé selon l'une des revendications précédentes, et qui comporte
    un réacteur (6) destiné à faire réagir, de manière catalytique, un mélange de réactifs contenant de la vapeur d'eau et des produits oxygénés tels que le méthanol et/ou l'éther diméthylique, pour obtenir des oléfines,
    un premier dispositif de séparation (8) qui est situé en aval du réacteur (6) et qui permet de diviser le mélange d'oléfines de manière à obtenir une fraction C1 - C4 et une fraction C5+,
    un dispositif de séparation supplémentaire (28) qui est situé en aval du premier dispositif de séparation (8) et qui permet d'isoler, à partir de la fraction C5+, une fraction de pentène et d'hexène, et
    un réacteur (36) permettant de soumettre la fraction de pentène et d'hexène à une éthérification au méthanol,
    caractérisé par une conduite de contournement (39) permettant d'introduire un débit partiel de la fraction de pentène et d'hexène dans la conduite (40) des fractions dont le nombre d'atomes de carbone est supérieur ou égal à sept, en contournant le réacteur (36).
  10. Installation selon la revendication 9, caractérisée en ce que le réacteur d'éthérification (36) est relié à une conduite (23) permettant d'acheminer une fraction C4.
  11. Installation selon les revendications 9 ou 10, caractérisée par une conduite de recyclage (31) permettant de recycler la fraction de pentène et d'hexène, en provenance du dispositif de séparation supplémentaire (28), vers le réacteur (6).
  12. Installation selon l'une des revendications 9 à 11, caractérisée en ce qu'un réacteur permettant d'effectuer une hydrogénation sélective est disposé en amont du réacteur d'éthérisation (36).
  13. Installation selon l'une des revendications 9 à 12, caractérisée en ce que le réacteur d'éthérisation (36) est un échangeur d'ions.
  14. Installation selon l'une des revendications 9 à 13, caractérisée en ce que le premier dispositif de séparation (8) est un réfrigérant et/ou le dispositif de séparation supplémentaire (28) est une colonne de distillation.
EP10737757.4A 2009-07-14 2010-07-03 Procédé et installation de production de carburants synthétiques Active EP2454218B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009032915A DE102009032915A1 (de) 2009-07-14 2009-07-14 Verfahren und Anlage zur Herstellung von synthetischen Kraftstoffen
PCT/EP2010/004032 WO2011006594A1 (fr) 2009-07-14 2010-07-03 Procédé et installation de production de carburants synthétiques

Publications (2)

Publication Number Publication Date
EP2454218A1 EP2454218A1 (fr) 2012-05-23
EP2454218B1 true EP2454218B1 (fr) 2015-09-02

Family

ID=42691165

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10737757.4A Active EP2454218B1 (fr) 2009-07-14 2010-07-03 Procédé et installation de production de carburants synthétiques

Country Status (6)

Country Link
US (1) US9028567B2 (fr)
EP (1) EP2454218B1 (fr)
CN (1) CN102471179B (fr)
DE (1) DE102009032915A1 (fr)
RU (1) RU2509070C2 (fr)
WO (1) WO2011006594A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007022175B4 (de) * 2007-05-11 2015-11-05 Air Liquide Global E&C Solutions Germany Gmbh Verfahren und Anlage zur Herstellung von synthetischen Kraftstoffen
CN102351629B (zh) * 2011-08-23 2013-11-20 洛阳市科创石化科技开发有限公司 一种利用甲醇生产丙烯和高辛烷值汽油的方法
RS59147B1 (sr) * 2012-11-14 2019-09-30 Evonik Fibres Gmbh Upravljanje sastavom gasa postrojenja za separaciju gasa sa membranama
DE102013101577B4 (de) * 2013-02-18 2019-01-31 L’AIR LIQUIDE Société Anonyme pour l’Etude et l’Exploitation des Procédés Georges Claude Verfahren und Anlage zur Herstellung von Olefinen aus Oxygenaten
WO2016079112A1 (fr) * 2014-11-17 2016-05-26 Haldor Topsøe A/S Recyclage d'impuretés de condensat de transformation dans tigas

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US530101A (en) * 1894-12-04 Door-check
US3482952A (en) 1968-04-29 1969-12-09 Chevron Res Process for production of gasoline
US3902870A (en) 1974-05-30 1975-09-02 Mobil Oil Corp Process for the production of gasoline
US4025572A (en) * 1976-05-12 1977-05-24 Mobil Oil Corporation Manufacture of hydrocarbons
US4198530A (en) 1978-06-29 1980-04-15 Atlantic Richfield Company Production of tertiary butyl methyl ether
FR2477570A1 (fr) 1980-03-10 1981-09-11 Inst Francais Du Petrole Hydrogenation et etherification d'une coupe insaturee c5 d'hydrocarbures en vue d'en ameliorer l'indice d'octane et d'en reduire la teneur en mono-olefines
US4684757A (en) 1986-07-18 1987-08-04 Mobil Oil Corporation Process for converting methanol to alkyl ethers, gasoline, distillate and alkylate liquid hydrocarbons
US4746761A (en) * 1986-07-18 1988-05-24 Mobil Oil Corporation Process for coverting methanol to alkyl ethers
US4826507A (en) 1987-12-08 1989-05-02 Mobil Oil Corporation Integrated etherification and oxygenates to gasoline process
US5024679A (en) * 1987-12-08 1991-06-18 Mobil Oil Corporation Olefins etherification and conversion to liquid fuels with paraffins dehydrogenation
US4788365A (en) * 1987-12-08 1988-11-29 Mobil Oil Corporation High octane gasoline and distillates from oxygenates
US4830635A (en) 1987-12-08 1989-05-16 Mobil Oil Corporation Production of liquid hydrocarbon and ether mixtures
US5130101A (en) 1989-04-28 1992-07-14 Mobil Oil Corporation Reactor system for conversion of alcohols to ether-rich gasoline
GB9027112D0 (en) 1990-12-13 1991-02-06 British Petroleum Co Plc Etherification
US5243090A (en) * 1991-03-06 1993-09-07 Mobil Oil Corporation Conversion of normal alkenes to tertiary alkyl ethers
CN1127242A (zh) 1995-01-16 1996-07-24 中国石油化工总公司 一种醚类的催化合成工艺
US5714662A (en) 1995-08-10 1998-02-03 Uop Process for producing light olefins from crude methanol
DE19723363A1 (de) 1997-06-04 1998-12-10 Metallgesellschaft Ag Verfahren zum Erzeugen von Ethylen, Propylen und wahlweise auch Butenisomeren aus Methanol- und/oder Dimethylether
DE10027159A1 (de) 2000-05-31 2001-12-13 Mg Technologies Ag Verfahren zum Erzeugen von Propylen aus Methanol
RU2236396C1 (ru) * 2003-06-02 2004-09-20 Фалькевич Генрих Семёнович Способ получения высокооктанового компонента бензина, содержащего метилтретбутиловый и метилтретамиловый эфиры
DE10346532A1 (de) * 2003-10-07 2005-05-12 Basf Ag Verfahren zur Herstellung von geringverzweigten Olefinen, Alkoholen, Aminen oder Aldehyden aus C4-Olefinen

Also Published As

Publication number Publication date
EP2454218A1 (fr) 2012-05-23
DE102009032915A1 (de) 2011-03-31
RU2012104886A (ru) 2013-08-20
CN102471179B (zh) 2015-02-25
US20120102829A1 (en) 2012-05-03
WO2011006594A1 (fr) 2011-01-20
US9028567B2 (en) 2015-05-12
RU2509070C2 (ru) 2014-03-10
CN102471179A (zh) 2012-05-23

Similar Documents

Publication Publication Date Title
DE69918017T2 (de) Verfahren zur Herstellung eines Treibmittelbestandteils
DE102007022175B4 (de) Verfahren und Anlage zur Herstellung von synthetischen Kraftstoffen
EP1844125B1 (fr) Procede de production de combustibles synthetiques a base d'oxygenats
DE102005048931B4 (de) Verfahren und Anlage zur Herstellung von C2-C4-Olefinen aus Methanol und/oder Dimethylether
WO2009039948A2 (fr) Procédé et installation pour la production d'hydrocarbures
EP2454218B1 (fr) Procédé et installation de production de carburants synthétiques
EP3191434A1 (fr) Procédé et installation pour la production d'hydrocarbures
DE69102419T2 (de) Umwandlung von lichten Kohlenwasserstoffen in Ether enthaltende Benzine.
DE102014118967A1 (de) Anlage und Verfahren zur Herstellung von Propylen aus Methanol
DE102013101577B4 (de) Verfahren und Anlage zur Herstellung von Olefinen aus Oxygenaten
EP2688859B1 (fr) Procédé et installation pour la préparation d'oléfines de bas poids moléculaire
EP3106450B1 (fr) Procede et installation de recuperation et d'utilisation d'olefines superieures lors de la synthese d'olefines a partir de produits oxygenes
DE69103312T2 (de) Ätherisierung von Benzin.
DE102013101578B4 (de) Verfahren und Anlage zur Herstellung von Olefinen aus Oxygenaten
DE2854250C2 (de) Verfahren zur Herstellung von t-Amyl- methyläther enthaltendem Benzin
EP3102553A1 (fr) Procédé et installation de production d'oléfines
EP3041916B1 (fr) Procédé de production d'hydrocarbures
EP3165515B1 (fr) Procédé et installation de synthèse d'oléfine a partir de produits oxygénés présentant un rendement en propylène élevé
EP3191433A1 (fr) Procédé et installation pour la production d'hydrocarbures
DE102019213499A1 (de) Verfahren zur Herstellung von Ethern
SA118400322B1 (ar) عملية من أجل التحويل إلى إيثر للنافثا الخفيفة الألفينية المختلطة والاختزال المتزامن للإيثانول في المنتج
EP3041917B1 (fr) Procédé de production d'hydrocarbures
DE102013014867A1 (de) Verfahren und Anlage zur Erzeugung von Kohlenwasserstoffprodukten
DE102013014802A1 (de) Verfahren und Anlage zur Erzeugung von Kohlenwasserstoffprodukten
DE102013014866A1 (de) Verfahren und Anlage zur Erzeugung von Kohlenwasserstoffprodukten

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

17P Request for examination filed

Effective date: 20111121

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: AIR LIQUIDE GLOBAL E&C SOLUTIONS GERMANY GMBH

17Q First examination report despatched

Effective date: 20140408

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20150320

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): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 746479

Country of ref document: AT

Kind code of ref document: T

Effective date: 20150915

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502010010210

Country of ref document: DE

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

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151203

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

Ref country code: NL

Ref legal event code: MP

Effective date: 20150902

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

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

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

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160102

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

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

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160104

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502010010210

Country of ref document: DE

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

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

26N No opposition filed

Effective date: 20160603

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

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

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

Ref country code: BE

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

Effective date: 20160731

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

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

Ref country code: CH

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

Effective date: 20160731

Ref country code: LI

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

Effective date: 20160731

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

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

Ref country code: IE

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

Effective date: 20160703

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

Ref country code: LU

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

Effective date: 20160703

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 746479

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160703

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

Ref country code: AT

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

Effective date: 20160703

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

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20100703

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

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

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

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

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

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

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150902

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

Ref country code: GB

Payment date: 20230720

Year of fee payment: 14

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

Ref country code: FR

Payment date: 20230725

Year of fee payment: 14

Ref country code: DE

Payment date: 20230719

Year of fee payment: 14