EP0241638A2 - Process for the preparation of an aromatic concentrate useful as a blending component for carburettor fuels - Google Patents

Process for the preparation of an aromatic concentrate useful as a blending component for carburettor fuels Download PDF

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Publication number
EP0241638A2
EP0241638A2 EP87100581A EP87100581A EP0241638A2 EP 0241638 A2 EP0241638 A2 EP 0241638A2 EP 87100581 A EP87100581 A EP 87100581A EP 87100581 A EP87100581 A EP 87100581A EP 0241638 A2 EP0241638 A2 EP 0241638A2
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EP
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Prior art keywords
aromatics
extractive distillation
aromatic
column
boiling
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EP87100581A
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German (de)
French (fr)
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EP0241638B1 (en
EP0241638A3 (en
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Gerhard Dr. Dipl.-Chem. Preusser
Gerd Dipl.-Ing. Emmerich
Martin Chem.-Ing. Schulze
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Krupp Koppers GmbH
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Krupp Koppers GmbH
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/08—Azeotropic or extractive distillation
    • 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

Definitions

  • the invention relates to a process for producing an aromatic concentrate suitable for use as a blending component for gasoline fuels from hydrocarbon mixtures with a boiling range between 40 and 170 ° C., which contain several aromatics in addition to non-aromatics.
  • octane improvers In addition to the increased use of alkylate and polymer spirits, certain alcohols, such as methanol, isopropanol and tert-butanol, and certain ethers, such as methyl tert-butyl ether and amyl ether, are also used as octane improvers. Very often, the required octane number is also set in the gasoline fuel by adding aromatic concentrates, which contain not only a little benzene but especially C7 to C9 aromatics.
  • aromatic concentrates suitable as blending components for gasoline fuels are becoming increasingly important.
  • These aromatic concentrates should not have too high a benzene content. This is sought not only because of the carcinogenic properties of benzene already mentioned, but above all because benzene has a lower octane-improving effect than other aromatics such as toluene.
  • aromatic hydrocarbon mixtures from petroleum processing, such as. B. Reformates and Platformates. Inhaled hydrocarbon mixtures with a high benzene content, such as pyrolysis gasoline or coke oven crude benzene on the other hand, for the reasons described above, it is less suitable for the stated purpose.
  • the aromatics concentrates have hitherto been separated from these feed hydrocarbon mixtures in practice exclusively by liquid-liquid extraction using customary solvents, such as, for example, polyethylene glycol, sulfolane , N-methylpyrrolidone and others.
  • customary solvents such as, for example, polyethylene glycol, sulfolane , N-methylpyrrolidone and others.
  • solvents such as, for example, polyethylene glycol, sulfolane , N-methylpyrrolidone and others.
  • solvents such as, for example, polyethylene glycol, sulfolane , N-methylpyrrolidone and others.
  • counter solvent such as pentane.
  • Liquid-liquid extraction therefore causes not only high operating costs but also high investment costs.
  • the invention is therefore based on the object of providing a method by which the aromatic concentrates of the type mentioned at the outset can be obtained in a particularly simple and inexpensive manner.
  • the process of the type mentioned at the outset which is used to achieve this object is characterized according to the invention in that the hydrocarbon feed mixture is subjected to an extractive distillation without prior separation into individual fractions using N-substituted morpholines, the substituents of which have no more than seven C atoms, as a selective solvent is, the low-boiling non-aromatics with a boiling range up to approx. 105 ° C practically completely and the higher-boiling non-aromatics with a boiling range between approx.
  • 105 and 160 ° C are predominantly distilled off as overhead raffinate from the extractive distillation column, while the main amount the aromatics and the remaining non-aromatics are withdrawn together with the solvent used as an extract from the bottom of the extractive distillation column, whereupon the solvent is distilled from the other hydrocarbons in a downstream stripping column is separated open of the extract and these are used in whole or in part as a blending component.
  • extractive distillation avoids the disadvantages of liquid-liquid extraction described above, since on the one hand the solvent used according to the invention is used without any addition of water and on the other hand - as is customary in extractive distillation - relatively simple columns can be used .
  • N-formylmorpholine has proven to be particularly suitable.
  • the figure shows a flow diagram of the method according to the invention in a highly simplified representation.
  • the feed hydrocarbon mixture that is processed is processed without any pre-fractionation introduced via line 1 into the central part of the extractive distillation column 2 provided with internals (trays).
  • the hydrocarbons of the raffinate escape overhead from the extractive distillation column 2 and pass via line 4 into column 5, in which the hydrocarbons of the raffinate are separated from the solvent residues by distillation.
  • the latter pass via line 6 into line 3, through which the solvent used is introduced into the upper part of the extractive distillation column 2.
  • the hydrocarbons of the raffinate freed from the solvent are withdrawn via the head 7 from the column 5 and fed to their further use.
  • the hydrocarbons of the extract are withdrawn together with the majority of the solvents via line 8 from the bottom of the extractive distillation column 2 and from there into the middle part of the stripping column 9, which may also be provided with internals (trays).
  • the hydrocarbons of the extract consisting mainly of aromatics are driven off from the solvent, the recovered solvent, which accumulates in the bottom of the stripping column 9, being returned via line 3 to the extractive distillation column 2.
  • the hydrocarbons of the extract freed from the solvent are drawn off from the stripping column 9 via the lines 10 and 11 and fed to their further use.
  • the flow diagram shown in the figure contains only those parts of the system which are absolutely necessary for the explanation of the method according to the invention, while all auxiliary devices which are not directly related to the invention were not shown in the flow diagram. This applies in particular to the heat exchangers for heat exchange between the individual process streams, the circulation cookers for heating the individual columns, the devices for regenerating or supplementing the used solvent, and all measuring and control devices.
  • the raffinates obtained when carrying out the process according to the invention can be obtained as so-called.
  • Chemical gasoline for further processing for example, these raffinates can be used as a starting material for ethylene pyrolysis or for isomerization processes.
  • the aromatic concentrates used as a blending component and obtained by the process according to the invention only have a low non-aromatic content of between 0.5 and 5.0% by weight.
  • N-formylmorpholine was used as the selective solvent for the extractive distillation.
  • the extractive distillation column 2 each had 50 trays.
  • the feed hydrocarbon mixture was introduced into the extractive distillation column 2 at a temperature of 70 ° C., and the top temperature of this column was in each case approximately 100 ° C.
  • process example 1 a so-called reformate from petroleum processing with an aromatic content of 65% by weight and an octane number (RON) of 92 was used as the input hydrocarbon mixture, process variant 2 being used.
  • process example 2 a so-called platformat with an aromatic content of 42% by weight and an octane number (RON) of 83 was used as the starting material, process variant 2 again being used.
  • process example 3 the same reformate as in process example 1 was finally used as the starting material. However, this starting material was worked up according to process variant 1.

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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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

In this process, feedstock hydrocarbon mixtures having a boiling range of between 40 and 170 DEG C are subjected without prior separation into individual fractions to an extractive distillation using N-substituted morpholines whose substituents contain no more than seven C atoms as selective solvent. In this process, virtually all of the low-boiling non-aromatics having a boiling range of up to approximately 105 DEG C and the vast majority of the higher-boiling aromatics having a boiling range of between approximately 105 and 160 DEG C are extracted as a refined product, while the aromatics which are used in total or in part as a blending component are to be found in the extract from the extractive distillation. <IMAGE>

Description

Die Erfindung betrifft ein Verfahren zur Herstellung eines zur Verwendung als Blendingkomponente für Verga­serkraftstoffe geeigneten Aromatenkonzentrates aus Ein­satzkohlenwasserstoffgemischen mit einem Siedebereich zwischen 40 und 170°C, die neben Nichtaromaten mehrere Aromaten enthalten.The invention relates to a process for producing an aromatic concentrate suitable for use as a blending component for gasoline fuels from hydrocarbon mixtures with a boiling range between 40 and 170 ° C., which contain several aromatics in addition to non-aromatics.

Die in den letzten Jahren im Interesse des Umweltschutzes in die Wege geleiteten Maßnahmen haben auf dem Gebiet des Kraftfahrzeugwesens dazu geführt, daß die Nachfrage nach bleifreien Vergaserkraftstoffen ständig gestiegen ist und auch in Zukunft noch weiter steigen wird. Durch diese bleifreien Vergaserkraftstoffe kann nämlich eine Vergif­tung der Katalysatoren vermieden werden, die in immer größerem Umfang den Otto-Motoren zur Verringerung des Schadstoffausstoßes nachgeschaltet werden.The measures taken in the last few years in the interest of environmental protection have led to the fact that the demand for unleaded petrol has increased and will continue to do so in the future. These lead-free carburetor fuels can in fact prevent poisoning of the catalytic converters, which are being used to an increasing extent downstream of the Otto engines to reduce pollutant emissions.

Gleichzeitig werden jedoch an die bleifreien Vergaser­kraftstoffe, insbesondere im Hinblick auf deren Klopf­festigkeit, die gleichen Qualitätsansprüche gestellt wie an die entsprechenden verbleiten Vergaserkraftstoffe. Die geforderten Octanzahlen müssen deshalb durch Zusatz anderer Stoffe und/oder durch eine andere Kraftstoffzu­sammensetzung erreicht werden. Es ist bereits seit län­gerer Zeit bekannt, daß durch einen Zusatz von Benzol die Klopffestigkeit des Vergaserkraftstoffes erhöht werden kann. Wegen der carcinogenen Eigenschaften des Benzols ist man jedoch in neuerer Zeit bestrebt, den Benzolge­halt im Kraftstoff möglichst niedrig zu halten. Dies hat deshalb dazu geführt, daß eine ganze Reihe anderer Methoden zur Octanzahlverbesserung entwickelt wurden. Neben dem verstärkten Einsatz von Alkylat- und Polymer­benzinen werden auch bestimmte Alkohole, wie z.B. Metha­nol, Isopropanol und tert.Butanol sowie bestimmte Äther, wie z.B. Methyl-tert.-butyläther und -amyläther, als Octanzahlverbesserer verwendet. Sehr häufig wird auch durch Zusatz von Aromatenkonzentraten, in denen neben wenig Benzol vor allem C₇ - bis C₉ -Aromaten enthalten sind, die geforderte Octanzahl im Vergaserkraftstoff eingestellt.At the same time, however, the same quality requirements are placed on the lead-free carburettor fuels, particularly with regard to their knock resistance, as on the corresponding leaded carburetor fuels. The required octane numbers must therefore be achieved by adding other substances and / or using a different fuel composition. It has been known for a long time that the addition of benzene Knock resistance of the carburetor fuel can be increased. Because of the carcinogenic properties of benzene, efforts have recently been made to keep the benzene content in the fuel as low as possible. As a result, a number of other methods of octane improvement have been developed. In addition to the increased use of alkylate and polymer spirits, certain alcohols, such as methanol, isopropanol and tert-butanol, and certain ethers, such as methyl tert-butyl ether and amyl ether, are also used as octane improvers. Very often, the required octane number is also set in the gasoline fuel by adding aromatic concentrates, which contain not only a little benzene but especially C₇ to C₉ aromatics.

Deshalb kommt der Gewinnung derartiger als Blending­komponente für Vergaserkraftstoffe geeigneter Aromaten­konzentrate eine ständig wachsende Bedeutung zu. Hier­bei sollen diese Aromatenkonzentrate einen nicht zu hohen Benzolgehalt aufweisen. Dies wird nicht nur wegen der bereits erwähnten carcinogenen Eigenschaften des Benzols angestrebt, sondern vor allem auch deshalb, weil das Benzol im Vergleich zu anderen Aromaten, wie z.B. Toluol, eine geringere octanzahlverbessernde Wir­kung besitzt. Als Ausgangsprodukt zur Herstellung sol­cher Aromatenkonzentrate eignen sich insbesondere aro­matenhaltige Kohlenwasserstoffgemische aus der Erdöl­verarbeitung, wie z. B. Reformate und Platformate. Einstzkohlenwasserstoffgemische mit hohem Benzolgehalt, wie z.B. Pyrolysebenzin oder Kokereirohbenzol, sind dagegen aus den weiter oben geschilderten Gründen für den genannten Zweck weniger geeignet.For this reason, the extraction of aromatic concentrates suitable as blending components for gasoline fuels is becoming increasingly important. These aromatic concentrates should not have too high a benzene content. This is sought not only because of the carcinogenic properties of benzene already mentioned, but above all because benzene has a lower octane-improving effect than other aromatics such as toluene. As a starting product for the production of such aromatic concentrates are particularly aromatic hydrocarbon mixtures from petroleum processing, such as. B. Reformates and Platformates. Inhaled hydrocarbon mixtures with a high benzene content, such as pyrolysis gasoline or coke oven crude benzene on the other hand, for the reasons described above, it is less suitable for the stated purpose.

Da die in Betracht kommenden Einsatzkohlenwasserstoff­gemische normalerweise einen weiten, zwischen 40 und 170°C liegenden Siedebereich aufweisen, erfolgte die Abtrennung der Aromatenkonzentrate aus diesen Einsatz­kohlenwasserstoffgemischen bisher in der Praxis aus­schließlich durch Flüssig-Flüssig-Extraktion unter Ver­wendung hierfür üblicher Lösungsmittel, wie z.B. Po­lyäthylenglykol, Sulfolan, N-Methylpyrrolidon und an­derer. Dem verwendeten Lösungsmittel werden hierbei normalerweise zwecks Erhöhung der Selektivität mehr oder weniger große Mengen an Wasser zugesetzt, was sich sehr nachteilig auf den Energiebedarf auswirkt. Außer­dem wird die Flüssig-lüssig-Extraktion vielfach unter Verwendung eines sogenannten Gegenlösungsmittels, wie z.B. Pentan, durchgeführt. Die Verwendung derartiger Zusätze stellt jedoch ohne Zweifel eine erhebliche Komplizierung des Verfahrens dar, da einerseits die dadurch gewonnenen Reinprodukte stets gewisse Mengen an diesen Fremdstoffen enthalten, welche nachträglich unter erhöhtem Aufwand an Energie und Apparatur ent­fernt werden müssen, und andererseits die Anwendung dieser Zusatzstoffe als solche zusätzliche Kosten ver­ursachen kann. Außerdem sind zur Durchführung der Flüssig-Flüssig-Extraktion wegen der dort herrschenden Viskositäts- und Temperaturverhältnisse aufwendige Extraktoren erforderlich, wie z.B. sogenannte Mixer-­Settler-Extraktoren oder Extraktoren mit bewegten Ein­bauten.Since the feed hydrocarbon mixtures in question normally have a wide boiling range between 40 and 170 ° C, the aromatics concentrates have hitherto been separated from these feed hydrocarbon mixtures in practice exclusively by liquid-liquid extraction using customary solvents, such as, for example, polyethylene glycol, sulfolane , N-methylpyrrolidone and others. To increase the selectivity, more or less large amounts of water are normally added to the solvent used, which has a very disadvantageous effect on the energy requirement. In addition, the liquid-liquid extraction is often carried out using a so-called counter solvent, such as pentane. However, the use of such additives is undoubtedly a considerable complication of the process, since on the one hand the pure products obtained thereby always contain certain amounts of these foreign substances, which have to be subsequently removed with increased expenditure on energy and equipment, and on the other hand the use of these additives as such may cause additional costs. In addition, to carry out the liquid-liquid extraction, because of the viscosity and temperature conditions there, complex extractors are required, such as so-called mixer-settler extractors or extractors with moving internals.

Die Flüssig-Flüssig-Extraktion verursacht daher neben hohen Betriebskosten auch noch hohe Investitionskosten. Der Erfindung liegt deshalb die Aufgabe zugrunde, ein Verfahren zu schaffen, durch das die Aromatenkonzentra­te der eingangs genannten Art in besonders einfacher und kostengünstiger Weise gewonnen werden können.Liquid-liquid extraction therefore causes not only high operating costs but also high investment costs. The invention is therefore based on the object of providing a method by which the aromatic concentrates of the type mentioned at the outset can be obtained in a particularly simple and inexpensive manner.

Das der Lösung dieser Aufgabe dienende Verfahren der eingangs genannten Art ist erfindungsgemäß dadurch ge­kennzeichnet, daß das Einsatzkohlenwasserstoffgemisch ohne vorherige Auftrennung in einzelne Fraktionen einer Extraktivdestillation unter Verwendung von N-substitu­ierten Morpholinen, deren Substituenten nicht mehr als sieben C-Atome aufweisen, als selektivem Lösungsmittel unterworfen wird, wobei die niedrig siedenden Nichtaro­maten mit einem Siedebereich bis ca. 105°C praktisch vollständig und die höher siedenden Nichtaromaten mit einem Siedebereich zwischen ca. 105 und 160°C zum über­wiegenden Teil als Raffinat über Kopf aus der Extraktiv­destillationskolonne abdestilliert werden, während die Hauptmenge der Aromaten sowie die restlichen Nicht­aromaten zusammen mit dem verwendeten Lösungsmittel als Extrakt aus dem Sumpf der Extraktivdestillationskolonne abgezogen werden, worauf das Lösungsmittel in einer nachgeschalteten Abtreiberkolonne destillativ von den übrigen Kohlenwasserstoffen des Extraktes abgetrennt wird und diese ganz oder teilweise als Blendingkompo­nente eingesetzt werden.The process of the type mentioned at the outset which is used to achieve this object is characterized according to the invention in that the hydrocarbon feed mixture is subjected to an extractive distillation without prior separation into individual fractions using N-substituted morpholines, the substituents of which have no more than seven C atoms, as a selective solvent is, the low-boiling non-aromatics with a boiling range up to approx. 105 ° C practically completely and the higher-boiling non-aromatics with a boiling range between approx. 105 and 160 ° C are predominantly distilled off as overhead raffinate from the extractive distillation column, while the main amount the aromatics and the remaining non-aromatics are withdrawn together with the solvent used as an extract from the bottom of the extractive distillation column, whereupon the solvent is distilled from the other hydrocarbons in a downstream stripping column is separated open of the extract and these are used in whole or in part as a blending component.

Im Hinblick auf den weiten Siedebereich des Einsatzkoh­lenwasserstoffgemisches muß es als durchaus überraschendes und nicht naheliegendes Ergebnis gewertet werden, daß es ohne jede Vorfraktionierung des Einsatzproduktes ge­lingt, dieses unmittelbar durch Extraktivdestillation in der erfindungsgemäß beanspruchten Art und Weise aufzutrennen. Bisher ist die Fachwelt nämlich stets von der Annahme ausgegangen, daß durch eine Extraktiv­destillation nur solche Einsatzprodukte aufgetrennt werden können, die einen möglichst engen Siedebereich aufweisen.In view of the wide boiling range of the feed hydrocarbon mixture, it must be quite surprising and not obvious result can be assessed that it is possible without any pre-fractionation of the feed product to separate it directly by extractive distillation in the manner claimed according to the invention. So far, experts have always assumed that extractive distillation can only be used to separate those feedstocks that have the narrowest possible boiling range.

Durch die Anwendung der Extraktivdestillation werden die weiter oben beschriebenen Nachteile der Flüssig-­Flüssig-Extraktion vermieden, da einerseits das erfin­dungsgemäß zur Anwendung gelangende Lösungsmittel ohne jeden Wasserzusatz verwendet wird und andererseits - ­wie bei der Extraktivdestillation allgemein üblich - ­verhältnismäßig einfach konstruierte Kolonnen zur An­wendung gelangen können.The use of extractive distillation avoids the disadvantages of liquid-liquid extraction described above, since on the one hand the solvent used according to the invention is used without any addition of water and on the other hand - as is customary in extractive distillation - relatively simple columns can be used .

Bei der Durchführung des erfindungsgemäßen Verfahrens kann mit einem sehr niedrigen Verhältnis von Einsatz­produkt zu Lösungsmittel, das im Bereich von 1 : 2 bis 1 : 3 liegt, gearbeitet werden. Unter den für die Durch­führung des erfindungsgemäßen Verfahrens in Frage kommen­den selektiven Lösungsmitteln hat sich das N-Formyl­morpholin als besonders geeignet erwiesen.When carrying out the process according to the invention, it is possible to work with a very low ratio of starting material to solvent, which is in the range from 1: 2 to 1: 3. Among the selective solvents that can be used to carry out the process according to the invention, N-formylmorpholine has proven to be particularly suitable.

Die Abbildung zeigt ein Fließschema des erfindungsge­mäßen Verfahrens in stark vereinfachter Darstellung. Hierbei wird das zur Verarbeitung gelangende Einsatz­kohlenwasserstoffgemisch ohne jede Vorfraktionierung über die Leitung 1 in den mittleren Teil der mit Ein­bauten (Böden) versehenen Extraktivdestillationsko­lonne 2 eingeleitet. Die Kohlenwasserstoffe des Raffi­nates entweichen dabei über Kopf aus der Extraktiv­destillationskolonne 2 und gelangen über die Leitung 4 in die Kolonne 5, in der die Kohlenwasserstoffe des Raffinates destillativ von den Lösungsmittelresten abgetrennt werden. Letztere gelangen über die Leitung 6 in die Leitung 3, durch die das verwendete Lösungsmit­tel in den Oberteil der Extraktivdestillationskolonne 2 eingeleitet wird. Die vom Lösungsmittel befreiten Kohlen­wasserstoffe des Raffinates werden über die Leitung 7 über Kopf aus der Kolonne 5 abgezogen und ihrer weiteren Verwendung zugeführt. Die Kohlenwasserstoffe des Ex­traktes werden zusammen mit der Hauptmenge der Lösungs­mittel über die Leitung 8 aus dem Sumpf der Extraktiv­destillationskolonne 2 abgezogen und von dort in den mittleren Teil der Abtreiberkolonne 9 eingeleitet, die gegebenenfalls auch mit Einbauten (Böden) versehen sein kann. In dieser Kolonne werden die hauptsächlich aus Aromaten bestehenden Kohlenwasserstoffe des Extraktes aus dem Lösungsmittel abgetrieben, wobei das wiederge­wonnene Lösungsmittel, das sich im Sumpf der Abtreiber­kolonne 9 anreichert, über die Leitung 3 zur Extraktiv­destillationskolonne 2 zurückgeführt wird. Die vom Lösungsmittel befreiten Kohlenwasserstoffe des Extrak­tes werden dagegen über die Leitungen 10 bzw. 11 aus der Abtreiberkolonne 9 abgezogen und ihrer weiteren Verwendung zugeführt.The figure shows a flow diagram of the method according to the invention in a highly simplified representation. Here, the feed hydrocarbon mixture that is processed is processed without any pre-fractionation introduced via line 1 into the central part of the extractive distillation column 2 provided with internals (trays). The hydrocarbons of the raffinate escape overhead from the extractive distillation column 2 and pass via line 4 into column 5, in which the hydrocarbons of the raffinate are separated from the solvent residues by distillation. The latter pass via line 6 into line 3, through which the solvent used is introduced into the upper part of the extractive distillation column 2. The hydrocarbons of the raffinate freed from the solvent are withdrawn via the head 7 from the column 5 and fed to their further use. The hydrocarbons of the extract are withdrawn together with the majority of the solvents via line 8 from the bottom of the extractive distillation column 2 and from there into the middle part of the stripping column 9, which may also be provided with internals (trays). In this column, the hydrocarbons of the extract consisting mainly of aromatics are driven off from the solvent, the recovered solvent, which accumulates in the bottom of the stripping column 9, being returned via line 3 to the extractive distillation column 2. The hydrocarbons of the extract freed from the solvent, on the other hand, are drawn off from the stripping column 9 via the lines 10 and 11 and fed to their further use.

Das in der Abbildung dargestellte Fließschema enthält nur die für die Erläuterung des erfindungsgemäßen Ver­fahrens unbedingt notwendigen Anlagenteile, während alle Nebeneinrichtungen, die nicht unmittelbar im Zu­sammenhang mit der Erfindung stehen, im Fließschema nicht dargestellt wurden. Dies gilt insbesondere für die Wärmeaustauscher zum Wärmeaustausch zwischen den einzelnen Prozeßströmen, die Umlaufkocher zur Beheizung der einzelnen Kolonnen, die Einrichtungen zur Regene­rierung bzw. Ergänzung des verbrauchten Lösungsmittels sowie sämtliche Meß- und Regeleinrichtungen.The flow diagram shown in the figure contains only those parts of the system which are absolutely necessary for the explanation of the method according to the invention, while all auxiliary devices which are not directly related to the invention were not shown in the flow diagram. This applies in particular to the heat exchangers for heat exchange between the individual process streams, the circulation cookers for heating the individual columns, the devices for regenerating or supplementing the used solvent, and all measuring and control devices.

Für die Durchführung des erfindungsgemäßen Verfahrens sind folgende Varianten möglich:

  • 1. Die Betriebsbedingungen in der Extraktivdestilla­tionskolonne 2 werden so eingestellt, daß sich das im Einsatzkohlenwasserstoffgemisch enthal­tene Benzol weitgehend in dem Extrakt anreichert und ein benzolarmes Raffinat anfällt. In der Ab­treiberkolonne 9 wird dann das im Extrakt ent­haltene Benzol von den übrigen Aromaten destilla­tiv abgetrennt und als verkaufsfähiges Reinben­zol mit einem Nichtaromatengehalt von < 1000 ppm als Kopfprodukt über die Leitung 10 abgezogen, während das als Blendingkomponente dienende Aro­matenkonzentrat, welches in diesem Falle praktisch mehr oder weniger benzolfrei ist, als Seitenstrom über die Leitung 11 oder über eine an dieser Stelle angeordnete, im Fließschema nicht dargestellte Seitenkolonne aus der Abtreiberkolonne 9 entfernt wird.
  • 2. In diesem Falle werden die Betriebsbedingungen der Extraktivdestillationskolonne 2 so eingestellt, daß ein Teil des im Einsatzkohlenwasserstoffge­misch enthaltenen Benzols mit ins Raffinat über­geht und im Aromatenkonzentrat des Extraktes nur noch ein Benzolgehalt verbleibt, der einen gewünsch­ten, unter 5 Gew.-% liegenden Maximalwert nicht überschreitet. Bei der Aufarbeitung des Extraktes in der Abtreiberkolonne 9 wird hierbei das an­fallende, als Blendingkomponente dienende Aroma­tenkonzentrat ausschließlich über die Leitung 10 abgezogen, während der Seitenabzug über die Lei­tung 11 außer Betrieb bleibt.
  • 3. Wenn einerseits der Benzolgehalt im Einsatzkohlen­wasserstoffgemisch relativ niedrig ist und anderer­seits die Anreicherung dieses Benzolgehaltes in dem als Blendingkomponente dienenden Aromatenkon­zentrat nicht als störend angesehen wird, kann schließlich die Extraktivdestillationskolonne 2 unter solchen Betriebsbedingungen betrieben wer­den, daß das gesamte Benzol praktisch vollständig in den Extrakt übergeht. In Abweichung von der Verfahrensvariante 1 findet in diesem Falle je­doch in der Abtreiberkolonne 9 keine Abtrennung des Benzols von den übrigen Aromaten statt. Das heißt, in diesem Falle wird das Aromatenkonzentrat in seiner Gesamtheit über die Leitung 10 aus der Abtreiberkolonne 9 abgezogen und der Seitenab­zug über die Leitung 11 bleibt außer Betrieb.
The following variants are possible for carrying out the method according to the invention:
  • 1. The operating conditions in the extractive distillation column 2 are set so that the benzene contained in the feed hydrocarbon mixture largely accumulates in the extract and a low-benzene raffinate is obtained. In the stripping column 9, the benzene contained in the extract is then separated from the other aromatics by distillation and withdrawn as salable pure benzene with a non-aromatic content of <1000 ppm as top product via line 10, while the aromatic concentrate serving as a blending component, which in this case is practically more or less is less benzene-free than side stream is removed from the stripping column 9 via the line 11 or via a side column which is arranged at this point and is not shown in the flow diagram.
  • 2. In this case, the operating conditions of the extractive distillation column 2 are set so that a part of the benzene contained in the hydrocarbon mixture is converted into the raffinate and only a benzene content remains in the aromatic concentrate of the extract which does not have a desired maximum value of less than 5% by weight exceeds. When working up the extract in the stripper column 9, the resulting aromatic concentrate serving as a blending component is drawn off exclusively via line 10, while the side take-off via line 11 remains out of operation.
  • 3. If, on the one hand, the benzene content in the feed hydrocarbon mixture is relatively low and, on the other hand, the enrichment of this benzene content in the aromatic concentrate serving as the blending component is not considered to be disruptive, the extractive distillation column 2 can finally be operated under such operating conditions that all of the benzene is practically completely converted into the extract . Deviating from process variant 1, however, in this case there is no separation of the benzene from the other aromatics in the stripping column 9. That is, in this case the aromatic concentrate is withdrawn in its entirety via line 10 from the stripping column 9 and the side discharge via line 11 remains inoperative.

Die bei der Durchführung des erfindungsgemäßen Verfahrens anfallenden Raffinate können als sogen. Chemiebenzin einer Weiterverarbeitung zugeführt werden. So können diese Raffinate beispielsweise als Ausgangsmaterial für die Äthylenpyrrolyse oder für Isomerisierungsprozesse eingesetzt werden. Die als Blendingkomponente verwen­deten, nach dem erfindungsgemäßen Verfahren gewonnenen Aromatenkonzentrate weisen nur noch einen geringen, zwischen 0,5 bis 5,0 Gew.% betragenden Nichtaromatenge­halt auf.The raffinates obtained when carrying out the process according to the invention can be obtained as so-called. Chemical gasoline for further processing. For example, these raffinates can be used as a starting material for ethylene pyrolysis or for isomerization processes. The aromatic concentrates used as a blending component and obtained by the process according to the invention only have a low non-aromatic content of between 0.5 and 5.0% by weight.

Die Wirksamkeit der erfindungsgemäßen Arbeitsweise wird durch die nachfolgenden Verfahrensbeispiele belegt. In allen drei Verfahrensbeispielen wurde dabei für die Extraktivdestillation N-Formylmorpholin als selekti­ves Lösungsmittel verwendet. Die Extraktivdestillati­onskolonne 2 besaß hierbei jeweils 50 Böden. Das Ein­satzkohlenwasserstoffgemisch wurde in allen drei Fällen mit einer Temperatur von 70°C in die Extraktivdestilla­tionskolonne 2 eingeleitet und die Kopftemperatur die­ser Kolonne lag jeweils bei etwa 100°C.The effectiveness of the procedure according to the invention is demonstrated by the following process examples. In all three process examples, N-formylmorpholine was used as the selective solvent for the extractive distillation. The extractive distillation column 2 each had 50 trays. In all three cases, the feed hydrocarbon mixture was introduced into the extractive distillation column 2 at a temperature of 70 ° C., and the top temperature of this column was in each case approximately 100 ° C.

Im Verfahrensbeispiel 1 wurde als Einsatzkohlenwasser­stoffgemisch ein sogenanntes Reformat aus der Erdölver­arbeitung mit einem Aromatengehalt von 65 Gew.-% und einer Octanzahl (ROZ) von 92 eingesetzt, wobei die Verfahrensvariante 2 zur Anwendung gelangte.In process example 1, a so-called reformate from petroleum processing with an aromatic content of 65% by weight and an octane number (RON) of 92 was used as the input hydrocarbon mixture, process variant 2 being used.

Im Verfahrensbeispiel 2 wurde ein sogenanntes Platfor­mat mit einem Aromatengehalt von 42 Gew.-% und einer Octanzahl (ROZ) von 83 als Ausgangsmaterial eingesetzt, wobei wiederum die Verfahrensvariante 2 zur Anwendung gelangte.In process example 2, a so-called platformat with an aromatic content of 42% by weight and an octane number (RON) of 83 was used as the starting material, process variant 2 again being used.

Im Verfahrensbeispiel 3 wurde schließlich nochmals das gleiche Reformat wie im Verfahrensbeispiel 1 als Aus­gangsmaterial eingesetzt. Die Aufarbeitung dieses Aus­gangsmaterials erfolgte hierbei jedoch nach der Ver­fahrensvariante 1.In process example 3, the same reformate as in process example 1 was finally used as the starting material. However, this starting material was worked up according to process variant 1.

Die wichtigsten Versuchsergebnisse sind in der nach­folgenden Tabelle zusammengefaßt.

Figure imgb0001
The most important test results are summarized in the table below.
Figure imgb0001

Claims (6)

1. Verfahren zur Herstellung eines zur Verwendung als Blen­dingkomponente für Vergaserkraftstoffe geeigneten Aroma­tenkonzentrates aus Einsatzkohlenwasserstoffgemischen mit einem Siedebereich zwischen 40 und 170°C, die neben Nichtaromaten mehrere Aromaten enthalten, dadurch ge­kennzeichnet, daß das Einsatzkohlenwasserstoffgemisch ohne vorherige Auftrennung in einzelne Fraktionen einer Extraktivdestillation unter Verwendung von N-substituier­ten Morpholinen, deren Substituenten nicht mehr als sieben C-Atome aufweisen, als selektivem Lösungsmittel unterwor­fen wird, wobei die niedrig siedenden Nichtaromaten mit ei­nem Siedebereich bis ca. 105°C praktisch vollständig und die höher siedenden Nichtaromaten mit einem Siedebe­reich zwischen ca. 105 und 160°C zum überwiegenden Teil als Raffinat über Kopf aus der Extraktivdestillationsko­lonne abgezogen werden, worauf das Lösungsmittel in einer nachgeschalteten Abtreiberkolonne destillativ von den übrigen Kohlenwasserstoffen des Extraktes abgetrennt wird und diese ganz oder teilweise als Blendingkomponen­te eingesetzt werden.1. A process for producing an aromatic concentrate suitable for use as a blending component for gasoline fuels from hydrocarbon mixtures with a boiling range between 40 and 170 ° C, which contain several aromatics in addition to non-aromatics, characterized in that the hydrocarbon mixture is used without prior separation into individual fractions of an extractive distillation using N-substituted morpholines, the substituents of which have no more than seven carbon atoms, are subjected to a selective solvent, the low-boiling non-aromatics with a boiling range up to approx. 105 ° C being practically complete and the higher-boiling non-aromatics with a boiling range between approx. 105 and 160 ° C. are withdrawn predominantly as raffinate overhead from the extractive distillation column, whereupon the solvent is removed by distillation from the remaining hydrocarbons of the extract in a downstream stripping column is running and these are used in whole or in part as a blending component. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als selektives Lösungsmittel N-Formylmorpholin verwendet wird.2. The method according to claim 1, characterized in that N-formylmorpholine is used as the selective solvent. 3. Verfahren nach den Ansprüchen 1 und 2, dadurch gekenn­zeichnet, daß die Extraktivdestillation mit einem Verhält­nis von Einsatzprodukt zu Lösungsmittel von 1 : 2 bis 1 : 3 durchgeführt wird.3. Process according to claims 1 and 2, characterized in that the extractive distillation is carried out with a ratio of starting material to solvent of 1: 2 to 1: 3. 4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekenn­zeichnet, daß die erzeugten Aromatenkonzentrate Nichtaro­matengehalte von 0,5 bis 5,0 Gew.-% aufweisen.4. Process according to claims 1 to 3, characterized in that the aromatic concentrates produced have non-aromatic contents of 0.5 to 5.0% by weight. 5. Verfahren nach den Ansprüchen 1 bis 4, dadurch gekenn­zeichnet, daß aus der Abtreiberkolonne als Kopfprodukt Reinbenzol mit einem Nichtaromatengehalt von<1000 ppm abgezogen wird, während die als Bleindingkompoente die­nenden Kohlenwasserstoffe als Seitenstrom oder über eine Seitenkolonne aus dem mittleren Teil der Abtreiberkolonne abgezogen werden.5. Process according to claims 1 to 4, characterized in that pure benzene with a non-aromatic content of <1000 ppm is withdrawn from the stripping column as the top product, while the hydrocarbons serving as bleinding components are withdrawn as a side stream or via a side column from the central part of the stripping column . 6. Verfahren nach den Ansprüchen 1 bis 5, dadurch gekenn­zeichnet, daß die Betriebsbedingungen in der Extraktiv­destillationskolonne so eingestellt werden, daß ein Teil des im Einsatzkohlenwasserstoffgemisch enthaltenen Ben­zols zusammen mit den Nichtaromaten als Raffinat über Kopf aus der Extraktivdestillationskolonne abdestilliert wird, und daß der im Extrakt verbleibende Benzolanteil einen gewünschten, unter 5 Gew.-% liegenden Maximalwert nicht überschreitet.6. Process according to claims 1 to 5, characterized in that the operating conditions in the extractive distillation column are set so that part of the benzene contained in the hydrocarbon mixture used is distilled off together with the non-aromatics as raffinate overhead from the extractive distillation column, and that in the extract remaining benzene content does not exceed a desired maximum value below 5% by weight.
EP87100581A 1986-04-12 1987-01-17 Process for the preparation of an aromatic concentrate useful as a blending component for carburettor fuels Expired - Lifetime EP0241638B1 (en)

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DE3612384 1986-04-12
DE19863612384 DE3612384A1 (en) 1986-04-12 1986-04-12 METHOD FOR PRODUCING AN AROMAT CONCENTRATE SUITABLE FOR USE AS A BLENDING COMPONENT FOR CARBURETTOR FUELS
DE19873726449 DE3726449A1 (en) 1986-04-12 1987-08-08 METHOD FOR PRODUCING AN AROMAT CONCENTRATE SUITABLE FOR USE AS A BLENDING COMPONENT FOR CARBURETTOR FUELS

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0329958A2 (en) * 1988-02-20 1989-08-30 Krupp Koppers GmbH Process for the preparation of an aromatic concentrate useful as a blending component for carburetion fuels

Families Citing this family (8)

* Cited by examiner, † Cited by third party
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DE3612384A1 (en) * 1986-04-12 1987-10-15 Krupp Koppers Gmbh METHOD FOR PRODUCING AN AROMAT CONCENTRATE SUITABLE FOR USE AS A BLENDING COMPONENT FOR CARBURETTOR FUELS
DE3942950A1 (en) * 1989-12-23 1991-06-27 Krupp Koppers Gmbh METHOD FOR THE SIMULTANEOUS PRODUCTION OF PURE BENZOL AND PURE TULUOL
DE4109632A1 (en) * 1991-03-23 1992-09-24 Krupp Koppers Gmbh METHOD FOR SEPARATING AROMATES BY EXTRACTIVE DISTILLATION
CN101808704B (en) * 2007-09-28 2012-11-28 巴斯夫欧洲公司 Method for obtaining aromatic hydrocarbons from a hydrocarbon mixture
CN101808962B (en) * 2007-09-28 2012-11-28 巴斯夫欧洲公司 Method for obtaining aromatic hydrocarbons from a hydrocarbon mixture
DE102011001587B4 (en) * 2010-08-05 2016-12-29 Flagsol Gmbh Process for treating a heat transfer medium of a solar thermal power plant
DE102014005337A1 (en) 2014-04-11 2015-10-15 Friedrich-Alexander-Universität Erlangen-Nürnberg Tonoplastoid proton / sugar antiporter proteins and their use to increase the sucrose concentration of a sucrose storage organ of plants
US20230183733A1 (en) 2020-05-20 2023-06-15 KWS SAAT SE & Co. KGaA Multiple virus resistance

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1568940C3 (en) * 1966-12-19 1978-12-07 Krupp-Koppers Gmbh, 4300 Essen Process for the separation of aromatics from hydrocarbon mixtures of any aromatic content
EP0154677A2 (en) * 1984-03-13 1985-09-18 Krupp Koppers GmbH Process for the separation of aromatics from hydrocarbon mixtures with any concentration of aromatics
EP0155992A2 (en) * 1984-03-14 1985-10-02 Krupp Koppers GmbH Process for the separation of aromatics from hydrocarbon mixtures with any concentration of aromatics

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2842484A (en) * 1954-12-30 1958-07-08 Union Oil Co Separation of hydrocarbons
US3216929A (en) * 1961-10-27 1965-11-09 Phillips Petroleum Co Method of making inherently stable jet fuels
IT1043581B (en) * 1974-12-17 1980-02-29 Krupp Koppers Gmbh PROCESS FOR THE OPERATION OF EXTRACTION AND EXTRACTION AND EXTRACTION DISTILLATION PLANTS
DE2916175A1 (en) * 1979-04-21 1980-10-23 Krupp Koppers Gmbh METHOD FOR CONTROLLING THE AMOUNT OF HEAT SUPPLIED TO AN EXTRACTIVE DISTILLATION COLUMN
DE3032780A1 (en) * 1980-08-30 1982-04-15 Krupp-Koppers Gmbh, 4300 Essen METHOD FOR PROCESSING THE SWAMP PRODUCT OF EXTRACTIVE DISTILLATION PROCESSES FOR THE PURIFICATION OF PURE HYDROCARBONS
DE3135319A1 (en) * 1981-09-05 1983-03-24 Krupp-Koppers Gmbh, 4300 Essen "METHOD FOR OBTAINING PURE AROMATES"
DE3612384A1 (en) * 1986-04-12 1987-10-15 Krupp Koppers Gmbh METHOD FOR PRODUCING AN AROMAT CONCENTRATE SUITABLE FOR USE AS A BLENDING COMPONENT FOR CARBURETTOR FUELS

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1568940C3 (en) * 1966-12-19 1978-12-07 Krupp-Koppers Gmbh, 4300 Essen Process for the separation of aromatics from hydrocarbon mixtures of any aromatic content
EP0154677A2 (en) * 1984-03-13 1985-09-18 Krupp Koppers GmbH Process for the separation of aromatics from hydrocarbon mixtures with any concentration of aromatics
EP0155992A2 (en) * 1984-03-14 1985-10-02 Krupp Koppers GmbH Process for the separation of aromatics from hydrocarbon mixtures with any concentration of aromatics

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0329958A2 (en) * 1988-02-20 1989-08-30 Krupp Koppers GmbH Process for the preparation of an aromatic concentrate useful as a blending component for carburetion fuels
EP0329958A3 (en) * 1988-02-20 1990-02-14 Krupp Koppers Gmbh Process for the preparation of an aromatic concentrate useful as a blending component for carburetion fuels

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