EP0305668B1 - Process for the production of a concentrate of aromatics suitable for use as a blending component for petrol - Google Patents
Process for the production of a concentrate of aromatics suitable for use as a blending component for petrol Download PDFInfo
- Publication number
- EP0305668B1 EP0305668B1 EP88110072A EP88110072A EP0305668B1 EP 0305668 B1 EP0305668 B1 EP 0305668B1 EP 88110072 A EP88110072 A EP 88110072A EP 88110072 A EP88110072 A EP 88110072A EP 0305668 B1 EP0305668 B1 EP 0305668B1
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- European Patent Office
- Prior art keywords
- distillation
- aromatics
- boiling
- extractive distillation
- blending component
- 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
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- 238000000034 method Methods 0.000 title claims description 22
- 239000012141 concentrate Substances 0.000 title claims description 15
- 238000002156 mixing Methods 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000004821 distillation Methods 0.000 claims description 37
- 238000009835 boiling Methods 0.000 claims description 26
- 238000000895 extractive distillation Methods 0.000 claims description 25
- 229930195733 hydrocarbon Natural products 0.000 claims description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- 239000000470 constituent Substances 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- -1 N-substituted morpholines Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 35
- 239000000047 product Substances 0.000 description 13
- 125000003118 aryl group Chemical group 0.000 description 12
- 238000010586 diagram Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940078552 o-xylene Drugs 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical group CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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, the hydrocarbon mixture being subjected to an extractive distillation using N-substituted morpholines and their substituents have no more than seven carbon atoms, is subjected as a selective solvent, and the low-boiling non-aromatics with a boiling range up to approx. 105 ° C are practically complete and the higher-boiling non-aromatics with a boiling range between approx.
- 105 and 160 ° C predominantly Part are distilled off as raffinate overhead from the extractive distillation column, while the majority of the aromatics and the remaining non-aromatics together with the solvent used as an extract from the bottom of the extractive distillation column e are withdrawn, whereupon the solvent is separated by distillation from the other hydrocarbons of the extract in a downstream stripping column and these are used in whole or in part as a blending component.
- a method of the generic type is described in DE-OS 36 12 384, which does not belong to the prior art. It is envisaged that the hydrocarbon used mixture is introduced into the extractive distillation column without prior separation into individual fractions. Particularly suitable feed hydrocarbon mixtures are reformates and platforms from petroleum processing with a not too high benzene content. Mixtures of such reformates and platforms with pyrolysis gasolines can also be used.
- the boiling point of these feedstocks is normally 170 ° C. In practice, however, it has been shown that this boiling point is not observed in many cases, since condensation and polymerization products with a boiling point higher than 170 ° C. occur in the upstream production processes, and the reformates and platformates accordingly contaminate. Since these higher-boiling condensation and polymerization products are present in the reformates and platforms in concentrations of up to about 30% by weight, they can lead to impairments when the process described in DE-OS 36 12 384 is carried out.
- the invention is therefore based on the object of improving the older method in such a way that the difficulties described above are avoided.
- This object is achieved according to the invention in that when working up feed hydrocarbon mixtures which contain constituents boiling above 170 ° C., the feed hydrocarbon mixture is subjected to a pre-distillation in which constituents boiling up to 169 ° C. (under normal conditions) are separated off by distillation and fed to the extractive distillation, while the distillation residue is added to the aromatic concentrate serving as the blending component.
- the process according to the invention therefore provides for a pre-distillation of the hydrocarbon feed mixture in such a way that the top product obtained contains only those constituents, which do not lead to permanent contamination of the solvent in the subsequent extractive distillation.
- higher-boiling constituents which would not be difficult or difficult to remove from the solvent remain in the distillation residue (bottom product) from the pre-distillation, which according to the invention is added to the aromatic concentrate serving as the blending component.
- the starting point here was the knowledge that the composition of the reformates and platforms normally used as starting material is generally such that non-aromatic compounds are not present in the fraction boiling above 170 ° C. or only in very small amounts.
- a typical reformate from petroleum processing has a proportion of about 3% by weight of higher-boiling constituents with a boiling point> 170 ° C., which remains in the distillation residue in the process according to the invention and is added to the aromatic concentrate serving as a blending component.
- the composition of this higher-boiling fraction is as follows:
- the pre-distillation can be carried out with a relatively low investment and operating costs (low number of trays and low reflux ratio), since a sharp quantitative separation is not necessary in this case.
- the operating conditions in the pre-distillation can even be set so that some of the o-xylene (bp 144 ° C) is also present in the distillation residue
- the pre-distillation remains because even in this boiling range there are normally only so few non-aromatics in the feed hydrocarbon mixture that they do not have a disturbing effect when added to the aromatic concentrate serving as a blending component.
- the non-aromatic content in the distillation residue of the pre-distillation is reduced anyway by the fact that azeotropes between aromatics and non-aromatics predominantly go into the top product of the pre-distillation and are therefore subjected to the subsequent extractive distillation process.
- the n-nonane forms an azeotrope with the o-xylene.
- a particularly economical embodiment of the method according to the invention is given when the pre-distillation is carried out under increased pressure.
- the pressure can be set so that the pre-distillation can be operated at a higher temperature than the extractive distillation, so that the overhead product vapors obtained in the pre-distillation can be used for column heating in the extractive distillation and the condensate obtained is introduced into the extractive distillation.
- the pre-distillation process uses a pressure of up to 15 bar.
- the figure shows the flow diagram of an embodiment of the method according to the invention in a highly simplified representation.
- the feed hydrocarbon mixture to be processed is first introduced via line 1 into column 2, in which the predistillation of the feed hydrocarbon mixture according to the invention is carried out is taken.
- the top product obtained there is introduced via line 3 into the central part of the extractive distillation column 4 provided with internals and / or packing elements.
- the hydrocarbons of the raffinate escape overhead from the extractive distillation column and pass via line 5 into column 6, in which the hydrocarbons of the raffinate are separated from the solvent residues by distillation.
- the latter pass via line 7 into line 8, through which the solvent used is introduced into the upper part of the extractive distillation column 4.
- the hydrocarbons of the raffinate freed from the solvent are withdrawn via the head 9 from the column 6 and fed to their further use.
- the hydrocarbons of the extract are withdrawn together with the main amount of the solvent via line 10 from the bottom of the extractive distillation column 4 and from there into the middle part of the stripping column 11, which is also provided with internals and / or packing elements.
- the hydrocarbons of the extract which consist mainly of aromatics, are driven off from the solvent, the recovered solvent, which accumulates in the bottom of the stripping column 11, being returned via line 8 to the extractive distillation column 4.
- the hydrocarbons of the extract freed from the solvent are withdrawn from the stripping column 11 via line 12 or 13 and fed to their further use.
- 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.
- the benzene contained in the extract is then separated from the other aromatics by distillation and withdrawn as salable pure benzene with a non-aromatics content of ⁇ 1000 ppm as overhead product via line 12, while in this case a practically more or less benzene-free aromatics concentrate as a side stream the line 13 or via a side column arranged at this point and not shown in the flow diagram is removed from the stripping column 11.
- the distillation residue from the pre-distillation is then added to this aromatic concentrate. This is withdrawn via line 14 from the bottom of column 2 and mixed with the product stream flowing in line 13 so that the end product stream serving as blending component can be withdrawn via line 13.
- the flow diagram shown in the figure contains only the parts of the system that 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 circulating cookers for heating the individual columns, the devices for regenerating or supplementing the used solvent, and all measuring and control devices.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
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, wobei das Einsatzkohlenwasserstoffgemisch einer Extraktivdestillation unter Verwendung von N-substituierten Morpholinen, deren Substituenten nicht mehr als sieben C-Atome aufweisen, als selektivem Lösungsmittel unterworfen wird, und 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 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, the hydrocarbon mixture being subjected to an extractive distillation using N-substituted morpholines and their substituents have no more than seven carbon atoms, is subjected as a selective solvent, and the low-boiling non-aromatics with a boiling range up to approx. 105 ° C are practically complete and the higher-boiling non-aromatics with a boiling range between approx. 105 and 160 ° C predominantly Part are distilled off as raffinate overhead from the extractive distillation column, while the majority of the aromatics and the remaining non-aromatics together with the solvent used as an extract from the bottom of the extractive distillation column e are withdrawn, whereupon the solvent is separated by distillation from the other hydrocarbons of the extract in a downstream stripping column and these are used in whole or in part as a blending component.
Ein Verfahren der gattungsgemäßen Art wird in der nicht zum Stand der Technik gehörenden DE-OS 36 12 384 beschrieben. Hierbei ist vorgesehen, daß das Einsatzkohlenwasserstoff gemisch ohne vorherige Auftrennung in einzelne Fraktionen in die Extraktivdestillationskolonne eingeleitet wird. Besonders geeignete Einsatzkohlenwasserstoffgemische sind dabei Reformate und Platformate aus der Erdölverarbeitung mit nicht zu hohem Benzolgehalt. Es können aber auch Gemische solcher Reformate und Platformate mit Pyrolysebenzinen eingesetzt werden.A method of the generic type is described in DE-OS 36 12 384, which does not belong to the prior art. It is envisaged that the hydrocarbon used mixture is introduced into the extractive distillation column without prior separation into individual fractions. Particularly suitable feed hydrocarbon mixtures are reformates and platforms from petroleum processing with a not too high benzene content. Mixtures of such reformates and platforms with pyrolysis gasolines can also be used.
Zwar liegt bei diesen Einsatzprodukten das Siedeende normalerweise bei 170°C. In der Praxis hat sich jedoch gezeigt, daß dieses Siedeende in vielen Fällen nicht eingehalten wird, da es in den vorgeschalteten Produktionsprozessen zur Bildung von Kondensations- und Polymerisationsprodukten kommt, die einen höheren Siedepunkt als 170°C aufweisen, und die die Reformate und Platformate entsprechend verunreinigen. Da diese höher siedenden Kondensations- und Polymerisationsprodukte in den Reformaten und Platformaten in Konzentrationen bis zu ca. 30 Gew.-% vorliegen, können sie bei der Durchführung des in der DE-OS 36 12 384 beschriebenen Verfahrens zu Beeinträchtigungen führen.The boiling point of these feedstocks is normally 170 ° C. In practice, however, it has been shown that this boiling point is not observed in many cases, since condensation and polymerization products with a boiling point higher than 170 ° C. occur in the upstream production processes, and the reformates and platformates accordingly contaminate. Since these higher-boiling condensation and polymerization products are present in the reformates and platforms in concentrations of up to about 30% by weight, they can lead to impairments when the process described in DE-OS 36 12 384 is carried out.
In der Praxis hat sich nämlich gezeigt, daß sich diese Kondensations- und Polymerisationsprodukte im selektiven Lösungsmittel anreichern, da sie von diesem destillativ praktisch nicht oder nur unvollständig abgetrennt werden können. Dies führt mit fortschreitender Betriebszeit zu einer immer starkeren Verunreinigung des im Kreislauf geführten Lösungsmittels, so daß dessen Selektivität ständig verringert und der Trenneffekt in der Extraktivdestillation entsprechend herabgesetzt wird.In practice, it has been shown that these condensation and polymerization products accumulate in the selective solvent, since they can practically not or only partially be separated from this by distillation. As the operating time progresses, this leads to an increasingly severe contamination of the circulating solvent, so that its selectivity is constantly reduced and the separation effect in the extractive distillation is correspondingly reduced.
Versuche, diese Kondensations- und Polymerisationsprodukte durch Destillation vom Lösungsmittel abzutrennen, haben _ wie bereits erwähnt wurde _ auch bei Anwendung eines hohen Destillationsaufwandes zu keinem befriedigenden Ergebnis geführt. Es hat sich nämlich gezeigt, daß ein Teil dieser Kondensations- und Polymerisationsprodukte in ihrem Siedebereich dem des Lösungsmittels entsprechen, so daß eine destillative Trennung praktisch unmöglich ist. Dieses Problem konnte deshalb bisher nur in der Weise gelöst werden, daß nach einer gewissen Betriebszeit ein vollständiger Austausch des verunreinigten Lösungsmittels vorgenommen wurde. Es liegt auf der Hand, daß dieses Verfahren äußerst kostspielig und damit unwirtschaftlich ist. Außerdem verursacht die Vernichtung des verunreinigten Lösungsmittels zusätzliche Kosten, da dieses keiner anderweitigen Verwendung bzw. Verwertung mehr zugeführt werden kann.Attempts to separate these condensation and polymerization products from the solvent by distillation have _ As already mentioned, a satisfactory result was not achieved even when using a high distillation effort. It has been shown that part of these condensation and polymerization products correspond in their boiling range to that of the solvent, so that separation by distillation is practically impossible. So far, this problem could only be solved in such a way that the contaminated solvent was completely replaced after a certain operating time. It is obvious that this process is extremely expensive and therefore uneconomical. In addition, the destruction of the contaminated solvent causes additional costs, since it cannot be used for any other purpose.
Der Erfindung liegt deshalb die Aufgabe zugrunde, das ältere Verfahren dahingehend zu verbessern, daß die vorstehend geschilderten Schwierigkeiten vermieden werden.The invention is therefore based on the object of improving the older method in such a way that the difficulties described above are avoided.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß bei der Aufarbeitung von Einsatzkohlenwasserstoffgemischen, welche oberhalb 170°C siedende Bestandteile enthalten, das Einsatzkohlenwasserstoffgemisch einer Vordestillation unterworfen wird, bei der bis 169°C (unter Normalbedingungen) siedenden Bestandteile destillativ abgetrennt und der Extraktivdestillation zugeführt werden, während der Destillationsrückstand dem als Blendingkomponente dienenden Aromatenkonzentrat zugesetzt wird.This object is achieved according to the invention in that when working up feed hydrocarbon mixtures which contain constituents boiling above 170 ° C., the feed hydrocarbon mixture is subjected to a pre-distillation in which constituents boiling up to 169 ° C. (under normal conditions) are separated off by distillation and fed to the extractive distillation, while the distillation residue is added to the aromatic concentrate serving as the blending component.
Das erfindungsgemäße Verfahren sieht also eine Vordestillation des Einsatzkohlenwasserstoffgemisches in der Weise vor, daß das anfallende Kopfprodukt nur solche Bestandteile enthält, die bei der nachfolgenden Extraktivdestillation zu keiner permanten Verunreinigung des Lösungsmittels führen. Höher siedende Bestandteile, die sich vom Lösungsmittel nicht oder nur sehr schwer abtrennen lassen würden, verbleiben demgegenüber im Destillationsrückstand (Sumpfprodukt) der Vordestillation, der erfindungsgemäß dem als Blendingkomponente dienenden Aromatenkonzentrat zugesetzt wird. Hierbei wurde von der Erkenntnis ausgegangen, daß die Zusammensetzung der normalerweise als Einsatzprodukt dienenden Reformate und Platformate in der Regel so ist, daß nichtaromatische Verbindungen in der oberhalb 170°C siedenden Fraktion nicht oder nur noch in ganz geringen Mengen vorhanden sind. So weist beispielsweise ein typisches Reformat aus der Erdölverarbeitung einen Anteil von etwa 3 Gew.-% an höher siedenden Bestandteilen mit einem Siedepunkt > 170°C auf, der beim erfindungsgemäßen Verfahren im Destillationsrückstand verbleibt und dem als Blendingkomponente dienenden Aromatenkonzentrat zugesetzt wird. Die Zusammensetzung dieser höher siedenden Fraktion ist hierbei wie folgt:
Die vorstehenden Prozentangaben beziehen sich dabei nicht auf die Gesamtmenge des Reformates, sondern auf die Zusammensetzung der oberhalb 170°C siedenden Fraktion.The above percentages do not refer to the total amount of the reformate, but to the composition of the fraction boiling above 170 ° C.
Bei der Durchführung des erfindungsgemäßen Verfahrens kann die Vordestillation mit einem verhältnismäßig geringen Investitions- und Betriebskostenaufwand (geringe Bodenzahl und geringes Rückflußverhältnis) betrieben werden, da eine scharfe quantitative Trennung in diesem Falle nicht erforderlich ist. So können beispielsweise die Betriebsbedingungen in der Vordestillation sogar so eingestellt werden, daß auch ein Teil des o-Xylols (Kp 144°C) im Destillationsrückstand der Vordestillation verbleibt, weil auch in diesem Siedebereich im Einsatzkohlenwasserstoffgemisch normalerweise nur so wenig Nichtaromaten vorhanden sind, daß sich diese beim Zusatz zu dem als Blendingkomponente dienenden Aromatenkonzentrat nicht störend bemerkbar machen. Außerdem ist hierbei zu berücksichtigen, daß der Nichtaromatenanteil im Destillationsrückstand der Vordestillation ohnehin dadurch vermindert wird, daß sich Azeotrope zwischen Aromaten und Nichtaromaten vorwiegend in das Kopfprodukt der Vordestillation gehen und damit dem nachfolgenden Extraktivdestillationsprozeß unterworfen werden. So bildet beispielsweise das n-Nonan ein Azeotrop mit dem o-Xylol.When carrying out the method according to the invention, the pre-distillation can be carried out with a relatively low investment and operating costs (low number of trays and low reflux ratio), since a sharp quantitative separation is not necessary in this case. For example, the operating conditions in the pre-distillation can even be set so that some of the o-xylene (bp 144 ° C) is also present in the distillation residue The pre-distillation remains because even in this boiling range there are normally only so few non-aromatics in the feed hydrocarbon mixture that they do not have a disturbing effect when added to the aromatic concentrate serving as a blending component. It must also be taken into account here that the non-aromatic content in the distillation residue of the pre-distillation is reduced anyway by the fact that azeotropes between aromatics and non-aromatics predominantly go into the top product of the pre-distillation and are therefore subjected to the subsequent extractive distillation process. For example, the n-nonane forms an azeotrope with the o-xylene.
Eine besonders wirtschaftliche Ausführungsform des erfindungsgemäßen Verfahrens ist dann gegeben, wenn die Vordestillation unter erhöhtem Druck betrieben wird. Hierbei kann der Druck jeweils so eingestellt werden, daß die Vordestillation bei höherer Temperatur betrieben werden kann als die Extraktivdestillation, so daß die in der Vordestillation anfallenden Kopfproduktdämpfe zur Kolonnenbeheizung in der Extraktivdestillation genutzt werden können und das dabei anfallende Kondensat in die Extraktivdestillation eingeleitet wird. Hierbei wird in der Vordestillation mit einem Druck bis zu 15 bar gearbeitet.A particularly economical embodiment of the method according to the invention is given when the pre-distillation is carried out under increased pressure. Here, the pressure can be set so that the pre-distillation can be operated at a higher temperature than the extractive distillation, so that the overhead product vapors obtained in the pre-distillation can be used for column heating in the extractive distillation and the condensate obtained is introduced into the extractive distillation. The pre-distillation process uses a pressure of up to 15 bar.
Die Abbildung zeigt das Fließschema einer Ausführungsform des erfindungsgemähen Verfahrens in stark vereinfachter Darstellung. Hierbei wird das zur Verarbeitung gelangende Einsatzkohlenwasserstoffgemisch zunächst über die Leitung 1 in die Kolonne 2 eingeleitet, in der die erfindungsgemäße Vordestillation des Einsatzkohlenwasserstoffgemisches vor genommen wird. Das dort anfallende Kopfprodukt wird über die Leitung 3 in den mittleren Teil der mit Einbauten und/oder Füllkörpern versehenen Extraktivdestillationskolonne 4 eingeleitet. Die Kohlenwasserstoffe des Raffinates entweichen dabei über Kopf aus der Extraktivdestillationskolonne und gelangen über die Leitung 5 in die Kolonne 6, in der die Kohlenwasserstoffe des Raffinates destillativ von den Lösungsmittelresten abgetrennt werden. Letztere gelangen über die Leitung 7 in die Leitung 8, durch die das verwendete Lösungsmittel in den Oberteil der Extraktivdestillationskolonne 4 eingeleitet wird. Die vom Lösungsmittel befreiten Kohlenwasserstoffe des Raffinates werden über die Leitung 9 über Kopf aus der Kolonne 6 abgezogen und ihrer weiteren Verwendung zugeführt. Die Kohlenwasserstoffe des Extraktes werden zusammen mit der Hauptmenge des Lösungsmittels über die Leitung 10 aus dem Sumpf der Extraktivdestillationskolonne 4 abgezogen und von dort in den mittleren Teil der Abtreiberkolonne 11 eingeleitet, die ebenfalls mit Einbauten und/oder Füllkörpern versehen ist. 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 11 anreichert, über die Leitung 8 zur Extraktivdestillationskolonne 4 zurückgeführt wird. Die vom Lösungsmittel befreiten Kohlenwasserstoffe des Extraktes werden dagegen über die Leitung 12 bzw. 13 aus der Abtreiberkolonne 11 abgezogen und ihrer weiteren Verwendung zugeführt.The figure shows the flow diagram of an embodiment of the method according to the invention in a highly simplified representation. Here, the feed hydrocarbon mixture to be processed is first introduced via line 1 into column 2, in which the predistillation of the feed hydrocarbon mixture according to the invention is carried out is taken. The top product obtained there is introduced via line 3 into the central part of the extractive distillation column 4 provided with internals and / or packing elements. The hydrocarbons of the raffinate escape overhead from the extractive distillation column and pass via line 5 into column 6, in which the hydrocarbons of the raffinate are separated from the solvent residues by distillation. The latter pass via line 7 into line 8, through which the solvent used is introduced into the upper part of the extractive distillation column 4. The hydrocarbons of the raffinate freed from the solvent are withdrawn via the head 9 from the column 6 and fed to their further use. The hydrocarbons of the extract are withdrawn together with the main amount of the solvent via
Im vorliegenden Falle wird davon ausgegangen, daß die Betriebsbedingungen in der Extraktivdestillationskolonne 2 so eingestellt werden, daß sich das im Einsatzkohlenwasserstoffgemisch enthaltene Benzol weitgehend in dem Extrakt anreichert und ein benzolarmes Raffinat anfällt. In der Abtreiberkolonne 11 wird dann das im Extrakt enthaltene Benzol von den übrigen Aromaten destillativ abgetrennt und als verkaufsfahiges Reinbenzol mit einem Nichtaromatengehalt von < 1000 ppm als Kopfprodukt über die Leitung 12 abgezogen, während ein in diesem Falle praktisch mehr oder weniger benzolfreies Aromatenkonzentrat als Seitenstrom über die Leitung 13 oder über eine an dieser Stelle angeordnete, im Fließschema nicht dargestellte Seitenkolonne aus der Abtreiberkolonne 11 entfernt wird. Diesem Aromatenkonzentrat wird dann erfindungsgemäß der Destillationsrückstand der Vordestillation zugesetzt. Dieser wird über die Leitung 14 aus dem Sumpf der Kolonne 2 abgezogen und dem in der Leitung 13 fließenden Produktstrom zugemischt, so daß über die Leitung 13 der als Blendingkomponente dienende Endproduktstrom abgezogen werden kann.In the present case, it is assumed that 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 11, the benzene contained in the extract is then separated from the other aromatics by distillation and withdrawn as salable pure benzene with a non-aromatics content of <1000 ppm as overhead product via line 12, while in this case a practically more or less benzene-free aromatics concentrate as a side stream the line 13 or via a side column arranged at this point and not shown in the flow diagram is removed from the stripping column 11. According to the invention, the distillation residue from the pre-distillation is then added to this aromatic concentrate. This is withdrawn via line 14 from the bottom of column 2 and mixed with the product stream flowing in line 13 so that the end product stream serving as blending component can be withdrawn via line 13.
Für die Durchführung des Verfahrens bestehen außerdem noch folgende Möglichkeiten:
- a) In diesem Falle werden die Betriebsbedingungen der Extraktivdestillationskolonne 4 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, normalerweise unter 5 Gew.-% liegenden Maximalwert nicht überschreitet. Bei der Aufarbeitung des Extraktes in der Abtreiberkolonne 11 wird hierbei das anfallende, als Blendingkomponente dienende Aromatenkonzentrat ausschließlich über die Leitung 12 abgezogen, während der Seitenabzug über die Leitung 13 außer Betrieb bleibt.
- b) 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 vollstandig in den Extrakt übergeht. In Abweichung von der zuerst beschriebenen Verfahrensvariante findet in diesem Falle jedoch in der Abtreiberkolonne 11 keine Abtrennung des Benzols von den übrigen Aromaten statt. Das heißt, in diesem Falle wird das Aromatenkonzentrat in seiner Gesamtheit über die Leitung 12 aus der Abtreiberkolonne 11 abgezogen und der Seitenabzug über die Leitung 13 bleibt hier ebenfalls außer Betrieb.
- a) In this case, the operating conditions of the extractive distillation column 4 are set so that a portion of the benzene contained in the feed hydrocarbon mixture passes into the raffinate and only a benzene content remains in the aromatic concentrate of the extract, which has a desired maximum value, which is normally below 5% by weight does not exceed. When processing the extract in In the stripping column 11, the resulting aromatic concentrate serving as a blending component is drawn off exclusively via line 12, while the side take-off via line 13 remains out of operation.
- b) 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 a nuisance, the extractive distillation column 2 can finally be operated under operating conditions such that all of the benzene is practically completely converted into the extract . In a departure from the process variant described first, in this case there is no separation of the benzene from the other aromatics in the stripping column 11. This means that in this case the aromatic concentrate is withdrawn in its entirety via line 12 from the stripping column 11 and the side discharge via line 13 also remains inoperative here.
Es versteht sich von selbst, daß in diesen beiden Fällen in Abweichung von der Darstellung im Fließschema der Zusatz des Destillationsrückstandes aus der Vordestillation zu dem über die Leitung 12 abgezogenen Aromatenkonzentrat erfolgt.It goes without saying that in these two cases, in deviation from the representation in the flow diagram, the distillation residue from the pre-distillation is added to the aromatic concentrate withdrawn via line 12.
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 the parts of the system that 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 circulating cookers for heating the individual columns, the devices for regenerating or supplementing the used solvent, and all measuring and control devices.
Die Wirksamkeit der erfindungsgemäßen Arbeitsweise wird durch das nachfolgende Verfahrensbeispiel belegt. Dieses bezieht sich dabei auf die Ausführungsform des erfindungsgemäßen Verfahrens, die dem in der Abbildung dargestellten Fließschema zugrundeliegt. Die wichtigsten Zahlenwerte sind in der nachfolgenden Tabelle zusammengefaßt. Als Einsatzprodukt wurde ein Reformat aus der Erdölverarbeitung mit einem Benzolgehalt von 4,3 Gew.-% verwendet.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT88110072T ATE64609T1 (en) | 1987-08-08 | 1988-06-24 | PROCESS FOR THE MANUFACTURE OF AN AROMATIC CONCENTRATE FOR USE AS A BLEND COMPONENT FOR CARBURETTOR FUELS. |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
| DE3726449 | 1987-08-08 | ||
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0305668A1 EP0305668A1 (en) | 1989-03-08 |
| EP0305668B1 true EP0305668B1 (en) | 1991-06-19 |
Family
ID=39361287
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87100581A Expired - Lifetime EP0241638B1 (en) | 1986-04-12 | 1987-01-17 | Process for the preparation of an aromatic concentrate useful as a blending component for carburettor fuels |
| EP88110072A Expired - Lifetime EP0305668B1 (en) | 1986-04-12 | 1988-06-24 | Process for the production of a concentrate of aromatics suitable for use as a blending component for petrol |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87100581A Expired - Lifetime EP0241638B1 (en) | 1986-04-12 | 1987-01-17 | Process for the preparation of an aromatic concentrate useful as a blending component for carburettor fuels |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4925535A (en) |
| EP (2) | EP0241638B1 (en) |
| JP (2) | JP2550060B2 (en) |
| AU (2) | AU589508B2 (en) |
| DE (2) | DE3612384A1 (en) |
| DK (2) | DK167362B1 (en) |
| ES (2) | ES2020200B3 (en) |
| FI (2) | FI85872C (en) |
| GR (2) | GR3001286T3 (en) |
| NO (2) | NO169595C (en) |
| SG (2) | SG20992G (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| DE3805383A1 (en) * | 1988-02-20 | 1989-08-31 | 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 |
| EP2195281A1 (en) * | 2007-09-28 | 2010-06-16 | Basf Se | Method for obtaining aromatic hydrocarbons from a hydrocarbon mixture |
| CN101808704B (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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1568940A1 (en) * | 1966-12-19 | 1970-07-16 | Koppers Gmbh Heinrich | Process for the separation of aromatics from hydrocarbon mixtures of any aromatic content |
Family Cites Families (9)
| 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" |
| DE3409030A1 (en) * | 1984-03-13 | 1985-09-19 | Krupp Koppers GmbH, 4300 Essen | METHOD FOR SEPARATING AROMATES FROM HYDROCARBON MIXTURES OF ANY AROMATE CONTENT |
| DE3409307A1 (en) * | 1984-03-14 | 1985-09-19 | Krupp Koppers GmbH, 4300 Essen | METHOD FOR SEPARATING AROMATES FROM HYDROCARBON MIXTURES OF ANY AROMATE CONTENT |
| 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 |
-
1986
- 1986-04-12 DE DE19863612384 patent/DE3612384A1/en not_active Withdrawn
-
1987
- 1987-01-17 EP EP87100581A patent/EP0241638B1/en not_active Expired - Lifetime
- 1987-01-17 ES ES87100581T patent/ES2020200B3/en not_active Expired - Lifetime
- 1987-01-21 FI FI870266A patent/FI85872C/en not_active IP Right Cessation
- 1987-04-08 DK DK179087A patent/DK167362B1/en not_active IP Right Cessation
- 1987-04-09 JP JP62085908A patent/JP2550060B2/en not_active Expired - Lifetime
- 1987-04-10 AU AU71395/87A patent/AU589508B2/en not_active Ceased
- 1987-04-13 NO NO871545A patent/NO169595C/en unknown
- 1987-08-08 DE DE19873726449 patent/DE3726449A1/en not_active Withdrawn
-
1988
- 1988-06-03 FI FI882636A patent/FI87657C/en not_active IP Right Cessation
- 1988-06-24 EP EP88110072A patent/EP0305668B1/en not_active Expired - Lifetime
- 1988-06-24 ES ES88110072T patent/ES2023231B3/en not_active Expired - Lifetime
- 1988-07-28 NO NO883356A patent/NO172248C/en not_active IP Right Cessation
- 1988-08-05 AU AU20427/88A patent/AU602997B2/en not_active Ceased
- 1988-08-05 DK DK441488A patent/DK441488A/en not_active Application Discontinuation
- 1988-08-08 JP JP63196226A patent/JP2563985B2/en not_active Expired - Lifetime
- 1988-08-08 US US07/230,187 patent/US4925535A/en not_active Expired - Fee Related
-
1991
- 1991-01-07 GR GR91400007T patent/GR3001286T3/en unknown
- 1991-08-02 GR GR91401121T patent/GR3002432T3/en unknown
-
1992
- 1992-03-04 SG SG209/92A patent/SG20992G/en unknown
- 1992-09-09 SG SG900/92A patent/SG90092G/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1568940A1 (en) * | 1966-12-19 | 1970-07-16 | Koppers Gmbh Heinrich | Process for the separation of aromatics from hydrocarbon mixtures of any aromatic content |
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