EP0142043B1 - Process for the recuperation of vaporizable oils from hydrogenation residues of heavy oils, bitumen, tars etc. - Google Patents
Process for the recuperation of vaporizable oils from hydrogenation residues of heavy oils, bitumen, tars etc. Download PDFInfo
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- EP0142043B1 EP0142043B1 EP84112309A EP84112309A EP0142043B1 EP 0142043 B1 EP0142043 B1 EP 0142043B1 EP 84112309 A EP84112309 A EP 84112309A EP 84112309 A EP84112309 A EP 84112309A EP 0142043 B1 EP0142043 B1 EP 0142043B1
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- hydrogenation
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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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
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- the invention relates to a method for obtaining evaporable oils from the residue of the hydrogenation of heavy or heavy oils, bitumen, tar, oils from oil shale or tar sand and the like by vacuum distillation.
- the oils obtained by vacuum distillation can be hydrated to higher quality products under relatively mild conditions.
- the process engineering of vacuum distillation of such hydrogenation residues is known, but the handling of the vacuum residue poses considerable problems. In particular, the discharge from the vacuum column and the transport for further processing are extremely difficult due to the high viscosity of the vacuum residue.
- the object of the present invention is to overcome these difficulties. According to the invention, this occurs in that the hydrogenation residue is fed from below into the liquid space of a single- or multi-shaft screw machine (7) via a positive-displacement pump system (5), which has a vaporization zone (8) and a smoldering zone (9) separated by a mechanical compression stage (16) ), occurs and is subjected to distillation under reduced pressure and subsequent smoldering.
- the hydrogenation residue which constantly increases its viscosity during the distillation, is continuously circulated by the screw and is thereby passed through the distillation zone of the screw machine, so that the evaporable constituents are removed from it.
- GB-A-288 148 discloses a process in which, inter alia, the residues of a coal or oil hydrogenation are conveyed through a screw machine and then treated in vacuo.
- a real forced conveyance is not specified with this method, because the screw essentially serves as a cleaning device and in which problems associated with coking of coke are by no means excluded.
- pressures of 0.01-0.6 bar preferably 0.02-0.1 bar
- the pressure drops from 0.6, preferably 0.1 bar to 0.01, preferably 0.02 bar over the length of the screw machine from the entry of the hydrogenation sludge to its exit. This measure reduces the risk of disturbances in the distillation process in the screw machine.
- the distillation of the hydrogenation residue in the screw machine is carried out in particular at temperatures of 200-400 ° C., preferably 250-350 ° C.
- the temperature increases from 200 ° C., preferably 250 ° C. to 400 ° C., preferably 350 ° C., over the length of the screw machine from the inlet to the outlet of the hydrogenation residue. This shortens the time during which the hydrogenation residue assumes high temperatures which favor changes and facilitates the further processing of the residue freed from the volatile constituents. Residues up to a final viscosity of approximately 2000 mPas (250 ° C.) can be handled in the distillate removal by the process according to the invention.
- the gases withdrawn in gaseous form from the screw machine are expediently mixed with the other hydrogenating oils, e.g. B. combines the hot separator leaving gaseous hydrogenation products and together with these further treatment, for. B. subjected to a hydrogenation.
- the non-evaporated material can be introduced from the screw machine into a cooling or granulating device, where it is solidified.
- the goods that can be stored and transported in this form can e.g. B. can be used as fuel or as a feed of a gasification plant.
- the unevaporated material is heated in the screw machine after distillation to higher temperatures, preferably 350-600 ° C., and is smelted at this temperature, in particular at atmospheric pressure or at a pressure below it.
- the screw machine expediently has a smoldering zone in addition to the distillation zone, into which the hydrogenation residue is conveyed through the screws after passing through the former.
- the sulfuric vapors generated are extracted separately from the oil vapors.
- the resulting coke can finally z. B. can be used as fuel.
- the screw machine expediently has a compression zone connected to a direct entry system into a gasification reactor.
- the present method is suitable for processing all hydrogenation residues which occur in the high pressure hydrogenation processes of heavy or heavy oils, bitumen, tar, oils from oil shale or tar sand and the like, in which the feedstock contains hydrogenation hydrogen and optionally in the presence of a catalyst at elevated pressure and elevated temperature, for example by the so-called Bergius-Pier process.
- a positive-displacement pump system 5 which also serves as a metering unit, is used as the conveying element for the feed stream.
- the product used in the vacuum screw machine consists of 0.86 t of oil with a boiling range of 200 - 550 ° C at normal pressure, 0.12 t of residue with a start of boiling of at least 550 ° C at normal pressure and 0.02 t of inorganic constituents.
- the vacuum screw machine 7 was equipped with a double screw and, in the case of the present example, was divided into an evaporation zone 8 and a smoldering zone 9 over the length of the screw cylinder.
- the hydrogenation residue used is heated to 350 ° C. at 0.1 bar. 0.75 t of volatile constituents are drawn off via the connection piece 10 and passed into the condensate container 12 via line 11 following cooling which is not shown in the flow diagram.
- the condensate container is connected to the vacuum line 13 and the condensate is drawn off via line 15.
- the residue obtained from the evaporation zone 8 contained 0.13 t of oil components with a boiling range of about 450-500 ° C. under normal pressure, 0.10 t of a residue boiling above 550 ° C. under normal pressure and 0.02 t of inorganic components.
- This residue was heated in the smoldering zone 9 adjoining the evaporation zone 8 from 350 ° C. over the length of the smoldering zone to gradually increase to 600 ° C., the evaporation zone 8 and smoldering zone 9 being separated by a mechanical compression stage 16, thereby compressing the residue he follows.
- the vacuum screw machine was heated by means of jacket heating by means of superheated steam in the evaporation zone 8 and by means of flue gas in the smoldering zone 9.
- the heating can also be carried out by means of electrically heated heating jaws or by induction heating or, in the case of jacket heating, by heat transfer oils.
Abstract
Description
Die Erfindung betrifft eine Verfahren zur Gewinnung von verdampfbaren Ölen aus dem Rückstand der Hydrierung von Schwer- oder Schwerstölen, Bitumen, Teer, Ölen aus Ölschiefer oder Teersand und dgl. durch eine Vakuumdestillation.The invention relates to a method for obtaining evaporable oils from the residue of the hydrogenation of heavy or heavy oils, bitumen, tar, oils from oil shale or tar sand and the like by vacuum distillation.
Zur Hydrierung von Schwer- und Schwerstölen, Bitumen, Teer, Ölen aus Ölschiefer oder Teersand und dergl. sind Verfahren bekannt, bei denen diese Einsatzstoffe bei Temperaturen von 250 - 550 °C, vorzugsweise 350 - 490 °C und Drücken von 50 - 700 bar, vorzugsweise 100 - 350 bar, gegebenenfalls in Gegenwart von Katalysatoren hydriert werden. Durch die Hydrierung dieser bei Normaldruck hochsiedenden Einsatzstoffe werden neben gasförmigen Kohlenwasserstoffen und bei Raumtemperatur zähviskosen bzw. festen Hydrierrückständen insbesondere niedriger siedende Flüssigprodukte des Benzin- und Mittelölsiedebereiches als Produkte erzeugt (s. W. Krönig, "Die katalytische Hydrierung von Kohlen, Teeren und Mineralölen", Springer Verlag, Berlin, Göttingen, Heidelberg 1950 insbesondere S. 77 - 91).For the hydrogenation of heavy and heavy oils, bitumen, tar, oils from oil shale or tar sand and the like. Methods are known in which these feedstocks at temperatures of 250-550 ° C., preferably 350-490 ° C. and pressures of 50-700 bar , preferably 100-350 bar, optionally in the presence of catalysts. The hydrogenation of these high-boiling feedstocks at normal pressure produces, in addition to gaseous hydrocarbons and viscous or solid hydrogenation residues at room temperature, in particular lower-boiling liquid products in the gasoline and medium-oil boiling range as products (see W. Krönig, "The Catalytic Hydrogenation of Coals, Tar and Mineral Oils" , Springer Verlag, Berlin, Göttingen, Heidelberg 1950, in particular pp. 77 - 91).
Die entsprechenden Technologien wurden in den Jahren 1920 bis 1965 zur technischen Reife entwickelt und eingesetzt. Das Basisverfahren war die Hydriertechnologie nach BERGIUS-PIER. Aufbauend auf dieses Verfahren wurden in neuerer Zeit spezielle Technologien entwickelt und im Pilotanlagen- bzw. großtechnischen Maßstab angewandt. Als neuere Entwicklungen sind insbesondere die H-OIL-Technologie, das LC-FINING sowie das VEBA COMBI CRACKING-Verfahren (VCC) zu nennen (s. u. a. R. M. Eccles, "Recent Technical Advances in H-OIL Upgrading of Heavy Crudes", Proc., Vol. II, 2nd World Congress of Chemical Engineering, 1981, S. 520 - 537); U. Graeser, K. Niemann, "Proven hydrogenation processes for upgrading residua being revived in Germany", Oil and Gas J., 22. März 1982, S. 121, 122, 125 - 127).The corresponding technologies were developed and used for technical maturity in the years 1920 to 1965. The basic process was the hydration technology according to BERGIUS-PIER. Building on this process, special technologies have recently been developed and applied on a pilot or large-scale scale. H-OIL technology, LC-FINING, are newer developments as well as the VEBA COMBI CRACKING process (VCC) (see below RM Eccles, "Recent Technical Advances in H-OIL Upgrading of Heavy Crudes", Proc., Vol. II, 2nd World Congress of Chemical Engineering, 1981, p. 520 - 537); U. Graeser, K. Niemann, "Proven hydrogenation processes for upgrading residua being revived in Germany", Oil and Gas J., March 22, 1982, pp. 121, 122, 125 - 127).
Allen diesen Verfahren ist gemeinsam, daß die Abtrennung der Hydrierrückstände von den gasförmigen bzw. kondensierbaren Produkten in Heißabscheidern erfolgt, wobei die Phasenseparierung unter Reaktionsdruck bei Reaktionstemperatur bzw. wenig darunter liegenden Temperaturen durchgeführt wird. Schwierigkeiten bietet dabei die Aufarbeitung der Hydrierrückstände. Diese enthalten neben Feststoffen wie z. B. Katalysatoren und nicht verdampfbaren flüssigen oder pastösen Bestandteilen wie z. B. Asphaltene wertvolle verdampfbare Produktöle, deren Abtrennung aus wirtschaftlichen Gründen zwingend ist.All of these processes have in common that the separation of the hydrogenation residues from the gaseous or condensable products takes place in hot separators, the phase separation being carried out under reaction pressure at reaction temperature or at temperatures below it. The processing of the hydrogenation residues presents difficulties. In addition to solids such. B. catalysts and non-evaporable liquid or pasty components such. B. Asphaltenes valuable vaporizable product oils, the separation of which is imperative for economic reasons.
Zur Abtrennung dieser verdampfbaren Ölbeimengungen wurden verschiedene Verfahren wie Filtration, Schleudern, Vakuumdestillation usw. angewandt. Die dabei gewonnenen Öle im Siedebereich des Vakuumgasöls werden z. B. durch weitere Hydrierung in marktfähige, niedriger siedende Produkte überführt. Allerdings enthalten die durch Filtration bzw. Schleudern abgetrennten Ölmengen z. T. erhebliche Beimengungen an schwerhydrierbaren öllöslichen hochmolekularen Stoffen wie z. B. Asphaltenen, die eine weitere hydrierende Aufarbeitung ungünstig beeinflussen bzw. deren Abbau verschärfte Hydrierbedingungen erfordert.Various processes such as filtration, spinning, vacuum distillation, etc. were used to separate these evaporable oil admixtures. The oils obtained in the boiling range of the vacuum gas oil are e.g. B. converted into marketable, lower-boiling products by further hydrogenation. However, the amounts of oil separated by filtration or spinning contain e.g. T. considerable admixtures of difficult to hydrate oil-soluble high molecular weight Fabrics such as B. asphaltenes, which adversely affect further hydrogenation or whose degradation requires more stringent hydrogenation conditions.
Die durch Vakuumdestillation gewonnenen Öle können unter verhältnismäßig milden Bedingungen zu höherwertigen Produkten aufhydriert werden. Die verfahrenstechnische Durchführung der Vakuumdestillation derartiger Hydrierrückstände ist zwar bekannt, doch wirft die Handhabung des Vakuumrückstandes erhebliche Probleme auf. Insbesondere gestaltet sich das Austragen aus der Vakuumkolonne sowie der Transport zur Weiterverarbeitung aufgrund der hohen Zähigkeit des Vakuumrückstandes äußerst schwierig.The oils obtained by vacuum distillation can be hydrated to higher quality products under relatively mild conditions. The process engineering of vacuum distillation of such hydrogenation residues is known, but the handling of the vacuum residue poses considerable problems. In particular, the discharge from the vacuum column and the transport for further processing are extremely difficult due to the high viscosity of the vacuum residue.
Die vorliegende Erfindung hat sich die Aufgabe gestellt, diese Schwierigkeiten zu überwinden. Erfindungsgemäß geschieht dies dadurch, daß der Hydrierrückstand über ein zwangsförderndes Pumpensystem (5) von unten her in den Flüssigraum einer ein- oder mehrwelligen Schneckenmaschine (7), die eine durch eine maschinentechnische Kopressionsstufe (16) getrennte Verdampfungszone (8) und eine Schwelzone (9) aufweist, eintritt und in dieser einer Destillation unter vermindertem Druck sowie einer sich anschließenden Schwelung unterworfe wird. Der während der Destillation ständig seine Viskosität erhöhende Hydrierrückstand wird durch die Schnecke laufend umgewälzt und dabei durch die Destillationszone der Schneckenmaschine geführt, so daß ihm die verdampfbaren Bestandteile entzogen werden.The object of the present invention is to overcome these difficulties. According to the invention, this occurs in that the hydrogenation residue is fed from below into the liquid space of a single- or multi-shaft screw machine (7) via a positive-displacement pump system (5), which has a vaporization zone (8) and a smoldering zone (9) separated by a mechanical compression stage (16) ), occurs and is subjected to distillation under reduced pressure and subsequent smoldering. The hydrogenation residue, which constantly increases its viscosity during the distillation, is continuously circulated by the screw and is thereby passed through the distillation zone of the screw machine, so that the evaporable constituents are removed from it.
Ein- oder mehrwellige Schneckenmaschinen mit Gas- oder Dampfabführung sind bekannt, z. B. aus den US-PSen 1 156 096 und 2 615 199. Sie wurden jedoch bisher trotz der Schwierigkeiten, die schon bei der Verarbeitung der Hydrierrückstände von Kohle in den 30er und 40er Jahren dieses Jahrhunderts auftraten, nicht zur Ölgewinnung aus Hydrierrückständen, sondern z. B. zur Entfernung von Gasen oder Monomeren-Dämpfen aus Kunststoffen eingesetzt (s. M. Herrmann "Schneckenmaschinen in der Verfahrenstechnik", Berlin/Heidelberg/New York 1972). In der Kunststoffindustrie stellt die Schneckenmaschine somit einen Teil des Polymerisationsreaktors dar, wobei über die Monomerenentfernung in der Vakuumzone ein Abbruch der Polymerisationsreaktion herbeigeführt wird, wohingegen im Fall der Hydrierung vorgenannter Einsatzstoffe die Feststoffanreicherung im Hydrierrückstand zielführend ist.Single or multi-shaft screw machines with gas or steam discharge are known, for. B. from US Pat. Nos. 1,156,096 and 2,615,199. However, despite the difficulties already encountered in processing the hydrogenation residues of coal in the 1930s and 1940s, they have not been used to extract oil from hydrogenation residues, but e.g. . B. used to remove gases or monomer vapors from plastics (see M. Herrmann "screw machines in process engineering", Berlin / Heidelberg / New York 1972). In the plastics industry, the screw machine thus forms part of the polymerization reactor, the polymerization reaction being terminated by removing the monomers in the vacuum zone, whereas in the case of the hydrogenation of the aforementioned starting materials, the solidification in the hydrogenation residue is expedient.
Aus der Druckschrift GB - A - 288 148 ist ein Verfahren bekannt, bei dem, inter alia, die Rückstände einer Kohle- oder Ölhydrierung durch eine Schneckenmaschine befördert werden und dann in vacuo behandelt werden. Eine echte Zwangsförderung ist mit diesem Verfahren nicht vorgegeben, weil die Schnecke im wesentlichen als Abreinigungsvorrichtung dient und bei welchem mit Koksanbackungen verbundene Probleme keineswegs ausgeschlossen sind.GB-A-288 148 discloses a process in which, inter alia, the residues of a coal or oil hydrogenation are conveyed through a screw machine and then treated in vacuo. A real forced conveyance is not specified with this method, because the screw essentially serves as a cleaning device and in which problems associated with coking of coke are by no means excluded.
Bei der Destillation des Hydrierrückstandes in der ein- oder mehrwelligen Schneckenmaschine werden insbesondere Drücke von 0,01 - 0,6 bar, vorzugsweise 0,02 - 0,1 bar angewandt. Nach einer Weiterbildung der Erfindung fällt über die Länge der Schneckenmaschine vom Eintritt des Hydrierabschlammes zu dessen Austritt der Druck von 0,6, vorzugsweise 0,1 bar auf 0,01, vorzugsweise 0,02 bar ab. Diese Maßnahme verringert die Gefahr von Störungen des Destillationsvorganges in der Schneckenmaschine.When distilling the hydrogenation residue in the single- or multi-shaft screw machine, pressures of 0.01-0.6 bar, preferably 0.02-0.1 bar, are used in particular. According to a development of the invention, the pressure drops from 0.6, preferably 0.1 bar to 0.01, preferably 0.02 bar over the length of the screw machine from the entry of the hydrogenation sludge to its exit. This measure reduces the risk of disturbances in the distillation process in the screw machine.
Die Destillation des Hydrierrückstandes in der Schneckenmaschine erfolgt insbesondere bei Temperaturen von 200 - 400 °C, vorzugsweise 250 - 350 °C. Nach einer weiteren Ausbildung der Erfindung steigt über die Länge der Schneckenmaschine vom Eintritt zum Austritt des Hydrierrückstandes die Temperatur von 200 °C, vorzugsweise 250 °C auf 400 °C, vorzugsweise 350 °C an. Hierdurch wird die Zeit, während der Hydrierrückstand hohe, Veränderungen begünstigende Temperaturen annimmt, verkürzt und die weitere Verarbeitung des von den flüchtigen Bestandteilen befreiten Rückstandes erleichtert. Nach dem erfindungsgemäßen Verfahren können Rückstände bis zu einer Endviskosität von etwa 2000 mPas (250 °C) bei der Destillatabtrennung gehandhabt werden.The distillation of the hydrogenation residue in the screw machine is carried out in particular at temperatures of 200-400 ° C., preferably 250-350 ° C. According to a further embodiment of the invention, the temperature increases from 200 ° C., preferably 250 ° C. to 400 ° C., preferably 350 ° C., over the length of the screw machine from the inlet to the outlet of the hydrogenation residue. This shortens the time during which the hydrogenation residue assumes high temperatures which favor changes and facilitates the further processing of the residue freed from the volatile constituents. Residues up to a final viscosity of approximately 2000 mPas (250 ° C.) can be handled in the distillate removal by the process according to the invention.
Die gasförmig aus der Schneckenmaschine abgezogenen Öle werden zweckmäßigerweise mit den übrigen Hydrierölen, z. B. den die Heißabscheider gasförmig verlassenden Hydrierprodukten vereinigt und zusammen mit diesen der Weiterbehandlung, z. B. einer Hydrierung unterworfen. Das nicht verdampfte Gut kann nach einer weiteren Ausbildung der Erfindung aus der Schneckenmaschine in eine Kühl- oder Granuliervorrichtung eingebracht werden, wo es verfestigt wird. Das in dieser Form lager- und transportfähige Gut kann z. B. als Brennmaterial oder als Einsatzprodukt einer Vergasungsanlage verwendet werden.The gases withdrawn in gaseous form from the screw machine are expediently mixed with the other hydrogenating oils, e.g. B. combines the hot separator leaving gaseous hydrogenation products and together with these further treatment, for. B. subjected to a hydrogenation. According to a further embodiment of the invention, the non-evaporated material can be introduced from the screw machine into a cooling or granulating device, where it is solidified. The goods that can be stored and transported in this form can e.g. B. can be used as fuel or as a feed of a gasification plant.
Nach einer anderen Ausbildung der Erfindung wird das nicht verdampfte Gut in der Schneckenmaschine nach der Destillation auf höhere Temperaturen, vorzugsweise 350 - 600 °C erhitzt und bei dieser Temperatur, insbesondere bei Atmosphärendruck oder auch bei einem darunter liegenden Druck geschwelt. Zweckmäßigerweise besitzt die Schneckenmaschine hierfür neben der Destillierzone eine Schwelzone, in die der Hydrierrückstand nach Durchlaufen der ersteren durch die Schnecken gefördert wird. Die entstandenen Schweldämpfe werden getrennt von den Öldämpfen abgezogen. Der anfallende Koks schließlich kann z. B. als Brennmaterial eingesetzt werden.According to another embodiment of the invention, the unevaporated material is heated in the screw machine after distillation to higher temperatures, preferably 350-600 ° C., and is smelted at this temperature, in particular at atmospheric pressure or at a pressure below it. For this purpose, the screw machine expediently has a smoldering zone in addition to the distillation zone, into which the hydrogenation residue is conveyed through the screws after passing through the former. The sulfuric vapors generated are extracted separately from the oil vapors. The resulting coke can finally z. B. can be used as fuel.
Besonders günstig ist es, das in der Schneckenmaschine nicht verdampfte Gut nach der Destillation weiter zu verdichten und direkt in einen Vergasungsreaktor einzubringen, in dem z. B. über Synthesegas der für die Hydrierung der Einsatzprodukte des Hydrierverfahrens notwendige Wasserstoff gewonnen wird. Zweckmäßigerweise besitzt die Schneckenmaschine hierfür neben der Destillierzone eine Verdichtungszone verbunden mit einem Direkteintragsystem in einen Vergasungsreaktor.It is particularly favorable to further compress the material not evaporated in the screw machine after the distillation and to introduce it directly into a gasification reactor in which, for. B. is obtained via synthesis gas of the hydrogen necessary for the hydrogenation of the feed products of the hydrogenation process. For this purpose, in addition to the distillation zone, the screw machine expediently has a compression zone connected to a direct entry system into a gasification reactor.
Das vorliegende Verfahren ist geeignet zur Verarbeitung sämtlicher Hydrierrückstände, die bei Hochdruckhydrierprozessen von Schwer- oder Schwerstölen, Bitumen, Teer, Ölen aus Ölschiefer oder Teersand und dergl. anfallen, bei denen der Einsatzstoff mit Hydrierwasserstoff und ggf. in Gegenwart eines Katalysators bei erhöhtem Druck und erhöhter Temperatur umgesetzt wird, beispielsweise nach dem sogenannten Bergius-Pier-Verfahren.The present method is suitable for processing all hydrogenation residues which occur in the high pressure hydrogenation processes of heavy or heavy oils, bitumen, tar, oils from oil shale or tar sand and the like, in which the feedstock contains hydrogenation hydrogen and optionally in the presence of a catalyst at elevated pressure and elevated temperature, for example by the so-called Bergius-Pier process.
Die Erfindung wird anhand des nachfolgenden Ausführungsbeispiels und der Zeichnung weiter erläutert.The invention is further explained on the basis of the exemplary embodiment below and the drawing.
Der Rückstand der Vakuumdestillation eines venezolanischen Rohöls mit einem Siedebeginn von oberhalb 325 °C wurde in einer Hydrieranlage, die im wesentlichen auf Basis eines weiterentwickelten Bergius-Pier-Verfahrens arbeitet, bei 300 bar und 450 °C unter Zusatz eines anorganischen Katalysatorsystems sowie unter Zugabe von Wasserstoff hydriert und über Leitung 1 einem Heißabscheider 2 zugeführt, in welchem bei Reaktionsdruck und Reaktionstemperatur die gasförmigen Reaktionsprodukte von den flüssigen und festen Bestandteilen des Reaktionsgemisches abgetrennt werden. Die gasförmigen Bestandteile werden über Leitung 3 abgezogen und in üblicher Weise weiterverarbeitet. Die nicht flüchtigen festen und flüssigen Bestandteile verlassen den Heißabscheider über Leitung 4 und werden nach Entspannung auf Atmosphärendruck über Stutzen 6 der Vakuumschneckenmaschine 7 zugeführt. Hierbei erfolgt der Eintritt in die Vakuumschneckenmaschine von unten her in den Flüssigraum, um damit einen Abschluß des Zulaufstromes der Produkte aus dem Heißabscheider zu der Vakuumzone der Vakuumschneckenmaschine 7 zu bekommen. Als Förderorgan für den Zulaufstrom wird ein zwangsförderndes Pumpensystem 5, welches gleichzeitig als Dosiereinheit dient, eingesetzt.The residue of the vacuum distillation of a Venezuelan crude oil with an initial boiling point of above 325 ° C was in a hydrogenation plant, which works essentially on the basis of an advanced Bergius-Pier process, at 300 bar and 450 ° C with the addition of an inorganic catalyst system and with the addition of Hydrogen is hydrogenated and fed via line 1 to a
Das Einsatzprodukt in die Vakuumschneckenmaschine setzt sich aus 0,86 t Öl mit einem Siedebereich von 200 - 550 °C bei Normaldruck, 0,12 t Rückstand mit einem Siedebeginn von mindestens 550 °C bei Normaldruck und 0,02 t anorganischen Bestandteilen zusammen.The product used in the vacuum screw machine consists of 0.86 t of oil with a boiling range of 200 - 550 ° C at normal pressure, 0.12 t of residue with a start of boiling of at least 550 ° C at normal pressure and 0.02 t of inorganic constituents.
Die Vakuumschneckenmaschine 7 war mit einer Doppelschnecke ausgerüstet und war im Falle des vorliegenden Beispiels über die Länge des Schneckenzylinders in eine Verdampfungszone 8 und in eine Schwelzone 9 unterteilt.The vacuum screw machine 7 was equipped with a double screw and, in the case of the present example, was divided into an
Über die Länge der Verdampfungszone 8 wird der eingesetzte Hydrierrückstand bei 0,1 bar auf 350 °C erhitzt. Es werden 0,75 t flüchtige Bestandteile über die Stutzen 10 abgezogen und über Leitung 11 im Anschluß an eine im Fließbild nicht dargestellte Abkühlung in den Kondensatbehälter 12 geleitet. Der Kondensatbehälter ist mit der Vakuumleitung 13 verbunden und das Kondensat wird über Leitung 15 abgezogen.Over the length of the
In der Verdampfungszone 8 war ein ständiges Ansteigen der Viskosität des eingesetzten Rückstandes zu beobachten. Die befürchteten Feststoffabsetzungen an der Schnecke sowie am Schneckenzylinder konnten nicht beobachtet werden.A constant increase in the viscosity of the residue used was observed in the
Der aus der Verdampfungszone 8 erhaltene Rückstand enthielt 0,13 t Öl-Bestandteile mit einem Siedebereich von etwa 450 - 500 °C unter Normaldruck, 0,10 t eines bei Normaldruck oberhalb von 550 °C siedenden Rückstandes sowie 0,02 t anorganischer Bestandteile. Dieser Rückstand wurde in der sich an die Verdampfungszone 8 anschließenden Schwelzone 9 von 350 °C über die Länge der Schwelzone an allmählich ansteigend auf 600 °C erhitzt, wobei Verdampfungszone 8 und Schwelzone 9 durch eine maschinentechnische Kompressionsstufe 16 getrennt sind, wodurch eine Verdichtung des Rückstandes erfolgt.The residue obtained from the
In der Schwelzone 9 werden weitere 0,21 t Destillat gewonnen, das über die Stutzen 14 und über Leitung 17 abgezogen wird. Der resultierende Rückstand enthielt im wesentlichen nur noch 0,02 t koksähnlicher Produkte und 0,02 t anorganischer Bestandteile und wurde in einer Austragszone 18 verdichtet und über Stutzen 19 und Leitung 20 abgezogen.In the
Die Beheizung der Vakuumschneckenmaschine erfolgte über eine Mantelbeheizung mittels überhitztem Dampf in der Verdampfungszone 8 und mittels Rauchgas in der Schwelzone 9.The vacuum screw machine was heated by means of jacket heating by means of superheated steam in the
In technisch äquivalenter Weise kann die Beheizung aber auch mittels elektrisch beheizter Heizbacken oder durch Induktionsheizung oder bei Mantelbeheizung durch Wärmeträgeröle erfolgen.In a technically equivalent manner, the heating can also be carried out by means of electrically heated heating jaws or by induction heating or, in the case of jacket heating, by heat transfer oils.
Claims (9)
- A process for the recovery of evaporable oils from the residue of the hydrogenation of heavy or very heavy oils, bitumen, tar, oils from oil shale or tar sand and the like by vacuum distillation, characterized in that the hydrogenation residue passes from below via a forced-delivery pump system (5) into the liquid chamber of a single-shaft or multi-shaft worm machine (7) having an evaporation zone (8), separated by a technical mechanical compression stage (16), and a low-temperature carbonization zone (9), and is distilled therein under reduced pressure and then subjected to low-temperature carbonization.
- A process according to claim 1, characterized in that distillation is performed at pressures of 0.01 to 0.6 bar, preferably 0.02 - 0.1 bar.
- A process according to claim 2, characterized in that over the length of the worm machine, from the inlet to the discharge of the hydrogenation residue, the pressure drops from 0.6, preferably 0.1 bar to 0.01, preferably 0.02 bar.
- A process according to one of claims 1 to 3, characterized in that distillation is performed at temperatures of 200 - 400°C, preferably 250 to 350°C.
- A process according to claim 4, characterized in that over the length of the worm machine, from the inlet to the discharge of the hydrogenation residue, the temperature rises from 200°C, preferably 250°C, to 400°C, preferably 350°C.
- A process according to one of claims 1 to 5, characterized in that following distillation, the unevaporated material is removed from the worm machine to a cooling or granulating device.
- A process according to one of claims 1 to 5, characterized in that following distillation, the unevaporated material in the worm machine is subjected to low-temperature carbonization, preferably at temperatures of 350 to 600°C.
- A process according to claim 7, characterized in that the low-temperature carbonization is performed at atmospheric pressure.
- A process according to one of claims 1 to 5, characterized in that following distillation, the unevaporated material is densified in the worm machine and introduced directly into a gasification reactor.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT84112309T ATE71133T1 (en) | 1983-10-15 | 1984-10-12 | PROCESS FOR RECOVERING VAPORABLE OILS FROM THE RESIDUE OF THE HYDRATION OF HEAVY OILS, BITUMEN, TAR AND SUCH. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3337623 | 1983-10-15 | ||
DE19833337623 DE3337623A1 (en) | 1983-10-15 | 1983-10-15 | METHOD FOR OBTAINING VAPORIZABLE OILS FROM THE RESIDUE OF THE HYDRATION OF HEAVY OR HEAVY OILS, BITUMEN, TAR AND THE LIKE. |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0142043A2 EP0142043A2 (en) | 1985-05-22 |
EP0142043A3 EP0142043A3 (en) | 1986-12-03 |
EP0142043B1 true EP0142043B1 (en) | 1992-01-02 |
Family
ID=6211990
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84112309A Expired - Lifetime EP0142043B1 (en) | 1983-10-15 | 1984-10-12 | Process for the recuperation of vaporizable oils from hydrogenation residues of heavy oils, bitumen, tars etc. |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0142043B1 (en) |
AT (1) | ATE71133T1 (en) |
CA (1) | CA1239105A (en) |
DD (1) | DD226587A5 (en) |
DE (2) | DE3337623A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3829986A1 (en) * | 1988-09-03 | 1990-03-15 | Enka Ag | Process for increasing the mesophase content in pitch |
WO2014113894A1 (en) * | 2013-01-25 | 2014-07-31 | Calaeris Energy & Environment Ltd. | Turbulent vacuum thermal separation methods and systems |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB288148A (en) * | 1927-03-31 | 1929-06-28 | Ig Farbenindustrie Ag | Improvements in the production of low boiling point and other hydrocarbons and derivatives thereof by the destructive hydrogenation of coals, oils and the like and in the treatment of the residues thereof |
DE704444C (en) * | 1940-02-13 | 1941-03-31 | Hydrierwerk Scholven Akt Ges | Process for the processing of oil-containing centrifugal residues from the pressure hydrogenation of ash-containing fuels |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB188686A (en) * | 1921-05-17 | 1922-11-17 | Herman Plauson | Improvements in the extraction of hydrocarbons from wood |
US1942373A (en) * | 1929-08-30 | 1934-01-02 | Barrett Co | Method of preparing creosoting compositions |
DE619298C (en) * | 1934-01-25 | 1935-09-27 | Edwin M F Guignard | Device for evaporation and distillation |
DE737780C (en) * | 1940-09-01 | 1943-07-23 | Dr Edwin M F Guignard | Kettle for fractional distillation of liquids |
US2615199A (en) * | 1945-05-15 | 1952-10-28 | Welding Engineers | Material treating apparatus |
DE2327353A1 (en) * | 1973-05-29 | 1975-01-02 | Otto & Co Gmbh Dr C | Liquid and gaseous low-sulphur fuels prodn. - by hydrogenation of solid fuels and purification of resulting gases |
DE2407217A1 (en) * | 1974-02-15 | 1975-09-04 | Kloeckner Humboldt Deutz Ag | Thermal treatment of granular material - partic drying and partial degassing of wet coal in a circulating inert gas |
-
1983
- 1983-10-15 DE DE19833337623 patent/DE3337623A1/en not_active Withdrawn
-
1984
- 1984-10-10 CA CA000465085A patent/CA1239105A/en not_active Expired
- 1984-10-12 AT AT84112309T patent/ATE71133T1/en not_active IP Right Cessation
- 1984-10-12 DD DD84268334A patent/DD226587A5/en not_active IP Right Cessation
- 1984-10-12 DE DE8484112309T patent/DE3485411D1/en not_active Expired - Fee Related
- 1984-10-12 EP EP84112309A patent/EP0142043B1/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB288148A (en) * | 1927-03-31 | 1929-06-28 | Ig Farbenindustrie Ag | Improvements in the production of low boiling point and other hydrocarbons and derivatives thereof by the destructive hydrogenation of coals, oils and the like and in the treatment of the residues thereof |
DE704444C (en) * | 1940-02-13 | 1941-03-31 | Hydrierwerk Scholven Akt Ges | Process for the processing of oil-containing centrifugal residues from the pressure hydrogenation of ash-containing fuels |
Also Published As
Publication number | Publication date |
---|---|
DD226587A5 (en) | 1985-08-28 |
EP0142043A3 (en) | 1986-12-03 |
EP0142043A2 (en) | 1985-05-22 |
DE3485411D1 (en) | 1992-02-20 |
ATE71133T1 (en) | 1992-01-15 |
CA1239105A (en) | 1988-07-12 |
DE3337623A1 (en) | 1985-04-25 |
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