EP0138215A2 - Process for upgrading coal hydrogenation residues - Google Patents

Process for upgrading coal hydrogenation residues Download PDF

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Publication number
EP0138215A2
EP0138215A2 EP84112308A EP84112308A EP0138215A2 EP 0138215 A2 EP0138215 A2 EP 0138215A2 EP 84112308 A EP84112308 A EP 84112308A EP 84112308 A EP84112308 A EP 84112308A EP 0138215 A2 EP0138215 A2 EP 0138215A2
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Prior art keywords
hydrogenation
screw machine
residue
bar
distillation
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German (de)
French (fr)
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EP0138215A3 (en
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Lothar Ing. Grad. Winckler
Klaus Dr. Dipl.-Chem. Fuhrmann
Ulrich Dr. Dipl.-Ing. Graeser
Peter Dipl.-Ing. Wenning
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Veba Oel Technologie und Automatisierung GmbH
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Veba Oel Technologie und Automatisierung 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
    • 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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  • coal is hydrogenated by reaction with hydrogen at temperatures of 250-500 ° C., preferably 350-490 ° C. and pressures of 50-700 bar, preferably 100-350 bar, in particular in the presence of catalysts becomes.
  • the products produced are solid or viscous hydrogenation residues at room temperature.
  • Both hard coal and lignite can be used in the hydrogenation (see W. Krönig, "The catalytic hydrogenation of coal, tars and mineral oils", Springer Verlag, Berlin, Göttingen, Heidelberg 1950).
  • the corresponding technologies were developed and used for technical maturity in the years 1920 to 1945.
  • the hydrogenation technologies according to BERGIUS-PIER and POTT-BROCHE are to be mentioned as basic processes.
  • oils obtained can be used as grinding oils or grinding oil components for the coal.
  • the amounts of oil separated by filtration or spinning contain e.g. T. considerable admixtures of non-evaporable, difficult to hydrogenate, oil-soluble intermediates such.
  • the object of the present invention is to overcome these difficulties. According to the invention, this is done in that the residue of the carbon hydrogenation is subjected to distillation under reduced pressure in a single- or multi-shaft screw machine, the evaporable components are drawn off and the remaining material is introduced into a cooling or granulating device.
  • the hydrogenation residue which constantly increases its viscosity during the distillation, is continuously circulated by screws and thereby passed through the distillation zone of the screw machine, the evaporable constituents being removed from it.
  • 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. They are used especially in plastics production, and are used there, inter alia, for gas or monomer removal from polymerization mixtures (see M. Herrmann, "Snail machines in process engineering", Springer Verlag, Berlin, Heidelberg, New York 1972). Although the difficulties associated with oil separation have been known since the beginning of the coal hydrogenation on an industrial scale, vacuum screw machines have not been used for processing carbohydrate residues.
  • the processing of hydrogenation residues has different objectives than in the production of plastics:
  • the screw machine is part of the polymerization reactor, whereby the polymerization reaction is terminated by removing the monomers in the vacuum zone, whereas in the case of coal hydrogenation, the enrichment of solids in the hydrogenation residue is effective is.
  • pressures of 0.01 to 0.06 bar preferably 0.02 to 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 rises from 200, preferably 250 ° C. to 400, preferably 350 ° C., under constant pressure or falling over the length of the screw machine. This shortens the time during which the hydrogenation residue assumes high temperatures which favor changes and facilitates 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 gaseous oils withdrawn from the screw machine are expediently used as grating oils or 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 rest is introduced from the screw machine directly into a cooling and granulating device.
  • the z. B. can consist of a cooled, circulating belt or a similar device, solidifies the introduced as a viscous mass and can be stored or transported, if necessary after comminution, without the risk of caking, running apart or the like. It is Z. B. usable as fuel or as a feed product of a gasification plant.
  • the present method is suitable for processing all hydrogenation residues which occur in high-pressure coal hydrogenation processes in which coal is mashed with grinding oil and reacted together with hydrogen hydrogen and, if appropriate, in the presence of a catalyst at elevated pressure and elevated temperature, for example by the so-called Bergius-Pier process .
  • a typical gas flame coal of the Ruhr area is mashed with a grinding oil returned from the process and fed together with the hydrogenation hydrogen and with the addition of an iron catalyst at 300 bar and 470 ° C after preheating via line 1 under process pressure hydrogenation reactor 2.
  • the reaction product leaves the reactor 2 via line 3 and is fed to the hot separator 4, in which, under process pressure and at 460 ° C., the products volatile under the prevailing conditions are separated from the solid or liquid reaction products.
  • a positive-conveying pump system 6 which also serves as a metering unit, is used as the conveying element for the feed stream.
  • a vacuum of 0.1 bar is generated in the screw machine 7, which is equipped with a twin screw, via a vacuum line 14.
  • the hydrogenation residue used, which is fed via nozzle 8 to the screw machine 7, contained 0.5 t of oil with a boiling point of 325 ° C. or above, 0.15 t of higher molecular components, which were about 0.1 t as asphaltenes and about 0 , 05 t were determined as pre-asphaltenes, and 0.35 t of inorganic components composed of 0.24 t of ash and 0.11 t of unreacted coal.
  • the ash content was determined to be 32% by weight of SiO 2 , 26% by weight of A1 2 0 3 , 25% by weight of Fe 2 0 3 and 17% by weight of other components.
  • the distillate was separated off at the pressure of 0.1 bar, the hydrogenation residue in the vacuum twin-screw machine 7 being heated from 350 to 450 ° C. during the distillate separation. It evaporated 0.40 t of distillable components of the oil portion, which were withdrawn via connection 9 from the evaporation zone 18 and after cooling, not shown, via line 10 and via condensate container 11 by means of line 13. The uncondensed portions were drawn off via condensate container 11 by means of line 12.
  • the softening point of the residue after passing through the evaporation zone was 180 ° C.
  • the viscosity of the same residue at 250 ° C was determined to be 1500 mPas.
  • the distillable constituents drawn off via line 13 can be returned to the hydrogenation as valuable grinding oil components.
  • the evaporation zone is separated from the discharge zone by a mechanical compression stage 19, which is realized in a known manner by suitable design of the screw and the arrangement of suitable screw elements in this area. This results in a compression of the residue, which contains only 0.1 t of residual oil, in addition to inorganic constituents and higher molecular weight intermediate products, before this residue is fed via connecting piece 14 and line 15 to a cooling belt 16 with subsequent granulating device 17.
  • the screw machine was heated by means of jacket heating of the screw machine using superheated steam.
  • 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 flue gas or heat transfer oils.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

In this process, a vacuum distillation takes place at pressures of 0.01 to 0.6 bar. To improve the handling of such residues, particularly with regard to the discharge from the vacuum column, the hydrogenation residue is subjected in a single-or multi-shaft screw machine to a vacuum distillation, the resulting gases and vapours being extracted and the unevaporated remainder being taken to a cooling and granulating device. <IMAGE>

Description

Zur Hydrierung von Kohle sind Verfahren bekannt, bei denen Kohle durch Reaktion mit Wasserstoff bei Temperaturen von 250 - 500 °C, vorzugsweise 350 bis 490 °C und Drücken von 50 - 700 bar, vorzugsweise 100 - 350 bar, insbesondere in Gegenwart von Katalysatoren hydriert wird. Als Produkte entstehen neben flüssigen und gasförmigen Kohlenwasserstoffen bei Raumtemperatur feste bzw. zähflüssige Hydrierrückstände. Sowohl Steinkohlen als auch Braunkohlen können dabei in die Hydrierung eingesetzt werden (s. W. Krönig, "Die katalytische Hydrierung von Kohlen, Teeren und Mineralölen", Springer Verlag, Berlin, Göttingen, Heidelberg 1950). Die entsprechenden Technologien wurden in den Jahren 1920 bis 1945 zur technischen Reife entwickelt und eingesetzt. Als Basisverfahren sind die Hydriertechnologien nach BERGIUS-PIER und POTT-BROCHE anzuführen.For the hydrogenation of coal, processes are known in which coal is hydrogenated by reaction with hydrogen at temperatures of 250-500 ° C., preferably 350-490 ° C. and pressures of 50-700 bar, preferably 100-350 bar, in particular in the presence of catalysts becomes. In addition to liquid and gaseous hydrocarbons, the products produced are solid or viscous hydrogenation residues at room temperature. Both hard coal and lignite can be used in the hydrogenation (see W. Krönig, "The catalytic hydrogenation of coal, tars and mineral oils", Springer Verlag, Berlin, Göttingen, Heidelberg 1950). The corresponding technologies were developed and used for technical maturity in the years 1920 to 1945. The hydrogenation technologies according to BERGIUS-PIER and POTT-BROCHE are to be mentioned as basic processes.

Aufbauend auf diesen Verfahren wurden in neuerer Zeit spezielle Technologien entwickelt und im Klein- bzw. Pilotanlagenmaßstab erprobt. Dazu sind insbesondere die EDS-Technologie, SRC, das H-COAL-Verfahren sowie die Neue Deutsche Technologie zu nennen. Letzteres wird seit 1981 in der Großversuchsanlage Bottrop erprobt (s. H. G. Frank u. A. Knop, "Kohleveredlung", Springer Verlag, Berlin, Heidelberg, New York 1979, S. 228 - 251).Based on these processes, special technologies have recently been developed and tested on a small or pilot plant scale. The EDS technology, SRC, the H-COAL process and the New German Technology are particularly worth mentioning. The latter has been tested in the Bottrop large-scale test facility since 1981 (see H. G. Frank and A. Knop, "Kohlveredlung", Springer Verlag, Berlin, Heidelberg, New York 1979, pp. 228-251).

Allen diesen Verfahren ist gemeinsam, daß die Abtrennung der Hydrierrückstände von den gasförmigen bzw. flüssigen Produkten in Heißabscheidern erfolgt, wobei die Phasenseparierung unter Reaktionsdruck bei Reaktionstemperatur bzw. wenig darunter liegenden Temperaturen erfolgt. Von besonderem Interesse ist dabei die Aufarbeitung der Hydrierrückstände, da diese neben Feststoffen wie nicht umgesetzter Kohle, Asche, Katalysatoren und nicht verdampfbaren flüssigen oder pastösen Zwischenprodukten wie Asphaltenen und Präasphaltenen wertvolle verdampfbare Produktöle enthalten, die zur Steigerung der Flüssigproduktausbeute abzutrennen sind.All of these processes have in common that the separation of the hydrogenation residues from the gaseous or liquid products takes place in hot separators, the phase separation taking place under reaction pressure at reaction temperature or temperatures below it. The processing of the hydrogenation residues is of particular interest since, in addition to solids such as unconverted coal, ash, catalysts and non-evaporable liquid or pasty intermediates such as asphaltenes and pre-asphaltenes, they contain valuable evaporable product oils which have to be separated off to increase the liquid product yield.

Zur Abtrennung dieser verdampfbaren Ölbeimengungen wurden verschiedene Verfahren wie Filtration, Schleudern, Vakuumdestillation usw. angewandt. Die gewonnenen Öle können als Anreibeöle bzw. Anreibeölkomponenten für die Einsatzkohle verwendet werden. Allerdings enthalten die durch Filtration bzw. Schleudern abgetrennten Ölmengen z. T. erhebliche Beimengungen an nicht verdampfbaren, schwer hydrierbaren, öllöslichen Zwischenprodukten wie z. B. Asphaltenen und Präasphaltenen, die den Hydrierprozeß 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 can be used as grinding oils or grinding oil components for the coal. However, the amounts of oil separated by filtration or spinning contain e.g. T. considerable admixtures of non-evaporable, difficult to hydrogenate, oil-soluble intermediates such. B. asphaltenes and pre-asphaltenes, which adversely affect the hydrogenation process or whose degradation requires more stringent hydrogenation conditions.

Die vorgenannten Schwierigkeiten werden durch Einsatz der Vakuumdestillation überwunden. Die durch Vakuumdestillation des Hydrierrückstandes gewonnenen Öle stellen hochwertige Anreiböle dar bzw. können unter verhältnismäßig milden Bedingungen weiter aufhydriert werden. Allerdings 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 stark feststoffangereicherten Materials äußerst schwierig.The aforementioned difficulties are overcome by using vacuum distillation. Those obtained by vacuum distillation of the hydrogenation residue Oils are high-quality rubbing oils or can be further hydrated under relatively mild conditions. However, handling 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 toughness of the highly solids-enriched material.

Die vorliegende Erfindung hat sich die Aufgabe gestellt, diese Schwierigkeiten zu überwinden. Erfindungsgemäß geschieht dies dadurch, daß der Rückstand der Kohlehydrierung in einer ein- oder mehrwelligen Schneckenmaschine einer Destillation unter vermindertem Druck unterworfen wird, hierbei die verdampfbaren Anteile abgezogen werden und das verbleibende Gut in eine Kühl- oder Granuliervorrichtung eingebracht wird. Der während der Destillation ständig seine Viskosität erhöhende Hydrierrückstand wird durch Schnecken laufend umgewälzt und dabei durch die Destillationszone der Schneckenmaschine geführt, wobei ihm die verdampfbaren Bestandteile entzogen werden.The object of the present invention is to overcome these difficulties. According to the invention, this is done in that the residue of the carbon hydrogenation is subjected to distillation under reduced pressure in a single- or multi-shaft screw machine, the evaporable components are drawn off and the remaining material is introduced into a cooling or granulating device. The hydrogenation residue, which constantly increases its viscosity during the distillation, is continuously circulated by screws and thereby passed through the distillation zone of the screw machine, the evaporable constituents being 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 werden speziell in der Kunststoffherstellung eingesetzt, und dienen dort u. a. zur Gas- bzw. Monomerenentfernung aus Polymerisationsgemischen (s. M. Herrmann, "Schnekkenmaschinen in der Verfahrenstechnik", Springer Verlag, Berlin, Heidelberg, New York 1972). Obwohl seit Beginn der im technischen Maßstab durchgeführten Kohlehydrierung die mit der Ölabtrennung verbundenen Schwierigkeiten bekannt waren, wurden Vakuumschneckenmaschinen bislang nicht für die Aufarbeitung von Kohlehydrierrückständen eingesetzt. Bei der Aufarbeitung von Hydrierrückständen liegen andere Zielsetzungen als bei der Kunststoffherstellung vor: In der Kunststoffindustrie stellt die Schneckenmaschine einen Teil des Polymerisationsreaktors dar, wobei über die Monomerenentfernung in der Vakuumzone ein Abbruch der Polymerisationsreaktion herbeigeführt wird, wohingegen im Fall der Kohlehydrierung 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. They are used especially in plastics production, and are used there, inter alia, for gas or monomer removal from polymerization mixtures (see M. Herrmann, "Snail machines in process engineering", Springer Verlag, Berlin, Heidelberg, New York 1972). Although the difficulties associated with oil separation have been known since the beginning of the coal hydrogenation on an industrial scale, vacuum screw machines have not been used for processing carbohydrate residues. The processing of hydrogenation residues has different objectives than in the production of plastics: In the plastics industry, the screw machine is part of the polymerization reactor, whereby the polymerization reaction is terminated by removing the monomers in the vacuum zone, whereas in the case of coal hydrogenation, the enrichment of solids in the hydrogenation residue is effective is.

Bei der Destillation des Hydrierrückstandes in der ein- oder mehrwelligen Schneckenmaschine werden insbesondere Drücke von 0,01 bis 0,06 bar, vorzugsweise 0,02 bis 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 to 0.06 bar, preferably 0.02 to 0.1 bar, are used in particular. According to a further 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, vorzugsweise 250 °C auf 400, vorzugsweise 350 °C unter konstantem bzw. über die Länge der Schneckenmaschine fallendem Druck an. Hierdurch wird die Zeit während der 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. Die gasförmig aus der Schneckenmaschine abgezogenen Öle werden zweckmäßigerweise als Anreibeöle eingesetzt oder mit den übrigen Hydrierölen, z. B. den die Heißabscheider gasförmig verlassenden Hydrierprodukten vereinigt und zusammen mit diesen der Weiterbehandlung, z. B. einer Hydrierung unterworfen.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. After a further embodiment of the invention increases Over the length of the screw machine from the inlet to the outlet of the hydrogenation residue, the temperature rises from 200, preferably 250 ° C. to 400, preferably 350 ° C., under constant pressure or falling over the length of the screw machine. This shortens the time during which the hydrogenation residue assumes high temperatures which favor changes and facilitates 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 gaseous oils withdrawn from the screw machine are expediently used as grating oils or 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.

Erfindungsgemäß wird der Rest, das nicht verdampfte Gut, aus der Schneckenmaschine direkt in eine Kühl-und Granuliervorrichtung eingebracht. In dieser Vorrichtung, die z. B. aus einem gekühlten, umlaufenden Band oder einer ähnlichen Einrichtung bestehen kann, erstarrt das als zähflüssige Masse eingebrachte Gut und kann, ggf. nach einer Zerkleinerung, ohne die Gefahr des Zusammenbackens, Auseinanderlaufens oder dergl. gelagert oder transportiert werden. Es ist z. B. als Brennmaterial oder als Einsatzprodukt einer Vergasungsanlage verwendbar.According to the invention, the rest, the unevaporated material, is introduced from the screw machine directly into a cooling and granulating device. In this device, the z. B. can consist of a cooled, circulating belt or a similar device, solidifies the introduced as a viscous mass and can be stored or transported, if necessary after comminution, without the risk of caking, running apart or the like. It is Z. B. usable as fuel or as a feed product of a gasification plant.

Das vorliegende Verfahren ist geeignet zur Verarbeitung sämtlicher Hydrierrückstände, die bei Hochdruckkohlehydrierprozessen anfallen, bei denen Kohle mit Anreibeöl angemaischt wird und gemeinsam mit Hydrierwasserstoff und gegebenenfalls 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 high-pressure coal hydrogenation processes in which coal is mashed with grinding oil and reacted together with hydrogen hydrogen and, if appropriate, 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.

Eine typische Gasflammkohle des Ruhrgebiets wird nach Zerkleinerung mit einem aus dem Verfahren zurückgeführten Anreibeöl angemaischt und gemeinsam mit dem Hydrierwasserstoff und unter Zugabe eines Eisenkatalysators bei 300 bar und 470 °C nach Vorheizung über Leitung 1 unter Prozeßdruck Hydrierreaktor 2 zugeführt.A typical gas flame coal of the Ruhr area is mashed with a grinding oil returned from the process and fed together with the hydrogenation hydrogen and with the addition of an iron catalyst at 300 bar and 470 ° C after preheating via line 1 under process pressure hydrogenation reactor 2.

Das Umsetzungsprodukt verläßt den Reaktor 2 über Leitung 3 und wird Heißabscheider 4 zugeführt, in welchem unter Prozeßdruck und bei 460 °C die Abtrennung der unter den herrschenden Bedingungen flüchtigen Produkte von den festen bzw. flüssigen Umsetzungsprodukten erfolgt.The reaction product leaves the reactor 2 via line 3 and is fed to the hot separator 4, in which, under process pressure and at 460 ° C., the products volatile under the prevailing conditions are separated from the solid or liquid reaction products.

Diese flüchtigen Produkte werden über Leitung 4a über Kopf abgezogen und in bekannter Weise weiter aufgearbeitet. Die festen und flüssigen Reaktionsprodukte werden nach Entspannung auf Atmosphärendruck über Leitung 5 in den Vakuumschneckenverdampfer 7 mit integrierter Verdichtungszone 19 eingespeist.These volatile products are withdrawn overhead via line 4a and processed further in a known manner. The solid and liquid reaction products are released into atmospheres after relaxation pressure is fed via line 5 into the vacuum screw evaporator 7 with integrated compression zone 19.

Hierbei erfolgt der Eintritt in den Vakuumschneckenverdampfer von unten her in den Flüssigraum, um damit einen Abschluß des Zulaufstromes der Produkte aus dem Heißabscheider zu der Vakuumverdampfungszone zu bekommen. Als Förderorgan für den Zulaufstrom wird ein zwangsförderndes Pumpensystem 6, welches gleichzeitig als Dosiereinheit dient, eingesetzt.In this case, the entry into the vacuum screw evaporator takes place from below into the liquid space in order to thereby conclude the feed flow of the products from the hot separator to the vacuum evaporation zone. A positive-conveying pump system 6, which also serves as a metering unit, is used as the conveying element for the feed stream.

Über Vakuumleitung 14 wird in der Schneckenmaschine 7, die mit einer Doppelschnecke ausgerüstet ist, ein Unterdruck von 0,1 bar erzeugt. Der eingesetzte Hydrierrückstand, der über Stutzen 8 der Schneckenmaschine 7 zugeführt wird, enthielt 0,5 t Öl mit einem Siedebeginn von 325 °C oder darüber, 0,15 t höhermolekulare Komponenten, die zu etwa 0,1 t als Asphaltene und zu etwa 0,05 t als Präasphaltene bestimmt wurden sowie 0,35 t anorganische Komponenten, die sich aus 0,24 t Asche und 0,11 t unumgesetzter Kohle zusammensetzen. Der Ascheanteil wurde zu 32 Gew.-% aus Si02, zu 26 Gew.-% aus A1203, zu 25 Gew.-% aus Fe203 und zu 17 Gew.-% aus sonstigen Komponenten bestehend bestimmt.A vacuum of 0.1 bar is generated in the screw machine 7, which is equipped with a twin screw, via a vacuum line 14. The hydrogenation residue used, which is fed via nozzle 8 to the screw machine 7, contained 0.5 t of oil with a boiling point of 325 ° C. or above, 0.15 t of higher molecular components, which were about 0.1 t as asphaltenes and about 0 , 05 t were determined as pre-asphaltenes, and 0.35 t of inorganic components composed of 0.24 t of ash and 0.11 t of unreacted coal. The ash content was determined to be 32% by weight of SiO 2 , 26% by weight of A1 2 0 3 , 25% by weight of Fe 2 0 3 and 17% by weight of other components.

Die Destillatabtrennung erfolgte bei dem Druck von 0,1 bar, wobei der Hydrierrückstand in der Vakuumdoppelschneckenmaschine 7 während der Destillatabtrennung von 350 auf 450 °C aufgeheizt wurde. Es verdampften 0,40 t an destillierfähigen Komponenten des Ölanteils, die über Stutzen 9 aus der Verdampfungszone 18 und nach nicht dargestellter Abkühlung über Leitung 10 und über Kondensatbehälter 11 mittels Leitung 13 abgezogen wurden. Die nichtkondensierten Anteile wurden über Kondensatbehälter 11 mittels Leitung 12 abgezogen.The distillate was separated off at the pressure of 0.1 bar, the hydrogenation residue in the vacuum twin-screw machine 7 being heated from 350 to 450 ° C. during the distillate separation. It evaporated 0.40 t of distillable components of the oil portion, which were withdrawn via connection 9 from the evaporation zone 18 and after cooling, not shown, via line 10 and via condensate container 11 by means of line 13. The uncondensed portions were drawn off via condensate container 11 by means of line 12.

Der Erweichungspunkt des Rückstandes nach Durchlaufen der Verdampfungszone betrug 180 °C. Die Viskosität desselben Rückstandes bei 250 °C wurde zu 1500 mPas bestimmt.The softening point of the residue after passing through the evaporation zone was 180 ° C. The viscosity of the same residue at 250 ° C was determined to be 1500 mPas.

Die über Leitung 13 abgezogenen destillierbaren Bestandteile können als wertvolle Anreibeölkomponenten in die Hydrierung zurückgeführt werden.The distillable constituents drawn off via line 13 can be returned to the hydrogenation as valuable grinding oil components.

Die Verdampfungszone ist von der Austragszone durch eine maschinentechnische Kompressionsstufe 19 getrennt, die durch eine geeignete Auslegung der Schnecke und die Anordnung geeigneter Schneckenelemente in diesem Bereich in bekannter Weise realisiert wird. Hierdurch erfolgt eine Verdichtung des neben anorganischen Bestandteilen und höhermolekularen Zwischenprodukten nur noch 0,1 t Restöl enthaltenden Rückstandes, bevor dieser über Stutzen 14 und Leitung 15 auf ein Kühlband 16 mit anschließender Granuliervorrichtung 17 gegeben wird.The evaporation zone is separated from the discharge zone by a mechanical compression stage 19, which is realized in a known manner by suitable design of the screw and the arrangement of suitable screw elements in this area. This results in a compression of the residue, which contains only 0.1 t of residual oil, in addition to inorganic constituents and higher molecular weight intermediate products, before this residue is fed via connecting piece 14 and line 15 to a cooling belt 16 with subsequent granulating device 17.

Die befürchteten Koksansätze am Schneckenvortrieb in der Ausdampfzone wurden nicht beobachtet. Auftretende Verkrustungen im Bereich des Abzugsstutzens 14 wurden mittels einer Kratzvorrichtung entfernt.The feared coke deposits on the screw jack in the evaporation zone were not observed. Any incrustations in the area of the discharge nozzle 14 were removed by means of a scratching device.

Die Beheizung der Schneckenmaschine erfolgte über eine Mantelbeheizung der Schneckenmaschine mittels überhitztem Dampf.The screw machine was heated by means of jacket heating of the screw machine using superheated steam.

In technisch äquivalenter Weise kann die Beheizung aber auch mittels elektrisch beheizter Heizbacken oder durch Induktionsheizung oder bei Mantelbeheizung durch Rauchgas oder 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 flue gas or heat transfer oils.

Claims (7)

1. Verfahren zur Aufarbeitung von Rückständen der Kohlehydrierung durch Vakuumdestillation, dadurch gekennzeichnet, daß der Hydrierrückstand in einer ein- oder mehrwelligen Schneckenmaschine einer Destillation unter vermindertem Druck unterworfen wird, die entstehenden Gase und Dämpfe abgezogen werden und der nicht verdampfte Rest in eine Kühl- oder Granuliervorrichtung eingebracht wird.1. A process for working up residues of coal hydrogenation by vacuum distillation, characterized in that the hydrogenation residue is subjected to distillation under reduced pressure in a single- or multi-shaft screw machine, the resulting gases and vapors are drawn off and the unevaporated residue in a cooling or Granulating device is introduced. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Destillation bei Drücken von 0,01 bis 0,6 bar, vorzugsweise 0,02 - 0,1 bar erfolgt.2. The method according to claim 1, characterized in that the distillation is carried out at pressures of 0.01 to 0.6 bar, preferably 0.02 - 0.1 bar. 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß über die Länge der Schneckenmaschine vom Eintritt zum Austritt des Hydrierrückstandes der Druck von 0,6, vorzugsweise 0,1 bar auf 0,01, vorzugsweise auf 0,02 bar abfällt.3. The method according to claim 2, characterized in that the pressure drops from 0.6, preferably 0.1 bar to 0.01, preferably to 0.02 bar over the length of the screw machine from the inlet to the outlet of the hydrogenation residue. 4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Destillation bei Temperaturen von 200 - 400 °C, vorzugsweise 250 bis 350 °C erfolgt.4. The method according to any one of claims 1 to 3, characterized in that the distillation is carried out at temperatures from 200 to 400 ° C, preferably 250 to 350 ° C. 5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß über die Länge der Schneckenmaschine vom Eintritt zum Austritt des Hydrierrückstandes die Temperatur von 200, vorzugsweise 250 °C auf 400, vorzugsweise 350 °C ansteigt.5. The method according to claim 4, characterized in that the temperature increases from 200, preferably 250 ° C to 400, preferably 350 ° C over the length of the screw machine from the inlet to the outlet of the hydrogenation residue. 6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Eintritt des flüssigen Hydrierrückstandes in die Schneckenmaschine (7) über ein zwangsförderndes Pumpensystem (6) von unten in den Flüssigraum erfolgt.6. The method according to any one of claims 1 to 5, characterized in that the entry of the liquid hydrogenation residue into the screw machine (7) via a positive pump system (6) from below into the liquid space. 7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Schneckenmaschine (7) eine Verdampfungszone (18) aufweist, an die sich eine maschinentechnische Kompressionsstufe (19) anschließt.7. The method according to any one of claims 1 to 6, characterized in that the screw machine (7) has an evaporation zone (18), which is followed by a mechanical compression stage (19).
EP84112308A 1983-10-15 1984-10-12 Process for upgrading coal hydrogenation residues Ceased EP0138215A3 (en)

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DE3337624 1983-10-15
DE19833337624 DE3337624A1 (en) 1983-10-15 1983-10-15 METHOD FOR PROCESSING RESIDUES IN CARBOHYDRATION

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GB2277527A (en) * 1993-03-27 1994-11-02 C G E James Birks Limited Organic waste treatment method and apparatus

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DE3829986A1 (en) * 1988-09-03 1990-03-15 Enka Ag Process for increasing the mesophase content in pitch

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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
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DE3227896A1 (en) * 1982-07-26 1984-01-26 Peter 7869 Holzinshaus Voelskow Process for thermal treatment, in particular low-temperature carbonisation, of organic wastes, and plant for carrying out the process

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FR550217A (en) * 1921-05-17 1923-03-01 Plauson S Parent Company Ltd Improvements in the distillation of wood, shale or similar materials
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
DE3227896A1 (en) * 1982-07-26 1984-01-26 Peter 7869 Holzinshaus Voelskow Process for thermal treatment, in particular low-temperature carbonisation, of organic wastes, and plant for carrying out the process

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Publication number Priority date Publication date Assignee Title
GB2277527A (en) * 1993-03-27 1994-11-02 C G E James Birks Limited Organic waste treatment method and apparatus

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CA1236418A (en) 1988-05-10
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DD224609A5 (en) 1985-07-10

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