EP0138213A2 - Pyrolysis of coal hydrogenation residues - Google Patents

Pyrolysis of coal hydrogenation residues Download PDF

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Publication number
EP0138213A2
EP0138213A2 EP84112303A EP84112303A EP0138213A2 EP 0138213 A2 EP0138213 A2 EP 0138213A2 EP 84112303 A EP84112303 A EP 84112303A EP 84112303 A EP84112303 A EP 84112303A EP 0138213 A2 EP0138213 A2 EP 0138213A2
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Prior art keywords
hydrogenation
screw machine
smoldering
residue
bar
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German (de)
French (fr)
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EP0138213A3 (en
EP0138213B1 (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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B7/00—Coke ovens with mechanical conveying means for the raw material inside the oven
    • C10B7/10—Coke ovens with mechanical conveying means for the raw material inside the oven with conveyor-screws

Definitions

  • coal is hydrogenated by reaction with hydrogen at temperatures of 250-550 ° 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 1920-1945.
  • the hydrogenation technologies according to BERGIUS-PIER and POTT-BROCHE are to be mentioned as basic processes.
  • the oils obtained can be used as grinding oils or grinding oil components for the coal. Smoldering was carried out in ball ovens or screw ovens. During the smoldering process, even the per se vaporizable oils are broken down pyrolytically, so that there is a loss of valuable hydrogenation products.
  • the evaporable oils can be removed by vacuum distillation of the hydrogenation residue.
  • the oils obtained are high-quality rubbing oils or can be further hydrated under relatively mild conditions. However, handling the vacuum residue poses considerable problems. The discharge from the vacuum is particularly effective umkolonne and the transport for further processing extremely difficult due to the high toughness of the highly solids-enriched material.
  • the object of the present invention is to overcome these difficulties and to improve the overall liquid product yield of the process. According to the invention, this is done by subjecting the residue of the carbon hydrogenation to distillation under reduced pressure in a single- or multi-shaft screw machine, in this case the evaporable components are drawn off and the remaining material is then smelted in the screw machine.
  • the hydrogenation residue which constantly increases its viscosity during the distillation and smoldering, is continuously circulated by screws and thereby passed through the distillation zone and the smoldering zone of the screw machine, the evaporable constituents first being withdrawn, then the volatile constituents obtainable by pyrolysis.
  • 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 carried out on a technical scale since the beginning ten coal hydrogenation, the difficulties associated with oil separation were known, 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 0.6 bar preferably 0.02 to 0.1 bar
  • the pressure drops from 0.6, preferably 0.1 bar to 0.01, preferably 0.02, 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 over the length of the screw machine from the entry to the exit of the hydrogenation residue from 200, preferably 250 ° C to 400, preferably 350 ° C under constant or falling over the length of the screw machine pressure. 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.
  • the non-evaporated material is heated to higher temperatures, preferably 350-600 ° C., and smelted at these temperatures, 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 resulting sulfur fumes are extracted separately from the oil vapors.
  • the resulting coke can finally z. B. can be used as fuel. 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 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 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.
  • 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. 0.40 t of distillable components of the oil portion evaporated, which were drawn off via the connecting pieces 9 from the evaporation zone 18 and, after cooling (not shown), via line 10 and via condensate container 13 by means of line 15.
  • the softening point of the residue after passing through the evaporation zone 18 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 15 can be returned to the hydrogenation as valuable grinding oil components.
  • Evaporation zone 18 and smoldering zone 19 are separated by a mechanical compression stage 11, 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 it enters the smoldering zone 19 and is heated to 600 ° C. here.
  • a mechanical compression stage 11 which is realized in a known manner by suitable design of the screw and the arrangement of suitable screw elements in this area.
  • the residue after the smoldering consisted of 87% by weight of inorganic components and 13% by weight of other residue components, in particular coke-like products, and was drawn off after passing through a compression zone 12 via connection piece 20 and line 21.
  • the screw machine was heated by means of jacket heating of the screw machine using superheated steam in the evaporation zone and flue gas in the smoldering zone.
  • 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

Bei diesem Verfahren zur Schwelung von Ruckständen der Kohlehydrierung erfolgt zunächst eine Vakuumdestillation des Hydrierrückstandes. Zwecks verbesserter Handhabung derartiger Rückstände insbesondere beim Austragen aus der Vakuumkolonne sowie dem Transport zur Weiterverarbeitung wird der Hydrierrückstand in einer ein- oder mehrwelligen Schneckenmaschine einer Destillation unter vermindertem Druck unterworfen, die entstehenden Gase und Dämpfe werden abgezogen und der nicht verdampfte Rest wird in der Schneckenmaschine einer Schwelung unterzogen.In this process for smoldering residues of the coal hydrogenation, the hydrogenation residue is first vacuum distilled. To improve the handling of such residues, particularly when discharging them from the vacuum column and for transport for further processing, 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 becomes one in the screw machine Subjected to smoldering.

Description

Zur Hydrierung von Kohle sind Verfahren bekannt, bei denen Kohle durch Reaktion mit Wasserstoff bei Temperaturen von 250 - 550 °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 - 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 250-550 ° 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 1920-1945. 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 unter anderem Schwelung oder Vakuumdestillation angewandt. Die gewonnenen Öle können als Anreibeöle bzw. Anreibölkomponenten für die Einsatzkohle verwendet werden. Die Schwelung wurde in Kugelöfen oder Schneckenöfen vorgenommen. Während der Schwelung erfolgt ein pyrolytischer Abbau selbst der an sich verdampfbaren Öle, so daß ein Verlust an wertvollen Hydrierprodukten eintritt. Durch Vakuumdestillation des Hydrierrückstandes können die verdampfbaren Öle abgetrennt werden. Die dabei gewonnenen Öle stellen hochwertige Anreibeöle 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.To remove these vaporizable oil admixtures, smoldering or vacuum distillation were used, among other things. The oils obtained can be used as grinding oils or grinding oil components for the coal. Smoldering was carried out in ball ovens or screw ovens. During the smoldering process, even the per se vaporizable oils are broken down pyrolytically, so that there is a loss of valuable hydrogenation products. The evaporable oils can be removed by vacuum distillation of the hydrogenation residue. The oils obtained are high-quality rubbing oils or can be further hydrated under relatively mild conditions. However, handling the vacuum residue poses considerable problems. The discharge from the vacuum is particularly effective umkolonne and the transport for further processing 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 und die Gesamtflüssigproduktausbeute des Verfahrens zu verbessern. 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 anschließend in der Schneckenmaschine geschwelt wird. Der während der Destillation und Schwelung ständig seine Viskosität erhöhende Hydrierrückstand wird durch Schnecken laufend umgewälzt und dabei durch die Destillationszone und die Schwelzone der Schneckenmaschine geführt, wobei ihm zunächst die verdampfbaren Bestandteile, dann die durch Pyrolyse gewinnbaren flüchtigen Bestandteile entzogen werden.The object of the present invention is to overcome these difficulties and to improve the overall liquid product yield of the process. According to the invention, this is done by subjecting the residue of the carbon hydrogenation to distillation under reduced pressure in a single- or multi-shaft screw machine, in this case the evaporable components are drawn off and the remaining material is then smelted in the screw machine. The hydrogenation residue, which constantly increases its viscosity during the distillation and smoldering, is continuously circulated by screws and thereby passed through the distillation zone and the smoldering zone of the screw machine, the evaporable constituents first being withdrawn, then the volatile constituents obtainable by pyrolysis.

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 carried out on a technical scale since the beginning ten coal hydrogenation, the difficulties associated with oil separation were known, 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 0,6 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 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 0.6 bar, preferably 0.02 to 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, 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 Hydrierrückstand hohe, Veränderungen begünstigende Temperaturen annimmt, verkürzt und die weitere Verarbeitung des von den flüchtigen Bestandteilen befreiten Rückstandes erleichtert.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 over the length of the screw machine from the entry to the exit of the hydrogenation residue from 200, preferably 250 ° C to 400, preferably 350 ° C under constant or falling over the length of the screw machine pressure. 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.

Das nicht verdampfte Gut wird nach der Destillation auf höhere Temperaturen, vorzugsweise 350 - 600 °C erhitzt und bei diesen Temperaturen, 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 entstehenden Schweldämpfe werden getrennt von den Öldämpfen abgezogen. Der anfallende Koks schließlich kann z. B. als Brennmaterial eingesetzt werden. Nach dem erfindungsgemäßen Verfahren können Rückstände bis zu einer Endviskosität von etwa 2000 mPas (250 °C) bei der Destillatabtrennung gehandhabt werden.After the distillation, the non-evaporated material is heated to higher temperatures, preferably 350-600 ° C., and smelted at these temperatures, 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 resulting sulfur fumes are extracted separately from the oil vapors. The resulting coke can finally z. B. can be used as fuel. 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 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. 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 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 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 Verdichtungs- und Schwelungszone eingespeist.These volatile products are withdrawn overhead via line 4a and processed further in a known manner. After relaxation to atmospheric pressure, the solid and liquid reaction products are fed via line 5 into the vacuum screw evaporator 7 with an integrated compression and smoldering zone.

Hierbei erfolgt der Eintritt in den Vakuumschneckenverdampfer 7 von unten her über Stutzen 8 in den Flüssigraum, um damit einen Abschluß des Zulaufstromes der Produkte aus dem Heißabscheider zu der Vakuumverdampfungszone 18 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 7 takes place from below via connecting piece 8 into the liquid space, in order to thereby conclude the feed flow of the products from the hot separator to the vacuum evaporation zone 18. 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 zusammensetzten. 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 die Stutzen 9 aus der Verdampfungszone 18 und nach nicht dargestellter Abkühlung über Leitung 10 und über Kondensatbehälter 13 mittels Leitung 15 abgezogen wurden.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. 0.40 t of distillable components of the oil portion evaporated, which were drawn off via the connecting pieces 9 from the evaporation zone 18 and, after cooling (not shown), via line 10 and via condensate container 13 by means of line 15.

Der Erweichungspunkt des Rückstandes nach Durchlaufen der Verdampfungszone 18 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 18 was 180 ° C. The viscosity of the same residue at 250 ° C was determined to be 1500 mPas.

Die über Leitung 15 abgezogenen destillierbaren Bestandteile können als wertvolle Anreibeölkomponenten in die Hydrierung zurückgeführt werden.The distillable constituents drawn off via line 15 can be returned to the hydrogenation as valuable grinding oil components.

Verdampfungszone 18 und Schwelzone 19 sind durch eine maschinentechnische Kompressionsstufe 11 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 in die Schwelzone 19 eintritt und hier auf 600 °C aufgeheizt wird. In der Schwelzone 19 werden weitere 0,2 t Destillat gewonnen, das über die Stutzen 16 und Leitung 17 aus der Schwelzone abgezogen wird und ebenfalls als wertvolle Anreibeölkomponente in die Hydrierung zurückgeführt werden kann.Evaporation zone 18 and smoldering zone 19 are separated by a mechanical compression stage 11, 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 it enters the smoldering zone 19 and is heated to 600 ° C. here. In the smoldering zone 19 another 0.2 t Distillate obtained, which is withdrawn from the smoldering zone via the connection 16 and line 17 and can also be recycled as a valuable grinding oil component into the hydrogenation.

Der Rückstand nach der Schwelung bestand zu 87 Gew.-% aus anorganischen Komponenten und zu 13 Gew.-% aus sonstigen Rückstandsbestandteilen, insbesondere koksartigen Produkten und wurde nach Durchlaufen einer Verdichtungszone 12 über Stutzen 20 und Leitung 21 abgezogen.The residue after the smoldering consisted of 87% by weight of inorganic components and 13% by weight of other residue components, in particular coke-like products, and was drawn off after passing through a compression zone 12 via connection piece 20 and line 21.

Die befürchteten Koksansätze am Schneckenvortrieb in der Schwelzone wurden nicht beobachtet.The feared coke deposits on the screw jack in the smoldering zone were not observed.

Die Beheizung der Schneckenmaschine erfolgte über eine Mantelbeheizung der Schneckenmaschine mittels überhitztem Dampf in der Ausdampfzone und Rauchgas in der Schwelzone.The screw machine was heated by means of jacket heating of the screw machine using superheated steam in the evaporation zone and flue gas in the smoldering zone.

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)

1. Verfahren zur Schwelung von Rückständen der Kohlehydrierung, 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 der Schneckenmaschine einer Schwelung unterworfen wird.1. A process for smoldering residues of coal hydrogenation, 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 is subjected to smoldering in the screw machine . 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Destillation bei Drücken von 0,01 - 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 - 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 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 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 die Schwelung bei Temperaturen von 350 bis 600 °C erfolgt.6. The method according to any one of claims 1 to 5, characterized in that the smoldering takes place at temperatures of 350 to 600 ° C. 7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Schwelung bei Atmosphärendruck erfolgt.7. The method according to any one of claims 1 to 6, characterized in that the smoldering takes place at atmospheric pressure. 8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der Eintritt des flüssigen Hydrierrückstandes in die Schneckenmaschine (7) über ein zwangsförderndes Pumpensystem (6) von unten her in den Flüssigraum erfolgt.8. The method according to any one of claims 1 to 7, 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. 9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Schneckenmaschine (7) eine Verdampfungszone (18) und eine Schwelzone (19) aufweist, die durch eine maschinentechnische Kompressionsstufe (11) voneinander getrennt sind.9. The method according to any one of claims 1 to 8, characterized in that the screw machine (7) has an evaporation zone (18) and a smoldering zone (19) which are separated from one another by a mechanical compression stage (11).
EP84112303A 1983-10-15 1984-10-12 Pyrolysis of coal hydrogenation residues Expired EP0138213B1 (en)

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DE3337622 1983-10-15
DE19833337622 DE3337622A1 (en) 1983-10-15 1983-10-15 METHOD FOR SMOKING RESIDUES OF CARBOHYDRATION

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EP0379705A1 (en) * 1988-12-28 1990-08-01 Apv Chemical Machinery Inc. An improved method of continously carbonizing a mixture of primarily organic waste material
GB2527830A (en) * 2014-07-03 2016-01-06 Dps Bristol Holdings Ltd Waste processing apparatus
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GB2527830A (en) * 2014-07-03 2016-01-06 Dps Bristol Holdings Ltd Waste processing apparatus
US10421919B2 (en) 2014-07-03 2019-09-24 Pyrocore S.A. Gasifier

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EP0138213A3 (en) 1986-10-01
EP0138213B1 (en) 1989-01-18
DE3476219D1 (en) 1989-03-02
DD232719A5 (en) 1986-02-05
DE3337622A1 (en) 1985-04-25
US4584060A (en) 1986-04-22
CA1226840A (en) 1987-09-15

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