WO1983001626A1 - Method for the treatment of residues obtained from hydrogenation of coal - Google Patents

Method for the treatment of residues obtained from hydrogenation of coal Download PDF

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Publication number
WO1983001626A1
WO1983001626A1 PCT/DE1982/000200 DE8200200W WO8301626A1 WO 1983001626 A1 WO1983001626 A1 WO 1983001626A1 DE 8200200 W DE8200200 W DE 8200200W WO 8301626 A1 WO8301626 A1 WO 8301626A1
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WIPO (PCT)
Prior art keywords
gasification
coal
hydrogenation
residues
mixture
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PCT/DE1982/000200
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German (de)
French (fr)
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Gesellschaft Für Kohleverflüssigung Mbh Gfk
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WÜRFEL, Helmut
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Priority to AU89963/82A priority Critical patent/AU8996382A/en
Publication of WO1983001626A1 publication Critical patent/WO1983001626A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • C10J3/30—Fuel charging devices
    • 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
    • C10G1/006—Combinations of processes provided in groups C10G1/02 - C10G1/08
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water

Definitions

  • the invention relates to a method for processing residues from the hydrogenation of coal.
  • the hydrogenation product obtained is separated into a gas phase and a liquid phase in a hot separator connected downstream of the hydrogenation reactor.
  • the liquid phase also contains asphaltenes, but also valuable distillate oils, which are separated as much as possible from the hydrogenation residue and used to mix the coal.
  • it has already been proposed to gasify the residue in a dust gasification plant in the presence of oxygen and water vapor, essentially to carbon monoxide and hydrogen.
  • the present invention has for its object to develop a simple and economical process for the treatment of residues from coal hydrogenation by gasification, which avoids these disadvantages.
  • This object is achieved in that the gasification of the residues in a countercurrent shaft carburetor takes place, the residues before the gasification are mixed with solids whose softening point is above the softening point of the residues, the mixture is at least partially briquetted and at least some of the heavy hydrocarbons contained in the gasification product are separated and used to mix the fresh coal to be hydrogenated becomes.
  • the ash When the briquetted mixture is gasified in the countercurrent shaft gasifier, the ash accumulates in a dry form, so that there can be no damage to the interior of the gasifier, such as is caused by the liquid, very corrosive ash.
  • Distillate oils or heavy hydrocarbons remaining in the hydrogenation residue are expelled from the heating briquettes in the gasifier, separated from the gasification product and used again for mixing the fresh coal to be hydrogenated.
  • the gas generated in the counter-current shaft gasifier can, at least in part, be converted to hydrogen, which is returned to the hydrogenation system as hydrogenation hydrogen.
  • coal is used as a solid, generally more gas is generated than is required to obtain hydrogenation hydrogen.
  • ash from the countercurrent shaft gasifier is used as a solid; the amount of coal and ash used can largely adapt the amount of gas generated to the requirements become.
  • H 2 O is therefore expediently injected in the form of water mist, so that, compared to the injection of steam, additional heat of evaporation is removed from the process and correspondingly less H 2 O is required. Waste water, for example from the gasification plant itself, can be used for the injection.
  • sulfur-binding substances for example lime, are already mixed into the mixture of hydrogenation residue and solids to be briquetted.
  • these are, according to a further feature of the invention, treated with an extractant, advantageously with a Koh lenwassersfoff fraction with a boiling end up to about 200 C, which is in the upper region of the Counterflow shaft gasifier is initiated.
  • the action of the supercritical extractant is based essentially on its high density, which is up to 40% of the density of the extractant in the liquid state, so that a particularly large amount of distillate oils can be absorbed by the extractant.
  • Lighter hydrocarbons, heavier hydrocarbons and thick tar are separated separately from the product gas. Some of the lighter hydrocarbons are called again. Extractant introduced into the gasification reactor, while the heavier hydrocarbons, at least partially, possibly with the thick tar, are returned to the hydrogenation system for mixing the fresh coal to be hydrogenated. Further explanations of the invention can be found in the exemplary embodiment shown schematically in the figure.
  • Coal mixed with grinding oil and a hydrogenation catalyst to form a slurry is pumped via line 1 at a pressure of approx. 200 bar and a temperature of approx. 420.degree. C. into a hydrogenation reactor 2 and in the presence of hydrogen supplied via line 3 at a temperature of approx 470 ° C hydrogenated.
  • the hydrogenation product withdrawn from the hydrogenation reactor 2 is subjected to a phase separation in a hot separator 4.
  • the vapor phase of the hydrogenation product consists essentially of hydrogen, other gases and vapors. It is withdrawn via a line 6 at the head of the hot separator 4.
  • the liquid phase also contains bitumen and solids, such as unused coal, ash and catalyst particles.
  • This bottom phase is drawn off at the bottom of the hot separator 4, cooled in a cooler 8, for example by giving off heat to fresh coal pulp or hydrogen hydrogen, and then expanded via a relaxation valve 10 into a mixing chamber 11.
  • the gases released during the expansion are withdrawn from the mixing chamber 11 via a line 12.
  • the remaining hydrogenation residue is diluted with naphtha supplied via a line 13 and which is removed from the cold separator from the hydrogenation system and then spun in a centrifuge 15.
  • the visual residue in which there is a residual portion of distillate oil and naphtha, coal or ash or coal and ash is added via a line 16, the mixture is mixed in a mixer 17 and then briquetted in a briquetting device 18.
  • the briquettes are passed through a lock 25 to a counter-current shaft gasifier 26 and gasified in the presence of O 2 and H 2 O.
  • O 2 is blown in via a line 27 and H 2 O is injected in the form of water via a line 28.
  • a supercritical extractant preferably a hydrocarbon fraction with a boiling end of up to about 200 ° C, is gasified via a line 29 at a temperature of about 400 ° C and a pressure of about 25 bar in the upper region of the counterflow shaft 26 initiated.
  • a low-boiling hydrocarbon fraction In a separating stage 30 downstream of the countercurrent chess gasifier 26, a low-boiling hydrocarbon fraction, the heavier hydrocarbons and thick tar, which can still contain dust, are separated off from the withdrawn product gases.
  • Part of the low-boiling hydrocarbon fraction is returned to the countercurrent shaft gasifier 26 as an extractant.
  • the heavier hydrocarbons are used as rubbing oil for the hydrogenation Fresh coal mixed in.
  • the thick tar is again added to the centrifugal residue. However, it can also be used entirely as a rubbing oil.
  • the processing of these products can also be carried out in parts of the plant which are required for the hydrogenation anyway.
  • the extraction agent and the heavy hydrocarbons can also be separated in the distillation 20.

Abstract

In a method for the treatment of residual material from hydrogenation of coal (2) gasified in presence of O2?, optionally in presence of H2?O as a gasifier agent, the gasification of the residual material is carried out in a counter-current gasification well (26). Before gasification, the residual material is mixed with solid materials (15) of which the softening point is above of that of the residual materials, and at least part of the mixture (18) is agglomerated. At least a portion of heavy hydrocarbons contained in the gasification product is separated and is used for conditioning fresh coal to be hydrogenated. As solid materials, coal and/or slags are introduced, preferably slags from the gasification well itself; their proportion is established in relation to the quantitative requirements of product gas.

Description

Verfahren zur Aufbereitung von Rückständen aus der Kohlehydr ierung Process for the treatment of residues from coal hydration
Die Erfindung betrifft ein Verfahren zur Aufbereitung von Rückständen aus der Kohlehydrierung.The invention relates to a method for processing residues from the hydrogenation of coal.
Bei der Hydrierung von Kohle in Gegenwart von Wasserstoff und einem Katalysator wird das anfallende Hydrierprodukt in einem dem Hydrierreak tor nachgeschalteten Heißabscheider in eine Gasphase und eine Flüssigphase get rennt.In the hydrogenation of coal in the presence of hydrogen and a catalyst, the hydrogenation product obtained is separated into a gas phase and a liquid phase in a hot separator connected downstream of the hydrogenation reactor.
In der Flüssigphase sind neben Feststoffen wie unverbrauchte Kohle, Asche und Katalysatorteilchen noch Asphaltene, aber auch wertvolle Destillatöle enthalten, die möglichst weitgehend vom Hydrierrückstand abgetrennt und zum Anmischen der Kohle verwendet werden. Zur Aufbereitung dieses Hydrierrückstandes wurde bereits vorgeschlagen, den Rückstand in einer Staubvergasungsanlage in Gegenwart von Sauerstoff und Wasserdampf im wesentlichen zu Kohlenmonoxid und Wasserstoff zu vergasen.In addition to solids such as unused coal, ash and catalyst particles, the liquid phase also contains asphaltenes, but also valuable distillate oils, which are separated as much as possible from the hydrogenation residue and used to mix the coal. To prepare this hydrogenation residue, it has already been proposed to gasify the residue in a dust gasification plant in the presence of oxygen and water vapor, essentially to carbon monoxide and hydrogen.
Nachteilig ist dabei jedoch, daß immer noch Destillatöle im Rückstand verbleiben, die mit diesem vergast und somit zerstört werden. Es wird daher angestrebt, diese Destillatöle möglichst vollständig aus dem Rückstand abzutrennen. Dafür ist bisher jedoch noch kein befriedigendes Verfahren bekannt. Bei der Vergasung des Hydrierrückstandes in einer Staubvergasungsan l age ergeben sich zudem erhebliche Schwierigkeiten durch die in flüssiger Form anfallende Asche. Die Asche ist in flüssiger Form aufgrund der in ihr enthaltenen Hydrierkatalysatoren sehr korrosiv und kann daher die I nnenausk le i düng des Vergasers stark angreifen.However, it is disadvantageous that distillate oils still remain in the residue, which are gasified with it and thus destroyed. The aim is therefore to remove these distillate oils as completely as possible from the residue. To date, however, no satisfactory method has been known for this. When gasifying the hydrogenation residue in a dust gasification system, there are also considerable difficulties due to the ash that is obtained in liquid form. The ash in liquid form is very corrosive due to the hydrogenation catalysts it contains and can therefore severely attack the inside of the carburettor.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein einfaches und wirtschaftliches Verfahren zur Aufbereitung von Rückständen aus der Kohlehydrierung durch Vergasung zu entwickeln, das diese Nachteile vermeidet.The present invention has for its object to develop a simple and economical process for the treatment of residues from coal hydrogenation by gasification, which avoids these disadvantages.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß die Vergasung der Rückstände in einem Gegenstrom-Schacht- vergaser erfolgt, wobei die Rückstände vor der Vergasung mit Feststoffen, deren Erweichungspunkt oberhalb des Erweichungspunktes der Rückstände liegt, vermischt werden, die Mischung zumindest teilweise brikettiert wird und wobei zumindest ein Teil der im Vergasungsprodukt enthaltenen schweren Kohlenwasserstoffe abgetrennt und zum Anmischen der zu hydrierenden Frischkohle verwendet wird.This object is achieved in that the gasification of the residues in a countercurrent shaft carburetor takes place, the residues before the gasification are mixed with solids whose softening point is above the softening point of the residues, the mixture is at least partially briquetted and at least some of the heavy hydrocarbons contained in the gasification product are separated and used to mix the fresh coal to be hydrogenated becomes.
Bei der Vergasung der brikettierten Mischung im Gegenstrom-Schachtvergaser fällt die Asche in trockener Form an, so daß es zu keinen Schäden an der Innenausk leidüng des Vergasers kommen kann, wie sie von der flüssigen, sehr korrosiven Asche hervorgerufen werden.When the briquetted mixture is gasified in the countercurrent shaft gasifier, the ash accumulates in a dry form, so that there can be no damage to the interior of the gasifier, such as is caused by the liquid, very corrosive ash.
Im Hydrierrückstand verbliebene Destillatöle bzw. schwere Kohlenwasserstoffe werden im Vergaser aus den sich erwärmenden Briketts abgetrieben, von dem Vergasungsprodukt abgetrennt und wieder zum Anmischen der zu hydrierenden Frischkohle verwendet.Distillate oils or heavy hydrocarbons remaining in the hydrogenation residue are expelled from the heating briquettes in the gasifier, separated from the gasification product and used again for mixing the fresh coal to be hydrogenated.
Es ist daher nicht mehr erforderlich, durch aufwendige Verfahren möglichst alle schweren Kohlenwasserstoffe aus dem Hydrierrückstand vor dessen Aufgabe in den Vergaser abzutrennen. Vielmehr kann ein Restgehalt an Destillatöl im Hydrierrückstand verbleiben, so daß weni - ger aufwendige Trennver fahren eingesetzt werden können.It is therefore no longer necessary to separate all heavy hydrocarbons from the hydrogenation residue into the carburetor before it is fed in, using complex processes. Rather, a residual distillate oil content can remain in the hydrogenation residue, so that less ger elaborate separation process can be used.
Die dem Hydrierrückstand vor der Brikettierung zugemischten Feststoffe verhindern, daß die Briketts bei Erwärmung fließen. Da ein relativ hoher Feststoffanteil von etwa 70 % notwendig ist, wird vorteilhaft Kohle als Feststoff eingesetzt. Das im Gegenst rom-Schacht vergaser erzeugte Gas kann, nach Reinigung und Abtrennung der kondensierbaren Kohlenwasserstoffe, zumindest teilweise zu Wasserstoff umgesetzt werden, der als Hydrierwasserstoff zur Hydrieranlage zurückgeführt wird.The solids mixed into the hydrogenation residue before briquetting prevent the briquettes from flowing when heated. Since a relatively high solid content of about 70% is necessary, coal is advantageously used as a solid. After cleaning and separating the condensable hydrocarbons, the gas generated in the counter-current shaft gasifier can, at least in part, be converted to hydrogen, which is returned to the hydrogenation system as hydrogenation hydrogen.
Wird Kohle als Feststoff eingesetzt, wird in der Regel wesentlich mehr Gas erzeugt als zur Gewinnung von Hydrierwasserstoff benötigt wird.If coal is used as a solid, generally more gas is generated than is required to obtain hydrogenation hydrogen.
Sofern keine wirtschaftliche Verwendung für das überschüssige Gas, insbesondere Methan, gegeben ist, wird gemäß einem weiteren Merkmal der Erfindung als Feststoff Asche aus dem Gegenstrom-Schachtvergaser eingesetzt, über die Anteile der eingesetzten Kohle und Asche kann die erzeugt.e Gasmenge weitgehend dem Bedarf angepaßt werden.If there is no economic use for the excess gas, in particular methane, according to a further feature of the invention, ash from the countercurrent shaft gasifier is used as a solid; the amount of coal and ash used can largely adapt the amount of gas generated to the requirements become.
Zur Kontrolle der Reaktions- und Aschetemperatur im Gegenstrom-Schachtvergaser muß in der Regel mehr H20 als für den Ver gasungsprozess eigentlich erforderlich ist, zugegeben werden. Zweckmäßigerweise w i rd daher das H2O in Form von Wassernebel eingedüst, so daß, im Vergleich zur Eindüsung von Dampf, dem Prozess zusätzlich Verdampfungswärme entzogen und entsprechend weniger H2O benötigt wird. Dabei kann zur Eindüsung ein Abwasser, beispielsweise aus der Vergasungsanlage selbst, verwendet werden.To control the reaction and ash temperature in the countercurrent shaft gasifier, more H 2 0 than usually is actually required for the gasification process. The H 2 O is therefore expediently injected in the form of water mist, so that, compared to the injection of steam, additional heat of evaporation is removed from the process and correspondingly less H 2 O is required. Waste water, for example from the gasification plant itself, can be used for the injection.
Um ein von Schwefelverbindungen weitgehend freies Produktgas zu erhalten, werden dem zu brikettierenden Gemisch aus Hydrierrückstand und Feststoffen bereits Schwefel b i ndende Stoffe, beispielsweise Kalk, zugemischt.In order to obtain a product gas largely free of sulfur compounds, sulfur-binding substances, for example lime, are already mixed into the mixture of hydrogenation residue and solids to be briquetted.
Zum Austreiben der im Hydrierrückstand enthaltenen schweren Kohlenwasserstoffe aus den sich erwärmenden Briketts werden diese, gemäß einem weiteren Merkmal der Erfindung, mit einem Extraktionsmittel, zweckmäßigerweise mit einer Koh lenwassersfoff-Fraktion mit einem Siedeende bis etwa 200 C, behandelt, das in den oberen Bereich des Gegenstrom-Schachtvergasers eingeleitet wird.To drive off the heavy hydrocarbons contained in the hydrogenation residue from the heating briquettes, these are, according to a further feature of the invention, treated with an extractant, advantageously with a Koh lenwassersfoff fraction with a boiling end up to about 200 C, which is in the upper region of the Counterflow shaft gasifier is initiated.
Die Wirkung des überkritischen Extraktionsmittels beruht im wesentlichen auf dessen hoher Dichte, die bis zu 40 % der Dichte des Extraktionsmittels im flüssigen Zustand beträgt, so daß eine besonders große Menge an Destillatölen von dem Extraktionsmittel aufgenommen werden kann. Aus dem Produktgas werden leichtere Kohlenwasserstoffe, schwerere Kohlenwasserstoffe und Dickteer separat abge trennt. Ein Teil der leichteren Kohlenwasserstoffe wird erneut als. Extraktionsmittel in den Vergasungsreaktor eingeleitet, während die schwereren Kohlenwasserstoffe, zumindest teilweise, ggf. mit dem Dickteer, in die Hydrieranlage zum Anmischen der zu hydrierenden Frischkohle zurückgeführt werden. Weitere Erläuterungen zu der Erfindung sind dem in der Figur schematisch dargestellten Aus führungsbeispiel zu entnehmen.The action of the supercritical extractant is based essentially on its high density, which is up to 40% of the density of the extractant in the liquid state, so that a particularly large amount of distillate oils can be absorbed by the extractant. Lighter hydrocarbons, heavier hydrocarbons and thick tar are separated separately from the product gas. Some of the lighter hydrocarbons are called again. Extractant introduced into the gasification reactor, while the heavier hydrocarbons, at least partially, possibly with the thick tar, are returned to the hydrogenation system for mixing the fresh coal to be hydrogenated. Further explanations of the invention can be found in the exemplary embodiment shown schematically in the figure.
Mit Anreiböl und einem Hydrierkatalysator zu einem Brei vermischte Kohle wird über eine Leitung 1 bei einem Druck von ca. 200 bar und einer Temperatur von ca. 420ºC in einen Hydrierreaktor 2 gepumpt und in Anwesenheit von über eine Leitung 3 zugeführtem Wasserstoff bei einer Temperatur von ca. 470ºC hydriert.Coal mixed with grinding oil and a hydrogenation catalyst to form a slurry is pumped via line 1 at a pressure of approx. 200 bar and a temperature of approx. 420.degree. C. into a hydrogenation reactor 2 and in the presence of hydrogen supplied via line 3 at a temperature of approx 470 ° C hydrogenated.
Das aus dem Hydrierreaktor 2 abgezogene Hydrierprodukt wird in einem Heißabscheider 4 einer Phasentrennung unterzogen. Die Dampfphase des Hydrierproduktes besteht im wesentlichen aus Wasserstoff, anderen Gasen und Dämpfen. Sie wird über eine Leitung 6 am Kopf des Heißabscheiders 4 abgezogen. Die flüssige Phase enthält neben wertvollen Destillatölen noch Bitumen und Feststoffe, beispielsweise unverbrauchte Kohle, Asche und Katalysatorteilchen. Diese Sumpfphase wird am Boden des Heißabscheiders 4 abgezogen, in einem Kühler 8 gekühlt, beispielsweise durch Wärmeabgabe an frischen Kohlebrei oder Hydrierwasserstoff, und anschließend über ein Entspannungsven til 10 in eine Mischkammer 11 entspannt. Die bei der Entspannung frei werdenden Gase werden über eine Leitung 12 aus der Mischkammer 11 abgezogen.The hydrogenation product withdrawn from the hydrogenation reactor 2 is subjected to a phase separation in a hot separator 4. The vapor phase of the hydrogenation product consists essentially of hydrogen, other gases and vapors. It is withdrawn via a line 6 at the head of the hot separator 4. In addition to valuable distillate oils, the liquid phase also contains bitumen and solids, such as unused coal, ash and catalyst particles. This bottom phase is drawn off at the bottom of the hot separator 4, cooled in a cooler 8, for example by giving off heat to fresh coal pulp or hydrogen hydrogen, and then expanded via a relaxation valve 10 into a mixing chamber 11. The gases released during the expansion are withdrawn from the mixing chamber 11 via a line 12.
Der verbleibende Hydrierrückstand wird mit über eine Leitung 13 zugeführtem Naphtha, das aus dem Kaltabschei der der Hydrieranlage entnommen wird, verdünnt und anschließend in einer Zentrifuge 15 geschleudert.The remaining hydrogenation residue is diluted with naphtha supplied via a line 13 and which is removed from the cold separator from the hydrogenation system and then spun in a centrifuge 15.
Der Dünnlauf der Zentrifuge 15, der bereits den größten Teil der im Hydrierrückstand enthaltenen Destillatöle enthält, wird über eine Leitung 19 in eine Destillation 20 gegeben und in Naphtha, Mitteldestillat und Anreiböl zerlegt, die getrennt über Leitungen 21, 22 bzw. 23 abgezogen werden.The thin barrel of the centrifuge 15, which already contains the majority of the distillate oils contained in the hydrogenation residue, is introduced into a distillation 20 via a line 19 and broken down into naphtha, middle distillate and grinding oil, which are drawn off separately via lines 21, 22 and 23.
Dem Seh leuder rücks tand, in dem ein Restanteil Destillatöl und Naphtha ist, wird über eine Leitung 16 Kohle oder Asche, oder Kohle und Asche zugegeben, die Mischung in einem Mischer 17 vermengt und anschließend in einer Brikettiereinrichtung 18 brikettiert. Die Briketts werden über eine Schleuse 25 einem Gegenst rom-Schacht vergaser 26 aufgegeben und in Gegenwart von O2 und H2O vergast. O2 wird über eine Leitung 27 eingeblasen und H2O über eine Leitung 28 in Form von Wasser eingedüst.The visual residue, in which there is a residual portion of distillate oil and naphtha, coal or ash or coal and ash is added via a line 16, the mixture is mixed in a mixer 17 and then briquetted in a briquetting device 18. The briquettes are passed through a lock 25 to a counter-current shaft gasifier 26 and gasified in the presence of O 2 and H 2 O. O 2 is blown in via a line 27 and H 2 O is injected in the form of water via a line 28.
Im oberen Bereich des Gegenstrom-Schachtvergasers 26 werden die im Seh Leuder rücks tand verbliebenen Kohlenwasserstoffe aus den sich erwärmenden Briketts ausgetrieben, bevor diese mit den Vergasungsmitteln reagieren. Zur Unterstützung dieses Prozesses wird über eine Leitung 29 ein überkritisches Extraktionsmittel, vorzugsweise eine Kohlenwasserstoff-Fraktion mit einem Siedeende bis etwa 200ºC, bei einer Temperatur von ca. 400ºC und einem Druck von ca. 25 bar in den oberen Bereich des Gegenst rom-Schacht vergasers 26 eingeleitet.In the upper area of the countercurrent shaft gasifier 26, the hydrocarbons remaining in the visible residue are expelled from the heating briquettes before they react with the gasifying agents. To support this process, a supercritical extractant, preferably a hydrocarbon fraction with a boiling end of up to about 200 ° C, is gasified via a line 29 at a temperature of about 400 ° C and a pressure of about 25 bar in the upper region of the counterflow shaft 26 initiated.
In einer dem Gegenstrom-Schach tvergaser 26 nachgeschalteten Trennstufe 30 werden aus den abgezogenen Produktgasen eine leicht siedende Kohlenwasserstoff-Fraktion, die schwereren Kohlenwasserstoffe sowie Dickteer, der noch Staub enthalten kann, abgetrennt.In a separating stage 30 downstream of the countercurrent chess gasifier 26, a low-boiling hydrocarbon fraction, the heavier hydrocarbons and thick tar, which can still contain dust, are separated off from the withdrawn product gases.
Ein Teil der Leicht siedenden Kohlenwasserstoff-Fraktion wird als Extraktionsmittel wieder in den Gegenstrom- Schachtvergaser 26 zurückgeführt. Die schwereren Kohlenwasserstoffe werden als Anreiböl der zu hydrierenden Frischkohle zugemischt. Der Dickteer wird erneut dem Schleuder rücks tand beigemengt. E r kann aber auch vollständig als Anreiböl mit verwendet werden.Part of the low-boiling hydrocarbon fraction is returned to the countercurrent shaft gasifier 26 as an extractant. The heavier hydrocarbons are used as rubbing oil for the hydrogenation Fresh coal mixed in. The thick tar is again added to the centrifugal residue. However, it can also be used entirely as a rubbing oil.
Da es sich bei den Produkten aus dem Gegenst rom-Schachtvergaser 26 um hydr i erkon forme Produkte handelt, kann die Aufbereitung dieser Produkte ggf. auch in Anlagenteilen, die für die Hydrierung ohnehin erforderlich sind, erfolgen. So kann beispielsweise die Trennung des Extraktionsmittels und der schweren Kohlenwasserstoffe auch in der Destillation 20 erfolgen. Since the products from the counter-current shaft gasifier 26 are hydrodynamic products, the processing of these products can also be carried out in parts of the plant which are required for the hydrogenation anyway. For example, the extraction agent and the heavy hydrocarbons can also be separated in the distillation 20.

Claims

Patentansprüche: Claims:
1. Verfahren zur Aufbereifung von Rückständen aus der KohLehydrierung durch Vergasung in Gegenwart von O2 und ggf. H2O als Vergasungsmittel, dadurch gekennzeichnet, daß die Vergasung der Rückstände in einem Gegenst rom-Schacht vergaser erfolgt, wobei die Rückstände vor der Vergasung mit Feststoffen, deren Erweichungspunkt oberhalb des Erweichungspunktes der Rückstände Liegt, vermischt werden, die Mischung zumindest teilweise brikettiert wird und wobei zumindest ein Teil der im Vergasungsprodukt enthaltenen schweren Kohlenwasserstoffe abgetrennt und zum Anmischen der zu hydrierenden Frischkohle verwendet wird.1. A process for the refinement of residues from the coal hydrogenation by gasification in the presence of O 2 and, if appropriate, H 2 O as the gasifying agent, characterized in that the gasification of the residues takes place in a counter-current shaft gasifier, the residues before the gasification with Solids, the softening point of which is above the softening point of the residues, are mixed, the mixture is at least partially briquetted and at least some of the heavy hydrocarbons contained in the gasification product are separated off and used to mix the fresh coal to be hydrogenated.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Feststoff zumindest teilweise Kohle einge- setzt wird.2. The method according to claim 1, characterized in that that coal is at least partially used as a solid.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß als Feststoff zumindest teilweise Asche aus dem Gegenstrom-Schacht vergaser eingesetzt wird.3. The method according to claim 1 or 2, characterized in that at least partially ash from the countercurrent shaft gasifier is used as a solid.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das H2O am Boden des Gegenstrom- Schachtvergasers in Form von Wassernebel eingedüst wird.4. The method according to any one of claims 1 to 3, characterized in that the H 2 O is injected at the bottom of the countercurrent shaft gasifier in the form of water mist.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der zu brikettierenden Mischung schwefeLbindende Stoffe zugegeben werden.5. The method according to any one of claims 1 to 4, characterized in that the mixture to be briquetted sulfur-binding substances are added.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Mischung vor ihrer Reaktion mit den Vergasungsmitteln mit Extraktionsmitteln unter überkritischen Bedingungen behandelt wird.6. The method according to any one of claims 1 to 5, characterized in that the mixture is treated with extractants under supercritical conditions before its reaction with the gasification agents.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß als Extraktionsmittel eine Kohlenwasserstoff- Fraktion mit einem Siedeende bis etwa 200ºC verwendet wird. 7. The method according to claim 6, characterized in that a hydrocarbon fraction with a boiling end up to about 200 ° C is used as the extractant.
8. Verfahren nach Anspruch 6 oder 1 , dadurch gekennzeichnet, daß das Extraktionsmittel von den schweren Kohlenwasserstoffen wieder abgetrennt wird. 8. The method according to claim 6 or 1, characterized in that the extractant is separated from the heavy hydrocarbons again.
PCT/DE1982/000200 1981-10-31 1982-10-07 Method for the treatment of residues obtained from hydrogenation of coal WO1983001626A1 (en)

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AU89963/82A AU8996382A (en) 1981-10-31 1982-10-07 Verfahren zum aufbereiten von ruckstanden aus der kohlehydrierung

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DE19813143353 DE3143353C2 (en) 1981-10-31 1981-10-31 Process for the treatment of residues from carbohydrate hydrogenation

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
EP0143106A2 (en) * 1983-11-14 1985-05-29 VOEST-ALPINE Aktiengesellschaft Method of working up heavy metal-containing residues from the chemical industry
WO1988000962A1 (en) * 1986-08-06 1988-02-11 C. Deilmann Ag Process for thermally treating watery oil sludges or the like

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Publication number Priority date Publication date Assignee Title
DE882283C (en) * 1944-02-26 1953-07-06 Basf Ag Process for the recovery of deoiled residues from coal liquefaction
USB395671I5 (en) * 1972-01-03 1975-01-28
DE2735829A1 (en) * 1977-08-09 1979-02-22 Metallgesellschaft Ag METHOD FOR PRODUCING HYDROCARBONS FROM COAL
EP0012457A1 (en) * 1978-12-11 1980-06-25 Metallgesellschaft Ag Process for the manufacture of shaped bodies from solid fuels for gasification
US4248605A (en) * 1979-07-30 1981-02-03 Conoco, Inc. Gasification of coal liquefaction residues

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE882283C (en) * 1944-02-26 1953-07-06 Basf Ag Process for the recovery of deoiled residues from coal liquefaction
USB395671I5 (en) * 1972-01-03 1975-01-28
DE2735829A1 (en) * 1977-08-09 1979-02-22 Metallgesellschaft Ag METHOD FOR PRODUCING HYDROCARBONS FROM COAL
EP0012457A1 (en) * 1978-12-11 1980-06-25 Metallgesellschaft Ag Process for the manufacture of shaped bodies from solid fuels for gasification
US4248605A (en) * 1979-07-30 1981-02-03 Conoco, Inc. Gasification of coal liquefaction residues

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0143106A2 (en) * 1983-11-14 1985-05-29 VOEST-ALPINE Aktiengesellschaft Method of working up heavy metal-containing residues from the chemical industry
EP0143106A3 (en) * 1983-11-14 1986-03-05 Aktiengesellschaft Voest-Alpine Method of working up heavy metal-containing residues from the chemical industry
WO1988000962A1 (en) * 1986-08-06 1988-02-11 C. Deilmann Ag Process for thermally treating watery oil sludges or the like

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DE3143353A1 (en) 1983-05-11

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