EP0161290B1 - Coal liquefaction process - Google Patents

Coal liquefaction process Download PDF

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Publication number
EP0161290B1
EP0161290B1 EP84904097A EP84904097A EP0161290B1 EP 0161290 B1 EP0161290 B1 EP 0161290B1 EP 84904097 A EP84904097 A EP 84904097A EP 84904097 A EP84904097 A EP 84904097A EP 0161290 B1 EP0161290 B1 EP 0161290B1
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coal
zone
reaction
reaction product
coking
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EP84904097A
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German (de)
French (fr)
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EP0161290A1 (en
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Helmut WÜRFEL
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GfK SE
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GfK SE
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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
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes

Definitions

  • the invention relates to a process for liquefying coal, in which the ground coal is mixed with grinding oil to form a pulp and liquefied under increased pressure and temperature in a reaction zone in the presence of hydrogen and, if appropriate, catalyst.
  • a process for liquefying coal has already become known, in which the coal to be processed is dried and finely ground, mixed with grinding oil, the resulting pulp of coal is pumped to reaction pressure, first by heat exchange with some of the reaction products and then in a preheater by supplying external heat heated to the light-off temperature of the liquefaction reaction and finally liquefied in a reaction zone in the presence of hydrogen and one or more suitable catalysts.
  • the product fraction leaving the reaction zone is broken down in a downstream hot separator into a vaporous top fraction consisting of gases, water of reaction and distillate oils as well as a solid fraction containing soil from undegraded coal, ash, catalyst particles, and other high-molecular, difficult-to-hydrogenate substances, especially asphaltenes, and heavy oil.
  • distillate oil depends very much on the hydrogenation conditions (e.g. pressure, temperature) in the reaction zone.
  • a satisfactory distillate oil yield e.g. B. over 5C% based on the coal used, only in very harsh hydrogenation conditions with temperatures in the range of about 480 ° C and pressures above 300 bar. It is obvious that such conditions are associated with extremely high investment costs and operating costs in a large-scale industrial plant, with considerable effects on the economy of the process.
  • the invention has for its object to develop a method of the type mentioned, in which the disadvantages described do not occur and which enables economical liquefaction of coal.
  • reaction product leaving the reaction zone is fed to a coking zone and that the hot gases and vapors withdrawing from the coking zone are cooled in direct heat exchange with the pulp to be heated.
  • An essential idea of the invention is not to restrict the liquefaction of the coal to a reaction zone operated under harsh hydrogenation conditions, as in the known process, but to include a further coking zone in the distillate oil production.
  • the liquefaction can be controlled in the reaction zone by lowering the pressure or the temperature, for example, so that initially primarily extract and only relatively little distillate oil are formed from the coal. Another large amount of distillate oil is then produced in the course of the coking.
  • the pressure in the reaction zone is generally below 300 bar, preferably between about 150 and 250 bar.
  • the coking of the reaction product withdrawn from the reaction zone is expediently carried out at temperatures between about 450 and 600 ° C., the temperature increase of the reaction product to be coked, which may be necessary, being brought about by supplying external heat by means of a conventional tube furnace. Also, by adding hydrogen, e.g. B. in the form of coke oven gas, the quality and the yield of distillates in the coking zone can be increased. To prevent coking in the course of heating the reaction product coking temperature, it proves to be expedient to add a hydrogen donate oil, in particular a higher-boiling fraction of the already hydrogen-refined oil gain, to the plant before it is heated.
  • a hydrogen donate oil in particular a higher-boiling fraction of the already hydrogen-refined oil gain
  • Another essential idea of the method according to the invention is to cool the hot gases and vapors withdrawing from the coking zone below the respective coking temperature, essentially distillate oil vapors, in the heat exchange with the fresh coal pulp to be treated, in order to heat up the coking zone for heating the To use coal-free.
  • the coal pulp is heated in direct heat exchange, ie. H. through intimate mixing of the hot gases and vapors with the fresh, possibly already fully or partially pumped coal paste.
  • direct heat exchange ie. H. through intimate mixing of the hot gases and vapors with the fresh, possibly already fully or partially pumped coal paste.
  • all of the water contained in the coal is driven out, so that the coal is almost completely dried during this heat exchange.
  • the hitherto customary, very complex drying in the course of coal preparation can thus be dispensed with completely or, at least to a large extent, if the charge coal has a high water content.
  • An additional, very significant advantage is that due to the strong heating of the coal in direct heat exchange with the hot product vapors from the coking zone, other gases that can be easily split off from the coal, such as, for example, B. methane, C0 2 and educational water, are released.
  • the coal to be supplied after the heat exchange of the reaction zone is thus already largely degassed, so that fewer gases are formed in the reaction zone itself. This in turn leads to a further increase in the hydrogen partial pressure in the reactor and thus to an improvement in the reaction conditions.
  • the heat of the fresh coal pulp to approximately the light-off temperature of the liquefaction reaction is no longer required for the use of coal pulp heat exchangers.
  • the amount of heat required for heating is supplied as part of the direct heat exchange between coal slurry and the hot coking vapors. Only for reasons of regulation and for starting up the system, a small tube furnace can be useful. Also, the time-consuming fine grinding of the coal to typically ⁇ 0.1 mm can now be omitted, since the coal on its way to the reaction zone is only conducted in pipes and not in heat exchangers in which it could settle.
  • the heavy distillates contained in these vapors condense. With the fresh coal pulp, these distillates reach the reaction or coking zone again and are broken down into the valuable product fractions naphtha and middle distillate.
  • the condensed heavy distillates are also very suitable as solvents for the coal and also lead to a dilution of the coal pulp. They in turn serve as "rubbing oil".
  • the fresh coal pulp can therefore be added as a thick pulp with up to 90% solids content. This thick slurry can be conveyed into the zone of direct heat exchange in a simple manner by means of low-wear screw conveyors.
  • the gases and vapors from the coking zone which are not condensed in the course of the direct heat exchange, essentially these are residual hydrogen, water vapor, low-boiling hydrocarbons and, in particular, hydrocarbons obtained as products in the naphtha and medium oil range, as well as the gases and vapors released when the coal is heated separated from the heated coal pulp and fed to a corresponding treatment.
  • Your residual heat can possibly be used to heat the required fresh hydrogen or the hydrogen-containing gas.
  • the entire reaction product withdrawing from the reaction zone can be fed to the coking zone.
  • the hot separator which is usually downstream of the reaction zone, is omitted.
  • the reaction product reaches the coking zone immediately below the temperature of the reaction zone of approximately 470 ° to 490 ° C., that is to say a temperature which is already in the range of the coking temperature, so that it still heats up to the coking temperature required amount of heat is only small. Possibly. the device for further heating can even be dispensed with entirely. In such a procedure, the unused residual hydrogen contained in the reaction product can also be used directly in the coking zone.
  • the gases and vapors still contained in the reaction product can also be in a hot separator downstream of the reaction zone at somewhat lower temperatures, essentially residual hydrogen, methane, etc. Gases and distillates in the naphtha and medium oil range are separated, so that the volume flow to be fed to the coking zone is reduced accordingly.
  • the gases and vapors separated in the hot separator can be fed directly to the direct heat exchange with the fresh coal pulp, so that the heat content of these gases and vapors can also be used here to heat the fresh coal pulp.
  • a particularly high-quality coke is to be produced in the coking zone, e.g. B. an electrode coke for metallurgical purposes, it makes sense to separate the substances still contained in the reaction product, such as unused coal, ash and catalyst particles, beforehand.
  • the solid separation can be carried out in a known manner, for. B. by filtration, sedimentation or centrifugation.
  • the reaction zone in two stages, the pressure of the second stage being higher than that of the first stage, which is preferably between about 10 and 50 bar .
  • the first reaction stage is operated at approximately the pressure of the coking zone, with the direct heat exchange between the coal slurry and the gases and vapors from the coking zone and possibly the gases and vapors from the top of the hot separator taking place in this first reaction stage.
  • the reaction product can be heated to the temperature of the coking zone by admixing a hot hydrogen-rich gas generated by partial oxidation of hydrocarbons.
  • the hydrogen content of this gas can then be used directly both to improve the coking and, if the reaction zone has two stages, to cover the hydrogen requirement in the first reaction zone.
  • the hot, hydrogen-containing gas can be generated by partial oxidation of methane, which forms hydrogen and carbon monoxide, among other things.
  • the hot hydrogen-containing gas can also be obtained by partial oxidation, i.e. by gasification, of the coke produced in the coking zone or, if a residue has been separated before the coking, by gasification of this residue.
  • the admixture of the hydrogen-rich gas to the reaction product to be coked is expediently carried out at a plurality of, at least two, points one behind the other in the direction of flow of the residue. This ensures a gradual, uniform heating of the residue, so that the coking temperature is only reached immediately before the reaction product is introduced into the coking zone. Possibly. it may also prove to be expedient to carry out the heating of the reaction product to be coked in two stages, with external heat being supplied in a tube furnace in a first stage and the hydrogen-containing hot gas being supplied in the second stage downstream of the first stage.
  • the coke accumulating in the coking zone is gasified, the raw gas obtained in the process is cleaned, partially converted and then at least partially subjected to a Fischer-Tropsch synthesis known per se for producing higher-boiling paraffinic hydrocarbons, in particular diesel oil.
  • Such a procedure is characterized by great flexibility with regard to gasoline or diesel oil production. If more Fischer-Tropsch products are required, the plant can be operated in a simple manner by reducing the pressure and temperature in the reaction zone or the coking zone to less distillate gain, which results in more coke for the gasification and the subsequent Fischer-Tropsch synthesis . Conversely, with an increased need for aromatic hydrocarbons for gasoline production, the conditions for treating the coal in the reaction zone or the coking zone can be tightened by increasing pressure and temperature or by increasing the hydrogen supply, so that more distillate and less coke for the Gasification occurs.
  • oil-based grating oils are distinguished from coal oils by an increased hydrogen content, which can be transferred to the coal to be treated even under particularly mild liquefaction conditions. If petroleum hydrogenation residue still containing catalyst is used as grinding oil, an additional catalyst for the coal treatment may also be dispensed with.
  • the method according to the invention is not limited to the processing of hard coal or brown coal. Rather, the same advantages can also be used to treat other carbonaceous substances, such as heavy oils derived from petroleum or oil sands or oil shale.
  • the fresh coal pulp to be treated is to be treated Mixer 2 fed and heated there in direct heat exchange with hot gases and vapors, the origin of which is explained below, to about the reaction start temperature of about 400 ° C.
  • the coal pulp is fed to a reaction zone 4 via a line 3 and there in the presence of hydrogen, which is introduced into the reaction zone 4 via a line 5, under relatively mild conditions, i.e. liquefied at a relatively low pressure of only about 200 bar and at a temperature of about 450 ° C.
  • the reaction product obtained in the reaction zone 4 is composed of a gaseous and a liquid solid-containing phase.
  • the hot gaseous phase which essentially contains the unused hydrogen, low-boiling hydrocarbons, such as methane, ethane and others, and distillates in the boiling range of naphtha and middle oil, is returned to the mixer 2 via a line 6, there with the fresh one Coal porridge mixed intimately and cooled in the heat exchange with the coal porridge.
  • the liquid solid-containing phase obtained in reaction zone 4 essentially consists of coal extract, ie bitumen, and of distillates in the boiling range, predominantly of heavy oil. In addition, this phase contains solids such as unreacted coal, ash and unused catalyst.
  • This liquid reaction product is fed via lines 7, 8, 9 and 10 to a furnace 11, where it is heated to a temperature of about 500 ° C. by indirect supply of external heat and then fed via lines 12, 13 and 14 into a coking zone 15.
  • the liquid solid-containing product fraction is coked in the coking zone 15.
  • gases and vapors are produced, especially distillates in the boiling range of naphtha and medium oil.
  • the product fraction to be coked is hydrogen via a line 16, for. B. in the form of coke oven gas added.
  • the product fraction to be coked can also be heated by directly admixing a hot hydrogen-containing gas mixture immediately before the product fraction enters the coking zone 15.
  • the product fraction is introduced via lines 7, 8, 17, 13 and 14 directly into the coking zone 15, while the hydrogen-containing hot gas is generated in a gas generator 18 by partial oxidation of methane or another hydrocarbon and is to be coked via line 19
  • Product fraction is added.
  • the partial oxidation can be controlled so that, on the one hand, sufficient heat is generated by the oxidation of carbon to carbon monoxide to heat the fraction to be coked to coking temperature, but on the other hand enough hydrogen is also generated for the coking zone.
  • the solids are separated from the coke before the reaction product is coked.
  • the liquid solid-containing reaction product from the reaction zone 4 via lines 7 and 20 is first fed to a solids separation device 21, in which the solids in a known manner, for. B. by filtration, sedimentation or centrifugation.
  • the product fraction which is now largely freed of solids and is to be coked, is withdrawn via a line 22 from the solids separation device and, depending on the selected type of further heating, via lines 9, 17, 13 and 14 or also via line 10, furnace 11 and the lines 12, 13 and 14 fed to the coking zone 15.
  • the solid-rich residue obtained in the solids separation device 21 is withdrawn from the system via a line 23. Possibly. This residue or at least part of the coke obtained in the coking zone 15 can be used in the gas generator 18 to produce the hydrogen-containing hot gas.
  • the vapors formed in the coking zone 15 are drawn off below the coking temperature of approximately 500 ° C. via a line 24 and are likewise fed to the mixer 2. These vapors, together with the vapors from line 6, heat up the fresh one Coal pulp to about the light-off temperature of the reaction zone 4, so that, and this is a major advantage of the proposed method, the supply of external heat in difficult-to-use heat exchangers for heating the fresh coal pulp can be dispensed with. In the course of the direct heat exchange of the above-mentioned vapors with the coal pulp, almost all of the water is expelled from the coal, so that the energy-consuming drying of the coal in the course of its preparation can also be dispensed with.
  • the resulting gases and vapors in the mixer 2 which consist essentially of residual hydrogen, water vapor, small amounts of low-boiling hydrocarbons, such as methane and ethane, among others, and in particular the product distillates in the naphtha and medium oil range, are via a line 25 from the System withdrawn and a further distillative processing, not shown here, due to their aromatic character, the distillates obtained are particularly suitable for the production of gasoline.
  • mixing stage 2 it may prove expedient to design mixing stage 2 as a first reaction stage for the coal and to operate the subsequent reaction zone as a second reaction stage under a higher pressure, so to speak.
  • the hydrogen supply via lines 16 and 19 is increased so that the hydrogen provided is sufficient not only for the coking zone, but also additionally for the first reaction stage, which is expediently operated under approximately the pressure of the coking zone .
  • the direct heat exchange between the hot product vapors and the starting material to be treated can be integrated directly into the reaction zone 4, which then expediently under approximately the pressure of the coking zone 15 is operated, which is approximately between 10 and 30 bar.
  • the distillate vapors obtained as the end product can be drawn off directly from the top of reaction zone 4.
  • the coke obtained in the coking zone 15 is fed via a feed 26 into a gasifier 27, preferably a fixed bed gasifier, and gasified there to form a raw gas containing carbon monoxide and hydrogen.
  • the required oxygen flows to the carburetor 27 via a line 28.
  • the raw gas from the gasifier 26 is cleaned and converted in a downstream system part 29 and then subjected to a known Fischer-Tropsch synthesis in a system 30. Due to their paraffinic character, the hydrocarbons produced in this plant are particularly advantageous for the production of diesel fuel.
  • the fresh coal pulp and / or the coking product fraction can also sulfur-binding substances such.

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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

In a coal liquefaction process with increase of the pressure and the temperature in a reaction zone, there is proposed to supply the reaction product leaving the reaction zone to a coking zone and to cool the gas and vapours formed therein and which are mainly fuel oil vapours, preferably by direct heat exchange with fresh coal pitch. The vapors and gas which have not condensed during such heat exchange are removed from the plant as final products. Said process enables to partially move the oil production from the reaction zone to the coking zone, so that the reaction zone may operate at low pressure. Furthermore, because of the direct heat exchange between the vapours and the fresh coal pitch, a major part of exothermal heat generated during the liquefaction reactions may be returned into the process.

Description

Die Erfindung betrifft ein Verfahren zum Verflüssigen von Kohle, bei dem die gemahlene Kohle mit Anreiböl zu einem Brei vermischt und unter erhöhtem Druck und erhöhter Temperatur in einer Reaktionszone in Gegenwart von Wasserstoff und ggf. Katalysator verflüssigt wird.The invention relates to a process for liquefying coal, in which the ground coal is mixed with grinding oil to form a pulp and liquefied under increased pressure and temperature in a reaction zone in the presence of hydrogen and, if appropriate, catalyst.

Es ist bereits ein Verfahren zum Verflüssigen von Kohle bekannt geworden, bei dem die zu verarbeitende Kohle getrocknet und feingemahlen, mit Anreiböl verrührt, der anfallende Kohlebrei auf Reaktionsdruck gepumpt, zunächst im Wärmetausch mit einem Teil der Reaktionsprodukte und dann in einem Vorerhitzer durch Zufuhr von Fremdwärme auf die Anspringtemperatur der Verflüssigungsreaktion erhitzt und schließlich in einer Reaktionszone in Gegenwart von Wasserstoff und einem oder mehreren geeigneten Katalysatoren verflüssigt wird. Die die Reaktionszone verlassende Produktfraktion wird in einem nachgeschalteten Heißabscheider in eine dampfförmige Kopffraktion aus Gasen, Reaktionswasser und Destillatölen sowie in eine feststoffhaltige Bodenfraktion aus nicht abgebauter Kohle, Asche, Katalysatorteilchen, anderen hochmolekularen schwer hydrierbaren Substanzen, wie vor allem Asphaltenen, und Schweröl zerlegt.A process for liquefying coal has already become known, in which the coal to be processed is dried and finely ground, mixed with grinding oil, the resulting pulp of coal is pumped to reaction pressure, first by heat exchange with some of the reaction products and then in a preheater by supplying external heat heated to the light-off temperature of the liquefaction reaction and finally liquefied in a reaction zone in the presence of hydrogen and one or more suitable catalysts. The product fraction leaving the reaction zone is broken down in a downstream hot separator into a vaporous top fraction consisting of gases, water of reaction and distillate oils as well as a solid fraction containing soil from undegraded coal, ash, catalyst particles, and other high-molecular, difficult-to-hydrogenate substances, especially asphaltenes, and heavy oil.

Während die Kopffraktion im Wärmetausch mit dem Kohlebrei abgekühlt und aus der Anlage abgezogen wird, werden aus der Bodenfraktion die noch anwesenden Destillate abgetrennt und als Anreiböl für die frische Kohle verwendet. Eine genaue Beschreibung dieses Verfahrens ist aus der folgenden Veröffentlichung zu entnehmen: Conference Proceedings: Synthetic Fuels States and Directions Vol, 1, Sections 1-17, May 1981.While the top fraction is cooled in the heat exchange with the coal pulp and withdrawn from the plant, the distillates still present are separated from the bottom fraction and used as grinding oil for the fresh coal. A detailed description of this method can be found in the following publication: Conference Proceedings: Synthetic Fuels States and Directions Vol, 1, Sections 1-17, May 1981.

Nachteile dieses bekannten Verfahrens liegen in dem hohen Verbrauch an Energie sowie in dem erheblichen apparativen Aufwand.Disadvantages of this known method lie in the high consumption of energy and in the considerable expenditure on equipment.

So muß die gesamte zu verarbeitende Kohle unter Einsatz von Fremdwärme in einem speziellen Trockner getrocknet werden. Bei einem normalen Wassergehalt bei z. B. Steinkohle als Einsatzprodukt von etwa 10 % wird zum Trocknen einer Tonne Kohle bereits eine Energiemenge von etwa 0,1 Gcal benötigt. Außerdem muß die Kohle in aufwendiger Weise auf eine Korngröße < 0,1 mm aufgemahlen werden. Auch erweist sich bei dem bekannten Verfahren der Wärmetausch zur Aufheizung des Kohlebreis als sehr schwierig. Einmal ist aufgrund der Viskosität des Kohlebreis eine gleichmäßig Beaufschlagung der Wärmetauscherflächen nur schwer zu erreichen. Zum anderen stößt die weitere Aufheizung des Kohlebreis im Vorerhitzer auf Schwierigkeiten, da infolge der hier bereits vorherrschenden hohen Temperaturen die im Kohlebrei suspendierte Kohle sehr stark aufquillt. Dies führt zu einer weiteren Erhöhung der Viskosität, so daß letztlich nur noch ein mit starkem Materialabtrieb verbundener pulsierrender Durchsatz des Kohlebreis durch den Vorerhitzer moglich ist. Dabei können Druckstöße bis zu 10 bar auftreten.The entire coal to be processed must be dried in a special dryer using external heat. With a normal water content at z. B. Hard coal as an input product of about 10% requires an amount of energy of about 0.1 Gcal to dry a ton of coal. In addition, the coal has to be ground to a grain size of <0.1 mm in a complex manner. In the known method, the heat exchange for heating the coal pulp also proves to be very difficult. On the one hand, due to the viscosity of the coal pulp, it is difficult to achieve uniform exposure to the heat exchanger surfaces. On the other hand, the further heating of the coal pulp in the preheater encounters difficulties because, due to the high temperatures already prevailing here, the coal suspended in the coal pulp swells very strongly. This leads to a further increase in the viscosity, so that ultimately only a pulsating throughput of the coal pulp through the preheater, which is connected with a strong material output, is possible. Pressure surges of up to 10 bar can occur.

Bei diesem bekannten Verfahren hängt darüber hinaus die gewünschte Ausbeute an Destillatöl sehr wesentlich von den Hydrierbedingungen (z. B. Druck, Temperatur) in der Reaktionszone ab. Im Grunde läßt sich eine befriedigende Destillatölausbeute, von z. B. über 5C % bezogen auf die eingesetzte Kohle, nur bei sehr scharfen Hydrierbedingungen mit Temperaturen im Bereich von etwa 480°C und Drücken oberhalb 300 bar erreichen. Es liegt auf der Hand, daß solche Bedingungen bei einer großtechnischen Anlage mit außerordentlich hohen Investitionskosten und Betriebskosten verbunden sind, mit erheblichen Auswirkungen auf die Wirtschaftlichkeit des Verfahrens.In this known process, moreover, the desired yield of distillate oil depends very much on the hydrogenation conditions (e.g. pressure, temperature) in the reaction zone. Basically, a satisfactory distillate oil yield, e.g. B. over 5C% based on the coal used, only in very harsh hydrogenation conditions with temperatures in the range of about 480 ° C and pressures above 300 bar. It is obvious that such conditions are associated with extremely high investment costs and operating costs in a large-scale industrial plant, with considerable effects on the economy of the process.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren der eingangs genannten Art zu entwickeln, bei dem die geschilderten Nachteile nicht auftreten und das eine wirtschaftliche Verflüssigung von Kohle ermöglicht.The invention has for its object to develop a method of the type mentioned, in which the disadvantages described do not occur and which enables economical liquefaction of coal.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß das die Reaktionszone verlassende Reaktionsprodukt einer Verkokungszone zugeführt wird und daß die aus der Verkokungszone abziehenden heißen Gase und Dämpfe im direkten Wärmetausch mit dem zu erwärmenden Kohlebrei abgekühlt werden.This object is achieved in that the reaction product leaving the reaction zone is fed to a coking zone and that the hot gases and vapors withdrawing from the coking zone are cooled in direct heat exchange with the pulp to be heated.

Ein wesentlicher Gedanke der Erfindung liegt darin, die Verflüssigung der Kohle nicht wie bei dem bekannten Verfahren auf eine unter scharfen Hydrierbedingungen betriebene Reaktionszone zu beschränken, sondern in die Destillatölerzeugung eine weitere Verkokungszone mit einzubeziehen. Dadurch kann in der Reaktionszone durch Erniedrigung des Druckes bzw. der Temperatur die Verflüssigung beispielsweise so gelenkt werden, daß zunächst vornehmlich Extrakt und nur verhältnismäßig wenig Destillatöl aus der Kohle gebildet werden. Anschließend wird im Zuge der Verkokung dann eine weitere große Menge an Destillatöl erzeugt. Der Druck in der Reaktionszone liegt in der Regel unterhalb 300 bar, vorzugsweise zwischen etwa 150 und 250 bar.An essential idea of the invention is not to restrict the liquefaction of the coal to a reaction zone operated under harsh hydrogenation conditions, as in the known process, but to include a further coking zone in the distillate oil production. As a result, the liquefaction can be controlled in the reaction zone by lowering the pressure or the temperature, for example, so that initially primarily extract and only relatively little distillate oil are formed from the coal. Another large amount of distillate oil is then produced in the course of the coking. The pressure in the reaction zone is generally below 300 bar, preferably between about 150 and 250 bar.

Durch die Erniedrigung des Druckes in der Reaktionszone lassen sich im Hinblick auf die apparative Auslegung sowie die benötigte Pumpenergie erhebliche Einsparungen erzielen. Hinzu kommt, daß aufgrund der milderen Verflüssigungsbedingungen in der Reaktionszone weniger Methan und andere gasförmige Kohlenwasserstoffe erzeugt werden, so daß der Wasserstoffverbrauch erheblich reduziert wird. Da zudem der Wasserstoff bei konstantem Gesamtdruck nun unter einem höheren Partialdruck zur Verfügung stehen kann, wodurch das Wasserstoffangebot in der Reaktionszone verbessert wird, braucht nicht unbedingt reiner Wasserstoff eingesetzt zu werden, sondern es kann ein kostengünstiger bereitzustellendes wasserstoffhaltiges Gasgemisch, wie z. B. Kokereigas, verwendet werden, bzw. beim Einsatz von reinem Wasserstoff kann der Druck in der Reaktionszone entsprechend gesenkt werden.By lowering the pressure in the reaction zone, considerable savings can be achieved in terms of apparatus design and the pump energy required. In addition, because of the milder liquefaction conditions, less methane and other gaseous hydrocarbons are generated in the reaction zone, so that the hydrogen consumption is considerably reduced. In addition, since the hydrogen can now be available at a constant total pressure under a higher partial pressure, which improves the hydrogen supply in the reaction zone, it is not absolutely necessary to use pure hydrogen, but a hydrogen-containing gas mixture, such as. B. coke oven gas used, or at Using pure hydrogen, the pressure in the reaction zone can be reduced accordingly.

Die Verkokung des aus der Reaktionszone abziehenden Reaktionsproduktes erfolgt zweckmäßigerweise bei Temperaturen zwischen etwa 450 und 600°C, wobei die ggf. erforderlich werdende Temperaturerhöhung des zu verkokenden Reaktionsproduktes durch Zufuhr von Fremdwärme mittels eines herkömmlichen Röhrenofens bewirkt werden kann. Auch kann durch Zugabe von Wasserstoff, z. B. in Form von Kokereigas, die Qualität und die Ausbeute an Destillaten in der Verkokungszone noch erhöht werden. Zur Verhinderung von Verkokungen im Zuge der Aufheizung des Reaktionsproduktes Verkokungstemperatur erweist es sich als zweckmäßig, diesem vor seiner Aufheizung ein Wasserstoff-Donatöl, insbesondere eine höhersiedende Fraktion des bereits wasserstoffraffinierten Ölgewinnes der Anlage, zuzumischen.The coking of the reaction product withdrawn from the reaction zone is expediently carried out at temperatures between about 450 and 600 ° C., the temperature increase of the reaction product to be coked, which may be necessary, being brought about by supplying external heat by means of a conventional tube furnace. Also, by adding hydrogen, e.g. B. in the form of coke oven gas, the quality and the yield of distillates in the coking zone can be increased. To prevent coking in the course of heating the reaction product coking temperature, it proves to be expedient to add a hydrogen donate oil, in particular a higher-boiling fraction of the already hydrogen-refined oil gain, to the plant before it is heated.

Ein weiterer wesentlicher Gedanke des erfindungsgemäßen Verfahrens liegt darin, die aus der Verkokungszone unter der jeweiligen Verkokungstemperatur abziehenden heißen Gase und Dämpfe, im wesentlichen sind dies Destillatöldämpfe, im Wärmetausch mit dem zu behandelnden frischen Kohlebrei abzukühlen, um das Wärmepotential aus der Verkokungszone für die Aufheizung des Kohlebreies zu nutzen.Another essential idea of the method according to the invention is to cool the hot gases and vapors withdrawing from the coking zone below the respective coking temperature, essentially distillate oil vapors, in the heat exchange with the fresh coal pulp to be treated, in order to heat up the coking zone for heating the To use coal-free.

Nach einem weiteren Merkmal der Erfindung erfolgt die Aufheizung des Kohlebreis im direkten Wärmetausch, d. h. durch innige Vermischung der heißen Gase und Dämpfe mit dem frischen, ggf. bereits vollständig oder teilweise auf Druck gepumpten Kohlebrei. Im Zuge der Erwärmung des Kohlebreis wird das gesamte in der Kohle enthaltene Wasser ausgetrieben, so daß die Kohle bei diesem Wärmetausch nahezu vollständig getrocknet wird. Bei der erfindungsgemäßen Verfahrensweise kann somit auf die bisher übliche, sehr aufwendige Trocknung im Zuge der Kohlevorbereitung vollständig oder bei hohem Wassergehalt der Einsatzkohle zumindest weitgehend verzichtet werden.According to a further feature of the invention, the coal pulp is heated in direct heat exchange, ie. H. through intimate mixing of the hot gases and vapors with the fresh, possibly already fully or partially pumped coal paste. In the course of the heating of the coal pulp, all of the water contained in the coal is driven out, so that the coal is almost completely dried during this heat exchange. In the procedure according to the invention, the hitherto customary, very complex drying in the course of coal preparation can thus be dispensed with completely or, at least to a large extent, if the charge coal has a high water content.

Als zusätzlicher, sehr bedeutender Vorteil ergibt sich, daß infolge der starken Erwärmung der Kohle im direkten Wärmetausch mit den heißen Produktdämpfen aus der Verkokungszone weitere aus der Kohle leicht abzuspaltende Gase, wie z. B. Methan, C02 und Bildungswasser, freigesetzt werden. Die nach dem Wärmetausch der Reaktionszone zuzuführende Kohle ist somit bereits weitgehend entgast, so daß sich in der Reaktionszone selbst weniger Gase bilden. Dies wiederum führt zu einer weiteren Erhöhung des Wasserstoffpartialdruckes im Reaktor und somit zu einer Verbesserung der Reaktionsbedingungen.An additional, very significant advantage is that due to the strong heating of the coal in direct heat exchange with the hot product vapors from the coking zone, other gases that can be easily split off from the coal, such as, for example, B. methane, C0 2 and educational water, are released. The coal to be supplied after the heat exchange of the reaction zone is thus already largely degassed, so that fewer gases are formed in the reaction zone itself. This in turn leads to a further increase in the hydrogen partial pressure in the reactor and thus to an improvement in the reaction conditions.

Hinzu kommt, daß nunmehr zur Aufheizung des frischen Kohlebreis auf etwa die Anspringtemperatur der Verflüssigungsreaktion keine mit Kohlebrei beaufschlagte Wärmetauscher mehr erforderlich sind. Die zur Aufheizung benötigte Wärmemenge wird im Zuge des direkten Wärmetauschs zwischen Kohlebrei und den heißen Verkokungsdämpfen zugeführt. Lediglich aus Regelungsgründen und zum Anfahren der Anlage kann ein nachgeschalteter kleiner Röhrenofen zweckmäßig sein. Auch kann nunmehr die aufwendige Feinmahlung der Kohle auf üblicherweise < 0,1 mm unterbleiben, da die Kohle auf ihrem Wege zur Reaktionszone nur in Rohren und nicht in Wärmetauschern geführt wird, in denen sie sich absetzen könnte.In addition, the heat of the fresh coal pulp to approximately the light-off temperature of the liquefaction reaction is no longer required for the use of coal pulp heat exchangers. The amount of heat required for heating is supplied as part of the direct heat exchange between coal slurry and the hot coking vapors. Only for reasons of regulation and for starting up the system, a small tube furnace can be useful. Also, the time-consuming fine grinding of the coal to typically <0.1 mm can now be omitted, since the coal on its way to the reaction zone is only conducted in pipes and not in heat exchangers in which it could settle.

Im Zuge des direkten Wärmetausches zwischen den Dämpfen aus der Verkokungszone und dem frischen Kohlebrei kondensieren die in diesen Dämpfen enthaltenden schweren Destillate. Diese Destillate gelangen mit dem frischen Kohlebrei erneut in die Reaktions- bzw. Verkokungszone und werden dabei in die wertvollen Produktfraktionen Naphtha und Mitteldestillat aufgespalten. Auch eignen sich die kondensierten schweren Destillate sehr gut als Lösungsmittel für die Kohle und führen darüber hinaus zu einer Verdünnung des Kohlebreis. Sie dienen somit ihrerseits als "Anreiböl". Bei dem erfindungsgemäßen Verfahren kann daher der frische Kohlebrei als Dickbrei mit bis zu 90 % Feststoffanteil zugegeben werden. Das Fördern dieses Dickbreies in die Zone des direkten Wärmetausches kann in einfacher Weise mittels verschleißarmer Förderschnecken erfolgen.In the course of the direct heat exchange between the vapors from the coking zone and the fresh coal pulp, the heavy distillates contained in these vapors condense. With the fresh coal pulp, these distillates reach the reaction or coking zone again and are broken down into the valuable product fractions naphtha and middle distillate. The condensed heavy distillates are also very suitable as solvents for the coal and also lead to a dilution of the coal pulp. They in turn serve as "rubbing oil". In the process according to the invention, the fresh coal pulp can therefore be added as a thick pulp with up to 90% solids content. This thick slurry can be conveyed into the zone of direct heat exchange in a simple manner by means of low-wear screw conveyors.

Die im Zuge des direkten Wärmetausches nicht kondensierten Gase und Dämpfe aus der Verkokungszone, im wesentlichen sind dies Restwasserstoff, Wasserdampf, tiefsiedende Kohlenwasserstoffe und insbesondere als Produkte gewonnene Kohlenwasserstoffe im Naphtha- und Mittelölbereich, sowie die bei der Erwärmung der Kohle freigesetzten Gase und Dämpfe, werden von dem erwärmten Kohlebrei abgetrennt und einer entsprechenden Aufbereitung zugeführt. Ihre Restwärme kann ggf. zur Erwärmung des benötigten Frischwasserstoffes oder des wasserstoffhaltigen Gases genutzt werden.The gases and vapors from the coking zone which are not condensed in the course of the direct heat exchange, essentially these are residual hydrogen, water vapor, low-boiling hydrocarbons and, in particular, hydrocarbons obtained as products in the naphtha and medium oil range, as well as the gases and vapors released when the coal is heated separated from the heated coal pulp and fed to a corresponding treatment. Your residual heat can possibly be used to heat the required fresh hydrogen or the hydrogen-containing gas.

Gemäß der Erfindung kann das gesamte, aus der Reaktionszone abziehende Reaktionsprodukt der Verkokungszone zugeführt werden. In diesem Falle entfällt der üblicherweise der Reaktionszone nachgeschaltate Heißabscheider. Als weiterer Vorteil kommt hinzu, daß das Reaktionsprodukt unmittelbar unter der Temperatur der Reaktionszone von etwa 470° bis 490° C, einer Temperatur also, die bereits im Bereich der Verkokungstemperatur liegt, in die Verkokungszone gelangt, so daß die zur Aufheizung auf die Verkokungstemperatur noch benötigte Wärmemenge nur gering ist. Ggf. kann sogar vollständig auf die Einrichtung zur weiteren Aufheizung verzichtet werden. Auch kann bei einer derartigen Verfahrensweise der im Reaktionsprodukt enthaltene, nicht verbrauchte Restwasserstoff direkt in der Verkokungszone genutzt werden.According to the invention, the entire reaction product withdrawing from the reaction zone can be fed to the coking zone. In this case, the hot separator, which is usually downstream of the reaction zone, is omitted. A further advantage is that the reaction product reaches the coking zone immediately below the temperature of the reaction zone of approximately 470 ° to 490 ° C., that is to say a temperature which is already in the range of the coking temperature, so that it still heats up to the coking temperature required amount of heat is only small. Possibly. the device for further heating can even be dispensed with entirely. In such a procedure, the unused residual hydrogen contained in the reaction product can also be used directly in the coking zone.

Andererseits können aber auch in einem der Reaktionszone nachgeschalteten Heißabscheider bei etwas niedrigeren Temperaturen die im Reaktionsprodukt noch enthaltenen Gase und Dämpfe, im wesentlichen sind dies Restwasserstoff, Methan u.a. Gase sowie Destillate im Naphtha- und Mittelölbereich, abgetrennt werden, so daß sich der der Verkokungszone zuzuführende Volumenstrom entsprechend verringert. In diesem Falle können die im Heißabscheider abgetrennten Gase und Dämpfe unmittelbar dem direkten Wärmetausch mit dem frischen Kohlebrei zugeführt werden, so daß auch hier der Wärmeinhalt dieser Gase und Dämpfe zur Aufheizung des frischen Kohlebreis genutzt werden kann.On the other hand, the gases and vapors still contained in the reaction product can also be in a hot separator downstream of the reaction zone at somewhat lower temperatures, essentially residual hydrogen, methane, etc. Gases and distillates in the naphtha and medium oil range are separated, so that the volume flow to be fed to the coking zone is reduced accordingly. In this case, the gases and vapors separated in the hot separator can be fed directly to the direct heat exchange with the fresh coal pulp, so that the heat content of these gases and vapors can also be used here to heat the fresh coal pulp.

Falls in der Verkokungszone ein besonders hochwertiger Koks erzeugt werden soll, z. B. ein Elektrodenkoks für metallurgische Zwecke, ist es sinnvoll, die in dem Reaktionsprodukt noch enthaltenden Stoffe, wie unverbrauchte Kohle, Asche und Katalysatorteilchen, vorher abzutrennen. Die Feststoffabtrennung kann in bekannter Weise z. B. durch Filtration, Sedimentation oder Zentrifugieren erfolgen.If a particularly high-quality coke is to be produced in the coking zone, e.g. B. an electrode coke for metallurgical purposes, it makes sense to separate the substances still contained in the reaction product, such as unused coal, ash and catalyst particles, beforehand. The solid separation can be carried out in a known manner, for. B. by filtration, sedimentation or centrifugation.

Insbesondere bei der Behandlung von schwer zu verflüssigenden Kohlen erweist es sich nach einem weiteren Merkmal der Erfindung als zweckmäßig, die Reaktionszone zweistufig auszubilden, wobei der Druck der zweiten Stufe höher als der der ersten Stufe, der vorzugsweise zwischen etwa 10 und 50 bar liegt, ist. Dabei wird die erste Reaktionsstufe unter etwa dem Druck der Verkokungszone betrieben, wobei der direkte Wärmetausch zwischen dem Kohlebrei und den Gasen und Dämpfen aus der Verkokungszone sowie ggf. den Gasen und Dämpfen vom Kopf des Heißabscheiders in dieser ersten Reaktionsstufe erfolgt.In particular in the treatment of hard-to-liquefy coals, it proves to be advantageous according to a further feature of the invention to design the reaction zone in two stages, the pressure of the second stage being higher than that of the first stage, which is preferably between about 10 and 50 bar . The first reaction stage is operated at approximately the pressure of the coking zone, with the direct heat exchange between the coal slurry and the gases and vapors from the coking zone and possibly the gases and vapors from the top of the hot separator taking place in this first reaction stage.

Um Verkokungen während des Aufheizens des Reaktionsproduktes zu vermeiden, kann nach einem weiteren Merkmal der Erfindung die Aufheizung des Reaktionsproduktes auf die Temperatur der Verkokungszone durch Zumischung eines heißen, durch partielle Oxidation von Kohlenwasserstoffen erzeugten wasserstoffreichen Gases erfolgen.In order to avoid coking during the heating of the reaction product, according to a further feature of the invention, the reaction product can be heated to the temperature of the coking zone by admixing a hot hydrogen-rich gas generated by partial oxidation of hydrocarbons.

Der Wasserstoffanteil dieses Gases kann dann unmittelbar sowohl zur Verbesserung der Verkokung als auch, falls die Reaktionszone zweistufig ausgebildet ist, zur Deckung des Wasserstoffbedarfes in der ersten Reaktionszone benutzt werden.The hydrogen content of this gas can then be used directly both to improve the coking and, if the reaction zone has two stages, to cover the hydrogen requirement in the first reaction zone.

Beispielsweise kann das heiße, wasserstoffhaltige Gas durch partielle Oxidation von Methan erzeugt werden, wobei sich unter anderem Wasserstoff und Kohlenmonoxid bildet. Selbstverständlich kann das heiße wasserstoffhaltige Gas aber auch durch partielle Oxidation, d.h. durch Vergasung, des in der Verkokungszone anfallenden Kokses oder, falls vor der Verkokung eine Rückstandsabtrennung stattgefunden hat, durch Vergasung dieses Rückstandes erzeugt werden.For example, the hot, hydrogen-containing gas can be generated by partial oxidation of methane, which forms hydrogen and carbon monoxide, among other things. Of course, the hot hydrogen-containing gas can also be obtained by partial oxidation, i.e. by gasification, of the coke produced in the coking zone or, if a residue has been separated before the coking, by gasification of this residue.

Die Zumischung des wasserstoffreichen Gases zu dem zu verkokenden Reaktionsprodukt erfolgt zweckmäßigerweise an mehreren, mindestens zwei in Fließrichtung des Rückstandes hintereinanderliegenden Stellen. Dadurch wird eine stufenweise gleichmäßige Erwärmung des Rückstandes gewährleistet, so daß die Verkokungstemperatur erst unmittelbar vor der Einleitung des Reaktionsproduktes in die Verkokungszone erreicht wird. Ggf. kann es sich auch als zweckmäßig erweisen, die Aufheizung des zu verkokenden Reaktionsproduktes in zwei Stufen durchzuführen, wobei in einer ersten Stufe Fremdwärme in einem Röhrenofen und in der der ersten Stufe nachgeschalteten zweiten Stufe das wasserstoffhaltige Heißgas zugeführt wird.The admixture of the hydrogen-rich gas to the reaction product to be coked is expediently carried out at a plurality of, at least two, points one behind the other in the direction of flow of the residue. This ensures a gradual, uniform heating of the residue, so that the coking temperature is only reached immediately before the reaction product is introduced into the coking zone. Possibly. it may also prove to be expedient to carry out the heating of the reaction product to be coked in two stages, with external heat being supplied in a tube furnace in a first stage and the hydrogen-containing hot gas being supplied in the second stage downstream of the first stage.

Nach einem weiteren Merkmal der Erfindung wird der in der Verkokungszone anfallender Koks vergast, das dabei gewonnene Rohgas gereinigt, teilkonvertiert und dann zumindest teilweise einer an sich bekannten Fischer-Tropsch-Synthese zur Erzeugung höhersiedender paraffinischer Kohlenwasserstoffe, insbesondere von Dieselöl, unterzogen.According to a further feature of the invention, the coke accumulating in the coking zone is gasified, the raw gas obtained in the process is cleaned, partially converted and then at least partially subjected to a Fischer-Tropsch synthesis known per se for producing higher-boiling paraffinic hydrocarbons, in particular diesel oil.

Auf diese Weise lassen sich in einer Anlage einmal Zuge der Verflüssigung und Verkokung der Kohle aromatische Kohlenwasserstoffe herstellen, die die Basis für die Gewinnung von Benzinen sind, während bei der Fischer-Tropsch-Synthese paraffinische Kohlenwasserstoffe anfallen, die sich besonders gut zur Erzeugung von Dieselöl eignen. Da aus dem zu vergasenden Koks bereits nahezu die gesamten Flüchtigen entwichen sind, fällt auch bei der Vergasung in einem aus heutiger Sicht am wirtschaftlichsten zu betreibenden Festbettvergaser ein nahezu sauberes, teerfreies Gas an, wodurch sich gegenüber der Vergasung von reiner Kohle der Aufwand zur Aufbereitung des für die Fischer-Tropsch-Synthese anstehenden Gases erheblich verringert.In this way, once the coal is liquefied and coked, aromatic hydrocarbons can be produced in one plant, which are the basis for the production of gasolines, while the Fischer-Tropsch synthesis produces paraffinic hydrocarbons, which are particularly good for producing diesel oil own. Since almost all of the volatiles have already escaped from the coke to be gasified, gasification in a fixed-bed gasifier, which is currently the most economical to operate, produces an almost clean, tar-free gas, which means that compared to gasifying pure coal, the effort required to process the for the Fischer-Tropsch synthesis of the gas present.

Über dies zeichnet sich eine derartige Verfahrensweise durch eine große Flexibilität im Hinblick auf die Benzin- bzw. Dieselölproduktion aus. Falls mehr Fischer-Tropsch-Produkte benötigt wird, kann die Anlage in einfacher Weise durch Senkung von Druck und Temperatur in der Reaktionszone bzw. der Verkokungszone auf weniger Destillatgewinn gefahren werden, wodurch mehr Koks für die Vergasung und die anschließende Fischer-Tropsch-Synthese anfällt. Umgekehrt können bei einem erhöhten Bedarf an aromatischen Kohlenwasserstoffen für die Benzinerzeugung die Bedingungen für die Behandlung der Kohle in der Reaktionszone bzw. der Verkokungszone durch Erhöhung von Druck und Temparatur oder auch durch Vergrößerung des Wasserstoffangebotes verschärft werden, so daß mehr Destillat und weniger Koks für die Vergasung anfällt.Such a procedure is characterized by great flexibility with regard to gasoline or diesel oil production. If more Fischer-Tropsch products are required, the plant can be operated in a simple manner by reducing the pressure and temperature in the reaction zone or the coking zone to less distillate gain, which results in more coke for the gasification and the subsequent Fischer-Tropsch synthesis . Conversely, with an increased need for aromatic hydrocarbons for gasoline production, the conditions for treating the coal in the reaction zone or the coking zone can be tightened by increasing pressure and temperature or by increasing the hydrogen supply, so that more distillate and less coke for the Gasification occurs.

Nach einem weiteren Merkmal der Erfindung erweist es sich als vorteilhaft, zum Anreiben der Kohle eine Schwerölfraktion oder bei der Verarbeitung von Erd-Öl anfallende Erdölrückstände, insbesondere noch Katalysator enthaltende Hydrierrückstände, zu verwenden. Derartige erdölstämmige Anreiböle zeichnen sich gegenüber Kohleölen durch einen erhöhten Wasserstoffanteil aus, der bereits bei besonders milden Verflüssigungsbedingungen auf die zu behandelnde Kohle übertragen werden kann. Auch kann bei der Verwendung von noch Katalysator enthaltenden Erdölhydrierrückstand als Anreiböl ggf. auf einen zusätzlichen Katalysator für die Kohlebehandlung verzichtet werden.According to a further feature of the invention, it proves to be advantageous to grind the coal with a heavy oil fraction or with oil residues, in particular catalyst, from the processing of petroleum containing hydrogenation residues to use. Such oil-based grating oils are distinguished from coal oils by an increased hydrogen content, which can be transferred to the coal to be treated even under particularly mild liquefaction conditions. If petroleum hydrogenation residue still containing catalyst is used as grinding oil, an additional catalyst for the coal treatment may also be dispensed with.

Das erfindungsgemäße Verfahren ist nicht auf die Verarbeitung von Stein- oder Braunkohle beschränkt. Vielmehr lassen sich mit den gleichen Vorteilen auch andere kohlenstoffhaltige Stoffe, wie insbesondere erdölstämmige Schweröle oder auch Ölsande oder Ölschiefer, behandeln.The method according to the invention is not limited to the processing of hard coal or brown coal. Rather, the same advantages can also be used to treat other carbonaceous substances, such as heavy oils derived from petroleum or oil sands or oil shale.

Weitere Erläuterungen zu der Erfindung sind dem in der Figur schematisch dargestellten Ausführungsbeispiel zu entnehmen.Further explanations of the invention can be found in the exemplary embodiment shown schematically in the figure.

Gemäß der Figur wird über eine Leitung 1 der zu behandelnde, bereits mit einem Anreiböl vermischte und auf einen Druck von etwa 20 bar gepumpte, frische Kohlebrei mit einem Kohleanteil von etwa 80 bis 90 Gew.-%, ggf. zusammen mit einem Katalysator, einem Mischer 2 zugeführt und dort im direkten Wärmetausch mit heißen Gasen und Dämpfen, deren Herkunft weiter hinten erläutert wird, auf etwa die Reaktionsanspringtemperatur von etwa 400° C aufgeheizt. Über eine Leitung 3 wird der Kohlebrei einer Reaktionszone 4 zugeführt und dort in Gegenwart von Wasserstoff, der über eine Leitung 5 in die Reaktionszone 4 eingeleitet wird, unter relativ milden Bedingungen, d.h. bei einem verhältnismäßig niedrigen Druck von nur etwa 200 bar und bei einer Temperatur von etwa 450° C verflüssigt.According to the figure, the fresh coal pulp to be treated, already mixed with a grinding oil and pumped to a pressure of about 20 bar, with a coal content of about 80 to 90% by weight, optionally together with a catalyst, is to be treated Mixer 2 fed and heated there in direct heat exchange with hot gases and vapors, the origin of which is explained below, to about the reaction start temperature of about 400 ° C. The coal pulp is fed to a reaction zone 4 via a line 3 and there in the presence of hydrogen, which is introduced into the reaction zone 4 via a line 5, under relatively mild conditions, i.e. liquefied at a relatively low pressure of only about 200 bar and at a temperature of about 450 ° C.

Das in der Reaktionszone 4 gewonnene Reaktionsprodukt setzt sich zusammen aus einer gasförmigen und einer flüssigen feststoffhaltigen Phase.The reaction product obtained in the reaction zone 4 is composed of a gaseous and a liquid solid-containing phase.

Im vorliegenden Ausführungsbeispiel wird die heiße gasförmige Phase, die im wesentlichen den nicht verbrauchten Wasserstoff, tiefsiedende Kohlenwasserstoffe, wie Methan, Äthan u.a., sowie Destillate im Siedebereich von Naphtha und Mittelöl enthält, über eine Leitung 6 in den Mischer 2 zurückgeführt, dort mit dem frischen Kohlebrei innig vermischt und dabei im Wärmetausch mit dem Kohlebrei abgekühlt.In the present exemplary embodiment, the hot gaseous phase, which essentially contains the unused hydrogen, low-boiling hydrocarbons, such as methane, ethane and others, and distillates in the boiling range of naphtha and middle oil, is returned to the mixer 2 via a line 6, there with the fresh one Coal porridge mixed intimately and cooled in the heat exchange with the coal porridge.

Die in der Reaktionszone 4 anfallende flüssige feststoffhaltige Phase besteht im wesentlichen aus Kohleextrakt, also Bitumen, sowie aus Destillaten im Siedebereich überwiegend von Schweröl. Darüber hinaus enthält diese Phase Feststoffe, wie nicht umgesetzte Kohle, Asche und unverbrauchter Katalysator. Dieses flüssige Reaktionsprodukt wird über Leitungen 7, 8, 9 und 10 einem Ofen 11 zugeführt, dort durch indirekte Zufuhr von Fremdwärme auf eine Temperatur von etwa 500°C erhitzt und anschließend über Leitungen 12, 13 und 14 in eine Verkokungszone 15 eingespeist. In der Verkokungszone 15 wird die flüssige feststoffhaltige Produktfraktion verkokt. Neben dem Endprodukt Koks entstehen dabei Gase und Dämpfe, insbesondere Destillate im Siedebereich von Naphtha und Mittelöl. Zur Verbesserung der Destillatqualität und zur Erhöhung der Destillatausbeute wird der zu verkokenden Produktfraktion über eine Leitung 16 Wasserstoff, z. B. in Form von Kokereigas, zugegeben.The liquid solid-containing phase obtained in reaction zone 4 essentially consists of coal extract, ie bitumen, and of distillates in the boiling range, predominantly of heavy oil. In addition, this phase contains solids such as unreacted coal, ash and unused catalyst. This liquid reaction product is fed via lines 7, 8, 9 and 10 to a furnace 11, where it is heated to a temperature of about 500 ° C. by indirect supply of external heat and then fed via lines 12, 13 and 14 into a coking zone 15. The liquid solid-containing product fraction is coked in the coking zone 15. In addition to the end product coke, gases and vapors are produced, especially distillates in the boiling range of naphtha and medium oil. To improve the quality of the distillate and to increase the yield of distillate, the product fraction to be coked is hydrogen via a line 16, for. B. in the form of coke oven gas added.

Nach einer weiteren Ausführungsform kann die Aufheizung der zu verkokenden Produktfraktion aber auch durch direkte Zumischung eines heißen wasserstoffhaltigen Gasgemisches unmittelbar vor Eintritt der Produktfraktion in die Verkokungszone 15 erfolgen. In diesem Falle wird die Produktfraktion über die Leitungen 7, 8,17,13 und 14 direkt in die Verkokungszone 15 eingeführt, während das wasserstoffhaltige Heißgas in einem Gaserzeuger 18 durch partielle Oxidation von Methan oder einem anderen Kohlenwasserstoff erzeugt und über Leitung 19 der zu verkokenden Produktfraktion zugemischt wird. Durch Regelung der Sauerstoffzufuhr zu dem Gaserzeuger 18 kann dabei die partielle Oxidation so gesteuert werden, daß einerseits durch die Oxidation von Kohlenstoff zu Kohlenmonoxid ausreichend Wärme zur Erhitzung der zu verkokenden Fraktion auf Verkokungstemperatur entsteht, daß andererseits aber auch genügend Wasserstoff für die Verkokungszone erzeugt wird.According to a further embodiment, the product fraction to be coked can also be heated by directly admixing a hot hydrogen-containing gas mixture immediately before the product fraction enters the coking zone 15. In this case, the product fraction is introduced via lines 7, 8, 17, 13 and 14 directly into the coking zone 15, while the hydrogen-containing hot gas is generated in a gas generator 18 by partial oxidation of methane or another hydrocarbon and is to be coked via line 19 Product fraction is added. By regulating the supply of oxygen to the gas generator 18, the partial oxidation can be controlled so that, on the one hand, sufficient heat is generated by the oxidation of carbon to carbon monoxide to heat the fraction to be coked to coking temperature, but on the other hand enough hydrogen is also generated for the coking zone.

Falls in der Verkokungszone 15 ein besonders reiner Koks erzeugt werden soll, beispielsweise für die Herstellung von Elektroden für metallurgische Prozesse, werden vor der Verkokung des Reaktionsproduktes die Feststoffe aus dieser abgetrennt. In diesem Falle wird das flüssige feststoffhaltige Reaktionsprodukt aus der Reaktionszone 4 über Leitungen 7 und 20 zunächst einer Feststoffabtrenneinrichtung 21 zugeführt, in der die Feststoffe in bekannter Weise, z. B. durch Filtration, Sedimentation oder auch durch Zentrifugieren, abgetrennt werden. Die nunmehr weitgehend von Feststoffen befreite zu verkokende Produktfraktion wird über eine Leitung 22 aus der Feststoffabtrenneinrichtung abgezogen und je nach der gewählten Art der weiteren Aufheizung über die Leitungen 9,17,13 und 14 oder auch über die Leitung 10, den Ofen 11 sowie die Leitungen 12, 13 und 14 der Verkokungszone 15 zugeführt. Derin der Feststoffabtrenneinrichtung 21 anfallende feststoffreiche Rückstand wird über eine Leitung 23 aus der Anlage abgezogen. Ggf. kann dieser Rückstand bzw. auch zumindest ein Teil des in der Verkokungszone 15 anfallenden Kokses in dem Gaserzeuger 18 zur Herstellung des wasserstoffhaltigen Heißgases genutzt werden.If a particularly pure coke is to be produced in the coking zone 15, for example for the production of electrodes for metallurgical processes, the solids are separated from the coke before the reaction product is coked. In this case, the liquid solid-containing reaction product from the reaction zone 4 via lines 7 and 20 is first fed to a solids separation device 21, in which the solids in a known manner, for. B. by filtration, sedimentation or centrifugation. The product fraction, which is now largely freed of solids and is to be coked, is withdrawn via a line 22 from the solids separation device and, depending on the selected type of further heating, via lines 9, 17, 13 and 14 or also via line 10, furnace 11 and the lines 12, 13 and 14 fed to the coking zone 15. The solid-rich residue obtained in the solids separation device 21 is withdrawn from the system via a line 23. Possibly. This residue or at least part of the coke obtained in the coking zone 15 can be used in the gas generator 18 to produce the hydrogen-containing hot gas.

Die in der Verkokungszone 15 entstehenden Dämpfe werden unter der Verkokungstemperatur von etwa 500°C über eine Leitung 24 abgezogen und ebenfalls dem Mischer 2 zugeleitet. Diese Dämpfe bewirken zusammen mit den Dämpfen aus Leitung 6 die Aufheizung des frischen Kohlebreis auf etwa die Anspringtemperatur der Reaktionszone 4, so daß, und hierin liegt ein wesentlicher Vorteil des vorgeschlagenen Verfahrens, auf die Zufuhr von Fremdwärme in schwer zu handhabenden Wärmetauschern zur Aufheizung des frischen Kohlebreis verzichtet werden kann. Im Zuge des direkten Wärmetausches der genannten Dämpfe mit dem Kohlebrei wird nahezu das ganze Wasser aus der Kohle ausgetrieben, so daß auch auf die energieaufwendige Trocknung der Kohle im Zuge ihrer Vorbereitung verzichtet werden kann.The vapors formed in the coking zone 15 are drawn off below the coking temperature of approximately 500 ° C. via a line 24 and are likewise fed to the mixer 2. These vapors, together with the vapors from line 6, heat up the fresh one Coal pulp to about the light-off temperature of the reaction zone 4, so that, and this is a major advantage of the proposed method, the supply of external heat in difficult-to-use heat exchangers for heating the fresh coal pulp can be dispensed with. In the course of the direct heat exchange of the above-mentioned vapors with the coal pulp, almost all of the water is expelled from the coal, so that the energy-consuming drying of the coal in the course of its preparation can also be dispensed with.

Die im Mischer 2 anfallenden Gase und Dämpfe, die sich im wesentlichen aus Restwasserstoff, Wasserdampf, geringen Mengen tiefsiedenden Kohlenwasserstoffen, wie Methan und Äthan u.a., und insbesondere den als Produkt anfallenden Destillaten im Naphtha- und Mittelölbereich zusammensetzen, werden über eine Leitung 25 aus der Anlage abgezogen und einer hier nicht dargestellten destillativen Weiterverarbeitung zugeführt, Aufgrund ihres aromatischen Charakters eignen sich die gewonnenen Destillate insbesondere zur Herstellung von Benzin.The resulting gases and vapors in the mixer 2, which consist essentially of residual hydrogen, water vapor, small amounts of low-boiling hydrocarbons, such as methane and ethane, among others, and in particular the product distillates in the naphtha and medium oil range, are via a line 25 from the System withdrawn and a further distillative processing, not shown here, due to their aromatic character, the distillates obtained are particularly suitable for the production of gasoline.

Besonders bei der Verwendung schwer aufschließbarer Kohlen kann es sich als zweckmäßig erweisen, die Mischstufe 2 bereits als eine erste Reaktionsstufe für die Kohle auszubilden und die sich anschließende Reaktionszone sozusagen als zweite Reaktionsstufe unter einem höheren Druck zu betreiben. In diesem Falle wird die Wasserstoffzufuhr über die Leitungen 16 bzw. 19 so erhöht, daß der zur Verfügung gestellte Wasserstoff nicht nur für die Verkokungszone, sonder zusätzlich auch noch für die erste Reaktionsstufe, die dabei zweckmäßigerweise unter etwa dem Druck der Verkokungszone betrieben wird, ausreicht.Particularly when using hard-to-digestible coals, it may prove expedient to design mixing stage 2 as a first reaction stage for the coal and to operate the subsequent reaction zone as a second reaction stage under a higher pressure, so to speak. In this case, the hydrogen supply via lines 16 and 19 is increased so that the hydrogen provided is sufficient not only for the coking zone, but also additionally for the first reaction stage, which is expediently operated under approximately the pressure of the coking zone .

Umgekehrt kann bei der Verarbeitung von leicht aufschließenden Kohlen, aber auch bei der Hydrierung von Schweröl oder Ölsanden, der direkte Wärmetausch zwischen den heißen Produktdämpfen und dem zu behandelnden Ausgangsstoff unmittelbar in die Reaktionszone 4 integriert werden, wobei diese dann zweckmäßigerweise unter etwa dem Druck der Verkokungszone 15 betrieben wird, der bei etwa zwischen 10 und 30 bar liegt. Die als Endprodukt gewonnenen Destillatdämpfe können in diesem Falle direkt vom Kopf der Reaktionszone 4 abgezogen werden.Conversely, in the processing of easily digesting coals, but also in the hydrogenation of heavy oil or oil sands, the direct heat exchange between the hot product vapors and the starting material to be treated can be integrated directly into the reaction zone 4, which then expediently under approximately the pressure of the coking zone 15 is operated, which is approximately between 10 and 30 bar. In this case, the distillate vapors obtained as the end product can be drawn off directly from the top of reaction zone 4.

Der in der Verkokungszone 15 anfallende Koks wird in diesem Ausführungsbeispiel über eine Zuführung 26 in einem Vergaser 27, vorzugsweise einem Festbettvergaser, eingespeist und dort zu einem kohlenmonoxid- und wasserstoffhaltigen Rohgas vergast. Der benötigte Sauerstoff strömt dem Vergaser 27 über eine Leitung 28 zu. Das Rohgas aus dem Vergaser 26 wird in einem nachgeschalteteen Anlagenteil 29 gereinigt und konvertiert und dann in einer Anlage 30 einer an sich bekannten Fischer-Tropsch-Synthese unterzogen. Die in dieser Anlage hergestellten Kohlenwasserstoffe eignen sich aufgrund ihres paraffinischen Charakters besonders vorteilhaft zur Herstellung von Dieseltreibstoff.In this exemplary embodiment, the coke obtained in the coking zone 15 is fed via a feed 26 into a gasifier 27, preferably a fixed bed gasifier, and gasified there to form a raw gas containing carbon monoxide and hydrogen. The required oxygen flows to the carburetor 27 via a line 28. The raw gas from the gasifier 26 is cleaned and converted in a downstream system part 29 and then subjected to a known Fischer-Tropsch synthesis in a system 30. Due to their paraffinic character, the hydrocarbons produced in this plant are particularly advantageous for the production of diesel fuel.

Nach dem vorgeschlagenen Verfahren gelingt es somit, in einer einzigen Anlage sowohl Treibstoff für Benzinmotoren als auch Treibstoff für Dieselmotoren zu produzieren, wobei je nach Erfordernis die Produktion leicht zugunsten einer Treibstoffart verschoben werden kann. Durch Milderung der Verfahrensbedingungen (Druck, Temperatur) in der Reaktions- oder der Verkokungszone reduziert sich z. B. die Produktion aromatischer Destillate zugunsten der Kokserzeugung während umgekehrt bei schärferen Hydrier- und Verkokungsbedingungen die Koksausbeute zugunsten der Destillatausbeute zurückgeht.According to the proposed method, it is thus possible to produce both fuel for gasoline engines and fuel for diesel engines in a single installation, production being easily shifted in favor of one type of fuel depending on requirements. By reducing the process conditions (pressure, temperature) in the reaction or coking zone, z. B. the production of aromatic distillates in favor of coke production while, conversely, with sharper hydrogenation and coking conditions, the coke yield decreases in favor of the distillate yield.

Zur Bindung des in der Kohle enthaltenen Schwefels, der bei der Verbrennung des Kokses, z. B. in einer Wirbelschichtfeuerung, freigesetzt würde, können dem frischen Kohlebrei und/oder der zu verkokenden Produktfraktion zudem schwefelbindende Stoffe, wie z. B. Kalziumoxid oder Kalziumkarbonat, zugegeben werden, wobei, wie sich gezeigt hat, diese Kalziumverbindungen aufgrund ihrer oberflächenaktiven Wirkung sogar zu einer weiteren Steigerung der Ölausbeute beitragen.To bind the sulfur contained in the coal, which during the combustion of the coke, for. B. would be released in a fluidized bed, the fresh coal pulp and / or the coking product fraction can also sulfur-binding substances such. As calcium oxide or calcium carbonate, are added, which, as has been shown, these calcium compounds even contribute to a further increase in the oil yield due to their surface-active effect.

Claims (20)

1. A process for the liquefication of coal, in which the ground coal is mixed with pasting oil to a paste and liquefied under increased pressure and increased temperature in a reaction zone in the presence of hydrogen and, if necessary, of a catalyst, characterised in that the reaction product leaving the reaction zone is led into a coking zone; and that the hot gases and vapours leaving the coking zone are cooled in direct heat exchange with the coal-paste to be heated.
2. A process as claimed in Claim 1,
characterised in that the hot gases and vapours leaving the coking zone are cooled in direct heat exchange with the coal-paste to be heated and that the portion of the gases and vapours not condensed in this heat exchange is separated from the heated coal-paste.
3. A process as claimed in Claim 1 or 2, characterised in that the gases and vapours contained in the reaction product of the reaction are separated and at least in part, are fed directly to the direct heat exchange with the coal-paste.
4. A process as claimed in one of Claims 1 to 3, characterised in that the pressure in the reaction zone is less than 300 bar, preferably between 150 and 250 bar.
5. A process as claimed in one of Claims 1 to 4, characterised in that the coking zone is operated at about the pressure of the reaction zone.
6. A process as claimed in one of Claims 1 to 5, characterised in that the reaction zone is formed in two stages, the pressure in the first stage being lower than the pressure in the second stage.
7. A process as claimed in Claim 6, characterised in that the pressure in the first reaction stage is between about 10 and 50 bar.
8. A process as claimed in Claim 6 or 7, characterised in that the first reaction zone is operated at about the pressure of the coking zone; and that the direct heat exchange between the vapours and gases from the coking zone and the coal-paste to be heated takes place in the first reaction zone.
9. A process as claimed in one of Claims 1 to 8, characterised in that before the coking of the reaction product, the solids contained therein are at least partially removed.
10. A process as claimed in one of Claims 1 to 9, characterised in that the reaction product is heated to a temperature of between about 450 and 600°C before it is coked.
11. A process as claimed in one of Claims 1 to 10, characterised in that the heating of the reaction product to be coked is effected by the indirect addition of external heat.
12. A process as claimed in one of Claims 1 to 11, characterised in that hydrogen is mixed with the reaction product to be coked.
13. A process as claimed in one of Claims 1 to 10, characterised in that the heating of the reaction product to be coked is effected by the addition of a hydrogen-containing hot gas obtained by the partial oxidation of a carbon- containing fuel.
14. A process as claimed in Claim 13, characterised in that the hot gas is added to the reaction product to be coked at at least two points lying one after the other in the direction of the flow of the reaction product.
15. A process as claimed in one of Claims 1 to 14, characterised in that the heating of the reaction product to be coked takes place in two stages, where in a first stage external heat is supplied, and in the second stage, which follows the first stage, a hydrogen-containing hot gas is supplied.
16. A process as claimed in one of Claims 1 to 15, characterised in that hydrogen-donor oils are added to the reaction product to be coked before it is heated to the coking temperature, in particular a high-boiling point fraction of the oil yield of the plant, already hydrogen-refined.
17. A process as claimed in one of Claims 1 to 16, characterised in that the coke produced in the coking zone is gasified and that the crude gas so obtained is subjected, after its purification and partial conversion, at least in part to a Fischer-Tropsch synthesis to produce high-boiling point paraffinic hydrocarbon fractions.
18. A process as claimed in one of Claims 1 to 17, characterised in that substances which combine with sulphur are added to the fresh coal and/or to the reaction product to be coked.
19. A process as claimed in one of Claims 1 to 18, characterised in that as pasting oil, there are used, at least in part, petroleum fractions and/or petroleum residues obtained in the processing of petroleum, particularly petroleum hydrogenation residues which still contain catalyst.
20. The use of the process as claimed in one or more of Claims 1 to 19, for processing heavy petroleum fractions, oil sands or oil shales.
EP84904097A 1983-11-05 1984-11-03 Coal liquefaction process Expired EP0161290B1 (en)

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JPH0753965A (en) * 1993-08-09 1995-02-28 Nkk Corp Liquefaction of coal
US20080256852A1 (en) * 2007-04-20 2008-10-23 Schobert Harold H Integrated process and apparatus for producing coal-based jet fuel, diesel fuel, and distillate fuels
CN103254922B (en) * 2013-04-17 2014-11-05 西安交通大学 Two-stage coal direct liquefaction method and system
IL227708A0 (en) * 2013-07-29 2013-12-31 S G B D Technologies Ltd Processing combustible material methods and systems
US9061953B2 (en) 2013-11-19 2015-06-23 Uop Llc Process for converting polycyclic aromatic compounds to monocyclic aromatic compounds

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US2852441A (en) * 1954-10-22 1958-09-16 Exxon Research Engineering Co Conversion of hydrocarbons
US3193486A (en) * 1962-10-23 1965-07-06 Sinclair Research Inc Process for recovering catalyst particles in residual oils obtained in the conversion of hydrocarbon oils
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DE2654635B2 (en) * 1976-12-02 1979-07-12 Ludwig Dr. 6703 Limburgerhof Raichle Process for the continuous production of hydrocarbon oils from coal by cracking pressure hydrogenation
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DE3141380A1 (en) * 1981-10-17 1983-05-05 GfK Gesellschaft für Kohleverflüssigung mbH, 6600 Saarbrücken METHOD FOR HYDROGENATING COAL

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