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WO2003033624A1 - Method for pyrolysis and gasification of biomass - Google Patents

Method for pyrolysis and gasification of biomass Download PDF

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Publication number
WO2003033624A1
WO2003033624A1 PCT/EP2002/011437 EP0211437W WO03033624A1 WO 2003033624 A1 WO2003033624 A1 WO 2003033624A1 EP 0211437 W EP0211437 W EP 0211437W WO 03033624 A1 WO03033624 A1 WO 03033624A1
Authority
WO
WIPO (PCT)
Prior art keywords
pyrolysis
oil
biomass
bio
coke
Prior art date
Application number
PCT/EP2002/011437
Other languages
German (de)
French (fr)
Inventor
Edmund Henrich
Eckhard Dinjus
Dietrich Meier
Original Assignee
Forschungszentrum Karlsruhe Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Forschungszentrum Karlsruhe Gmbh filed Critical Forschungszentrum Karlsruhe Gmbh
Priority to EP02801333A priority Critical patent/EP1436367A1/en
Publication of WO2003033624A1 publication Critical patent/WO2003033624A1/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
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/466—Entrained flow processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • 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
    • C10J2300/0926—Slurries comprising bio-oil or bio-coke, i.e. charcoal, obtained, e.g. by fast pyrolysis of biomass
    • 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
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1643—Conversion of synthesis gas to energy
    • C10J2300/165—Conversion of synthesis gas to energy integrated with a gas turbine or gas motor
    • 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
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • 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
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1665—Conversion of synthesis gas to chemicals to alcohols, e.g. methanol or ethanol
    • 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
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1671—Integration of gasification processes with another plant or parts within the plant with the production of electricity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin

Definitions

  • the invention relates to a method for treating biomass according to the first claim.
  • biomass is to be understood to mean all agricultural and forestry residual and waste products, in particular straw, leaves, hay, residual wood and wood waste, which may be contaminated or blended with household waste, in particular with paper, cardboard and plastics ,
  • flash pyrolysis One method for the treatment of biomass is rapid pyrolysis, which is sometimes also referred to as "flash pyrolysis”.
  • shredded, dry biomass is rapidly heated to approximately 500 ° C. in the absence of air, the resulting sulfurized vapors quickly, that is to say
  • the process is carried out under normal or slight negative pressure and is therefore technically uncomplicated. It supplies carbonization gas, bio-oil and pyrolysis coke in products in varying proportions which can be influenced by the process parameters
  • the main product is generally bio-oil, the use of which as a fuel for the substitution of corresponding mineral oil products is discussed.
  • the carbonization gas is often used internally for heating purposes, while the usability of pyrolysis coke is limited.
  • bio oil In contrast to organic oils, bio oil typically contains 10 to 35% by weight of water. It is in petroleum products and non-polar organic solvents are insoluble, on the other hand miscible with water, the so-called pyrolysis lignin precipitating out with greater dilution. When distilling, almost half of the initial mass remains in the distillation residue.
  • Rapid pyrolysis is described in detail in a number of publications, for example in the article by A.V. Bridgwater. "An Introduction to Fast Pyrolysis of Biomass for Fuels and Chemicals” in Fast Pyrolysis of Biomass: A Handbook by A. Bridgwater et al, cpl-press, Aston University May 1999. This article also describes the devices for carrying out rapid pyrolysis.
  • the entrained flow gasifier consists of an outer cylindrical pressure jacket and an internally cooled, also cylindrical reaction chamber which is inserted into the upper part of the pressure jacket in such a way that an annular gap remains between the two components.
  • a pilot flame is maintained in the reaction chamber, which is filled with gas and technical oxygen is generated.
  • the fuel is fed separately into the flame zone.
  • the two input stages of the Noell conversion process include pyrolysis and entrained-flow gasification.
  • the following stages concern the cleaning of the resulting products and the waste water.
  • the pyrolysis is carried out in an externally heated rotary tube.
  • Solid pyrolysis coke and a raw pyrolysis gas are produced by pyrolysis.
  • the raw pyrolysis gas is cooled, with small amounts of condensed hydrocarbons being separated off, as well as any water and coke dust present.
  • Solid ingredients of the liquid hydrocarbons are separated in a decanter.
  • a further cooling stage and decanting result in an additional purification of the pyrolysis gas which is used in the subsequent entrained-flow gasification.
  • the pilot flame of the entrained-flow gasifier can be fed through the pyrolysis gas if required.
  • the pyrolysis coke from the upstream pyrolysis is used as fuel. This coke has to be ground very finely beforehand.
  • a specially developed pneumatic metering system is used to feed the entrained-flow gasifier.
  • a major advantage of the entrained flow gasifier is that the hot inside of the reaction chamber, which is provided with a silicon carbide lining, is covered during operation by a mineral so-called "slag fur", which protects the material from the corrosive conditions.
  • the invention has for its object to provide a multi-stage process for the treatment of biomass, which comprises a pyrolysis stage and a subsequent entrained flow pressure gasification, in which pyrolysis coke is used as a fuel which the feed of the pyrolysis coke can be made easier.
  • the fuel pyrolysis coke is fed to the entrained flow gasifier in the form of a pumpable slurry. This avoids the problems that arise when the fuel is fed in a dust-fine, solid form into an entrained-flow gasifier maintained at a high overpressure.
  • Bio oil is used as a slurry.
  • bio oil forms as the main product alongside the products pyrolysis gas and pyrolysis coke. Because of these proportions, the entire pyrolysis coke produced can be slurried in bio-oil.
  • the rapid pyrolysis is preferably carried out at operating parameters such that 40 to 80% by weight of bio oil and 10 to 30% by weight of pyrolysis coke are formed.
  • a slurry of the pyrolysis coke produced in the resulting bio-oil produces an oil sludge which is particularly suitable in terms of the pumping and feeding properties. Pressures in the range from atmospheric pressure to a rough vacuum and temperatures in the range from 400 ° C. to 600 ° C. are well suited for carrying out the rapid pyrolysis.
  • the residence time of the steam until condensation should be in the range of 0.5 to 5 seconds.
  • the entrained-flow gasification is carried out in the type of entrained-flow gasifier described in the publication mentioned at the beginning.
  • the operating pressure maintained in the entrained flow gasifier should be at least 50 bar; the maximum pressure results from the condition that supercritical conditions in the entrained-flow gasifier are avoided. Pressures of 50 bar and more are required, for example, for catalyzed low-pressure methanol synthesis if additional synthesis gas compressors are to be dispensed with. However, pressures up to 200 bar are possible.
  • a high operating pressure in the entrained-flow gasifier has the advantage that the synthesis gas can be cleaned more easily with a corresponding pressure at higher pollutant concentrations and in smaller devices. A high operating pressure ensures a high reaction speed and a high material turnover.
  • the temperature in the entrained flow gasifier should be in the range from 1200 ° C to 1800 ° C; this causes the slag fur to run as intended on the inner walls of the reaction space.
  • the method according to the invention enables the use of the entire usable energy content of the biomass for the synthesis gas generation in the subsequent entrained-flow gasification, without the need to provide more than one metering device for fuel on the entrained-flow gasifier.
  • the pyrolysis gas from rapid pyrolysis is suitable for maintaining the pilot flame or for atomizing oil sludge. It is particularly advantageous that cleaning steps or chemical preparation process for the bio-oil can be dispensed with, since it is mixed with the pyrolysis coke anyway.
  • all the condensates, in particular the “slurry products”, for example from decanters for cleaning synthesis gas can be added to the pyrolysis oil, so that the cleaning of the product streams from rapid pyrolysis is considerably simplified.
  • Bio oil or oil sludge is also easier to transport and store and more flexible to use than dusty pyrolysis coal.
  • the invention opens up the possibility of bringing together bio-oils or oil sludges from several decentralized rapid pyrolysis devices and further processing them in a large, central entrained-flow gasifier. In these cases it makes sense to use the pyrolysis gas directly in rapid pyrolysis.
  • the pyrolysis gas of a rapid pyrolysis usually contains only 10% or even less of the total calorific value of the starting biomass, so that 90% or more of the energy content of the original biomass still reaches the entrained-flow gasifier.
  • the figure shows a basic technical concept for the production of fuel and electricity from biomass.
  • the biomass After delivery and, if necessary, intermediate storage, the biomass is subjected to a pretreatment which includes comminution and post-drying. Then it is fed to rapid pyrolysis, which - as already mentioned above - can be carried out most easily at atmospheric pressure.
  • the operating temperature is around 500 ° C and is usually maintained via a heat transfer circuit.
  • Rapid pyrolysis products are carbonization gas, bio-oil and py- rolysekoks. These products can be obtained, for example, in a ratio of 15:60:25% by weight.
  • Use options for the carbonization gas are the use as fuel gas z. B. in the rapid pyrolysis itself, the power generation in gas engines or turbines and the use as an atomizing gas or fuel gas for the pilot burner of the subsequent entrained flow gasification.
  • the bio oil is used to make the coke slurry.
  • the pyrolysis coke is ground beforehand.
  • the biomass used contains high amounts of potassium and chlorine, such as straw or other rapidly growing biomass, it may be useful to remove potassium chloride and other soluble potassium / chlorine compounds from the pyrolysis coke, for example in a washing device, with water before the slurry.
  • the typical calorific value of pyrolysis coke is almost twice the calorific value of bio-oil, while the calorific value of pyrolysis gas is only roughly half of the calorific value of bio-oil.
  • the oil sludge that results from the slurry of the pyrolysis coke in the bio-oil is then pumped into the entrained-flow gasifier with the help of a high-pressure pump.
  • the entrained flow gasifier can be operated, for example, at a little over 50 bar and a temperature of 1500 ° C.
  • the pilot flame is e.g. B. operated with pyrolysis gas from rapid pyrolysis or with synthesis gas from the entrained flow gasifier and technical oxygen.
  • the proportion of oxygen should be about one third to one quarter based on the total oxygen requirement for the oxidation of the ingredients.
  • a sufficiently high reaction temperature must be guaranteed so that the chemical reaction proceeds as completely as possible and the operational drainage of the slag fur is guaranteed.
  • the raw synthesis gas leaving the entrained flow gasifier can be used as a high-temperature fuel gas or as a reducing gas. However, it can also be processed and converted into valuable chemical products, such as fuels.
  • the pure synthesis gas leaving the gas processing unit is suitable for methanol synthesis, as a fuel substitute or for other chemical syntheses, for example for carrying out oxosynthesis or, after a shift reaction, for hydrogenation.
  • the synthesis gas that is not converted during synthesis can be emitted in gas turbines, gas engines or GUD systems.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Treatment Of Sludge (AREA)

Abstract

The aim of the invention is to provide a simple method for the treatment of biomass, during which a synthesis gas is produced. According to the inventive method, a) the biomass is subjected to fast pyrolysis, forming bio-oil and pyrolysis coke, b) the pyrolysis coke in the bio-oil is reduced to an oil mud, c) the oil mud is compressed in an entrained bed gasifier which is maintained at an overpressure, and d) said oil mud is transformed into a raw synthesis gas in the entrained bed gasifier.

Description

VERFAHREN ZUR PYROLYSE UND VERGASUNG VON BIOMASSE METHOD FOR THE PYROLYSIS AND GASIFICATION OF BIOMASS
Die Erfindung betrifft ein Verfahren zur Behandlung von Biomasse gemäß dem ersten Patentanspruch.The invention relates to a method for treating biomass according to the first claim.
Die Energieerzeugung durch Verbrennung von Biomasse oder der aus Biomasse erzeugten Produkte hat den Vorteil, dass die Kohlendioxid-Bilanz insgesamt ausgeglichen ist. Aus diesem Grund werden derzeit viele Verfahren zur energetischen Verwertung von Biomasse und deren Produkte entwickelt.The generation of energy by burning biomass or products made from biomass has the advantage that the overall carbon dioxide balance is balanced. For this reason, many processes for the energetic utilization of biomass and its products are currently being developed.
Unter dem Begriff „Biomasse" sollen im folgenden alle land- und forstwirtschaftlichen Rest- und Abfallprodukte, insbesondere Stroh, Laub, Heu, Restholz und Holzabfälle verstanden werden, die ggf. mit Hausmüll, insbesondere mit Papier, Pappe und Kunststoffen verunreinigt oder verschnitten sein können.In the following, the term “biomass” is to be understood to mean all agricultural and forestry residual and waste products, in particular straw, leaves, hay, residual wood and wood waste, which may be contaminated or blended with household waste, in particular with paper, cardboard and plastics ,
Ein Verfahren zur Behandlung von Biomasse ist die Schnellpyrolyse, die manchmal auch als „Flash-Pyrolyse" bezeichnet wird. Bei diesem Verfahren wird zerkleinerte, trockene Biomasse unter Luftabschluss schnell auf ca. 500°C erhitzt, wobei die entstehenden Schweldämpfe schnell, .das heißt, nach einer Verweilzeit von etwa einer Sekunde, kondensiert werden. Das Verfahren wird unter Normal- oder leichtem Unterdruck durchgeführt und ist aus diesem Grund technisch unkompliziert. Es liefert als Produkte Schwelgas, Bioöl und Pyrolysekoks in wechselnden, durch die Verfahrensparameter jedoch beeinflussbaren Anteilen. Das Hauptprodukt ist im allgemeinen das Bioöl, dessen Verwendung als Brennstoff zur Substitution entsprechender Mineralölprodukte diskutiert wird. Das Schwelgas wird häufig anlagenintern zu Heizzwecken eingesetzt, während die Verwendbarkeit des Pyrolysekokses begrenzt ist.One method for the treatment of biomass is rapid pyrolysis, which is sometimes also referred to as "flash pyrolysis". In this method, shredded, dry biomass is rapidly heated to approximately 500 ° C. in the absence of air, the resulting sulfurized vapors quickly, that is to say The process is carried out under normal or slight negative pressure and is therefore technically uncomplicated. It supplies carbonization gas, bio-oil and pyrolysis coke in products in varying proportions which can be influenced by the process parameters The main product is generally bio-oil, the use of which as a fuel for the substitution of corresponding mineral oil products is discussed.The carbonization gas is often used internally for heating purposes, while the usability of pyrolysis coke is limited.
Bioöl enthält im Unterschied zu organischen Ölen typischerweise 10 bis 35 Gew.-% Wasser. Es ist in Mineralölprodukten und unpolaren organischen Lösungsmitteln nicht löslich, dagegen mit Wasser mischbar, wobei bei grösserer Verdünnung das sogenannte Pyrolyselignin ausfällt. Beim Destillieren verbleibt fast die Hälfte der Ausgangsmasse im Destillationsrückstand.In contrast to organic oils, bio oil typically contains 10 to 35% by weight of water. It is in petroleum products and non-polar organic solvents are insoluble, on the other hand miscible with water, the so-called pyrolysis lignin precipitating out with greater dilution. When distilling, almost half of the initial mass remains in the distillation residue.
Die Schnellpyrolyse ist in einer Reihe von Druckschriften eingehend beschrieben, beispielsweise in dem Artikel von A. V. Bridgwater. „An Introduction to Fast Pyrolysis of Biomass for Fuels and Chemicals" in Fast Pyrolysis of Biomass : A Handbook von A. Bridgwater et al, cpl-press, Aston University May 1999. In diesem Artikel sind auch die Vorrichtungen zur Durchführung der Schnellpyrolyse beschrieben.Rapid pyrolysis is described in detail in a number of publications, for example in the article by A.V. Bridgwater. "An Introduction to Fast Pyrolysis of Biomass for Fuels and Chemicals" in Fast Pyrolysis of Biomass: A Handbook by A. Bridgwater et al, cpl-press, Aston University May 1999. This article also describes the devices for carrying out rapid pyrolysis.
Zur Behandlung von Biomasse sind außerdem bereits Flugstromvergaser vorgeschlagen wordenIn addition, entrained-flow gasifiers have already been proposed for treating biomass
(http: //www.itas . fzk. de/deu/Jahresberichte/jahr97PSA.htm, Abschnitt „Nutzung von Nachwachsenden Rohstoffen und Behandlung von Reststoffen aus Pflanzen") .(http: //www.itas. fzk. de / deu / Jahresberichte / Jahres97PSA.htm, section "Use of renewable raw materials and treatment of residues from plants").
Eine detaillierte Beschreibung von Flugstromvergasern findet sich in „NOELL-Konversionsverfa ren zur Verwertung und Entsorgung von Abfällen" von Jürgen Carl und Peter Fritz, EF-Verlag für Energie- und Umwelttechnik GmbH (1994), insbesondere in dem Abschnitt „Darstellung des NOELL-Konversionsverfahrens" von Manfred Schingnitz.A detailed description of entrained-flow gasifiers can be found in "NOELL conversion processes for recycling and disposal of waste" by Jürgen Carl and Peter Fritz, EF-Verlag für Energie- und Umwelttechnik GmbH (1994), in particular in the section "Presentation of the NOELL conversion process "by Manfred Schingnitz.
In diesem Abschnitt wird der Aufbau und die Funktionsweise eines Flugstromvergasers eingehend anhand einer Abbildung beschrieben. Der Flugstromvergaser besteht aus einem äußeren zylindrischen Druckmantel und einem innenliegenden gekühlten, ebenfalls zylindrischen Reaktionsraum, der in den oberen Teil des Druckmantels in der Weise eingesetzt ist, dass zwischen den beiden Komponenten ein Ringspalt verbleibt. Im Reaktionsraum wird eine Pilotflamme aufrechterhalten, die mit Gas und technischem Sauerstoff erzeugt wird. In die Flammenzone wird separat der Brennstoff eingespeist.In this section, the structure and operation of an entrained-flow gasifier is described in detail using an illustration. The entrained flow gasifier consists of an outer cylindrical pressure jacket and an internally cooled, also cylindrical reaction chamber which is inserted into the upper part of the pressure jacket in such a way that an annular gap remains between the two components. A pilot flame is maintained in the reaction chamber, which is filled with gas and technical oxygen is generated. The fuel is fed separately into the flame zone.
Die beiden Eingangsstufen des Noell-Konversionsverfahrens umfassen eine Pyrolyse und eine Flugstromvergasung. Nachfolgende Stufen betreffen die Reinigung der entstehenden Produkte und des Abwassers.The two input stages of the Noell conversion process include pyrolysis and entrained-flow gasification. The following stages concern the cleaning of the resulting products and the waste water.
Die Pyrolyse wird in einem außenbeheizten Drehrohr durchgeführt. Durch die Pyrolyse wird fester Pyrolysekoks sowie ein Pyrolyserohgas erzeugt. Das Pyrolyserohgas wird abgekühlt, wobei geringe Mengen enthaltener kondensierter Kohlenwasserstoffe ebenso wie ggf. vorhandenes Wasser und Koksstaub abgetrennt werden. In einem Dekanter werden feste Inhaltsstoffe der flüssigen Kohlenwasserstoffe separiert. Eine weitere Kühlstufe und Dekantierung bewirkt eine zusätzliche Reinigung des Pyrolysegases, das bei der nachfolgenden Flugstromvergasung eingesetzt wird.The pyrolysis is carried out in an externally heated rotary tube. Solid pyrolysis coke and a raw pyrolysis gas are produced by pyrolysis. The raw pyrolysis gas is cooled, with small amounts of condensed hydrocarbons being separated off, as well as any water and coke dust present. Solid ingredients of the liquid hydrocarbons are separated in a decanter. A further cooling stage and decanting result in an additional purification of the pyrolysis gas which is used in the subsequent entrained-flow gasification.
Die Pilotflamme des Flugstromvergasers kann bei Bedarf durch das Pyrolysegas gespeist werden. Als Brennstoff wird der Pyrolysekoks aus der vorgeschalteten Pyrolyse eingesetzt. Dieser Koks muss zuvor sehr fein gemahlen werden. Zur Einspeisung in den Flugstromvergaser wird ein speziell entwickeltes pneumatisches Dosiersystem verwendet. Ein wesentlicher Vorteil des Flugstromvergasers ist, dass die heiße Innenseite des Reaktionsraumes, die mit einer Siliziu carbid-Auskleidung versehen ist, im Laufe des Betriebs von einem mineralischen sogenannten „Schlackenpelz" bedeckt wird, die das Material vor den korrosiven Bedingungen schützt.The pilot flame of the entrained-flow gasifier can be fed through the pyrolysis gas if required. The pyrolysis coke from the upstream pyrolysis is used as fuel. This coke has to be ground very finely beforehand. A specially developed pneumatic metering system is used to feed the entrained-flow gasifier. A major advantage of the entrained flow gasifier is that the hot inside of the reaction chamber, which is provided with a silicon carbide lining, is covered during operation by a mineral so-called "slag fur", which protects the material from the corrosive conditions.
Der Erfindung liegt die Aufgabe zugrunde, ein mehrstufiges Verfahren zur Behandlung von Biomasse anzugeben, das eine Pyrolysestufe und eine nachfolgende Flugstromdruckvergasung umfaßt, in der Pyrolysekoks als Brennstoff eingesetzt wird, bei dem die Einspeisung des Pyrolysekokses einfacher gestaltet werden kann.The invention has for its object to provide a multi-stage process for the treatment of biomass, which comprises a pyrolysis stage and a subsequent entrained flow pressure gasification, in which pyrolysis coke is used as a fuel which the feed of the pyrolysis coke can be made easier.
Die Aufgabe der Erfindung wird durch das im ersten Patentanspruch beschriebene Verfahren gelöst. Bevorzugte Ausführungsformen des Verfahrens sind Gegenstand der Ansprüche 2 bis 6.The object of the invention is achieved by the method described in the first claim. Preferred embodiments of the method are the subject of claims 2 to 6.
Erfindungsgemäß wird dem Flugstromvergaser der Brennstoff Pyrolysekoks in Form einer pumpbaren Aufschlämmung zugeführt. Damit werden die Probleme vermieden, die sich bei einer Einspeisung des Brennstoffs in staubfeiner, fester Form in einen auf hohem Überdruck gehaltenen Flugstromvergaser ergeben. Als AufSchlämmmittel wird Bioöl eingesetzt.According to the invention, the fuel pyrolysis coke is fed to the entrained flow gasifier in the form of a pumpable slurry. This avoids the problems that arise when the fuel is fed in a dust-fine, solid form into an entrained-flow gasifier maintained at a high overpressure. Bio oil is used as a slurry.
Bioöl bildet sich bei einer Schnellpyrolyse als Hauptprodukt neben den Produkten Pyrolysegas und Pyrolysekoks. Wegen dieser Mengenverhältnisse kann der gesamte entstehende Pyrolysekoks in Bioöl aufgeschlämmt werden. Vorzugsweise wird die Schnellpyrolyse bei solchen Betriebsparametern durchgeführt, dass sich 40 bis 80 Gew.-% Bioöl und 10 bis 30 Gew.-% Pyrolysekoks bilden. In diesem Fall bewirkt eine Aufschlämmung des erzeugten Pyrolysekokses in dem entstandenen Bioöl einen in Bezug auf die Pump- und Einspeiseeigenschaften besonders geeigneten Olschlamm. Zur Durchführung der Schnellpyrolyse sind Drücke im Bereich des Atmosphärendrucks bis zum Grobvakuum und Temperaturen im Bereich von 400°C bis 600°C gut geeignet. Die Verweilzeit des Schweldampfes bis zur Kondensation soll im Bereich von 0,5 bis 5 Sekunden liegen.In rapid pyrolysis, bio oil forms as the main product alongside the products pyrolysis gas and pyrolysis coke. Because of these proportions, the entire pyrolysis coke produced can be slurried in bio-oil. The rapid pyrolysis is preferably carried out at operating parameters such that 40 to 80% by weight of bio oil and 10 to 30% by weight of pyrolysis coke are formed. In this case, a slurry of the pyrolysis coke produced in the resulting bio-oil produces an oil sludge which is particularly suitable in terms of the pumping and feeding properties. Pressures in the range from atmospheric pressure to a rough vacuum and temperatures in the range from 400 ° C. to 600 ° C. are well suited for carrying out the rapid pyrolysis. The residence time of the steam until condensation should be in the range of 0.5 to 5 seconds.
Die Flugstromvergasung wird in dem Flugstromvergasertyp durchgeführt, der in der eingangs genannten Druckschrift beschrieben ist. Der im Flugstromvergaser aufrechterhaltene Betriebsdruck sollte mindestens 50 bar betragen; der Höchstdruck ergibt sich aus der Bedingung, dass überkritische Zustände im Flugstromvergaser vermieden werden. Drücke von 50 bar und mehr sind beispielsweise für die katalysierte Niederdruck-Methanolsynthese erforderlich, wenn auf zusätzliche Synthesegas-Kompressoren verzichtet werden soll. Drücke bis zu 200 bar sind jedoch möglich. Ein hoher Betriebsdruck im Flugstromvergaser bietet den Vorteil, dass das Synthesegas mit einem entsprechenden Druck bei höheren Schadstoffkonzentrationen und in kleineren Vorrichtungen einfacher gereinigt werden kann. Ein hoher Betriebsdruck gewährleistet eine hohe Reaktionsgeschwindigkeit und einen hohen Stoffumsatz. Die Temperatur im Flugstromvergaser sollte im Bereich von 1200 °C bis 1800°C liegen; dies bewirkt, dass der Schlackepelz bestimmungsgemäß an den Innenwänden des Reaktionsraumes abläuft.The entrained-flow gasification is carried out in the type of entrained-flow gasifier described in the publication mentioned at the beginning. The operating pressure maintained in the entrained flow gasifier should be at least 50 bar; the maximum pressure results from the condition that supercritical conditions in the entrained-flow gasifier are avoided. Pressures of 50 bar and more are required, for example, for catalyzed low-pressure methanol synthesis if additional synthesis gas compressors are to be dispensed with. However, pressures up to 200 bar are possible. A high operating pressure in the entrained-flow gasifier has the advantage that the synthesis gas can be cleaned more easily with a corresponding pressure at higher pollutant concentrations and in smaller devices. A high operating pressure ensures a high reaction speed and a high material turnover. The temperature in the entrained flow gasifier should be in the range from 1200 ° C to 1800 ° C; this causes the slag fur to run as intended on the inner walls of the reaction space.
Bei Bedarf - vor allem dann, wenn „schmutzige" Biomasse mit einem hohen Anteil nicht flüchtiger Asche eingesetzt wird - empfiehlt es sich, den Pyrolysekoks vor dem Aufschlämmen mit dem Bioöl mit Wasser zu waschen. Dabei werden insbesondere die Elemente Kalium und Chlor entfernt, die in der nachfolgenden Flugstromvergasung und der Synthesegas-Aufbereitung Probleme bereiten könnten. Zur Vermehrung und zur qualitativen Verbesserung des Schlackenpelzes im Flugstromvergaser kann dem Olschlamm ein anorganischer Schlackebildner in Form eines aschereichen Kokses aus einer anderen Quelle und/oder eines pulverförmigen Mineralstoffs zugesetzt werden. Dabei ist es unerheblich, ob man diese Stoffe bereits mit dem Pyrolysekoks oder mit dem Olschlamm vermischt.If necessary - especially if "dirty" biomass with a high proportion of non-volatile ash is used - it is advisable to wash the pyrolysis coke with water before slurrying with the bio-oil. The elements potassium and chlorine, in particular, are removed In the subsequent entrained-flow gasification and synthesis gas preparation, problems can be caused to increase and improve the quality of the slag fur in the entrained-flow gasifier by adding an inorganic slag generator in the form of an ash-rich coke from another source and / or a powdered mineral irrelevant whether these substances are already mixed with the pyrolysis coke or with the oil sludge.
Das erfindungsgemäße Verfahren ermöglicht den Einsatz des gesamten nutzbaren Energieinhaltes der Biomasse für die Synthesegaserzeugung in der nachfolgenden Flugstromvergasung, ohne dass am Flugstromvergaser mehr als eine Dosiervorrichtung für Brennstoff vorgesehen werden muss. Das Pyrolysegas aus der Schnellpyrolyse eignet sich zur Aufrechterhaltung der Pilotflamme oder zum Zerstäuben von Olschlamm. Von besonderem Vorteil ist, dass auf Reinigungsschritte oder auf chemische Auf- bereitungsverfahren für das Bioöl verzichtet werden kann, da es ohnehin mit dem Pyrolysekoks vermischt wird. Dem Pyrolyseöl können außerdem alle Kondensate, insbesondere die „Slur- ryprodukte" beispielsweise aus Dekantern für die Synthesegasreinigung zugeschlagen werden, so dass sich die Reinigung der Produktströme aus der Schnellpyrolyse wesentlich vereinfacht.The method according to the invention enables the use of the entire usable energy content of the biomass for the synthesis gas generation in the subsequent entrained-flow gasification, without the need to provide more than one metering device for fuel on the entrained-flow gasifier. The pyrolysis gas from rapid pyrolysis is suitable for maintaining the pilot flame or for atomizing oil sludge. It is particularly advantageous that cleaning steps or chemical preparation process for the bio-oil can be dispensed with, since it is mixed with the pyrolysis coke anyway. In addition, all the condensates, in particular the “slurry products”, for example from decanters for cleaning synthesis gas, can be added to the pyrolysis oil, so that the cleaning of the product streams from rapid pyrolysis is considerably simplified.
Bioöl oder Olschlamm lassen sich zudem einfacher transportieren und lagern sowie flexibler nutzen als staubförmige Pyrolysekohle. Die Erfindung eröffnet die Möglichkeit, Bioöle oder Ölschlämme aus mehreren dezentralen Schnellpyrolyseeinrichtungen zusammenzubringen und in einem großen, zentralen Flugstromvergaser weiter zu verarbeiten. In diesen Fällen ist es sinnvoll, das Pyrolysegas direkt in der Schnellpyrolyse einzusetzen. Im Pyrolysegas einer Schnellpyrolyse ist meist nur um 10 % oder sogar weniger des gesamten Heizwertes der Ausgangs- Biomasse enthalten, so dass immer noch 90 % oder mehr des Energiegehaltes der ursprünglichen Biomasse in den Flugstromvergaser gelangt.Bio oil or oil sludge is also easier to transport and store and more flexible to use than dusty pyrolysis coal. The invention opens up the possibility of bringing together bio-oils or oil sludges from several decentralized rapid pyrolysis devices and further processing them in a large, central entrained-flow gasifier. In these cases it makes sense to use the pyrolysis gas directly in rapid pyrolysis. The pyrolysis gas of a rapid pyrolysis usually contains only 10% or even less of the total calorific value of the starting biomass, so that 90% or more of the energy content of the original biomass still reaches the entrained-flow gasifier.
Die Erfindung wird im folgenden anhand einer Figur näher erläutert.The invention is explained in more detail below with reference to a figure.
Die Figur zeigt ein technisches Grundkonzept zur Erzeugung von Kraftstoff und Strom aus Biomasse.The figure shows a basic technical concept for the production of fuel and electricity from biomass.
Die Biomasse wird nach Anlieferung und ggf. Zwischenlagerung einer Vorbehandlung unterworfen, die eine Zerkleinerung und eine Nachtrocknung umfasst. Dann wird sie der Schnellpyrolyse zugeführt, die - wie bereits oben erwähnt - am einfachsten bei Atmosphärendruck durchgeführt werden kann. Die Betriebstemperatur liegt bei ca. 500 °C und wird in der Regel über einen Wärmeträgerkreislauf aufrechterhalten.After delivery and, if necessary, intermediate storage, the biomass is subjected to a pretreatment which includes comminution and post-drying. Then it is fed to rapid pyrolysis, which - as already mentioned above - can be carried out most easily at atmospheric pressure. The operating temperature is around 500 ° C and is usually maintained via a heat transfer circuit.
Die Produkte der Schnellpyrolyse sind Schwelgas, Bioöl und Py- rolysekoks. Diese Produkte können beispielsweise in einem Verhältnis von 15 : 60 : 25 Gew.-% anfallen. Verwendungsoptionen für das Schwelgas sind der Einsatz als Brenngas z. B. bei der Schnellpyrolyse selbst, die Verstromung in Gasmotoren oder Turbinen und die Verwendung als Zerstäubergas oder Brenngas für den Pilotbrenner der nachfolgenden Flugstromvergasung. Das Bioöl wird zur Herstellung der Koksaufschlämmung eingesetzt. Der Pyrolysekoks wird zuvor fein vermählen. Enthält die eingesetzte Biomasse hohe Kalium- und Chloranteile wie beispielsweise Stroh oder andere schnell wachsende Biomasse, kann es sinnvoll sein, den Pyrolysekoks vor der Aufschlämmung beispielsweise in einer Waschvorrichtung mit Wasser von Kaliumchlorid und anderen löslichen Kalium/Chlor-Verbindungen zu befreien.Rapid pyrolysis products are carbonization gas, bio-oil and py- rolysekoks. These products can be obtained, for example, in a ratio of 15:60:25% by weight. Use options for the carbonization gas are the use as fuel gas z. B. in the rapid pyrolysis itself, the power generation in gas engines or turbines and the use as an atomizing gas or fuel gas for the pilot burner of the subsequent entrained flow gasification. The bio oil is used to make the coke slurry. The pyrolysis coke is ground beforehand. If the biomass used contains high amounts of potassium and chlorine, such as straw or other rapidly growing biomass, it may be useful to remove potassium chloride and other soluble potassium / chlorine compounds from the pyrolysis coke, for example in a washing device, with water before the slurry.
Der typische Heizwert des Pyrolysekokses ist fast doppelt so hoch wie der Heizwert des Bioöls, während der Heizwert des Pyrolysegases nur grob die Hälfte des Heizwertes von Bioöl beträgt .The typical calorific value of pyrolysis coke is almost twice the calorific value of bio-oil, while the calorific value of pyrolysis gas is only roughly half of the calorific value of bio-oil.
Der Olschlamm, der sich aus der Aufschlämmung des Pyrolysekokses im Bioöl ergibt, wird anschließend mit Hilfe einer Hochdruckpumpe in den Flugstromvergaser gefördert. Der Flugstromvergaser kann beispielsweise bei etwas über 50 bar und einer Temperatur von 1500°C betrieben werden. Die Pilotflamme wird z. B. mit Pyrolysegas aus der Schnellpyrolyse oder mit Synthesegas aus dem Flugstromvergaser sowie technischem Sauerstoff betrieben. Der Sauerstoffanteil soll etwa ein Drittel bis ein Viertel bezogen auf den gesamten Sauerstoffbedarf zur Oxidati- on der Inhaltsstoffe betragen. Dabei muss eine ausreichend hohe Reaktionstemperatur gewährleistet sein, damit die chemische Reaktion möglichst vollständig abläuft und der betriebsgemäße Abfluss des Schlackepelzes garantiert ist. Infolge des unterstöchiometrischen Sauerstoffanteils herrschen im Flugstromvergaser reduzierende Bedingungen. Das den Flugstromvergaser verlassende Rohsynthesegas kann als Hochtemperatur-Brenngas oder als Reduktionsgas eingesetzt werden. Es kann aber auch aufbereitet und zu wertvollen Chemieprodukten, beispielsweise Kraftstoffen, umgesetzt werden. Das die Gasaufbereitung verlassende Reinsynthesegas eignet sich zur Methanolsynthese, als Kraftstoffersatz oder für andere Synthesen in der Chemie, etwa zur Durchführung von Oxosynthe- sen oder, nach einer Shift-Reaktion, von Hydrierungen. Das bei einer Synthese nicht umgesetzte Synthesegas kann in Gasturbinen, Gasmotoren oder GUD-Systemen verströmt werden. The oil sludge that results from the slurry of the pyrolysis coke in the bio-oil is then pumped into the entrained-flow gasifier with the help of a high-pressure pump. The entrained flow gasifier can be operated, for example, at a little over 50 bar and a temperature of 1500 ° C. The pilot flame is e.g. B. operated with pyrolysis gas from rapid pyrolysis or with synthesis gas from the entrained flow gasifier and technical oxygen. The proportion of oxygen should be about one third to one quarter based on the total oxygen requirement for the oxidation of the ingredients. A sufficiently high reaction temperature must be guaranteed so that the chemical reaction proceeds as completely as possible and the operational drainage of the slag fur is guaranteed. As a result of the substoichiometric proportion of oxygen, there are reducing conditions in the entrained-flow gasifier. The raw synthesis gas leaving the entrained flow gasifier can be used as a high-temperature fuel gas or as a reducing gas. However, it can also be processed and converted into valuable chemical products, such as fuels. The pure synthesis gas leaving the gas processing unit is suitable for methanol synthesis, as a fuel substitute or for other chemical syntheses, for example for carrying out oxosynthesis or, after a shift reaction, for hydrogenation. The synthesis gas that is not converted during synthesis can be emitted in gas turbines, gas engines or GUD systems.

Claims

Patentansprüche : Claims:
1. Verfahren zur Behandlung von Biomasse, bei dem a) die Biomasse einer Schnellpyrolyse unterworfen wird, wobei sich Bioöl und Pyrolysekoks bilden, b) der Pyrolysekoks in dem Bioöl zu einem Olschlamm aufgeschlämmt wird, c) der Olschlamm in einen auf einem Überdruck gehaltenen1. Process for the treatment of biomass, in which a) the biomass is subjected to rapid pyrolysis, whereby bio-oil and pyrolysis coke are formed, b) the pyrolysis coke is slurried in the bio-oil to an oil sludge, c) the oil sludge is kept in an overpressure
Flugstromvergaser gepresst und d) in dem Flugstromvergaser zu einem Rohsynthesegas umgesetzt wird.Entrained flow gasifier and d) converted into a raw synthesis gas in the entrained flow gasifier.
2. Verfahren nach Anspruch 1, bei dem die Biomasse ein landwirtschaftliches Abfallprodukt darstellt .2. The method of claim 1, wherein the biomass is an agricultural waste product.
3. Verfahren nach Anspruch 1 oder 2, bei dem die Schnellpyrolyse bei solchen Bedingungen durchgeführt wird, dass sich aus der Biomasse 40 bis 80 Gew.-% Bioöl und 10 bis 30 Gew.-% Pyrolysekoks bilden.3. The method of claim 1 or 2, wherein the rapid pyrolysis is carried out under conditions such that 40 to 80 wt .-% bio oil and 10 to 30 wt .-% pyrolysis coke form from the biomass.
4. Verfahren nach Anspruch 1, 2 oder 3, bei dem der Olschlamm in dem Flugstromvergaser bei 25 bar bis 200 bar und 1200 °C bis 1800 °C bei Sauerstoffunterschuss umgesetzt wird.4. The method according to claim 1, 2 or 3, wherein the oil sludge in the entrained flow gasifier is reacted at 25 bar to 200 bar and 1200 ° C to 1800 ° C with oxygen deficiency.
5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem vor dem Aufschlämmen des Pyrolysekokses lösliche Inhaltsstoffe durch Waschen mit Wasser ausgewaschen werden. erfahren nach einem der Ansprüche 1 bis 5, bei dem dem Olschlamm ein anorganischer Schlackebildner in Form eines aschereichen Kokses und/oder eines pulverförmigen Minerals zugesetzt werden. 5. The method according to any one of claims 1 to 4, in which soluble ingredients are washed out by washing with water before slurrying the pyrolysis coke. experience according to one of claims 1 to 5, in which an inorganic slag former in the form of a high-ash coke and / or a powdery mineral are added to the oil sludge.
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