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EP1520900B1 - A method of gasifying liquid pyrolysis products - Google Patents

A method of gasifying liquid pyrolysis products Download PDF

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Publication number
EP1520900B1
EP1520900B1 EP04018777A EP04018777A EP1520900B1 EP 1520900 B1 EP1520900 B1 EP 1520900B1 EP 04018777 A EP04018777 A EP 04018777A EP 04018777 A EP04018777 A EP 04018777A EP 1520900 B1 EP1520900 B1 EP 1520900B1
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EP
European Patent Office
Prior art keywords
pyrolysis
organic
aqueous phase
bio
oil
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
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EP04018777A
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German (de)
French (fr)
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EP1520900A1 (en
Inventor
Edmund Dr. Henrich
Eckhard Prof.Dr. Dinjus
Dietrich Meier
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Karlsruher Institut fuer Technologie KIT
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Forschungszentrum Karlsruhe GmbH
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—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
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C10J2300/092—Wood, cellulose
    • 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
    • C10J2300/0943—Coke
    • 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
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • 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
    • C10J2300/1696—Integration of gasification processes with another plant or parts within the plant with phase separation, e.g. after condensation

Definitions

  • the invention relates to a process for the gasification of pyrolysis condensates according to the first claim.
  • biomass ie waste from agriculture and forestry, especially wood waste, of particular interest. Since, from a technical point of view, liquid and gaseous energy carriers are preferred, there are a number of attempts to convert the solid, difficult-to-handle biomass into such energy sources.
  • the pyrolysis is a good way. Above all, wood waste, but also other dry lignocellulosic waste, can be effectively converted into a so-called bio-oil by rapid pyrolysis in which the waste is heated to high temperatures for a few seconds.
  • the bio-oil thus obtained has some decisive disadvantages. Above all, it is not stable and storable. Rather, it tends to demix after a more or less long time, forming an aqueous and an organic phase.
  • the aqueous phase may contain more or less large amounts of water-soluble organic compounds, especially acetic acid, alcohols and other hydrocarbons with oxygen or other heteroatoms.
  • the bio-oil can be reacted in a gasifier, in particular in an entrained-flow gasifier, in order to obtain a higher-quality energy source.
  • the bio-oil is converted in the air flow gasifier with pure oxygen in substoichiometric ratio.
  • GB 2 109 400 discloses a method of treating biomass in which the biomass is subjected to rapid pyrolysis to form bio-oil and pyrolysis coke and in which the bio-oil is reacted in an entrained-flow gasifier.
  • the aqueous phase contains a sufficiently high amount of combustible organic compounds, there is no danger. However, it is extremely dangerous if the aqueous phase has a low calorific value, thus essentially consists only of water and contains hardly any flammable compounds in dissolved form. Then, in the entrained-flow gasifier, an excess of oxygen arises for some time, which can result in an explosion as a result of the mixing of previously produced synthesis gas. Since the composition of the bio-oil and thus the composition of the aqueous phase varies according to the nature of the starting biomass, it can not be reliably predicted whether the mentioned danger exists. In addition, depending on the nature of the storage, the compositions of the organic and the aqueous phase may be different for one and the same bio-oil, for example because low-boiling constituents have volatilized.
  • the invention is therefore an object of the invention to provide a method for the gasification of pyrolysis condensates, in which the entrained flow gasifier can be operated safely.
  • the entrained flow gasifier can be operated safely.
  • the basic idea of the invention is to anticipate the segregation of the bio-oil in order to ensure a safe operation of the entrained-flow gasifier, namely to separate the bio-oil into an aqueous and an organic phase.
  • the organic phase contains in any case a sufficiently high calorific value to avoid dangerous operating conditions in the entrained flow gasifier; It is therefore fed continuously and without interruption the entrainment gasifier.
  • the aqueous phase is fed separately into the entrained flow gasifier, it is irrelevant whether the feed is continuous or discontinuous - at intervals - occurs. In this way, it can not come to a superstoichiometric concentration of oxygen in the carburetor.
  • the feed can be made in two different feed nozzles, but also in a common feed nozzle.
  • the separation of the bio-oil in the two phases is preferably carried out in such a way that the organic phase has at most a low water content, in any case a water content below 25, better below 20 wt .-%.
  • the water content of the aqueous phase is preferably at least 50% by weight.
  • the separation of the bio-oil into the two phases preferably takes place by fractional condensation during the production of the bio-oil in the rapid pyrolysis.
  • the fast pyrolysis is carried out with lignocellulose wherein the lignocellulose is contacted with sand or other suitable heat transfer medium having a temperature of 500 ° C to 600 ° C for a period of 1 to 10 seconds.
  • the educated Bio-oil is subjected to the mentioned fractional condensation, so that the described two phases arise.
  • bio-oil could be separated by prolonged storage and decantation into two phases.
  • Both the organic and the aqueous phase prove to be long-term stable, so that there are no safety concerns against prolonged, separate storage. Both phases can be stored with or without the addition of 3 wt .-% straw ash at room temperature over a period of 15 months, for example, in gas cylinders sealed under air, without any significant segregation occurs. Composition, density, calorific value and viscosity remain practically the same over the storage period.
  • one or both phases can be admixed with pulverulent pyrolysis coke and / or a slag fur former before being fed into the gasifier.
  • the pyrolysis coke stabilizes the operation of the carburetor because of the additional fuel, while the slag furler protects the interior of the carburetor against the corrosive and aggressive conditions.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Processing Of Solid Wastes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Method for gasification of pyrolysis condensates comprises: (a) separating the condensate into a liquid organic and a liquid aqueous phase; (b) feeding the two phases separately or together, along with a sub-stoichiometric amount of oxygen into a gasifier, the organic phase being fed continuously into it.

Description

Die Erfindung betrifft ein Verfahren zur Vergasung von Pyrolysekondensaten gemäß dem ersten Patentanspruch.The invention relates to a process for the gasification of pyrolysis condensates according to the first claim.

Als Energieträger ist aus Umweltschutzgründen seit einiger Zeit Biomasse, also Abfall aus der Land- und Forstwirtschaft, insbesondere Holzabfall, von besonderem Interesse. Da aus technischer Sicht flüssige und gasförmige Energieträger bevorzugt werden, gibt es eine Reihe von Versuchen, die feste, umständlich zu handhabende Biomasse in solche Energieträger zu konvertieren.As an energy source for environmental reasons for some time biomass, ie waste from agriculture and forestry, especially wood waste, of particular interest. Since, from a technical point of view, liquid and gaseous energy carriers are preferred, there are a number of attempts to convert the solid, difficult-to-handle biomass into such energy sources.

Dabei ist die Pyrolyse ein gut geeigneter Weg. Vor allem Holzabfälle, aber auch andere trockene Lignocellulose-Abfälle, lassen sich durch Schnellpyrolyse, bei der die Abfälle für wenige Sekunden auf hohe Temperaturen erhitzt werden, effektiv in ein sogenanntes Bioöl konvertieren.The pyrolysis is a good way. Above all, wood waste, but also other dry lignocellulosic waste, can be effectively converted into a so-called bio-oil by rapid pyrolysis in which the waste is heated to high temperatures for a few seconds.

Leider hat das so gewonnene Bioöl einige entscheidende Nachteile. Es ist vor allem nicht stabil und lagerfähig. Vielmehr neigt es nach mehr oder weniger langer Zeit zur Entmischung, wobei sich eine wässrige und eine organische Phase bilden. Die wässrige Phase kann mehr oder weniger große Mengen wasserlöslicher organischer Verbindungen enthalten, insbesondere Essigsäure, Alkohole und andere Kohlenwasserstoffe mit Sauerstoff oder weiteren Heteroatomen.Unfortunately, the bio-oil thus obtained has some decisive disadvantages. Above all, it is not stable and storable. Rather, it tends to demix after a more or less long time, forming an aqueous and an organic phase. The aqueous phase may contain more or less large amounts of water-soluble organic compounds, especially acetic acid, alcohols and other hydrocarbons with oxygen or other heteroatoms.

Das Bioöl kann in einem Vergaser, insbesondere in einem Flugstrom-Druckvergaser umgesetzt werden, um einen höherwertigen Energieträger zu erhalten. Hierbei wird das Bioöl im Flugstromvergaser mit reinem Sauerstoff in unterstöchiometrischem Verhältnis umgesetzt.The bio-oil can be reacted in a gasifier, in particular in an entrained-flow gasifier, in order to obtain a higher-quality energy source. Here, the bio-oil is converted in the air flow gasifier with pure oxygen in substoichiometric ratio.

Die Patentschrift GB 2 109 400 offenbart ein Verfahren zur Behandlung von Biomasse, bei dem die Biomasse einer Schnellpyrolyse unterworfen wird wobei sich Bioöl und Pyrolysekoks bilden und bei dem das Bioöl in einem Flugstromvergaser umgesetzt wird.GB 2 109 400 discloses a method of treating biomass in which the biomass is subjected to rapid pyrolysis to form bio-oil and pyrolysis coke and in which the bio-oil is reacted in an entrained-flow gasifier.

Es hat sich jedoch gezeigt, dass bei der Einspeisung des Bioöls in den Flugstromvergaser gravierende Sicherheitsprobleme auftauchen können. Diese Sicherheitsprobleme hängen mit der erwähnten Neigung des Bioöls zur Entmischung zusammen. Da das Bioöl zur Vergasung in einem Tank bevorratet werden muss, besteht die Gefahr, dass aus dem Tank für kürzere oder längere Zeit ausschließlich die wässrige Phase des Bioöls entnommen wird. Die Gefahr besteht insbesondere dann, wenn der Tankinhalt nicht kontinuierlich und nicht ausreichend effizient durchmischt werden kann. Wegen der kurzen Verweilzeit des Bioöls im Flugstromvergaser - typischerweise einige Sekunden - tritt dabei ein Betriebszustand ein, in dem der Sauerstoff ausschließlich mit der wässrigen Phase in Berührung kommt.However, it has been shown that when feeding the bio-oil into the entrained-flow gasifier, serious safety problems can arise. These safety issues are related to the mentioned tendency of the bio-oil to segregate. Since bio-oil must be stored in a tank for gasification, there is a risk that only the aqueous phase of the bio-oil will be removed from the tank for a shorter or longer period of time. The danger exists in particular if the tank contents can not be mixed continuously and not sufficiently efficiently. Because of the short residence time of the bio-oil in the entrained-flow gasifier - typically a few seconds - an operating state occurs in which the oxygen only comes into contact with the aqueous phase.

An sich braucht sich dabei nicht unbedingt ein gefährlicher Betriebszustand einzustellen. Enthält die wässrige Phase eine ausreichend hohe Menge an brennbaren organischen Verbindungen, besteht keine Gefahr. Äußerst gefährlich ist es jedoch, wenn die wässrige Phase einen niedrigen Heizwert aufweist, somit im Wesentlichen nur aus Wasser besteht und kaum brennbare Verbindungen in gelöster Form enthält. Dann stellt sich im Flugstromvergaser für einige Zeit ein Sauerstoffüberschuss ein, der in Folge der Vermischung zuvor erzeugtem Synthesegas zur Explosion führen kann. Da die Zusammensetzung des Bioöls und damit die Zusammensetzung der wässrigen Phase je nach der Art der Ausgangs-Biomasse variiert, lässt sich nicht zuverlässig vorhersagen, ob die erwähnte Gefahr besteht. Hinzu kommt, dass die Zusammensetzungen der organischen und der wässrigen Phase je nach Art der Lagerung bei ein und demselben Bioöl unterschiedlich sein können, etwa weil sich niedrig siedende Bestandteile verflüchtigt haben.In itself, not necessarily a dangerous operating state needs to be adjusted. If the aqueous phase contains a sufficiently high amount of combustible organic compounds, there is no danger. However, it is extremely dangerous if the aqueous phase has a low calorific value, thus essentially consists only of water and contains hardly any flammable compounds in dissolved form. Then, in the entrained-flow gasifier, an excess of oxygen arises for some time, which can result in an explosion as a result of the mixing of previously produced synthesis gas. Since the composition of the bio-oil and thus the composition of the aqueous phase varies according to the nature of the starting biomass, it can not be reliably predicted whether the mentioned danger exists. In addition, depending on the nature of the storage, the compositions of the organic and the aqueous phase may be different for one and the same bio-oil, for example because low-boiling constituents have volatilized.

Der Erfindung liegt somit die Aufgabe zugrunde, ein Verfahren zur Vergasung von Pyrolysekondensaten anzugeben, bei dem der Flugstromvergaser sicher betrieben werden kann. In den weiteren Ansprüchen werden bevorzugte Ausgestaltungen des Verfahrens angegeben.The invention is therefore an object of the invention to provide a method for the gasification of pyrolysis condensates, in which the entrained flow gasifier can be operated safely. In the other Claims of preferred embodiments of the method are given.

Der Grundgedanke der Erfindung besteht darin, die Entmischung des Bioöls vorwegzunehmen, um auf diese Weise einen sicheren Betrieb des Flugstromvergasers zu gewährleisten, und zwar soll das Bioöl in eine wässrige und eine organische Phase getrennt werden. Die organische Phase enthält in jedem Fall einen ausreichend hohen Brennwert, um gefährliche Betriebszustände im Flugstromvergaser zu vermeiden; sie wird daher kontinuierlich und ohne Unterbrechung dem Flugstromvergaser zugeführt. Die wässrige Phase wird separat in den Flugstromvergaser eingespeist, wobei es unerheblich ist, ob die Einspeisung kontinuierlich oder diskontinuierlich - etwa in Intervallen - erfolgt. Auf diese Weise kann es nicht zu einer überstöchiometrischen Konzentration des Sauerstoffs im Vergaser kommen. Die Einspeisung kann in zwei verschiedenen Einspeisedüsen, aber auch in einer gemeinsamen Einspeisedüse erfolgen.The basic idea of the invention is to anticipate the segregation of the bio-oil in order to ensure a safe operation of the entrained-flow gasifier, namely to separate the bio-oil into an aqueous and an organic phase. The organic phase contains in any case a sufficiently high calorific value to avoid dangerous operating conditions in the entrained flow gasifier; It is therefore fed continuously and without interruption the entrainment gasifier. The aqueous phase is fed separately into the entrained flow gasifier, it is irrelevant whether the feed is continuous or discontinuous - at intervals - occurs. In this way, it can not come to a superstoichiometric concentration of oxygen in the carburetor. The feed can be made in two different feed nozzles, but also in a common feed nozzle.

Die Trennung des Bioöls in die zwei Phasen wird vorzugsweise in der Weise durchgeführt, dass die organische Phase allenfalls einen geringen Wassergehalt, auf jeden Fall einen Wassergehalt unter 25, besser unter 20 Gew.-% aufweist. Der Wassergehalt der wässrigen Phase beträgt demgegenüber vorzugsweise mindestens 50 Gew.-%. Die beiden Phasen können unter diesen Bedingungen längere Zeit gelagert werden und neigen nicht mehr zu einer erneuten Phasentrennung.The separation of the bio-oil in the two phases is preferably carried out in such a way that the organic phase has at most a low water content, in any case a water content below 25, better below 20 wt .-%. In contrast, the water content of the aqueous phase is preferably at least 50% by weight. The two phases can be stored under these conditions for a longer time and no longer tend to rephase separation.

Die Trennung des Bioöls in die zwei Phasen erfolgt vorzugsweise durch fraktionierte Kondensation während der Erzeugung des Bioöls in der Schnellpyrolyse. Vorzugsweise wird die Schnellpyrolyse mit Lignocellulose durchgeführt, wobei die Lignocellulose mit Sand oder einem anderen geeigneten Wärmeträger, der eine Temperatur von 500°C bis 600°C aufweist, für die Dauer von 1 bis 10 Sekunden in Kontakt gebracht wird. Das gebildete Bioöl wird der erwähnten fraktionierten Kondensation unterworfen, so dass die beschriebenen beiden Phasen entstehen. Alternativ könnte Bioöl durch längere Lagerung und Dekantieren in zwei Phasen aufgetrennt werden.The separation of the bio-oil into the two phases preferably takes place by fractional condensation during the production of the bio-oil in the rapid pyrolysis. Preferably, the fast pyrolysis is carried out with lignocellulose wherein the lignocellulose is contacted with sand or other suitable heat transfer medium having a temperature of 500 ° C to 600 ° C for a period of 1 to 10 seconds. The educated Bio-oil is subjected to the mentioned fractional condensation, so that the described two phases arise. Alternatively, bio-oil could be separated by prolonged storage and decantation into two phases.

Aus Vorversuchen ergibt sich, dass sich das Bioöl unter den erwähnten Randbedingungen in eine organische Rohholzteer-Phase und eine wässrige Rohholzessig-Phase auftrennt. Diese Phasentrennung kann in einer technischen Anlage leicht durch eine fraktionierte Kondensation erreicht werden. Die Untersuchung der Phasen ergab für die organische Phase einen Feststoffgehalt zwischen 26 und 29 Gew.-%, eine Dichte von 1250 bis 1290 kg/m3, eine Viskosität bei Zimmertemperatur von ca. 5 Pas und einen Heizwert von 20,8 bis 21,5 MJ/kg. Die entsprechenden Werte für die wässrige Phase sind: Feststoff 29 Gew.-%, Dichte ca. 1200 kg/m3, Viskosität bei Zimmertemperatur ca. 1 Pas und einen Heizwert von lediglich 9 MJ/kg.Preliminary results show that the bio-oil separates under the mentioned boundary conditions into an organic raw wood tar phase and an aqueous raw wood vinegar phase. This phase separation can be easily achieved in a technical plant by a fractional condensation. Examination of the phases showed for the organic phase a solids content between 26 and 29 wt .-%, a density of 1250 to 1290 kg / m 3 , a viscosity at room temperature of about 5 Pas and a calorific value of 20.8 to 21, 5 MJ / kg. The corresponding values for the aqueous phase are: solids 29% by weight, density about 1200 kg / m 3 , viscosity at room temperature about 1 Pas and a calorific value of only 9 MJ / kg.

Sowohl die organische als auch die wässrige Phase erweisen sich als langzeitstabil, so dass gegen eine längere, getrennte Lagerung keine Sicherheitsbedenken bestehen. Beide Phasen können mit oder ohne Zusatz von 3 Gew.-% Strohasche bei Zimmertemperatur über einen Zeitraum von 15 Monaten beispielsweise in unter Luft verschlossenen Gasflaschen gelagert werden, ohne dass eine nennenswerte Entmischung eintritt. Zusammensetzung, Dichte, Heizwert und Viskosität bleiben über die Lagerzeit hinweg praktisch gleich.Both the organic and the aqueous phase prove to be long-term stable, so that there are no safety concerns against prolonged, separate storage. Both phases can be stored with or without the addition of 3 wt .-% straw ash at room temperature over a period of 15 months, for example, in gas cylinders sealed under air, without any significant segregation occurs. Composition, density, calorific value and viscosity remain practically the same over the storage period.

Bei Bedarf kann einer oder beiden Phasen vor der Einspeisung in den Vergaser pulverförmiger Pyrolysekoks und/oder ein Schlackepelzbildner zugemischt werden. Der Pyrolysekoks stabilisiert den Betrieb des Vergasers wegen des zusätzlichen Brennstoffes, während durch den Schlackepelzbildner der Innenraum des Vergasers gegen die korrosiven und aggressiven Bedingungen geschützt wird.If necessary, one or both phases can be admixed with pulverulent pyrolysis coke and / or a slag fur former before being fed into the gasifier. The pyrolysis coke stabilizes the operation of the carburetor because of the additional fuel, while the slag furler protects the interior of the carburetor against the corrosive and aggressive conditions.

Claims (3)

  1. Method for gasification of pyrolysis condensates having the steps:
    - the pyrolysis condensates are separated into a liquid organic and a liquid aqueous phase,
    - the organic and the aqueous phase are separately or jointly fed together with sub-stoichiometric oxygen into a gasifier, however
    - at least the organic phase being supplied continuously and without interruption to the gasifier.
  2. Method according to claim 1, in which the pyrolysis condensates are produced by a rapid pyrolysis of lignocellulose,
    - the lignocellulose being brought into contact for 1 to 10 seconds with a heat transfer medium having a temperature of 500°C to 600°C and
    - the thereby produced pyrolysis condensate being separated into the organic and the aqueous phase by a fractionated condensation.
  3. Method according to claim 2, in which a pulverulent pyrolysis coke and/or a slag skin former is mixed with one of the two phases.
EP04018777A 2003-10-01 2004-08-07 A method of gasifying liquid pyrolysis products Expired - Lifetime EP1520900B1 (en)

Applications Claiming Priority (2)

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DE10345672 2003-10-01
DE10345672A DE10345672B4 (en) 2003-10-01 2003-10-01 Process for the gasification of pyrolysis condensates

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EP1520900B1 true EP1520900B1 (en) 2007-05-16

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005049375A1 (en) * 2005-10-15 2007-04-26 Forschungszentrum Karlsruhe Gmbh Process for the preparation and preparation of quick pyrolysis products from biomass for a flow stream pressure gasification
EP2236588B1 (en) 2009-04-02 2012-07-04 General Electric Company Process for use of pyrolysis water
EP2236587A1 (en) 2009-04-02 2010-10-06 General Electric Company Modified bio-slurry and process for its production and gasification
IT1398667B1 (en) * 2009-06-18 2013-03-08 Vaiani PROCEDURE AND PLANT FOR THE PRODUCTION OF BIOMASS SYNTHESIS GASES AND / OR WASTE IN GENERAL

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Publication number Priority date Publication date Assignee Title
GB2109400B (en) * 1981-10-02 1985-08-14 Foster Wheeler Power Prod Thermal conversion systems
DE4123406C2 (en) * 1991-07-15 1995-02-02 Engineering Der Voest Alpine I Process for the gasification of inferior solid fuels in a shaft-shaped gasification reactor
GB9224783D0 (en) * 1992-11-26 1993-01-13 Univ Waterloo An improved process for the thermal conversion of biomass to liquids
DE19609721C2 (en) * 1996-03-13 2002-09-12 Noell Krc Energie & Umwelt Process for the energetic utilization of residual and waste materials as well as low calorific fuels in a steam power plant
DE10151054A1 (en) * 2001-10-16 2003-04-30 Karlsruhe Forschzent Process for the treatment of biomass

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ATE362503T1 (en) 2007-06-15
DE10345672B4 (en) 2005-12-29
DE502004003825D1 (en) 2007-06-28
EP1520900A1 (en) 2005-04-06
DE10345672A1 (en) 2005-05-19

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