DE19955150A1 - Generation of hydrogen, useful in fuel cell, uses supercritical water with added hydrocarbons and/or alcohols and no catalyst - Google Patents

Generation of hydrogen, useful in fuel cell, uses supercritical water with added hydrocarbons and/or alcohols and no catalyst

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Publication number
DE19955150A1
DE19955150A1 DE19955150A DE19955150A DE19955150A1 DE 19955150 A1 DE19955150 A1 DE 19955150A1 DE 19955150 A DE19955150 A DE 19955150A DE 19955150 A DE19955150 A DE 19955150A DE 19955150 A1 DE19955150 A1 DE 19955150A1
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Germany
Prior art keywords
hydrogen
alcohols
catalyst
fuel cell
supercritical water
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Granted
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DE19955150A
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German (de)
Other versions
DE19955150B4 (en
Inventor
Helmut Schmieder
Nikolaos Boukis
Eckhard Dinjus
Johannes Penninger
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Karlsruher Institut fuer Technologie KIT
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Forschungszentrum Karlsruhe GmbH
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Priority to DE19955150A priority Critical patent/DE19955150B4/en
Publication of DE19955150A1 publication Critical patent/DE19955150A1/en
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    • 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
    • C01B3/34—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 by reaction of hydrocarbons with gasifying agents
    • 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
    • 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
    • C01B3/34—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 by reaction of hydrocarbons with gasifying agents
    • C01B3/346—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 by reaction of hydrocarbons with gasifying agents using heat generated by superheated steam
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Fuel Cell (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Generation of hydrogen comprises adding hydrocarbons and/or alcohols to supercritical water, without addition of a catalyst.

Description

Die Erfindung betrifft ein Verfahren zur Erzeugung von Wasser­ stoff gemäß dem Patentanspruch.The invention relates to a method for producing water fabric according to the claim.

In der Veröffentlichung von H. R. Holgate et al. "Glucose Hydro­ lysis and Oxidation in Supercritical Water", Reactors, Kinetics and Catalysts Vol. 41, No. 3 (1995) 637-648 wird über die Oxida­ tion von Glucose zu Wasserstoff und Kohlendioxid berichtet. Glucose wird als Modellsubstanz für Biomasse verwendet. Die Oxi­ dation wird ohne Einsatz eines Katalysators mit Zugabe von Sau­ erstoff in überkritischem Wasser bei 246 bar und 425°C bis 600°C durchgeführt. Glucose wird allerdings in einer sehr geringen Konzentration - 1 × 10-3 mol/l - eingesetzt. Die Autoren berich­ ten im Abschnitt "Products of glucose hydrolysis", daß bei höhe­ ren Konzentrationen (0,1 bis 0,8 mol/l) Methan als Reaktionspro­ dukt zunehmend stabiler wird und sich anstelle von Wasserstoff und Kohlendioxid bildet.In the publication by HR Holgate et al. "Glucose Hydrolysis and Oxidation in Supercritical Water", Reactors, Kinetics and Catalysts Vol. 41, No. 3 ( 1995 ) 637-648 reports the oxidation of glucose to hydrogen and carbon dioxide. Glucose is used as a model substance for biomass. The oxidation is carried out without the use of a catalyst with the addition of oxygen in supercritical water at 246 bar and 425 ° C to 600 ° C. However, glucose is used in a very low concentration - 1 × 10 -3 mol / l. The authors report in the "Products of glucose hydrolysis" section that methane as a reaction product becomes increasingly stable at higher concentrations (0.1 to 0.8 mol / l) and forms instead of hydrogen and carbon dioxide.

Die Ergebnisse von H. R. Holgate werden (ohne die Quelle zu zi­ tieren) im einleitenden Teil der WO 96/30464 erwähnt.The results of H. R. Holgate are (without referring to the source animals) mentioned in the introductory part of WO 96/30464.

Der Erfindung liegt die Aufgabe zugrunde, ein weiteres Verfahren zur Erzeugung von Wasserstoff aus einer überkritischen wäßrigen Lösung anzugeben, mit dessen Hilfe sich der Wasserstoffanteil von organischen Verbindungen und der durch CO-Konversion aus der Wasserspaltung resultierende Anteil ohne Einsatz eines Katalysa­ tors nahezu vollständig in gasförmigen Wasserstoff konvertieren läßt, wobei die Ausgangsverbindung in höheren Konzentrationen einsetzbar ist und auf die Zugabe von Sauerstoff verzichtet werden kann.The object of the invention is a further method for the production of hydrogen from a supercritical aqueous Specify solution with the help of which the hydrogen content of organic compounds and by CO conversion from the Water splitting resulting portion without the use of a catalytic converter Convert tors almost completely into gaseous hydrogen lets, the starting compound in higher concentrations can be used and does not add oxygen can be.

Die Aufgabe wird durch das im ersten Patentanspruch beschriebene Verfahren gelöst. In den Unteransprüchen sind bevorzugte Ausge­ staltungen des Verfahrens beschrieben. The object is achieved by that described in the first claim Procedure solved. In the dependent claims are preferred Ausge events of the method described.  

Mit dem erfindungsgemäßen Verfahren lassen sich Kohlenwasser­ stoffe und Alkohole umsetzen. Als Kohlenwasserstoffe eignen ge­ radkettige und verzweigte Alkane, Alkene und Alkine sowie Aroma­ ten. Statt der betreffenden Alkane, Alkene und Alkine können auch die entsprechenden Alkohole eingesetzt werden. Bevorzugt werden jedoch Methanol und Ethanol.The process according to the invention can be used to produce hydrocarbons implement substances and alcohols. Suitable as hydrocarbons are ge Radkettige and branched alkanes, alkenes and alkynes as well as aroma Instead of the relevant alkanes, alkenes and alkynes the corresponding alcohols can also be used. Prefers however, methanol and ethanol.

Die Konzentration der Kohlenwasserstoffe und/oder der Alkohole sollte mindestens 0,1 mol/l betragen. In diesem Konzentrations­ bereich ist Glucose in überkritischem Wasser nicht mehr voll­ ständig in Wasserstoff und Kohlendioxid umsetzbar. Aus Gründen der energetischen Effizienz des Verfahrens sind möglichst hohe Konzentrationen anzustreben, etwa bis zu mehreren mol/l.The concentration of hydrocarbons and / or alcohols should be at least 0.1 mol / l. In this concentration range is no longer full in supercritical water constantly convertible into hydrogen and carbon dioxide. For reasons The energetic efficiency of the process is as high as possible To strive for concentrations, up to several mol / l.

Die Temperatur der Umsetzung liegt bevorzugt bei 550°C bis 700°C und der Druck bei ca. 250 bar. Auf die Zugabe von Sauerstoff kann gegebenenfalls verzichtet werden. Der Einsatz eines Kataly­ sators ist nicht notwendig. Dennoch kann in einem einzigen Reak­ tionsschritt ein vollständiger Umsatz erzielt werden.The temperature of the reaction is preferably 550 ° C to 700 ° C and the pressure at approx. 250 bar. On the addition of oxygen can be omitted if necessary. The use of a Kataly sators is not necessary. Still, in a single reak step a complete turnover can be achieved.

Das Verfahren kann mit besonderem Vorteil zur Herstellung von Wasserstoff für Brennstoffzellen eingesetzt werden. Für diesen Einsatzzweck ist es jedoch von entscheidender Bedeutung, daß während des Verfahrens praktisch kein Ruß und möglichst wenig Kohlenmonoxid gebildet wird. Die Bildung von Ruß und Kohlenmon­ oxid wird erfindungsgemäß selbst dann praktisch vollständig un­ terdrückt, wenn man die bevorzugten hohen Temperaturen von 550°C bis 700°C einstellt. Die weitgehende Unterdrückung der Bildung von Kohlenmonoxid ist deswegen überraschend, weil die Reaktion
The method can be used with particular advantage for the production of hydrogen for fuel cells. For this purpose, it is of crucial importance that practically no soot and as little carbon monoxide as possible is formed during the process. According to the invention, the formation of soot and carbon monoxide is practically completely suppressed even if the preferred high temperatures of 550 ° C. to 700 ° C. are set. The extensive suppression of carbon monoxide formation is surprising because of the reaction

CO + H2O ↔ CO2 + H2
CO + H 2 O ↔ CO 2 + H 2

bei diesen Temperaturen langsam verläuft. Mit dem erfindungsge­ mäßen Verfahren können somit beispielsweise die in Benzin ent­ haltenen Kohlenwasserstoffe und niedrige Alkohole zu Wasserstoff umgesetzt werden, wobei zum einen eine hohe Ausbeute erzielbar ist und zum anderen die Reaktionsprodukte nicht mehr aufwendig aufgearbeitet werden müssen.runs slowly at these temperatures. With the fiction Thus, for example, methods in petrol can be used hydrocarbons and low alcohols to hydrogen be implemented, on the one hand a high yield can be achieved and the reaction products are no longer expensive have to be worked up.

Die Erfindung wird im folgenden anhand von Figuren und Ausfüh­ rungsbeispielen näher erläutert.The invention is described below with reference to figures and design tion examples explained in more detail.

Es zeigenShow it

Fig. 1 ein Verfahrensschema, Fig. 1 is a process diagram,

Fig. 2 eine Versuchsanlage zur Durchführung des Verfahrens. Fig. 2 shows a test facility for performing the method.

In Fig. 1 ist das Verfahrensschema einer Anlage zur Erzeugung von Wasserstoff für eine Brennstoffzelle 1 dargestellt. Aus ei­ nem Tank 2 wird über eine Hochdruckpumpe 3 ein hydrothermaler Reaktor 4, der unter überkritischen Bedingungen für Wasser ge­ halten wird, mit Kohlenwasserstoffen und/oder Alkoholen be­ schickt. Dabei bilden sich unter den Betriebsbedingungen gasför­ mige Stoffe, hauptsächlich der erwünschte Wasserstoff und Koh­ lendioxid, neben gasförmigen Verunreinigungen. In einer ersten Phasentrenneinrichtung 5 werden die gegebenenfalls aus Heteroa­ tomen der Kohlenwasserstoffe oder Alkohole gebildeten Verbindun­ gen wie z. B. Schwefelwasserstoff, Chlorwasserstoff und Salze abgetrennt. Wenn das Edukt keine Heteroatome enthält, wird die wäßrige Phase ohne vorherige Entspannung rezykliert. Nach Durch­ lauf durch einen Kühler 6 gelangen die Reaktionsprodukte in eine weitere Phasentrenneinrichtung 7, in der das Kohlendioxid abgetrennt wird. Der verbleibende, hoch konzentrierte Wasser­ stoff wird einem Wasserstoff-Speicher 8 zugeführt, aus dem die Brennstoffzelle 1 beschickt wird. Das in der Brennstoffzelle produzierte Wässer wird mit dem Edukt vermischt und somit rezy­ kliert.In Fig. 1 the process diagram of a plant for producing hydrogen for a fuel cell 1 is shown. From a tank 2 , a hydrothermal reactor 4 , which is kept under supercritical conditions for water, is sent with hydrocarbons and / or alcohols via a high-pressure pump 3 . Under the operating conditions, gaseous substances, mainly the desired hydrogen and carbon dioxide, are formed in addition to gaseous impurities. In a first phase separation device 5 , the compounds possibly formed from heteroatoms of the hydrocarbons or alcohols, such as, for. B. separated hydrogen sulfide, hydrogen chloride and salts. If the starting material contains no heteroatoms, the aqueous phase is recycled without prior relaxation. After passing through a cooler 6 , the reaction products enter a further phase separation device 7 , in which the carbon dioxide is separated off. The remaining, highly concentrated water is fed to a hydrogen storage 8 , from which the fuel cell 1 is charged. The water produced in the fuel cell is mixed with the educt and thus recycled.

Beispielexample

Zur Demonstration des Verfahrens im Labormaßstab wurde eine Lö­ sung von 5 Gew.-% Methanol in Wasser als Edukt eingesetzt.To demonstrate the process on a laboratory scale, a Lö Solution of 5 wt .-% methanol in water used as starting material.

Fig. 2 zeigt die hierbei verwendete Versuchsanlage. Fig. 2 shows the experimental plant used here.

Die Lösung wurde durch eine Hochdruckpumpe 1 einem Vorratsgefäß 2 entnommen und auf 250 bar komprimiert. Die Förderrate war 1 ml Lösung pro Minute. Die komprimierte Lösung wurde in einen Rohr­ reaktor 3 aus der Legierung Inconel 625 (Werkstoffnummer 2.4856) mit 8 mm Innendurchmesser, 14,4 mm Außendurchmesser und 1000 mm Länge eingespeist, der mit einer Heizvorrichtung 4 und einem Kühler 5 versehen war. Ein entsprechender Rohrreaktor ist in der DE 297 19 196 U beschrieben. Das Innenvolumen betrug ca. 20 cm3 und die Verweilzeit bei 600°C und einer Dichte der Lösung von 0,07 g/cm3 ca. 1,6 min. Mit dem Kühler 5 wurden die Ein- und Ausgangsbereiche des Reaktors gekühlt.The solution was removed from a storage vessel 2 by a high-pressure pump 1 and compressed to 250 bar. The delivery rate was 1 ml solution per minute. The compressed solution was fed into a tubular reactor 3 made of the Inconel 625 alloy (material number 2.4856 ) with 8 mm inner diameter, 14.4 mm outer diameter and 1000 mm length, which was provided with a heating device 4 and a cooler 5 . A corresponding tubular reactor is described in DE 297 19 196 U. The internal volume was approx. 20 cm 3 and the residence time at 600 ° C. and a solution density of 0.07 g / cm 3 was approx. 1.6 min. The inlet and outlet areas of the reactor were cooled with the cooler 5 .

Die Reaktorkonfiguration erlaubte einen kontrollierten, relativ flachen Temperaturgradienten im Ausgangsbereich. Die Verweilzeit im Temperaturbereich 300 bis 200°C, die für die Wasser-Gas- Shift-Reaktion von besonderer Bedeutung ist, betrug am Ausgang ca. 36 sec. Die Innenoberfläche des Reaktors war zusammengesetzt aus Cr-, Ni- und Mo-Oxiden. Die Innnenoberfläche im Temperatur­ berich 300 bis 200°C betrug ca. 90 cm2. Der Versuch dauerte etwa 1000 Stunden und wurde ohne prozeßinhärente Störungen beendet. Das Gasprodukt bestand im Mittel aus 71,9 Vol.-% Wasserstoff, 24,4 Vol.-% Kohlendioxid, 0,8 Vol.-% Kohlenmonoxid und 0,4 Vol.- % Methan. Der TOC-Gehalt des wäßrigen Effluents war 31 ppm, ent­ sprechend über 99,8% Umsatz.The reactor configuration allowed a controlled, relatively flat temperature gradient in the exit area. The residence time in the temperature range from 300 to 200 ° C., which is of particular importance for the water-gas shift reaction, was approximately 36 seconds at the outlet. The inner surface of the reactor was composed of Cr, Ni and Mo oxides. The inner surface in the temperature range 300 to 200 ° C was about 90 cm 2 . The test lasted about 1000 hours and was ended without any process-inherent disturbances. The gas product consisted on average of 71.9% by volume of hydrogen, 24.4% by volume of carbon dioxide, 0.8% by volume of carbon monoxide and 0.4% by volume of methane. The TOC content of the aqueous effluent was 31 ppm, corresponding to over 99.8% conversion.

Claims (3)

1. Verfahren zur Erzeugung von Wasserstoff, bei dem Kohlenwas­ serstoffe und/oder Alkohole in überkritischem Wasser ohne Einsatz eines Katalysators umgesetzt werden.1. Process for the production of hydrogen, in which coal water substances and / or alcohols in supercritical water without Be implemented using a catalyst. 2. Verfahren nach Anspruch 1 mit einer Konzentration der Kohlen­ wasserstoffe und/oder Alkohole von mindestens 0,1 mol/l.2. The method according to claim 1 with a concentration of the coals Hydrogen and / or alcohols of at least 0.1 mol / l. 3. Verfahren nach Anspruch 1 oder 2, bei dem die Umsetzung ohne Zugabe von Sauerstoff erfolgt.3. The method according to claim 1 or 2, wherein the implementation without Oxygen is added.
DE19955150A 1999-11-17 1999-11-17 Process for the production of hydrogen Expired - Fee Related DE19955150B4 (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10135431A1 (en) * 2001-07-20 2003-02-13 Karlsruhe Forschzent Process for pre-treating a nickel-based alloy reactor for producing hydrogen, comprises passing a super critical aqueous solution of an oxidant through the reactor at a specified temperature and pressure
GB2381533A (en) * 2001-07-27 2003-05-07 Bosch Gmbh Robert Supercritical reformer
DE10162202A1 (en) * 2001-12-18 2003-07-10 Fraunhofer Ges Forschung Hydrocarbon reformer
DE10259928A1 (en) * 2002-12-20 2004-07-22 Forschungszentrum Karlsruhe Gmbh De-gassing of biomasses with suppression of coke and tar formation and achievement of high hydrogen yields is achieved in a two-stage process using supercritical water
EP1496013A1 (en) * 2002-04-12 2005-01-12 Suntory Limited Process for production of hydrogen and carbonyl compounds by reacting sub- or super-critical water with alcohols
EP1812353A1 (en) * 2004-11-15 2007-08-01 Chematur Engineering Ab Reactor and method for supercritical water oxidation
DE102004031023B4 (en) * 2004-06-26 2007-10-25 Forschungszentrum Karlsruhe Gmbh Process for converting organic starting materials into oil-like products
ITMI20121537A1 (en) * 2012-09-17 2014-03-18 Maurizio Archetti APPARATUS AND METHOD FOR GASIFICATION OF LIQUID FUEL
EP3434382A1 (en) 2017-07-27 2019-01-30 iGas energy GmbH Fractional deposition of valuable substances from aqueous multi-component mixtures
WO2021118550A1 (en) * 2019-12-11 2021-06-17 Bl Technologies, Inc. Carbon measurements in aqueous samples using oxidation at elevated temperatures and pressures created by resistive heating
JP7498776B2 (en) 2019-12-11 2024-06-12 ビーエル テクノロジーズ、インコーポレイテッド Carbon Measurements in Aqueous Samples Using Oxidation at High Temperature and Pressure Produced by Resistive Heating

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* Cited by examiner, † Cited by third party
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US4113446A (en) * 1975-07-22 1978-09-12 Massachusetts Institute Of Technology Gasification process
DE3118348C2 (en) * 1980-05-08 1991-06-20 Modar Inc., Natick, Mass., Us

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JPH11502891A (en) * 1995-03-31 1999-03-09 ユニバーシティ オブ ハワイ Supercritical gasification of wet biomass using catalyst
NO317870B1 (en) * 1998-09-16 2004-12-27 Statoil Asa Process for Producing a H <N> 2 </N> Rich Gas and a CO <N> 2 </N> Rich Gas at High Pressure

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US4113446A (en) * 1975-07-22 1978-09-12 Massachusetts Institute Of Technology Gasification process
DE3118348C2 (en) * 1980-05-08 1991-06-20 Modar Inc., Natick, Mass., Us

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10135431C2 (en) * 2001-07-20 2003-07-10 Karlsruhe Forschzent Process for the pretreatment of reactors for the production of hydrogen and reactor
DE10135431A1 (en) * 2001-07-20 2003-02-13 Karlsruhe Forschzent Process for pre-treating a nickel-based alloy reactor for producing hydrogen, comprises passing a super critical aqueous solution of an oxidant through the reactor at a specified temperature and pressure
GB2381533A (en) * 2001-07-27 2003-05-07 Bosch Gmbh Robert Supercritical reformer
DE10162202B4 (en) * 2001-12-18 2007-12-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Hydrocarbon reformer
DE10162202A1 (en) * 2001-12-18 2003-07-10 Fraunhofer Ges Forschung Hydrocarbon reformer
EP1496013A1 (en) * 2002-04-12 2005-01-12 Suntory Limited Process for production of hydrogen and carbonyl compounds by reacting sub- or super-critical water with alcohols
EP1496013A4 (en) * 2002-04-12 2010-09-08 Suntory Holdings Ltd Process for production of hydrogen and carbonyl compounds by reacting sub- or super-critical water with alcohols
DE10259928A1 (en) * 2002-12-20 2004-07-22 Forschungszentrum Karlsruhe Gmbh De-gassing of biomasses with suppression of coke and tar formation and achievement of high hydrogen yields is achieved in a two-stage process using supercritical water
DE10259928B4 (en) * 2002-12-20 2006-05-24 Forschungszentrum Karlsruhe Gmbh Process for the treatment of biomass
DE102004031023B4 (en) * 2004-06-26 2007-10-25 Forschungszentrum Karlsruhe Gmbh Process for converting organic starting materials into oil-like products
EP1812353A1 (en) * 2004-11-15 2007-08-01 Chematur Engineering Ab Reactor and method for supercritical water oxidation
EP1812353A4 (en) * 2004-11-15 2010-10-06 Hollingford Ltd Reactor and method for supercritical water oxidation
ITMI20121537A1 (en) * 2012-09-17 2014-03-18 Maurizio Archetti APPARATUS AND METHOD FOR GASIFICATION OF LIQUID FUEL
EP3434382A1 (en) 2017-07-27 2019-01-30 iGas energy GmbH Fractional deposition of valuable substances from aqueous multi-component mixtures
WO2019020209A1 (en) 2017-07-27 2019-01-31 Igas Energy Gmbh Fractioned separation of valuable substances from aqueous many-component mixtures
US11584672B2 (en) 2017-07-27 2023-02-21 Igas Energy Gmbh Fractioned separation of valuable substances from aqueous many-component mixtures
WO2021118550A1 (en) * 2019-12-11 2021-06-17 Bl Technologies, Inc. Carbon measurements in aqueous samples using oxidation at elevated temperatures and pressures created by resistive heating
JP7498776B2 (en) 2019-12-11 2024-06-12 ビーエル テクノロジーズ、インコーポレイテッド Carbon Measurements in Aqueous Samples Using Oxidation at High Temperature and Pressure Produced by Resistive Heating

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