DE19955150B4 - Process for the production of hydrogen - Google Patents
Process for the production of hydrogen Download PDFInfo
- Publication number
- DE19955150B4 DE19955150B4 DE19955150A DE19955150A DE19955150B4 DE 19955150 B4 DE19955150 B4 DE 19955150B4 DE 19955150 A DE19955150 A DE 19955150A DE 19955150 A DE19955150 A DE 19955150A DE 19955150 B4 DE19955150 B4 DE 19955150B4
- Authority
- DE
- Germany
- Prior art keywords
- hydrogen
- hydrocarbons
- alcohols
- production
- reaction
- 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 - Fee Related
Links
Classifications
-
- 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
Abstract
Verfahren zur Erzeugung von Wasserstoff, bei dem Kohlenwasserstoffe mit Ausnahme von Erdgas und Methan und/oder Alkohole bei einer Temperatur von 550°C bis 700°C in überkritischem Wasser ohne Einsatz eines Katalysators umgesetzt werden.A process for producing hydrogen in which hydrocarbons other than natural gas and methane and / or alcohols are reacted at a temperature of 550 ° C to 700 ° C in supercritical water without the use of a catalyst.
Description
Die Erfindung betrifft ein Verfahren zur Erzeugung von Wasserstoff gemäß dem Patentanspruch.The The invention relates to a method for producing hydrogen according to the claim.
In der Veröffentlichung von H. R. Holgate et al. ”Glucose Hydrolysis and Oxidation in Supercritical Water”, Reactors, Kinetics and Catalysts Vol. 41, No. 3 (1995) 637–648 wird über die Oxidation von Glucose zu Wasserstoff und Kohlendioxid berichtet. Glucose wird als Modellsubstanz für Biomasse verwendet. Die Oxidation wird ohne Einsatz eines Katalysators mit Zugabe von Sauerstoff 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 berichten im Abschnitt ”Products of glucose hydrolysis”, daß bei höheren Konzentrationen (0,1 bis 0,8 mol/l) Methan als Reaktionsprodukt 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. 3 (1995) 637-648 reports the oxidation of glucose to hydrogen and carbon dioxide. Glucose is used as 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 section "Products of glucose hydrolysis" that at higher concentrations (0.1 to 0.8 mol / l) methane as the reaction product becomes increasingly more stable and forms instead of hydrogen and carbon dioxide.
Die
Ergebnisse von H. R. Holgate werden (ohne die Quelle zu zitieren)
im einleitenden Teil der
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 Katalysators nahezu vollständig in gasförmigen Wasserstoff konvertieren läßt, wobei die Ausgangsverbindung in höheren Konzentrationen einsetzbar ist und auf die Zugabe von Sauerstoff verzichtet werden kann.Of the Invention is based on the object, a further method for Indicate generation of hydrogen from a supercritical aqueous solution, with its help, the hydrogen content of organic compounds and that resulting from CO splitting from water splitting Share without use of a catalyst almost completely in gaseous Converts hydrogen, wherein the starting compound in higher Concentrations can be used and on the addition of oxygen can be waived.
Die Aufgabe wird durch das im ersten Patentanspruch beschriebene Verfahren gelöst. In den Unteransprüchen sind bevorzugte Ausgestaltungen des Verfahrens beschrieben.The The object is achieved by the method described in the first claim solved. In the dependent claims preferred embodiments of the method are described.
Mit dem erfindungsgemäßen Verfahren lassen sich Kohlenwasserstoffe und Alkohole umsetzen. Als Kohlenwasserstoffe eignen geradkettige und verzweigte Alkane, Alkene und Alkine sowie Aromaten. Statt der betreffenden Alkane, Alkene und Alkine können auch die entsprechenden Alkohole eingesetzt werden. Bevorzugt werden jedoch Methanol und Ethanol.With the method according to the invention Hydrocarbons and alcohols can be converted. As hydrocarbons are straight-chain and branched alkanes, alkenes and alkynes as well Aromatics. Instead of the relevant alkanes, alkenes and alkynes can also the corresponding alcohols are used. To be favoured however, methanol and ethanol.
Die Konzentration der Kohlenwasserstoffe und/oder der Alkohole sollte mindestens 0,1 mol/l betragen. In diesem Konzentrationsbereich ist Glucose in überkritischem Wasser nicht mehr vollständig 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 at least 0.1 mol / l. In this concentration range is Glucose in supercritical Water is no longer complete convertible into hydrogen and carbon dioxide. Because of energetic efficiency of the process are highest possible concentrations to strive for up to several mol / l.
Die Temperatur der Umsetzung liegt 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 Katalysators ist nicht notwendig. Dennoch kann in einem einzigen Reaktionsschritt ein vollständiger Umsatz erzielt werden.The Temperature of the reaction is 550 ° C to 700 ° C and the pressure at about 250 bar. The addition of oxygen may be omitted become. The use of a catalyst is not necessary. Yet can be a complete reaction in a single reaction step 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 Kohlenmonoxid
wird erfindungsgemäß selbst
dann praktisch vollständig
unterdrückt,
wenn man die hohen Temperaturen von 550°C bis 700°C einstellt. Die weitgehende
Unterdrückung
der Bildung von Kohlenmonoxid ist deswegen überraschend, weil die Reaktion
Die Erfindung wird im folgenden anhand von Figuren und Ausführungsbeispielen näher erläutert.The Invention will be described below with reference to figures and embodiments explained in more detail.
Es zeigenIt demonstrate
In
Beispielexample
Zur Demonstration des Verfahrens im Labormaßstab wurde eine Lösung von 5 Gew.-% Methanol in Wasser als Edukt eingesetzt.to Demonstration of the process on a laboratory scale was a solution of 5 wt .-% methanol used in water as starting material.
Die
Lösung
wurde durch eine Hochdruckpumpe
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 Temperaturberich 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, entsprechend über 99,8% Umsatz.The reactor configuration allowed for a controlled, relatively shallow temperature gradient in the exit region. The residence time in the temperature range 300 to 200 ° C, which is of particular importance for the water-gas shift reaction, was at the exit about 36 sec. The inner surface of the reactor was composed of Cr, Ni and Mo oxides. The Innnenoberfläche in Temperaturberich 300 to 200 ° C was about 90 cm 2 . The trial lasted about 1000 hours and was completed without any inherent process 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)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19955150A DE19955150B4 (en) | 1999-11-17 | 1999-11-17 | Process for the production of hydrogen |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19955150A DE19955150B4 (en) | 1999-11-17 | 1999-11-17 | Process for the production of hydrogen |
Publications (2)
Publication Number | Publication Date |
---|---|
DE19955150A1 DE19955150A1 (en) | 2001-06-13 |
DE19955150B4 true DE19955150B4 (en) | 2010-08-05 |
Family
ID=7929247
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19955150A Expired - Fee Related DE19955150B4 (en) | 1999-11-17 | 1999-11-17 | Process for the production of hydrogen |
Country Status (1)
Country | Link |
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DE (1) | DE19955150B4 (en) |
Families Citing this family (10)
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 |
DE10136769A1 (en) * | 2001-07-27 | 2003-02-13 | Bosch Gmbh Robert | Reformer unit for generating a reformate |
DE10162202B4 (en) * | 2001-12-18 | 2007-12-27 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Hydrocarbon reformer |
US7166753B2 (en) * | 2002-04-12 | 2007-01-23 | Suntory Limited | Process for production of hydrogen and carbonyl compounds by reacting sub- or super-critical water with alcohols |
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 |
SE528840C2 (en) * | 2004-11-15 | 2007-02-27 | Chematur Eng Ab | Reactor and process for supercritical water oxidation |
ITMI20121537A1 (en) * | 2012-09-17 | 2014-03-18 | Maurizio Archetti | APPARATUS AND METHOD FOR GASIFICATION OF LIQUID FUEL |
DK3434382T3 (en) | 2017-07-27 | 2019-12-16 | Igas Energy Gmbh | FRACTIONED SEPARATION OF VALUABLE SUBSTANCES FROM Aqueous Multicomponent 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 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 | |
WO1996030464A1 (en) * | 1995-03-31 | 1996-10-03 | University Of Hawaii | Catalytic supercritical gasification of wet biomass |
WO2000018681A1 (en) * | 1998-09-16 | 2000-04-06 | Den Norske Stats Oljeselskap A.S | Method for preparing a h2-rich gas and a co2-rich gas at high pressure |
-
1999
- 1999-11-17 DE DE19955150A patent/DE19955150B4/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 | |
WO1996030464A1 (en) * | 1995-03-31 | 1996-10-03 | University Of Hawaii | Catalytic supercritical gasification of wet biomass |
WO2000018681A1 (en) * | 1998-09-16 | 2000-04-06 | Den Norske Stats Oljeselskap A.S | Method for preparing a h2-rich gas and a co2-rich gas at high pressure |
Non-Patent Citations (3)
Title |
---|
URL:http://www.roempp.com/prod/roempp.php (gutachtlich) * |
URL:http://www.thermo.com/eThermo/CMA/PDFs/Article s/articlesFile 15914.pdf (gutachtlich) * |
URL:http://www.thermo.com/eThermo/CMA/PDFs/Article s/articlesFile 15914.pdf (gutachtlich) URL:http://www.roempp.com/prod/roempp.php (gutachtlich) |
Also Published As
Publication number | Publication date |
---|---|
DE19955150A1 (en) | 2001-06-13 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
OP8 | Request for examination as to paragraph 44 patent law | ||
8127 | New person/name/address of the applicant |
Owner name: KARLSRUHER INSTITUT FUER TECHNOLOGIE, 76131 KA, DE |
|
8364 | No opposition during term of opposition | ||
R119 | Application deemed withdrawn, or ip right lapsed, due to non-payment of renewal fee |
Effective date: 20140603 |