MethanolMethanol asas anan EnergyEnergy CarrierCarrier PeterPeter Biedermann,Biedermann, ThomasThomas Grube,Grube, BerndBernd HöhleinHöhlein (Hrsg.)(Hrsg.) Energietechnik Energy Technology Schriften des Forschungszentrums Jülich Reihe Energietechnik / Energy Technology Band / Volume 55 Forschungszentrum Jülich GmbH Institut für Werkstoffe und Verfahren der Energietechnik (IWV) IWV-3: Energieverfahrenstechnik Methanol as an Energy Carrier Peter Biedermann, Thomas Grube, Bernd Höhlein (Hrsg.) Schriften des Forschungszentrums Jülich Reihe Energietechnik / Energy Technology Band / Volume 55 ISSN 1433-5522 ISBN 3-89336-446-3 Bibliographic information published by Die Deutsche Bibliothek. Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data is available in the Internet at <http://dnb.ddb.de>. Publisher Forschungszentrum Jülich GmbH and Distributor: Zentralbibliothek, Verlag 52425 Jülich Phone: +49 2461 61-5368 · Telefax: +49 2461 61-6103 e-mail: [email protected] Internet: http://www.fz-juelich.de/zb Cover Design: Grafische Betriebe, Forschungszentrum Jülich GmbH Printer: Grafische Betriebe, Forschungszentrum Jülich GmbH Copyright: Forschungszentrum Jülich 2006 Schriften des Forschungszentrums Jülich Reihe Energietechnik / Energy Technology Band / Volume 55 ISSN 1433-5522 ISBN-10: 3-89336-446-3 ISBN-13: 978-3-89336-446-6 Neither this book nor any part of it may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher. Authors Chapter 1: Bernd Höhlein, Forschungszentrum Jülich GmbH 1 Wolfgang Seuser, De Witt & Co Inc. Europe, Hus- ton/Texas Chapter 2–4: Bernd Höhlein, Forschungszentrum Jülich GmbH 1 Thomas Grube, Peter Biedermann, Forschungszentrum Jülich GmbH Chapter 3.4: Jürgen Mergel, Hendrik Dohle, Forschungszentrum Jü- lich GmbH Chapter 5: Jens R. Rostrup-Nielsen, Haldor Topsøe A/S, Lyngby, Denmark Chapter 6.1–6.5: Ib Dybkjær, Torben Topsøe A/S, Lyngby, Denmark Chapter 6.6-6.7: John Bøgild Hansen, Haldor Topsøe A/ mark Chapter 7: Hubert Bielawa, Lurgi Öl•Gas•Chem furt/Main (2003), Waldemar furt/Main (2006) Chapter 8: Bernd Höhlein, Forschungszentrum Jülich Gmb Chapter 8.5: Detlef Stolten, Pete Jülich GmbH Chapter 9: Georg Erdmann, Technische Universitä Ludmilla Schlecht, Technische Universi Chapter 10: Gerhard Isenberg, Raphael Edinger, DaimlerChrysler AG, Stuttgart Chapter 11: Peter Biedermann, Forschungszentrum Jülich GmbH Chapter 11.3: Martin Pokojski, Uwe Radke, BEWAG AG Berlin 2 Chapter 12: Bernd Höhlein, Forschungszentrum Jülich GmbH 1 Editorial 1 2 Rena Anglo-Saxon units of measurement The Anglo-Saxon units of measurement commonly used in the respective subject area have not been converted into the SI system, but conversion and estimation aids are provided. Trademarks The abbreviations used with ® or ™ in the text are trademarks of the companies Haldor Topsøe AS, Lurgi AG and Volkswagen AG respectively, which stand for a technical process. Preface The present volume is based on volume 28 “Methanol als Energieträger” (Methanol as an Energy Carrier) published in the Energy Technology series in 2003 (ISBN 3-89336-338-6). It has above all been supplemented by additional contributions to the chapters on DMFC and methanol prepara- tion: – DMFC (Chapter 3) – Synthesis gas (Chapter 5) – Process engineering of methanol synthesis (Chapter 6) – Methanol and MCFC (Berlin project) (Chapter 11.3) The chapters of the 2003 editon have been updated. However, this was not possible in each case for costs or prices because of the dramatic price increases at the end of 2005. The editors would like to thank Ms M. Heinz from the Language Service at the Central Library of Research Centre Jülich for the translation of the German text into English and for useful advice. vii 0 Contents 0 Contents.................................................................................. vii 0.1 Figures and Tables............................................................ xii 0.1.1 Figures ......................................................................... xii 0.1.2 Tables ......................................................................... xiv 0.2 Abstract ........................................................................ xvii 1 Introduction .............................................................................. 1 1.1 Fuel supply for the transport sector...................................... 1 1.2 Global situation of methanol................................................ 3 1.3 Summary of Chapter 1 ....................................................... 6 2 Possible energy carriers for road traffic ......................................... 9 2.1 Costs and emissions..........................................................10 2.2 Summary of Chapter 2 ......................................................13 3 Methanol and alternative fuels for road traffic ...............................14 3.1 Methanol for MTBE production ............................................17 3.2 M85 for direct-injection combustion engines .........................17 3.3 Methanol for fuel cells with reformers ..................................19 3.4 Methanol for fuel cells without reformers (DMFC) .................25 3.4.1 Fuel for direct fuel cells...................................................26 3.4.2 Principle of the DMFC .....................................................27 3.4.3 Development areas ........................................................28 3.4.3.1 Electrode structure ...................................................30 3.4.3.2 New membrane materials ..........................................31 3.4.3.3 Selective catalysts ....................................................32 3.4.4 Applications ..................................................................33 3.4.5 Outlook ........................................................................34 3.5 Methanol for fuel cell powered passenger cars in the USA.......34 3.6 Summary of Chapter 3 ......................................................35 4 Methanol production..................................................................36 4.1 Methanol from natural gas .................................................37 4.1.1 Synthesis gas production ................................................37 4.1.2 Methanol synthesis.........................................................38 4.1.3 Life cycle cost and energy balance....................................39 Contents viii 4.2 Methanol from coal ...........................................................41 4.3 Summary of Chapter 4 ......................................................43 5 Synthesis gas ..........................................................................44 5.1 Applications .....................................................................44 5.1.1 Principles......................................................................44 5.1.2 Natural gas conversion ...................................................44 5.1.3 Coal conversion .............................................................46 5.2 Synthesis gas technologies ................................................47 5.2.1 Steam reforming............................................................48 5.2.2 CO2 reforming ...............................................................51 5.3 Synthesis gas for methanol ................................................53 5.3.1 Stoichiometry................................................................53 5.3.2 Choice of technology ......................................................54 5.4 Direct conversion..............................................................55 5.5 Summary of Chapter 5 ......................................................56 6 Process engineering of methanol synthesis ...................................58 6.1 Methanol production technology..........................................58 6.2 Synthesis gas preparation .................................................59 6.2.1 One-step reforming........................................................60 6.2.2 Two-step reforming........................................................61 6.2.3 Autothermal reforming ...................................................63 6.2.4 Gas-heated reforming.....................................................64 6.2.5 Choice between reforming technologies.............................65 6.2.6 Gasification ...................................................................66 6.2.7 Co-production of methanol in ammonia plants ...................67 6.3 Methanol synthesis ..........................................................67 6.3.1 Thermodynamics ...........................................................67 6.3.2 Catalysts ......................................................................68 6.3.3 Reaction mechanism ......................................................68 6.3.4 Kinetics ........................................................................69 6.3.5 By-products ..................................................................70 6.3.6 Design of methanol synthesis reactors ..............................71 6.3.6.1 Quench reactor ........................................................71 6.3.6.2 Adiabatic reactor ......................................................72 Contents ix 6.3.6.3 Boiling water reactor.................................................72