May 1993 • NREL!I'P-421-5150 Status and Fu Opportunities for Conversion of S thesis Gas to Liquid Energy Is: Final Report G. Mills Center for Catalytic Science and Technology, Department of Chemical Engineering, University of Delaware, Newark, Delaware �·� ...r1 �··, •1�=• �-- National·� Renewable Energy Laboratory 1617 Cole Boulevard Golden, CO 80401-3393 A national laboratory of the U.S. Department of Energy Managed by the Midwest Research Institute for the U.S. Department of Energy Under Contract No. DE-AC 36-83CH10093 1 J NREL{fP-421-5150 • UC Category: 245 • DE93010025 [ I Status and Fu Opportunities for Conversion of S esis Gas to Liquid Energy Final Report '(! G. Mills Center for Catalytic Science and Technology, Department of Chemical Engineering, University of Delaware, Newark, Delaware NREL technical monitors: R. Overend and R. Bain " JI National Renewable Energy Laboratory i 1617 Cole Boulevard ! Golden, Colorado 80401-3393 Operated by Midwest Research Institute for the U.S. Department of Energy under Contract No. DE-AC02-83CH10093 Prepared under subcontract number HZ 1-11208-1 May 1993 f NOTICE ' ' This reportwas prepared as an account of work sponsored by an agency of the United Statesgovernment. Neither the United States government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, com­ pleteness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or serviceby trade name, trademark, manufacturer, or otherwisedoes not necessarily con­ stitute or imply its endorsement, recommendation, or favoring by the United States government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States government or any agency thereof. Printed in the United States of America Available from: National Technical Information Service U.S. Department of Commerce 5285 Port Royal Road . Springfield, VA 22161 Price: Microfiche A01 Printed Copy A09 Codes are used for pricing all publications. The code is determined by the number of pages in the publication. Information pertaining to the pricing codes can be found in the current issue of the following publications which are generally available in most libraries: Energy Research Abstracts (ERA); Govern­ ment Reports Announcements and Index ( GRA and I); Scientific and TechnicalAbstract Reports(STAR); and publication NTIS-PR-360 available from NTIS at the above address. Acknowledgments Appreciation is expressed to Dr. Ralph P. Overend and Dr. Richard L. Bain of the National Renewable Energy Laboratory (NREL) for valuable technical guidance, to Rene Texeira (NREL) fo r expert editing, and to Paulette A. Warren, also of NREL, fo r efficient administrative support. Special thanks are extended to those who contributed by sharing ideas during site visits and discussions at meetings and to those who commented constructively on this report in draft fo rm. Appreciation is due to the many individuals whose names are recognized in the references fo r their contribution of scientificand engineering information. It is they who are the real authors. It is my hope that this report will assist in advancing catalytic science and technology of syngas fo r energy purposes by bringing to the attention of researchers informationthey did not previously know and by assisting those making research choices through delineating possible advantageous opportunities. G. Alex Mills, Senior Scientist Center fo r Catalytic Science and Technology Department of Chemical Engineering University of Delaware iii Contents Executive Summary Status ................................................................ E-1 E.1 Overview . E-1 E.2 Oxygenate Fuels .................................................... E-3 E.2.1 Methanol Manufacture ........................................... E-3 E.2. 1.1 More Effective Heat Removal ................................ E-3 E.2.1.2 Methanol Removal From Reactor to Achieve Higher Conversion . E-4 E.2.1.3 Novel Catalysts for Methanol Synthesis . .. E-4 E.2.2 Coproduction of Methanol and Electricity . E-4 E.2.3 Coproduction of Methanol and Dimethyl Ether .......................... E-4 E.2. 4 Increased Energy Efficiency in Methanol Use . E-5 E.2.5 Mixed Alcohols ................................................ E-5 E.2.6 Ethanol . E-5 E.2.7 Isobutanol .................................................... E-5 E.2.8 Methyl Tertiary Butyl Ether . E-6 E.3 Hydrocarbon Fuels . E-6 E.3.1 Fixed- fluidized-bed Fischer-Tropsch (PI) Synthesis Reactor ................. E-6 E.3.2 Synthesis to Wax, Hydrocrack to Diesel and Gasoline ..................... E-6 E.3.3 ·Slurry Phase FT ................................................ E-7 E.3.4 Methanol-to-Gasoline and Related Processes . E-7 E.4 Chemistry of Syngas Catalysis . E-7 E.5 Economics ......................................................... E-8 Future Research Opportunities . E-9 E.6 Potential . E-9 E.7 Integral Syngas Production/Fuel Synthesis . ..E-10 E.8 Fundamental Catalytic Science and Engineering ...............................E-10 Status . 1 1.0 Introduction . 1 2.0 Oxyfuels . 4 2.1 Overview . 4 2.1.1 Ethanol . 6 iv Contents (Continued) I J 2. 1. 2 Isobutanol . .. .. .. .. .. .. .. 6 2. 1. 3 Mixed Higher Alcohols ........................................ 7 2. 1. 4 M1'BE ................................... .......... ....... 7 2. 2 Methanol Manufacture . 7 2. 2. 1 More Effective Heat Removal. 8 2. 2. 1. 1 Slurry Catalyst Operation for Heat Control . 8 2. 2. 1. 2 Fluid Bed or Superconverter for Heat Control . · 10 2. 2.2Methanol Removal to Achieve Higher Conversion . 10 2. 2. 2. 1 GS1FR, RSIPR . 10 2. 2. 2.2 s�................................................ 10 2. 2. 2. 3 Condensing Methanol Principle . .. .. .. 11 2. 2. 3 Novel Catalysts for Methanol Synthesis ............................. 13 2. 2.3.1 Alloys: Raney ......................................... 13 2. 2.3.2 Alloys: Cu-Rare Earths .................................. 13 2. 2. 3. 3 SupportedPlatinum Group VIII Metals ........................ 14 2. 2. 3. 4 Methyl Formate ........................................ 14 2. 2. 3. 5 Brookhaven Homogeneous Catalytic Process .................... 15 2. 2. 3. 6 Biocatalysis ........................................... 15 2. 3 Coproduction of Methanol and Electricity ................................ 15 2. 4 Coproduction of Methanol and Dimethyl Ether : . .. 16 2. 5 Utilization of Methanol . .. .. .. 21 2. 6 Mixed Alcohols .................................................. 23 2. 6.1 Alkali-Modified MeOH Catalysts ................................. 23 2. 6.2 Catalyst Modified By Co Or Ni ..................... ............ 28 2. 6.3 Alkali-promoted MoSx Catalysts .................................. 29 2. 6.4 Supported Platinum Group For Higher Alcohols ...................... 30 2. 7 Ethanol . .. .. 31 2. 8 Isobutanol ..................................................... 33 3. 0 Hydrocarbon Fuels . 38 3. 1 Overview . 38 3. 1.1Mossgas Project . 38 3. 2 Fixed Fluidized-bed Ff Synthesis Reactor . 41 3. 2. 1 SASOL . 41 3. 3 Synthesis of Wax and Hydrocracking to Diesel and Gasoline . 41 3. 3. 1 Shell . 41 3. 3. 1. 1 Hydrocracking of Waxes . 47 3. 3. 2 Exxon . 49 3. 3. 3 Institut Fran<;ais du Petrole . 51 3. 4 Slurry-phase Ff . 51 3. 4. 1 Fuelco Slurry FT Plant Operation . 52 3. 4.2 Cobalt Catalyst for Slurry-phase Ff . 54 3. 5 MTG and Related Processes . ... ... 55 3. 5.1 TIGAS . 55 v Contents (Concluded) 4.0 Chemistry of Syngas Catalysis . 60 4.1 Methanol . 60 4.1.1 Schottky Junctions . 62 4.1.2 Supported Platinum Group VIII Metals . .. 62 4.2 Higher Alcohols . 62 4.3 Hydrocarbons . 64 5.0 Economics . 70 5.1 Oxygenate Fuels ..........................·. 71 5.2 HydrocarbonFuels . 74 Future Research Opportunities . 79 6.0 Potential . 79 6.1 Integral Syngas Production/Fuel Synthesis . 83 6.2 Fundamental Catalytic Science and Engineering . 83 References . 84 Appendix . 97 vi List of Figures Figure E-1..