Utilization of Renewable Oxygenates as Gasoline Blending Components Janet Yanowitz Ecoengineering, Inc. Earl Christensen and Robert L. McCormick Center for Transportation Technologies and Systems National Renewable Energy Laboratory NREL is a national laboratory of the U.S. Department of Energy, Office of Energy Efficiency & Renewable Energy, operated by the Alliance for Sustainable Energy, LLC. Technical Report NREL/TP-5400-50791 August 2011 Contract No. DE-AC36-08GO28308 Utilization of Renewable Oxygenates as Gasoline Blending Components Janet Yanowitz Ecoengineering, Inc. Earl Christensen and Robert L. McCormick Center for Transportation Technologies and Systems National Renewable Energy Laboratory Prepared under Task No. FC08.9451 NREL is a national laboratory of the U.S. Department of Energy, Office of Energy Efficiency & Renewable Energy, operated by the Alliance for Sustainable Energy, LLC. National Renewable Energy Laboratory Technical Report 1617 Cole Boulevard NREL/TP-5400-50791 Golden, Colorado 80401 August 2011 303-275-3000 • www.nrel.gov Contract No. DE-AC36-08GO28308 NOTICE This report was prepared as an account of work sponsored by an agency of the United States government. 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, completeness, 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 service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States government or any agency thereof. 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TABLE OF CONTENTS 1 INTRODUCTION ................................................................................................................................... 1 2 CHEMICAL STRUCTURE .................................................................................................................... 3 3 PRODUCTION ...................................................................................................................................... 5 3.1 Alcohols by Fermentation ................................................................................................ 5 3.2 Alcohols via Synthesis Gas .............................................................................................. 6 3.3 Cellulose Hydrolysis ........................................................................................................ 8 4 REGULATIONS AND STANDARDS ................................................................................................. 11 4.1 Federal Requirements ..................................................................................................... 11 4.1.1 Substantially Similar Requirement ......................................................................... 11 4.1.2 Fuel Registration and Health Effects Testing ......................................................... 12 4.1.3 Other Federal Requirements ................................................................................... 12 4.2 State Requirements ......................................................................................................... 14 4.2.1 ASTM and NIST Specifications ............................................................................. 14 4.2.2 Other State Requirements ....................................................................................... 16 4.3 Transportation and Distribution System Requirements ................................................. 16 5 CHEMICAL PROPERTIES ................................................................................................................. 19 5.1 Alcohols ......................................................................................................................... 19 5.2 Cellulose-Derived Oxygenates ....................................................................................... 19 6 SAFETY AND ENVIRONMENTAL HAZARDS .................................................................................. 24 6.1 Safety .............................................................................................................................. 24 6.2 Toxicity .......................................................................................................................... 25 6.3 Environmental Considerations ....................................................................................... 26 7 USE IN SPARK-IGNITION ENGINES ................................................................................................ 28 7.1 Energy Density ............................................................................................................... 28 7.2 Volatility......................................................................................................................... 29 7.3 Phase Separation ............................................................................................................ 33 7.4 Materials Compatibility.................................................................................................. 37 7.5 Driveability ..................................................................................................................... 38 7.6 Octane Rating ................................................................................................................. 38 7.7 Heat of Vaporization ...................................................................................................... 39 iii 7.8 Tailpipe Emissions ......................................................................................................... 40 7.9 Viscosity ......................................................................................................................... 41 7.10 Impurities ....................................................................................................................... 41 8 CONCLUSIONS AND RESEARCH NEEDS ...................................................................................... 42 9 REFERENCES .................................................................................................................................... 44 iv List of Tables Table 1. Products from mixed alcohol synthesis via synthesis gas .................................................7 Table 2. Substantially Similar Fuel Blends and Fuel Blends with Waivers ..................................13 Table 3. ASTM 4814-10b, Chemical and Physical Properties of Spark-Ignition Fuels ................15 Table 4. ASTM D4806-11, Chemical and Physical Properties for Denatured Fuel Ethanol for Blending with Gasoline ..................................................................................................................17 Table 5. Chemical and Physical Properties of Gasoline and Alcohols ..........................................20 Table 6. Chemical and Physical Properties of Biofuels Compared to Gasoline ............................22 Table 7. Oral Toxicity of Gasoline and Various Oxygenates ........................................................26 Table 8. Mole Fraction of Water in the Organic Phase and Aqueous Phases When Combined with 15% Alcohol/n-Heptane Blend84 ...........................................................................................35 List of Figures Figure 1. Propanol isomers ..............................................................................................................3 Figure 2. Butanol isomers ................................................................................................................3 Figure 3. Pentanol isomers ...............................................................................................................3 Figure 4. Chemical structure of cellulose-derived oxygenates ........................................................4 Figure 5. Simplified scheme showing conversion of C6 sugar (as in cellulose) to cellulose- derived oxygenates (after Palkovits, Lange et al., and Alonso et al.). .............................................9 Figure 6. Simplified scheme showing conversion of C5 sugar (pentose as in hemicellulose) to cellulose-derived oxygenates .........................................................................................................10 Figure 7. Vapor pressure of alcohol/gasoline blends .....................................................................31