1、 Alcohols and EthersA Technical Assessment of TheirApplication as Fuels and Fuel ComponentsAPI PUBLICATION 4261THIRD EDITION, JUNE 2001Alcohols and EthersA Technical Assessment of TheirApplication as Fuels and Fuel ComponentsDownstream SegmentAPI PUBLICATION 4261THIRD EDITION, JUNE 2001(Based on inf
2、ormation available through November 1999)SPECIAL NOTESAPI publications necessarily address problems of a general nature. With respect to partic-ular circumstances, local, state, and federal laws and regulations should be reviewed.API is not undertaking to meet the duties of employers, manufacturers,
3、 or suppliers towarn and properly train and equip their employees, and others exposed, concerning healthand safety risks and precautions, nor undertaking their obligations under local, state, or fed-eral laws.Information concerning safety and health risks and proper precautions with respect to par-t
4、icular materials and conditions should be obtained from the employer, the manufacturer orsupplier of that material, or the material safety data sheet.Nothing contained in any API publication is to be construed as granting any right, byimplication or otherwise, for the manufacture, sale, or use of an
5、y method, apparatus, or prod-uct covered by letters patent. Neither should anything contained in the publication be con-strued as insuring anyone against liability for infringement of letters patent.Generally, API standards and publications are reviewed and revised, reafrmed, or with-drawn at least
6、every ve years. Sometimes a one-time extension of up to two years will beadded to this review cycle. The status of the publication can be ascertained from the APIDownstream Segment telephone (202) 682-8000. A catalog of API publications and mate-rials is published annually and updated quarterly by A
7、PI, 1220 L Street, N.W., Washington,D.C. 20005.All rights reserved. No part of this work may be reproduced, stored in a retrieval system, or transmitted by any means, electronic, mechanical, photocopying, recording, or otherwise, without prior written permission from the publisher. Contact the Publi
8、sher, API Publishing Services, 1220 L Street, N.W., Washington, D.C. 20005.Copyright 2001 American Petroleum InstituteFOREWORDThis publication was prepared by a task force of the Fuels Committee, a committee of theAPI Downstream Segment. Dr. Robert Barter and Dr. Bruce Bauman of APIs Regulatoryand S
9、cientic Affairs Department assisted the work. It is based on published information andon private reports made available through November 1999 from API member companies.The assistance of these companies is gratefully acknowledged. Richard L. Courtney, Her-man L. Muller, and Robert E. Reynolds served
10、as consultants to the task force.Task Force Members:Lewis M. Gibbs, Chairman Jim Williams, SecretaryChevron Products Company American Petroleum InstituteRichmond, California Washington, D.C.James M. DeJovine Dennis P. FeistBP, plc Equilon Enterprises, LLCCarson, California Houston, TexasAPI publicat
11、ions may be used by anyone desiring to do so. Every effort has been made bythe Institute to assure the accuracy and reliability of the data contained in them; however, theInstitute makes no representation, warranty, or guarantee in connection with this publicationand hereby expressly disclaims any l
12、iability or responsibility for loss or damage resultingfrom its use or for the violation of any federal, state, or municipal regulation with which thispublication may conict.Suggested revisions are invited and should be submitted to Jim Williams, DownstreamSegment, American Petroleum Institute, 1220
13、 L Street, N.W., Washington, D.C. 20005.iiiCONTENTSPage1 INTRODUCTION AND SCOPE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11.2 Re
14、ferences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 CHEMICAL AND PHYSICAL PROPERTIES OF ALCOHOLS AND ETHERS. . . 12.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
15、. . . . . . 12.2 Heating Value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22.3 Molecular Polarity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22.4 Polar Properties of Alcohols . . . .
16、 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22.5 Other Differences. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
17、 . . . . . . . . . . . 63 OXYGENATES PRODUCTION TECHNOLOGY, CAPACITY, AND COSTS. . . . 63.1 Methanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63.2 Ethanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
18、. . . . . . . . . . . . . . . . . . . . 113.3 Tertiary-Butyl Alcohol (TBA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133.4 Other Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133.5 Methyl Tertiary-Bu
19、tyl Ether (MTBE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133.6 Tertiary-Amyl Methyl Ether (TAME) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133.7 Diisopropyl Ether (DIPE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
20、. . 133.8 Ethyl Tertiary-Butyl Ether (ETBE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143.9 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144 REGULATION OF ALCOHOLS AND ETHERS . . . . . . . . . . . .
21、 . . . . . . . . . . . . . . . 154.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154.2 Clean Air Act Requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164.3 Leaded Gasoline. . . .
22、 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204.4 Pump Labeling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204.5 Neat and Near-Neat Alcohols Fuels . . . . . . . . . . . . . . . . . . . . . . .
23、. . . . . . . . . . . 204.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205 ALCOHOLS AND ETHERS BLENDED WITH GASOLINE . . . . . . . . . . . . . . . . . 215.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
24、 . . . . . . . . . . . . . . . . . . . . . . . . . . . 215.2 Heating Value Effects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215.3 Effects on Blend Volatility. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215.4 Lab
25、oratory Octane Effects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265.5 Water Sensitivity and Tolerance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265.6 Volume Expansion of Gasoline-EtOH Blends . . . . . . . . . . . . . . . . . .
26、 . . . . . . . . 295.7 Vehicle Performance of Gasoline-Oxygenate Blends. . . . . . . . . . . . . . . . . . . . . 295.8 Vehicle Technology Factors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295.9 The Auto/Oil Air Quality Improvement Research Program . . . . . . .
27、 . . . . . . . . . 325.10 Effects of Gasoline-Oxygenate Blends on Vehicle Emissions . . . . . . . . . . . . . . 325.11 Effects of Gasoline-Oxygenate Blends on Driveability . . . . . . . . . . . . . . . . . . . 375.12 Effects of Gasoline-Oxygenate Blends on Fuel Economy . . . . . . . . . . . . . . .
28、. . 525.13 Compatibility of Fuel System Materials with Oxygenated Gasolines . . . . . . . . 545.14 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 556 NEAT AND NEAR-NEAT ALCOHOLS FOR FUELING AUTOMOTIVE VEHICLES . . . . . . . . .
29、. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 596.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59vPage6.2 Alcohol Combustion Characteristics. . . . . . . . . . . . . . .
30、 . . . . . . . . . . . . . . . . . . . 606.3 Spark-Ignition Engine Operation with Neat Alcohol . . . . . . . . . . . . . . . . . . . . . 606.4 Spark-Ignition Engine Operation with Near-Neat Alcohol . . . . . . . . . . . . . . . . 706.5 Alcohol Fuels for Compression-Ignition Engines . . . . . . . . .
31、 . . . . . . . . . . . . . . 786.6 Materials Compatibility, Corrosion, and Engine Wear . . . . . . . . . . . . . . . . . . . . 826.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 837 GASOLINE OXYGENATE BLENDS IN NON-AUTOMOTIVE
32、FUEL USES . . . 918 DISTRIBUTION AND STORAGE OF ALCOHOLS, GASOLINE-ALCOHOL BLENDS, AND GASOLINE-ETHER BLENDSTRANSPORTATION, MARKETING, SAFETY AND FIRE PROTECTION, AND MEASUREMENT . . 988.1 Current Gasoline Distribution System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 988.2 Dis
33、tribution and Storage of Gasoline-Alcohol BlendsRenery, Pipelines, Terminals, and Service Stations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 988.3 Distribution and Storage of Neat or Near-Neat Alcohols-Renery, Pipelines, Terminals, and Service Stations. . . . . . . .
34、 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1018.4 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1039 OXYGENATES IN GROUND WATER: OCCURRENCE, BEHAVIOR, AND REMEDIATION . . . . . . . . . . . . . . . . . . . . . . .
35、. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1049.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1049.2 Environmental Behavior and Fate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1059
36、.3 Remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1069.4 Regulatory Guidelines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1069.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . .
37、 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1069.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10710 TOXICITY OF ALCOHOLS AND ETHERS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10810.1 Alcohols .
38、. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10810.2 Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11810.3 References . . . . . . . . . . . . . . . . . . . . . .
39、. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110APPENDIX A GLOSSARY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113APPENDIX B PROPERTIES OF OXYGENATES, GASOLINE, AND NO. 2 DIESEL FUEL. . . . . . . . . . . . . . . . . . . . . . . . . .
40、. . . . . . . . . . . . . 117Figures1 Molecular Structures of Water, Methanol, Ethanol, MTBE, and Gasoline . . . . . . . 52 Methanol Production ProcessSimplied Diagram . . . . . . . . . . . . . . . . . . . . . . . . 73 City Comparison: Full Cost M85 Minus Gasoline Price, Base Case . . . . . . . . .
41、. 104 Ethanol Production ProcessSimplied Design. . . . . . . . . . . . . . . . . . . . . . . . . . 105 Relationship Between Volume Percent Oxygenate and WeightPercent Oxygen in 0.748 Relative Density Gasoline . . . . . . . . . . . . . . . . . . . . . . . 186 Effect of Oxygenates on Distillation. . .
42、 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227 Effect of Oxygenate on Vapor Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238 Effect of EtOH Addition on Vapor Pressure of Base Gasoline . . . . . . . . . . . . . . . 259 Effect of Commingling a Gaso
43、line and a Gasoline-EtOH Blend of the Same RVP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2510 Calculated Versus Measured Temperature for V/L= 20. . . . . . . . . . . . . . . . . . . . . 26viPage11 Effect of EtOH and Butane on Vapor-Liquid R
44、atio . . . . . . . . . . . . . . . . . . . . . . . . 2712 Photograph of Gasoline-Alcohol Phase Separation . . . . . . . . . . . . . . . . . . . . . . . . 2813 Water Tolerance of Gasoline10% EtOH Blend . . . . . . . . . . . . . . . . . . . . . . . . . 3014 Effect of Oxygenates on Mass Emissions RVP/O
45、xygenate Matrix, Current Fleet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3415 Effect of Oxygenates on Toxic Exhaust Emissions RVP/Oxygenate Matrix, Current Fleet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3516 Effect of Oxygenate on Mass Exhaust Emi
46、ssions from High Emitting Vehicles . 3617 Effect of MTBE on Mass Exhaust Emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3718 Effect of MTBE on Mass Toxic Emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3919 Customer Satisfaction as a Function of Driveability
47、Index . . . . . . . . . . . . . . . . . . 4920 Driver Satisfaction vs. DI for All-Hydrocarbon and 15% MTBE Fuels . . . . . . . . 5021 Effect of Volatility Parameter T50on Driveability . . . . . . . . . . . . . . . . . . . . . . . . . 5322 Neat MeOH Startability of Engines at Low Temperatures . . . .
48、 . . . . . . . . . . . . . . 6623 General Motors Methanol Vehicle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6824 Simulated Cold Starting Minimum Temperatures Based on Laboratory Bench Tests. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
49、 . . . . . . 6925 Minimum Starting Temperature With Various Methanol Blends. . . . . . . . . . . . . . 7126 1996 FFV Taurus (Ethanol and Methanol). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7227 Vapor Pressure of GasolineMethanol Blends. . . . . . . . . . . . . . . . . . . . . . . . . . . 7428 Auto/Oil AQIRP 1993 FFV/VFV FleetFTP Exhaust Emissions. . . . . . . . . . . . 7629 Auto/Oil 1993 FFV/VFV FleetAverage Exhaust Toxic Emissions . . . . . . . . . . 7730 Volkswagen Jetta Methanol Vehicle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
