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5 Fuel Additives FUELS AND FUEL-ADDITIVES FUELS AND FUEL-ADDITIVES S. P. Srivastava Jenő Hancsók Copyright © 2014 by John Wiley & Sons, Inc. All rights reserved Published by John Wiley & Sons, Inc., Hoboken, New Jersey Published simultaneously in Canada No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750–8400, fax (978) 750–4470, or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748–6011, fax (201) 748–6008, or online at http://www.wiley.com/go/permission. Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your situation. You should consult with a professional where appropriate. Neither the publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages. For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at (800) 762–2974, outside the United States at (317) 572–3993 or fax (317) 572–4002. Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic formats. For more information about Wiley products, visit our web site at www.wiley.com. Library of Congress Cataloging-in-Publication Data Srivastava, S.P., 1940– Fuels and fuel-additives / S.P. Srivastava, Jenő Hancsók. pages cm Includes bibliographical references and index. ISBN 978-0-470-90186-1 (cloth) 1. Motor fuels–Additives. I. Hancsók, Jenő. 1947– II. Title. TP343.H336 2013 665.5′3827–dc23 2013023527 Printed in the United States of America 10 9 8 7 6 5 4 3 2 1 Contents PREFACE ix 1 Petroleum-Based Fuels – An Outlook 1 1.1 Introduction 1 1.2 Environmental Issues 4 1.3 Classification of Fuels 6 References 8 2 Emission Regulation of Automotive Vehicles and Quality of Automotive Fuels 11 2.1 Direct Regulation of Emissions 11 2.1.1 Emission Standards in Europe 13 2.1.2 US (EPA) Emission Standards 14 2.1.3 Emission Regulation in Japan 25 2.1.4 Emission Standards in India 25 2.1.5 Emission Standards in China 33 2.2 Indirect Emission Regulations (International Standards) 34 References 45 3 Fuels from Crude Oil (Petroleum) 48 3.1 Crude Oil 48 3.2 Crude Oil Refining 52 3.2.1 Separation and Extraction Processes 52 3.2.2 Change of Quality and Yield of Hydrocarbon Fractions 57 References 105 4 Alternative Fuels 121 4.1 Light (Gaseous) Hydrocarbons 123 4.2 Propane-Butane Gas 123 4.3 Mixtures of Synthetic Liquid Hydrocarbons 127 4.3.1 Liquid Synthetic Hydrocarbon Mixtures from Synthesis Gas 128 4.3.2 Biogas Oils from Triglycerides 133 v vi CONTENTS 4.3.3 Production of Bioparaffins from Lignocellulose and Carbohydrates 136 4.4 Oxygen-Containing Engine Fuels and Blending Components 136 4.4.1 Alcohols 137 4.4.2 Ethers 144 4.4.3 Vegetable Oils and Their Oxygen-Containing Derivatives 145 4.5 Hydrogen 152 4.5.1 Production of Hydrogen 152 4.5.2 Main Characteristic of Hydrogen 156 4.5.3 Hydrogen Storage on Vehicle and Reloading 157 References 159 5 Fuel Additives 177 5.1 Consumption of Additives (Demands) 182 5.2 Engine Deposits and Their Control 184 5.2.1 Deposits in Gasoline Engines 184 5.2.2 Deposit Control Additives (Detergent Dispersants) 188 5.2.3 Deposits and Their Control in Diesel Engines 201 5.2.4 Detergent Additives and Exhaust Emissions 204 5.2.5 Tests for DD Additives in Engines 205 5.2.6 Advantages of Using DD Additives in Fuels 208 5.3 Antiknock Additives (Octane Number Improvers) 209 5.3.1 “Knocking” 209 5.3.2 Octane Number 209 5.3.3 Octane Number Improver Additives 210 5.4 Cetane Number Improver 213 5.4.1 Cetane Number Improver Additives 215 5.4.2 Cetane Number Measurement 217 5.4.3 Cetane Index 217 5.5 Fuel Antioxidants (Stabilizers) 217 5.5.1 Increasing Storage Stability 218 5.5.2 Oxidation of Fuels 218 5.5.3 Chemical Mechanism of Antioxidants 219 5.5.4 Types of Antioxidants 220 5.6 Metal Deactivators/Passivators 223 5.7 Corrosion Inhibitors 225 5.7.1 Mechanism of Rusting/Corrosion 225 5.7.2 Anticorrosion Compounds 227 5.8 Antistatic Agents 228 CONTENTS vii 5.9 Lubricity Improvers 229 5.10 Friction Modifiers 233 5.11 Dehazer and Demulsifiers 237 5.12 Combustion Improvers 238 5.12.1 Conventional Approaches 239 5.12.2 Unconventional Approaches 242 5.13 Flow Improvers and Paraffin Dispersants of Fuels 243 5.13.1 Characteristics of Middle Distillate Fuel at Low Temperatures 245 5.13.2 Pour Point Depressants 246 5.13.3 Flow Improver Additives 247 5.13.4 Paraffin Dispersants 248 5.13.5 Distillate Operability Test (DOT Test) 253 5.14 Drag Reducers 253 5.15 Anti-Icing Additives 255 5.16 Antifoam Additives 255 5.17 Biocides 256 5.18 Coloring Matters and Markers 256 5.19 Additive Compositions 256 References 257 6 Blending of Fuels 270 6.1 Blending of Gasolines 270 6.2 Blending of Diesel Gasoils 271 7 Properties of Motor Fuels and Their Effects on Engines and the Environment 277 7.1 Effects of Gasoline Properties on Engines and the Environment 277 7.1.1 Combustion Process (Octane Number) 278 7.1.2 Volatility of Engine Gasolines 286 7.1.3 Stability of Gasolines 290 7.1.4 Corrosive Properties 293 7.1.5 Chemical Composition 294 7.1.6 Other Properties 297 7.2 Effects of Properties of Diesel Gasoils on Engines and the Environment 299 7.2.1 Ignition and Combustion Properties of Diesel Gasoils 300 7.2.2 Density and Energy Content of Diesel Gasoils 300 7.2.3 Distillation Properties of Diesel Fuels 301 7.2.4 Chemical Composition 303 viii CONTENTS 7.2.5 Stability of Diesel Gasoils 303 7.2.6 Corrosion Properties 305 7.2.7 Lubricating Properties 305 7.2.8 Low-Temperature Flow Properties 306 7.2.9 Effects of Chemical Composition on Emissions 306 7.2.10 Other Properties 310 References 311 8 Aviation Fuels 316 8.1 Aviation Gasolines 316 8.1.1 Aviation Gasoline Grades 317 8.1.2 Aviation Gasoline Additives 317 8.1.3 Automotive Gasoline for Aircraft 319 8.2 Jet Fuels 320 8.2.1 Main Quality Requirements and Properties of Jet Fuels 320 8.2.2 Aviation Turbine Fuel Specifications 321 8.2.3 Production of Aviation Turbine Fuels 324 8.2.4 Additives of Jet Fuel 328 References 331 9 Fuel Oils and Marine Fuels 333 9.1 Classification of Fuel Oils 334 9.1.1 Characteristics of Fuel Oils 335 9.1.2 Classification of Heating Fuels for Power Plants 336 9.1.3 Classification of Bunker Fuels 338 9.2 Production of Fuel Oils 341 9.3 Fuel Oil Stability and Compatibility 346 9.4 Additives for Residual Fuels 347 References 348 GLOSSARY: COMMON TERMINOLOGY IN FUELS AND ADDITIVES 351 INDEX 359 Preface Petroleum based fuels are being used for over 100 years and the specifications of such fuels have evolved to meet the changing demands of the users. New processes have been used to convert maximum refinery streams into useful distillate fuels of accept- able quality at reasonable profits. Technically many products can be conveniently used as fuels, such as methanol, ethanol, other alcohols, gasoline, diesel, gas oil, dimethyl ether, natural gas, liquefied petroleum gas, compressed natural gas, coal derived liquid fuels, bio fuels, hydrogen and many others. However, engine technologies have devel- oped around gasoline and diesel fuels over others. The pricing of the crude oil also favors petroleum fuels in the engines. Whenever, crude oil prices go up, alternate fuels are extensively discussed and investigated. Based on the current oil availability and prices, the use of petroleum based fuels and lubricants will continue in the current century. However, alternate fuels will find their place wherever, cost benefit analysis permits or regulations force their use. According to an IFP study, gasoline demand seems to be static and is likely to decrease in future, whereas diesel and kerosene mar- kets will grow by 5%. It is an indication that in future, the use of hydro-conversion technologies will increase in their refineries and FCC throughput will decrease. Environmental considerations, regulation of emission norms, energy efficiency and new engine technologies during the last twenty years have been responsible for dramatic changes in the fuels and additive quality. The dynamics of these changes and their interrelationship need to be properly understood, since the subject has now become quite complex.
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