HYDROCARBON CHEMISTRY

HYDROCARBON CHEMISTRY SECOND EDITION George A. Olah Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California Los Angeles, California Árpád Molnár Department of Organic Chemistry University of Szeged Szeged, Hungary A JOHN WILEY & SONS, INC., PUBLICATION

HYDROCARBON CHEMISTRY

Dedicated to Katherine Bogdanovich Loker, friend and generous supporter of hydrocarbon research.

HYDROCARBON CHEMISTRY SECOND EDITION George A. Olah Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California Los Angeles, California Árpád Molnár Department of Organic Chemistry University of Szeged Szeged, Hungary A JOHN WILEY & SONS, INC., PUBLICATION

Copyright # 2003 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, e-mail: permreq@wiley.com. 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 please contact our Customer Care Department within the U.S. at 877-762-2974, outside the U.S. 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, however, may not be available in electronic format. Library of Congress Cataloging-in-Publication Data: Olah, George A. (George Andrew), 1927 Hydrocarbon chemistry / George A. Olah, Arpad Molnar. 2nd ed. p. cm. Includes index. ISBN 0-471-41782-3 (Cloth) 1. Hydrocarbons. I. Moln^aar. ^aarp^aad, 1942 II. Title. QD305.H5 043 2003 547 0.01 dc21 2002154116 Printed in the United States of America 10 9 8 7 6 5 4 3 2 1

CONTENTS Preface to the Second Edition Preface to the First Edition Introduction xix xxi xxiii 1 General Aspects 1 1.1. Hydrocarbons and Their Classes / 1 1.2. Energy Hydrocarbon Relationship / 2 1.3. Hydrocarbon Sources and Separation / 4 1.3.1. Natural Gas / 5 1.3.2. Petroleum or Crude Oil / 6 1.3.3. Heavy Oils, Shale, and Tar Sand / 7 1.3.4. Coal and Its Liquefaction / 8 1.4. Petroleum Refining and Upgrading / 10 1.4.1. Distillation of Crude Petroleum / 10 1.4.2. Hydrocarbon Refining and Conversion Processes / 11 1.5. Finite, Nonrenewable Hydrocarbon Resources / 13 1.6. Hydrocarbon Synthesis / 14 1.6.1. Syngas (CO H 2 )-Based Fischer Tropsch Synthesis / 15 1.6.2. Methyl Alcohol Conversion / 16 1.6.3. Carbon Dioxide Conversion / 17 1.6.4. Direct Methane Conversion / 17 1.7. Chemical Nature of Hydrocarbon Conversion Reactions / 20 1.7.1. Homolytic (Free-Radical) Reactions / 20 1.7.2. Heterolytic (Ionic) Reactions / 20 1.8. Use of Hydrocarbons / 23 1.8.1. Refined Petroleum Products / 23 1.8.2. Transportation Fuels / 23 1.8.3. Chemicals and Plastics / 25 References and Notes / 25 v

vi CONTENTS 2 Hydrocarbon from Petroleum and Natural Gas 30 2.1. Cracking / 30 2.1.1. Cracking Processes / 30 2.1.2. Mechanism of Cracking / 33 2.1.3. Comparison of Cracking Operations / 36 2.2. Reforming / 38 2.2.1. Thermal Reforming / 39 2.2.2. Catalytic Reforming / 40 Hydroforming / 40 Metal-Catalyzed Reforming / 41 2.3. Dehydrogenation with Olefin Production / 44 2.3.1. Thermal Dehydrogenation / 45 2.3.2. Catalytic Dehydrogenation to Alkenes / 46 2.3.3. Practical Applications / 47 C 2 C 3 Alkenes / 47 C 4 Alkenes / 48 1,3-Butadiene and Isoprene / 48 Higher Olefins / 49 Styrene / 50 2.4. Upgrading of Natural-Gas Liquids / 50 2.5. Aromatics Production / 51 2.5.1. Catalytic Dehydrogenation and Dehydrocyclization / 51 2.5.2. Practical Applications / 56 2.6. Recent Developments / 57 2.6.1. Cracking / 57 2.6.2. Reforming / 60 2.6.3. Dehydrogenation with Olefin Production / 62 Catalytic Dehydrogenation / 62 Oxidative Dehydrogenation / 64 2.6.4. Aromatics Production / 66 References / 70 3 Synthesis from C 1 Sources 85 3.1. Nature s C 1 Chemistry / 86 3.2. The Chemical Reduction and Recycling of CO 2 /86 3.2.1. Catalytic Reduction / 88 Heterogeneous Hydrogenation / 88 Homogeneous Hydrogenation / 94 3.2.2. Other Reductions / 95 Ionic Reduction / 95

CONTENTS vii Electrochemical and Electrocatalytic Reduction / 96 Photoreduction / 97 Enzymatic Reduction / 99 3.3. Fischer Tropsch Chemistry / 100 3.3.1. Catalysts / 102 3.3.2. Mechanism / 103 3.3.3. Related Processes / 107 3.4. Direct Coupling of Methane / 109 3.4.1. Catalytic Oxidative Condensation / 109 3.4.2. High-Temperature Self-Coupling / 113 3.5. Hydrocarbons through Methane Derivatives / 114 3.5.1. Hydrocarbons through Methanol / 114 Methanol Synthesis / 114 Methanol Conversion to Hydrocarbons / 117 3.5.2. Hydrocarbons through Methyl Halides / 123 3.5.3. Hydrocarbons through Sulfurated Methanes / 123 3.6. Recent Developments / 124 3.6.1. Fischer Tropsch Chemistry / 124 Fischer Tropsch Synthesis / 124 Related Processes / 127 3.6.2. Direct Coupling of Methane / 129 Catalytic Oxidative Condensation / 129 Other Processes / 130 3.6.3. Hydrocarbons through Methane Derivatives / 132 Methanol Synthesis / 132 Methanol Conversion to Hydrocarbons / 136 References / 137 4 Isomerization 160 4.1. Acid-Catalyzed Isomerization / 161 4.1.1. Alkanes / 161 Mechanism / 165 4.1.2. Arylalkanes / 170 Side-Chain Isomerization / 170 Positional Isomerization / 170 4.1.3. Alkenes and Dienes / 174 4.2. Base-Catalyzed Isomerization / 177 4.2.1. Alkenes / 177 4.2.2. The Reversible Acetylene Allene Transformation / 180

viii CONTENTS 4.3. Metal-Catalyzed Isomerization / 182 4.3.1. Alkanes / 182 4.3.2. Alkenes / 185 4.4. Pericyclic Rearrangements / 189 4.5. Practical Applications / 192 4.5.1. Isomerization of C 4 C 6 Hydrocarbons / 192 Alkanes / 192 Alkenes / 193 4.5.2. Isomerization of Xylenes / 193 4.6. Recent Developments / 194 4.6.1. Acid-Catalyzed and Bifunctional Isomerization / 194 Alkanes / 194 Alkenes / 196 Xylenes / 197 The Acetylene Allene Rearrangement / 198 4.6.2. Metal-Catalyzed Isomerization / 199 4.6.3. Pericyclic Rearrangements / 199 References / 201 5 Alkylation 215 5.1. Acid-Catalyzed Alkylation / 215 5.1.1. Alkylation of Alkanes with Alkenes / 215 5.1.2. Alkylation of Alkanes under Superacidic Conditions / 221 Alkylolysis (Alkylative Cleavage) / 225 5.1.3. Alkylation of Alkenes and Alkynes / 225 Alkylation of Alkenes with Organic Halides / 225 Alkylation of Alkynes / 227 Alkylation with Carbonyl Compounds: The Prins Reaction / 228 5.1.4. Alkylation of Aromatics / 229 Catalysts / 230 Alkylation with Alkyl Halides / 232 Alkylation with Alkenes / 238 Alkylation with Alkanes / 241 Alkylation with Alcohols / 244 Transalkylation and Dealkylation / 246 5.2. Base-Catalyzed Alkylation / 248 5.3. Alkylation through Organometallics / 250 5.4. Miscellaneous Alkylations / 253 5.5. Practical Applications / 254

CONTENTS ix 5.5.1. Isoalkane Alkene Alkylation / 254 5.5.2. Ethylbenzene / 257 5.5.3. Cumene / 258 5.5.4. Xylenes / 258 5.5.5. p-ethyltoluene / 259 5.5.6. Detergent Alkylates / 260 5.6. Recent Developments / 260 5.6.1. Alkane Alkene Alkylation / 260 5.6.2. The Prins Reaction / 262 5.6.3. Alkylation of Aromatics / 262 Solid Acid Catalysts / 262 Specific Examples / 265 Side-Chain Alkylation / 267 Transalkylation / 268 5.6.4. Miscellaneous Alkylations / 268 References / 269 6 Addition 284 6.1. Hydration / 284 6.1.1. Alkenes and Dienes / 285 6.1.2. Alkynes / 287 6.1.3. Practical Applications / 288 Production of Alcohols by Hydration of Alkenes / 288 Production of Octane-Enhancing Oxygenates / 289 Acetaldehyde / 290 6.2. HX addition / 290 6.2.1. Hydrohalogenation / 290 Alkenes / 290 Dienes / 295 Alkynes / 296 6.2.2. Hypohalous Acids and Hypohalites / 297 6.2.3. Hydrogen Cyanide / 299 6.2.4. Practical Applications / 301 Ethyl Chloride / 301 Hydrochlorination of 1,3-Butadiene / 301 Vinyl Chloride / 301 Ethylene Chlorohydrin / 302 Propylene Chlorohydrin / 302 Adiponitrile / 303 Acrylonitrile / 303 6.3. Halogen Addition / 304 6.3.1. Alkenes / 304

x CONTENTS 6.3.2. Dienes / 308 6.3.3. Alkynes / 310 6.3.4. Practical Applications / 310 Vinyl Chloride / 310 Chlorination of 1,3-Butadiene / 312 6.4. Ammonia and Amine Addition / 312 6.4.1. Alkenes / 312 6.4.2. Dienes / 313 6.4.3. Alkynes / 314 6.5. Hydrometallation / 315 6.5.1. Hydroboration / 315 Alkenes / 316 Dienes / 319 Alkynes / 320 6.5.2. Hydroalanation / 321 6.5.3. Hydrosilylation / 322 Alkenes / 323 Dienes / 324 Alkynes / 325 6.5.4. Hydrozirconation / 326 6.6. Halometallation / 327 6.7. Solvometallation / 329 6.7.1. Solvomercuration / 329 6.7.2. Oxythallation / 330 6.8. Carbometallation / 330 6.9. Cycloaddition / 332 6.10. Recent Developments / 336 6.10.1. Hydration / 336 6.10.2. Hydrohalogenation / 336 6.10.3. Halogen Addition / 337 6.10.4. Hydroamination / 339 6.10.5. Hydrometallation / 341 Hydroboration / 341 Hydrosilylation / 342 Hydrozirconation / 344 Other Hydrometallations / 345 6.10.6. Halometallation / 345 6.10.7. Solvometallation / 346 6.10.8. Carbometallation / 346 6.10.9. Cycloaddition / 347 References / 349

CONTENTS xi 7 Carbonylation 371 7.1. Hydroformylation / 371 7.1.1. Alkenes / 372 7.1.2. Dienes and Alkynes / 377 7.1.3. Synthesis of Aldehydes and Alcohols by the Oxo Reaction / 377 7.2. Carboxylation / 379 7.2.1. Koch Reaction / 379 7.2.2. Carboxylation Catalyzed by Transition Metals / 381 Alkenes and Dienes / 381 Alkynes / 383 Alcohols / 383 7.2.3. Carboxylation of Saturated Hydrocarbons / 384 7.2.4. Practical Applications / 384 Neocarboxylic Acids / 384 Hydrocarboxymethylation of Long-Chain Alkenes / 385 Propionic Acid / 385 Acrylic Acid and Acrylates / 385 Acetic Acid / 386 Dimethyl Carbonate / 386 7.3. Aminomethylation / 386 7.4. Recent Developments / 387 7.4.1. Hydroformylation / 387 Alkynes / 389 Asymmetric Hydroformylation / 390 7.4.2. Formylation of Alkanes / 390 7.4.3. Carboxylation / 391 Alkenes and Alkynes / 391 Alkanes / 392 7.4.4. Aminomethylation / 394 References / 395 8 Acylation 407 8.1. Acylation of Aromatics / 407 8.1.1. General Characteristics / 407 8.1.2. Catalysts and Reaction Conditions / 409 8.1.3. Recent Developments / 410 New Soluble Catalysts / 410 Solid Catalysts / 412

xii CONTENTS 8.2. Related Acylations / 413 8.2.1. Formylation / 413 The Gattermann Koch Reaction / 413 The Gattermann Reaction / 415 Other Formylations / 416 8.2.2. The Houben Hoesch Synthesis / 417 8.3. Acylation of Aliphatic Compounds / 417 8.3.1. Acylation of Alkenes / 418 8.3.2. Acylation of Alkynes / 420 8.3.3. Acylation of Alkanes / 421 References / 422 9 Oxidation Oxygenation 427 9.1. Oxidation of Alkanes / 427 9.1.1. Oxidation to Alcohols and Carbonyl Compounds / 427 Autoxidation of Alkanes / 427 Oxidation of Methane / 429 Oxidation of Other Saturated Hydrocarbons / 434 9.1.2. Oxidations Resulting in Carbon Carbon Bond Cleavage / 444 Metal Oxidants / 444 Electrophilic Reagents / 445 Oxygenolysis / 449 9.2. Oxidation of Alkenes / 449 9.2.1. Epoxidation / 449 Direct Oxidation with Stoichiometric Oxidants / 449 Metal-Catalyzed Epoxidation / 454 Epoxidations Catalyzed by Metalloporphyrins / 458 Asymmetric Epoxidation / 460 9.2.2. Reactions with Molecular Oxygen / 461 Autoxidation / 461 Reactions with Singlet Oxygen / 462 9.2.3. Bis-hydroxylation / 467 9.2.4. Vinylic Oxidation / 470 Oxidation to Carbonyl Compounds / 471 Vinylic Acetoxylation / 475 9.2.5. Oxidative Cleavage / 477 Ozonation / 477 Other Oxidants / 482 9.2.6. Allylic Oxidation / 483

CONTENTS xiii Allylic Hydroxylation and Acyloxylation / 484 Oxidation to a,b-unsaturated Carbonyl Compounds / 487 9.3. Oxidation of Alkynes / 488 9.3.1. Oxidation to Carbonyl Compounds / 488 9.3.2. Oxidative Cleavage / 490 9.4. Oxidation of Aromatics / 491 9.4.1. Ring Oxygenation / 491 Oxidation to Phenols / 491 Ring Acyloxylation / 495 Oxidation to Quinones / 496 Oxidation to Arene Oxides and Arene Diols / 497 Oxidation with Singlet Oxygen / 498 9.4.2. Oxidative Ring Cleavage / 499 9.4.3. Benzylic Oxidation / 500 Oxidation of Methyl-Substituted Aromatics / 500 Oxidation of Other Arenes / 502 Benzylic Acetoxylation / 503 9.5. Practical Applications / 504 9.5.1. Oxidation of Alkanes / 504 Acetic Acid / 504 Oxidation of Cyclohexane / 505 Oxidation of Cyclododecane / 505 sec-alcohols / 506 9.5.2. Oxygenation of Alkenes and Dienes / 506 Ethylene Oxide / 506 Propylene Oxide / 508 Acetaldehyde and Acetone / 509 Vinyl Acetate / 509 1,4-Diacetoxy-2-butene / 510 Acrolein and Acrylic Acid / 510 Methacrolein and Methacrylic Acid / 511 9.5.3. Ammoxidation / 511 Acrylonitrile / 511 Other Processes / 512 9.5.4. Oxidation of Arenes / 513 Phenol and Acetone / 513 Benzoic Acid / 514 Terephthalic Acid / 514 Maleic Anhydride / 515 Phthalic Anhydride / 517 Anthraquinone / 519