Hydrocarbon Chemistry E-Book

George A. Olah

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch
• Veröffentlichungsjahr: 2017

Seitenzahl: 2217

Beschreibung

This book provides an unparalleled contemporary assessment of Hydrocarbon Chemistry - presenting basic concepts, current research, and future applications. * Comprehensive and updated review and discussion of the field of Hydrocarbon Chemistry * Includes literature coverage since the publication of the previous edition * Expands or adds coverage of: carboxylation, sustainable hydrocarbons, extraterrestrial hydrocarbons * Addresses a topic of special relevance in contemporary science, since hydrocarbons play a role as a possible replacement for coal, petroleum oil, and natural gas as well as their environmentally safe use * Reviews of prior edition: "...literature coverage is comprehensive and ideal for quickly reviewing specific topics...of most value to industrial chemists..." (Angewandte Chemie) and "...useful for chemical engineers as well as engineers in the chemical and petrochemical industries." (Petroleum Science and Technology)

Leseprobe

Hydrocarbon Chemistry

Volume 1 and Volume 2

Third Edition

George A. Olah

Loker Hydrocarbon Research Institute and Department of Chemistry University of Southern California, Los Angeles, California

Árpád Molnár

Department of Organic ChemistryUniversity of Szeged, Szeged, Hungary

G. K. Surya Prakash

Loker Hydrocarbon Research Institute and Department of ChemistryUniversity of Southern California, Los Angeles, California

This edition first published 2018© 2018 by John Wiley & Sons, Inc

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The right of George A. Olah, Árpád Molnár and G. K. Surya Prakash to be identified as the authors of this work has been asserted in accordance with law.

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Library of Congress Cataloging-in-Publication Data

Names: Olah, George A. (George Andrew), 1927–2017, author. | Molnár, Árpád, 1942– author. |   Prakash, G. K. Surya, author.Title: Hydrocarbon chemistry / George A. Olah, Árpád Molnár, G.K. Surya Prakash, Loker   Hydrocarbon Research Institute and Department of Chemistry, University of Southern California,   Los Angeles, California, Department of Organic Chemistry, University of Szeged, Szeged, Hungary.Description: Third edition. | Hoboken, NJ : Wiley, [2018] | Includes bibliographical references and   index. |Identifiers: LCCN 2017022048 (print) | LCCN 2017023298 (ebook) | ISBN 9781119390527 (pdf) |   ISBN 9781119390534 (epub) | ISBN 9781119390510 (hardback)Subjects: LCSH: Hydrocarbons. | BISAC: SCIENCE / Chemistry / Organic. | SCIENCE / Chemistry /   Industrial & Technical. | TECHNOLOGY & ENGINEERING / Petroleum.Classification: LCC QD305.H5 (ebook) | LCC QD305.H5 O43 2018 (print) | DDC 547/.01--dc23LC record available at https://lccn.loc.gov/2017022048

Cover image: © HelenStocker/GettyimagesCover design by Wiley

Contents

Volume 1

1 Introduction and General Aspects

1.1 Hydrocarbons and Their Classes

1.2 Energy–Hydrocarbon Relationships

1.3 Hydrocarbon Sources

1.4 Hydrocarbon Production from Natural Sources

1.5 Hydrocarbon Synthesis

1.6 Nonrenewable and Renewable Hydrocarbons

1.7 Regenerative Hydrocarbons from CO2 Emission Capture and Recycling

1.8 Hydrocarbon Functionalization Reactions

1.9 Use of Hydrocarbons, Petroleum Oil

References

2 Hydrocarbons from Petroleum and Natural Gas

2.1 Cracking

2.2 Reforming

2.3 Dehydrogenation with Olefin Production

2.4 Upgrading of Natural-Gas Liquids

2.5 Aromatics Production

References

3 Synthesis from C1 Sources

3.1 Aspects of C1 Chemistry

3.2 Chemical Reduction to Methanol and Oxygenates; Recycling of CO2

3.3 Fischer–Tropsch Chemistry

3.4 Methanol Synthesis

3.5 Oligocondensation of Methane

3.6 Hydrocarbons from Methane Derivatives

References

4 Isomerization

4.1 Acid-Catalyzed and Bifunctional Isomerization

4.2 Base-Catalyzed Isomerization

4.3 Metal-Catalyzed Isomerization

4.4 Pericyclic Rearrangements

4.5 Practical Applications

References

5 Alkylations

5.1 Acid-Catalyzed Alkylation

5.2 Base-Catalyzed Alkylation

5.3 Alkylation through Organometallics

5.4 Miscellaneous Alkylations

5.5 Practical Applications

References

6 Addition Reactions

6.1 Hydration

6.2 HX Addition

6.3 Halogen Addition

6.4 Addition to Form C–N Bonds

6.5 Addition to Form C–O, C–S, and C–P Bonds

6.6 Hydrometalation

6.7 Halometalation

6.8 Solvometalation

6.9 Carbometalation

6.10 Cycloaddition

References

7 Carbonylation and Carboxylation

7.1 Carbonylation

7.2 Carboxylation

References

8 Acylation

8.1 Acylation of Aromatics

8.2 Acylation of Aliphatic Compounds

References

Volume 2

9 Oxidation–Oxygenation

9.1 Oxidation of Alkanes

9.2 Oxidation of Alkenes

9.3 Oxidation of Alkynes

9.4 Oxidation of Aromatics

9.5 Practical Applications

References

10 Heterosubstitution

10.1 Electrophilic (Acid-Catalyzed) Substitution

10.2 Free-Radical Substitution

10.3 Formation of C–N Bonds

10.4 Formation of Carbon–Metal Bonds

10.5 Miscellaneous Derivatives

References

11 Reduction–Hydrogenation

11.1 Heterogeneous Catalytic Hydrogenation

11.2 Homogeneous Catalytic Hydrogenation

11.3 Transfer Hydrogenation

11.4 Chemical and Electrochemical Reduction

11.5 Ionic Hydrogenation

11.6 Hydrogenolysis of Saturated Hydrocarbons

11.7 Practical Applications

References

12 Metathesis

12.1 Metathesis of Acyclic Alkenes

12.2 Alkane Metathesis

12.3 Metathesis of Alkynes

12.4 Ring-Closing Metathesis

12.5 Ring-Opening Metathesis and Ring-Opening Metathesis Polymerization

12.6 Practical Applications

References

13 Oligomerization and Polymerization

13.1 Oligomerization

13.2 Polymerization

References

14 Outlook

14.1 Sustainable Hydrocarbon Chemistry for the Future

14.2 Extraterrestrial Hydrocarbon Chemistry

References

Index

EULA

List of Tables

Table 1.1 U.S. Energy Consumption by Sources (%)

3

Table 1.2 Power Generated in Industrial Countries by Nonfossil Fuels (2010)

Table 1.3 H/C Ratio of Natural Hydrocarbon Sources

Table 1.4 Composition (%) of Typical Light and Heavy Oils

Table 1.5 Composition of Natural Gas [weight percent (wt%)]

Table 1.6 Fractions of Typical Distillation of Crude Petroleum

Table 1.7 World Oil and Natural Gas Reserves (in Billion Tons of Oil Equivalent) from 1960 to 20152

Table 4.1 Temperature-Dependent Isomerization Equilibria of C4–C6 Alkanes15

Table 5.1 Product Composition (wt%) in the Alkylation of Isobutane with C4 Alkenes

Table 11.1 Product Distribution of Heptane Hydrogenolysis483

Table 13.1 Product Composition of Ethylene Oligomerizations and Thermal Cracking227

List of Illustrations

Figure 1.1 World energy consumption history and projections.

Figure 1.2 Schematic representation of structural groups and connecting bridges in bituminous coal. Source: Wiser 1984.7b Reproduced with permission of Springer. Copyright 2017.

Figure 14.1 “George Olah” carbon dioxide to renewable methanol plant in Iceland.

Guide

Cover

Table of Contents

Preface to the Third Edition

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Preface to the Third Edition

Some 15 years passed since the second edition and almost a quarter century since the original edition of our book. The field of hydrocarbon chemistry is continuing to rapidly grow and expand both in its scientific scope and significances and provides the most promising approach to replace oil and eventually all fossil fuel. It is also able to render the use of still existing substantial fossil fuels environmentally adaptable by capturing and recycling CO2 and recycling it through material to new fuels and chemical raw material. All these developments mandated a third edition to be published. We thank our publisher for making the book available in a completely updated and extended new edition.

Hydrocarbons became of increasingly significant not only to chemists but to the public at large. Nature's gift of fossil fuel sources is increasingly exhausted, and we need seriously consider to find replacement for coal, petroleum oil, and natural gas as well as their environmentally safe use. Whereas chemistry was considered to be a terrestrial science, recent direct observation and study of extraterrestrial hydrocarbons and their chemistry is changing the scope and significance of hydrocarbon chemistry as the connecting science effecting other sciences.

In order to keep our book updated and extended, we are gratified that our colleague and friend Surya Prakash joined us as coauthor for the third edition.

Our book on hydrocarbon chemistry has over the years become a fundamental text of this field. We hope that this new edition will continue to serve the purpose and goals we intended.

Los Angeles, California

Szeged, Hungary

November 2016

George A. Olah

Árpád Molnár

G.K. Surya Prakash

Preface to the Second Edition

Seven years has passed since the publication of the first edition of our book. It is rewarding that the favorable reception of and interest in hydrocarbon chemistry called for a second edition. All chapters were updated (generally considering literature through 2001) by adding sections on recent developments to review new advances and results. Two new chapters were also added on acylation as well as emerging areas and trends (including green chemistry, combinatorial chemistry, fluorous biphase catalysis, solvent-free chemistry, and synthesis via CO2 recycling from the atmosphere). Because of its importance, a more detailed treatment of chemical reduction of CO2 as a source for hydrocarbons is also included in Chapter 3. The new edition should keep our book current and of continuing use for interested readers.

We hope that Hydrocarbon Chemistry will continue to serve its purpose and the goals that we originally intended.

Los Angeles, California

Szeged, Hungary

March 2002

George A. Olah

Árpád Molnár

Preface to the First Edition

The idea of a comprehensive monograph treating the hydrocarbon chemistry as an entity emphasizing basic chemistry, while also relating to the practical aspects of the broad field, originally developed in the late 1970s by G. A. Olah and the late Louis Schmerling, a pioneer of hydrocarbon chemistry. The project was pursued albeit intermittently through the following years, producing a number of draft chapters. It became, however, clear that the task was more formidable than initially anticipated. Progress was consequently slow, and much of the initial writings became outdated in view of rapid progress. The project as originally envisaged became clearly no longer viable. A new start was needed and made in 1992 with Á. Molnár coming to the Loker Hydrocarbon Research Institute for 2 years as Moulton Distinguished Visiting Fellow. We hope that our efforts on Hydrocarbon Chemistry will be of use to those interested in this broad and fascinating field, which also has great practical significance.

Los Angeles, California

Szeged, Hungary

March 1995

George A. Olah

Árpád Molnár

Introduction

Hydrocarbons and their transformations play a major role in chemistry. Industrial applications, basic to our everyday life, face new challenges from diminishing petroleum supplies, regulatory problems, and environmental concerns. Chemists must find answers to these challenges. Understanding the involved chemistry and finding new approaches is a field of vigorous development.

Hydrocarbon chemistry (i.e., that of carbon- and hydrogen-containing compounds) covers a broad area of organic chemistry that at the same time is also of great practical importance. It includes the chemistry of saturated hydrocarbons (alkanes, cycloalkanes), as well as that of unsaturated alkenes and diene, acetylenes, and aromatics. Whereas numerous texts and monographs discuss selected areas of the field, a comprehensive up-to-date treatment as an entity encompassing both basic chemistry and practical applications is lacking. The aim of our book is to bring together all major aspects of hydrocarbon chemistry, including fundamental and applied (industrial) aspects in a single volume. In order to achieve this, it is necessary to be selective, and we needed to limit our discussion.

The book is arranged in 14 chapters. After discussing general aspects, separation of hydrocarbon from natural sources and synthesis from C1 precursors with the most recent developments for possible future applications, each chapter deals with a specific type of transformation of hydrocarbons. Involved fundamental chemistry, including reactivity and selectivity, as well as stereochemical considerations and mechanistic aspects are discussed, as are practical applications. In view of the immense literature, the coverage cannot be comprehensive and is therefore selective, reflecting the authors' own experience in the field. It was attempted nevertheless to cover all major aspects with references generally until the late 2016.

The chemistry of the major processes of petrochemical industry, including cracking, reforming, isomerization, and alkylation, is covered in Chapters 2, 4, and 5, respectively. The increasingly important C1 chemistry—that of one-carbon compounds (CO2, CO, methane and its derivatives)—is discussed in Chapter 3 (Synthesis from C1 sources).

Chapter 6 (Addition), Chapter 7 (Carbonylation and carboxylation), Chapter 8 (Acylation), Chapter 10 (Heterosubstitution) deal with derivatization reactions to form carbon–heteroatom bonds. The important broad field of hydrocarbon oxidations is covered in Chapter 9 (Oxidation–oxygenation). Both the chemistry brought about by conventional oxidizing agents and the most recent developments introducing selectively oxygen functionality into hydrocarbons are discussed. The hydrogenation (catalytic and chemical) and reduction techniques (homogeneous catalytic, ionic, and electrochemical), as well as hydrogenolysis are similarly discussed in Chapter 11 (Reduction–hydrogenation).

Chapter 12 deals with metathesis; Chapter 13 deals with oligomerization and polymerization of hydrocarbons. Each of these fields is of substantial practical significance and treated accordingly emphasizing basic chemistry and significant practical applications. Challenges in the new century and possible solutions relevant to hydrocarbon chemistry are discussed in Chapter 14 (Emerging areas and trends).

Hydrocarbon chemistry addresses a wide range of readers. We hope that research and industrial chemists, college and university teachers, and advanced undergraduate and graduate students alike will find it useful. Since it gives a general overview of the field, it should also be useful for chemical engineers and in the chemical and petrochemical industry in general. Finally, we believe that it may serve well as supplementary textbook in courses dealing with aspects of the diverse and significant field.