Chemestry Petrochemical Processses

This book is dedicated to the memory of Professor Lewis Hatch (1912–1991), a scholar, an educator, and a sincere friend.

C h e m i s t ry o f
PETROCHEMICAL PROCESSES
2nd Edition

Copyright © 1994, 2000 by Gulf Publishing Company, Houston, Texas. All rights reserved. Printed in the United States of America. This book, or parts thereof, may not be reproduced in any form without permissionof the publisher. Gulf Publishing Company Book Division P.O. Box 2608, Houston, Texas 77252-2608 Library of Congress Cataloging-in-Publication Data Printed on acid-free paper (∞).

Contents
Preface to Second Edition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi Preface to First Edition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii CHAPTER ONE PrimaryRaw Materials for Petrochemicals . . . . . . . . . . . . . . . . . 1
Introduction 1 Natural Gas 1 Natural Gas Treatment Processes 3, Natural Gas Liquids 8, Properties of Natural Gas 10 Crude Oils 11 Composition of Crude Oils 12, Properties of Crude Oils 19, Crude Oil Classification 21 Coal, Oil Shale, Tar Sand, and Gas Hydrates 22 References 26

CHAPTER TWO Hydrocarbon Intermediates . . . . . .. . . . . . . . . . . . . . . . . . . . . . .29
Introduction 29 Paraffinic Hydrocarbons 29 Methane 30, Ethane 30, Propane 31, Butanes 31 Olefinic Hydrocarbons 32 Ethylene 32, Propylene 33, Butylenes 34 Dienes 36 Butadiene 37, Isoprene 37 Aromatic Hydrocarbons 37 Extraction of Aromatics 38 Liquid Petroleum Fractions and Residues 42 Naphtha 43, Kerosine 45, Gas Oil 46, Residual Fuel Oil 47References 47
v

CHAPTER THREE Crude Oil Processing and Production of Hydrocarbon Intermediates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Introduction 49 Physical Separation Processes 49 Atmospheric Distillation 50, Vacuum Distillation 51, Absorption Process 52, Adsorption Process 52, Solvent Extraction 53 Conversion Processes 54 Thermal Conversion Processes55, Catalytic Conversion Processes 60 Production of Olefins 91 Steam Cracking of Hydrocarbons 91, Production of Diolefins 101 References 107

CHAPTER FOUR Nonhydrocarbon Intermediates . . . . . . . . . . . . . . . . . . . . . . . . . 111
Introduction 111 Hydrogen 111 Sulfur 114 Uses of Sulfur 116, The Claus Process 116, Sulfuric Acid 117 Carbon Black 118 The Channel Process 119, The FurnaceBlack Process 119, The Thermal Process 119, Properties and Uses of Carbon Black 120 Synthesis Gas 121 Uses of Synthesis Gas 123 Naphthenic Acids 130 Uses of Naphthenic Acid and Its Salts 130 Cresylic Acid 131 Uses of Cresylic Acid 133 References 133

CHAPTER FIVE Chemicals Based on Methane . . . . . . . . . . . . . . . . . . . . . . . . . . 135
Introduction 135 Chemicals Based on DirectReactions of Methane 136 Carbon Disulfide 136, Hydrogen Cyanide 137, Chloromethanes 138

vi

Chemicals Based on Synthesis Gas 143 Ammonia 144, Methyl Alcohol 149, Oxo Aldehydes and Alcohols 163, Ethylene Glycol 166 References 167

CHAPTER SIX Ethane and Higher Paraffins-Based Chemicals . . . . . . . . . . . . . 169
Introduction 169 Ethane Chemicals 169 Propane Chemicals 171 Oxidation of Propane171, Chlorination of Propane, 172, Dehydrogenation of Propane 172, Nitration of Propane 173 n-Butane Chemicals 174 Oxidation of n-Butane 175, Aromatics Production 177, Isomerization of n-Butane 180 Isobutane Chemicals 180 Naphtha-Based Chemicals 181 Chemicals from High Molecular Weight n-Paraffins 182 Oxidation of Paraffins 183, Chlorination of n-Paraffins 184, Sulfonation of n-Paraffins 185,Fermentation Using n-Paraffins 185 References 186

CHAPTER SEVEN Chemicals Based on Ethylene . . . . . . . . . . . . . . . . . . . . . . . . . . 188
Introduction 188 Oxidation of Ethylene 189 Derivatives of Ethylene Oxide 192, Acetaldehyde 198, Oxidative Carbonylation of Ethylene 201 Chlorination of Ethylene 201 Vinyl Chloride 202, Perchloro- and Trichloroethylene 203 Hydration of Ethylene 204...