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 permission of 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 (∞). CChheemmiissttrryy ooff PETROCHEMICAL PROCESSES 2nd Edition This book is dedicated to the memory of Professor Lewis Hatch (1912–1991), a scholar, an educator, and a sincere friend. Frontmatter 1/22/01 10:54 AM Page iv v Contents Preface to Second Edition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi Preface to First Edition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii CHAPTER ONE Primary Raw 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 47 References 47 Frontmatter 1/22/01 10:54 AM Page 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 Processes 55, 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 Furnace Black 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 Direct Reactions of Methane 136 Carbon Disulfide 136, Hydrogen Cyanide 137, Chloromethanes 138 vi Frontmatter 1/22/01 10:54 AM Page 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 Propane 171, 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 Oligomerization of Ethylene 205 Alpha Olefins Production 206, Linear Alcohols 207, Butene-l 209 Alkylation Using Ethylene 210 References 211 vii Frontmatter 1/22/01 10:54 AM Page vii CHAPTER EIGHT Chemicals Based on Propylene . . . . . . . . . . . . . . . . . . . . . . . . . 213 Introduction 213 Oxidation of Propylene 214 Acrolein 215, Mechanism of Propene Oxidation 215, Acrylic Acid 217, Ammoxidation of Propylene 218, Propylene Oxide 221 Oxyacylation of Propylene 226 Chlorination of Propylene 226 Hydration of Propylene 227 Properties and Uses of Isopropanol 228 Addition of Organic Acids to Propene 232 Hydroformylation of Propylene: The Oxo Reaction 232 Disproportionation of Propylene (Metathesis) 234 Alkylation Using Propylene 235 References 236 CHAPTER NINE C 4 Olefins and Diolefins-Based Chemicals . . . . . . . . . . . . . . . . 238 Introduction 238 Chemicals from n-Butenes 238 Oxidation of Butenes 239, Oligomerization of Butenes 248 Chemicals from Isobutylene 249 Oxidation of Isobutylene 250, Epoxidation of Isobutylene 251, Addition of Alcohols to Isobutylene 252, Hydration of Isobutylene 253, Carbonylation of Isobutylene 255, Dimerization of Isobutylene 255 Chemicals from Butadiene 255 Adiponitrile 256, Hexamethylenediamine 257, Adipic Acid 257, Butanediol 258, Chloroprene 258, Cyclic Oligomers of Butadiene 259 References 260 CHAPTER TEN Chemicals Based on Benzene, Toluene, and Xylenes . . . . . . . . . 262 Introduction 262 Reactions and Chemicals of Benzene 262 viii Frontmatter 1/22/01 10:54 AM Page viii Alkylation of Benzene 263, Chlorination of Benzene 276, Nitration of Benzene 278, Oxidation of Benzene 280, Hydrogenation of Benzene 281 Reactions and Chemicals of Toluene 284 Dealkylation of Toluene 284, Disproportionation of Toluene 285, Oxidation of Toluene 286, Chlorination of Toluene 291, Nitration of Toluene 292, Carbonylation of Toluene 294 Chemicals from Xylenes 294 Terephthalic Acid 295, Phthalic Anhydride 296, Isophthalic Acid 297 References 299 CHAPTER ELEVEN Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301 Introduction 301 Monomers, Polymers, and Copolymers 302 Polymerization Reactions 303 Addition Polymerization 304, Condensation Polymerization 312, Ring Opening Polymerization 314 Polymerization Techniques 315 Physical Properties of Polymers 317 Crystallinity 317, Melting Point 317, Viscosity 317, Molecular Weight 318, Classification of Polymers 320 References 321 CHAPTER TWELVE Synthetic Petroleum-Based Polymers . . . . . . . . . . . . . . . . . . . . 323 Introduction 323 Thermoplastics 324 Polyethylene 324, Polypropylene 329, Polyvinyl Chloride 332, Polystyrene 334, Nylon Resins 336, Thermoplastic Polyesters 336, Polycarbonates 337, Polyether Sulfones 339, Poly(phenylene) Oxide 340, Polyacetals 341 Thermosetting Plastics 342 Polyurethanes 342, Epoxy Resins 344, Unsaturated Polyesters 346, Phenol-Formaldehyde Resins 346, Amino Resins 348 ix Frontmatter 1/22/01 10:54 AM Page ix Synthetic Rubber 350 Butadiene Polymers and Copolymers 352, Nitrile Rubber 353, Polyisoprene 354, Polychloroprene 356, Butyl Rubber 356, Ethylene Propylene Rubber 357, Thermoplastic Elastomers 358 Synthetic Fibers 359 Polyester Fibers 359, Polyamides 362, Acrylic and Modacrylic Fibers 368, Carbon Fibers 369, Polypropylene Fibers 370 References 371 Appendix One: Conversion Factors . . . . . . . . . . . . . . . . . . . . . . 374 Appendix Two: Selected Properties of Hydrogen, Important C 1 –C 10 Paraffins, Methylcyclopentane, and Cyclohexane . . . . 376 Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378 About the Authors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392 x Frontmatter 1/22/01 10:54 AM Page x Preface to Second Edition When the first edition of Chemistry of Petrochemical Processes was written, the intention was to introduce to the users a simplified approach to a diversified subject dealing with the chemistry and technology of var- ious petroleum and petrochemical process. It reviewed the mechanisms of many reactions as well as the operational parameters (temperature, pressure, residence times, etc.) that directly effect products’ yields and composition. To enable the readers to follow the flow of the reactants and products, the processes were illustrated with simplified flow diagrams. Although the basic concept and the arrangement of the chapters is this second edition are the same as the first, this new edition includes many minor additions and updates related to the advances in processing and catalysis. The petrochemical industry is a huge field that encompasses many commercial chemicals and polymers. As an example of the magnitude of the petrochemical market, the current global production of polyolefins alone is more than 80 billion tons per year and is expected to grow at a rate of 4–5% per year. Such growth necessitates much work be invested to improve processing technique and catalyst design and ensure good product qualities. This is primarily achieved by the search for new cata- lysts that are active and selective. The following are some of the impor- tant additions to the text: • Because ethylene and propylene are the major building blocks for petro- chemicals, alternative ways for their production have always been sought. The main route for producing ethylene and propylene is steam cracking, which is an energy extensive process. Fluid catalytic cracking (FCC) is also used to supplement the demand for these light olefins. A new process that produces a higher percentage of light olefins than FCC is deep catalytic cracking (DCC), and it is described in Chapter 3. xi Frontmatter 1/22/01 10:54 AM Page xi xii • The search for alternative ways to produce monomers and chemicals from sources other than oil, such as coal, has revived working using Fisher Tropseh technology, which produces in addition to fuels, light olefins, sulfur, phenols, etc. These could be used as feedstocks for petrochemicals as indicated in Chapter 4. • Catalysts for many petroleum and petrochemical processes represent a substantial fraction of capital and operation costs. Heterogeneous catalysts are more commonly used due to the ease of separating the products. Homogeneous catalysts, on the other hand, are normally more selective and operate under milder conditions than heteroge- neous types, but lack the simplicity and ease of product separation. This problem has successfully been solved for the oxo reaction by using rhodium modified with triphenylphosphine ligands that are water soluble. Thus, lyophilic products could be easily separated from the catalyst in the aqueous phase. A water soluble cobalt cluster can effectively hydroformylate higher olefins in a two-phase system using polyethylene glycol as the polar medium. This approach is described in Chapter 5. • In the polymer filed, new-generation metallocenes, which are cur- rently used in many polyethylene and polypropylene processes, can polymerize proplylene in two different modes: alternating blocks of rigid isotactic and flexible atactic. These new developments and other changes and approaches related to polymerization are noted in Chapters 11 and 12. I hope the new additions that I felt necessary for updating this book are satisfactory to the readers. Sami Matar, Ph.D. Frontmatter 1/22/01 10:54 AM Page xii Preface to First Edition Petrochemicals in general are compounds and polymers derived direct- ly or indirectly from petroleum and used in the chemical market. Among the major petrochemical products are plastics, synthetic fibers, synthetic rubber, detergents, and nitrogen fertilizers. Many other important chem- ical industries such as paints, adhesives, aerosols, insecticides, and phar- maceuticals may involve one or more petrochemical products within their manufacturing steps. The primary raw materials for the production of petrochemicals are natural gas and crude oil. However, other carbonaceous substances such as coal, oil shale, and tar sand can be processed (expensively) to produce these chemicals. The petrochemical industry is mainly based on three types of interme- diates, which are derived from the primary raw materials. These are the C 2 -C 4 olefins, the C 6 -C 8 aromatic hydrocarbons, and synthesis gas (an H 2 /CO 2 mixture). In general, crude oils and natural gases are composed of a mixture of relatively unreactive hydrocarbons with variable amounts of nonhydro- carbon compounds. This mixture is essentially free from olefins. However, the C 2 and heavier hydrocarbons from these two sources (nat- ural gas and crude oil) can be converted to light olefins suitable as start- ing materials for petrochemicals production. The C 6 -C 8 aromatic hydrocarbons—though present in crude oil—are generally so low in concentration that it is not technically or economical- ly feasible to separate them. However, an aromatic-rich mixture can be obtained from catalytic reforming and cracking processes, which can be further extracted to obtain the required aromatics for petrochemical use. Liquefied petroleum gases (C 3 -C 4 ) from natural gas and refinery gas streams can also be catalytically converted into a liquid hydrocarbon mixture rich in C6-C8 aromatics. xiii Frontmatter 1/22/01 10:54 AM Page xiii [...]... some of the important tests used to determine the properties of crude oils Density, Specific Gravity and API Gravity Density is defined as the mass of unit volume of a material at a specific temperature A more useful unit used by the petroleum industry is Chapter 1 1/22/01 20 10:55 AM Page 20 Chemistry of Petrochemical Processes specific gravity, which is the ratio of the weight of a given volume of. .. capable of converting mercaptans (RSH) to caustic insoluble disulfides (RSSR), is used for streams rich in mercaptans after removal of H2S Air is used to oxidize the mercaptans to disulfides The caustic solution is then recycled for regeneration The Merox process (Fig 1-3) is mainly used for treatment of refinery gas streams.5 Chapter 1 1/22/01 6 10:55 AM Page 6 Chemistry of Petrochemical Processes. .. examples of non-acidic sulfur compounds found in crude fractions Extensive research has been carried out to identify some sulfur compounds in a narrow light petroleum fraction.17 Examples of some sulfur compounds from the two types are: Acidic Sulfur Compounds Non-acidic Sulfur Compounds Chapter 1 1/22/01 16 10:55 AM Page 16 Chemistry of Petrochemical Processes Sour crudes contain a high percentage of hydrogen... 18 10:55 AM Page 18 Chemistry of Petrochemical Processes Non-acidic oxygen compounds such as esters, ketones, and amides are less abundant than acidic compounds They are of no commercial value The following shows some of the oxygen compounds commonly found in crude oils: Acidic Oxygen Compounds Non-Acidic Oxygen Compounds Chapter 1 1/22/01 10:55 AM Page 19 Primary Raw Materials for Petrochemicals 19... Physical Adsorption In these processes, a solid with a high surface area is used Molecular sieves (zeolites) are widely used and are capable of adsorbing large amounts of gases In practice, more than one adsorption bed is used for continuous operation One bed is in use while the other is being regenerated Chapter 1 1/22/01 4 10:55 AM Page 4 Chemistry of Petrochemical Processes Figure 1-1 The Selexol... wells) Associated gas, on the other hand, is present in contact with and/or dissolved in crude oil and is coproduced with it The principal component of most 1 Chapter 1 1/22/01 2 10:55 AM Page 2 Chemistry of Petrochemical Processes Table 1-1 Composition of non-associated and associated natural gases1 Non-associated gas Associated gas Component Salt Lake US Kliffside US Abqaiq Saudi Arabia North Sea... of hydrocarbon intermediates and petroleum fractions obtained from natural gas and crude oils Crude oil processing is mainly aimed towards the production of fuels, so only a small fraction of the products is used for the synthesis of olefins and aromatics In Chapter 3, the different crude oil processes are reviewed with special emphasis on those conversion techniques employed for the dual purpose of. .. Molecular sieves are competitive only when the quantities of hydrogen sulfide and carbon disulfide are low Molecular sieves are also capable of adsorbing water in addition to the acid gases Chemical Absorption (Chemisorption) These processes are characterized by a high capability of absorbing large amounts of acid gases They use a solution of a relatively weak base, such as monoethanolamine The acid... 75% of carbonyl sulfides (COS), while the mono- reacts irreversibly with 95% of the COS and forms a degradation product that must be disposed of Diglycolamine (DGA), is another amine solvent used in the Econamine process (Fig 1-2).4 Absorption of acid gases occurs in an absorber containing an aqueous solution of DGA, and the heated rich Chapter 1 1/22/01 10:55 AM Page 5 Primary Raw Materials for Petrochemicals... steam cracking processes geared specially for producing olefins and diolefins In addition to being major sources of hydrocarbon-based petrochemicals, crude oils and natural gases are precursors of a special group of compounds or mixtures that are classified as nonhydrocarbon intermediates Among these are the synthesis gas mixture, hydrogen, sulfur, and carbon black These materials are of great economic . 77252-2608 Library of Congress Cataloging-in-Publication Data Printed on acid-free paper (∞). CChheemmiissttrryy ooff PETROCHEMICAL PROCESSES 2nd Edition This book is dedicated to the memory of Professor. viii Alkylation of Benzene 263, Chlorination of Benzene 276, Nitration of Benzene 278, Oxidation of Benzene 280, Hydrogenation of Benzene 281 Reactions and Chemicals of Toluene 284 Dealkylation of Toluene. . . . 392 x Frontmatter 1/22/01 10:54 AM Page x Preface to Second Edition When the first edition of Chemistry of Petrochemical Processes was written, the intention was to introduce to the users