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Chemical Process Safety
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Table of Contents

Preface xv About the Authors xviiOn the Cover xviiiNomenclature xix
Chapter 1: Introduction 11-1 Safety Programs 21-2 Engineering Ethics 41-3 Accident and Loss Statistics 41-4 Acceptable Risk 121-5 Public Perceptions 141-6 The Nature of the Accident Process 151-7 Inherent Safety 201-8 Seven Significant Disasters 23Suggested Reading 31Problems 32 Chapter 2: Toxicology 372-1 How Toxicants Enter Biological Organisms 382-2 How Toxicants Are Eliminated from Biological Organisms 412-3 Effects of Toxicants on Biological Organisms 422-4 Toxicological Studies 432-5 Dose versus Response 442-6 Models for Dose and Response Curves 502-7 Relative Toxicity 562-8 Threshold Limit Values 562-9 National Fire Protection Association (NFPA) Diamond 58On-Line Resources 59Suggested Reading 60Problems 60 Chapter 3: Industrial Hygiene 653-1 Government Regulations 663-2 Industrial Hygiene: Anticipation and Identification 783-3 Industrial Hygiene: Evaluation 843-4 Industrial Hygiene: Control 99On-Line Resources 109Suggested Reading 109Problems 110 Chapter 4: Source Models 1194-1 Introduction to Source Models 1194-2 Flow of Liquid through a Hole 1224-3 Flow of Liquid through a Hole in a Tank 1264-4 Flow of Liquids through Pipes 1314-5 Flow of Gases or Vapors through Holes 1404-6 Flow of Gases or Vapors through Pipes 1464-7 Flashing Liquids 1634-8 Liquid Pool Evaporation or Boiling 1694-9 Realistic and Worst-Case Releases 1704-10 Conservative Analysis 172Suggested Reading 173Problems 174 Chapter 5: Toxic Release and Dispersion Models 1855-1 Parameters Affecting Dispersion 1865-2 Neutrally Buoyant Dispersion Models 1905-3 Dense Gas Dispersion 2095-4 Dense Gas Transition to Neutrally Buoyant Gas 2195-5 Toxic Effect Criteria 2255-6 Effect of Release Momentum and Buoyancy 2335-7 Release Mitigation 234Suggested Reading 235Problems 236 Chapter 6: Fires and Explosions 2456-1 The Fire Triangle 2456-2 Distinction between Fires and Explosions 2476-3 Definitions 2476-4 Flammability Characteristics of Liquids and Vapors 2496-5 Limiting Oxygen Concentration and Inerting 2606-6 Flammability Diagram 2626-7 Ignition Energy 2706-8 Autoignition 2706-9 Auto-Oxidation 2716-10 Adiabatic Compression 2726-11 Ignition Sources 2736-12 Sprays and Mists 2746-13 Explosions 275Suggested Reading 304Problems 305 Chapter 7: Concepts to Prevent Fires and Explosions 3177-1 Inerting 3187-2 Static Electricity 3337-3 Controlling Static Electricity 3567-4 Explosion-Proof Equipment and Instruments 3637-5 Ventilation 3677-6 Sprinkler Systems 3707-7 Miscellaneous Concepts for Preventing Fires and Explosions 374Suggested Reading 374Problems 375 Chapter 8: Chemical Reactivity 3818-1 Background Understanding 3828-2 Commitment,Awareness, and Identification of Reactive Chemical Hazards 3848-3 Characterization of Reactive Chemical Hazards Using Calorimeters 3908-4 Controlling Reactive Hazards 416Suggested Reading 418Problems 418 Chapter 9: Introduction to Reliefs 4299-1 Relief Concepts 4309-2 Definitions 4329-3 Location of Reliefs 4339-4 Relief Types and Characteristics 4369-5 Relief Scenarios 4439-6 Data for Sizing Reliefs 4449-7 Relief Systems 444Suggested Reading 452Problems 453 Chapter 10: Relief Sizing 45910-1 Conventional Spring-Operated Reliefs in Liquid Service 46010-2 Conventional Spring-Operated Reliefs in Vapor or Gas Service 46610-3 Rupture Disc Reliefs in Liquid Service 47010-4 Rupture Disc Reliefs in Vapor or Gas Service 47110-5 Two-Phase Flow during Runaway Reaction Relief 47210-6 Pilot-Operated and Bucking-Pin Reliefs 48110-7 Deflagration Venting for Dust and Vapor Explosions 48110-8 Venting for Fires External to Process Vessels 48810-9 Reliefs for Thermal Expansion of Process Fluids 492Suggested Reading 496Problems 497 Chapter 11: Hazards Identification 50511-1 Process Hazards Checklists 50811-2 Hazards Surveys 50811-3 Hazards and Operability Studies 52411-4 Safety Reviews 53011-5 Other Methods 537Suggested Reading 538Problems 538 Chapter 12: Risk Assessment 54912-1 Review of Probability Theory 55012-2 Event Trees 56412-3 Fault Trees 56912-4 QRA and LOPA 577Suggested Reading 588Problems 588 Chapter 13: Safety Procedures and Designs 59713-1 Process Safety Hierarchy 59813-2 Managing Safety 59913-3 Best Practices 60013-4 Procedures-Operating 60013-5 Procedures-Permits 60113-6 Procedures-Safety Reviews and Accident Investigations 60313-7 Designs for Process Safety 60413-8 Miscellaneous Designs for Fires and Explosions 61513-9 Designs for Runaway Reactions 61513-10 Designs for Handling Dusts 616Suggested Reading 617Problems 618 Chapter 14: Case Histories 62114-1 Static Electricity 62214-2 Chemical Reactivity 62614-3 System Designs 63114-4 Procedures 63714-5 Training 64214-6 Conclusion 645Suggested Reading 646Problems 646 Appendix A: Unit Conversion Constants 649 Appendix B: Flammability Data for Selected Hydrocarbons 653 Appendix C: Detailed Equations for Flammability Diagrams 659Equations Useful for Gas Mixtures 659Equations Useful for Placing Vessels into and out of Service 664 Appendix D: Formal Safety Review Report for Example 10-4 669 Appendix E: Saturation Vapor Pressure Data 679 Appendix F: Special Types of Reactive Chemicals 681 Appendix G: Hazardous Chemicals Data for a Variety of Chemical Substances 687 Index 695

Preface xv About the Authors xvii On the Cover xviii Nomenclature xix Chapter 1: Introduction 1 1-1 Safety Programs 2 1-2 Engineering Ethics 4 1-3 Accident and Loss Statistics 4 1-4 Acceptable Risk 12 1-5 Public Perceptions 14 1-6 The Nature of the Accident Process 15 1-7 Inherent Safety 20 1-8 Seven Significant Disasters 23 Suggested Reading 31 Problems 32 Chapter 2: Toxicology 37 2-1 How Toxicants Enter Biological Organisms 38 2-2 How Toxicants Are Eliminated from Biological Organisms 41 2-3 Effects of Toxicants on Biological Organisms 42 2-4 Toxicological Studies 43 2-5 Dose versus Response 44 2-6 Models for Dose and Response Curves 50 2-7 Relative Toxicity 56 2-8 Threshold Limit Values 56 2-9 National Fire Protection Association (NFPA) Diamond 58 On-Line Resources 59 Suggested Reading 60 Problems 60 Chapter 3: Industrial Hygiene 65 3-1 Government Regulations 66 3-2 Industrial Hygiene: Anticipation and Identification 78 3-3 Industrial Hygiene: Evaluation 84 3-4 Industrial Hygiene: Control 99 On-Line Resources 109 Suggested Reading 109 Problems 110 Chapter 4: Source Models 119 4-1 Introduction to Source Models 119 4-2 Flow of Liquid through a Hole 122 4-3 Flow of Liquid through a Hole in a Tank 126 4-4 Flow of Liquids through Pipes 131 4-5 Flow of Gases or Vapors through Holes 140 4-6 Flow of Gases or Vapors through Pipes 146 4-7 Flashing Liquids 163 4-8 Liquid Pool Evaporation or Boiling 169 4-9 Realistic and Worst-Case Releases 170 4-10 Conservative Analysis 172 Suggested Reading 173 Problems 174 Chapter 5: Toxic Release and Dispersion Models 185 5-1 Parameters Affecting Dispersion 186 5-2 Neutrally Buoyant Dispersion Models 190 5-3 Dense Gas Dispersion 209 5-4 Dense Gas Transition to Neutrally Buoyant Gas 219 5-5 Toxic Effect Criteria 225 5-6 Effect of Release Momentum and Buoyancy 233 5-7 Release Mitigation 234 Suggested Reading 235 Problems 236 Chapter 6: Fires and Explosions 245 6-1 The Fire Triangle 245 6-2 Distinction between Fires and Explosions 247 6-3 Definitions 247 6-4 Flammability Characteristics of Liquids and Vapors 249 6-5 Limiting Oxygen Concentration and Inerting 260 6-6 Flammability Diagram 262 6-7 Ignition Energy 270 6-8 Autoignition 270 6-9 Auto-Oxidation 271 6-10 Adiabatic Compression 272 6-11 Ignition Sources 273 6-12 Sprays and Mists 274 6-13 Explosions 275 Suggested Reading 304 Problems 305 Chapter 7: Concepts to Prevent Fires and Explosions 317 7-1 Inerting 318 7-2 Static Electricity 333 7-3 Controlling Static Electricity 356 7-4 Explosion-Proof Equipment and Instruments 363 7-5 Ventilation 367 7-6 Sprinkler Systems 370 7-7 Miscellaneous Concepts for Preventing Fires and Explosions 374 Suggested Reading 374 Problems 375 Chapter 8: Chemical Reactivity 381 8-1 Background Understanding 382 8-2 Commitment,Awareness, and Identification of Reactive Chemical Hazards 384 8-3 Characterization of Reactive Chemical Hazards Using Calorimeters 390 8-4 Controlling Reactive Hazards 416 Suggested Reading 418 Problems 418 Chapter 9: Introduction to Reliefs 429 9-1 Relief Concepts 430 9-2 Definitions 432 9-3 Location of Reliefs 433 9-4 Relief Types and Characteristics 436 9-5 Relief Scenarios 443 9-6 Data for Sizing Reliefs 444 9-7 Relief Systems 444 Suggested Reading 452 Problems 453 Chapter 10: Relief Sizing 459 10-1 Conventional Spring-Operated Reliefs in Liquid Service 460 10-2 Conventional Spring-Operated Reliefs in Vapor or Gas Service 466 10-3 Rupture Disc Reliefs in Liquid Service 470 10-4 Rupture Disc Reliefs in Vapor or Gas Service 471 10-5 Two-Phase Flow during Runaway Reaction Relief 472 10-6 Pilot-Operated and Bucking-Pin Reliefs 481 10-7 Deflagration Venting for Dust and Vapor Explosions 481 10-8 Venting for Fires External to Process Vessels 488 10-9 Reliefs for Thermal Expansion of Process Fluids 492 Suggested Reading 496 Problems 497 Chapter 11: Hazards Identification 505 11-1 Process Hazards Checklists 508 11-2 Hazards Surveys 508 11-3 Hazards and Operability Studies 524 11-4 Safety Reviews 530 11-5 Other Methods 537 Suggested Reading 538 Problems 538 Chapter 12: Risk Assessment 549 12-1 Review of Probability Theory 550 12-2 Event Trees 564 12-3 Fault Trees 569 12-4 QRA and LOPA 577 Suggested Reading 588 Problems 588 Chapter 13: Safety Procedures and Designs 597 13-1 Process Safety Hierarchy 598 13-2 Managing Safety 599 13-3 Best Practices 600 13-4 Procedures--Operating 600 13-5 Procedures--Permits 601 13-6 Procedures--Safety Reviews and Accident Investigations 603 13-7 Designs for Process Safety 604 13-8 Miscellaneous Designs for Fires and Explosions 615 13-9 Designs for Runaway Reactions 615 13-10 Designs for Handling Dusts 616 Suggested Reading 617 Problems 618 Chapter 14: Case Histories 621 14-1 Static Electricity 622 14-2 Chemical Reactivity 626 14-3 System Designs 631 14-4 Procedures 637 14-5 Training 642 14-6 Conclusion 645 Suggested Reading 646 Problems 646 Appendix A: Unit Conversion Constants 649 Appendix B: Flammability Data for Selected Hydrocarbons 653 Appendix C: Detailed Equations for Flammability Diagrams 659 Equations Useful for Gas Mixtures 659 Equations Useful for Placing Vessels into and out of Service 664 Appendix D: Formal Safety Review Report for Example 10-4 669 Appendix E: Saturation Vapor Pressure Data 679 Appendix F: Special Types of Reactive Chemicals 681 Appendix G: Hazardous Chemicals Data for a Variety of Chemical Substances 687 Index 695

About the Author

Daniel A. Crowl is Herbert H. Dow Professor for Chemical Process Safety at Michigan Tech. He serves on the AIChE Center for Chemical Process Safety (CCPS) Safety and Chemical Engineering Education (SACHE) Committee, and is author/editor of several AIChE books on process safety. His awards include AIChE's Bill Doyle Award; the ACS Chemical Health and Safety Award; the Walton/Miller award from AIChE's Safety and Health Division; and the AIChE Board's Gary Leach Award. He is a Fellow of AIChE, ACS Safety and Health Division , and CCPS.

Joseph F. Louvar is Research Professor at Wayne State University's College of Engineering, where he teaches chemical process safety, risk assessment, and process design. He was recently the CCPS staff consultant for the Undergraduate Education Committee, commonly known as the Safety and Chemical Engineering Education Committee (AIChE's SACHE) and has previously chaired this committee for over ten years. His books include Health and Environmental Risk Analysis: Fundamentals with Applications (Prentice Hall, 1997).

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