Guidelines for Inherently Safer Chemical Processes

Preface vii Acknowledgements ix Figures xxiii Tables xxvi 1. Introduction 1 1.1 Objectives, Intended Audience, and Scope of this Book 1 1.1.1 Objectives 1 1.1.2 Intended Audience 2 1.1.3 Scope 2 1.2 Integration of this Guidance with Other CCPS Guidance 2 1.3 Organization of this Book 3 1.4 History of Inherent Safety 4 1.5 References 9 2. The Concept of Inherent Safety 12 2.1 Inherent Safety and Process Risk Management 12 2.2 Inherent Safety Defined 15 2.3 Shared characteristics 16 2.4 Inherently Safer Strategies 18 2.5 Inherent safety throughout the process Life cycle 22 2.6 Inherently Safer Approaches 24 2.6.1 Orders of Inherent Safety 27 2.7 Layers of Protection 30 2.8 Integrating Inherent Safety in Process Risk Management Systems 32 2.9 Summary 40 2.10 References 40 3. Minimize - An Inherently Safer Strategy 44 3.1 Minimize 44 3.2 Reactors 47 3.3 Continuous Stirred Tank Reactors 48 3.4 Tubular Reactors 49 3.5 Loop Reactors 49 3.6 Reactive Distillation 51 3.7 Storage of Hazardous Materials 54 3.8 Process Piping 57 3.9 Process Equipment 58 3.10 Limitation of Effects 60 3.11 References 61 4. Substitute - An Inherently Safer Strategy 64 4.1 Reaction Chemistry 64 4.2 Green Chemistry 72 4.3 Solvents 73 4.4 Refrigerants 75 4.5 Firefighting Agents 76 4.6 Heat Transfer Media 76 4.7 Informed Substitution 77 4.8 References 83 5. Moderate - An Inherently Safer Strategy 87 5.1 Dilution 87 5.2 Refrigeration 88 5.3 Less Energetic Process Conditions 91 5.4 Secondary Containment - Dikes and Containment Buildings 94 5.5 Segregation 98 5.6 References 100 6. Simplify - An Inherently Safer Strategy 103 6.1 Leaving Things Out 104 6.2 Eliminating Unnecessary Spares 105 6.3 Inherently Robust Process Equipment 107 6.4 Preventing Runaway Reactions 110 6.5 Simplifying Heat Transfer 113 6.6 Simplifying Liquid Transfer 114 6.7 Reactor Geometry 116 6.8 Optimizing Catalyst Selectivity 116 6.9 Separation of Process Steps 116 6.10 Limitation of Available Energy 119 6.11 Simplification of the Human-Machine Interface 120 6.11.1 Overview 120 6.11.2 Equipment Layout, Accessibility, and Operability 121 6.11.3 Maintainability 121 6.11.4 Error Prevention 123 6.11.5 Design of Equipment and Controls - Making Status Clear 123 6.12 Summary 124 6.13 References 124 7. Applying Inherent Safety Strategies to Protection Layers 126 7.1 Operating Procedures 128 7.2 Maintenance Procedures 129 7.3 Relocation 129 7.4 Containment 130 7.5 More Robust Process Equipment and Design 131 7.6 Simplified Process Equipment and Design 132 7.7 Distributed Control Systems 133 7.8 Summary 134 7.9 References 134 8. Life Cycle Stages 136 8.1 General Principles Across All Life cycle Stages 136 8.2 Concept 137 8.3 Research 139 8.3.1 Inherently Safer Synthesis 141 8.3.2 Types of Hazards Associated with Research 142 8.3.3 Hazards Identification Methods 148 8.4 Design Development 159 8.4.1 Unit Operations - General 160 8.4.2 Unit Operations - Specific 161 8.5 Detailed Engineering Design 169 8.5.1 Process Design Basis 170 8.5.2 Equipment 171 8.5.3 Process Controls 175 8.5.4 Utility & Supporting Systems 179 8.5.5 Batch Processes 180 8.5.6 Other Design Considerations 182 8.6 Procurement, Construction, and Commissioning 183 8.7 Operations & Maintenance 185 8.7.1 Preservation of Inherent Safety 185 8.7.2 Inherent Safety - Continuous Improvement 187 8.8 Change Management 191 8.9 Decommissioning 192 8.10 Transportation 195 8.10.1 Location Relative to Raw Materials 197 8.10.2 Shipping Conditions 198 8.10.3 Transportation Mode and Route Selection 199 8.10.4 Improved Transportation Containers 200 8.10.5 Administrative Controls 201 8.10.6 Management of Transportation Containers On-site 202 8.11 References 203 9. Inherent Safety and Security 212 9.1 Introduction 212 9.2 Chemical Security Risk 213 9.3 Security Strategies 217 9.4 Countermeasures 219 9.5 Assessing Security Vulnerabilities 220 9.6 Inherent Safety and Chemical Security 221 9.7 Limitations to Implementing IS Concepts in Security Management 226 9.8 Conclusion 228 9.9 References 229 10. Implementing Inherently Safer Design 230 10.1 Introduction 230 10.2 Management System Approach for IS 231 10.3 Education and awareness 232 10.3.1 Making IS a Corporate Philosophy 232 10.3.2 IS in Education 233 10.4 Organizational culture 234 10.4.1 Multiple Demands of IS in the PSM program 235 10.4.2 Incorporating IS into Normal Design Process 236 10.5 Inherent Safety Reviews 241 10.5.1 Inherent Safety Review Objectives 242 10.5.2 Good Preparation is Required for Effective Inherent Safety Reviews 243 10.5.3 Inherent Safety Review Timing 244 10.5.4 Inherent Safety Review Team Composition 246 10.5.5 Inherent Safety Review Process Overview 246 10.5.6 Focus of Inherent Safety Reviews at Different Stages 250 10.5.7 Stage in the Process Life Cycle 252 10.6 Reactive Chemicals Screening 256 10.7 Inherent Safety Review Training 258 10.8 Documentation of the Inherently Safer Design Features of a Process 260 10.8.1 IS Review Documentation 261 10.8.2 Time Required for an Inherent Safety Review 263 10.9 Summary 264 10.10 References 265 11. Inherent Safety & the Elements of a RBPS Program 268 11.1 Process Safety Culture 270 11.2 Compliance with Standards 271 11.3 Workforce Involvement 272 11.4 Process Knowledge Management 272 11.5 Hazard Identification and Risk Analysis 273 11.6 Safe Work Practices 280 11.7 Asset Integrity and Reliability 282 11.8 Contractor Management 284 11.9 Training and Performance Assurance / Process Safety Competency 285 11.10 Management of Change / Operational Readiness 286 11.11 Conduct of Operations / Operating Procedures 290 11.11.1 Minimization 291 11.11.2 Simplification 294 11.12 Emergency Management 296 11.13 Incident Investigation 297 11.14 Measurements and Metrics / Auditing / Management Review and Continuous Improvement 297 11.15 Summary 299 11.16 References 299 12. Tools for IS Implementation 302 12.1 IS Review Methods - Overview 302 12.1.1 Three Approaches 302 12.1.2 Formal IS Reviews 303 12.1.3 IS Review Methods 304 12.1.4 Research & Development Application 304 12.1.5 PHA - Incorporation into HAZOP or other PHA Techniques 305 12.1.6 "What-If?" Method 307 12.1.7 Checklist Method 308 12.1.8 Consequence-Based Methods 311 12.1.9 Other Methods 312 12.2 Summary 317 12.3 References 318 13. Inherently Safer Design Conflicts 320 13.1 Introduction 320 13.2 Examples of inherent safety conflicts 324 13.2.1 Continuous vs. batch reactor 324 13.2.2 Reduced toxicity vs. reactive hazard 327 13.2.3 Reduced inventory vs. dynamic stability 328 13.2.4 Risk transfer vs. risk reduction 329 13.2.5 Inherent safety and security conflicts 331 13.3 Inherent safety - Environmental Hazards 332 13.3.1 PCBs 332 13.3.2 CFCs 332 13.4 Inherent Safety and Health Conflicts 333 13.4.1 Water Disinfection 333 13.5 Inherent safety and economic conflicts 334 13.5.1 Existing plants - operational vs. re-investment economics in a capital-intensive industry 334 13.5.2 Often more economical, but not necessarily 336 13.6 Tools for understanding and resolving conflicts 337 13.6.1 Tools for understanding and resolving conflicts 339 13.7 Measuring inherent safety characteristics 343 13.7.1 Dow Fire and Explosion Index 344 13.7.2 Dow Chemical Exposure Index 344 13.7.3 Mond Index 344 13.7.4 Proposed Inherent Safety indices 345 13.8 Summary 346 13.9 References 347 14. Inherent Safety Regulatory Initiatives 350 14.1 Inherent Safety Regulatory Developments and Issues 350 14.2 Experience with Inherent Safety Provisions in United States Regulations 351 14.2.1 Inherently Safer Regulatory Requirements - Contra Costa County, California, USA 352 14.2.2 New Jersey Toxic Catastrophe Prevention Act (TCPA) and Prescriptive Order for Chemical Plant Security 370 14.2.3 Inherently Safer Systems Requirements - California Accidental Release Prevention (CalARP) Regulations 378 14.2.4 Safer Technology & Alternatives Analysis - Revised US EPA Risk Management Program (RMP) Rule 380 14.3 Issues in Regulating Inherent Safety 382 14.3.1 Consistent Understanding of Inherent Safety 383 14.3.2 Needed Tools 384 14.4 Summary 385 14.5 References 386 15. Worked Examples and Case Studies 388 15.1 Introduction 388 15.2 Application of an Inherent Safety Strategic Approach to a Process 388 15.3 Case studies from carrithers 394 15.3.1 An Exothermic Batch Reaction 395 15.3.2 Refrigeration of Monomethylamine 398 15.3.3 Elimination of a Chlorine Water Treatment System 399 15.3.4 Reduction of Chlorine Transfer Line Size 400 15.3.5 Substitution of Aqueous Ammonia for Anhydrous Ammonia 400 15.3.6 Limitation of Magnitude of Deviations for Aqueous Ammonia 403 15.3.7 A Vessel Entry Example 408 15.4 Process Route Selection - Early R&D Example 411 15.5 Example of an Inherently Safer Study of a Steam Production Facility 412 15.5.1 Facility Description 412 15.5.2 Initial Design Proposal (Liquid Anhydrous Ammonia) 412 15.5.3 Aqueous Ammonia Design Proposal 413 15.5.4 Final Round of Option Selection 415 15.5.5 Consequence Analysis 416 15.5.6 Conclusion and Action 417 15.5.7 Conclusion 419 15.6 Case Study: Bhopal 419 15.6.1 Minimization 420 15.6.2 Substitution 420 15.6.3 Moderation 420 15.6.4 Simplification 421 15.7 Example: Inherently Safer Process for Production of Trialkyl Phosphate Esters 421 15.8 Summaries in brief: Examples by IS Strategy 422 15.8.1 Minimize 423 15.8.2 Substitute 425 15.8.3 Moderate 427 15.8.4 Simplify 429 15.9 Additional literature giving examples of inherently Safer Operations 430 15.10 References 431 16. Future Initiatives 433 16.1 Incorporating Inherently Safer Design into Process Safety Management 433 16.2 Encouraging Invention within the Chemical and Chemical Engineering Community 434 16.3 Including Inherent Safety into the Education of Chemists and Chemical Engineers 434 16.4 Developing Inherently Safer Design Databases and Libraries 434 16.5 Developing Tools to Apply Inherently Safer Design 435 16.5.1 The Broad View and Life Cycle Cost of Alternatives 435 16.5.2 Benefits of Reliability Analysis 436 16.5.3 Potential Energy 436 16.5.4 A Table of Distances and Consequence/Risk-Based Siting 437 16.5.5 Quantitative Measures of Inherent Safety 437 16.5.6 Other Suggestions 438 16.6 References 439 Appendix A. Inherently Safer Technology (IST) Checklist 442 A.1 IST Checklist Procedure 442 A.2 IST Checklist Questions 444 Appendix B. Inherent Safety Analysis Approaches 455 B.1 Inherent Safety Analysis - Guided Checklist Process Hazard Analysis (PHA) 459 B.2 Inherent Safety Analysis - Independent Process Hazard Analysis (PHA) 464 B.3 Inherent Safety Analysis - Integral to Process Hazard Analysis (PHA) 467 Glossary 469 Index 497

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