INHERENTLY SAFER CHEMICAL PROCESSESA LIFE CYCLE APPROACH

GUIDELINES FOR

3THIRD

EDITION

Guidelines for Inherently Safer Chemical Processes: A Life Cycle Approach

3rd Edition

Guidelines for Inherently Safer Chemical Processes: A Life Cycle Approach

3rd Edition

This edition first published 2020© 2020 the American Institute of Chemical Engineers

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Hardback ISBN: 9781119529163

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It is sincerely hoped that the information presented in this document will lead to an even more impressive safety record for the entire industry; however, neither the American Institute of Chemical Engineers, its consultants, CCPS Technical Steering Committee and Subcommittee members, their employers, their employers' officers and directors, nor AcuTech Group, Inc. and its employees and subcontractors warrant or represent, expressly or by implication, the correctness or accuracy of the content of the information presented in this document. As between (1) American Institute of Chemical Engineers, its consultants, CCPS Technical Steering Committee and Subcommittee members, their employers, their employers' officers and directors, and AcuTech Group, Inc. and its employees and subcontractors, and (2) the user of this document, the user accepts any legal liability or responsibility whatsoever for the consequence of its use or misuse.

Preface The American Institute of Chemical Engineers (AIChE) has been involved with process safety and loss prevention issues in the chemical, petrochemical, hydrocarbon process and related industries and facilities for more than 50 years. AIChE publications and symposia are information resources for chemical engineers and other professionals on the causes of process incidents and the means of preventing their occurrences and mitigating their consequences.

In 1985, the Center for Chemical Process Safety (CCPS), a Technology Alliance of the AIChE, was established specifically to develop and disseminate technical information for use in the prevention of major chemical process incidents. With the support and direction of the CCPS Advisory and Managing Boards, a multifaceted program was initiated to address the need for Process Safety and Risk Management systems capable of reducing potential exposures to the public, the environment, personnel, and facilities. This program includes:

developing and publishing Guidelines and Concept Books relating to specific areas of Process Safety and Risk Management publishing a monthly newsletter, Process Safety Beacon organizing, convening and conducting seminars, symposia, training programs, and meetings on process safety-related matters cooperation with other organizations, both internationally and domestically, to promote process safety.

CCPS activities are supported by more than 200 corporations that provide funding and professional expertise. Several government agencies and academic institutions also participate in CCPS endeavors.

In 1989, CCPS published Guidelines for Technical Management of Chemical Process Safety, which presented a model for process safety management characterized by twelve distinct, essential and interrelated elements. These Guidelines were refined over the ensuing years and updated in the Guidelines for Risk Based Process Safety (2007), which

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expanded the definition of process safety and risk management into twenty distinct elements.

The previous editions of this book, which were part of the “Concept Series,” supported many of those twenty key elements of process safety, as identified in the Guidelines for Risk Based Process Safety, including process safety competency, workforce involvement, hazard identification and risk analysis, auditing, and management review and continuous improvement. The purpose of this guideline series book is to update the previous 2nd edition concept book in order to demonstrate the on-going and improved application of inherently safer strategies throughout all the stages of the chemical process life cycle, including additional case studies and examples of inherently safer design (ISD) implementation.

Inherently safer (IS) concepts continue to be well-received by industry and there has been significant advancement in the concept since the original version of this book was published in 1996. Both the original 1996 concept book and the 2009 update are frequently cited as authoritative sources on inherent safety, and, as such, it is important that an updated edition be published. The Third Edition will reflect not only the most current knowledge on the subject but will harness the concepts introduced in the first two editions, provide additional examples of IS and provide a guideline for the practical application of inherent safety techniques.

This book encourages engineers, process safety experts, and others involved in analyzing and reducing the risks from chemical processes to make conservative choices that apply the principles and spirit of inherent safety to the extent feasible. The discussion and examples range from the basic process chemistry through the details of the design of hardware and procedures. Inherently safer thinking can be applied at all levels of the process design, from the overall concept through the detailed equipment design and procedure development.

Acknowledgements The American Institute of Chemical Engineers (AIChE) and its Center for Chemical Process Safety (CCPS) thank the subcommittee members and their CCPS member companies for their generous efforts and technical contributions to this book. CCPS also thanks the members of the CCPS Technical Steering Committee for their advice and support.

Guidelines for Inherently Safer Chemical Processes A Life Cycle Approach, 3rd edition

The Chair of the subcommittee was John Wincek, originally of Croda, Inc. and currently of Dekra. The CCPS staff consultant was Dan Sliva.

The Subcommittee members were:

Steve Arendt ABS Group Susan Bayley Linde Process Plants, Inc. Prashanti Bhupathi Reliance Wayne Chastain Eastman Oliva Cheng Chevron Corporation Robert Coover Praxair Carolina Del Din PSRG Jonas Duarte Lanxess Emmanuelle Hagey Nova chemicals Scott Haney Marathon Petroleum Company Dennis Hendershot CCPS Reyyan Koc Karabocek ExxonMobil Nicole Loontjens Americas Styrenics Dan Miller CCPS Emeritus Jitesh Patel New Jersey DEP Katherine P er m Arkema Sabrina Petruele Pluspetrol Morgan Reed MMI Engineering Sonny Sachdeva PSRG Randy Sawyer Contra Costa Health Services Dallas L. Singleton Jacobs Scott Wallace Olin Bob Weber PSRG

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This manuscript was written by AcuTech Group team of Rich Santo, Dave Moore, Cara Hamel, Mike Hazzan, Dave Heller, Marty Rose. It was copy edited by Megan Fennell under the direction of Anil Gokhale of CCPS.

Peer Reviewers

Before publication, all CCPS books receive a thorough peer review. CCPS gratefully acknowledges the thoughtful comments and suggestions of the following peer reviewers. Their work enhanced the accuracy and clarity of these guidelines.

Denise Chastain-Knight Exida Alan Evankovich AVAN Engineering Graffar Keshavarz NovaChem Beverly Perozzo NovaChem Gill Sigmon Advansix Ken Tague ADM Rob Savarese EmeraldMaterials

Contents 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

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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

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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 Clear123

6.12 Summary 124

6.13 References 124

7. Applying Inherent Safety Strategies to Protection Layers 126

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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

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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

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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

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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

1 .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

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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

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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

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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

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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 Siting437

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

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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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Figures Figure 2.1: Hierarchy of Controls

Figure 2.2: Application of Inherent Safety Throughout the Process Life Cycle

Figure 2.3: Inherent Safety Considerations in Hierarchy of Controls

Figure 2.4: Layers of Protection

Figure 3.1: A Loop Reactor Production System

Figure 3.2: Conventional process for methyl acetate

Figure 3.3: Reactive distillation methyl acetate process

Figure 4.1: Framework for Assessing Safer Chemical Alternatives

Figure 5.1: A refrigerated chlorine storage system with collection sump with vapor containment

Figure 5.2: A liquefied gas storage facility

Figure 5.3: A diking design for a flammable liquid

Figure 5.4: A chemical process totally contained in a large pressure vessel

Figure 6.1: A traditional methyl acetate process using separate reaction and distillation steps

Figure 6.2: The Eastman Chemical reactive distillation process for methyl acetate

Figure 6.3: Old (a) and new (b) designs for a two-batch reaction system

Figure 6.4: Fluidic pump system

Figure 6.5: A complex batch reactor for a multistep process

Figure 6.6: The same process as Figure 6.5 in a series of simpler reactors

Figure 8.1: Stages in the Life Cycle of a Chemical Process

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Figure 8.2: Process Design Safe Operating Limits

Figure 8.3: Proper and improper piping design

Figure 8.4: Operating Ranges and Limits

Figure 8.5: An example of poor assignment of equipment identification numbers

Figure 8.6: An illogical arrangement of burner controls for a kitchen stove

Figure 9.1: Security Layers of Protection or Defense in Depth

Figure 9.2: Elements in a CCPS Security Vulnerability Assessment

Figure 10.1: Management leadership is the foundation for process safety management

Figure 10.2: Inherent Safety Review Preparation

Figure 10.3: Inherent Safety Review Process

Figure 10.4: Applicability of inherently safer design at various stages of process and plant development.

Figure 11.1: Plug Valve Operator

Figure 11.2: Valve Gearbox Designs

Figure 11.3: Inherent Safety-Based Management of Change Process

Figure 11.4: Inherent Safety-Based Incident Investigation Methodology

Figure 12.1: Example of Potential Design Solutions for Reactor Failure

Figure 13.1 and 13.2: Examples of batch (top) and continuous (bottom) process

Figure 13.4: Process safety system design solutions for a heat exchanger failure scenario

Figure 14.1: Major Chemical Accidents and Releases (MCAR)

Figure 14.2: ISO Stationary Sources MCARs

Figure 14.3: County and Richmond ISO MCARs

Figure 15.1: Initial Process

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Figure 15.2: Modified process

Figure 15.3: Original batch reaction system

Figure 15.4: Modified, inherently safer batch reactor system

Figure 15.5: Comparison of centerline vapor cloud concentration

Figure 15.6: Aqueous Ammonia: Limitations of Magnitude of Deviations

Figure 15.7: Nitrogen supply line routed over the vessel manway

Figures 15.8a and 15.8b: Two examples of nitrogen supply lines piped to vessels across the manway

Figure 15.9: Initial ammonia supply proposal: Liquid anhydrous ammonia supply

Figure 15.10: Aqueous Ammonia Supply Proposal

Figure 15.11: Anhydrous ammonia vapor option

Figure 15.12: Alternative route for carbaryl production

Figure 15.13: Dow LaPorte Phosgene Inventory Reduction

Figure 15.14: Use of Chlorine Vapor for Liquid Chlorine

Figure 15.15: Streamlined METEORTM Ethylene Oxide Recovery System

Figure 15.16: Dike and Secondary Containment System

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Tables Table 2.1: Strategies for Inherently Safer Design

Table 2.2: Examples of Process Risk Management Categories

Table 3.1: Effect of Reactor Design on Size and Productivity for a Gas-Liquid Reaction

Table 6.1: Summary of Reaction Testing Methods

Table 8.1: Types of Process Safety Hazards

Table 8.2: Representative Potentially Hazardous Molecular Groupings

Table 8.3: An Example Chemical Reactivity Matrix

Table 8.4: Reactive Combinations of Chemicals

Table 8.5: INSET Toolkit Stages

Table 8.6: Surface Compactness of Heat Exchangers

Table 10.1: Inherent Safety Review Team Composition

Table 10.2: Focus of Different Inherent Safety Reviews

Table 11.1: Inherent Safety Checklist for PHAs

Table 11.2 MOC IS Checklist

Table 12.1: Guideword Matrix

Table 12.2: Inherent Safety Guidewords

Table 12.3: Examples of Potential Accident Consequence Analysis as a Measure of Inherent Safety

Table 12.4: Summary of INSET Tools

Table 13.1: Comparison of ISD attributes of air travel and automobile travel

Table 13.2: Some inherent safety advantages and disadvantages of alternative process solvents

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Table 13.3: Process Safety System Design Solutions for a Heat Exchanger Failure Scenario

Table 13.4: An example of a Weighted Scoring Decision Matrix

Table 14.1: Summary of Contra Costa County IST Measures Implemented from 2002 - Present

Table 14.2: Summary of IST Measures Implemented or Scheduled by Sector

Table 15.1: Effect of Refrigeration on Distance to ERPG-3 Concentration for a 2-inch (5.1 cm) Monomethylamine Pipe Rupture

Table 15.2: Effect of Reduction of Line Size on Hazard Zone from Potential Failure of a Chlorine Transfer Line

Table 15.3: Total vapor pressure of aqueous ammonia

Table 15.4: Mass Comparison for Ammonia Transfer Options

Table A.1: IST Checklist Substitute Questions

Table A.2: IST Checklist Minimize Questions

Table A.3: IST Checklist Moderate Questions

Table A.4: IST Checklist Simplify Questions

Table A.5: IST Checklist Location/Siting/Transportation Questions

Table B.1: Generic Risk Matrix (R)

Table B.2: Generic Severity (S) Rankings

Table B.3: Generic Likelihood (L) Descriptors

Table B.4: Case summary: Inherent Safety Analysis--Checklist Process Hazard Analysis (PHA)

Table B.5: Inherent Safety Analysis--Independent Process Hazard Analysis (PHA)

Table B.6: Inherent Safety Analysis--Integral Process Hazard Analysis (PHA)