Daniel A. Crowl/Joseph F.

Lowar

C'-

A m aam -

11-111-1-1

Process

I 5econd

Edition

Prentice Hl International Series al in the Physical and Chemlcal Engineering Sciences

I

Chemical Process Safety

ISBN 0-13-OZ817b-5

9 780130 1 8 1 7 6 3

PRENTICE HALL INTERNATIONAL SERIES IN THE PHYSICAL AND CHEMICAL ENGINEERING SCIENCES NEALR. AMUNDSON, SERIES EDITOR, University of Houston

ANDREAS ACRIVOS, Stanford University JOHN DAHLER, Universityof Minnesota H. SCOTT FOGLER, University of Michigan THOMAS HANRATTY, J. University of Illinois JOHN . PRAUSNITZ, M University of California L. E. SCRIVEN, University of Minnesota

BALZHISER, SAMUELS, ELIASSEN Chemical Engineering Thermodynamics AND BEQUETTE Process Control: Modeling, Design and Simulation BEQUETTE Process Dynamics BIEGLER, GROSSMAN, WESTERBERGSystematic Methods of Chemical Process AND Design BROSILOW JOSEPH Techniques of Model-Based Control AND CROWL AND LOUVAR Chemical Process Safety: Fundamentals with Applications, 2nd edition CONSTANTINIDES MOSTOUFI Numerical Methods for Chemical Engineers AND with MATLAB Applications CUTLIP AND SHACHAM Problem Solving in Chemical Engineering with Numerical Methods DENN Process Fluid Mechanics DOYLE Process Control Modules: A Software Laboratory for Control Design ELLIOT AND LIRA Introductory Chemical Engineering Thermodynamics FOGLER Elements of Chemical Reaction Engineering, 3rd edition Basic Principles and Calculations in Chemical Engineering, 6th edition HIMMELBLAU HINESAND MADDOX Mass Transfer KYLE Chemical and Process Thermodynamics, 3rd edition PRAUSNITZ, LICHTENTHALER, DE AZEVEDO Molecular Thermodynamics AND of Fluid-Phase Equilibria, 3rd edition PRENTICE Electrochemical Engineering Principles SHULER AND KARGI Bioprocess Engineering, 2nd edition STEPHANOPOULOS Chemical Process Control TESTER AND MODELL Thennodynainics and Its Applications, 3rd edition TURTON, BAILIE,WHITING, AND SHAEIWITZAnalysis, Synthesis and Design of Chemical Processes WILKES Fluid Mechanics for Chemical Engineering

Prentice Hall International Series in the Physical and Chemical Engineering Sciences

Chemical Process Safety
Fundamentals with Applications
Second Edition

Daniel A. Crow1
Michigan Technological University

Joseph F. Louvar
Wayne State University

Prentice Hall PTR Upper Saddle River, New Jersey 07458 www.phptr.com

Library of Congress Cataloging-in-Publication data Crowl, Daniel A. Chemical process safety : fundamentals with applications I Daniel A. Crowl, Joseph F. Louvar. - 2nd ed. p. cm. - (Prentice Hall international series in the physical and chemical engineering sciences) Includes bibliographical references and index. ISBN 0-13-018176-5 1. Chemical plants -Safety measures. I. Louvar, Joseph F. 11. Title. 111. Series.

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O 2002 by Prentice Hall PTR Prentice Hall, Inc. Upper Saddle River, NJ 07458
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Contents

Preface xiii Nomenclature xv

1

Introduction 1
Safety Programs 2 Engineering Ethics 4 Accident and Loss Statistics 4 Acceptable Risk 12 Public Perceptions 14 The Nature of the Accident Process Inherent Safety 20 Four Significant Disasters 23 Flixborough, England 23 Bhopal, India 25 Seveso, Italy 26 Pasadena, Texas 27 Suggested Reading 29 Problems 30

15

2

Toxicology 35
2-1 How Toxicants Enter Biological Organisms 36 Gastrointestinal Tract 37 Skin 37 Respiratory System 38 How Toxicants Are Eliminated from Biological Organisms 39 Effects of Toxicants on Biological Organisms 40 Toxicological Studies 41 Dose versus Response 42

2-2 2-3 2-4 2-5

vi

Contents

2-6 2-7 2-8

Models for Dose and Response Curves 48 Relative Toxicity 54 Threshold Limit Values 54 Suggested Reading 59 Problems 59

3

Industrial Hygiene 63
3-1 Government Regulations 64 Laws and Regulations 64 Creating a Law 64 Creating a Regulation 64 OSHA: Process Safety Management 68 EPA: Risk Management Plan 71 Industrial Hygiene: Identification 74 Material Safety Data Sheets 74 Industrial Hygiene: Evaluation 78 Evaluating Exposures to Volatile Toxicants by Monitoring 79 Evaluation of Worker Exposures to Dusts 83 Evaluating Worker Exposures to Noise 84 Estimating Worker Exposures to Toxic Vapors 85 Industrial Hygiene: Control 94 Respirators 96 Ventilation 97 Suggested Reading 103 Problems 104

3-2 3-3

3-4

Source Models 109
4-1 4-2 4-3 4-4 Introduction to Source Models 109 Flow of Liquid through a Hole 112 Flow of Liquid through a Hole in a Tank 116 Flow of Liquids through Pipes 121 2-K Method 124 4-5 Flow of Vapor through Holes 130 4-6 Flow of Gases through Pipes 136 Adiabatic Flows 136 Isothermal Flows 143 4-7 Flashing Liquids 151 4-8 Liquid Pool Evaporation or Boiling 157 4-9 Realistic and Worst-Case Releases 159 4-10 Conservative Analysis 159 Suggested Reading 161 Problems 162

Contents

vii

5

Toxic Release and Dispersion Models 171
5-1 Parameters Affecting Dispersion 172 5-2 Neutrally Buoyant Dispersion Models 176 Case 1:Steady-State Continuous Point Release with No Wind 180 Case 2: Puff with No Wind 181 Case 3: Non-Steady-State Continuous Point Release with No Wind 182 Case 4: Steady-State Continuous Point Source Release with Wind 183 Case 5: Puff with No Wind and Eddy Diffusivity Is a Function of Direction 183 Case 6: Steady-State Continuous Point Source Release with Wind and Eddy Diffusivity Is a Function of Direction 184 Case 7: Puff with Wind 184 Case 8: Puff with No Wind and with Source on Ground 185 Case 9: Steady-State Plume with Source on Ground 185 Case 10: Continuous Steady-State Source with Source at Height Hr above the Ground 186 Pasquill-Gifford Model 186 Case 11: Puff with Instantaneous Point Source at Ground Level, Coordinates Fixed at Release Point, Constant Wind Only in x Direction with Constant Velocity u 190 Case 12: Plume with Continuous Steady-State Source at Ground Level and Wind Moving in x Direction at Constant Velocity u 191 Case 13: Plume with Continuous Steady-State Source at Height Hr above Ground Level and Wind Moving in x Direction at Constant Velocity u 192 Case 14: Puff with Instantaneous Point Source at Height Hr above Ground Level and a Coordinate System on the Ground That Moves with the Puff 193 Case 15: Puff with Instantaneous Point Source at Height Hr above Ground Level and a Coordinate System Fixed on the Ground at the Release Point 194 Worst-Case Conditions 194 Limitations to Pasquill-Gifford Dispersion Modeling 194 5-3 Dense Gas Dispersion 195 5-4 Toxic Effect Criteria 199 5-5 Effect of Release Momentum and Buoyancy 212 5-6 Release Mitigation 213 Suggested Reading 214 Problems 215

6

Fires and Explosions 225
6-1 6-2 The Fire Triangle 225 Distinction between Fires and Explosions 227

-

-

-

-

-

viii

Contents

6-3 6-4

6-5 6-6 6-7 6-8 6-9 6-10 6-11 6-12 6-13

Definitions 227 Flammability Characteristics of Liquids and Vapors 229 Liquids 230 Gases and Vapors 233 Vapor Mixtures 233 Flammability Limit Dependence on Temperature 235 Flammability Limit Dependence on Pressure 236 Estimating Flammability Limits 236 Limiting Oxygen Concentration and Inerting 238 Flammability Diagram 240 Ignition Energy 248 Autoignition 249 Auto-Oxidation 249 Adiabatic Compression 249 Ignition Sources 251 Sprays and Mists 252 Explosions 252 Detonation and Deflagration 253 Confined Explosions 255 Blast Damage Resulting from Overpressure 265 TNT Equivalency 269 TNO Multi-Energy Method 271 Energy of Chemical Explosions 274 Energy of Mechanical Explosions 276 Missile Damage 279 Blast Damage to People 279 Vapor Cloud Explosions 281 Boiling-Liquid Expanding-Vapor Explosions 282 Suggested Reading 282 Problems 283

7

Designs to Prevent Fires and Explosions 291
7-1 Inerting 292 Vacuum Purging 292 Pressure Purging 295 Combined Pressure-Vacuum Purging 297 Vacuum and Pressure Purging with Impure Nitrogen 298 Advantages and Disadvantages of the Various Pressure and Vacuum Tnerting Procedures 299 Sweep-Through Purging 299 Siphon Purging 301 Using the Flammability Diagram To Avoid Flammable Atmospheres 301 Static Electricity 307 Fundamentals of Static Charge 307

7-2

--

Contents

ix

7-3

7-4

7-5

7-6 7-7

Charge Accumulation 308 Electrostatic Discharges 309 Energy from Electrostatic Discharges 311 Energy of Electrostatic Ignition Sources 312 Streaming Current 313 Electrostatic Voltage Drops 316 Energy of Charged Capacitors 316 Capacitance of a Body 321 Balance of Charges 324 Controlling Static Electricity 330 General Design Methods To Prevent Electrostatic Ignitions 333 Relaxation 332 Bonding and Grounding 332 Dip Pipes 333 Increasing Conductivity with Additives 336 Handling Solids without Flammable Vapors 337 Handling Solids with Flammable Vapors 337 Explosion-Proof Equipment and Instruments 337 Explosion-Proof Housings 339 Area and Material Classification 339 Design of an XP Area 340 Ventilation 340 Open-Air Plants 340 Plants Inside Buildings 341 Sprinkler Systems 343 Miscellaneous Designs for Preventing Fires and Explosions 347 Suggested Reading 347 Problems 348

8

Introduction to Reliefs 353
8-1 Relief Concepts 354 8-2 Definitions 356 8-3 Location of Reliefs 357 8-4 Relief Types 360 8-5 Relief Scenarios 364 8-6 Data for Sizing Reliefs 365 8-7 Relief Systems 368 Relief Installation Practices 368 Relief Design Considerations 368 Horizontal Knockout Drum 371 Flares 375 Scrubbers 376 Condensers 376 Suggested Reading 376 Problems 377

x

Contents

9

Relief Sizing 383
9-1 9-2 9-3 9-4 9-5 9-6 Conventional Spring-Operated Reliefs in Liquid Service 384 Conventional Spring-Operated Reliefs in Vapor or Gas Service 389 Rupture Disc Reliefs in Liquid Service 394 Rupture Disc Reliefs in Vapor or Gas Service 394 Two-Phase Flow during Runaway Reaction Relief 395 Simplified Nomograph Method 401 Deflagration Venting for Dust and Vapor Explosions 404 Vents for Low-Pressure Structures 406 Vents for High-Pressure Structures 408 Venting for Fires External to Process Vessels 411 Reliefs for Thermal Expansion of Process Fluids 415 Suggested Reading 418 Problems 420

9-7 9-8

10

Hazards Identification 429
10-1 10-2 10-3 10-4 10-5 Process Hazards Checklists 432 Hazards Surveys 432 Hazards and Operability Studies 448 Safety Reviews 454 Other Methods 459 Suggested Reading 460 Problems 460

11

Risk Assessment 471
11-1 Review of Probability Theory 472 Interactions between Process Units 474 Revealed and Unrevealed Failures 480 Probability of Coincidence 484 Redundancy 486 Common Mode Failures 486 11-2 Event Trees 486 11-3 Fault Trees 491 Determining the Minimal Cut Sets 494 Quantitative Calculations Using the Fault Tree 497 Advantages and Disadvantages of Fault Trees 498 Relationship between Fault Trees and Event Trees 498 11-4 QRA and LOPA 499 Quantitative Risk Analysis 499 Layer of Protection Analysis 500 Consequence 503 Frequency 503 Suggested Reading 507 Problems 508

Contents

xi

Accident Investigations 515
Learning from Accidents 515 Layered Investigations 516 Investigation Process 518 Investigation Summary 519 Aids for Diagnosis 521 Fires 522 Explosions 522 Sources of Ignition in Vessels 523 Pressure Effects 523 Medical Evidence 525 Miscellaneous Aids to Diagnosis 525 12-6 Aids for Recommendations 528 Control Plant Modifications 528 User-Friendly Designs 529 Block Valves 529 Double Block and Bleed 530 Preventive Maintenance 530 Analyzers 531 Suggested Reading 532 Problems 532 12-1 12-2 12-3 12-4 12-5

13

Case Histories 535
13-1 Static Electricity 536 Tank Car Loading Explosion 536 Explosion in a Centrifuge 536 Duct System Explosion 537 Conductor in a Solids Storage Bin 537 Pigment and Filter 536 Pipefitter's Helper 536 Lessons Learned 536 13-2 Chemical Reactivity 540 Bottle of Isopropyl Ether 540 Nitrobenzene Sulfonic Acid Decomposition 540 Organic Oxidation 541 Lessons Learned 541 13-3 System Designs 546 Ethylene Oxide Explosion 546 Ethylene Explosion 546 Butadiene Explosion 546 Light Hydrocarbon Explosion 547 Pump Vibration 547 Pump Failure 547 Ethylene Explosion (1) 548

xii

Contents

Ethylene Explosion (2) 548 Ethylene Oxide Explosion 548 Lessons Learned 549 13-4 Procedures 551 Leak Testing a Vessel 552 Man Working in Vessel 552 Vinyl Chloride Explosion 552 Dangerous Water Expansion 553 Phenol-Formaldehyde Runaway Reaction 553 Conditions and Secondary Reaction Cause Explosion 554 Fuel-Blending Tank Explosion 555 Lessons Learned 556 13-5 Conclusion 556 Suggested Reading 557 Problems 557

Appendix A: Unit Conversion Constants 561 Appendix B: Flammability Data for Selected Hydrocarbons 565 Appendix C: Detailed Equations for Flammability Diagrams 571
Equations Useful for Placing Vessels into and out of Service 576

Appendix D: Formal Safety Review Report for Example 10-4 581 Appendix E: Saturation Vapor Pressure Data 591

The T . explosion venting. source modeling. fundamentals of electrostatics. It is appropriate for an industrial reference. or a graduate course in chemical process safety. A complete set of problem solutions is available to instructors using the book in their curriculum. and case histories. providing instructors with the opportunity to emphasize their topics of interest. including chemical and mechanical engineers and chemists.Preface his second edition of Chemical Process Safety is designed to enhance the process of teaching and applying the fundamentals of chemical process safety. This application requires a significant quantity of fundamental knowledge and technology. The primary objective of this textbook is to encapsulate the important technical fundamentals of chemical process safety. This new edition also includes selected materials from the latest AICHE Center for Chemical Process Safety (CCPS) books and is now an excellent introduction to the CCPS library. It can be used by anyone interested in improving chemical process safety. This second edition also includes more problems (now 30 per chapter). a senior-level undergraduate course. More material is presented than can be accommodated in a 3-credit course. The emphasis on the fundamentals will help the student and practicing scientist to understand the concepts and apply them accordingly. The second edition has been rewritten to include new process safety technology and new references that have appeared since the first edition was published in 1990. We continue to believe that a textbook on safety is possible only with both industrial and academic inputs. It also includes our combined experiences of teaching process safety in both industry and academia during the past 10 years. flammability characterization. The industrial input ensures that the material is industrially relevant. These changes fulfill the requests of many professors who have used this textbook. Significant modifications were made to the following topics: dispersion modeling.

B. Howard and S. The members of these committees are the experts in safety.) has accumulated significant industrial experience since the writing of the first edition. is not to be complete but to provide a starting point for those who wish to learn about this important area. This new emphasis on process safety is the result of the positive influences from industry and the Accreditation Board for Engineering and Technology (ABET). Darby of Texas A&M University. they have found that the concepts in this text and the accompanying problems and solutions are easy to learn and teach. We hope that this textbook helps prevent chemical plant and university accidents and contributes to a much safer future. Since the first edition was published. The purpose of this book. Willey of Northeastern University. one has over 30 years of relevant experience in industry (J. Powers from Dow Chemical Company. Crowl and Joseph E: Louvar . who provided patience. F. this textbook is an excellent application of the fundamental topics that are taught in the first three years of the undergraduate education. just as it is a part of all the industrial experiences. A. Wehman of the BASF Corporation. Professors have also found that industrial employees are enthusiastic and willing to give specific lectures on safety to enhance their courses. This book. Some will remark that our presentation is not complete or that some details are missing. for example. and encouragement throughout the writing of the first and second editions. understanding.) and the other (D. D. We also continue to acknowledge and thank all the members of the Undergraduate Education Committee of the Center for Chemical Process Safety and the Safety and Loss Prevention Committee of the American Institute of Chemical Engineers. we continue to believe that chemical process safety should be part of every undergraduate and graduate course in chemistry and chemical and mechanical engineering. Boicourt and J. has a companion text titled Health and Environmental Risk Analysis that extends the topics relevant to risk analysis. R. This textbook is designed for a dedicated course in chemical process safety. Based on faculty feedback. W. however. Finally. who have extensive industrial experience and are now consultants. We thank many of our friends who continue to teach us the fundamentals of chemical process safety. We are honored to be members of both committees. Daniel A. we continue to acknowledge our families. many universities have developed courses or course content in chemical process safety. Grossel. However. their enthusiasm and knowledge have been truly educational and a key inspiration to the development of this text. This text is an excellent reference for these courses. This textbook can also be used as a reference for a design course. Those who have been especially helpful include G. and R. Hendershot from Rohm and Haas. Although professors normally have little background in chemical process safety. R.xiv Preface academic input ensures that the material is presented on a fundamental basis to help professors and students understand the concepts. Although the authors are (now) both from universities. C. Welker of the University of Arkansas. L.

or process component availability tank cross sectional area (length2) change in Helmoltz free energy (energylmole) mass concentration (masslvolume) or capacitance (Farads) discharge coefficients (unitless) or concentration at a specified time (mass/volume) concentration of dense gas (volume fraction) heat capacity at constant pressure (energylmass deg) heat capacity at constant volume (energylmass deg) concentration in parts per million by volume deflagration vent constant (pressure1'*) average or mean mass concentration (mass/volume) diameter (length) particle diameter (length) diameter of flare stack (length) diffusion coefficient (arealtime characteristic source dimension for continuous releases of dense gases (length) characteristic source dimension for instantaneous releases of dense gas (length) reference diffusion coefficient (arealtime) molecular diffusivity (area /time) total integrated dose due to a passing puff of vapor (mass timelvolume) activation energy (energylmole) emergency response planning guideline (see Table 5-6) .Nomenclature Do D". Dtid E a ERPG velocity of sound (lengthltime) area (length2)or Helmholtz free energy (energy).

y or z direction (areattime) overpressure correction for relief sizing (unitless) explosion constant for dusts (length pressureltime) viscosity correction for relief sizing (unitless) . AH" I ID IDLH 10 Is ISOC j J k kl. given by Equation 4-38 explosion constant for vapors (length pressureltime) eddy diffusivity in x. Krn KG Kj KP Kst K" emergency exposure guidance levels (see section 5.4) Fanning friction factor (unitless) or frequency (lltime) failure density function mass fraction of vapor (unitless) frictional fluid flow loss term (energy mass) or force or environment factor fatal accident rate (fatalitiesIlO8 hours) forced expired volume (literslsec) forced vital capacity (liters) gravitational acceleration (lengthltime2) gravitational constant initial cloud buoyancy factor (lengthltime2) Gibbs free energy (energylmole) or mass flux (masslarea time) mass flux during relief (masstarea time) change in Gibbs free energy (energylmole) specific enthalpy (energylmass) fluid level above leak in tank (length) initial fluid level above leak in tank (length) leak height above ground level (length) enthalpy (energylrnole) or height (length) flare height (length) effective release height in plume model (length) change in enthalpy (energylrnole) heat of combustion (energylmass) release height correction given by Equation 5-64 enthalpy of vaporization (energylmass) sound intensity (decibels) pipe internal diameter (length) immediately dangerous to life and health (see section 5. k2 ks K Kb Kf Ki.xvi Nomenclature EEGL f f(t) fv F FAR FEV FVC g gc go G GT A G h h~ h"L hs H H f H I AH AC H AH.4) reference sound intensity (decibels) streaming current (amps) in-service oxygen concentration (volume percent oxygen) number of inerting purge cycles (unitless) electrical work (energy) non-ideal mixing factor for ventilation (unitless) constants in probit a equations thermal conductivity of soil (energyllength time deg) mass transfer coefficient (lengthltime) backpressure correction for relief sizing (unitless) excess head loss for fluid flow (dimensionless) constants in excess head loss.

Qv r R R R d RHI rf R P reference mass transfer coefficient (lengthltime) constant eddy diffusivity (arealtime) length lower explosion limit (volume %) lower flammability limit (volume %) limiting oxygen concentration (volume percent oxygen) mass total mass contained in reactor vessel (mass) mass of TNT mass of vapor molecular weight (masslmole) reference molecular weight (masslmole) Mach number (unitless) See LOC mean time between coincidence (time) mean time between failure (time) number of moles out of service fuel concentration (volume percent fuel) partial pressure (forcelarea) number of dangerous process episodes scaled overpressure for explosions (unitless) total pressure or probability backpressure for relief sizing (psig) permissable exposure level (see section 5.4) probability of failure on demand gauge pressure (forcelarea) maximum pressure for relief sizing (psig) set pressure for relief sizing (psig) saturation vapor pressure heat (energylmass) or heat intensity (energylarea time) heat intensity of flare (energyltime area) heat flux from ground (energylarea time) specific energy release rate at set pressure during reactor relief (energylmass) heat (energy) or electrical charge (coulombs) mass discharge rate (massltime) instantaneous mass release (mass) ventilation rate (volumeltime) radius (length) electrical resistance (ohms) or reliability Sachs scaled distance. defined by equation 6-25 (unitless) release duration for heavy gas releases (time) reaction hazard index defined by Equation 13-1 vessel filling rate (time-') ideal gas constant (pressure volume/mole deg) . MSOC MTBC MTBF n OSFC P P d P s P Pb PEL PFD P P Pmax f's pa st 4 4 f q g 4 s Q Q".Nomenclature xvii KO K* L LEL LFL = LEL LOC m "no ~ T N T mv M Mo Ma MOC. Q.

xviii Nomenclature Re S s m SPEGL t td te tl.4) time positive phase duration of a blast (time) emptying time time to form a puff of vapor vessel wall thickness (length) worker shift time venting time for reactor relief temperature (deg) material decomposition temperature (deg) time interval threshold limit value (ppm or mg/m3 by volume) maximum temperature during reactor relief (deg) saturation temperature at set pressure during reactor relief (deg) time weighted average (ppm or mg/m3 by volume) toxic dispersion method (see section 5.4) velocity (lengthltime) dropout velocity of a particle (lengthltime) average velocity (lengthltime) mean or average velocity (lengthhime) internal energy (energylmole) or overall heat transfer coefficient (energylarea time) or process component unavailability upper explosion limit (volume %) upper flammability limit (volume %) specific volume (volumelmass) specific volume of liquid (volumelmass) specific volume of vapor (volumelmass) specific volume change with liquid vaporization (volumelmass) total volume or electrical potential (volts) container volume width (length) expansion work (energy) shaft work (energy) mole fraction or Cartesian coordinate (length) distance from flare at grade (length) mole fraction of vapor (unitless) or Cartesian coordinate (length) probit variable (unitless) gas expansion factor (unitless) height above datum (length) or Cartesian coordinate (length) or compressibility (unitless) scaled distance for explosions (lengthlma~sl'~) . t" tw At" T Td T i TLV Tm TWA TXD U - Ud U (4 U UEL UFL = UEL v Vf vg vfs v v c W w e w s X X f Y Y YG Z Reynolds number (unitless) entropy (energylmole deg) or stress (forcelarea) material strength (forcelarea) short term public exposure guideline (see section 5.

Nomenclature xix Greek Letters velocity correction factor (unitless) or thermal diffusivity (arealtime) thermal expansion coefficient (deg-') double layer thickness (length) pipe roughness (length) or emissivity (unitless) relative dielectric constant (unitless) permittivity constant for free space (charge2/forcelength2) explosion efficiency (unitless) nonideal filling factor (unitless) heat capacity ratio (unitless) conductivity (mholcm) function defined by Equation 9-6 frequency of dangerous episodes average frequency of dangerous episodes viscosity (mass/length/time) or mean value or failure rate (faultsltime) vapor viscosity (mass/length/time) overall discharge coefficient used in Equation 9-15 (unitless) density (mass/volume) liquid density (mass/volume) reference density for specific gravity (mass/volume) vapor density (mass/volume) standard deviation (unitless) dispersion coefficient (length) relaxation time inspection period for unrevealed failures operation period for a process component period required to repair a component period of unavailability for unrevealed failures zeta potential (volts) Subscripts ambient combustion formation or liquid vapor or gas higher pressure initiating event purges lower pressure maximum set pressure initial or reference Superscripts 0 I standard stochastic or random variable .

.

Since 1950. It is reasonable to conclude that the growth of an industry is also dependent on technological advances. Robert M. More complex processes require more complex safety technology. which is entering an era of more complex processes: higher pressure. 1. Fawcett and W. safety is equal in importance to production and has developed into a scientific discipline that includes many highly technical and complex theories and practices. Professor Solow concluded that the bulk of an economy's growth is the result of technological advances. p. "To know is to survive and to ignore fundamentals is to court disaster. received the Nobel Prize in economics for his work in determining the sources of economic growth. (New York: Wiley. Wood. dispersion models representing the spread of toxic vapor through a plant after a release. Safety andAccident Prevention in Chemical Operations. H. more reactive chemicals. Many industrialists even believe that the development and application of safety technology is actually a constraint on the growth of the chemical industry.Introduction n 1987. H. Today. Fawcett said." l This book sets out the fundamentals of chemical process safety. chemical engineers will need a more detailed and fundamental understanding of safety. an economist at the Massachusetts Institute of Technology. As chemical process technology becomes more complex. This is especially true in the chemical industry. and 'H. 1982). and exotic chemistry. H. Examples of the technology of safety include hydrodynamic models representing two-phase flow through a vessel relief. Solow. I . 2d ed. S.significant technological advances have been made in chemical process safety.

or moving equipment. First. Despite substantial safety programs by the chemical industry. 1-1 Safety Programs A successful safety program requires several ingredients. safety shoes. and risk are frequently-used terms in chemical process safety. but for convenience. Chemical plants contain a large variety of hazards. headlines of the type shown in Figure 1-1 continue to appear in the newspapers. The main emphasis was on worker safety. or economic loss in terms of both the incident likelihood and the magnitude of the loss or injury. and a variety of rules and regulations. the potential always exists for an accident of catastrophic proportions. there are the usual mechanical hazards that cause worker injuries from tripping. "safety" has been replaced by "loss prevention." This term includes hazard identification. Much more recently. As will be shown later. property. Second. Hazard: a chemical or physical condition that has the potential to cause damage to people. environmental damage. falling. Risk: a measure of human injury. there are chemical hazards. as shown in Figure 1-2. the words "safety" and "loss prevention" will be used synonymously throughout.- 2 Chapter I Introduction mathematical techniques to determine the various ways that processes can fail and the probability of failure. The word "safety" used to mean the older strategy of accident prevention through the use of hard hats. Recent advances in chemical plant safety emphasize the use of appropriate technological tools to provide information for making safety decisions with respect to plant design and operation. These ingredients are System Attitude Fundamentals Experience Time You . chemical plants are the safest of all manufacturing facilities. These include fire and explosion hazards. However. hazard. technical evaluation. and the design of new engineering features to prevent loss. The subject of this text is loss prevention. or the environment. reactivity hazards. Their definitions are Safety or loss prevention: the prevention of accidents through the use of appropriate technologies to identify the hazards of a chemical plant and eliminate them before an accident occurs. and toxic hazards. Safety.

the participants must understand and use the fundamentals of chemical process safety in the design. the participants must have a positive attitude. . and operation of their plants. (2) to do what needs to be done. and (3) to record that the required tasks are done. Third. Fourth. the program needs a system (1)to record what needs to be done to have an outstanding safety program.1-1 Safety Programs 3 Figure 1-1 Headlines are indicative of the public's concern over chemical safety. This includes the willingness to do some of the thankless work that is required for success. First. Second. It is especially recommended that employees (1)read and understand Fundamentals Attitude \ Experience Figure 1-2 The ingredients of a successful safety program. everyone must learn from the experience of history or be doomed to repeat it. construction.

checklists. 1-3 Accident and Loss Statistics Accident and loss statistics are important measures of the effectiveness of safety programs. These statistics are valuable for determining whether a process is safe or whether a safety procedure is working effectively. A good safety program eliminates the existing hazards as they are identified. A good safety program identifies and eliminates existing safety hazards. The older concept of identifying a few employees to be responsible for safety is inadequate by today's standards. The company earns profits for its shareholders. shown in Table 1-1. community. This includes time to study. everyone (you) should take the responsibility to contribute to the safety program. Part of this responsibility is described in the Engineering Ethics statement developed by the American Institute of Chemical Engineers (AICHE). hazard identification techniques. An outstanding safety program has management systems that prevent the existence of safety hazards. Fifth. The commonly used management systems directed toward eliminating the existence of hazards include safety reviews. safety audits. Unfortunately. and proper application of technical knowledge. All employees have the responsibility to be knowledgeable about safety and to practice safety. everyone should recognize that safety takes time. time to record results (for history). The three systems considered here are . and engineers must provide a service to the company by maintaining and improving these profits. These statistics must be used carefully. Engineers have a responsibility to themselves. and the engineering profession. Like most statistics they are only averages and do not reflect the potential for single episodes involving substantial losses. whereas an outstanding safety program prevents the existence of a hazard in the first place. time to share experiences. It is important to recognize the distinction between a good and an outstanding safety program. family. The most effective means of implementing a safety program is to make it everyone's responsibility in a chemical process plant.4 Chapter 1 Introduction case histories of past accidents and (2) ask people in their own and other organizations for their experience and advice. Sixth. Engineers are responsible for minimizing losses and providing a safe and secure environment for the company's employees. Safety must be given importance equal to production. no single method is capable of measuring all required aspects. 1-2 Engineering Ethics Most engineers are employed by private companies that provide wages and benefits for their services. fellow workers. time to do the work. A safety program must have the commitment from all levels within the organization. and time to train or be trained. Many statistical methods are available to characterize accident and loss performance.

Engineers shall build their professional reputations on the merits of their services. The OSHA incidence rate is calculated from the number of occupational injuries and illnesses and the total number of employee hours worked during the applicable period. 3. Engineers shall hold paramount the safety. Fundamental canons 1. Table 1-2 contains several OSHA definitions applicable to accident statistics. striving to increase the competence and prestige of the engineering profession. Engineers shall issue public statements only in an objective and truthful manner. and dignity of the engineering profession. OSHA incidence rate. Engineers shall act in professional matters for each employer or client as faithful agents or trustees. their employers. 5. integrity. The following equation is used: OSHA incidence rate (based on injuries and illness) Number of injuries and illnesses X 200. 7. Engineers shall perform services only in areas of their competence. fatal accident rate (FAR). Engineers shall continue their professional development throughout their careers and shall provide opportunities for the professional development of those engineers under their supervision. 6. 2. Engineers shall act in such a manner as to uphold and enhance the honor. = . honor. OSHA stands for the Occupational Safety andHealth Administration of the United States government.000 hours of worker exposure to a hazard.1-3 Accident and Loss Statistics 5 Table 1-1 American Institute of Chemical Engineers Code of Professional Ethics Fundamental principles Engineers shall uphold and advance the integrity. 2. and dignity of the engineering profession by 1. health. 4. and shall avoid conflicts of interest. being honest and impartial and serving with fidelity the public. 3.000 Total hours worked by all employees during period covered. The OSHA incidence rate is therefore based on 200. The OSHA incidence rate is based on cases per 100 worker years. All three methods report the number of accidents and/or fatalities for a fixed number of workers during a specified period. and welfare of the public in the performance of their professional duties. using their knowledge and skill for the enhancement of human welfare. OSHA is responsible for ensuring that workers are provided with a safe working environment. and clients. and fatality rate. A worker year is assumed to contain 2000 hours (50 work weekslyear X 40 hourslweek). or deaths per person per year.

broken bones. It includes acute and chronic illnesses or diseases that may be caused by inhalation. Any abnormal condition or disorder. or burn that results from a work accident or from a single instantaneous exposure in the work environment. sprain. Injuries that result in the injured person not being able to perform their regular duties but being able to perform duties consistent with their normal work. Any injury such as a cut. Incident rate Lost workdays Medical treatment Occupational injury Occupational illness Recordable cases Recordable fatality cases Recordable nonfatal cases without lost workdays Recordable lost workday cases due to restricted duty Recordable cases with days away from work Recordable medical cases 'Injury Facts. and so forth that do not ordinarily require medical care. ZOSHAregulations. 1999 ed. Such one-time treatment and follow-up visits for the purpose of observation are considered first aid even though provided by a physician or registered professional personnel. Medical injuries include cuts requiring stitches. 151. including deaths. 1999). Number of occupational injuries and/or illnesses or lost workdays per 100 full-time employees. regardless of the time between the injury and death or the length of the illness. (Chicago: National Safety Council. Medical treatment does not include first aid treatment even though provided by a physician or registered professional personnel. or direct contact. and injury with loss of consciousness. Injuries that require treatment that must be administered by a physician or under the standing orders of a physician. during which the employee could not perform all or any part of his or her normal assignment during all or any part of the workday or shift because of the occupational injury or illness. Injuries that result in death. that is. burns. caused by exposure to environmental factors associated with employment. cuts. . 29 CFR 1904. Number of days (consecutive or not) after but not including the day of injury or illness during which the employee would have worked but could not do so. p. Injuries that result in the injured person not being able to return to work on their next regular workday.Table 1-2 Glossary of Terms Used by OSHA and Industry to Represent Work-Related L o s s e ~ ~ . Treatment administered by a physician or by registered professional personnel under the standing orders of a physician. ingestion. other than one resulting from an occupational injury. injury requiring prescription medication. splinters. Cases involving an occupational injury or occupational illness. absorption.12. The injured person is able to return to work and perform his or her regular duties. Cases of occupational injury or illness that do not involve fatalities or lost workdays but do result in (1) transfer to another job or termination of employment or (2) medical treatment other than first aid or (3) diagnosis of occupational illness or (4) loss of consciousness or (5) restriction of work or motion. ~ Term First aid Definition Any one-time treatment and any follow-up visits for the purpose of observation of minor scratches. second-degree burns (burns with blisters).

= . The applicable equation is Number of fatalities per year Fatality rate = Total number of people in applicable population. The OSHA incidence rate provides information on all types of work-related injuries and illnesses. This approach is useful for performing calculations on the general population. The OSHA incidence rate cannot be readily converted to a FAR or fatality rate because it contains both injury and fatality information. where the number of exposed hours is poorly defined. Number of lost workdays X 200. The resulting equation is Number of fatalities X 10' FAR = Total hours worked by all employees during period covered. On the other hand. A FAR can be converted to a fatality rate (or vice versa) if the number of exposed hours is known. TheFAR is usedmostly by the British chemicalindustry. a plant might experience many small accidents with resulting injuries but no fatalities. An employee working a ten-hour shift is at greater total risk than one working an eight-hour shift. including fatalities. fatality data cannot be extracted from the OSHA incidence rate without additional information. The definition of a lost workday is given in Table 1-2. . Both the OSHA incidence rate and the FAR depend on the number of exposed hours.1-3 Accident and Loss Statistics 7 An incidence rate can also be based on lost workdays instead of injuries and illnesses. This statistic is used here because there are some useful and interesting FAR data available in the open literature. Thus the FAR is based on 10' working hours. The FAR reports the number of fatalities based on 1000 employees working their entire lifetime. The employees are assumed to work a total of 50 years.000 Total hours worked by all employees during period covered. This system is independent of the number of hours actually worked and reports only the number of fatalities expected per person per year. The last method considered is the fatality rate or deaths per person per year. For instance. This provides a better representation of worker accidents than systems based on fatalities alone. For this case OSHA incidence rate (based on lost workdavs) .

1985 ed. p. 30. However.p. compute the deaths per person per year. being run over).26 1.07 1.28 19982 0.8 Chapter 1 Introduction Table 1-3 Accident Statistics for Selected Industries OSHA incident rate (cases involving days away from work and deaths) Industry Chemicals and allied products Motor vehicles Steel Paper Coal mining Food Construction Agricultural Meat products Trucking All manufacturing FAR (deaths) 1985l 0. "rank P.68 19863 4. 2 of the workers will die as a result of their employment throughout all of their working lifetimes.6 7. (Chicago: National Safety Council.0 40 67 10 19904 1. "Eliminating Potential Process Hazards. Kletz. If an employee works a standard 8-hr shift 300 days per year. Loss Prevention in the Process Industries (London: Butterworths.89 0. Lees.2 is reported in Table 1-3for the chemical industry. 1996).7 1. Approximately half these deaths are due to ordinary industrial accidents (falling down stairs. . One of these deaths will be due to direct chemical exposure.96 2.6 0. (London: Butterworths.88 4. Solution Deaths per person per year = (8 hrlday) x (300 dayslyr) x (2 deaths/108hr) = 4. 2d ed.p. A FAR of 1. (Chicago: National Safety Council.^ The FAR figures show that if 1000 workers begin employment in the chemical industry.53 5. 1986).08 1.35 6.54 2. 66. Example 1-1 A process has a reported FAR of 2. 1999 ed.0 1. 1985).3 5. 1999). the other half to chemical exposure^.81 0. 1.28 0. Loss Prevention in the Process Industries. Typical accident statistics for various industries are shown in Table 1-3.27 7.35 0.2 'Accident Facts. ZInjury Facts. Lees." Chemical Engineering (Apr.06 2.2 0. 219.10 1.49 1.3 8.p. A.8 X lo-'. 4FrankP.22 3. 20 of these same 2T.28 3. 177.1985).0 3.

(b) the FAR. Of those that perish from disease. 178. Table 1-4 indicates that canoeing is much more dangerous than traveling by motorcycle. Lees. The table is divided into voluntary and involuntary risks. It is also evident that many common everyday activities are substantially more dangerous than working in a chemical plant.p. This phenomenon is due to the number of exposed hours. Loss Prevention in the Process Industries.p. what will happen to (a) the OSHA incidence rate. For example. 1996). ZFrank P.~ Table 1-4 lists the FARs for various common activities.K. (c) the fatality rate. 2d ed. The total number of motorcycle fatalities is larger because more people travel by motorcycle than canoe. 9/96. 1000 people will die as a result of nonindustrial accidents (mostly at home or on the road) and 370 will die from disease.~ FAR (deaths110' hours) Fatality rate (deaths per person per year) Activity Voluntary activity Staying at home Traveling by Car Bicycle Air Motorcycle Canoeing Rock climbing Smoking (20 cigaretteslday) Involuntary activity Struck by meteorite Struck by lightning (U. Based on these data.K.) Run over by vehicle 57 96 240 660 1000 4000 17 X lo-" 4 x lo-5 500 X 6 X lo-" 1 x lo-7 150 X lo-' 600 X lo-' 'Frank P. Canoeing produces more fatalities per hour of activity than traveling by motorcycle. it appears that individuals are willing to take a substantially greater risk if it is voluntary.1-3 Accident and Loss Statistics 9 Table 1-4 Fatality Statistics for Common Nonindustrial Acti~itiesl.'' . (London: Buttenvorths. and (d) the total number of fatalities? "letz. Example 1-2 If twice as many people used motorcycles for the same average amount of time each. Loss Prevention in the Process Industries (London: Butterworths.) Fire (U. "Eliminating Potential Process Hazards. 40 will die as a direct result of ~moking. 1986). Lees. despite general perceptions otherwise.

the rock climbers probably spend more time traveling by car than rock climbing. The FAR will remain unchanged for the same reason as in part a. (b) the FAR. 4Kletz. c. for example. as. the statement might be correct but more data are required. Example 1-3 If all riders used their motorcycles twice as much. or deaths per person per year. The FAR will remain unchanged for the same reason as in part a.4 It is human nature to perceive the accident with the greater loss of life as the greater tragedy. the second accident kills more people. In both cases the risk taken by an individual operator is the same. the operator is the sole fatality. d. consider two separate chemical plants. The number of fatalities will double. The fatality rate will double. For example. The same reasoning applies as for Example 1-2. As a result. in the Bhopal. The fatality rate. Accident statistics do not include information on the total number of deaths from a single incident. When the plant explodes. The OSHA incidence rate will remain the same. tragedy. In both cases the FAR and OSHA incidence rate are the same.10 Chapter 1 Introduction Solution a. why is there so much concern about chemical plant safety? The concern has to do with the industry's potential for many deaths. d. Is this statement supported by the accident statistics? Solution The data from Table 1-4 show that traveling by car (FAR = 57) is safer than rock climbing (FAR = 4000). but there are a correspondingly larger number of exposed hours. but the total number of hours exposed will double as well. and (d) the total number of fatalities? Solution a. Accident statistics can be somewhat misleading in this respect. b. The fatality rate does not depend on exposed hours. The number of injuries and deaths will double. "Eliminating Potential Process Hazards. Rock climbing produces many more fatalities per exposed hour than traveling by car. The OSHA incidence rate will remain the same. The second plant employs 10 operators. will double. part a. The potential for large loss of life gives the perception that the chemical industry is unsafe. When this plant explodes all 10 operators succumb. The first plant employs a single operator. Twice as many fatalities will occur within this group. Recognizing that the chemical industry is safe. Both plants have a probability of explosion and complete devastation once every 1000 years." . c. However. what will happen to (a) the OSHA incidence rate. The total number of fatalities will double. Example 1-4 A friend states that more rock climbers are killed traveling by automobile than are killed rock climbing. India. (c) the fatality rate. b.

Accidents of this type are much more common than fatalities. and the average amount lost per incident have steadily increased. Finally.1-3 Accident and Loss Statistics N u m b e r o f Accidents Figure 1-3 The accident pyramid. As shown by K l e t ~if. an increase in chemical plant size." Inspections. people are spared from injury (good humanity). the price of the product increases and sales diminish. like most business situations." . These losses can be substantial. 1998). initial expenditures are made ~ on safety. Loss data5 published for losses after 1966 and in 10-year increments indicate that the total number of losses. excessive expenditures for safety equipment to solve single safety problems may make the system unduly complex and consequently may cause new safety SLarge Property Damage Losses in the Hydrocarbon-Chemical Industries: A Thirty-Year Review (New York: J & H Marsh & McLennan Inc. Indeed.A. and an increase in the use of more complicated and dangerous chemicals. but the cost is decreased sales. plants are prevented from blowing up and experienced workers are spared. but it may not be as much as before and not as much as achieved by spending money elsewhere. and time. p. "No Damage" accidents are frequently called "near misses" and provide a good opportunity for companies to determine that a problem exists and to correct it before a more serious accident occurs. Property damage and loss of production must also be considered in loss prevention. From a technical viewpoint.The numbers provided are only approximate. safety reviews and careful evaluation of near misses will identify hazardous conditions that can be corrected before real accidents occur. Safety is good business and. Kletz.. This results in increased return because of reduced loss expenditures. "Eliminating Potential Process Hazards. The exact numbers vary by industry. The total loss figure has doubled every 10 years despite increased efforts by the chemical process industry to improve safety. The increases are mostly due to an expansion in the number of chemical plants. even higher safety expenditures result in uncompetitive product pricing: The company will go out of business. Each company needs to determine an appropriate level for safety expenditures. 6T. the total dollar amount lost. If safety expenditures increase. This is demonstrated in the accident pyramid shown in Figure 1-3. This is part of risk management. then the return increases more. 2. It is frequently said that "the cause of an accident is visible the day before it occurs. location. If safety expenditures increase further. has an optimal level of activity beyond which there are diminishing returns.

Engineers need to also consider other alternatives when designing safety improvements. the programs should include off-the-job safety. and fires and explosions. company safety programs are directed toward preventing injuries to employees.000 (21.Because most.000 2. Although the emphasis of this book is the prevention of chemical-related accidents. the data in Figure 1-4 show that safety programs need to include training to prevent injuries resulting from transportation.2003 lZnjury Facts. It is also important to recognize the causes of accidental deaths.4%) 28.200 200 28. falling.5%) 3. it is helpful to analyze the manner in which workplace fatalities occur (see Figure 1-4). problems because of this complexity. 1999 ed. especially training to prevent accidents with motor vehicles. This excessive expense could have a higher safety return if assigned to a different safety problem.1%) 92. At some point in the design stage someone needs to decide if the risks are "accept- .12 Chapter I Introduction Table 1-5 All Accidental Deaths1 Type of death Motor-vehicle Public nonwork Work Home Subtotal Work Nonmotor-vehicle Motor-vehicle Subtotal Home Nonmotor-vehicle Motor-vehicle Subtotal Public2 Subtotal Total accidental deaths 1998 Deaths 38. 1999). etc. Every chemical process has a certain amount of risk associated with it.100 200 41. 2.200 (43. 2Public accidents are any accidents other than motor-vehicle accidents that occur in the use of public facilities or premises (swimming. as shown in Table 1-5.100 (5. 3The true total is lower than the sum of the subtotals because some accidents are in more than one category.900 2. When organizations focus on the root causes of worker injuries. if not all.) and deaths resulting from natural disasters even if they happened in the home.100 5.400 (30. assaults.000 20. 1-4 Acceptable Risk We cannot eliminate risk entirely.p. hunting. mechanical and chemical exposures.0%) 20. (Chicago: National Safety Council.

. are the risks greater than the normal day-to-day risks taken by individuals in their nonindustrial environment? Certainly it would require a substantial effort and considerable expense to design a process with a risk comparable to being struck by lightning (see Table 1-4). this risk may be too high because the risks resulting from multiple exposures are additive.1-4 Acceptable Risk 13 Transportation incidents (n = 2. DC: US Department of Labor. Is it satisfactory to design a process with a risk comparable to the risk of sitting at home? For a single chemical process in a plant composed of several processes. 1999). Source: News.' 7Modern site layouts require sufficient separation of plants within the site to minimize risks of multiple exposures. The total number of workplace fatalities was 6026." That is. able. Aug.630) Assaults and violent acts (n = 960) Contact with objects and equipment (n = 941) Falls (n = 702) Exposure due to harmful substances and environments (n = 572) Fires and explosions (n = 205) I I Highway Worker struck by vehicle highway Aircraft Other Homicide Suicide Struck by object Other Electrocutions Other I I I I I I I 5 10 15 20 25 Accidents (%) 30 35 40 45 Figure 1-4 The manner in which workplace fatalities occurred in 1998. 4. USDL 99-208 (Washington.

with a small margin to those who considered the good and harm to be equal. or about the same amount of each?" Source: The Detroit News.-29% --------More Harm Than Good -- 38% Same Amount of Good a n d H a r m Figure 1-5 Results from a public opinion survey asking the question "Would you say chemicals do more good than harm. The results of a public opinion survey on the hazards of chemicals are shown in Figure 1-5. is to eliminate synthetic fibers produced by chemicals and use natural fibers such as cotton. The results show an almost even three-way split. The major objection is due to the involuntary nature of acceptable risk. more harm than good. As suggested by Kletz? accident statistics demonstrate that this will result in a greater number of fatalities because the FAR for agriculture is higher. Some naturalists suggest eliminating chemical plant hazards by "returning to nature." . Engineers must make every effort to minimize risks within the economic constraints of the process. "Eliminating Potential Process Hazards. 8T. No engineer should ever design a process that he or she knows will result in certain human loss or injury. Kletz. A. for example.This survey asked the participants if they would say chemicals do more good than harm. or about the same amount of each. more harm than good. 1-5 Public Perceptions The general public has great difficulty with the concept of acceptable risk. Frequently these civilians are not aware that there is any risk at all.14 Chapter 1 Introduction 28% More Good Than H a r m . despite any statistics. Chemical plant designers who specify the acceptable risk are assuming that these risks are satisfactory to the civilians living near the plant." One alternative.

1998). As illustrated. Solution Penicillin.1-6 The Nature of the Accident Process Table 1-6 Type of accident Fire Explosion Toxic release Three Types of Chemical Plant Accidents Probability of occurrence High Intermediate Low Potential for fatalities Low Intermediate High Potential for economic loss Intermediate High Low Example 1-5 List six different products produced by chemical engineers that are of significant benefit to mankind. . Used by permission of Marsh Inc. 2. fires are the most common. paper.. b. plastic. vapor cloud explosions ac- r Other 3% Figure 1-6 Types of loss for large hydrocarbonchemical plant accidents. With respect to fatalities. It is important to study these patterns in order to anticipate the types of accidents that will occur. Economic loss is consistently high for accidents involving explosions. the order reverses. concrete. 1-6 The Nature of the Accident Process Chemical plant accidents follow typical patterns. followed by explosion and toxic release. Source: Large Property Damage Losses in the Hydrocarbon-Chemical Industries: A Thirty-Year Review (New York: Marsh Inc. with toxic release having the greatest potential for fatalities. An analysis of the largest chemical plant accidents (based on worldwide accidents and 1998 dollars) is provided in Figure 1-6. synthetic rubber. where a large cloud of volatile and flammable vapor is released and dispersed throughout the plant site followed by ignition and explosion of the cloud. gasoline. The most damaging type of explosion is an unconfined vapor cloud explosion. As shown in Table 1-6.

valves.. 1998). The Mechanical Operator error Unknown Process upsets Natural hazards Design Sabotage and arson Figure 1-7 Causes of losses in the largest hydrocarbon-chemicalplant accidents. and cleanup liabilities can be significant. Failures of this type are usually due to a problem with maintenance. mechanical failures could all be due to human error as a result of improper maintenance or inspection. except those caused by natural hazards. Personnel injuries. . Almost all accidents. legal compensation. By far the largest cause of loss in a chemical plant is due to mechanical failure. and control equipment will fail if not properly maintained. Human error is frequently used to describe a cause of losses. For instance. 2. Toxic release typically results in little damage to capital equipment. power or cooling water failures account for 11% of the losses. Figure 1-7 presents the causes of losses for the largest chemical accidents. For example. p. Source: Large Property Damage Losses in the Hydrocarbon-ChemicalIndustries: A Thirty-Year Review (New York: J & H Marsh & McLennan Inc. valves are not opened or closed in the proper sequence or reactants are not charged to a reactor in the correct order. Process upsets caused by. employee losses. The "other" category of Figure 1-6includes losses resulting from floods and windstorms. for example.16 Chapter I Introduction count for the largest percentage of these large losses. Used by permission of Marsh Inc. The second largest cause is operator error. can be attributed to human error. Pumps.

compared to the previous 5 years between 1987 and 1996. term "operator error. Piping system failure represents the bulk of the accidents. Reprinted by permission. Source: A Thirty-Year Review of One Hundred of the Largest Property Damage Losses in the Hydrocarbon-Chemical Industries (New York: Marsh Inc. An interesting result of this study is that the most complicated mechanical components (pumps and compressors) are minimally responsible for large losses. that is. This increase corresponds to the trend of building larger and more complex plants. on February 24. . includes human errors made on-site that lead directly to the loss. Figure 1-8 presents a survey of the type of hardware associated with large accidents. is likely the result of governmental regulations that were implemented in the United States during this time.." used in Figure 1-7." This rule became effective on May 26.1992. The lower losses in the last 5-year period. followed by storage tanks and reactors. The loss distribution for the hydrocarbon and chemical industry over 5-year intervals is shown in Figure 1-9. The number and magnitude of the losses increase over each consecutive 10-year period for the past 30 years. 1987). OSHA published its final rule "Process Safety Management of Highly Hazardous Chemicals.1-6 The Nature of the Accident Process 17 Piping systems Miscellaneous or unknown Storage tanks Reactor piping systems Process holding tanks Heat exchangers Valves Process towers Compressors Pumps Gauges 0 5 10 15 20 25 30 35 40 45 50 I Number of accidents Figure 1-8 Hardware associated with largest losses.

. (1. A cloud of flammable vapor rapidly forms and is ignited by a nearby truck..161. The explosion and fire quickly spread to nearby equipment. The impact of these regulations occurred in subsequent years. p. Other countries are adopting similar regulations. I n - P B 0.34) (1. 3.39) 5 Losses (0. and termination (the event or events that stop the accident or diminish it in size). In the example the worker tripped to initiate the accident.sses in the Hydrocarbon-Chemical Industries (Chicago: M & M Protection Consultants. 2. p. propagation (the event or events that maintain or expand the accident).0 - a a 1. the valve stem shears off and flammable liquid begins to spew out.000. The resulting fire lasts for six days until all flammable materials in the plant are consumed. 2. (There were also 7 offshore accidents in this 30-year period.18 Chapter 1 Introduction .) Source: Large Property Damage Losses in the Hydrocarbon-Chemical Industries: A Thirty-Year Review (New York: J & H Marsh & McLennan Inc. The following chemical plant accident illustrates these steps. The event was terminated by consumption of all flammable materials. Used by permission of Marsh Inc. he grabs a nearby valve stem. Most accidents follow a three-step sequence: initiation (the event that starts the accident). 1998).L g a .5 - (0.04) 27 Losses (1. 1986). 9 0 n e Hundred Largest Losses: A Thirty-Year Review of Property Lo. 1992.48) " 1.0 - r. and the plant is completely destroyed.44) 17 Losses 18 Losses 16 Losses 9 Losses Figure 1-9 Loss distribution for onshore accidents for 5-year intervals over a 30-year period. To prevent the fall.5 . The accident was propagated by the shearing of the valve and the resulting explosion and growing fire.0 . Accidents follow a three-step process.It demonstrates an important point: Even the simplest accident can result in a major catastrophe. K . A worker walking across a high walkway in a process plant stumbles and falls toward the edge. This disaster occurred in 1969yand led to an economic loss of $4. Unfortunately.

Severe flame impingement on an 11. propagation. Table 1-7 presents a few ways to accomplish this. In practice this is not effective: It is unrealistic to expect elimination of all initiations. waste heat recovery and super-heater train resulted in its near total destruction. The resulting vapor cloud probably ignited from the ignition system of enginedriven recompressors. accidents can be stopped by eliminating the initiating step. 10. A much more effective approach is to work on all three areas to ensure that accidents.000-horsepower gas turbine-driven compressor. do not propagate and will terminate as quickly as possible. In theory. l0One Hundred Largest Losses.35 MCFID) gas producing plant allowed the release of rich oil and gas at 850 psi and -40°F. Breaking pipelines added more fuel to the fire. and termination steps for this accident.1-6 The Nature of the Accident Process 19 Table 1-7 Step Initiation Defeating the Accident Process Desired effect Diminish Procedure -- Grounding and bonding Inerting Explosion proof electrical Guardrails and guards Maintenance procedures Hot work permits Human factors design Process design Awareness of dangerous properties of chemicals Emergency material transfer Reduce inventories of flammable materials Equipment spacing and layout Nonflammable construction materials Installation of check and emergency shutoff valves Firefighting equipment and procedures Relief systems Sprinkler systems Installation of check and emergency shutoff valves Propagation Diminish Termination Increase Safety engineering involves eliminating the initiating step and replacing the propagation steps with termination events. The 75' high X 10' diameter absorber tower eventually collapsed across the pipe rack and on two exchanger trains. Identify the initiation. once initiated. Example 1-6 The following accident report has been filed lo: Failure of a threaded 1%" drain connection on a rich oil line at the base of an absorber tower in a large (1. p. .

The major approach to inherently safer process designs is divided into the following categories: intensification substitution attenuation limitation of effects simplification/error tolerance llCCPS. Guidelines for Engineering Design for Process Safety (New York: American Institute of Chemical Engineers. 1993). and they are free to consider basic process alternatives. it is helpful to know the definitions of terms that are commonly used in the descriptions (see Table 1-8). such as changes to the fundamental chemistry and technology. Inherent safety is a part of all layers of protection.20 Chapter 1 introduction Failure of threaded 172"drain connection Release of rich oil and gas. . it is especially directed toward process design features. ignition of vapor cloud by recompressors. 1996). 12CCPS. formation of vapor cloud. and more reliable. In general. redundancy. The best approach to prevent accidents is to add process design features to prevent hazardous situations. An inherently safer plant is more tolerant of operator errors and abnormal conditions. the safety of a process relies on multiple layers of protection. A process that does not require complex safety interlocks and elaborate procedures is simpler. and emergency response plans. the study of case histories is an especially important step in the process of accident prevention. Inherently safer plants are tolerant of errors and are often the most cost effective. Smaller equipment. The first layer of protection is the process design features. interlocks. alarms. interlocks. operated at less severe temperatures and pressures. Solution Initiation: Propagation: 1-7 Inherent Safety An inherently safe plant11J2relies on chemistry and physics to prevent accidents rather than on control systems. protective systems. easier to operate. and special operating procedures to prevent accidents.Inherently Safer Chemical Processes: A Life Cycle Approach (New York: American Institute of Chemical Engineers. has lower capital and operating costs. At these early stages process engineers and chemists have the maximum degree of freedom in the plant and process specifications. the potential for major improvements is the greatest at the earliest stages of process development. Although a process or plant can be modified to increase inherent safety at any time in its life cycle. collapse of absorber tower across pipe rack Termination: Consumption of combustible materials in process As mentioned previously. safety shutdown systems. Subsequent layers include control systems. To understand these histories. however.

or a conditional probability. Guidelines for Consequence Analysis of Chemical Releases (New York: American Institute of Chemical Engineers. When possible. The development of a quantitative estimate of risk based on an engineering evaluation and mathematical techniques for combining estimates of incident consequences and frequencies. hazardous materials should be produced and consumed in situ. A measure of human injury. distillation columns. or property damage. not the result of the event. and pipelines. A measure of the expected effects of the results of an incident. a probability of occurrence during some time interval. the following four words have recently been recommended to describe inherent safety: minimize (intensification) substitute (substitution) moderate (attenuation and limitation of effects) simplify (simplification and error tolerance). death. A measure of the expected probability or frequency of occurrence of an event. 1999). . This minimizes the storage and transportation of hazardous raw materials and intermediates. Minimizing entails reducing the hazards by using smaller quantities of hazardous substances in the reactors. This may be expressed as a frequency.1-7 Inherent Safety 21 Table 1-8 Term Accident Hazard Incident Consequence Likelihood Definitions for Case Histories1 Definition The occurrence of a sequence of events that produce unintended injury. In an attempt to make these categories more understandable. The types of inherent safety techniques that are used in the chemical industry are illustrated in Table 1-9 and are described more fully in what follows. "Accident" refers to the event. The description should contain information relevant to defining the root causes. property. environmental damage. either through a relative ranking of risk reduction strategies or through comparison with risk targets. A chemical or physical condition that has the potential for causing damage to people. A description of the events that result in an accident or incident. not all incidents propagate into accidents. Some companies add or subtract categories to their program to fine-tune their understanding and application. not all events propagate into incidents. storage vessels. or economic loss in terms of both the incident likelihood and the magnitude of the loss or injury. or the environment. The process by which the results of a risk analysis are used to make decisions. Risk Risk analysis Risk assessment Scenario 'CCPS. The loss of containment of material or energy. These five categories are the predominant ones used since the development of this concept.

flanged Use solvents that are less toxic Use mechanical gauges vs. water-based paints and adhesives and aqueous or dry flowable formulations for agricultural chemicals).and explosion-resistant barricades Separate systems and controls into blocks that arc easy to comprehend and understand Label pipes for easy "walking the line" Label vessels and controls to enhance understanding Minimize (intensification) Substitute (substitution) Moderate (attenuation and limitation of effects) Simplify (simplification and error tolerance) Vapor released from spills can be minimized by designing dikes so that flammable and toxic materials will not accumulate around leaking tanks. substitutions should also be considered as an alternative or companion concept. that is. While minimization possibilities are being investigated. Smaller tanks also reduce the hazards of a release. boiling points. mercury Use chemicals with higher flash points. Another alternative to substitution is moderation. that is. packing Use welded pipe vs. When possible. safer materials should be used in place of hazardous ones. This can be accomplished by using alternative chemistry that allows the use of less hazardous materials or less severe processing conditions. toxic or flammable solvents should be replaced with less hazardous solvents (for example. using a hazardous material un- .Chapter 1 Introduction Table 1-9 TYpe Inherent Safety Techniques Typical techniques Change from large batch reactor to a smaller continuous reactor Reduce storage inventory of raw materials Improve control to reduce inventory of hazardous intermediate chemicals Reduce process hold-up Use mechanical pump seals vs. and other less hazardous properties Use water as a heat transfer fluid instead of hot oil Use vacuum to reduce boiling point Reduce process temperatures and pressures Refrigerate storage vessels Dissolve hazardous material in safe solvent Operate at conditions where reactor runaway is not possible Place control rooms away from operations Separate pump rooms from other rooms Acoustically insulate noisy lines and equipment Barricade control rooms and tanks Keep piping systems neat and visually easy to follow Design control panels that are easy to comprehend Design plants for easy and safe maintenance Pick equipment that requires less maintenance Pick equipment with low failure rates Add fire.

(1) piping systems can be designed to minimize leaks or failures. continuous monitoring. Simpler plants are friendlier than complex plants because they provide fewer opportunities for error and because they contain less equipment that can cause problems. All these accidents had a significant impact on public perceptions and the chemical engineering profession that added new emphasis and standards in the practice of safety. (2) transfer systems can be designed to minimize the potential for leaks. The four most cited accidents (Flixborough. For example. occurred on a Saturday in June 1974. Simplification reduces the opportunities for errors and misoperation. the reason for complexity in a plant is the need to add equipment and automation to control the hazards. Seveso. Flixborough. and using proper support of lines to minimize stress and subsequent failures. and (4) processing under less severe temperature or pressure conditions. (2) refrigerating to lower the vapor pressure. special precautions are included to ensure worker protection. a basic raw material for the production of nylon. Containment buildings are sometimes used to moderate the impact of a spill of an especially toxic material. England. safety achieved a much higher priority in that country. Chapter 13 presents case histories in considerably more detail. This information is used to improve procedures to prevent similar accidents in the future. such as remote controls. using spiral wound gaskets and flexible graphitetype gaskets that are less prone to catastrophic failures. it had a major impact on chemical engineering in the United Kingdom. . England. The Flixborough Works of Nypro Limited was designed to produce 70. The process uses cyclohexane. England The accident at Flixborough. As a result of the accident. The Flixborough accident is perhaps the most documented chemical plant disaster. and Pasadena. Italy.000 tons per year of caprolactam.1-8 Four Significant Disasters 23 der less hazardous conditions. and restricted access. using welded pipes for flammable and toxic chemicals and avoiding the use of threaded pipe. India. (5) equipment and controls can be placed in a logical order. (4) fail-safe valves can be added. The design o an inherently safe and simple piping system includes minimizing the use of f sight glasses. Bhopal. Texas) are presented here. The British government insisted on an extensive investigation. Although it was not reported to any great extent in the United States. and bellows. flexible connectors. Less hazardous conditions or less hazardous forms of a material include (1) diluting to a lower vapor pressure to reduce the release concentration. (3) process steps and units can be separated to prevent the domino effect. (3) handling larger particle size solids to minimize dust. Often. When containment is used. and (6) the status of the process can be made visible and clear at all times. 1-8 Four Significant Disasters The study of case histories provides valuable information to chemical engineers involved with safety.

The resulting fire in the plant burned for over 10 days. The feed pipes connecting the reactors were 28 inches in diameter. . Several months before the accident occurred. Upon rupture of the bypass. The process where the accident occurred consisted of six reactors in series. First. The loss of the reactor would reduce the yield but would enable continued production because unreacted cyclohexane is separated and recycled at a later stage.24 Chapter 1 Introduction which has properties similar to gasoline. Inspection showed a vertical crack in its stainless steel structure. The resulting explosion leveled the entire plant facility. the connections to reactor 4 and reactor 6 were made using flexible bellows-type piping. and 36 others were injured. Eighteen of these fatalities occurred in the main control room when the ceiling collapsed. This accident could have been prevented by following proper safety procedures. Damage extended to 1821 nearby houses and 167 shops and factories. Loss of life would have been substantially greater had the accident occurred on a weekday when the administrative offices were filled with employees. In these reactors cyclohexane was oxidized to cyclohexanone and then to cyclohexanol using injected air in the presence of a catalyst. the cyclohexane volatilizes immediately when depressurized to atmospheric conditions. Each reactor normally contained about 20 tons of cyclohexane. An additional decision was made to continue operating by connecting reactor 4 directly to reactor 6 in the series. including the administrative offices. an estimated 30 tons of cyclohexane volatilized and formed a large vapor cloud. Under the process conditions in use at Flixborough (155°C and 7.9 atm). the Bellows Temporary Pipe Section Figure 1-10 A failure of a temporary pipe section replacing reactor 5 caused the Flixborough accident.It is hypothesized that the bypass pipe section ruptured because of inadequate support and overflexing of the pipe section as a result of internal reactor pressures. as shown in Figure 1-10. The cloud was ignited by an unknown source an estimated 45 seconds after the release. Fifty-three civilians were reported injured. Because only 20-inch pipe stock was available at the plant. The decision was made to remove the reactor for repairs. The liquid reaction mass was gravity-fed through the series of reactors. reactor 5 in the series was found to be leaking. Twenty-eight people died.

has received considerably more attention than the Flixborough accident. a well-executed safety review could have identified the problem. India. and 450 gallons of gasoline. 26. The maximum exposure concentration of MIC for workers over an 8-hour period is 0. Unfortunately. The plant was partially owned by Union Carbide and partially owned locally. on December 3. 1984. Finally. The exact cause of the contamination of the MIC is not known. Its boiling point at atmospheric conditions is 39.and it has a vapor pressure of 348 mm Hg at 20°C.02 ppm (parts per million). the bypass modification was substandard in design.1-8 Four Significant Disasters 25 bypass line was installed without a safety review or adequate supervision by experienced engineering personnel. any modifications should be of the same quality as the construction of the remainder of the plant. the scrubber and flare systems were not operating.1°C. particularly intermediates. If the accident was caused by a problem with the process. MIC is an extremely dangerous compound. with inadequate cooling the temperature will increase and the MIC will boil. A chemical reaction heated the MIC to a temperature past its boiling point.000 gallons of toluene. should also have been minimized. The toxic cloud spread to the adjacent town. and flammable. volatile. Inventories of dangerous chemicals. a shantytown eventually grew around the immediate area.000 gallons of cyclohexane. Somehow a storage tank containing a large amount of MIC became contaminated with water or some other substance. The nearest civilian inhabitants were 1. No plant workers were injured or killed.5 miles away when the plant was constructed. Although the reaction rate is slow. Individuals exposed to concentrations of MIC vapors above 21 ppm experience severe irritation of the nose and throat. The vapor is about twice as heavy as air. It is reactive. The plant pesticides.000 more.000 gallons of naphtha. . MIC reacts exothermically with water. As a rule. The unit using the MIC was not operating because of a local labor dispute. MIC demonstrates a number of dangerous physical properties. An estimated 25 tons of toxic MIC vapor was released. The MIC vapors traveled through a pressure relief system and into a scrubber and flare system installed to consume the MIC in the event of a release. Death at large concentrations of vapor is due to respiratory distress. The bypass was sketched on the floor of the machine shop using chalk! Second. India The Bhopal. The Bhopal plant is in the state of Madhya Pradesh in central India. An intermediate compound in this process is methyl isocyanate (MIC). ensuring that the vapors will stay close to the ground once released. 66. MIC storage tanks are typically refrigerated to prevent this problem. Because the plant was the dominant source of employment in the area. killing over 2000 civilians and injuring an estimated 20. The scrubber and flare system should have been fully operational to prevent the release. 11. for a variety of reasons. accident. the plant site contained excessively large inventories of dangerous compounds. No plant equipment was damaged.400 gallons of benzene. toxic. These inventories contributed to the fires after the initial blast. This is due to the more than 2000 civilian casualties that resulted. Bhopal. This included 330.

The lower reaction suggests an alternative reaction scheme using a less hazardous intermediate. One such design produces and consumes the MIC in a highly localized area of the process. The product was hexachlorophene.000 inhabitants. An alternative reaction scheme is shown at the bottom of the figure and involves a less dangerous chloroformate intermediate. p. Italy Seveso is a small town of approximately 17. Seveso. with trichlorophenol produced as an intermediate. During normal operation. with an inventory of MIC of less than 20 pounds. Italy. 15 miles from Milan.CNHCH3 I CH3N=C=0 + a-Naphthol Carbaryl Nonmethyl isocyanate route a-Na~hthol chloroformate Figure 1-11 The upper reaction is the methyl isocyanate route used at Bhopal. 1 1 . a . Another solution is to redesign the process to reduce the inventory of hazardous MIC.26 Chapter 1 Introduction Methyl isocyanate route CH3NH2+ COCI. Adapted from Chemical and Engineering News (Feb. a bactericide. The plant was owned by the Icmesa Chemical Company. 30. Methylamine Phosgene - CH3N = C = 0 Methyl isocyanate + 2HCI 0 II OH I 0 . 1985). The reaction scheme used at Bhopal is shown at the top of Figure 1-11 and includes the dangerous intermediate MIC.

the hazards could have been identified and corrected before the accidents occurred. Less than 200 g of TCDD was released. 4 eventually died from the exposure. and capital losses of over $715 million. resulting in a higher than normal operating temperature and increased production of TCDD. TCDD is perhaps the most potent toxin known to humans. the product plugs the settling leg.Usually the polyethylene particles (product) settle in the settling leg and are removed through the product takeoff valve. the condition it remains in today.1-8 Four Significant Disasters 27 small amount of TCDD (2. as illustrated in Figure 1-12. The most severely contaminated area immediately adjacent to the plant was fenced. The release occurred in the polyethylene product takeoff system.000 pounds of a flammable mixture containing ethylene. Of the 50 men assigned to clean up the release. The damage resulting from the explosion made it impossible to reconstruct the actual accident scenario. in 1963 the plant was finally disassembled brick by brick. 1989. Because TCDD is also insoluble in water. An estimated 2 kg of TCDD was released through a relief system in a white cloud over Seveso. This explosion occurred in a high-density polyethylene plant after the accidental release of 85. Over 600 people were evacuated. on October 23.7. A subsequent heavy rain washed the TCDD into the soil. Because of poor communications with local authorities. hexane. Occasionally. and an additional 2000 people were given blood tests. by following proper procedures. the initiation steps would not have occurred. On July 10. Animal studies have shown TCDD to be fatal in doses as small as lo-' times the body weight. encased in concrete and dumped into the ocean. by using proper hazard evaluation procedures. First. Approximately 10 square miles were contaminated. resulted in 23 fatalities. The release formed a large gas cloud instantaneously because the system was under high pressure and temperature. isobutane. However. The Seveso and Duphar accidents could have been avoided if proper containment systems had been used to contain the reactor releases. India. and the plug . civilian evacuation was not started until several days later.3. and hydrogen. evidence showed that the standard operating procedures were not appropriately followed. Second. Texas. an acne-like disease that can persist for several years. 1976. The cloud was ignited about 2 minutes after the release by an unidentified ignition source. TCDD is so toxic and persistent that for a smaller but similar release of TCDD in Duphar. decontamination is difficult. the trichlorophenol reactor went out of control. Pasadena. 314 injuries. and the contamination was confined to the plant. over 250 cases of chloracne were reported. Texas A massive explosion in Pasadena. By then. The proper application of fundamental engineering safety principles would have prevented the two accidents.8-tetrachlorodibenzoparadioxin) produced in the reactor as is an undesirable side-product. Nonlethal doses of TCDD result in chloracne.

procedure includes closing the DEMCO valve.-& Removed before accident (standard procedure) take. the DEMCO valve was in the open position._ I. \ L DEMCO valve (ball valve) r n--~. Then the product takeoff valve is removed to give access to the plugged leg. The OSHA investigation13found that (1)no process hazard analysis had been performed in the polyethylene plant. a double130ccupational Safety and Health Administration. DC: US Department of Labor. and locking the valve in the closed position. and as a result. 1990). (2) the single-block (DEMCO) valve on the settling leg was not designed to fail to a safe closed position when the air failed. the product takeoff valve was removed. (3) rather than relying on a single-block valve. is removed by maintenance personnel. This scenario was a serious violation of well-established and well-understood procedures and created the conditions that permitted the release and subsequent explosion.and safe . . Figure 1-12 Polyethylene plant settling leg and product takeoff system. The normal . removing the air lines. The accident investigation evidence showed that this safe procedure was not followed.. and the lockout device was removed. specifically. many serious safety deficiencies were ignored or overlooked.28 Chapter I Introduction A Air to open Lock-out device Air to close CfX-\ d/ -. The Pasadena Accident: A Report to the President (Washington.

and enforcement of effective permit systems (for example. (London: Butterworth-Heinemann. Lees. Bethea. Willey. Loss Prevention in the Process Industries. app. p.Suggested Reading 29 block-and-bleed valving arrangement or a blind flange after the single-block valve should have been used. Suggested Reading General Aspects of Chemical Process Safety Robert M. Other factors that contributed to the severity of this disaster were also cited: (1)proximity of high-occupancy structures (control rooms) to hazardous operation. "What Really Happened at Seveso. Wood. 16-18. 1996). Ronald J. p. 1998). 1-5.1976). 3. The Bhopal Disaster (New York: American Institute of Chemical Engineers. 27. 1." Chemical Engineering (May 16. ch. app. Lees. Loss Prevention in the Process Industries. Explosion and Fire at Pasadena. Bhopal Chemical and Engineering News (Feb. Bethea. ch. v. 2. eds. Process Safety Management with Case Histories: Flixborough. Lees. pp. (2) inadequate separation between buildings. Sambeth. 1985). 1996). 44-47 Flixborough Robert M.1983). 2d ed. 1980).. Lees. Kletz. and (5) no permanent combustible gas detection and alarm system was located in the region of the reactors. v. line opening). Seveso Chemical and Engineering News (Aug. Loss Prevention in the Process Industries. 11. v. Pasadena. Texas (New York: American Institute of Chemical Engineers. Frank P. . 2d ed. Loss Prevention in the Process Industries. and (3) crowded process equipment. 23. implementation. 1. Fawcett and William S. 1 (London: Butterworths. 2. Safety and Accident Prevention in Chemical Operations. (New York: Wiley. Frank P. ch. Howard H. 1994). J. 14.1985). General Case Histories Trevor A. 1982). and Other Zncidents (New York: American Institute of Chemical Engineers. What Went Wrong? Case Histories of Process Plant Disasters (Houston: Gulf Publishing. (4) no provision was made for the development.

The ensuing fire exposed a fractionation tower and horizontal receiver drums. assuming worker exposure to all three units simultaneously? b.40% in process area 2.5. and 40% in process area 3. which ignited.000 gal of LPGs for almost 6 hr before being blocked in and the fires extinguished. Assume now that the units are far enough apart that an accident in one would not affect the workers in another. The explosions and heat caused loss of insulation from the 8-ft x 122-ft fractionator tower. An alkylation unit was being started up after shutdown because of an electrical outage. and 1. An employee works in a plant with a FAR of 4. b. Both engine-driven fire pumps failed. a. A plant employs 1500full-time workers in a process with aFAR of 5. Should the worker be satisfied or alarmed? What is the FAR (assuming normal working hours) and the deaths per person per year? What should her chances be. The units have FARs of 0. Liquid products from 5 of 26 salt dome caverns fed the fire with an estimated 18.- - 30 Chapter 1 . If this employee works a 4-hr shift.14 Suggest ways to prevent and contain the accidents. respectively. rupturing pipelines. what is the expected deaths per person per year? 1-2. how many miles must be driven before a fatality is expected? 1-4. where they ignited. it was decided to clean the strainer. followed by butane vapors. How many hours must be traveled by car for each hour of rock climbing to make the risks of fatality by car equal to the risk of fatality by rock climbing? 1-7. and termination steps for the following accident reports. flashing back to the flange. 200 days per year. propagation. Three process units are in a plant. A worker is told her chances of being killed by a particular process are 1in every 500 years. one because intense radiated heat damaged its ignition wires and the other because the explosion broke a sight glass fuel gauge. When adequate circulation could not be maintained in a deisobutanizer heater circuit. causing it to weaken and fall across two major pipeI40ne Hundred Largest Losses.0. How many industrialrelated deaths are expected each year? 1-6. Consider Example 1-4.0. Assuming that a car travels at an average speed of 50 miles per hour. spilling diesel fuel. Workers had depressurized the pipe and removed all but three of the flange bolts when a pressure release blew a black material from the flange. The large vapor cloud estimated to cover an area of 44 acres was ignited about 4-5 min later by an unknown source. These drums exploded. what is his overall FAR? 1-3. which added more fuel. destroying the fire pump engine.000-30. a. If a worker spends 20% of his time in process area 1. Introduction Problems 1-1. assuming an average chemical plant? 1-5. These vapors were carried to a furnace 100 ft away. . What is the overall FAR for the plant.3. A contractor accidentally cut into a 10-in propane line operating at 800 psi at a natural gas liquids terminal. Identify the initiation.

he says. can inherent safety help? 1-13.000 passenger miles.Problems 31 lines. An investigation shows that the accident was the fault of the dead employee. e. what would you emphasize in a safety program? 1-12. The fault was traced to a 10-in valve that had been prevented from closing the last %-inch by a fine powder of carbon and iron oxide. A university has 1200 full-time employees. c. What did you observe to make you leave? What conclusions might you reach about the attitudes of the people who manage and operate this store? b. a. After all. 1-16. Extinguishment. What did you observe tomake youleave? What . allowing liquid butane to be released. took 2% hours. When the flange was opened. a number of unsafe practices are performed at the plant. He is a few years away from retirement after working his way up from the very bottom. f. fearing that the plant might explode at any moment. this powder blew out. You have just begun work at a chemical plant. What is the worst thing that could happen to you as a chemical engineer in industry? 1-15. The other employees elsewhere in the plant site. The president of the company. You bring up these problems to your immediate supervisor. breaking piping -which added more fuel to the fire. What is the appropriate response from the following groups? a.000. d. Do the accident statistics support this claim? In 1984 the airline industry posted 4 deaths per 10. The airline industry claims commercial airline transport has fewer deaths per mile than any other means of transportation. who manually charged the wrong ingredient to a reactor vessel. "We've operated this plant for 40 years without an accident. preferring not to do any business there. The other employees who work in the process area affected. After several weeks on the job you determine that the plant manager runs the plant with an iron fist. The union. what would you emphasize? 1-11. Middle management. 1-10. Compute the OSHA incidence rate based on injuries and lost workdays. Also. What conclusions can you derive from Figure 1-9? 1-14. including some that could lead to catastrophic results. In a particular year this university had 38 reportable lost-time injuries with a resulting 274 lost workdays." What would you do in this situation? 1-17. Based on the causes of the largest losses (Figure 1-7). b. 1-8. You walk into a store and after a short while you decide to leave. An explosion has occurred in your plant and an employee has been killed. You walk into a chemical plant and after a short while you decide to leave. Based on workplace fatalities (Figure 1-4) and assuming you are responsible for a safety program of an organization. achieved basically by isolating the fuel sources. What additional information is required to compute a FAR? a fatality rate? 1-9. Upper management. but he decides to do nothing for fear that the plant manager will be upset. After reviewing the answers of Problems 1-10 and 1-11.

the operator closes the valve to stop the filling. which flashes into vapor and ruptures the tank. and toxic liquid sprays throughout the work area. The operator first opens a valve on a supply line and carefully watches the level on a level indicator until the tank is filled (a long time later). Can you explain? 1-19.32 Chapter 1 Introduction conclusions might you reach about the attitudes of the people who manage and operate this chemical plant? Comment on the similarities of parts a and b. the tank contains residual water. Unfortunately. The level gauge was calibrated to work with a liquid having a specific gravity of 0. If the usual liquid is replaced with a new liquid with a specific gravity of 0. What happened? 1-20. What is the ratio in volume between water vapor at 300 K and liquid water at 300 K at saturated conditions? b. To prevent this. Water will flash into vapor almost explosively if heated under certain conditions. drained. A cover plate on a pump housing is held in place by eight bolts. What will happen if the pump continues to operate? 1-24. On one unit the equipment was numbered JlOOl upward. Unfortunately. This can lead to pump damage and/or a rapid increase in the temperature of the liquid shut inside the pump. 1-18. The liquid level in a tank 10 m in height is determined by measuring the pressure at the bottom of the tank. Once the filling is complete. causing an upset in the plant. What is this procedure? 1-21. what is the maximum temperature increase expected in the water in "Clhr? Assume a constant water heat capacity of 1kcal/kg/"C. Hot oil is accidentally pumped into a storage vessel. If the tank is 10 m in diameter and 5 m high. A pipe fitter is instructed to repair the pump. Pumps can be shut-in by closing the valves on the inlet and outlet sides of the pump. A screwdriver is used to pry off the cover. the tank now overfills twice per year.8. however. how many kilograms of water at 300 K are required to produce .9. If the pump is rated at 1HP. With the installation of the alarm. An operator was verbally told to prepare pump JAlOOl for repairs. what is the reading on the level gauge? Is it possible that the tank will overflow without the level gauge indicating the situation? 1-22. an alarm was installed on the level gauge to alert the operator to a high-level condition. and cleaned before repair. he prepared pump Jl001 instead. The fitter removes all eight bolts only to find the cover plate stuck on the housing. One of the categories of inherent safety is simplificationlerror tolerance. The cover flies off suddenly. a. Clearly the pump unit should have been isolated. When the original allocation of numbers ran out the new equipment was numbered JAlOOl upward. Once a year the operator is distracted and the tank is overfilled. A particular pump contains 4 kg of water. What instrumentation could you add to the tank described in Problem 1-21 to eliminate problems? 1-23. There is. a better procedure for removing the cover plate. will the tank be overfilled or underfilled? If the actual liquid level is 8 m. A large storage tank is filled manually by an operator. Careful numbering of process equipment is important to avoid confusion.

During a maintenance procedure. Large storage tanks are designed to withstand low pressures and vacuums. a.. You are unable to identify the contents of the drum. She said that she routinely performed this operation years ago. what is the resulting pressure (in inches of water gauge) if the person's weight is distributed across the entire roof? b. A large storage tank was sucked in when the vent to the outside became plugged and the operator turned on the pump to empty the tank. At about 4 A. The plant has been down for extensive maintenance and repair. based on the FAR? 1-27. A car leaves New York City and travels the 2800-mi distance to Los Angeles at an average speed of 50 mph. followed by considerable damage to the column. An experienced maintenance person suggests that she can remove the slip plate without depressurizing the line. During normal operation. Since you are in charge. 1-30. Consider liquid water at 25°C and 1 atm. This is identical to the OSHA incidence rate based on incidents in which the employee is unable to continue their normal duties. the burst pressure of the tank? 1-25. If the roof was flooded with 8 in of water (equivalent to the maximum pressure). water was trapped between two valves. what would you do? . If a 200-lb person stands in the middle of the tank roof. If the plant had 2 lost-time incidents last year. 1-29. .M. There are many ways to solve this problem. Typically they are constructed to withstand no more than 8 in of water gauge pressure and 2. one valve was opened and the hot oil came in contact with the cold water.5 in of water gauge vacuum. what is the LTIR? 1-26. A plant site has 1200 full-time employees working 40 hrlweek and 50 weekslyr. What are the FARs for the two methods of transportation? Which travel method is safest. You are in charge of bringing the plant up and on-line. A 50-gal drum with bulged ends is found in the storage yard of your plant. Please describe just one approach. A particular tank is 30 ft in diameter. Problems 33 enough water vapor to pressurize the tank to 8 in of water gauge pressure. An alternative travel plan is to fly on a commercial airline for 4%hr. A slip plate or blind has accidentally been left in one of the process lines. what is the total weight (in pounds) of the water? c. How did this happen? Note: A person can easily blow to a pressure of greater than 20 in of water gauge. There is considerable pressure from the sales department to deliver product. A column was used to strip low-volatile materials from a high-temperature heat transfer fluid. Another way of measuring accident performance is by the LTIR. The result was almost sudden vaporization of the water. or lost-time injury rate. Develop a procedure to handle this hazard. How many times does the volume increase if the water is vaporized at 100°C and 1 atm? 1-28. a problem develops.

.

a topic considered in chapter 3. there is none which is not a poison. the way toxicants are eliminated from biological organisms. fibers. an early investigator of toxicology during the 1500s. The right dose differentiates a poison and a remedy. and radiation. the word poison could not be defined adequately. stated the problem: "All substances are poisons. toxicology is more adequately defined as the qualitative and quantitative study of the adverse effects of toxicants on biological organisms. The last area is essentially industrial hygiene.Toxicology ecause of the quantity and variety of chemicals used by the chemical process industries. A toxicant can be a chemical or physical agent. The toxic hazard of B ." Harmless substances. Toxic hazard is the likelihood of damage to biological organisms based on exposure resulting from transport and other physical factors of usage. Many years ago. The toxicity of a chemical or physical agent is a property of the agent describing its effect on biological organisms. Paracelsus. noise. Today. a known cause of lung damage and cancer. toxicology was defined as the science of poisons. Unfortunately. and methods to prevent or reduce the entry of toxicants into biological organisms. including dusts. only harmless ways of using substances. A good example of a physical agent is asbestos fiber. such as water. A fundamental principle of toxicology is There are no harmless substances. chemical engineers must be knowledgeable about the way toxicants enter biological organisms. The first three areas are related to toxicology. can become fatal if delivered to the biological organism in large enough doses. the effects of toxicants on biological organisms.

2-1 How Toxicants Enter Biological Organisms For higher-order organisms the path of the chemical agent through the body is well defined. dermal absorption: through skin membrane. The toxicity. A common misconception is that damage occurs in the organ where the toxicant is most concentrated. inhalation. The blood-level concentration is a function of a wide range of parameters. Toxicants enter biological organisms by the following routes: ingestion: through the mouth into the stomach.Chapter 2 Toxicology a substance can be reduced by the application of appropriate industrial hygiene techniques. Toxicants entering through ingestion are frequently modified or excreted in bile. cannot be changed. Some toxicants are absorbed rapidly through the skin. it moves into the bloodstream and is eventually eliminated or it is transported to the target organ. Figure 2-1 shows the expected blood-level concentration as a function of time and route of entry. the usual exposure is by vapor. and dermal absorption generally result in the toxicant entering the bloodstream unaltered. is stored in humans mostly in the bone structure. injection: through cuts into the skin. After the toxicant enters the organism. Lead. Injection usually results in the highest blood-level con- Table 2-1 Entry route Ingestion Inhalation Injection Entry Routes for Toxicants and Methods for Control Entry organ Mouth or stomach Mouth or nose Cuts in skin Skin Method for control Enforcement of rules on eating. hoods. and smoking Ventilation. respirators. Injection. Of the four routes of entry. Inhalation is the easiest to quantify by the direct measurement of airborne concentrations. for instance. but small solid and liquid particles can also contribute. For corrosive chemicals the damage to the organism can occur without absorption or transport through the bloodstream. and other personal protection equipment Proper protective clothing Proper protective clothing Dermal absorption . All these entry routes are controlled by the application of proper industrial hygiene techniques. inhalation: through the mouth or nose into the lungs. the inhalation and dermal routes are the most significant to industrial facilities. These control techniques are discussed in more detail in chapter 3 on industrial hygiene. drinking. summarized in Table 2-1. Toxicants that enter by injection and dermal absorption are difficult to measure and quantify. but the damage occurs in many organs. so large variations in this behavior are expected. however. The damage is exerted at the target organ.

the skin. biotransformation. dried cells that are resistant to permeation by toxicants. its molecular weight. distribution. Gastrointestinal Tract The GI tract plays the most significant role in toxicants entering the body through ingestion. Skin The skin plays important roles in both the dermal absorption and injection routes of entry. and the respiratory system play significant roles in the various routes of entry. followed by inhalation. acidity. centration. The peak concentration generally occurs earliest with injection. The gastrointestinal (GI) tract. ingestion. Absorption also occurs through . This layer consists of dead. The type of chemical.2-1 How Toxicants Enter Biological Organisms 37 Figure 2-1 Toxic blood level concentration a s a function o route o exposure. Airborne particles (either solid or liquid) can also lodge in the mucus of the upper respiratory tract and be swallowed.-and absorption. and many other factors affect the rate of absorption. The skin is composed of an outer layer called the stratum corneum. and excretion. The rate and selectivity of absorption by the GI tract are highly dependent on many conditions. Wide variations f f f are expected as a result o rate and extent of absorption. susceptibility to attack by intestinal flora. Injection includes both entry by absorption through cuts and mechanical injection with hypodermic needles. rate of movement through the GI tract. followed by inhalation. Food or drink is the usual mechanism of exposure. molecule size and shape. and absorption. Mechanical injection can occur as a result of improper hypodermic needle storage in a laboratory drawer. ingestion.

and humidifying the air. These materials either react or dissolve in the mucus to form acids and bases. and hydroxides (ammonium hydroxide. The bronchial tubes carry fresh air from the trachea through a series of branching tubes to the alveoli. However. Fresh air brought in through the nose is completely saturated with water and regulated to the proper temperature by the time it reaches the larynx. The presence of water increases the skin hydration and results in increased permeability and absorption. An estimated 300 million alveoli are found in a normal lung. The main function of the respiratory system is to exchange oxygen and carbon dioxide between the blood and the inhaled air. sinuses. These alveoli contribute a total surface area of approximately 70 m2. do show remarkable skin permeability. heating. chlorine. sodium dusts. The upper respiratory tract is responsible for filtering. oxides (nitrogen oxides. and other miscellaneous . Small capillaries found in the walls of the alveoli transport the blood. for example. however. The mucus lining the upper respiratory tract assists in filtering. hydrogen bromide). Phenol. sodium oxide). this skin demonstrates increased porosity. Lower respiratory toxicants include monomers (such as acrylonitrile). including the bronchi and the alveoli. The upper respiratory system is composed of the nose. These demands increase significantly with physical exertion. bromine). Toxicants in the lower respiratory tract affect the alveoli by physically blocking the transfer of gases (as with insoluble dusts) or reacting with the wall of the alveoli to produce corrosive or toxic substances. but this is normally negligible. A few chemicals. Most chemicals are not absorbed readily by the skin. The absorption properties of the skin vary as a function of location and the degree of hydration. pharynx (section between the mouth and esophagus). The upper and lower respiratory tracts respond differently to the presence of toxicants. The respiratory system is divided into two areas: the upper and the lower respiratory system. The alveoli are small blind air sacs where the gas exchange with the blood occurs. Approximately 8 L of air are breathed per minute. an estimated 100 ml of blood is in the capillaries at any moment. for example. and potassium hydroxides). larynx (the voice box). The skin on the palm of the hand is thicker than skin found elsewhere. The lower respiratory system is composed of the lungs and its smaller structures. sulfur oxides. The upper respiratory tract is affected mostly by toxicants that are water soluble. In 1minute a normal person at rest uses an estimated 250 ml of oxygen and expels approximately 200 ml of carbon dioxide. Upper respiratory toxicants include hydrogen halides (hydrogen chloride. resulting in higher toxicant absorption. and the trachea or windpipe. Phosgene gas. halides (fluorine.38 Chapter 2 Toxicology the hair follicles and sweat glands. mouth. Only a fraction of the total air within the lung is exchanged with each breath. Respiratory System The respiratory system plays a significant role in toxicants entering the body through inhalation. requires only a small area of skin for the body to absorb an adequate amount to result in death. reacts with the water on the alveoli wall to produce HCl and carbon monoxide.

methyl cyanide. and dermal absorption. the stored chemical agents will be released into the bloodstream. The detoxification occurs by biotransformation. or dermal absorption generally arrive in the bloodstream unchanged. Particles less than 1pm in diameter can reach the alveoli. For dusts the following simple rule usually applies: The smaller the dust particles. The final mechanism for elimination is storage. Chloroform and alcohol. and other organs. detoxification: by changing the chemical into something less harmful by biotransformation. kidneys. and lungs. skin. lungs. injection. damage can occur to the kidneys. or lungs. whereas substances that enter through inhalation. Particles that enter the alveoli are removed slowly. Particles with diameters betwcen 2 and 5 pm generally reach the bronchial system. the farther they penetrate into the respiratory system. phosgene. The toxicants are extracted by the kidneys from the bloodstream and are excreted in the urine. particularly those that are volatile. and kidney. Other routes of excretion are the skin (by means of sweat). blood. Compounds with lower molecular weights enter the bloodstream and are excreted by the kidneys. Biotransformation reactions can also occur in the blood. The kidneys are the dominant means of excretion in the human body. injection. liver. silica. and soot. are excreted partially by this route.2-2 How Toxicants Are Eliminated from Biological Organisms 39 substances such as hydrogen sulfide. In general. liver. asbestos dust. acrolein. liver. Dusts and other insoluble materials present a particular difficulty to the lungs. intestinal tract wall. significantly reducing the organism's ability to excrete the substance. resulting in possible damage. liver. The lungs are also a means for elimination of substances. For massive exposures to chemical agents. They eliminate substances that enter the body by ingestion. This process involves depositing the chemical agent mostly in the fatty areas of the organism but also in the bones. hair. and nails. storage: in the fatty tissue. inhalation. . 2-2 How Toxicants Are Eliminated from Biological Organisms Toxicants are eliminated or rendered inactive by the following routes: excretion: through the kidneys. The liver is the dominant organ in the detoxification process. Particles greater than 5 km in diameter are usually filtered by the upper respiratory system. These routes are usually minor compared to the excretion processes of the kidneys. for example. Toxicants that are ingested into the digestive tract are frequently excreted by the liver. chemical compounds with molecular weights greater than about 300 are excreted by the liver into bile. The digestive tract tends to selectively detoxify certain agents. in which the chemical agents are transformed by reaction into either harmless or less harmful substances. Storage can create a future problem if the organism's food supply is reduced and the fatty deposits are metabolized. or other organs.

and platelet count are performed easily and inexpensively. hemoglobin content. possibly as a result of fibrosis (an increase in the interstitial fibrous tissue in the lung). Nervous system disorders are diagnosed by examining the patient's mental status. to FVC X 100 (FEV. and hair and nail appearance are indicative of possible toxic exposures. Respiratory problems are diagnosed using a spirometer. An increase in the RV is indicative of deterioration of the alveoli. Measurements of the red and white blood cells. .). possibly because of emphysema. This is accomplished through a variety of medical tests. such as asthma or bronchitis. and (4) the ratio of the observed FEV. cranial nerve function. pigmentation. (3) forced expiratory flow in the middle range of the vital capacity (FEV 25-75%). The air remaining in the lung after exhalation is called the residual volume (RV). The results from these tests must be compared to a medical baseline study. Changes in skin texture. Many chemical companies perform baseline studies on new employees before employment. with units in liters. An electroencephalogram (EEG) tests higher brain and nervous system functions. marked changes are seen only after substantial exposure and damage. The patient exhales as hard and as fast as possible into the device. (2) the forced expired volume measured at 1second (FEV. The problem is to determine whether exposures have occurred before substantial symptoms are present.40 Chapter 2 Toxicology Table 2-2 Various Responses to Toxicants Effects that are irreversible Carcinogen causes cancer Mutagen causes chromosome damage Reproductive hazard causes damage to reproductive system Teratogen causes birth defects Effects that may or may not be reversible Dermatotoxic affects skin Hernotoxic affects blood Hepatoto. vascularity. and sensory systems. called the forced vital capacity (FVC). However. The RV measurement requires a specialized tracer test with helium. measured in liters per second. Blood counts are also used to determine toxic exposures. blood counts are frequently insensitive to toxic exposure. The spirometer measures (1)the total volume exhaled. performed before any exposure.wic affects liver Nephrotoxic affects kidneys Neurotoxic affects nervous system Pulmonotoxic affects lungs 2-3 Effects of Toxicants on Biological Organisms Table 2-2 lists some of the effects or responses from toxic exposure./FVC%). motor system reflexes. Reductions in FVC are due to reduction in the lung or chest volume. with units in liters per second. Reductions in expiration flow rate are indicative of bronchial disease.

For studies determining the effects on specific organs such as the lungs. The toxicant must be identified with respect to its chemical composition and its physical state. For studies of genetic effects. Chronic toxicity studies are difficult to perform because of the time involved. the period of the test.2-4 Toxicological Studies 41 Kidney function is determined through a variety of tests that measure the chemical content and quantity of urine. Each physical state preferentially enters the body by a different route and requires a different toxicological study. an exposure that results in a delayed response. Liver function is determined through a variety of chemical tests on the blood and urine. appropriate procedures are established to ensure that the agent is handled properly. The period of the test depends on whether long. For example. For early kidney damage proteins or sugars are found in the urine. . This enables researchers to apply the results obtained from small animals such as mice (fractions of a kilogram in body weight) to humans (about 70 kg for males and 60 kg for females). kidneys. most toxicological studies are based on acute exposures. Before undertaking a toxicological study. The selection depends on the effects considered and other factors such as the cost and availability of the test organism. The dose units depend on the method of delivery. higher organisms are a necessity. or liver. The test organism can range from a simple single cell up through the higher animals. 2-4 Toxicological Studies A major objective of a toxicological study is to quantify the effects of the suspect toxicant on a target organism. Once the effects of a suspect agent have been quantified. single-cell organisms might be satisfactory. For gaseous airborne substances the dose is measured in either parts per million (ppm) or milligrams of agent per cubic meter of air (mg/m3). benzene can exist in either liquid or vapor form. the effect or response to be monitored. the dose range. Chronic toxicity is the effect of multiple exposures occurring over a long period of time. The toxicological study can be complicated by latency. Acute toxicity is the effect of a single exposure or a series of exposures close together in a short period of time. the target or test organism. For most toxicological studies animals are used. the following items must be identified: the toxicant. For substances delivered directly into the organism (by ingestion or injection).For airborne particulates the dose is measured in milligrams of agent per cubic meter of air (mg/m3)or millions of particles per cubic foot (mppcf).or short-term effects are of interest. the dose is measured in milligrams of agent per kilogram of body weight. usually with the hope that the results can be extrapolated to humans.

and other factors. . A plot of the type shown in Figure 2-2 is prepared with the data. Curves of the form shown in Figure 2-2 are frequently represented by a normal or Gaussian distribution. Given the same dose of vapors. For example. Each individual is exposed to the same dose and the response is recorded. These differences are a result of age. diet. and p is the mean. general health. Consider a toxicological test run on a large number of individuals. whereas other individuals will be severely irritated (high response). given by the equation where f(x) is the probability (or fraction) of individuals experiencing a specific response. x is the response. sex. consider the effects of an irritant vapor on human eyes.42 Chapter 2 Toxicology 2-5 Dose versus Response Biological organisms respond differently to the same dose of a toxicant. a is the standard deviation. weight. some individuals will barely notice any irritation (weak or low response). L I Low response Average response High response Figure 2-2 A Gaussian or normal distribution representing the biological response to exposure to a toxicant. The fraction or percentage of individuals experiencing a specific response is plotted.

Figure 2-3 Effect of the standard deviation on a normal distribution with a mean of 0. and the standard deviation determines the shape. the distribution curve becomes more pronounced around the mean value. the response interval within 1 standard deviation of the mean represents 68% of the individuals. as shown in Figure 2-4a.5% of the total individuals (Figure 2-4b). .2-5 Dose versus Response 43 The standard deviation and mean characterize the shape and the location of the normal distribution curve. Figure 2-3 shows the effect of the standard deviation on the shape. The mean determines the location of the curve with respect to the x axis. They are computed from the original data fixi) using the equations where n is the number of data points. respectively. In particular. The quantity u 2is called the variance. As the standard deviation decreases. The area under the entire curve represents 100% of the individuals.The distribution becomes more pronounced around the mean as the standard deviation decreases. The area under the curve of Figure 2-2 represents the percentage of individuals affected for a specified response interval. A response interval of 2 standard deviations represents 95.

with 0 indicating no response and 10 indicating a high response. The responses are recorded on a scale from 0 to 10. Example 2-1 Seventy-five people are tested for skin irritation because of a specific dose of a substance.44 Chapter 2 Toxicology p-20 ~1 p+2u (b) Figure 2-4 Percentage of individuals affected based on a response between one and two standard deviations of the mean. The number of individuals exhibiting a specific response is given in the following table: .

An alternative method is to plot the percentage of individuals versus the response. Determine the mean and the standard deviation. b. The number of individuals affected is plotted versus the response.2-5 Dose versus Response 45 Response Number of individuals affected a. The histogram is shown in Figure 2-5. Plot the normal distribution on the histogram of the original data. . Plot a histogram of the number of individuals affected versus the response. Response Figure 2-5 Percentage of individuals affected based on response. c. Solution a.

we find The distribution is converted to a function representing the number of individuals affected by multiplying by the total number of individuals. Substituting the mean and standard deviations.46 Chapter 2 Toxicology b.4.51)~(10)+ (3 .4. in this case 75.51)'(5) + (2 . Table 2-3 Theoretical Frequency and Number of People Affected for Each Response for Example 2-1 . The mean is computed using Equation 2-2: The standard deviation is computed using Equation 2-3: u2 = [(I - 4. The corresponding values are shown in Table 2-3 and Figure 2-5. The normal distribution is computed using Equation 2-1.51)~(13) c.

For convenience. the response versus log dose curve of Figure 2-7 is called a lethal dose curve. as shown in Figure 2-7. This form provides a much straighter line in the middle of the response curve than the simple response versus dose form of Figure 2-6.2-5 Dose versus Response 47 Dose Figure 2-6 Dose-response curve. If the response of interest is death or lethality. the response is plotted versus the logarithm of the dose. The standard deviation and mean response are determined from the data for each dose. The bars around the data points represent the standard deviation in response to a specific dose. A typical result is shown in Figure 2-6. The toxicological experiment is repeated for a number of different doses. . A complete dose-response curve is produced by plotting the cumulative mean response at each dose. Error bars are drawn at +a around the mean. This form presents a much straighter function than the one shown in Figure 2-6. For comparison purposes the dose that results in 50% Logarithm of the dose Figure 2-7 Response versus log dose curve. and normal curves similar to Figure 2-3 are drawn.

Finally. Furthermore.. such as liver or lung damage). radiation. impact. TD. including exposure to heat. ED. response-dose curves are developed using acute toxicity data. toxic dose. This is called the LD. 1 0 Q (I) 50 F X 0 .- 10 EDlo ED50 TD50 LD50 Logarithm of the dose Figure 2-8 The various types o response vs. 2-6 Models for Dose and Response Curves Response versus dose curves can be drawn for a wide variety of exposures. the response-log dose curve is called the effective dose (ED) curve. Other values such as LD.. For gases. or T D curve. or antagonistically (both counteract each other). Most often. synergistically (the combined effect is more than the individual effects). sex.48 Chapter 2 Toxicology a . If the response to the chemical or agent is minor and reversible (such as minor eye irritation). If several chemicals are involved. For computational purposes the response versus dose curve is not convenient. the toxicants might interact additively (the combined effect is the sum of the individual effects). if the response to the agent is toxic (an undesirable response that is not lethal but is irreversible. LC (lethal concentration) is used. ED. LD. the data are complicated by differences in group age. dose (lethal dose for 50% of the subjects). and method of delivery. the response-log dose curve is called the toxic dose. pressure. Chronic toxicity data are usually considerably different. lethal dose. lethality of the subjects is frequently reported. . an analytical equation is preferred. effective dose. and so forth are also used.. log f dose curves. and sound. or LD. are sometimes also reported. potentiately (presence of one increases the effect of the other).. For gases.. Values for ED5. The relationship between the various types of response-log dose curves is shown in Figure 2-8. LC (lethal concentration) data are used.

1971).. The probit relationship of Equation 2-4 transforms the sigmoid shape of the normal response versus dose curve into a straight line when plotted using a linear probit scale. Table 2-5 lists a variety of probit equations for a number of different types of exposures. Standard curve-fittingtechniques are used to determine the best-fitting straight line. Reprinted by permission. Probit Analysis (Cambridge: Cambridge University Press. ! The causative factor represents the dose t The probit variable Y is computed from lPhillip L. Probit Analysis. Industrial Toxicology: Safety and Health Applications in the Workplace (New York: Van Nostrand Reinhold.' For single exposures the probit (probit = probability unit) method is particularly suited. The probit variable Y is related to the probability P by2 Equation 2-4 provides a relationship between the probability P and the probit variable Y. 23. J. Finney. Williams and James L. (Source: D. eds. 23. 3d ed. p. p. . 1971). providing a straight-line equivalent to the response-dose curve. as shown in Figure 2-10. 1985).2-6 Models for Dose and Response Curves Percentages Figure 2-9 The relationship between percentages and probits. (Cambridge: Cambridge University Press. 2D. Burson. Finney. Many methods exist for representing the response-dose curve. J. 379. This relationship is plotted in Figure 2-9 and tabulated in Table 2-4. p.

p..- - - - 'D.. Source: D.50 Chapter 2 Toxicology Table 2-4 Transformation from Percentages to Probits1 . (Cambridge: Cambridge University Press. J. Finney. Probit Analysis. .(Cambridge: Cambridge University Press. 1971). J. Finney. 25. Log Dose Figure 2-10 The probit transformation converts the sigmoidal response vs. 1971). 3d ed. Prohlt Analysi~. p. Reprinted by permission. 24. log dose curve into a straight line when plotted on a linear probit scale. Reprinted by permission.

92 1.'T : 2 C2.14. p.8 -18.9 -37.79 1.85 -13.0 1.82 4.1995).Guidelines for Consequence Analysis of Chemical Releases (New York: American Institute of Chemical Engineers. 1986).O 2.85 3." in Proceedings of the29th Loss Prevention Symposium (American Institute of Chemical Engineers.'T -46.2-6 Models for Dose and Response Curves 51 Table 2-5 Probit Correlations for a Variety of Exposures (The causative variable is representative of the magnitude of the exposure.1 -27. ."T I C'.56 2. July 31.26 2.51 1.0~ C C1.'T Z c2.98 -8.'T Z C1.29 -6. Purgh.O 0. 1999).79 -19.79 4. 3Richard W.1 -39.'T Z C1.1 -23.67 -6.19 -16.27 -7. 254.7 0.69 0. ZCCPS. p.9 k 2 ire' Burn deaths from flash fire Burn deaths from pool burning Explosion' Deaths from lung hemorrhage Eardrum ruptures Deaths from impact Injuries from impact Injuries from flying fragments Structural damage Glass breakage Toxic release2 Ammonia deaths Carbon monoxide deaths Chlorine deaths Ethylene oxide deaths" Hydrogen chloride deaths Nitrogen dioxide deaths Phosgene deaths Propylene oxide deaths Sulfur dioxide deaths Toluene teI:'3/104 tZ4'"1o4 PO 2.OT C C2. Lees.42 -15.45 4. I.4 3. = effective radiation intensity (W/m2) t = time duration of pool burning (s) I = radiation intensity from pool burning (W/mz) p" = peak overpressure (N/m2) J = impulse (N s/m2) C = concentration (ppm) T = time interval (min) 'Selected from Frank P.OT Z C2. "Quantitative Evaluation of Inhalation Toxicity Hazards.56 Po J J J Po Po C C2.92 2. Loss Prevention in the Process Industries (London: Butterworths.'T Z C1.9 .) Probit parameters Type of injury or damage Causative variable 4 -14. 208.1 -35.41 ! = effective time duration (s) .

Example 2-2 Determine the percentage of people who will die as a result of burns from pool burning if the probit variable Y is 4. Example 2. A.500 84.3 Eisenberg? reported the following data on the effect of explosion peak overpressures on eardrum rupture in humans: Percentage affected 1 10 50 90 Peak overpressure (N/m2) 16. The results are: Percentage Probit ?N.500 19. as shown in Table 2-5.52 Chapter 2 Toxicology For spreadsheet computations a more useful expression for performing the conversion from probits to percentage is given by where erf is the error function. Solution The percentage is converted to a probit variable using Table 2-4.300 43. Vulnerability Model: A Simulutton System for Assessing Damage Resulting from Marine Spills. Eisenberg. 1975). .300 Confirm the probit correlation for this type of exposure. and other software programs. as follows: where the error function is a mathematical function found in spreadsheets. NTIS Report AD-A015-245 (Springfield. VA: National Technical Information Service. Mathcad. The same percentage can be computed using Equation 2-6. Compare results from Table 2-4 and Equation 2-6. Solution The percentage from Table 2-4 is 27%.39.

The straight line verifies the values reported in Table 2-5. The sigmoid curve of Figure 2-11 is drawn after converting the probit correlation back to percentages. Figure 2-12 is a plot of the probit variable (with a linear probit scale) versus the natural logarithm of the peak overpressure.2-6 Models for Dose and Response Curves 53 90 - 80 - u I J a. 302010- 10 11 9 12 In (Overpressure. 7 + C I a e. 706050. This demonstrates the classical sigmoid shape of the response versus log dose curve. Figure 2-11 is a plot of the percentage affected versus the natural logarithm of the peak overpressure. N/mZ) Figure 2-11 Percentage affected versus the natural logarithm of the peak overpressure for Example 2-3. 40- - +- U a. In (Overpressure. ~ / r n ~ ) Figure 2-12 Probit versus the natural logarithm of the peak overpressure for Example 2-3. .

called threshold limit values (TLVs).5-5 g 5-15 g >15 g Probable lethal dose for a 70-kg person A taste A teaspoonful An ounce A pint A quart More than a quart 'N. There are three different types of TLVs (TLV-TWA. This table covers a range of doses from 1. p. called a permissible exposure level (PEL). Below this dose the body is able to detoxify and eliminate the agent without any detectable effects. per kilogram of body weight <1. If the slopes of the curves differ substantially. eight hours per day and five days per week..0 -50 mg 50 -500 mg 0. Dangerous Properties of Industrial Materials (New York: Van Nostrand Reinhold. The complete data show that chemical B is more toxic at lower doses. More TLV-TWA data are available than TWA-STEL or TLV-C data. 1984). Care must be taken when comparing two response-dose curves when partial data are available. The American Conference of Governmental Industrial Hygienists (ACGIH) has established threshold doses. but for small doses the response is not detectable.Chapter 2 Toxicology Table 2-6 Hodge-Sterner Table for Degree of Toxicity1 Degree of toxicity Dangerously toxic Seriously toxic Highly toxic Moderately toxic Slightly toxic Extremely low toxicity Experimental LD. TLV-STEL. Toxicants are compared for relative toxicity based on the LD. . If only a single data point is available in the upper part of the curves. The exposure occurs only during normal working hours. then chemical A is more toxic. ED. The TLV was formerly called the maximum allowable concentration (MAC). In reaIity the response is only identically zero when the dose is zero. OSHA has defined its own threshold dose. If the response-dose curve for chemical A is to the right of the response-dose curve for chemical B. The TLV refers to airborne concentrations that correspond to conditions under which no adverse effects are normally expected during a worker's lifetime. 1. 2-8 Threshold Limit Values The lowest value on the response versus dose curve is called the threshold dose. and TLV-C) with precise definition~ provided in Table 2-7.000 mg/kg. Irving Sax. it might appear that chemical A is always more toxic than chemical B. 2-7 Relative Toxicity Table 2-6 shows the Hodge-Sterner table for the degree of toxicity.0 mg/kg to 15.0 mg 1. the situation shown in Figure 2-13 might occur. or TD curves. for a large number of chemical agents.

The maximum concentration to which workers can be exposed for a period of up to 15 minutes continuously without suffering (1) intolerable irritation. whereas toxicant B is more toxic at low doses. impair self-rescue. Short-term exposure limit. The concentration that should not be exceeded. . without adverse effects. Excursions above the limit are allowed if compensated by excursions below the limit. provided that no more than 4 excursions per day are permitted. Table 2-7 TLV type TLV-TWA Definitions for Threshold Limit Values (TLVs)' Definition Time-weighted average for a normal 8-hour workday or 40-hour work week. even instantaneously. TLV-STEL TLV-C 'TLVs should not be used for (1) a relative index of toxicity. uninterrupted exposure. with at least 60 minutes between exposure periods. and provided that the daily TLV-TWA is not exceeded. Ceiling limit. (2) chronic or irreversible tissue change. ( 2 ) air pollution work. or (3) assessment of toxic hazard from continuous. day after day. (3) narcosis of sufficient degree to increase accident proneness. Toxicant A is more toxic at high doses. to which nearly all workers can be exposed. or materially reduce worker efficiency.2-8 Threshold Limit Values 55 Logarithm of the Dose Figure 2-13 Two toxicants with differing relative toxicities at different doses.

TLVs are often somewhat more conservative.. Another quantity frequently reported is the amount immediately dangerous to life and health (IDLH). or. mg/m3or mppcf (millions of particles per cubic foot of air). the PEL values are not as numerous and are not updated as frequently. These toxicants have zero thresholds. TLV and PEL values for a variety of toxicants are provided in Table 2-8.56 Chapter 2 Toxicology PEL values follow the TLV-TWA of the ACGIH closely. For vapors. for dusts. mg/m3 (milligrams of vapor per cubic meter of air). 25°C PPm mg/m3. P i s the absolute pressure in atm.. Table 2-8 TLVs and PELSfor a Variety of Chemical Substances TLV-TWA2 OSHA PEL3 PPm Acetaldehyde Acetic acid Acetone Acrolein Acrylic acid (skin) Acrylonitrile4(skin) Ammonia Aniline (skin) Arsine ~enzene~ Biphenyl Bromine Butane Caprolactum (vapor) Carbon dioxide Carbon monoxide Carbon tetrachloride4 (skin) Chlorine mg lm3. TLVs are reported using ppm (parts per million by volume). For some toxicants (particularly carcinogens) exposures at any level are not permitted. = Concentration in ppm = - 22. 25°C . Exposures to this quantity and above should be avoided under any circumstances. However.4 T M 273 (-) (i) (mgim3) where T is the temperature in degrees Kelvin. mg/m3 is converted to ppm using the equation c.. and M is the molecular weight in g/g-mol.

5 11 2.2 1.1 100 200 25 10 100 400 10 100 200 1000 1 1 400 10 0.5 0.9 1 610 (continued) . 25°C 50 1030 200 100 1010 1720 0.6 1.5 0.37 9.1 400 790 75 18 360 1400 18 435 890 2600 4 2 1200 25 0.25 200 mg/m3.1 100 400 500 0.3 2 0.2-8 Threshold Limit Values 57 Table 2-8 (continued) TLV-TWA~ OSHA PEL3 Substance' Chloroform4 Cyclohexane Cyclohexanol (skin) Cyclohexanone (skin) Cyclohexene Cyclopentane Diborane 1.7 176 7.2 435 22 2600 40 2 1200 1.1 100 200 5 200 10 25 400 5 100 5 1000 10 1 400 0.1 405 790 15 705 18 90 1400 9.4 14 1 150 983 1040 0.l Dichloroethane 1.3 5 2 300 400 1 50 TLV-C: 5 TLV-C: 10 TLV-C: 3 1 10 TLV-C: 0.1 50 400 250 0.5 1 0.4 28 1 300 980 2100 0.1 0.2 Dichloroethylene Diethylamine Diethyl ketone Dimethylamine Dioxane (skin) Ethyl acetate Ethylamine Ethyl benzene Ethyl bromide Ethyl chloride Ethylene dichloride Ethylene oxide4 Ethyl ether Ethyl mercaptan Fluorine Formaldehyde4 Formic acid Furfural (skin) Gasoline Heptane Hexachloroethane Hexane Hydrogen chloride Hydrogen cyanide (skin) Hydrogen fluoride Hydrogen peroxide Hydrogen sulfide Iodine Isobutyl alcohol Isopropyl alcohol Isopropyl ether Ketene Maleic anhydride Methyl acetate PPm 10 300 50 25 300 600 0.25 200 mg/m3.9 1 606 PPm 50 300 50 50 300 0. 25°C 240 1050 200 200 1015 0.6 1.4 8 900 1600 9.1 9 20 2000 10 1800 7 11 2.75 5 5 500 1 500 5 10 3 1 20 0.

58 Chapter 2 Toxicology Table 2-8 (continued) TLV-TWA2 OSHA PEL3 PPm Methyl acetylene Methyl alcohol Methylamine Methyl bromide (skin) Methyl chloride Methylene chloride4 Methyl ethyl ketone Methyl formate Methyl isocyanate (skin) Methyl mercaptan Naphthalene Nitric acid Nitric oxide Nitrobenzene (skin) Nitrogen dioxide Nitromethane Nonane Octane Oxalic acid Ozone Pentane Phenol (skin) Phosgene Phosphine Phosphoric acid Phthalic anhydride Pyridine Styrene Sulfur dioxide Toluene (skin) Trichloroethylene Triethylamine Turpentine Vinyl acetate Vinyl chlorides Xylene mg lm3. 5th ed.25°C PPm mg/m3. 2000).cdc.gov/niosh. 25°C 'Latest NIOSH Pocket Guide information is available at the NIOSH web site: https//www. (Cincinnati: American Conference o f Governmental Industrial Hygienists. 1991-1994). 4Possible carcinogen. 'NIOSH Pocket Guide to Chemical Hazards (Cincinnati: National Institute for Occupational Safety and Health. 'Human carcinogen. 2Documentation of the Threshold Limit Values and Biological Exposure Indices. .

T. 1986). Probit Analysis D. Martin. Williams and James L. 1985). Phillip L. 5J. The rotenone was applied in a medium of 0. 20. 14. 2d ed. J. and cannot be used to assess the impact of continuous exposures to toxicants.Problems 59 The ACGIH clearly points out that the TLVs should not be used as a relative index of toxicity (see Figure 2-8). (1942). Fawcett and William S. Irving Sax. J. 29: 69-81. Integrated Risk Information System (IRIS) (Cincinnati: Center for Environmental Research Information.. "The Problem of the Evaluation of Rotenone-Containing Plants. 2d ed. should not be used for air pollution work. Finney. Loss Prevention in the Process Industries. Wood. with Further Observations on the Rotenone Equivalent Method of Assessing the Toxicity of Derris Root..5% saponin. Biol. and 25. 1991). 5th ed. 6th ed.p. Suggested Reading Toxicology Howard H. Finney4 reported the data of Martin5involving the toxicity of rotenone to the insect species Macrosiphoniella sanborni. Lees. 1971).15. Threshold Limit Values Documentation of the Threshold Limit Values and Biological Exposure Indices. . Health Effects Assessment Summary Tables (HEASH). (New York: Van Nostrand Reinhold. Derive Equation 2-7. Every effort must be made to reduce worker exposures to toxicants to below the PEL and lower if possible. Lees. Frank P. The TLV assumes that workers are exposed only during a normal eight-hour workday. The Toxicity of 1Elliptone and of Poisons Applied Jointly. eds. Probit Analysis (Cambridge: Cambridge University Press. sec. 1984). VI. Finney. eds. 207. OERR 9200. Safety and Accident Prevention in Chemical Operations. (New York: Wiley. Dangerous Properties of Industrial Materials. 4D. Industrial Toxicology: Safety and Health Applications in the Workplace (New York: Van Nostrand Reinhold. 1996). 1986). 1. (London: Butterworths. updated regularly). Problems 2-1. Frank P. p. Probit Analysis (Cambridge: Cambridge University Press. 1971).6-303 (Cincinnati: Center for Environmental Research Information. Burson. (Cincinnati: American Conference of Governmental Industrial Hygienists." Ann. Appl. Loss Prevention in the Process Industries (London: Butterworths. 1982). 2-2. ch. N.

A certain volatile substance evaporates from an open container into a room of volume 1000 ft3. 2-5. how many ft3/min of fresh air must be supplied to ensure that the concentration of the volatile is maintained below its TLV of 100 ppm? The temperature is 77°F and the pressure is 1atm. The evaporation rate is determined to be 100 mglmin. where P is the overpressure in psi and r is the distance from the blast in feet.1. b. What fraction of structures will be damaged by exposure to this overpressure? What fraction of people exposed will die as a result of lung hemorrhage? What fraction will have eardrums ruptured? What conclusions about the effects of this blast can be drawn? 2-4. Compare the probit and number of insects affected predicted by the straight-line fit to the actual data. A blast produces a peak overpressure of 47. plot the percentage of insects affected versus the natural logarithm of the dose. part c. How would poor mixing affect the quantity of air required? 2-6. the data were represented by the normal distribution function .000 N/m2. The plant employs 500 people who work in an area from 10 to 500 ft from the potential blast site.8 log r. The insects were examined and classified one day after spraying. The peak overpressure expected as a result of the explosion of a tank in a plant facility is approximated by the equation log P = 4. determine a straight line that fits the data. If the air in the room is assumed to be well mixed. 2-3.60 Chapter 2 Toxicology containing 5% alcohol. Be sure to state any additional assumptions. Convert the data to a probit variable. Estimate the number of fatalities expected as a result of lung hemorrhage and the number of eardrums ruptured as a result of this blast. Assume a volatile species molecular weight of 100. In Example 2-1.2 . and plot the probit versus the natural logarithm of the dose. From the given data. If the result is linear. Under most circumstances the air in a room cannot be assumed to be well mixed. The obtained data were: Dose of rotenone (mg/l) Number of insects Number affected a.

The NIOSH web site states that deaths occur as a result of ammonia exposures between 5. 150 pprn for 2 hours.cdc.7899. 2-18. 58.Problems 61 Use this distribution function to determine the fraction of individuals demonstrating a response between the range of 2.000 and 10. and chlorine. carbon monoxide. The following physical property data are for acetone: molecular weight.5. Use the NIOSH web site to determine and compare the PEL and the IDLH concentration of ethylene oxide and ethanol. ethylene oxide.gov/niosh) to acquire the meaning and definition of IDLH concentration. Use the probit equation (Equation 2-5) to determine the expected fatalities for people exposed for 2 hours to each of the IDLH concentrations of ammonia. Use the NIOSH web site to determine an escape time period for a person subjected to an IDLH concentration. Use Equation 2-7 to convert the TLV in pprn to the TLV in mg/m3for benzene. and hydrogen chloride.1. and hydrogen chloride. 2-11. 2-9. ethylene trichloride. in minutes. b. Determine the expected number of fatalities. 2-13. Determine the duration times. Use the NIOSH web site to determine the number of deaths that occurred in 1992 as a result of asbestos. fluorine. 2-14. ethanol. How much acetone liquid (in milliliters) is required to produce a vapor concentration of 200 pprn in a room of dimension 3 X 4 X 10 m? The temperature is 25°C and the pressure is 1 atm. and ethylene oxide. 2000 pprn for 2 hours. Determine the concentration of ethylene oxide that will cause a 50% fatality rate if the exposure occurs for 30 min. IDLH concentration. and specific gravity. d. 300 pprn for 3 hours. benzene. . c. Assume 25°C and 1 atm.5 to 7. 2-7. 2-10. and TLV for ethylene oxide. 2-17. Use the NIOSH web site to determine and compare the PEL. 2-12. 1000 pprn for 1hour. 2-19. how many deaths will be expected? a. Compare the result to the results from the probit equation (Table 2-5). A group of 100 people is exposed to phosgene in two consecutive periods as follows: (a) 10 pprn for 30 min and (b) 1 pprn for 300 min.for ammonia. 2-15. 2-20. 2-8. that a group of 100 people can be exposed to 1500 pprn of carbon monoxide to result in (a) 0% fatalities and (b) 50% fatalities. If 500 workers in a plant are exposed to the following concentrations of ammonia for the given number of hours. IDLH concentration. Use the NIOSH web site (www. 2-16. Use the NIOSH web site to determine and compare the PEL. chlorine. and LC5(. 0. carbon monoxide.000 pprn over a 30-min period.

Lotus. Using the following data.: Dose of rotenone (mg/l) 10. 1998). 2-24.. b.28 to percentage affected. medium. Use a small enough distance increment so that the results are essentially independent of the increment size. 2-25. low) for the single dose of a chemical that causes 50% deaths. 100 pprn for 5 min. Your spreadsheet output should have designated columns for the distance.1 3. Use Joseph F. NJ: Prentice Hall. Health and Environmental Risk Analysis. 5. b. Health and Environmental Risk Analysis: Fundamentals with Applications (Upper Saddle River. 287288. Determine the potential deaths resulting from the following exposure to chlorine: a. percentages. 2-26. medium. Use the results of Problem 2-21 to establish the recommended distance between the control room and the tank if the control room is designed to withstand overpressures of (a) 1psi and (b) 3 psi. 2-29. c. 100 pprn for 50 min. and compare with the values shown in Table 2-4. 50 pprn for 2 min. Louvar and B. probit values.72. Estimate the exposure concentration in pprn that will result in fatalities for 80% of the exposed individuals if they are exposed to phosgene for 4 min. low) for the inhalation of toxic chemicals. to find the toxicity levels (high. pressure. use a lookup function or an equivalent function.7 5. Use Equation 2-6 to convert probits of 3. c. Use Louvar and Louvar. 2-23. "2-30. determine the probit constants and the LC. Diane Louvar. and 6. and the number of individuals affected for each increment. Excel) to solve Problem 2-4. You should also have two spreadsheet cells that provide the total number of individuals with eardrum ruptures and lung hemorrhage deaths.2 2 . 2-27. Determine the potential deaths resulting from the following exposure to chlorine: a. Estimate the exposure concentration in pprn that will result in fatalities for 80% of the exposed individuals if they are exposed to chlorine for 4 min. Break the distance from 10 ft to 500 ft into several intervals. 200 pprn for 15 min. 287-288. 50 pprn for 20 min. 4 .8 2.2 7. For converting from probits to percentages. Use a spreadsheet program (such as QuattroPro. pp. 2-28. pp.0.62 Chapter 2 Toxicology '2-21. to find the toxicity levels (high. 200 pprn for 150 min.6 Number of insects 50 49 46 48 50 Number affected (deaths) 44 42 24 16 6 .

Typical projects involving industrial hygiene are monitoring toxic airborne vapor concentrations. reducing toxic airborne vapors through the use of ventilation. In this chapter we describe the relationship between laws and regulations as an introduction to industrial hygiene. evaluation. The three phases in any industrial hygiene project are identification. developing procedures for the handling of hazardous materials. and control: Identification: determination of the presence or possibility of workplace exposures. and other physical factors to ensure that workers are not exposed to harmful levels. radiation. and monitoring and reducing noise. selecting proper personal protective equipment to prevent worker exposure. and control of occupational conditions that cause sickness and injury. heat. Industrial hygiene is a science devoted to the identification. Industrial hygienists are also responsible for selecting and using instrumentation to monitor the workplace during the identification and control phases of industrial hygiene projects. Evaluation: determination of the magnitude of the exposure. the industrial hygienist makes recommendations relevant to control I . Many of the results in this area are due to civic concern and ethics. sometimes manifested in laws and regulations. evaluation.Industrial Hygiene ndustry and society are continuing to focus on reducing personnel and environmental damage resulting from accidents. Control: application of appropriate technology to reduce workplace exposures to acceptable levels. In chemical plants and laboratories the industrial hygienist works closely with safety professionals as an integral part of a safety and loss prevention program. After identifying and evaluating the hazards.

safety professionals. To make the laws work on a day-today level. becomes a law. quantities of the toxic chemicals that are legally emitted into the air. To put these laws into effect. After the regulation is in effect. Regulations set specific rules about what is legal and what is not legal. If approved. and what penalties are given if the legal limits are exceeded. Congress authorizes governmental organizations.64 Chapter 3 Industrial Hygiene techniques. For example. Congress authorizes certain government organizations. who has the option to either approve it or veto it.] The code is the official record of all federal laws. A bill is a document that. including the EPA and OSHA. including the Environmental Protection Agency (EPA) and OSHA. Congress is responsible for passing laws that govern the United States. Step 2: If both houses of Congress approve the bill. . it is sent to the president. the USC requires the appropriate respirator protection. For example. how is it put into practice? Laws often do not include the details for compliance. but it does not specify the detailed types or limitations of respirators. the EPA has the responsibility (1) to help citizens comply with the law and (2) to enforce the regulation. Step 3: The complete text of the law is published in the United States Code (USC). it becomes a law that is called an act. and plant operations personnel work together to ensure that the control measures are applied and maintained. to create and enforce regulations. Creating a Law A law is created with a three-step process: Step 1:A member of Congress proposes a bill. to create regulations and/or standards. Creating a Regulation After the law is official. 3-1 Government Regulations Laws and Regulations Laws and regulations are major tools for protecting people and the environment. It has been clearly demonstrated that toxic chemicals can be handled safely when principles of industrial hygiene are appropriately applied. The industrial hygienist. a regulation relevant to the Clean Air Act will specify levels of specific toxic chemicals that are safe. if approved.

and (4) training professionals for administering the programs of the act. B. To appreciate the significance of the OSHAct. Fundamentals of Industrial Hygiene.3-1 Government Regulations 65 The process for creating a regulation andlor standard has two steps: Step 1:The authorized organization or agency decides when a regulation is needed. 758-777.. which manages and administers the government's responsibilities specified in the OSHAct. The concepts promulgated by the Walsh-Healy Act. sufficient funding was committed to create and support the Occupational Safety and Health Administration (OSHA). pp. and proposes a regulation. 2d ed. and it is simultaneously codified by publishing it in the Code of Federal Regulations (CFR). it is helpful to review regulations and practices2 before 1970. Olishifski. In 1970 the US Congress enacted a health and safety law that continues to have a significant impact on the practices of industrial hygiene in the chemical industry: the Occupational Safety and Health Act of 1970 (OSHAct). As a result of the OSHAct. these regulations were never sufficientlysupported to carry out a satisfactory program. The organization then researches. ' NIOSH develops data and information regarding hazards. The proposal is listed in the Federal Register (FR) so that the public can evaluate it and send comments to the organization. (2) developing criteria for handling toxic materials. These comments are used to revise the regulation. and developing and maintaining safety and health records. although not adequate by today's standards. This 1936 act also initiated significant research related to the cause. and OSHA uses these data to promulgate standards.ed. and control of occupational disease. This act defined clear procedures for establishing regulations. which conducts research and technical assistance programs for improving the protection and maintenance of workers' health. Step 2: After a regulation is rewritten. Between 1936and 1970a number of states enacted their own safety and health regulations. recognition. were the forerunners of our current occupational health and safety regulations. This produced relatively inconsistent and ineffective results. Examples of NIOSH responsibilities include (1) measuring health effects of exposure in the work environment. staffs and funds were too small to carry out effective programs. 1979). and the National Institute for Occupational Safety and Health (NIOSH). (Chicago:National Safety Council. During this era. it is posted in the Federal Register as a final rule. develops. The OSHAct of 1970 was developed to solve these problems and to give a nationally consistent program with the funding necessary to manage it effectively. (3) establishing safe levels of exposure. conducting investigations for compliance. Some laws and regulations particularly relevant to the chemical indus2J. Before 1936 regulations concerning occupational health were poorly administered by state and local governmental agencies. . Although some progress was made. In 1936 the federal government enacted the Walsh-Healy Act to establish federal safety and health standards for activities relating to federal contracts.

66 Chapter 3 Industrial Hygiene Table 3-1 Number A Few Laws (USC) and Regulations (CFR) Description Occupational Safety and Health Act (1970) Clean Air Act (1970) Clean Water Act (1977) Clean Air Act Amendments (1990) Toxic Substances Control Act I1 (1992) Safe Drinking Water Act Amendment (1996) Underground Storage Tank Leak Tests (1988) Annual Toxic Release Report. Criminal penalties can be invoked. substantial new legislation controlling the workplace and community environment has been enacted. .20 40 CFR 370. and applications of the OSHAct will continue to develop as standards are promulgated. Table 3-3 provides a summary of Table 3-2 Highlights of OSHA's Right of Enforcement Employers must admit OSHA compliance officers into their plant sites for safety inspections with no advance notice. OSHA is authorized. The OSHAct makes employers responsible for providing safe and healthy working conditions for their employees. these standards will continue to create an environment for improving process designs and process conditions relevant to the safety and health of workers and the surrounding communities. Government regulation will continue to be a significant part of the practice of chemical process safety.65 29 CFR 1910. As illustrated in this table. SARA 311 (1991) Process Safety Management (1992) Risk Management Program (1996) Respirator Program (1998) 29 USC 651 42 USC 7401 33 USC 1251 42 USC 7401 15 USC 2601 42 USC 300f 40 CFR 280. to conduct inspections. Highlights of OSHA enforcement rights are illustrated in Table 3-2. SARA 313 (1989) Training.1450 40 CFR 370.119 40 CFR 68. they can issue citations and financial penalties. The implications. interpretations. OSHA officers finding conditions of imminent danger may request plant shutdowns. Especially within the chemical industry. and when violations of the safety and health standards are found. however. OSHA's right of inspection includes safety and health records.30 29 CFR 1910. Hazardous Materials Technician.20 29 CFR 1910. HAZMAT (1989) Exposure to Hazardous Chemicals in Laboratories (1990) Annual Inventory of Hazardous Chemicals. the distinction between laws (USC) and regulations (CFR) is global versus detail. A search warrant may be required to show probable cause. Since the OSHAct was signed into law.120 29 CFR 1910.134 try are shown in Table 3-1.

Research. Fungicide. Drug.3-1 Government Regulations 67 Table 3-3 Federal Legislation Relevant to Chemical Process Safety1 Date Abbreviation RHA FDCA FIFRA DCA FWPCA FFA AEA FWA FHSA SWDA MNMSA NEPA I'MHSA "AA I'PPA WQI RSA RRA OSHA NCA FEPCA IlMTA CPSA MPRSA CWA CZMA ESA SDWA TSA ESECA TSCA RCRA FMSHA SMCRA UMTCA PTSA CERCLA HSWA AHERA SARA EPCRA TSCA Act River and Harbor Act Federal Food. and Rodenticide Act Dangerous Cargo Act Federal Water Pollution Control Act Flammable Fabrics Act Atomic Energy Act Fish and Wildlife Act of 1956 Federal Hazardous Substances Labeling Act Solid Waste Disposal Act ' Metal and Non-Metallic Mine Safety Act National Environmental Policy Act Federal Coal Mine Health and Safety Act Clean Air Act Poison Prevention Packaging Act of 1970 Water Quality Improvement Act of 1970 Federal Railroad Safety Act of 1970 Resource Recovery Act of 1970 Occupational Safety and Health Act Noise Control Act of 1972 Federal Environmental Pollution Control Act Hazardous Materials Transportation Act Consumer Product Safety Act Marine Protection. Compensation. and Cosmetic Act Federal Insecticide. and Sanctuary Act of 1972 Clean Water Act Coastal Zone Management Act Endangered Species Act of 1973 Safe Drinking Water Act Transportation Safety Act of 1974 Energy Supply and Environmental Coordination Act Toxic Substances Control Act Resource Conservation and Recovery Act Federal Mine Safety and Health Act Surface Mine Control and Reclamation Act Uranium Mill Tailings Control Act Port and Tanker Safety Act Comprehensive Environmental Response. and Liability Act of 1980 (Superfund) Hazardous and Solid Waste Amendments Asbestos Hazard Emergency Response Act Superfund Amendments and Reauthorization Act Emergency Planning and Community Right-to-Know Act Toxic Substances Control Act (continued) .

It is recognized by industry and the government as an excellent regulation that will reduce the number and magnitude of accidents -if it is understood and practiced as intended.gov/oshsrrl-toclosha-std-toc relevant safety legislation. and compositions. contractors. such as temperatures. management of change.html. OSHA published the final rule "Process Safety Management of Highly Hazardous Chemicals. emergency planning and response.1992. incident investigations. and trade secrets. Process safety management (PSM) was developed after the Bhopal accident (1985).gov/epuhome and www.epa. operating procedures. OSHA: Process Safety Management On February 24.osha-slc. and process limitations. to prevent similar accidents. it sets general requirements for the management of hazardous chemicals." This standard is performance oriented. Consequences of process deviations are also required. A description of this legislation is well beyond the scope and goals of this textbook. However.68 Chapter 3 Industrial Hygiene Table 3-3 (continued) Date Abbreviation Act WQA OPA CAAA PPA TSCA-TI - NEPA HMTAA SDWA FQPA . that is. process safety information. Employee participation requires active employee participation in all the major elements of PSM. it is important that chemical engineers be aware of the law to ensure that their facilities comply. A brief description of each section is given in what follows. process chemistry. hot work permits. Water Quality Act Oil Pollution Act of 1990 Clean Air Act Amendments Pollution Prevention Act of 1990 Residential Lead-Based Paint Hazard Abatement Act Federal Facility Compliance Act National Environmental Policy Act Hazardous Materials Transportation Act Amendments Safe Drinking Water Act Amendment Food Quality Protection Act lInformation from the EPA and OSHA web sites: www. flows. training. mechanical integrity. pressures. The PSM standard has 14 major sections: employee participation. and Figure 3-1 shows how the amount of legislation has increased. audits. This . This information includes block flow diagrams or process flow diagrams. pre-startup safety review. Process safety information is compiled and made available to all employees to facilitate the understanding and identification of hazards. process hazard analysis. Employers must develop and document a plan of action to specify this participation.

and for less complex processes a less rigorous process. and other appropriate and experienced specialists. or fault trees. industrial hygienists. chemists. including engiI . . process safety information is needed before training.3-1 Government Regulations 69 X 0 1900 1910 X I I I I I I I I 1920 1930 1940 1950 Year 1960 1970 1980 1990 I 2000 Figure 3-1 Number of federal laws relevant to chemical process safety. failure mode and effects analysis. a hazards and operability (HAZOP) study for a complex process. operators. process hazards analysis. and accident investigations. checklists. neers. . such as what-if scenarios. Process hazard analysis ( P H A ) must be performed by a team of experts. management of change. The PHA needs to include a method that fits the complexity of the process.

such as hot work. startup after normal and emergency shutdowns. special or unique hazards. . (3) the appropriate training is completed. authorization signatures. (2) training regarding preventive maintenance. The mechanical integrity section of the PSM standard ensures that the equipment. startups.70 Chapter 3 Industrial Hygiene Employers must ensure that the recommendations from the PHA are acted on in a timely manner. The requirements include (1)written procedures to maintain functioning systems. identification of openings where sparks may drop. identification of flammable materials in the area. controls. These operating procedures are updated frequently. These instructions need to be clearly written and consistent with the process safety information.. engineering and administrative controls. including emergency shutdowns. Maintenance and operations personnel receive initial training and refresher training. operating limits and consequences of deviations. relief systems. the equipment involved in the work. and emergency procedures are in place. initial startup. with the frequency being set by the operating personnel. An effective training program helps employees understand the hazards associated with the tasks they perform. the employees need to consider the contractors' safety performance in addition to their skills. quality control specifications for all chemicals. normal shutdown. . or using spark-producing equipment). the types and numbers of fire extinguishers. and safety control systems and functions. The permit requires dates authorized for hot work. and normal operations. (4) a process to correct deficiencies. Even when selecting contractors. and ( 5 ) a process to ensure that all equipment and spare parts are suitable. at a minimum. normal operations. Operators need to understand the hazards associated with every task. exposure precautions. the operators decide on the frequency of the refresher training. Refresher training is given every three years and more often if necessary. The PSM standard ascertains that a system is in place to prepare and issue hot workpermits before conducting hot work activities (welding. emergency shutdown. a system to maintain and document certification. piping. hazardous properties of the chemicals. Operating procedures that facilitate the safe operation of the plant must be documented. and alarms are mechanically sound and operational. operating. Safe work practices also need to be documented. maintenance. Every PSM process needs an updated PHA at least every five years after the initial analysis is completed. They need to cover. an inspection before the work. emergency operations. A pre-startup safety review is a special safety review that is conducted after a modification to the process or operating conditions has been made and before the startup. and (4) the recommendations from the PHA are implemented or resolved. safety and health considerations. (3) periodic inspections and testing based on vendor recommendations. Contractors are trained to perform their tasks safely to the same extent as employees. (2) the safety. temporary operations. identification of fire watches. In this review a team of reviewers ensures that (1) the system is constructed in accordance with the design specifications. grinding. and confined space. lockout/tagout.

40 CFR 68. . who are knowledgeable about the system. The RMP regulation is aimed at decreasing the number and magnitude of accidental releases of toxic and flammable substances. including operators. Employers must investigate all incidents that have or could have resulted in a major release or accident within 48 hours of the event. process equipment. and a pre-startup review is conducted. verification that combustible materials are removed or covered appropriately. whereas PSM is designed to protect on-site people. The audit reports need to be retained as long as the process exists. After the change has been made.1996). the employers are required to appropriately use the investigation recommendations. DC: US Government Printing Office. Under the audits section of the PSM standard employers are required to certify that they have evaluated their compliance with the standard at least every three years. The intent of the PSM element for emergency planning and response is to require employers to respond effectively to the release of highly hazardous chemicals. identification and closure of open vessels or ducts. 20. Under the management of change section of the PSM standard employees are required to develop and implement documented procedures to manage changes in the process chemistry. it must be reviewed to ascertain that it will not affect the safety of the operation. all the affected employees are trained. After the investigation. and veritication that welded walls are not flammable. The PSM standard mandates incident investigation.? This regulationis also a response to the Bhopal accident. The recommendations from the audit must be followed. the EPA published the Risk Management Plan (RMP) as a final rule. the RMP is designed to protect off-site people and the environment. The RMP is required for plant sites that use more "ode of Federal Regulations. Although the regulation requires this activity for companies with more than 10 employees.3-1 Government Regulations 71 verification that the surrounding area is not explosive. this element should be part of a program for even the smallest organizations that handle hazardous chemicals. Before a change occurs (except for replacementin-kind). and operating procedures. The regulation requires an investigation team composed of people. subpart B (Washington. Although the RMP is similar to the PSM regulation i n many respects. The trade secrets section of the PSM standard ensures that all contractors are given all the information relevant to operating in the plant safely.1996. Some personnel may need to sign secrecy agreements before they receive this information. Jun. It is recognized by industry and the government as an excellent regulation that will reduce the number and magnitude of accidents if it is understood and practiced as intended. EPA: Risk Management Plan On June 20.

The releases must include the worst-case scenario and the more likely but significant accident release scenarios. the standard includes lookup tables for all the listed substances to help a facility determine the impact distances for specific release scenarios. and local authorities. Those with no off-site potential damage are not required to be reported. whereas PSM covers every covered process on the site. documentation. Dispersion model calculations are normally used to estimate downwind concentrations. documentation that is maintained on the site and submitted to federal. For those not interested in using dispersion models. state. is self-explanatory. therefore the release rate for liquid spills corresponds to the evaporation rate. Hazard assessment is a consequence analysis for a range of potential hazardous chemical releases. fires. these concentrations are the basis for determining the consequences resulting from toxicity.72 Chapter 3 Industrial Hygiene than a specified threshold quantity of regulated highly hazardous chemicals. Passive mitigation measures (for example. including the history of such releases at the facility. and more likely releases are analyzed for each toxic substance covered by the rule. This information is also shared with the local community. and only one flammable substance is analyzed for other more likely scenarios. The RMP document is updated when the process or chemistry changes or when a governmental audit requests an update. dikes) can be used in the calculation process. The RMP has the following elements: hazard assessment. The release scenarios that have a potential to reach the public are of the greatest concern. emergency response program. and/or explosions.5 m/s wind speed). prevention program. Therefore the results are not a true determination of risk. The EPA requires the following consequence analyses: (1) A single worst-case release scenario is analyzed for all covered flammable materials on the site. Alternative cases for flammable substances cover scenarios that may cause substantial damage off site and on site. The fourth part. The RMP requires only an analysis of the consequence and not the probability. Alternative release cases for toxic substances cover scenarios with toxic concentrations beyond the fenceline. The worst-case scenario is based on releasing the entire contents of a vessel or piping system in a 10-minute period under worst-case meteorological conditions (F stability and 1. The first three parts of the regulation are described briefly in the following paragraphs. A risk matrix can be used to characterize the worst-case and more likely scenarios. The RMP is a site responsibility (the site may have several processes). because risk is composed of both conse- . and (2) a single worst-case release scenario is analyzed for all toxic substances on the site.

1-5. the Resource Conservation and Recovery Act (RCRA). Fortunately. As shown in Table 3-4. The prevention program has 11 elements. although differences exist because the EPA and OSHA have different responsibilities. and the second column shows the corresponding element of the prevention program (some elements have no equivalence). Training is for all employees on the topics relevant to emergency response. compared to the 14 elements of the PSM standard. pp. . It also establishes procedures for notifying the local community and the appropriate emergency response agencies. A more detailed description of the required consequence analyses can be found el~ewhere." Process Safety Progress (Spring 1997). many of these elements are duplicated.3-1 Government Regulations 73 Table 3-4 Comparison of the PSM and RMP Prevention Programs RMP (EPA) Process safety information Hazard evaluation Standard operating procedures (No equivalence) Training (No equivalence) Pre-startup review Maintenance (No equivalence) Management of change Accident investigations Emergency response Safety audits (No equivalence) Risk assessment PSM program (OSHA) Process safety information Process hazards analysis Operating procedures Employee participation Training Contractors Pre-startup review Mechanical integrity Hot work permit Management of change Incident investigations Emergency planning and response Compliance audits Trade secrets (No equivalence) quence and probability.~ The second requirement of the RMP is a prevention program. As with similar OSHA regulations. The requirements include drills to test the plan and to evaluate its effectiveness. Crowl. and the 4Daniel A. and the plan must be revised based on the findings of these drills. The plan must be coordinated with local emergency response plans developed by Local Emergency Planning Committees (LEPCs) and local emergency response agencies. "Consequence Modeling for the EPA Risk Management Plan (RMP). the EPA made a deliberate attempt to retain the same requirements wherever possible. The first column in Table 3-4 lists each element of the PSM program. The emergency response program delineates the steps to be taken by the facility's employees in response to accidental releases of hazardous materials.

The quality of this identification step is often a function of the number of resources used and the quality of the questions asked. 3-2 Industrial Hygiene: Identification One of the major responsibilities of the industrial hygienist is to identify and solve potential health problems within plants.74 Chapter 3 Industrial Hygiene Spill Prevention Control under the Clean Water Act.This list of potential hazards and their risk is used during the evaluation and control phase of the project. the potential hazards and methods of contact are identified and recorded. safety reviews. In this identification step it is often necessary to collate and integrate the available information to identify new potential problems resulting from the combined effects of multiple exposures. Material Safety Data Sheets One of the most important references used during an industrial hygiene study involving toxic chemicals is the material safety data sheet (MSDS). Resources for evaluating the hazards and developing control methods are allocated on a priority basis. the potential hazards are numerous. and management. Determining the potential for hazards to result in an accident (risk assessment) is frequently part of the identification step (see chapter 11). the emergency response plan must be maintained at the facility and must include descriptions of all mitigating systems. When toxic and/or flammable chemicals are handled. This list of potential hazards together with the required data for hazard identification (see Table 3-6) is commonly used during the identification step of industrial hygiene projects. During the identification step. As illustrated in Table 3-5. skill. and operating procedures. and attention to detail. engineers. the potentially hazardous conditions may be numerous . To achieve this operating success. process designers. and information from operating personnel. Chemical process technology. concern. To be safe under these conditions requires discipline. operating conditions. equipment vendor descriptions. The sources of information include process design descriptions. operators. especially because the listed hazards can also act in combination.in large plants there may be thousands. laboratory personnel. giving the appropriate time and attention to the most significant hazards. A sample MSDS is shown in Fig- . and managers. however. For these reasons industrial hygiene (particularly identification) must be a part of the education process of chemists. operating instructions. information from chemical suppliers. The identification step requires a thorough study of the chemical process. is so complex that this task requires the concerted efforts of industrial hygienists. The industrial hygienist helps the effectiveness of the overall program by working with these plant personnel. The different resources may have different operating and technical emphases unique to pieces of equipment or specific chemicals. all potential hazards must be identified and controlled. Many hazardous chemicals are handled safely on a daily basis within chemical plants.

(2) a commercial source. and vapors Noise levels of equipment Types and degree of radiation ure 3-2. dusts.3-2 Industrial Hygiene: Identification Table 3-5 ldentification of Potential Hazards1 Potential hazards Liquids Vapors Dusts Fumes Noise Radiation Temperature Mechanical Entry mode of toxicants Inhalation Body absorption (skin or eyes) Ingestion Injection Potential damage Lungs Ears Nervous system Kidneys Circulatory system Skin Eyes Liver Reproductive organs Other organs 'Olishifski. The industrial hygienist or safety professional must interpret the physical and toxicological properties to determine the hazards associated with a chemical. Fundamentals of Industrial Hygiene. The MSDS lists the physical properties of a substance that may be required to determine the potential hazards of the substance.- - - - Threshold limit values (TLVs) Odor threshold for vapors Physical state Vapor pressure of liquids Sensitivity of chemical to temperature or impact Rates and heats of reaction Hazardous by-products Reactivity with other chemicals Explosive concentrations of chemicals. or (3) a private library developed by the chemical plant. 24-26. . MSDSs are available from (1) the chemical manufacturer. Table 3-6 Data Useful for Health ldentification p p -. These properties are also used to develop a strategy for the proper control and handling of these chemicals. pp.

Most companies use their own MSDS format.F i r e a n d E x p l o s ~ o nHazard Data Flammable Limlls LEL UEL plash Point (MetOod Us&) Exttngu~snlng Wedla Specla1 Ffre Flgntlng P<aeducer Unusual Ftre and Ezolos on Hazards (Reproduce locallyi OSHA 174 S e ~ l1985 Figure 3-2 Material safety data sheet.l Acetale 1) - bluQ8itty tn Water Appearance and Wor Sect~on IV . .S.nea It any item e nor appncable or Pa inlormaron . Sfare and ZIP Code) U.Chapter 3 Industrial Hygiene 5-210 MATERIAL SAFETY DATA SHEET 31 9203 Mater~al Safety Data Sheet May be used to comply with OSHA s Hazard Communlcat~onStandard 25 CFR 1910 1200 Slandard must be requsements consulted lor spec111c IDENTITY (As UsW on LaOel and bslJ Sectlon I Manulacturer s Name Address (Number Street Cl3. Department of Labor O c c u ~ a ~ ~ oSafety and Health Adrnn. (optional) of S e c t l o n II .1i I 1 Vapor Pressure lmm Hg I Vapor Densty (AIR = 1) Melting Polnl €vaporarcon Rate IBu3.S av81Iable rhe space mvsr be maned ro indica e rnar Emergency TeIephone Number Telephone Numcer lor Intormat~on Dale Preparea S~gnalure Prepare.swat~on nal (Non-Mandatory Form) Form Approved OM0 No 1218-0072 @ Note Blank spaces are not perm.P h y s ~ c a l / C h e m ~ cC h a r a c t e n s t ~ c s al Speclhc Gravlv I H D .Hazardous l n g r e d ~ e n t s / l d e n t l t ylnformatlon OSHA PEL ACGlH TLV Other Ltm8ls Recommended Hazardous Components (Specific Chemcal ldenrtry Common Narnels)) P o ioplronali Sectton Ill Botllng Poinl .

Health nszard Data I Skln'J Ingestdon? Route(s)ol Enlv Health Hazards (Acvm and C h m ) Carcnnogen!ctty NTP7 IARC Morographs? OSHA Regulaled? Sagns and Symptoms or Exposure -- Medeal Condanons Generally Aggravated b . i .- - 3-2 Industrial Hygiene: Identification 77 - 31 9204 REFERENCE FILE Scctlon V SlablLn\ .Relcthrlty Data U M W Stable C o n d W to Avad --- lncompattblllty (Malertals 10 Awe H~ardous DewmpOQ~t~On BypmduM or Hazardws PolymertzaUon May Occur Wnll C o n d l t ~ Avotd lo Na Occur Inhalaton? Section Vi . Exposure Emergency and Ftrst Aid Procedures Section VII Precaut~ons Safe Handling and Use for Steps to Be Taken in Case Maler8al Is Released or Spvlled - Wane Dnsposal M a h M Plscautlons lo Be Taken m Handllng and Slorlng Ofher Precaullons - Section Vlll Ventllatlon .+l-m -5.Control Measures Local Exhaust Specla1 Olher Eye P~MBnlcn Resp~r~dwy Pmtat~on (Spany Tlpe) Mechanical (Gemw) PrMBnlva Gloves Olhw PfUBntve Cblhlng or Equtpment WwWHyglenlc Pracltcer PW 2 Q usoro 916 .

colorless liquid with no fire or explosion hazard. I. High concentrations produce a narcotic effect. Large doses can cause death. Corrosive action on all body tissues. Reacts violently with a number of substances. Highly reactive with a wide variety of substances. A wide variety of organic compounds that are mostly narcotic in effect. A skin and eye irritant. It is a possible carcinogen. Lewis. eyes. Control techniques are presented in more detail in section 3-4. Clear. colorless liquid with a slight fire hazard and moderate explosion hazard. 2000). Clear. and mucous membranes and by ingestion and inhalation. Most ethers are dangerously flammable and explosive. Irritant to skin and eyes. A white. hydrochloric acid. toluene. Absorbed readily through the skin. benzene. Acute and chronic exposures occur with concentrations greater than 200 ppm. the likelihood of large and small leaks must be considered. Hydrochloric acid Phenol Sodium hydroxide Benzene Ether 3-3 Industrial Hygiene: Evaluation The evaluation phase determines the extent and degree of employee exposure to toxicants and physical hazards in the workplace environment. ed. Identify the potential hazards in this laboratory. sodium hydroxide. 5R. No hazard.. Entry into the body is mostly by vapor inhalation. and ether. colorless liquid with a dangerous fire hazard and a moderate explosion hazard. (New York: Wiley. The following table summarizes the results: Chemical Sodium chloride Toluene Description and potential hazard Common table salt. 10th ed. . Solution Sax5 provided the technical information required to solve this problem. Clear. It is a moderate fire hazard. Sax's Dangerous Properties of Industrial Materials. During the evaluation phase. Exposures to skin areas as small as 64 in2have resulted in death in less than 1 hr.Chapter 3 Industrial Hygiene Example 3-1 A survey of a laboratory is made and the following chemical species are identified: Sodium chloride. Entry into the body is mostly by inhalation. It is a moderate irritant to the skin. Emits toxic fumes when heated. phenol. crystalline mass that is most frequently found in solution form. During the evaluation study. the various types of existing control measures and their effectiveness are also studied. Throat irritation occurs with concentrations of 35 ppm. but it is also absorbed through the skin.

Small leaks of these substances might not become obvious for months or even years. To establish the effectiveness of existing controls. burning eyes. however. Chronic effects. There may be permanent and serious impairments from such exposures. such as TLVs. is the worker shift time in hours. In this case ready access to a clean environment is important. There is rarely lasting damage to individuals if they are removed promptly from the contaminated area. if a worker is exposed for 12 hours to a concentration of chemical equal to the TLV-TWA. independent of the length of time actually worked in the shift. After the exposure data are obtained. Thus. may lead to immediate acute effects. samples are taken to determine the workers' exposure to conditions that may be harmful. because the computation is normalized to 8 hours. controls must be implemented immediately. mostly by small leaks. Many toxic chemical vapors are colorless and odorless (or the toxic concentration might be below the odor threshold). Continuous monitoring is not the usual situation because most facilities do not have the necessary equipment available.or IDLH concentrations. PELS. If problems are evident. Longer term and permanent controls are subsequently developed. that is. C(t) is the concentration (in ppm or mg/m3) of the chemical in the air and t. Special attention must be directed toward preventing and controlling low concentrations of toxic gases. temporary controls such as personal protective equipment can be used. These standards together with the actual concentrations are used to identify the potential hazards requiring better or more control measures. such as unconsciousness. then the TLV-TWA has been exceeded. or fits of coughing. Evaluating Exposures to Volatile Toxicants by Monitoring A direct method for determining worker exposures is by continuously monitoring the air concentrations of toxicants on-line in a work environment. . through large leaks.3-3 Industrial Hygiene: Evaluation 79 Sudden exposures to high concentrations. In these circumstances some provision for continuous evaluation is necessary. The integral is always divided by 8 hours. continuous or frequent and periodic sampling and analysis is important. arise from repeated exposures to low concentrations. it is necessary to compare actual exposure levels to acceptable occupational health standards. For continuous concentration data C(t) the TWA (time-weighted average) concentration is computed using the equation TWA = where 1 6 '"C ( t )dt.

If the sum in Equation 3-3 exceeds 1. one procedure is to assume that the effects of the toxicants are additive (unless other information to the contrary is available). For mixtures of toxicants with different effects (such as an acid vapor mixed with lead fume) the TLVs cannot be assumed to be additive. and is (TLV-TWA). The mixture TLV-TWA can be computed from If the sum of the concentrations of the toxicants in the mixture exceeds this amount. TWA concentration is computed by TWA = CITl C2T2 . is the TLV-TWA for chemical species i. If we assume that the concentration Ci fixed (6r averaged) the over the period of time Ti. + + 8 hr All monitoring systems have drawbacks because (1) the workers move in and out of the exposed workplace and (2) the concentration of toxicants may vary at different locations in the work area. representing worker exis posures at fixed points in time. then the workers are overexposed. If more than one chemical is present in the workplace. and 10 ppm of propylene oxide (TLV-TWA of 20 ppm). The combined exposures from multiple toxicants with different TLV-TWAs is determined from the equation where n is the total number of toxicants.80 Chapter 3 Industrial Hygiene The more usual case is for intermittent samples to be obtained. Industrial hygienists play an important role in the selection and placement of workplace monitoring equipment and the interpretation of the data. . Ci the concentration of chemical i with respect to the other toxicants. 20 ppm of cyclohexanol (TLV-TWA of 50 ppm). + CnT. Example 3-2 Air contains 5 ppm of diethylamine (TLV-TWA of 10 ppm). . What is the mixture TLV-TWA and has this level been exceeded? .then the workers are overexposed.

. The total mixture concentration is 5 + 20 10 = 35 ppm. Additional control measures need to be developed.. (TLV-TWA). Example 3-3 Determine the 8-hr TWA worker exposure if the worker is exposed to toluene vapors as follows: Duration of exposure (hr) Measured concentration (PP~) Solution Using Equation 3-2. . The workers are overexposed under these circumstances. the TLV-TWA has been exceeded. TWA = CITl + C2T2+ C3T3 8 llO(2) - + 330(2) + 90(4) 8 = 155 ppm. Because the TLV for toluene is 100 ppm.3-3 Industrial Hygiene: Evaluation 81 Solution From Equation 3-4. An alternative approach is to use Equation 3-3: + Because this quantity is greater than 1. the worker is overexposed. = 5 5 + 20 + 10 20 10 = 25 ppm. On a temporary and immediate basis all employees working in this environment need to wear the appropriate respirators.

pheptane (0. the partial pressures in the vapor are determined: p.5)(28.378 400 50 + Because the vapor will always be the same concentration.4 mm Hg.3 mm Hg. From Dalton's law the mole fractions on a toxicant basis are The mixture TLV is computed using Equation 3-4: TLVmix = 1 = 109.PYt.2 mm Hg.4 mm Hg) = 23. Basic Principles and Calculations in Chemical Engineering.2 + 14.1) = 37. The total pressure of the toxicants is (23. Using Raoult's law.p. 1989).2 mm Hg) = 14.. psat ol. the vapor composition is computed using standard vapor-liquid equilibrium calculations. Assuming that Raoult's and Dalton's laws apply to this system under these conditions.0.1 mm Hg. = 28. Himmelblau. (Englewood Cliffs.2mm Hg. . Himmelblauh provided the following data at the specified temperature: PEpta.7 ppm....5)(46. = 46. 5th ed. = pto.622 ..uene= (0. the vapor composition is determined directly from the saturation vapor pressures of the pure components. the TLVs for the individual species in the mixture are "avid M. 685. = x. 0. Assuming that the composition of the liquid does not change as it evaporates (the quantity is large).82 Chapter 3 Industrial Hygiene Example 3-4 Determine the mixture TLV at 25OC and 1 atm pressure of a mixture derived from the following liquid: Component Heptane Toluene Mole percent 50 50 Species TLV (ppm) 400 50 Solution The solution requires the concentration of the heptane and toluene in the vapor phase. NJ: Prentice-Hall.

. Dust evaluation calculations are performed in a manner identical to that used for volatile vapors. Evaluation of Worker Exposures to Dusts Industrial hygiene studies include any contaminant that may cause health injuries.7 ppm) = 68.622)(109. = (0. Toxicological theory teaches that dust particles that present the greatest hazard to the lungs are normally in the respirable particle size range of 0. should be consulted when confronted with this type of problem. = 6. whereas those smaller than 0. dusts. The main reason for sampling for atmospheric particulates is to estimate the concentrations that are inhaled and deposited in the lungs. of course.2-0. = (0.7 Solution From Equation 3-4: TLV of mixture = 1 c.8 mppcf. industrial hygienists. TLV. Example 3-5 Determine the TLV for a uniform mixture of dusts containing the following particles: Type of dust Nonasbestiform talc Quartz Concentration TLV (wt.5 ppm. TLV. For mixtures of vapors the individual species' TLVs in the mixture are significantly reduced from the TLVs of the pure substance.7 ppm) = 41.378)(109.2 ppm.. fit this category. c 2 ----. more control measures will be needed.5 pm are usually unable to penetrate the lungs. .8 mppcf. Instead of using ppm as a concentration unit.5 p m (see chapter 2). Sampling methods and the interpretation of data relevant to health hazards are relatively complex. who are specialists in this technology.+ TLV.- - - 3-3 Industrial Hygiene: Evaluation TLV. Special control measures will be required when the actual particle count (of the size range specified in the standards or by an industrial hygienist) exceeds 6. Particles larger than 0. mg/m3or mppcf (millions of particles per cubic foot) is more convenient. If the actual concentration exceeds these levels.%) (mppcf) 70 30 20 2.2 pm settle out too slowly and are mostly exhaled with the air. .

3d ed.Chapter 3 Industrial Hygiene Evaluating Worker Exposures to Noise Noise problems are common in chemical plants. the hearing threshold is set at 0 dBA. p. Noise evaluation calculations are performed identically to calculations for vapors. Table 3-7 Sound Intensity Levels for a Variety of Common Activities l Sound intensity level (dB) Source of noise Riveting (painful) Punch press Passing truck Factory Noisy office Conventional speech Private office Average residence Recording studio Whisper Threshold of good hearing Threshold of excellent youthful hearing - 'B.. then the difference in intensity levels in decibels is given by Noise intensity (dB) 10 log. the industrial hygienist should immediately make the appropriate noise measurements and develop recommendations. this type of problem is also evaluated by industrial hygienists. Thus a sound 10 times as intense as another has an intensity level 10 dB greater. 1988). (Chicago: National Safety Council. = - (t).. ed. Table 3-7 contains dBA levels for a variety of common activities. . An absolute sound scale (in dBA for absolute decibels) is defined by establishing an intensity reference. Fundamenta1. If one sound is at intensity I and another sound is at intensity I.. 168. Plog. Some permissible noise exposure levels for single sources are provided in Table 3-8. A decibel (dB) is a relative logarithmic scale used to compare the intensities of two sounds. If a noise problem is suspected. For convenience. Noise levels are measured in decibels.s oj'lndustrial Hygiene. except that dBA is used instead of ppm and hours of exposure is used instead of concentration. A.

3-3 Industrial Hygiene: Evaluation

85

Table 3-8

Permissible Noise Exposures
Maximum exposure (hr)

Sound level (dB4

B. A. Plog, ed., Fundamentals of Industrial Hygiene, 3d ed. (Chicago: National Safety Council, 1988), p. 176.

'

Example 3-6
Determine whether the following noise level is permissible with no additional control features:

Noise level (dBA)
85 95 110

Duration (hr)
3.6 3.0 0.5

Maximum allowed (hr)
no limit 4 0.5

Solution
From Equation 3-3:

2

3

c,

-

-

(TLV-TWA),

3.6 nolimit

3 0.5 + - + - = 1.75. 4 05

Because the sum exceeds 1.0, employees in this environment are immediately required to wear ear protection. On a longer-term basis, noise reduction control methods should be developed for the specific pieces of equipment with excessive noise levels.

Estimating Worker Exposures to Toxic Vapors
The best procedure to determine exposures to toxic vapors is to measure the vapor concentrations directly. For design purposes estimates of vapor concentrations are frequently required in enclosed spaces, above open containers, where drums are filled, and in the area of spills.

86

Chapter 3

Industrial Hygiene

C o n c e n t r a t i o n of V o l a t i l e , (Mass/Volurne)

C

Volatile

R a t e Out, Time)

kO vC

E v o l u t i o n R a t e of V o l a t i l e , (Mass/Time)

0

Figure 3-3

Mass balance for volatile vapor in an enclosure.

Consider the enclosed volume shown in Figure 3-3. This enclosure is ventilated by a constant volume airflow. Volatile vapors are evolved within the enclosure. An estimate of the concentration of volatile in the air is required. Let C be the concentration of volatile vapor in the enclosure (masslvolume), V be the volume of the enclosure (volume), Q , be the ventilation rate (volume/time), k be the nonideal mixing factor (unitless), and Q , be the evolution rate of volatile material (massltime). The nonideal mixing factor k accounts for conditions in the enclosure that are less than well mixed. It follows that Total mass of volatile in volume Accumulation of mass of volatile Mass rate of volatile material resulting from evolution Mass rate of volatile material out
=

VC,

= = =

d(VC) dt

dC V?

Q,, kQ,C.

3-3 Industrial Hygiene: Evaluation

87

Because accumulation equals mass in minus mass out, the dynamic mass balance on the volatile species is

At steady state the accumulation term is 0, and Equation 3-6 is solved for C:

Equation 3-7 is converted to the more convenient concentration units of ppm by direct application of thk ideal gas law. Let rn represent mass, p represent density, and the subscripts v and b denote the volatile and bulk gas species, respectively. Then:

where

R, is the ideal gas constant, T is the absolute ambient temperature, P is the absolute pressure, and M is the molecular weight of the volatile species.
The term m,/Vb is identical to the concentration of volatile computed using Equation 3-7. Substituting Equation 3-7 into Equation 3-8 yields

Equation 3-9 is used to determine the average concentration (in ppm) of any volatile species in an enclosure given a source term Q , and a ventilation rate Q,. It can be applied to the following types of exposures: a worker standing near a pool of volatile liquid, a worker standing near an opening to a storage tank, or a worker standing near an open container of volatile liquid. Equation 3-9 includes the following important assumptions: The calculated concentration is an average concentration in the enclosure. Localized conditions could result in significantly higher concentrations; workers directly above an open container might be exposed to higher concentrations. A steady-state condition is assumed; that is, the accumulation term in the mass balance is zero.

Chapter 3

Industrial Hygiene

The nonideal mixing factor varies from 0.1 to 0.5 for most practical situation^.^ For perfect mixing k = 1. Example 3-7
An open toluene container in an enclosure is weighed as a function of time, and it is determined that the average evaporation rate is 0.1 g/min. The ventilation rate is 100 ft"/min. The temperature is 80°F and the pressure is 1atm. Estimate the concentration of toluene vapor in the enclosure, and compare your answer to the TLV for toluene of 50 ppm.

Solution
Because the value of k is not known directly, it must be used as a parameter. From Equation 3-9

From the data provided Qm = 0.1 g/min = 2.20 X lb,/min, R, = 0.7302 ft3 atmllb-mol OR, T = 80°F = 54OoR, Q, = 100 ft"/min, M = 92 lbm/lb-mol, P = 1 atm. Substituting into the equation for kcppm:

=

9.43 ppm.

Because k varies from 0.1 to 0.5, the concentration is expected to vary from 18.9 ppm to 94.3 ppm. Actual vapor sampling is recommended to ensure that the TLV is not exceeded.

Estimating the Vaporization Rate of a Liquid Liquids with high saturation vapor pressures evaporate faster. As a result, the evaporation rate (massltime) is expected to be a function of the saturation vapor pressure. In reality, for vaporization into stagnant air, the vaporization rate is proportional to the difference be-

7R. Craig Matthiessen, "Estimating Chemical Exposure Levels in the Workplace," Chemical Engineering
Progress (April 1986), p. 30.

3-3 Industrial Hygiene: Evaluation

tween the saturation vapor pressure and the partial pressure of the vapor in the stagnant air; that is

where

PSat the saturation vapor pressure of the pure liquid at the temperature of the liquid and is p is the partial pressure of the vapor in the bulk stagnant gas above the liquid.

A more generalized expression for the vaporization rate is available8:

where
Q, is the evaporation rate (massltime),

M is the molecular weight of the volatile substance, K is a mass transfer coefficient (lengthltime) for an area A, R, is the ideal gas constant, and TLis the absolute temperature of the liquid.
For many situations, Pmt >>p, and Equation 3-11 is simplified to

Equation 3-12 is used to estimate the vaporization rate of volatile from an open vessel or from a spill of liquid. The vaporization rate or source term, determined by Equation 3-12, is used in Equation 3-9 to estimate the concentration (in ppm) of a volatile in an enclosure resulting from evaporation of a liquid:

%even R. Hanna and Peter J. Drivas, Guidelines for the Use of Vapor Cloud Dispersion Models (New York: American Institute of Chemical Engineers, 1987).

90

Chapter 3

Industrial Hygiene

For most situations T = TL,and Equation 3-13 is simplified to

The gas mass transfer coefficient is estimated using the relationshipy

where

a is a constant and D is the gas-phase diffusion coefficient.
Equation 3-15 is used to determine the ratio of the mass transfer coefficients between the species of interest K and a reference species KO:

The gas-phase diffusion coefficientsare estimated from the molecular weights M of the species lo:

Equation 3-17 is combined with Equation 3-16, giving

Water is most frequently used as a reference substance; it has a mass transfer coefficientll of 0.83 cmls.

Example 3-8
A large open tank with a 5-ft diameter contains toluene. Estimate the evaporation rate from this tank assuming a temperature of 77°F and a pressure of 1 atm. If the ventilation rate is 3000 ft3/min,
estimate the concentration of toluene in this workplace enclosure. "ouis J. Thibodeaux, Chemodynamics (New York: Wiley, 1979), p. 85. 'OGordon M. Barrow, Physical Chemistry, 2d ed. (New York: McGraw-Hill, 1966), p. 19. llMatthiessen, "Estimating Chemical Exposure," p. 33.

3-3 Industrial Hygiene: Evaluation

Solution
The molecular weight of toluene is 92. The mass transfer coefficient is estimated from Equation 3-18 using water as a reference:

The saturation vapor pressure is given in Example 3-4:

P: ",= 28.2 mm Hg :: ,,
The pool area is

=

0.0371 atm.

The evaporation rate is computed using Equation 3-12:

- (92 lb,/lb-mo1)(0.949 ft/min)(l9.6 ft2)(0.0371atm) (0.7302 ft" atmllb-mol0R)(537"R)

The concentration is estimated using Equation 3-14 with k as a parameter:

-

(0.949 ft/min)(l9.6 ft2)(0.0371 atm) (3000 ft"min)(l atm)

x lo6

=

230 ppm.

The concentration will range from 460 ppm to 2300 ppm, depending on the value of k. Because the TLV for toluene is 50 ppm, additional ventilation is recommended, or the amount of exposed surface area should be reduced. The amount of ventilation required to reduce the worst-case concentration (2300 ppm) to 50 ppm is
Q, = (3000 ft3/min)

ppm (2300ppm )

=

138,000 fr3/min.

This represents an impractical level of general ventilation. Potential solutions to this problem include containing the toluene in a closed vessel or using local ventilation at the vessel opening.

Chapter 3

Industrial Hygiene

Total S o u r c e = E v a p o r a t i o n + Displaced Air
\

Y

Liquid

Filling

Vapor

Evaporation

-

w_ L
-

-

Liquid

-- -

-4

-

Figure 3-4

-

D r u m o r Vessel

Evaporation and displacement from a filling vessel.

Estimating Worker Exposures during Vessel Filling Operations For vessels being filled with liquid, volatile emissions are generated from two sources, as shown in Figure 3-4. These sources are
evaporation of the liquid, represented by Equation 3-14, and displacement of the vapor in the vapor space by the liquid filling the vessel. The net generation of volatile is the sum of the two sources:

where (Q,), represents the source resulting from evaporation and (Q,), represents the source resulting from displacement. The source term (Q,), is computed using Equation 3-12. (Q,), is determined by assuming that the vapor is completely saturated with the volatile. An adjustment is introduced later for less than saturated conditions. Let

V , be the volume of the container (volume), r, be the constant filling rate of the vessel (time-'),

3-3 Industrial Hygiene: Evaluation

93

Pmt be the saturation vapor pressure of the volatile liquid, and TLbe the absolute temperature of the container and liquid.
It follows that rfVcis the volumetric rate of bulk vapor being displaced from the drum (volumeltime). Also, if pv is the density of the volatile vapor, rfVcpv the mass rate of volatile disis placed from the container (massltime). Using the ideal gas law,

and it follows that

Equation 3-21 can be modified for container vapors that are not saturated with the volatile. Let 4 represent this adjustment factor; then,

For splash filling (filling from the top of a container with the liquid splashing to the bottom), 4 = 1. For subsurface filling12(by a dip leg to the bottom of the tank), 4 = 0.5. The net source term resulting from filling is derived by combining Equations 3-12 and 3-22 with Equation 3-19:

This source term is substituted into Equation 3-9 to compute the vapor concentration (in ppm) in an enclosure resulting from a filling operation. The assumption that T = TLis also invoked. The result is

kQVP

(c$rfVc+ K A )

X

10'.

For many practical situations the evaporation term KA is much smaller than the displacement term and can be neglected.
I2Matthiessen, "Estimating Chemical Exposure," p. 33

94

Chapter 3

Industrial Hygiene

Example 3-9
Railroad cars are being splash-filled with toluene. The 10,000-galcars are being filled at the rate of one every 8 hr. The filling hole in the tank car is 4 in. in diameter. Estimate the concentration of toluene vapor as a result of this filling operation. The ventilation rate is estimated at 3000 ftqmin. The temperature is 77°F and the pressure is 1atm.

Solution
The concentration is estimated using Equation 3-24. From Example 3-8, K P"& 0.0371 atm. The area of the filling hole is
=

0.949 ft/min and

Thus

KA
The filling rate r,, is

=

(0.949 ft/min)(0.0872 ft2) = 0.0827 ft3/min.

For splash filling the nonideal filling factor 4 is 1.0. The displacement term in Equation 3-24 is 4 r f V , = (1.0)(0.00208min-')(10,000 gal) (7.4fgal)
=

2.78 ftvmin.

As expected, the evaporation term is small compared to the displacement term. The concentration is computed from Equation 3-24, using k as a parameter:
= -=
=

Psat+rfV,
QvP

(0.0371 atm)(2.78 ft"/min) (3000 ft3/min)(latm)

kc,,,

x

lo6

34.4 ppm.

The actual concentration could range from 69 ppm to 344 ppm, depending on the value of k . Sampling to ensure that the concentration is below 50 ppm is recommended. For subsurface filling, = 0.5, and the concentration range is reduced to 35-172 ppm.

+

3-4 Industrial Hygiene: Control
After potential health hazards a r e identified a n d evaluated, t h e appropriate control techniques must b e developed a n d installed. This requires the application of appropriate technology for reducing workplace exposures.

3-4 Industrial Hygiene: Control

95

Table 3-9

Chemical Plant Control Techniques
Typical techniques

Type and explanation Enclosures Enclose room or equipment and place under negative pressure.

Enclose hazardous operations such as sample points. Seal rooms, sewers, ventilation, and the like. Use analyzers and instruments to observe inside equipment. Shield high-temperature surfaces. Pneumatically convey dusty material. Use properly designed hoods. Use hoods for charging and discharging. Use ventilation at drumming station. Use local exhaust at sample points. Keep exhaust systems under negative pressure. Design locker rooms with good ventilation and special areas or enclosures for contaminated clothing. Design ventilation to isolate operations from rooms and offices. Design filter press rooms with directional ventilation. Clean vessels chemically vs. sandblasting. Use water sprays for cleaning. Clean areas frequently. Use water sprays to shield trenches or pump seals. Use dikes around tanks and pumps. Provide water and steam connections for area washing. Provide lines for flushing and cleaning. Provide well-designed sewer system with emergency containment. Use safety glasses and face shields. Use aprons, arm shields, and space suits. Wear appropriate respirators; airline respirators are required when oxygen concentration is less than 19.5%.

Local ventilation Contain and exhaust hazardous substances.

Dilution ventilation Design ventilation systems to control low-level toxics.

Wet methods Use wet methods to minimize contamination with dusts.

Good housekeeping Keep toxicants and dusts contained.

Personal protection As last line of defense.

The types of control techniques used in the chemical industry are illustrated in Table 3-9. Designing control methods is an important and creative task. During the design process, the designer must pay particular attention to ensure that the newly designed control technique provides the desired control and that the new control technique itself does not create another hazard, sometimes even more hazardous than the original problem. The two major control techniques are environmental controls and personal protection. Environmental control reduces exposure by reducing the concentration of toxicants in the workplace environment. This includes enclosure, local ventilation, dilution ventilation, wet methods,

96

Chapter 3

Industrial Hygiene

Table 3-10

Personal Protective Equipment, Not Including Respirators1
Description
-

Hard hat Safety glasses Chemical splash goggles, gas-tight Steel-toed safety shoes Wraparound face shield Vinyl apron Splash suit Umbilical cord suit Rubber oversleeves PVC-coa ted gloves PVC and nitrile knee boots Ear plugs must always be consulted.

Protects head from falling equipment and bumps Impact-resistant lenses Suitable for liquids and fumes Protects against dropped equipment Fiberglass, resistant to most chemicals Resists most chemicals Viton or butyl rubber for nonflammable exposures Used with external air supply Protects forearms Resists acids and bases Resists acids, oils, and greases Protects against high noise levels

Lab Safety Supply Catalog (Janesvelle,WI:Lab Safety Supply Inc.).Manufacturers' technical specifications

and good housekeeping, as discussed previously. Personal protection prevents or reduces exposure by providing a barrier between the worker and the workplace environment. This barrier is usually worn by the worker, hence the designation "personal." Typical types of personal protective equipment are listed in Table 3-10.

Respirators
Respirators are routinely found in chemical laboratories and plants. Respirators should be used only on a temporary basis, until regular control methods can be implemented; as emergency equipment, to ensure worker safety in the event of an accident; as a last resort, in the event that environmental control techniques are unable to provide satisfactory protection. Respirators always compromise worker ability. A worker with a respirator is unable to perform or respond as well as a worker without one. Various types of respirators are listed in Table 3-11. Respirators can be used improperly and/or can be damaged to the extent that they do not provide the needed protection. OSHA and NIOSH have developed standards for using respirators,l"ncluding fit testing (to ensure that the device does not leak excessively), periodic in-

13NIOSH Respirator Decision Logic, DHHS-NIOSH Publication 87-1-8 (Washington, DC: US Department of Health and Human Services, May 1987).

3-4 Industrial Hygiene: Control

97

Table 3-11
TYPe Mouth and nose dust mask

Respirators Useful to Chemical Industry
Example of commercial brand
MSA Dustfoe@ 88' MSA Comfo Classic cartridge

Limitations
0, > 19.5%; single use; PEL > 0.05 mg/m3 0, > 19.5%; GMA cartridge (black) for concentrations less than the IDLH concentration for organic vapors; GMC cartridge (orange) for concentrations less than the IDLH concentration for Cl,, HC1, and SO, 0, > 19.5%; type N canister for concentrations less than 100 times PEL and less than the IDLH concentration for acid gases, CO, ammonia, and organic vapors; escape concentrations of 2% for acid gases, CO, and organic vapors and 3% for ammonia; escape capacity less than 6 min
Good for toxic and noxious gases with concentrations below and above the IDLH concentration. Capacity between 30 and 60 min per specifications

Mouth and nose with chemical cartridge

Full face mask with chemical canister

MSA Industrial Canister, Gas Mask3

Self-contained breathing apparatus (SCBA)

MSA MMR XtremeB Air Mask4

'MSA Home Page 2000, Air-purifying Respirators, Conventionally Maintained, DustfoeB Respirator (Pittsburgh, PA: MSA International). 2MSA Home Page 2000, Air-purifying Respirators, Conventionally Maintained, Comfo Classic. 'MSA Home Page 2000, Air-purifying Respirators, Conventionally Maintained, Replacement Canisters for Gas Masks. 4MSA Home Page 2000, Supplied Air Respirators, Self-Contained Breathing Apparatus.

spections (to ensure that the equipment works properly), specified use applications (to ensure that the equipment is used for the correct job), training (to ensure that it is used properly), and record keeping (to ensure that the program is operating efficiently). All industrial users of respirators are legally bound to understand and fulfill these OSHA requirements.

Ventilation
For environmental control of airborne toxic material the most common method of choice is ventilation, for the following reasons: Ventilation can quickly remove dangerous concentrations of flammable and toxic materials. Ventilation can be highly localized, reducing the quantity of air moved and the equipment size. Ventilation equipment is readily available and can be easily installed. Ventilation equipment can be added to an existing facility.

1 psi) that moves the air. pulling air out. There are two types of ventilation techniques: local and dilution ventilation. The negative pressure system ensures that contaminants do not leak into workplace environments. This ensures that leaks in the system draw air in from the workplace rather than expel contaminated air from the ducts into the workplace. Ventilation systems are composed of fans and ducts. This is shown in Figure 3-5. and (2) remove the contaminant before workers are exposed. Exhaust 2 n d Floor Leakage O u t of Ducts Blower I st Floor / Hood Intake Positive Pressure Ventilation Exhaust A ------. and the cost to heat or cool the large quantities of fresh air can be large. with the fans located at the exhaust end of the system. The best system is a negative pressure system. These operating costs need to be considered when evaluating alternatives. The fans produce a small pressure drop (less than 0.98 Chapter 3 Industrial Hygiene The major disadvantage of ventilation is the operating cost. . Substantial electrical energy may be needed to drive the potentially large fans. 2nd Floor --z---- Leakage into Ducts 1st Floor -s-- H o d Intake Negative Pressure Ventilation Figure 3-5 The difference between a positive and a negative pressure ventilation system. Ventilation is based on two principles: (1)dilute the contaminant below the target concentration.

Source: N. the sash should never be fully opened because contaminants might escape. to ensure adequate fresh air. p. This ensures the availability of fresh Figure 3-6 Standard utility laboratory hood. There are several types of hoods: An enclosed hood completely contains the source of contaminant. The most common example of an enclosed hood is the laboratory hood. 4th ed. Reprinted by permisdon of John Wiley & Sons. Irving Sax. minimally. Dangerous Properties of lndustrial Materials. (New York: Van Nostrand Reinhold. shown in Figure 3-7. Another type of laboratory hood is the bypass hood. 74. The baffle at the rear of the hood ensures that contaminants are removed from the working surface and the rear lower corner. A hood is a device that either completely encloses the source of contaminant and/or moves the air in such a fashion as to carry the contaminant to an exhaust device. A push-pull hood uses a stream of air from a supply to push contaminants toward an exhaust system. 1975). A standard laboratory utility hood is shown in Figure 3-6. Inc. For this design bypass air is supplied through a grill at the top of the hood. Airflow patterns and control velocity are dependent on sash height. Fresh air is drawn through the window area of the hood and is removed out the top through a duct. The airflow profiles within the hood are highly dependent on the location of the window sash.3-4 Industrial Hygiene: Control Local Ventilation The most common example of local ventilation is the hood. . A receiving hood is an exterior hood that uses the discharge motion of the contaminant for collection. An exterior hood continuously draws contaminants into an exhaust from some distance away. It is important to keep the sash open a few inches. Likewise.

Irving Sax. (New York: Van Nostrand Reinhold. The disadvantages of hoods are that they limit workspace and can be used only for small. is determined using the equation Q. = LWU. bench-scale or pilot plant equipment. provide a containment device in the event of fire or explosion. For a duct of cross-sectional area A and average air velocity E (distanceltime). (3-26) . require minimal airflow. air to sweep out contaminants in the hood. Most hood calculations assume plug flow. the volume of air moved per unit time Q. Source: N. p.100 Chapter 3 Industrial Hygiene Figure 3-7 Standard bypass laboratory hood. and provide a shield to the worker by means of a sliding door on the hood. The advantages of enclosed hoods are that they completely eliminate exposure to workers. is computed from For a rectangular duct of width Wand length L. 75. The bypass air is controlled by the height of the sash. Reprinted by permission of John Wiley & Sons. Q. 4th ed. 1975). Dangerous Properties of Industrial Materials. Inc. The bypass air supply is reduced as the hood sash is opened.

1986). For general operation a control velocity of between 80 and 120 feet per minute (fpm) is desired. . Consider the simple box-type enclosed hood shown in Figure 3-8. However. backflow of contaminated air is possible. For general operation a control velocity between 80 and 120 feet per minute (fpm) is suggested. experience has shown that higher velocities can lead to the formation of a turbulent eddy from the bottom of the sash. 19th ed. and the evolution rate of the contaminant.14 141ndustrial Ventilation: A Manual of Recommended Practice. This face or control velocity (referring to the face of the hood) ensures that contaminants do not exit from the hood. Arrows are frequently used to indicate the proper sash height to ensure a specified face velocity. The airflow velocity is a function of the sash height and the blower speed. the depth of the hood. Instruments are available for measuring the airflow velocity at specific points of the hood window opening. The design strategy is to provide a fixed velocity of air at the opening of the hood. (Cincinnati: American Conference of Governmental Industrial Hygienists. The required control velocity depends on the toxicity of the material.3-4 Industrial Hygiene: Control 101 Exhaust Q = Volumetric Flow Rote. Testing is an OSHA requirement. ~ o l u m e / T i r n e . L = Length W = Width i = Required Control Velocity Figure 3-8 Determining the total volumetric air flow rate for a boxtype hood. Shallower hoods need higher control velocities to prevent contaminants from exiting the front. Design equations are available for a wide variety of hood and duct shapes.

For exposures to multiple sources the dilution air requirement is computed for each individual source. The following restrictions should be considered before implementing dilution ventilation: The contaminant must not be highly toxic. . dilution ventilation is necessary. Irving Sax. The elephant trunk is simply a flexible vent duct that is positioned near a source of contaminant. Other types of local ventilation methods include "elephant trunks" and free-hanging canopies and plenums. 29. p. These methods will most likely expose workers to toxicants. Equations 3-9.3-12. the nonideal mixing factor used with these equations. but in diluted amounts. Scrubbing systems must not be required to treat the air before exhaust into the environment. The contaminant must be evolved at a uniform rate. Workers must remain a suitable distance from the source to ensure proper dilution of the contaminant. where the airflow prevents worker exposure. and 3-14 are used to compute the ventilation rates required. Free-hanging canopies and plenums can be either fixed in position or attached to a flexible duct to enable movement. the TLV-TWA. Dilution Ventilation If the contaminant cannot be placed in a hood and must be used in an open area or room. A certain painting operation evaporates an estimated 3 gal of xylene in an 8-hr shift.. Example 3-10 Xylene is used as a solvent in paint. Determine the quantity of dilution ventilation air required to maintain the xylene concentration below 100 ppm. operating expenses can be substantial. 6th ed.102 Chapter 3 . The ventilation quality is rated as average. Industrial Hygiene Table 3-12 Nonideal Mixing Factor k for Various Dilution Ventilation Conditions1 Mixing factor: Ventilation condition Poor 117 118 1/11 Vapor Dust concentration concentration (PP~) (mppcf) over 500 101-500 0-100 Average 114 115 118 Good 113 114 117 Excellent 112 50 20 5 113 116 'N. Dangerous Properties. Table 3-12 lists values for k. dilution ventilation always exposes the worker but in amounts diluted by fresh air. It is most frequently used for loading and unloading toxic materials from drums and vessels. The total dilution requirement is the sum of the individual dilution requirements. Dilution ventilation always requires more airflow than local ventilation. Unlike hood ventilation. The values reported here are the reciprocal of Sax's values.

ed.Suggested Reading 103 Also.. eds. sec. . For a hood with an open area of 50 ft2. The specific gravity of the xylene is 0. k With Equation 3-9. ed. 2 and 3.125. eds. B. 2d ed. compute the air required if the operation is carried out in an enclosed hood with an opening of 50 ft2 and a face velocity of 100 ftlmin.using Equation 3-25 and assuming a required control velocity of 100 fpm.. Cralley. 6th ed. Solution The evaporation rate of xylene is Q = m (g ) (&) 0. Suggested Reading Industrial Hygiene Lewis J.864. Safety. The temperature is 77°F and the pressure is 1 atm. (New York: Van Nostrand Reinhold. 1998). C. Richard A. Fundamentals of Industrial Hygiene. (Chicago: National Safety Council. 1-3 (New York: Macmillan. 1984). Olishifski. Health. B.864) From Table 3-12. = 13. Scheff.1337 ft" (T) 62. Engineering Design for the Control of Workplace Hazards (New York: McGraw-Hill. for average ventilation and a vapor concentration of 100 ppm.300 ft3/min required dilution air.. Dangerous Properties of Industrial Materials. J.: = 118 = 0. A. 3d ed. Fundamentals of Industrial Hygiene.4 Ib. Industrial Hygiene Aspects of Plant Operations. 1988). we solve for Q. Irving Sax. A. Plog. we get The hood requires significantly less airflow than dilution ventilation and prevents worker exposure completely. (Chicago: National Safety Council. 1984). and its molecular weight is 106. Wentz. Cralley and Lester V. 1987).. and Environmental Protection (Boston: WCBIMcGraw-Hill. 1979). N. (0. Wadden and Peter A. v.

(c) what are their threshold quantities? The chemicals are acrolein. and describe the three program categories that are used for consequence modeling. and describe the endpoint parameters for consequence analyses for the worst-case scenarios. What additional information might you request to perform an appropriate assessment of the risk associated with these chemicals? 3-13.104 Chapter 3 Industrial Hygiene Ventilation Industrial Ventilation: A Manual of Recommended Practice. and completes the shift at 5 P. and ethanol. If they are listed.. methyl ethyl ketone. Review the RMP (40 CFR 68) to determine the conditions that need to be used for dispersion modeling for the worst-case scenarios. Problems 3-1.130) and (b) are listed as toxic or flammable. and cyclohexane. Determine (a) whether the following chemicals are covered under the PSM regulation and (b) their threshold quantities: ammonia (anhydrous). formaldehyde. phosgene. A process plant inventories the following chemicals: vinyl chloride. Determine (a) whether the following chemicals are covered under the PSM regulation (29 CFR 1910. Describe several typical alternative case scenarios for an RMP study. and methanol. ethylene oxide. 1986). where it can be assumed that no exposure to the chemical occurs. hydrogen selenide. hydrogen selenide. 3-10. A worker begins a work shift at 8 A. hydrogen chloride. The TLV-TWA for a substance is 150 ppm. 3-5.M. 19th ed. (c) what are their threshold quantities? The chemicals are ammonia (anhydrous). 3-2. phosgene. . If they are listed. 3-12. 3-6. Determine whether the following chemicals (a) are covered under the RMP and (b) are listed as toxic or flammable. ethylene oxide. propane. 3-11. Review the RMP (40 CFR 68) to determine the conditions that need to be used for dispersion modeling for the alternative case scenarios. A one-hour lunch break is included between 12 noon and 1P. Review the details of the RMP (40 CFR 68).M. describe why the threshold quantities are lower for the PSM-regulated chemicals than for the RMP-regulated chemicals. and ethanol. styrene. 3-9. methane. Determine the hazards associated with these chemicals. 3-7. Review the details of the RMP (40 CFR 68). formaldehyde. Review the details of the RMP (40 CFR 68). ch. and methanol. methane. hydrogen chloride. Determine whether the following chemicals (a) are covered under the RMP (40 CFR 68. 3-4.M. (Cincinnati: American Conference of Governmental Industrial Hygienists. ethylene oxide. and describe the endpoint parameters for consequence analyses for the alternative case scenarios. Wadden and Scheff. Engineering Design. 5. In reviewing the results of Problems 3-1 to 3-4. propane.119) and (b) their threshold quantities: acrolein. 3-8. 3-3.

1:17 P. Concentration (PP~) 110 130 143 162 142 157 159 165 153 130 3-14. 6th ed.M. Concentration (PP~) 5:05 P.M. Sax.M.M.l-dichloroethane. The data in the following table were taken in a work area: Time 8:01 A.M. 11:22 A.M. 10:07 A. (New York: Van Nostrand Reinhold. 12:08 P.M. 5:00 P.M. Sax" provided the following working equation for determining the dilution air requirements resulting from evaporation of a solvent: (3.M.M. a TLV-STEL of 250 ppm. . (molecular weight)(TLV)(k) where CFM is the ft3/minof dilution air required. p. 1212 P. 9:17 A.M. what are the violations? Assume that the worker is at lunch between the hours of 12 noon to 1 P.M.M. 2:03 P. 3-15. What assumptions are inherent in this equation? CFM = "N.M. 11:20 A.of liquid evaporatedlmin) . A worker on an 8-hour shift is exposed to this toxic vapor. Is the exposure within compliance? If not. 3:09 P. 10:05 A. and is not exposed to the chemical during that time.M.M.M. Air contains 4 ppm of carbon tetrachloride and 25 ppm of 1. Compute the mixture TLV. I. Dangerous Properties of Industrial Materials. A substance has a TLV-TWA of 200 ppm.M. 400 P.M. 3:13 P.87 X 108)(lb. and a TLV-C of 300 ppm. 1984). Has the worker exceeded the TLV specification? Time 8:10 A. 3-16. Show that this equation is the same as Equation 3-9. 9:05 A. 2:05 P.M. 4:01 P. and determine whether this value has been exceeded.Problems 105 The data were taken in the work area at the times indicated. 28. 1:06 P.M.

A mixture composed of 50 mol % benzene is used in a chemical plant. A drum with a 2-in-diameter bung is used to contain the mixture. The temperature is 80°F and the total pressure is 1 atm. determine the time required to evaporate all the toluene in the drum. 3-19.) Molecular weight Specific gravity TLV ( P P ~ ) 78. A drum contains 42 gal of toluene.9008 16. and A. T is the temperature in K.36 -53. A certain plant operation evaporates 2 pintlhr of toluene and 1 pint18-hr shift of benzene. 3-22.52 -52. Equations 3-12 and 3-14 represent the evaporation of a pure liquid. If the lid of the drum is left open (lid diameter = 3 ft). The temperature is 85°F. Benzene and toluene form an ideal liquid mixture. Determine the mixture TLV b. 3-18.Chapter 3 Industrial Hygiene Problems 3-17 through 3-22 apply to toluene and benzene.8794 10 92. B.866 50 Saturation vapor pressures: where Pmt is the saturation vapor pressure in mm Hg. Determine the ventilation rate required to maintain the vapor concentration below the TLV.11 0. Compute the density of pure air and the density of air contaminated with 100 ppm benzene. Estimate the concentration of toluene (in ppm) near the drum if the local ventilation rate is 1000 ft3/min. 3-21. The temperature is 80°F. a. Do the densities of these two gases differ enough to ensure a higher concentration on floors and other low spots? The temperature is 70°F and the pressure is 1 atm.The pressure is 1 atm. given by the following: Benzene Toluene 15. and the pressure is 1 atm. The temperature is 80°F. Compute the concentration (in ppm) of the saturated vapor with air above a solution of pure toluene. and C a r e the constants. Determine the ventilation rate required to maintain the vapor concentration below the TLV.H. Compute the concentration (inppm) of the equilibriumvaporwith air above a solution of 50 mol % toluene and benzene.51 3096. and the pressure is 1 atm. The following data are wailable for these materials: Benzene (C6H6) Toluene (C. The ventilation quality within the vicinity of this operation is average. .0137 2788. Modify these equations to represent the evaporation of a mixture of ideal miscible liquids. 3-20.13 0. c.67 3-17. Determine the evaporation rate per unit area for this mixture.

5% are dangerous.7. The drums are being splashfilled at the rate of 30 drums per hour. 33. 3-27. The molecular weight of gasoline is approximately 94. To reduce air pollution. . 3-25.000gal of delivered gasoline. The bung opening through which the drums are being filled has an area of 8 cm2. Compute the volumetric flow rate of air required." p. The passageway area is 7 ft2. Oxygen concentrations within tanks and enclosures can be reduced significantly by small amounts of inert elements! I6Matthieson. how many gallons of gasoline are recovered free for the station owner with each fill-up? For 10. Assume an average automobile tank size of 14 gal. The human body is sensitive to reductions in oxygen concentration. The vapor pressure of the 2-butoxyethanol is 0. Normal air contains about 21% oxygen by volume. Estimate the concentration (in ppm) of the vapor near the passageway opening.6 mm Hg. and concentrations below 16% can cause distress. "Estimating Chemical Exposure. If the vapor in the tank is saturated with gasoline vapor at a vapor pressure of 4.6 psi at these conditions.6 psi. Respiratory equipment without self-contained air supplies must never be used in atmospheres below 19. Compute the cubic feet of additional nitrogen at 77OF and 1 atm that will reduce the oxygen concentration within the tank to (a) 19. The air velocity required at the end of the elephant trunk is 100 ftlmin.Problems 107 3-23.6 mm Hg under these conditions.The TLV for gasoline is 300 ppm. A storage tank of 1000 ft3 capacity must be cleaned before reuse. gasoline filling stations are installing scavenger systems to remove the gasoline vapors ejected from the automobile tank during the filling operation. This is accomplished by an elephant trunk ventilation system installed as part of the filler hose. Proper procedures must be used to ensure that the oxygen concentration of the air within the tank is adequate. 3-28. Estimate the concentration (in ppm) of gasoline vapor as a result of this filling operation.16 A worker is standing near an open passageway of a tank containing 2-butoxyethanol (molecular weight = 118). A 6-in-diameter elephant trunk is used to remove contaminants near the open bung of a drum during a filling operation. and its vapor pressure at 77'F is 4. how many gallons are recovered? The molecular weight of gasoline is about 94. Assume a ventilation rate of 3000 ft3/min. A gasoline tank in a standard automobile contains about 14 gal of gasoline and can be filled in about 3 min. Equations 3-12 and 3-14 can be applied to nonenclosed exposures by using an effective ventilation rate. concentrations below 19.Estimate the ambient vapor concentration if the ventilation rate is 3000 ft3/min. Fifty-five-gallon drums are being filled with 2-butoxyethanol.5% and (b) 16%.5% oxygen.The vapor pressure of 2-butoxyethanol is 0. 3-24. The effective ventilation rate for outside exposures has been estimated at 3000 ft3/min. and its liquid specific gravity is 0. 3-26.

- -- Chapter 3 Industrial Hygiene 3-29. and calculate the total air flow rate. The hood depth is 18 in. It is desired to operate the hood of Problem 3-29 so that the vapor concentration in the hood plenum is below the lower explosion limit of 12. The molecular weight of TCE is 131. A laboratory hood has an opening 4 ft in length by 3 ft in height.3 lb per hour.4.5% by volume. . The amount of TCE evaporated within the hood is 5. Estimate the minimum control velocity required to achieve this objective. 3-30. The TCE will be used in liquid form at room temperature. This hood will be used for an operation involving trichloroethylene (TCE) (TLVTWA: 50 ppm). The temperature is 70°F and the pressure is 1 atm. Determine an appropriate control velocity for this hood.

A dispersion model is subsequently used to describe how the material is transported downwind and dispersed to some concentration levels. M 4-1 Introduction to Source Models Source models are constructed from fundamental or empirical equations representing the physicochemical processes occurring during the release of materials. More details are provided elsewhere. a hole in a tank or pipe. Source models are an important part of the consequence modeling procedure shown in Figure 4-1. solid. Environmental impacts could also be considered. but we do not do so here. flammable. runaway reaction. such as thermal radiation and explosion overpressures. and sheltering or evacuation. vapor. which might include toxic properties and energy content.' Accidents begin with an incident. Effect models convert these incident-specific results into effects on people (injury or death) and structures. or fire external to the vessel. and explosive materials. foam systems. or a combination). which tend to reduce the magnitude of potential effects in real incidents. such as water sprays. which usually results in the loss of containment of material from the process. liquid. source models are selected to describe how materials are discharged from the process. and the state of the discharge (that is. Additional refinement is provided by mitigation factors.Source Models ost accidents in chemical plants result in spills of toxic. The source model provides a description of the rate of discharge. For flammable releases fire and explosion models convert the source model information on the release into energy hazard potentials. 1999). The material has hazardous properties. Once the incident is known. the total quantity discharged (or total time of discharge). For a reasonably complex 'Guidelines for Consequence Analysis of Chemical Releases (New York: American Institute of Chemical Engineers. Typical incidents might include the rupture or break of a pipeline. 109 .

Adapted from Guidelines for Consequence Analysis for Chemical Releases (New 'fork: American Institute of Chemical Engineers. . 1999). of Individuals Affected Property Damage CHAPTER Selection of Fire and Explosion Model TNT Equivalency Multi-Energy Explosion Fireball Baker-Strehlow Others Results may Include: Blast Overpressure Radiant Heat Flux CHAPTER 2 C Mitigation Factors: Escape Emergency Response Shelter in Place Containment Dikes Other I 1 Consequence Model Figure 4-1 Consequence analysis procedure.Chapter 4 Source Models Selection of a Release Incident Rupture or Break in Pipeline Hole in a Tank or Pipeline Runaway Reaction Fire External to Vessel Other Selection of Source Model to Describe Release Incident Results may Include: Total Quantity Released (or Release Duration) Release Rate Material Phase 1 CHAPTER 4 C Selection of Dispersion Model (if applicable) Neutrally Buoyant Heavier than Air Others Results may Include: Downwind Concentration Area Affected Duration CHAPTER 5 I C Selection of Effect Model Response vs. Dose Probit Model Others Results may Include: Toxic Response No.

a leak below the liquid level will result in a stream of liquid flashing partially into vapor. Relief systems. are also potential sources of released material. releasing a substantial amount of material in a short time. a leak results in a jet of gas or vapor. For the limited aperture case material is released at a slow enough rate that upstream conditions are not immediately affected. leaks in flanges. For gases or vapors stored in a tank. designed to prevent the overpressuring of tanks and process vessels. Small liquid droplets or aerosols might also form from the flashing stream. Limited aperture releases are conceptualized in Figure 4-2. and pumps. . A leak in the vapor space above the liquid can result in either a vapor stream or a two-phase stream composed of vapor and liquid.4-1 Introduction to Source Models 111 Crack Valve (Body a n d Seals) - Severed o r Ruptured Pipe Pump (Body and Seals) Pipe Connection Figure 4-2 Various types of limited aperture releases. Release mechanisms are classified into wide and limited aperture releases. with the possibility of transport away from the leak by wind currents. Frequently the results are only estimates because the physical properties of the materials are not adequately characterized or because the physical processes themselves are not completely understood. This ensures that a design is on the safe side. depending on the physical properties of the material. Some development and modification of the original models is normally required to fit the specific situation. An excellent example is the overpressuring and explosion of a storage tank. For these releases material is ejected from holes and cracks in tanks and pipes. the assumption of constant upstream pressure is frequently valid. and severed or ruptured pipes. For liquids a leak below the liquid level in the tank results in a stream of escaping liquid. In the wide aperture case a large hole develops in the process unit. the parameters should be selected to maximize the release rate and quantity. Figure 4-3 shows how the physical state of the material affects the release mechanism. plant many source models are needed to describe the release. If uncertainty exists. valves. If the liquid is stored under pressure above its atmospheric boiling point.

specific to certain materials. flow of liquid through a hole in a tank. flow of liquids through pipes.Chapter 4 Source Models Gas Vapor or Two-Phase Vapor/Liquid \ . -Jd!fkL Liquid o r Liquid Flashing into V a p o r Liquid Figure 4-3 Vapor and liquid are ejected from process units in either single. There are several basic source models that are used repeatedly and will be developed in detail here.or two-phase states. Other source models. flow of gases through pipes. flashing liquids. are introduced in subsequent chapters. flow of vapor through holes. These source models are flow of liquid through a hole. 4-2 Flow of Liquid through a Hole A mechanical energy balance describes the various energy forms associated with flowing fluids: . and liquid pool evaporation or boiling.

p is the fluid density (mass/volume).. and m is the mass flow rate (massltime). is the shaft work (force length). so A P = P. is defined as . as shown in Figure 4-4..0 for turbulent flow. a = 1. The external pressure is atmospheric. The shaft work is zero. z is the height above datum (length). F is the net frictional loss term (length forcelmass). The frictional losses in the leak are approximated by a constant discharge coefficient C.0 for plug flow. a is the unitless velocity profile correction factor with the following values: a = 0.the average discharge velocity from the leak: i A new discharge coefficient C. within the process unit. and the velocity of the fluid within the process unit is assumed negligible. g is the acceleration due to gravity (lengthltime2). defined as The modifications are substituted into the mechanical energy balance (Equation 4-1) to determine i . For this limited aperture release. Frictional forces between the moving liquid and the wall of the leak convert some of the kinetic energy of the liquid into thermal energy. so Az = 0. and a + 1.- - - - 4-2 Flow of Liquid through a Hole 113 where P is the pressure (forcelarea).. The A function represents the final minus the initial state. The pressure of the liquid contained within the process unit is converted to kinetic energy as the fluid escapes through the leak. resulting in a reduced velocity. g. and Consider a process unit that develops a small hole. u is the average instantaneous velocity of the fluid (lengthltime). W. The change in elevation of the fluid during the discharge through the hole is also negligible. is the gravitational constant (length masslforce time2).5 for laminar flow.. assume a constant gauge pressure P. For incompressible liquids the density is constant.

. (London: Butterworths. Loss Prevention in the Process Industries. The resulting equation for the velocity of fluid exiting the leak is The mass flow rate Q . p. 2d ed. with some frictional flow losses in the hole. The energy of the liquid resulting from its pressure in the vessel is converted to kinetic energy. 1517.= 0 A = Leak Area p = Liquid Density Figure 4-4 Liquid escaping through a hole in a process unit. 1996).114 Chapter 4 Source Models Liquid Pressurized within Process Unit External Surroundings P = Pg U1 . The following guidelines are suggested: 2Frank P. The discharge coefficient C. is a complicated function of the Reynolds number of the Auid escaping through the leak and the diameter of the hole. resulting from a hole of area A is given by The total mass of liquid spilled depends on the total time that the leak is active.0 - P = 1 atm u2= U Az = 0 W. Lees.

The area of the hole is The density of the benzene is The leak mass flow rate is given by Equation 4-7. use a value of 1.61. 'Robert H. the discharge coefficient is approximately 0.61 is assumed for this orifice-type leak: e m = AC..0 to maximize the computed flows. A discharge coefficient of 0. Perry and Don W.a total of 90 minutes. The specific gravity of benzene is 0. The leak is assumed to be active between 1 P. 7th ed. the plant operator notices a drop in pressure in a pipeline transporting benzene.- - - 4-2 Flow of Liquid through a Hole For sharp-edged orifices and for Reynolds numbers greater than 30.8794.81.is indicative of a leak in the pipeline.M. = 1090 gal.M. Perry's Chemical Engineers Handbook.M. Estimate the total amount of benzene spilled. When the discharge coefficient is unknown or uncertain.- The total quantity of benzene spilled is (1. 10-16. approaches the value 0.and 2:30 P.pp..48 lbm/s)(90min)(60 slmin) = 7990 lb. a 114-in-diameter leak is found in the pipeline and immediately repaired. 1997). For short sections of pipe attached to a vessel (with a length-diameter ratio not less than 3). (New York: McGrawHill.' Example 4-1 At 1P. The pressure is immediately restored to 100 psig. Green. C. For a well-rounded nozzle the discharge coefficient approaches 1. . Solution The drop in pressure observed at 1 P.M.000. At 2:30 P. More details on discharge coefficients for these types of liquid discharges are provided elsewhere.M. For these conditions the exit velocity of the fluid is independent of the size of the hole.

the average instantaneous discharge velocity from the leak: where hL is the liquid height above the leak. A hole develops at a height hLbelow the fluid level. A new discharge coefficient C. The shaft work W. 4-3 Flow of Liquid through a Hole in a Tank A storage tank is shown in Figure 4-5. and the external gauge pressure is atmospheric. and the velocity of the fluid in the tank is zero. The flow of liquid through this hole is represented by the mechanical energy balance (Equation 4-1) and the incompressible assumption. = O Liquid D e n s i t y A = L e a k Cross Sectional Area atm Figure 4-5 An orifice-type leak in a process vessel. The energy resulting from the pressure of the fluid height above the leak is converted to kinetic energy as the fluid exits through the hole..116 Chapter 4 Source Models Process Vessel .. A dimensionless discharge coefficient C. is defined as The mechanical energy balance (Equation 4-1) is solved for E. Some energy is lost because of frictional fluid flow. is defined as . or 0. The gauge pressure on the tank is P. as shown in Equation 4-2. is zero.

on the surface of the liquid is constant.: This equation is integrated to .to any height h. resulting from a hole of area A is given by As the tank empties. we can obtain a differential equation representing the change in the fluid height: Equation 4-15 is rearranged and integrated from an initial height hO.4-3 Flow of Liquid through a Hole in a Tank 117 The resulting equation for the instantaneous velocity of fluid exiting the leak is The instantaneous mass flow rate Q. For a tank of constant cross-sectional area A. This would occur if the vessel was padded with an inert gas to prevent explosion or was vented to the atmosphere. the liquid height decreases and the velocity and mass flow rate decrease. By substituting Equations 4-12 and 4-13 into Equation 4-14 and by assuming constant tank cross-section and liquid density. is given by Equation 4-12. the total mass of liquid in the tank above the leak is The rate of change of mass within the tank is where Q.. Assume that the gauge pressure P.

= 0 and Equation 4-20 reduces to Example 4-2 A cylindrical tank 20 ft high and 8 ft in diameter is used to store benzene. = 0: If the vessel is at atmospheric pressure.8794. The specific gravity of benzene at these conditions is 0. Solution The density of the benzene is . P. and (c) the maximum mass flow rate of benzene through the leak. The liquid level within the tank is presently at 17 ft. A 1-in puncture occurs in the tank 5 ft off the ground because of the careless driving of a forklift truck.118 Chapter 4 Source Models Solving for h. (b) the time required for the benzene to leak out. The time t. The tank is padded with nitrogen to a constant regulated pressure of 1 atm gauge to prevent explosion. the liquid level height in the tank. yields Equation 4-18 is substituted into Equation 4-12 to obtain the mass discharge rate at any time t: The first term on the right-hand side of Equation 4-19 is the initial mass discharge rate at hL = hL. for the vessel to empty to the level of the leak is found by solving Equation 4-18 for t after setting h. Estimate (a) the gallons of benzene spilled..

48 gal/ft3) = 4506 gal. The volume of benzene above the leak is V = A.0 ft.4-3 Flow of Liquid through a Hole in a Tank 119 The area of the tank is The area of the leak is The gauge pressure is a. Equation 4-19 is used to compute the mass flow rate: .2 ft2)(17ft - 5 ft)(7.9 lbm/ft3 + (2)(32. However.12x 10"lb. c. The maximum discharge occurs at t = 0 at a liquid level of 17. the maximum discharge occurs when the hole is first opened./ft2) 54. I This appears to be more than adequate time to stop the leak or to invoke an emergency procedure to reduce the impact of the leak. The length of time for the benzene to leak out is given by Equation 4-20: (2)(32.17 ft-lbm/lbf-s2)(2.hE = (50.22ft2/s2)= 3386 s 1 - v'Zis2 = 56.17 ftls2)(12ft) = (469 s2/ft)(7.4 min. b. This is the total benzene that will leak out.

we have By substituting into Equation 4-24. we obtain If the hole is at the bottom of the vessel. . which is the same result as Equation 4-21. then Equation 4-26 is integrated from h = 0 to h Equation 4-26 then provides the emptying time for the vessel: = h. then combining Equations 4-12 and 4-14. For a vessel with the shape of a vertical cylinder.. we get By rearranging and integrating. Assume that the head space above the liquid is at atmospheric pressure.120 Chapter 4 Source Models A general equation to represent the draining time for any vessel of any geometry is developed as follows. we obtain which results in the general equation for the draining time for any vessel: Equation 4-24 does not assume that the hole is at the bottom of the vessel.

Flow of incompressible liquids through pipes is described by the mechanical energy balance (Equation 4-1) combined with the incompressible fluid assumption (Equation 4-2). 4-4 Flow of Liquids through Pipes A pipe transporting liquid is shown in Figure 4-6. .4-4 Flow of Liquids through Pipes 121 Figure 4-6 Liquid flowing through a pipe. For each frictional device a loss term of the following form is used: where K. fittings such as valves. Frictional forces between the liquid and the wall of the pipe convert kinetic energy into thermal energy. and pipe entrances and exits. A pressure gradient across the pipe is the driving force for the movement of liquid. is the excess head loss due to the pipe or pipe fitting (dimensionless) and u is the fluid velocity (lengthltime). This results in a decrease in the liquid velocity and a decrease in the liquid pressure. The frictional flow losses between the fluid and the pipe wall result in a pressure drop across the pipe length. The net result is The frictional loss term F i n Equation 4-28 represents the loss of mechanical energy resulting from friction and includes losses resulting from flow through lengths of pipe. orifices. elbows. Kinetic energy changes are frequently negligible.

Figure 4-7 is a plot of the Fanning friction factor versus Reynolds number with the pipe roughness. L is the flow path length (length). p. E (mm) For fluids flowing through pipes the excess head loss term Kf given by is where f is the Fanning friction factor (unitless). For laminar flow the Fanning friction factor is given by f =- 16 Re' For turbulent flow the data shown in Figure 4-7 are represented by the Colebrook equation: An alternative form of Equation 4-32. Engineering Flow and Heat Exchange (New York: Plenum Press. as a parameter. useful for determining the Reynolds number from the friction factor f . 1984). &Id. 22. Table 4-1 provides values of E for various types of clean pipe. is . The Fanning friction factor f is a function of the Reynolds number Re and the roughness of the pipe E . and d is the flow path diameter (length).122 Chapter 4 Source Models Table 4-1 Roughness Factor E for Clean Pipes1 Pipe material Riveted steel Concrete Cast iron Galvanized iron Commercial steel Wrought iron Drawn tubing Glass Plastic 'Selected from Octave Levenspiel.

as shown by the nearly constant friction factors at high Reynolds number in Figure 4-7. p. Engineering Flow and Heat Exchange (New York: Plenum Press. For this case Equation 4-33 is simplified to . f is independent of the Reynolds number.4-4 Flow of Liquids through Pipes 123 Figure 4-7 Plot of Fanning friction factor fversus Reynolds number. 20. Source: Octave Levenspiel. For fully developed turbulent flow in rough pipes. 1984). Reprinted by permission.

The 2-K method defines the excess head loss in terms of two constants.-410g - fl ~ i d 5. the Reynolds number and the pipe internal diameter: where K. and other flow obstructions the traditional method has been to use an equivalent pipe length Le. 5W. This equation is -1 . are constants (dimensionless). and K. 6 ~B. Industrial Engineering and Chemistry Fundamentals (1979).0452 log A ) (3. 7. 1988). inlets. Chen. 89-92.000 the following Blasius approximation to Equation 4-35 is useful: A single equation has been proposed by Chen4 to provide the friction factor f over the entire range of Reynolds numbers shown in Figure 4-7. valves. Chemical Engineering.Chapter 4 Source Models For smooth pipes. The problem with this method is that the specified length is coupled to the friction factor. 24. in Equation 4-30. is the excess head loss (dimensionless).Hooper. 4N.7065 Re where 2-K Method For pipe fittings. 18: 296. Hooper. K. B. and outlets. (Aug.. pp.= 4 log- 1 ~e fl 1. . An improved approach is to use the 2-K which uses the actual flow path length in Equation 4-30 -equivalent lengths are not used and provides a more detailed approach for pipe fittings. . E = 0 and Equation 4-32 reduces to . (Nov.255 fl For smooth pipe with a Reynolds number less than 100. pp. 96-100. Chemical Engineering..1981). H.

Hooper.5) Mitered. all types KI 800 800 800 1000 800 800 800 800 500 500 500 500 1000 1000 1000 Km 0. Chemical Engineering.25 0.. p.8 Standard Angle or Y-type Dam type Lift Swing Tilting disk 1500 1000 1000 800 2000 1500 1000 4.25 0.5): 1 weld (90") 2 welds (45") 3 welds (30") 4 welds (22. and ID. flangedlwelded Long radius (rlD = IS). is the internal diameter of the flow path (inches). Table 4-2 contains a list of K values for use in Equation 4-38 for various types of fittings and .20 0.1981).5") Standard (rlD = I).5") 5 welds (18") Standard (rlD = I)..40 0.30 Tees Used as elbows Standard.35 0. threaded Long radius..00 2. P = 0.50 Run-through Valves Gate. Re is the Reynolds number (dimensionless). threaded Standard (rlD = I). P = 1.4-4 Flow of Liquids through Pipes 125 Table 4-2 Fittings Elbows 90" 2-K Constants for Loss Coefficients in Fittings and Valves1 Description of fitting Standard (rlD = I).50 0. (Aug.60 0.27 0.20 1.00 0. 2 welds (22. threaded Standard.9 Reduced trim. all types Mitered (rlD = 1.35 0. ball or plug Globe Diaphragm Butterfly Check lWilliam B. flangedlwelded Stub-in branch Threaded Flangedlwelded Stub-in branch Full line size.15 0.30 0.25 10. 1weld (45") Mitered. flangedlwelded Long radius (rlD = IS).15 0. 97..25 0.0 1.0 Reduced trim. all types Long radius (rlD = 1.15 0. 24.00 2. threaded Standard (rlD = I). P = 0.

The K factors for the entrance and exit effects account for the changes in kinetic energy through these piping changes.000) the first term in Equation 4-39 is negligible and Kf = K. 96-100 8W. Equations are also available for orifices7 and for changes in pipe sizes. C. For high Reynolds numbers (that is. provided by Equations 4-30. 7W. and fittings. and type of pipe. = 1.126 Chapter 4 Source Models For pipe entrances and exits Equation 4-38 is modified to account for the change in kinetic energy: For pipe entrances. Thus 2 K. = 160 and K. Determine the initial fluid velocity at point 1. pressures and elevation changes across the piping system. = 0 and K. number and type of fittings in the pipe. 24.000.8 The 2-K method also represents liquid discharge through holes.. = 0.0 for a Bordatype entrance.0 for the exit. This must be done carefully because the individual terms in Equation 4-28 are highly dependent on this specification. 2. including entrances. For pipe exits. Specify the initial point (point 1) and the final point (point 2). . For low Reynolds numbers (that is. Re > 10.4-38. For a simple hole in a tank with no pipe connections or fittings the friction is caused only by the entrance and exit effects of the hole. pipe lengths. 3. Chemical Engineering.61. K. (Nov.0. 89-92. B. Kf = 0. The result is where C Kf is the sum of all excess head loss terms. so no additional kinetic energy terms in the mechanical energy balance must be considered. work input or output to the fluid resulting from pumps. 7. pp. Given: the length. Chemical Engineering. exits. Re < 50) the first term dominates and Kf = K. = 0. turbines. = 1. From the 2-K method an expression for the discharge coefficient for liquid discharge through a hole can be determined. B. For Reynolds numbers greater than 10. Hooper. including density and viscosity. The solution procedure to determine the mass flow rate of discharged material from a piping system is as follows: 1.5. and from Equation 4-40. (Aug..63. diameter. properties of the fluid. which nearly matches the suggested value of 0. Determine the pressures and elevations at points 1and 2. pp. etc. and 4-39. K. Hooper. = 1.IRe.50 for a normal entrance and K.1988).5 for the entrance and Kf = 1.1981).

and no shaft work. Use the velocity at point 2. Determine the mass flow rate using the equation m = pGA. 7. Sum the head loss terms. Guess a value for the velocity at point 2. Example 4-3 Water contaminated with small amounts of hazardous waste is gravity-drained out of a large storage tank through a straight commercial steel pipe. the solution is direct. Determine the excess head loss terms for the pipe (using Equation 4-30). 8.- 4-4 Flow of Liquids through Pipes 4. then the computation is completed.8 m above the pipe outlet. then this is not required. If fully developed turbulent flow is expected. Solution The draining operation is shown in Figure 4-8. 100mm ID (internal diameter). and compute the net frictional loss term using Equation 4-29. and substitute into the equation. If the sum of all the terms in Equation 4-28 is zero. Assuming negligible kinetic energy changks. Compute values for all the terms in Equation 4-28. The entire pipe assembly is mostly horizontal. no pressure changes. If the liquid level in the tank is 5. leaving the velocity at point 2 as a variable. 5. The pipe is 100m long with a gate valve near the tank. Substitute the known terms into Equation 4-28. go back to step 4 and repeat the calculation. . Determine the friction factor for the pipe using Equations 4-31 through 4-37. If not. 6. for the fittings (using Equation 4-38). Solve for the velocity directly. and the pipe is accidently severed 33 m from the tank. and for any entrance and exit effects (using Equation 4-39). If fully developed turbulent flow is expected.- -I Draining geometry for example 4-3. the mechanical energy balance (Equation 4-28) applied between points 1and 2 reduces to Gate Valve ID C o m m e r c i a l Steel Pipe Figure 4-8 33 m . compute the flow rate of material escaping from the pipe.

For the pipe exit. The gravitational term in the mechanical energy equation is given by . and it follows that = (660f + 0. The K factor for the gate valve is found in Table 4-2.128 Chapter 4 Source Models For water The K factors for the entrance and exit effects are determined using Equation 4-39.60. For the pipe length. and the K factor for the pipe length is given by Equation 4-30. For the pipe entrance. For the gate valve. Thus 2 Kf = 1320f + 1.80)Z2. Summing the K factors gives For Re > 10.000 the first term in the equation is small.

. The trial and error solution is shown in the following table: Guessed ii (m 1s) Re f F Calculated ii (m 1s) Thus the velocity of the liquid discharging from the pipe is 3. we obtain This result is close to the more exact trial and error solution. Then By substituting and solving. Equation 4-34 produces a friction factor value of 0. The table also shows that the friction factor f changes little with the Reynolds number. Thus we can approximate it using Equation 4-34 for fully developed turbulent flow in rough pipes.1 m)(G)(1000 kg/m3) 1. the solution is found by trial and error.0 x lo5.0041. . from Table 4-1.0 x 10-"glm s = 1. E = 0. For commercial steel pipe.0046 mrn and Because the friction factor f and the frictional loss term Fare functions of the Reynolds number and velocity.66 mls.4-4 Flow of Liquids through Pipes Because there is no pressure change and no pump or shaft work. the mechanical energy balance (Equation 2-28) reduces to Solving for the exit velocity and substituting for the height change gives The Reynolds number is given by Re=-= dip P (0.

130 Chapter 4 Source Models The-cross-sectionalarea of the pipe is The mass flow rate is given by This represents a significant flow rate. 4-5 Flow of Vapor through Holes For flowing liquids the kinetic energy changes are frequently negligible and the physical properties (particularly the density) are constant. Free expansion release source models require only the diameter of the leak. For throttling releases the gas issues through a small crack with large frictional losses. Assuming a 15-min emergency response period to stop the release. For free expansion releases most of the pressure energy is converted to kinetic energy. The density. Assuming negligible potential energy changes and no shaft work results in a reduced form of the mechanical energy balance describing compressible flow through holes: . pressure. In addition to the material released by the flow. and temperature change as the gas or vapor exits through the leak. they are not considered here.000kg of hazardous waste will be spilled. Energy contained within the gas or vapor as a result of its pressure is converted into kinetic energy as the gas or vapor escapes and expands through the hole. a total of 26. the assumption of isentropic behavior is usually valid. A free expansion leak is shown in Figure 4-9.3 times the speed of sound in gas). or modification of the piping system to include additional control valves to stop the flow. replacement of the pipe by one with a smaller diameter. An alternative system must be designed to limit the release. For flowing gases and vapors these assumptions are valid only for small pressure changes (P11P2< 2) and low velocities (<0. Gas and vapor discharges are classified into throttling and free expansion releases. the liquid contained within the pipe between the valve and the rupture will also spill. The mechanical energy balance (Equation 4-1) describes the flow of compressible gases and vapors. This could include a reduction in the emergency response period. Source models for throttling releases require detailed information on the physical structure of the leak. little of the energy inherent to the gas pressure is converted to kinetic energy.

is defined in a similiar fashion to the coefficient defined in section 4-2: Equation 4-42 is combined with Equation 4-41 and integrated between any two convenient points. The result is For any ideal gas undergoing an isentropic expansion. (4-44) py where y is the ratio of the heat capacities.IC. T) and velocity change during the expansion.4-5 Flow of Vapor through Holes 131 Gas Pressurized Within Process Unit External Surroundings At Throat: Figure 4-9 A free expansion gas leak. The gas expands isentropically through the hole. pvy = -= P constant. identical to that in Equation 4-5.. The gas properties (P. Substituting Equation 4-44 into Equation 4-43. defining a new discharge coefficient C. and inte- . A discharge coefficient C.. An initial point (denoted by subscript "0") is selected where the velocity is zero and the pressure is Po. The integration is carried to any arbitrary final point (denoted without a subscript). y = C.

R. Thus: . the following statements are valid: (1) The velocity of the fluid at the throat of the leak is the velocity of sound at the prevailing conditions.. For many safety studies the maximum flow rate of vapor through the hole is required. Using the continuity equation and the ideal gas law for isentropic expansions in the form results in an expression for the mass flow rate: Equation 4-48 describes the mass flow rate at any point during the isentropic expansion.. This is determined by differentiating Equation 4-48 with respect to PIP. For downstream pressures less than PC. The result is solved for the pressure ratio resulting in the maximum flow: The choked pressure Pchoked the maximum downstream pressure resulting in maximum flow is through the hole or pipe. and Tois the temperature of the source... is the ideal gas constant. critical. and (2) the velocity and mass flow rate cannot be increased further by reducing the downstream pressure. or sonicjlow and is illustrated in Figure 4-10..132 Chapter 4 Source Models grating results in an equation representing the velocity of the fluid at any point during the isentropic expansion: The second form incorporates the ideal gas law for the initial density p. and setting the derivative equal to zero. they are independent of the downstream conditions. This type of flow is called choked. An interesting feature of Equation 4-49 is that for ideal gases the choked pressure is a function only of the heat capacity ratio y.

Conditions leading to choked flow are common in the process industries. Gas Monotonic Diatomic and air Triatomic Y -1.67 ~1. and R.8 psia.528 = 27.528P0 0. The gas velocity is sonic at the throat. if the upstream pressure is greater than 14.40 -1.1 psig.32 Pchoked 0. or 13. To is the temperature of the source. is the ideal gas constant.4-5 Flow of Vapor through Holes 133 Gas Pressurized Within Unit External Surroundi Process < 'choked At Throat: 'choked - U r Sonic Velocity Figure 4-10 Choked flow of gas through a hole.710. The maximum flow is determined by substituting Equation 4-49 into Equation 4-48: where M is the molecular weight of the escapilig vapor or gas. The mass flow rate is independent of the downstream pressure. .7 psia).542P0 For an air leak to atmospheric conditions (PChoked = 14. the flow will be choked and maximized through the leak.487P0 0.

Technical Paper 410 (New York: Crane Co. . For sharp-edged orifices with Reynolds numbers greater than 30.000 (and not choked). Flow of Flutds Through Valves.61 is indicated. Chilton. Fzttzngs. and Pipes.134 Chapter 4 Source Models Table 4-3 Heat Capacity Ratios y for Selected Gases1 Chemical formula or symbol Approximate molecular weight (M) Heat capacity ratio y = C. 7th ed. Chemical Engineers Handbook.0 is recommended. Gas Acetylene Air Ammonia Argon Butane Carbon dioxide Carbon monoxide Chlorine Ethane Ethylene Helium Hydrogen chloride Hydrogen Hydrogen sulfide Methane Methyl chloride Natural gas Nitric oxide Nitrogen Nitrous oxide Oxygen Propane Propene (propylene) Sulfur dioxide -- - - - - - lCrane Co. However. pp. is uncertain. (New York: McGraw-Hill... a conservative value of 1.. Perry and Cecil H. a constant discharge coefficient C. 1997).IC.^ For these flows and for situations where C. of 0. 9Robert H. Values for the heat capacity ratio y for a variety of gases are provided in Table 4-3. 10-16. for choked flows the discharge coefficient increases as the downstream pressure decrease^. 1986).

0. The area of the hole is The discharge coefficient C. for nitrogen y = 1.. = 0. Solution From Table 4-3.41.1 psia will result in choked flow through the leak. Po = 200 + 14. choked flow is expected and Equation 4-50 applies.7 = 214. T o = 80 + 460 = 540°R. Determine the mass flow rate through this leak. is assumed to be 1. Then from Equation 4-49 Thus PCh.7) psia = 113.1-in hole forms in a tank containing nitrogen at 200 psig and 80°F. .1 psia An external pressure less than 113. Also.7 psia.527(200 + 14. Because the external pressure is atmospheric in this case.4-5 Flow of Vapor through Holes 135 Example 4-4 A 0. using Equation 4-50... Then.

136 Chapter 4 Source Models 4-6 Flow of Gases through Pipes Vapor flow through pipes is modeled using two special cases: adiabatic and isothermal behavior. For this particular case the outlet velocity is less than the sonic velocity. These frictional forces increase the temperature of the gas. it expands because of a decrease in pressure. For this case it is more conveniently written in the form . The kinetic energy is extracted from the thermal energy of the gas. either an increase or a decrease in the gas temperature is possible. For both the isothermal and adiabatic cases it is convenient to define a Mach (Ma) number as the ratio of the gas velocity to the velocity of sound in the gas at the prevailing conditions: where a is the velocity of sound. The velocity of sound is determined using the thermodynamic relationship which for an ideal gas is equivalent to which demonstrates that for ideal gases the sonic velocity is a function of temperature only. The flow is driven by a pressure gradient across the pipe. This expansion leads to an increase in velocity and an increase in the kinetic energy of the gas. a decrease in temperature occurs. The isothermal case corresponds to flow through an uninsulated pipe maintained at a constant temperature. Unfortunately. The adiabatic case corresponds to rapid vapor flow through an insulated pipe. As the gas flows through the pipe. an underwater pipeline is an excellent example. Adiabatic Flows An adiabatic pipe containing a flowing vapor is shown in Figure 4-11. the real case is difficult to model and no generalized and useful equations are available. For air at 20°C the velocity of sound is 344 m/s (1129 ftls). Depending on the magnitude of the kinetic and frictional energy terms. The mechanical energy balance (Equation 4-1) also applies to adiabatic flows. frictional forces are present between the gas and the pipe wall. However. Real vapor flows behave somewhere between the adiabatic and isothermal cases.

The following assumptions are valid for this case: is valid for gases. For this open steady flow process the total energy balance is given by iidii g dh+-+-dz=6q--. 1 -I P = [ U2 < Ma. This assumption is valid only at high Reynolds numbers. Assuming a straight pipe without any valves or fittings. Ma I . A total energy balance is useful for describing the temperature changes within the flowing gas. age 6WS m gc . Equations 4-29 and 4-30 can be combined and then differentiated to result in Because no mechanical linkages are present. The gas temperature might increase or decrease. Ma.4-6 Flow of Gases through Pipes 137 '2 > 'choked ---------- U2> U. < 1 For Surroundings. depending on the magnitude of the frictional losses. > 'choked Figure 4-1 1 Adiabatic nonchoked flow of gas through a pipe. > Sonic Velocity Ma. An important part of the frictional loss term is the assumption of a constant Fanning friction factor f across the length of the pipe.

These assumptions are applied to Equations 4-55 and 4-54. The various energy contributions are identified. The following assumptions are invoked: dh = C.1 Maf. The compressibility term accounts for the change in velocity resulting from the expansion of the gas./E/I \ = Ma2P2 YgcM RgT2' where G is the mass flux with units of mass/(area time) and (4-60) kinetic energy compressibility friction Equation 4-60 relates the Mach numbers to the frictional losses in the pipe.1° T2 -- TI -- 3. The equations are combined. Y 2 Ma2 Y . dz = 0 is valid for gases. after considerable effort. 6q = 0 because the pipe is adiabatic. 43. Engineering Flow and Heat Exchange (New York: Plenum Press. Equations 4-59 and 4-60 are converted to a more convenient and useful form by replacing the Mach numbers with temperatures and pressures.138 Chapter 4 Source Models where h is the enthalpy of the gas and q is the heat. 1986). = 1 + 2 P. and manipulated to yield. 6Ws = 0 because no mechanical linkages are present. integrated (between the initial point denoted by subscript "0" and any arbitrary final point). using Equations 4-56 through 4-58: "'Octave Levenspiel. PI Ma2 = G pii = MalPl . where Y. glg. . p. d T for an ideal gas..

The gas exiting the to pipe makes an abrupt change from Pchoked the ambient pressure.\ \ t u2 = Sonic Velocity Ma2 = 1 Ma1 Sonic Velocity Reached at Exit of Pipe / f Figure 4-12 Adiabatic choked flow of gas through a pipe. P < PChoked * Q=O /\ TI --------------- 7/7\ ' " 1 II Ii \\ * - - 3 Choked 12 --------------. For choked flow Equations 4-56 through 4-60 are simplified by setting Ma2 = 1. The results are Tchoked -2Y1 - TI y + 1' y+l' Pchoked -Ma. PI Pchoked -PI +1 . Determine T2from Equation 4-61. 3. inside diameter ( d ) . This assumption can be checked later but is normally valid.0. This case is shown in Figure 4-12. When the sonic velocity is reached. Determine the Fanning friction factor f from Equation 4-34. For long pipes or for large pressure differences across the pipe the velocity of the gas can approach the sonic velocity. independent of the downstream pressure. the gas flow is called choked.). the gas velocity at the end of the pipe remains constant at the sonic velocity. The pressure at the end of the pipe will remain at PC. Determine pipe roughness E from Table 4-1. even if this pressure is greater than the ambient pressure. the procedure is as follows: 1. To compute the mass flux G.. For most problems the pipe length (L). Compute the total mass flux G from Equation 4-62. flow through the pipe remains choked and the constant. and downstream pressure (P2)are known. 2. The maximum velocity is reached at the end of the pipe. If the downstream pressure is decreased below the choked pressure Pchoked. If the upstream pressure is increased or if the downstream pressure is decreased. This assumes fully developed turbulent flow at high Reynolds numbers. Compute &Id.. upstream temperature ( T I )and pressure (P.. The gas reaches the sonic velocity at the end of the pipe. 4.- 4-6 Flow of Gases through Pipes For Surroundings.

. are the excess head loss terms. p. pipe lengths. is a gas expansion factor (unitless). and upstream pressure (PI) and temperature ( T I ) known.inside diameter (d). Determine Ma. Flow of Fluids Through Valves. 3. To compute the mass flux G.. and C K. Determine the Fanning friction factor f using Equation 4-34. 2. Determine the mass flux Gchoked Equation 4-66. from Equations 4-63 through 4-67 for adiabatic pipe flow can be modified to use the 2-K method discussed previously by substituting C Kf for 4fLld. is the downstream gas pressure (forcelarea). A is the area of the discharge (length2). Fittings.Chapter 4 Source Models Choked flow occurs if the downstream pressure is less than Pchoked. Crane Co. including pipe entrances and exits. P. Technical Report 410 (New York. from Equation 4-67. Y. is the upstream gas density (mass/volume). is checked using EquaThis tion 4-64. This assumes fully developed turbulent flow at high Reynolds numbers. 1986).. . g. and Pipes. Determine Pchoked Equation 5-64 to confirm operation at choked conditions. llCrane Co. For ideal gas flow the mass flow for both sonic and nonsonic conditions is represented by the Darcy formula: l1 where G is the mass flux (masslarea-time). m is the mass flow rate of gas (massltime). is the gravitational constant (force/mass-acceleration). The procedure can be simplified by defining a gas expansion factor Y. This assumption can be checked later but is normally valid. from 4. For most problems involving choked adiabatic flows the pipe length ( L ) . PI is the upstream gas pressure (forcelarea). are the procedure is as follows: 1. and fittings (unitless).

where A. The result is where Ma. Kf Z must be substituted for 4fLld to include the effects of pipes and fittings. The next step in the procedure is to determine the sonic pressure ratio. are specified. K. pressure ratio (P. with the value of Y . If less than the ratio from Equation 4-64. = A(ln Kf)3+ B(ln K~)'+ C(ln K. then the flow is sonic or choked and the pressure drop predicted by Equation 4-64is used to continue the calculation. The procedure to determine the adiabatic mass flow rate through a pipe or hole is as follows: 1. total number and type of fittings. This computation can be done once and for all with the reAs the sults shown in Figures 4-13 and 4-14. upstream gas density. within 1%. equation for the gas expansion An factor for choked flow is obtained by equating Equation 4-68to Equation 4-66 and solving for Y. The gas expansion factor Y. . Figure 4-14shows the expansion factor for y = 1. is determined using Equation 4-67. and type. 2.P.2 to y = 1.For most accidental discharges of gases the flow is fully developed turbulent flow.) + D. in Equation 4-68depends only on the heat capacity ratio of the gas y and the frictional elements in the flow path C Kf. Assume fully developed turbulent flow to determine the friction factor for the pipe and the excess head loss terms for the fittings and pipe entrances and exits. Given: y based on the type of gas. is the upstream Mach number. the expansion factor Y . by guessing values of the upstream Mach number and determining whether the guessed value meets the equation objectives. Finally.4. and D are constants. The solution is obtained by trial and error. total pressure drop. The results are shown in Table 4-4and are valid for the K. The Reynolds number can be calculated at the completion of the calculation to check this assumption. Sum the individual excess head loss terms to get C. is calculated from Equation 4-69.. pipe length. The expansion factor Y. This can be easily done using a spreadsheet.)IP. The functional results of Figures 4-13and 4-14can be fitted using an equation of the form In Y. The procedure to determine the gas expansion factor is as follows..67. and the solution is direct. First. . = K. The calculation to determine the expansion factor can be completed once y and the frictional loss terms C K. ranges indicated. has little dependence on y. This means that for pipes the friction factor is independent of the Reynolds number and that for fittings K. shown in Figure 4-13. the upstream Mach number Ma. then the flow is not sonic and the actual pressure drop ratio is used. diameter. This is found from Equation 4-64. is a weak function of the heat capacity ratio y.4-6 Flow of Gases through Pipes 141 The excess head loss terms Z Kfare found using the 2-K method presented earlier in section 4-4. varying by less than 1% from the value at y = 1. C.If the actual ratio is greater than the ratio from Equation 4-64. pipe entrances and exits.4 over the range from y = 1. B.

. From AICHE/CCPS. for adiabatic pipe flow for y = 1. From AICHE/CCPS. Kf 15 20 Figure 4-14 The expansion factor Y. Guidelines for Consequence Analysis of Chemical Releases (New York: American Institute of Chemical Engineers. 1999). Guidelines for Consequence Analysis of Chemical Releases (New York: American Institute of Chemical Engineers.4. I I I I 0 0 10 20 30 Excess head loss. 0 1 0 I I I I 5 10 Excess head loss.2 All points at or above function are sonic flow conditions.142 Chapter 4 Source Models 0. 1999). Kf 40 I 50 Figure 4-13 Sonic pressure drop for adiabatic pipe flow for various heat capacity ratios.

5.213 D 0.P.0009 0. and the Sonic Pressure Drop Ratio (P. A pressure gradient across T = Constanl For Surroundings. 4.0013 B -0. lsothermal Flows Isothermal flow of gas in a pipe with friction is shown in Figure 4-15.P. Use the sonic choking pressure determined in step 3 in this expression.. .1-100 0.1-300 0.)lP.1-300 'The correlations are within 1%of the actual value in the specified range. .5633 Range of K.2 Sonic pressure drop ratio y = 1.1-100 0. interpolating a value from the table. 0.0185 -0. Determine the expansion factor from Figure 4-14. or using the equations provided in Table 4-4.261 0. or use the equation provided in Table 4-4. P 1 P2 > P choked Ma2 <1 Figure 4-15 Isothermal nonchoked flow of gas through a pipe. interpolate it from the table.1141 0. All areas above the curves in Figure 4-13 represent sonic flow. by using Figure 4-13 directly. Sonic pressure drop ratio y = 1.2 Function value y Expansion factor Y .6455 -0.238 0. Calculate the mass flow rate using Equation 4-68..)IPI from the specified pressure drop.5304 -0. For this case the gas velocity is assumed to be well below the sonic velocity of the gas.0006 0. Either read the value off of the figure. ZTheequation used to fit the expansion factor and the sonic pressure drop ratio is of the form 3.4-6 Flow of Gases through Pipes 143 Table 4-4 Correlations1for the Expansion Factor Y. Determine the sonic choking pressure P.0302 -0.4 Sonic pressure drop ratio y = 1.7248 -0.0287 C 0.67 A 0. Check this value against Figure 4-13 to determine whether the flow is sonic. Calculate (PI . This method is applicable to gas discharges through piping systems and holes.0308 -0. as a Function of the Excess Head Loss K.0011 0.

P z Ma1 --PI Ma2' P 2 Ma1 . p. The following assumptions are valid for this case: is valid for gases. By applying the assumptions to Equation 4-54 and manipulating them considerably. Isothermal flow is represented by the mechanical energy balance in the form shown in Equation 4-54. The pressure at the end of the pipe is equal to the pressure of the surroundings. and because no mechanical linkages are present. the velocity must increase to maintain the same mass flow rate. Engineering Flow. 46.144 Chapter 4 Source Models the pipe provides the driving force for the gas transport./g. As the gas expands through the pressure gradient. assuming constant f. Y~CM friction where G is the mass flux with units of mass/(area time). The temperature is constant across the entire pipe length. and kinetic energy compressibility The various energy terms in Equation 4-74 have been identified. A total energy balance is not required because the temperature is constant. and. .-PI Maz' Ma. 12Levenspiel. by combining Equations 4-29 and 4-30 and differentiating. we obtain12 T2 = TI. PI G = pii - = .

as shown in Figure 4-16. 13Levenspiel. Determine the Fanning friction factor f using Equation 4-34. p. .and upstream and downstream pressures (PI and PI). p 1 -- Pchoked P1 El - Malfi.*. 46. Levenspiell3 showed that the maximum velocity possible during the isothermal flow of gas in a pipe is not the sonic velocity. The result is A typical problem is to determine the mass flux G given the pipe length ( L ) .4-6 Flow of Gases through Pipes 145 A more convenient form of Equation 4-74 is in terms of pressure instead of Mach numbers. This form is achieved by using Equations 4-70 through 4-72. Thus for choked flow in an isothermal pipe. Engineering Flow. as in the adiabatic case. 2.Ma. This assumes fully developed turbulent flow at high Reynolds numbers. This assumption can be checked later but is usually valid.The procedure is as follows: 1.inside diameter ( d ) . Compute the mass flux G from Equation 4-75. the following equations apply: Tchoked = T 1 ? Pchoked -- . - Uchoked -- 1 Ma1*' = Gchoked pU = plUl = MalPl d z - pchoked E. In terms of the Mach number the maximum velocity is This result is shown by starting with the mechanical energy balance and rearranging it into the following form: The quantity -(dPldL) +CCJwhen Ma -+ 1 / G .

depending on the relative magnitude of the frictional and kinetic energy terms. from Equation 4-83. The Crane Co. For choked flows the adiabatic choking pressure is less than the isothermal choking pressure. and temperature (T) are known. 3. the actual flow rate is less than the adiabatic prediction and greater than the isothermal prediction. upstream pressure ( P . Determine the Fanning friction factor using Equation 4-34. where Gchokedthe mass flux with units of mass/(area time). Levenspiel l 4 showed that the adiabatic model always predicts a flow larger than the actual flow. For gas releases through pipes the issue of whether the release occurs adiabatically or isothermally is important. This assumes fully developed turbulent flow at high Reynolds numbers. and is 1 For most typical problems the pipe length (L). p.15 reported that "when compressible fluids discharge from the end of a reason14~evenspiel. provided that the source pressure and temperature are the same.. The mass flux G is determined using the following procedure: 1. Engineering Flow. l5Crane Co. 2. Flow of Fluids. Determine Ma. Example 4-5 shows that for pipe flow problems the difference between the adiabatic and the isothermal results is generally small. ) . P < PChoked T p1 TI U I = Constant / 7/ 1I I\ \\ ---------------t --------------- P2 = b P~hoked T2 = TI u2 = aly Ma2 = l l y Ma1 /" Velocity of a17 Reached at Exit of Pipe ' Figure 4-16 Isothermal choked flow of gas through a pipe. This assumption can be checked later but is usually valid.146 Chapter 4 Source Models For Surroundings. inside diameter (d). For real pipe flows from a source at a fixed pressure and temperature. 45. The maximum velocity is reached at the end of the pipe. For adiabatic flows the temperature of the gas may increase or decrease. . For both cases the velocity of the gas increases because of the expansion of the gas as the pressure decreases. Determine the mass flux G from Equation 4-82.

09 X lo4 lb.7 psia = 3. The maximum flow rate through the orifice occurs under choked conditions. Finally.4 and .528)(214. t h e adiabatic flow model is t h e model of choice for compressible gas discharges through pipes..7 = 214. Decide which result most closely corresponds to the real situation..049 in.. Choked flow can be expected because the system is venting to atmospheric conditions.4-6 Flow of Gases through Pipes 147 ably short pipe of uniform cross-sectional area into an area of larger cross section. As a result. and (c) an isothermal pipe. under choked sonic flow conditions isothermal conditions are difficult t o achieve practically because of t h e rapid speed of t h e gas flow.. P. For nitrogen.. (b) an adiabatic pipe. Determine the required minimum mass flow rate of nitrogen through the relief device to prevent the pressure from rising within the tank in the event of a regulator failure. The nitrogen in a particular facility is supplied from a 200-psig source. It is regulated to 81-psig and supplied to the storage vessel through 33 ft of commercial steel pipe with an internal diameter of 1.63 X lo4lbf/ftZ. The area of the pipe is The absolute pressure of the nitrogen source is Po = 200 + 14. Which mass flow rate should be used? Solution a. Determine the mass flow rate assuming (a) an orifice with a throat diameter equal to the pipe diameter. To prevent rupture of the storage vessel. This will exceed the pressure rating of the storage vessel.4 psia 1. for a diatomic gas. the vessel will be exposed to the full 200psig pressure from the nitrogen source. y = 1.7 psia) = 113. The choked pressure from Equation 4-49 is. Example 4-5 The vapor space above liquid ethylene oxide (EO) in storage tanks must be purged of oxygen and then padded with 81-psig nitrogen to prevent explosion. Equa: tion 4-50 provides the maximum mass flow rate./ft2. In the event of a failure of the nitrogen regulator. it must be equipped with a relief device to vent this nitrogen." C r a n e supported this statement with experimental d a t a on pipes having lengths of 130 a n d 220 pipe diameters discharging air t o t h e atmosphere. = = (0. the flow is usually considered t o b e adiabatic.

049 in)(l ft/l2 in) This equation is solved by trial and error for the value of Ma. The diameter of the pipe in millimeters is (1.4 + 1)Ma2 1 (5 - - 1 +1.4 mmlin) = 26. Thus b. Assume adiabatic choked flow conditions. y = 1.4+1 --ln[2 2+(1.4 ) [ (4)(0.046 mm.Without any additional information. Substituting the numbers provided gives 1.049 in) (25. E = 0.148 Chapter 4 Source Models The molecular weight of nitrogen is 28 lbm/lb-mol. = 1. Thus From Equation 4-34 For nitrogen. For commercial steel pipe.4-1)Ma2 (1.0. from Table 4-1. The results are tabulated as follows: Guessed Ma Value of left-hand side of equation .6 mm.00564)(33 ft ) (1. assume a unit discharge coefficient C.4. The upstream Mach number is determined from Equation 4-67: with Y . given by Equation 4-56.

4 psia = 7.PI p 2 - 0.7 psia)(28 lbllb-mol) = 1. The gas density under the upstream conditions is PI = P1M RgT (214. Then from Equation 4-56 and from Equations 4-63 and 4-64 PChoked (0. The sonic pressure ratio is given in Figure 4-13 (or the equations in Table 4-4).4 psia to ensure choked flow.4-6 Flow of Gases through Pipes 149 This last guessed Mach number gives a result close to zero. For y = 1.11 X 10"lbf/ft2 The pipe outlet pressure must be less than 49. = 0. The mass flux is computed using Equation 4-66: The simplified procedure with a direct solution can also be used.56 p. -.4 and K. = 8.037 1b/ft3.7 psia) = = 49.770 * P2 = 49.731 psia ft3/lb-molo~)(5400~) . The first consideration is whether the flow is sonic. It follows that the flow is sonic because the downstream pressure is less than 49. The friction factor f has already been determined: For this solution only the pipe friction will be considered and the exit effects will be ignored. From Figure 4-14 (or Table 4-4) the gas expansion factor Y .69.4 psia.4 psia.230)(214. (10. The excess head loss resulting from the pipe length is given by Equation 4-30.

0 psia = = The mass flow rate is computed using Equation 4-82: = 8.245 0.526 -0. Substituting the numbers provided. c. although with a lot less effort. we obtain (aThe solution is found by trial and error: 1 Guessed Ma 0. ~ a . ? l b . / i n 2 ) ( 0 .362 0.150 Chapter 4 Source Models By substituting this value into Equation 4-68 and using the choking pressure determined for P. 2 4 4 ) ~ 62.24 0. Pchaked P . f i = ( 2 1 4 . For the isothermal case the upstream Mach number is given by Equation 4-83. we obtain This result is essentially identical to the previous result.244 Value of left-hand side of equation 0.005 t Final result - The choked pressure is.097 0. . from Equation 4-79..25 0.93 x 10' lbf/ft2.

T . If m is the mass of original liquid. A choking design based on an orifice calculation might not be choked in reality because of high downstream pressures. the mass of liquid vaporized m . The orifice calculation. or other containment device develops a leak.4 49. For most real situations the heat transfer characteristics cannot be easily determined. sometimes explosively. then the excess energy contained in the superheated liquid is given by This energy vaporizes the liquid. the heat capacity of the liquid (energylmass deg).81 1. C. Thus the adiabatic pipe method is the method of choice. If the tank.4-7 Flashing Liquids 151 The results are summarized in the following table: Pchoked Qm Case Orifice Adiabatic pipe Isothermal pipe (psi4 113. Finally. note that the adiabatic and isothermal pipe methods produce results that are reasonably close. it will always produce the larger number for a conservative safety design. is easier to apply.. is given by . as in the adiabatic and isothermal pipe methods. The orifice method always produces a larger value than the adiabatic pipe method. the liquid will partially flash into vapor.0 (Ibm/s) 4. Flashing occurs so rapidly that the process is assumed to be adiabatic. The results show that this approach results in a large result for this case.76 A standard procedure for these types of problems is to represent the discharge through the pipe as an orifice. pipe. with a substantial difference between the orifice and the adiabaticlisothermal cases. however. the depressurized boiling point of the liquid. ensuring a conservative safety design. the temperature of the liquid before depressurization. If AH.4 62.16 1. The excess energy contained in the superheated liquid vaporizes the liquid and lowers the temperature to the new boiling point. 4-7 Flashing Liquids Liquids stored under pressure above their normal boiling point temperature present substantial problems because of flashing. is the heat of vaporization of the liquid. requiring only the pipe diameter and the upstream supply pressure and temperature. Also note that the computed choked pressures differ for each case. The configurational details of the piping are not required. and T.

(b) Equation 4-86.6 psia.Solving for the fraction of the liquid vaporized. From the steam tables P = 134.6 Btu/lb. The final temperature is the boiling point at 1atm. of saturated liquid water is contained in a vessel at 350°F. or 212°F. over the temperature range Toto Tb. we obtain Example 4-6 One lb.): where and are the mean heat capacity and the mean latent heat of vaporization. The vessel ruptures and the pressure is reduced to 1 atm. Solution a. The change in liquid mass m resulting from a change in temperature T is given by Equation 4-87 is integrated between the initial temperature To (with liquid mass m) and the final boiling point temperature Tb (with liquid mass m . A more general expression without this assumption is derived as follows. H = 321. fv = m. The initial state is saturated liquid water at To = 350°F.lm.. respectively.m. Compute the fraction of material vaporized using (a) the steam tables. and (c) Equation 4-90. At this temperature and under saturated conditions .152 Chapter 4 Source Models The fraction of the liquid vaporized is Equation 4-86 assumes constant physical properties over the temperature range To to Tb.

= 920.(1.(T. = 1150. Hinitial the fraction of vapor (or quality) = and is computed from that is. 14.T.0.7 Btullb. are - C..212)"F 970. = Because the process occurs adiabatically. AH.8557 Both expressions work about as well compared to the actual value from the steam table.)I=] = = = 1 .)] 1 .) . OF. A H . From Equation 4-86 C. = 1. .G ( ~ ..exp[-(1.. For liquid water at 212'F C. Hfina.. = 1.04 Btullb. . "F)(350 . AH. b.. Substituting into Equation 4-90 gives f.01 Btullb. "F)(350 .01 Btullb. 1 .. HIiquid 180. The mean properties for liquid water between To and T.T.04 Btullb. .4-7 Flashing Liquids 153 H.4 Btullb.3 Btullb.59% of the mass of the original liquid is vaporized. = 970. OF. f" = i c.3 Btullb.e x p [ .7 Btullb..212)"F/(920.07 Btu llb.

Determine the mass flow rate through the leak. 133. and the liquid does not have time to flash within the hole. Procedures are available to solve this problem. A pipe of diameter 0. The result will be valid only for liquids stored at a pressure higher than the saturation vapor pressure. allowing the flashing ammonia to escape. A good approximation is to assume a choked pressure equal to the saturation vapor pressure of the flashing liquid. 4th ed. the flash calculation is complicated considerably. equilibrium flashing conditions are achieved and the flow is choked. 314. Equilibrium flashing conditions can be assumed. P is the pressure within the tank. Then 16J. Assume a discharge coefficient of 0.17If the fluid path length of the release is short (through a hole in a thin-walled container).16 Flashing liquids escaping through holes and pipes require special consideration because two-phase flow conditions may be present.p. (New York: McGraw-Hill. The equations describing incompressible fluid flow through holes apply (see section 4-2). Smith and H. Van Ness. Solution Equation 4-91 applies for the case of equilibrium flashing conditions. because the more volatile components flash preferentially. With this assumption the mass flow rate is given by where A is the area of the release. If the fluid path length through the release is greater than 10 cm (through a pipe or thickwalled container). Fauske. p. "Hans K. C. The saturation vapor pressure of liquid ammonia at this temperature is 0. Introduction to Chemical Engineering Thermodynamics.968 X 106Pa. is the discharge coefficient (unitless).4 X lo6 Pa. . p.M. C. is Example 4-7 Liquid ammonia is stored in a tank at 24'C and a pressure of 1.154 Chapter 4 Source Models For flashing liquids composed of many miscible substances. "Flashing Flows or: Some Practical Guidelines for Emergency Releases. the fluid flashes external to the hole.61. 1987). and PSat the saturation vapor eressure of the flashing liquid at ambient temperature. nonequilibrium conditions exist.0945 m breaks off a short distance from the vessel (the tank). and its density is 603 kg/m3." Plantloperations Progress (July 1985). Several special cases need consideration. is the density of the liquid (mass/volume).

we obtain Equation 4-95 contains a maximum. at which choked flow occurs. A much more detailed approach is required. Consider a fluid that is initially quiescent and is accelerated through the leak.4-7 Flashing Liquids 155 For liquids stored at their saturation vapor pressure. from a mechanical energy balance (Equation 4-l). Assume that kinetic energy is dominant and that potential energy effects are negligible. Under choked flow conditions. dGldP = 0. Then. we can write A mass velocity G with units of mass/(area time) is defined by Combining Equation 4-93 with Equation 4-92 and assuming that the mass velocity is constant results in Solving for the mass velocity G and assuming that point 2 can be defined at any point along the flow path. Differentiating Equation 4-95 and setting the result equal to zero gives . P = P". and realizing that the specific volume (with units of volume/mass) v = llp. and Equation 4-91 is no longer valid.

and f is the mass fraction of vapor. from Equation 4-86. : dP AH. = -A H . Kletz. is the liquid specific volume. dT' and from the Clausius-Clapyron equation. TC. ." in Eleventh Loss Prevention Symposium (New York: American Institute of Chemical Engineers.lx IsTrevor A... v. The mass flow rate is determined by combining Equation 4-103 with Equation 4-98: Note that the temperature Tin Equation 4-104 is the absolute temperature from the ClausiusClapyron equation and is not associated with the heat capacity. we obtain The two-phase specific volume is given by where vfgis the difference in specific volume between vapor and liquid. C* d f . These aerosol droplets are readily entrained by the wind and transported away from the release site. The assumption that the quantity of droplets formed is equal to the amount of material flashed is frequently made.-- dv v. at saturation dP dT - AH. Tvk' Substituting Equations 4-102 and z-101 into Equation 4-100 yields . Small droplets of liquid also form in a jet of flashing vapor.. Differentiating Equation 4-99 with respect to pressure gives But. 1977). "Unconfined Vapor Cloud Explosions.156 Chapter 4 Source Models Solving Equation 4-97 for G. .

M is the molecular weight of the pure material. PSat 1. .4-8 Liquid Pool Evaporation or Boiling 157 Example 4-8 Propylene is stored at 25°C in a tank at its saturation pressure.18 x 10"Jlkg K)(298 K)(1 N mlJ) 4-8 Liquid Pool Evaporation or Boiling The case for evaporation of a volatile from a pool of liquid has already been considered in chapter 3.15 x lo6 Pa. is R. Estimate the mass flow rate through the hole under these conditions for propylene: = 3. = 2. A is the area of exposure. we obtain x (2. K is the mass transfer coefficient (lengthltime). vfg = 0. The area of the leak is Using Equation 4-104. AH. A 1-cm-diameter hole develops in the tank. Solution Equation 4-104 applies to this case. The total mass flow rate from the evaporating pool is given by Equation 3-12: where Q. = C. Pat the saturation vapor pressure of the liquid. is the mass vaporization rate (massltime). is the ideal gas constant. and TLis the temperature of the liquid.042 m"kg.18 X 10" Jlkg K.34 X 10"Jlkg.

More details on boiling pools is provided elsewhere. is the thermal diffusivity of the soil (areattime). is the thermal conductivity of the soil (energytlength-time-degree). and above) require a more detailed heat transfer mechanism. Thus where . For a spill onto an insulated dike floor these fluxes may be the only energy contributions. solar heat fluxes and convective heat transfer from the atmosphere become important. is the heat transfer for the pool from the ground. Q. The initial stage of boiling is usually controlled by the heat transfer from the ground. The higher hydrocarbons (C. The heat transfer from the ground is modeled with a simple onedimensional heat conduction equation.158 Chapter 4 Source Models For liquids boiling from a pool the boiling rate is limited by the heat transfer from the surroundings to the liquid in the pool.19 19Guidelinesfor Consequence Analysis of Chemical Releases (1999). T. The rate of boiling is determined by assuming that all the heat is used to boil the liquid. k. a. This is especially true for a spill of liquid with a normal boiling point below ambient temperature or ground temperature. This approach seems to work adequately for liquefied natural gas (LNG) and perhaps for ethane and ethylene. A is the area of the pool (area). . is the heat of vaporization of the liquid in the pool (energylmass). At later times. and (3) by radiation from the sun andtor adjacent sources such as a fire. T is the temperature of the liquid pool (degree). and t is the time after spill (time). q. is the heat flux from the ground (energylarea-time). determined by Equation 4-105 (energylarea-time). This model also neglects possible water freezing effects in the ground. (2) from the air by conduction and convection. Heat is transferred (1) from the ground by conduction. is the mass boiling rate (massltime). given by where q. and AH. is the temperature of the soil (degree). Equation 4-105 is not considered conservative. which can significantly alter the heat transfer behavior.

An equation of state (perhaps nonideal) is required to determine the tank pressure given the total mass. consider a problem requiring an estimate of the gas discharge rate from a hole in a storage tank.4-10 Conservative Analysis 159 4-9 Realistic and Worst-Case Releases Table 4-5 lists a number of realistic and worst-case releases. For example. then the worst-case releases must be used. However. The worst-case releases are those that assume almost catastrophic failure of the process. By doing so. These uncertainties arise because of (1)an incomplete understanding of the geometry of the release (that is. then the realistic cases would be selected. . (2) unknown or poorly characterized physical properties. To illustrate conservative modeling. The complete dynamic solution to this problem is difficult. including consequence models. The discharge rate depends on a number of parameters. and (4) unknown or poorly understood mixture behavior. Uncertainties that arise during the consequence modeling procedure are treated by assigning conservative values to some of these unknowns. For any particular modeling study several receptors might be present that require different decisions for conservative design. dispersion modeling based on a groundlevel release will maximize the consequence for the surrounding community but will not maximize the consequence for plant workers at the top of a process structure. including (1)the hole area. rather than assuming that an entire storage vessel fails catastrophically. the hole size). The reality of the situation is that the maximum discharge rate of gas occurs when the leak first occurs. The realistic releases represent the incident outcomes with a high probability of occurring. to name a few. 4-10 Conservative Analysis All models. resulting in near instantaneous release of the entire process inventory or release over a short period of time. if a study is being completed to meet the requirements of the EPA Risk Management Plan. If an internal company study is being completed to determine the actual consequences of plant releases. (2) the pressure within and outside the tank. however. with the discharge rate decreasing as a function of time as the pressure within the tank decreases. have uncertainties. defining the limits of the design envelope. Thus. The selection of the release case depends on the requirements of the consequence study. with the intent of estimating the toxicological impact. (3) the physical properties of the gas. a conservative estimate of the consequence is obtained. should be made to achieve a result consistent with the demands of the problem. (3) a poor understanding of the chemical or release process. This ensures that the resulting engineering design to mitigate or remove the hazard is overdesigned. it is more realistic to assume that a high probability exists that the release will occur from the disconnection of the largest pipe connected to the tank. Every effort. to name a few. requiring a mass discharge model cross-coupled to a material balance on the contents of the tank. and (4) the temperature of the gas. This discharge rate is used to estimate the downwind concentrations of the gas.

Assume that gases liquefied by refrigeration at atmospheric pressure are released at their boiling points. based on data for the previous 3 years. unless meteorological data indicate otherwise. Assume that the release occurs at ground level. Complicated temperature effects are also possible. assume rupture equal to that of a 2-inchdiameter pipe. 2USEPA. Use the pipe criteria. A much simpler procedure is to calculate the mass discharge rate at the instant the leak occurs. The actual discharge rate at later times will always be less. For diameters 2-4 in. . RMP Offsite Consequence Analysis Guidance (Washington. Assume urban or rural topography.5 m/s wind speed. as appropriate. Refer to pressure relief calculation. assume the entire quantity is released within 10 min. A modeling effort of this detail is not necessarily required to estimate the consequence. Assume a rupture based on the largest diameter process pipe attached to the vessel. To estimate the release rate.DC: US Environmental Protection Agency. and the downwind concentrations will always be less. or at process temperature. Incident characteristic Realistic release incidents Process pipes Hoses Pressure relief devices relieving directly to the atmosphere Vessels Other Assume full bore rupture. Assume release of the largest quantity of substance handled on site in a single process vessel at any time. 1994). or the incidents can be developed from the outcome of a review or derived from hazard analysis studies. All material released is assumed to be airborne. In this fashion a conservative result is ensured. Consider liquids to be released at the highest daily maximum temperature. 1. Assume F stability. assume rupture area equal to 20% of the pipe cross-sectional area. For diameters greater than 4 in.160 Chapter 4 Source Models Table 4-5 Guidelines for Selection of Process Incidents Guideline Rupture of the largest diameter process pipe as follows: For diameters smaller than 2 in. assume a full bore rupture. whichever is highest. Worst-case incidents2 Quantity Wind speed 1 stability Ambient temperature I humidity Height of release Topography Temperature of release substance 'Dowk Chemical Exposure Index Guide (New York: American Institute of Chemical Engineers. 1996). Use calculated total release rate at set pressure. assuming a fixed temperature and pressure within the tank equal to the initial temperature and pressure. Assume the highest daily maximum temperature and average humidity. Incidents can be established based on the plant's experience.

For this reason. this maximizes the consequence and ensures a conservative result. Lees. leading to a potential overdesign of the mitigation procedures or safety systems. . Hanna and Peter J. p. (New York: McGraw-Hill. 1996). Drivas. p. Lees. Flow of Vapor through Pipes Levenspiel. 1516. 1984).Suggested Reading 161 For the hole area a possible decision is to consider the area of the largest pipe connected to the tank. Guidelines for Chemical Process Quantitative Risk Analysis (New York: American Institute of Chemical Engineers. in particular. AICHEICCPS. ch. Flashing Liquids Steven R. Again. This occurs. 2. 15/10. Flow of Liquid through Holes Frank P. Guidelines for Use of Vapor Dispersion Models. Levenspiel. 5. 2001). Loss Prevention in the Process Industries. Flow of Vapor through Holes Lees. Guidelines for Consequence Analysis of Chemical Releases (New York: American Institute of Chemical Engineers. 24-32. Loss Prevention. if several decisions are made during the analysis. Unfortunately. consequence analysis should be approached with intelligence. 3. 1996). p. Warren L. Smith. 2d ed. 48-51. Unit Operations of Chemical Engineering. 2d ed. Engineering Flow. ch. ch. McCabe. 15/22. and Peter Harriott. Julian C. because pipe disconnections are a frequent source of tank leaks. tempered with a good dose of reality and common sense. (London: Butterworths. 6th ed. Loss Prevention. Engineering Flow. 2000). This procedure is continued until all the model parameters are specified. 1999). pp. (New York: American Institute of Chemical Engineers. Suggested Reading Consequence Modeling AICHE/CCPS. with each decision producing a maximum result. pp. Flow of Liquid through Pipes Octave Levenspiel. Engineering Flow and Heat Exchange (New York: Plenum Press. this procedure can result in a consequence that is many times larger than the actual.

4-2. 31. .866. Hydrogen sulfide gas is stored in a tank at 100 psig and 80°F. A 0. The ambient pressure is 1 atm. a. Develop an equation describing the gas pressure as a function of time if the tank develops a leak. 4-3. Determine the leakage rate. The TLV-TWA for hydrogen sulfide gas is 10 ppm. pp. The pressure in the pipeline at the point of the leak is 100 psig. Estimate the distance from the tank the stream of liquid will hit the ground. The diameter of the leak is estimated to be 0. If a 10-mm hole forms 3 m above the ground. Hint: For a freely falling body the time to reach the ground is given by where t is the time. and other hardware affect this result? 4-6. Estimate the diameter of a hole in the tank leading to a local hydrogen sulfide concentration equal to the TLV. At the time. Guidelines. 4-4.20-in hole develops in a pipeline containing toluene. The specific gravity of toluene is 0.39.1 bar gauge to prevent a flammable atmosphere within the tank. Estimate the mass flow rate of benzene through the leak. The tank is pressurized with nitrogen to 0. valves. Determine whether this stream will be contained by a 1-m-high dike located 1 m from the tank wall. The liquid in the tank has a density of 490 kg/m3. and g is the acceleration due to gravity. the upstream pressure in the pipeline is 50 psig and the downstream pressure is 40 psig. For incompressible flow in a horizontal pipe of constant diameter and without fittings or valves show that the pressure is a linear function of pipe length. 4-5. what is the initial mass discharge rate of liquid (in kgls)? b. A storage tank is 10 m high. h is the initial height above the ground.1 in. Assume choked flow and a constant tank gas temperature of To. A 100-ft-long horizontal pipeline transporting benzene develops a leak 43 ft from the high-pressure end.162 Chapter 4 Source Models Liquid Pool Evaporation and Boiling Hanna and Drivas. At a particular time the liquid level is 5 m high within the tank. The local ventilation rate is 2000 ft3/min and is deemed average. The specific gravity of benzene is 0. A tank contains pressurized gas. Problems 4-1.8794. What other assumptions are required for this result? Is this result valid for nonhorizontal pipes? How will the presence of fittings.

Compute the pressure in the pipe at the location shown on Figure 4-17..1 m below the pipe outlet of the first tank. The density of turpentine at these conditions is 55 lb/ft3./ft3. compute the fluid pressure at the leak.4 lb.0ft after the leak was repaired. A 31. This point is 27 m in equivalent pipe length from the first tank.049 in) at 4-8. An investigation finds that the leak was 0. Compute the flow rate (in kgls) from the leak. compute the pressure assuming that the valve is wide open. I 10. and (c) the total time the leak was active.8 X lop3kg/m s. The leak is repaired. Records show that the turpentine level in the tank was 17.1 m above the pipe outlet. The pipe is plastic PVC pipe with an internal diameter of 50 mm. Vent 1 m 1- 1- "I-. The flow rate through the pipe is 10. The pipe section is horizontal and without fittings or valves. The liquid in the pipe is crude oil with a density of 928 kg/m3and a viscosity of 0. The tank is vented to the atmosphere. At a certain time the liquid level in the first tank is 4. If the pressure at one point in the pipe is 103 psig and a small leak develops 22 ft downstream. The viscosity of the solution is 1.1 in in diameter and 7 ft above the tank bottom. The power input to the pump is 2 kW and is 50% efficient..000 L/hr.004 kg/m s. 400 gallhr. The morning inspection of the tank farm finds a leak in the turpentine tank. at a point 2.3 ft before the leak occurred and 13. and the density is 1600 kg/m3.5% hydrochloric acid solution is pumped from one storage tank to another. 4-10. 4-9. The tank diameter is 15 ft. Determine (a) the total amount of turpentine spilled. For water at these conditions the viscosity is 1. (b) the maximum spill rate. the pipe is severed between the pump and the second tank. 4-11. Water is pumped through a 1-in schedule 40 pipe (internal diameter = 1. The pipe is commercial steel pipe with an internal diameter of 50 mm.0 centipoise and the density is 62. Because of an accident.Problems 163 4-7.000 liters - Per Hour Leo4 O c c u r s H e r e Figure 4-17 Process configuration for Problem 4-1 1 . If a globe valve is added to the pipe section of Problem 4-7. nd .

Unfortunately. If the pipe shears off at the tank bottom. 4-12. Assume a hole diameter of 0.164 Chapter 4 Source Models 1 5 0 mm ID P i p e Figure 4-18 Tank draining pro- cess for Problem 4-12. If the drain pipe shears 2 meters below the tank. estimate the initial mass flow rate of nitrogen from the tank. A cylinder in the laboratory contains nitrogen at 2200 psia. The heating coils consist of 20 ft of the pipe wound in a coil within the reactor. If the tubing separates from the apparatus. the reactor vessel will be exposed to the full 125-psigpressure of the steam. estimate the flow of nitrogen from the tubing.25-in (internal diameter) drawncopper tubing. Assuming adiabatic flow through the pipe. a. A laboratory apparatus uses nitrogen at 250 psig. estimate the initial mass flow rate of material out of the drain pipe.5-in schedule 80 pipe (internal diameter = 0. The steam is supplied from a main header through similar pipe with an equivalent length of 53 ft. 4-15. If the heating coil pipe shears accidently. 4-16.546 in). b. to the apparatus through 15 ft of 0. leaving a 50-mm hole. Assuming the leak in the coil is represented by an orifice.5 in. b. Compute the maximum mass flow rate of steam from the sheared coils using two approaches: a. increasing the temperature and pressure. The nitrogen in the tank is at 75°F. Steam is supplied to the heating coils of a reactor vessel at 125 psig. A home hot water heater contains 40 gal of water. Because of a failure of the heat control. The coils are 0. heat is continuously applied to the water in the tank. The nitrogen is supplied from a cylinder. the reactor must be equipped with a relief system to discharge the steam in the event of a coil shear. estimate the initial mass flow rate. exceeding the vessel's pressure rating. The crude oil has a density of 928 kg/m3and a viscosity of 0. allowing the tank contents to leak out. through a regulator. 4-13. and the oil level is 7 m at the time. and there is concern that the drain pipe might shear off below the tank.004 kglm s. A tank with a drain pipe is shown in Figure 4-18. saturated. the relief valve is clogged and the pressure rises past the maxi- . What is the force created by the jet of nitrogen? 4-14. As a result. If the cylinder falls and the valve is sheared off. The tank contains crude oil.

23 x 4. A tank 100 ft in diameter and 20 ft tall is filled with crude oil to within 2 ft of the top of the tank. At 250 psig the tank ruptures. and the specific gravity of crude oil is 0.048 0. One accident scenario is that a 6-in-diameter line connected to the bottom of the tank might break loose from the tank. Estimate the quantity of water flashed. c. R. Calculate the mass flux (kg/m2s) for the following tank leaks given that the storage pressure is equal to the vapor pressure at 25°C: Toxic material a. V. Propane b. Unfortunately. allowing crude oil to drain out. TLis the initial low absolute temperature. is the ideal gas constant. Is the worker overexposed? 4-19.95 x 1X 0. If a 30-min emergency response time is required to stop the leak.5 X 1. The tank is vented to the atmosphere. these vents also allow volatile materials to escape. M is the molecular weight of the volatile. If the temperature changes from 4°C to 30°C over a period = of 12 hr.75 x 3.56 X lo5 10' 10' 10' v. and THis the final absolute temperature..4 mm Hg). Derive the equation form.9. estimate the concentration (in ppm) of toluene in the air. Estimate the rate of emission of toluene (in kgls).39 X 10' lo6 10" lo6 Heat of vaporization (J/kg) 3. b.17 X 3. Use an average temperature and an effective ventilation rate of 3000 ft"/min.Problems 165 mum pressure of the vessel.09 Heat capacity (J/ kg K) 2. Sulfur dioxide 10" lo" lo3 4-18. A storage tank is 15 m in diameter and 10 m tall. Large storage tanks need a breather vent (technically called a conservation vent) to allow air to move into and out of the tank as a result of temperature and pressure changes and a change in the tank liquid level.56 X 0. 4-17. a.077 0.. PSat 36.127 0.33 x 1. Pmt is the saturation vapor pressure of the liquid. estimate the maximum amount of crude oil (in gallons) leaked. Methyl chloride d. If a worker is standing near the vent. It is currently half full of toluene (M = 92.49 x 1.is the vapor volume of the tank. . (m3/kg) 0. An expression that can be used to estimate the volatile emission rate in a storage tank resulting from a single change in temperature is given by where rn is the total mass of volatile released.36 X 103 c. Ammonia Pressure (Pa) 0. resulting in potential worker exposures.

The transfer will be accomplished by pumping the crude oil through a 200-mm (internal diameter) commercial steel pipe to another tank 40 m in diameter and 10 m high. the liquid level h. and the crude oil is typically at a level of 9 m. C. At the current time the liquid height is within 1m of the top of the tank. If the liquid level is increased. A storage tank contains water contaminated with a small quantity of a soluble hazardous waste material. is given by the following differential equation: where hLis the liquid level height above the leak. or the same? . slower. Estimate the maximum mass flow rate (in kgls) of the gas if the initial pressure in the tank is 800 kPa gauge. a. If the cross-sectional area of the tank is increased. What is the driving force that pushes the water out of the hole in the tank? c. The pipeline represents 50 m of equivalent pipe. a. 4-21. how long will it take to empty the tank? c. b. does the liquid level change faster.. A is the cross-sectional area of the leak. If a hole develops in the tank. 4-23. and the ambient pressure is 1atm. Assume an initial liquid level above the leak of h.166 Chapter 4 Source Models 4-20. slower. is the cross-sectional area of the tank. A 3-cm (internal diameter) pipe has broken off of a 1-ton pig (or tank) of nitrogen. What conclusions can be drawn about the viability of this approach? The density of the crude oil is 928 kg/m3with a viscosity of 0. A storage tank is vented to the atmosphere.61). One accident mitigation procedure is called emergency material transfer. how much liquid (in m3) is spilled if an emergency response procedure requires 30 min to stop the flow? b. Estimate the minimum pump size (in HP) required to pump the entire tank empty in 1hr. is the constant discharge coefficient (= 0.004 kg/m s. What is the final liquid level (in m)? c. What is the maximum spill rate of liquid (in kg/s)? Assume that the tank is vented. A. If a 3-cm (internal diameter) feed pipe at the bottom of the tank breaks off. does the liquid level change faster. If a 100-HPpump (80% efficient) is available. Integrate the equation to determine an expression for the liquid level height as a function of time. The tank is 3 m in diameter and 6 m high. and g is the acceleration due to gravity. The temperature is 25"C. 4-22. a. b. or the same? d. in which the material is transported away from the accident site before it becomes involved. We plan on mitigating a crude oil tank fire scenario by pumping the tank empty in 1hr total time. Assume a pump efficiency of 80%. The crude oil storage tank is 30 m in diameter.

What would be the significance of the leak if the liquid were flammable? toxic? 4-24. how long will it take for the water to drain down to the leak? What is the total amount of liquid (in gallons) discharged? f. What was the original liquid level in the tank? 4-27. Calculate the orifice diameter required to reduce the flow from the nitrogen line to 0. m is the mass flow rate. b. This is not enough to prevent overpressuring of the reactor in the event of a regulator failure. is the work input to the pump. The tank contains a hazardous material dissolved in mostly water. This means that the process is designed in such a fashion as to prevent hazards from resulting in an accident. estimate the length of time for the leak. L is the length of the pipe.79 m. A leak occurred in the tank because a 0. f is the Fanning friction factor. A cylindrical tank 10 ft high and 20 ft in diameter is used to store water. the liquid level in the diked area had reached a height of 0.5 lb. d is the diameter of the pipe. a./s. One inherently safer design method is to install an orifice in the nitrogen supply line to limit the flow of nitrogen. Show that for any pump the maximum liquid discharge velocity is given by . If the liquid level in the tank at the end of the spill was 8. What new safety or operational problems might arise as a result of installing the orifice? 4-26. The liquid level in the tank is initially at 7 ft. a. Estimate the total amount of liquid spilled (in m3 and in kg). b. c. Be sure to list clearly your assumptions! 4-25. Use a mechanical energy balance to show that the pump work required to pump a liquid through a pipe from one tank to another is given by where W . p is the density of the liquid. The tank is vented to the atmosphere. If a 1-in puncture occurs 2 ft off the bottom of the tank.5 Ib.1-m-diameter pipe located 1m above the bottom of the tank was accidentally disconnected. By the time the liquid flow was stopped. A 10-m-diameter round tank sits on the ground within a 20-m-square diked area. In Example 4-5 the maximum flow through the nitrogen line was determined in order to size the relief device. Suppose that the reactor of Example 4-5 is equipped with a relief device capable of relieving nitrogen from the reactor vessel at the rate of 0./s.Problems 167 e. An important concept in process safety is inherent safety.5 m above the tank bottom. and A is the cross-sectional area of the pipe. a.

4-30. a. and its viscosity is 0. Calculate the number of kilograms per year of ideal gas that can be transported through the following pipe sizes. what is the maximum temperature increase expected in the water in "Clhr? Assume a constant heat capacity for the water of 1kcal/kg°C. What is the total quantity (in kg) leaked? . b. Make sure you list your assumptions in your solution. b. where u is the maximum liquid discharge velocity. This can lead to a rapid increase in the temperature of the liquid blocked inside the pump. a temperature of 25"C. Pumps can be blocked in by closing valves on the inlet and outlet sides of the pump. c. 4-31. At what height is the leak? c. 50 cm internal diameter. 5 cm internal diameter. c. A 1-kW pump discharges water through a 50-mm (internal diameter) pump outlet. 5 cm internal diameter. an oil barrel is 42 gal. a pressure of 689 kPa gauge. If the pump is rated at 1HP. The tank is 10 m high and 10 m in diameter. Make sure that you clearly state and justify any assumptions! Remember. If the pressure in the well reservoir is a constant 500 psig. assuming a constant liquid velocity of 1mls: a. and a molecular weight of 44: a. 4-32. and it contains a liquid with a specific gravity of 0. and about how long did it last? b. The strip chart in Figure 4-19 displays the history of a leak in a storage tank. 50 cm internal diameter. Comment on the magnitude of the result and the necessity for large pipe sizes in a chemical plant. W. p is the density of the liquid. No other pumping or filling operations occur during this time. 25 cm internal diameter. What will happen if the pump continues to operate? Calculate the number of liters per year of liquid that can be transported through the following pipe sizes. What is the maximum velocity of the liquid from this pump? What is the maximum discharge rate (in kgls)? Consider an oil well drilled to a depth of 1000 ft and connected to the surface with 4-in (internal diameter) commercial steel pipe.- - - 168 Chapter 4 Source Models 4-28. what is the expected flow rate of liquid oil (in barrels per day) at the surface if the surface pipe is open to the atmosphere? Assume 1000 ft of equivalent pipe and no gas flow with the oil. assuming a gas velocity of 3 m/s. 4-29. d. A pump contains 4 kg of water. 3 cm internal diameter. 3 cm internal diameter. When did the leak start. d. is the pump shaft work.93.9. and A is the pump outlet discharge area. The specific gravity of the oil is 0. Comment on the magnitude of the result and the necessity for large pipe sizes in a chemical plant. 25 cm internal diameter. b.4 centipoise.

4-33. is the discharge coefficient. assuming an effective ventilation rate for the outdoors of 3000 ft3/min. 4-34. C. A storage vessel containing carbon tetrachloride (CCI. . a.) is contained within a diked area with dimensions of 10 m x 10 m. A is the area of the hole. Estimate the leak hole diameter (in cm). The atomic weight of chlorine is 35. estimate the CC14 vapor concentration near the vessel (in ppm). The temperature of the liquid is 35"C. e. What spill rate (in kgls) from the storage vessel is required to completely fill the floor of the dike with liquid? b. If one of the accident scenarios for this vessel results in a leak with a discharge rate of 1 kgls. Show that for a spherical storage vessel containing liquid at an initial height h. the time for the liquid to drain from a hole in the bottom of the sphere is given by where D is the inside diameter of the sphere. and g is the acceleration due to gravity.Problems 169 1- 0 I I I I I I I I I I I I 1 I I I 0 200 400 600 800 1000 Time after midnight (min) 1200 1400 1600 Figure 4-19 Strip chart data for Problem 4-32. Estimate the maximum discharge rate of the fluid (in kgts).4. The storage tank is in a horizontal bullet configuration with legs to raise the vessel well above the dike floor. and the ambient pressure is 1atm. d.

92 WI m K Temperature of liquid pool: 109 K Temperature of soil: 293 K Heat of vaporization of pool: 498 kJ1kg at 109 K .16 X lo-' m2/s Thermal conductivity of soil: 0. Estimate the vaporization rate resulting from heating from the ground at 10 s after the instantaneous spill of 1500 m3 of liquefied natural gas (LNG) into a rectangular concrete dike of dimensions 7 m by 10 m. You will need the following data: Thermal diffusivity of soil: 4.170 Chapter 4 Source Models 4-35.

several criteria are available to estimate the impact or effect. The toxic release model represents the first three steps in the consequence modeling procedure. This requires a toxic release model.Toxic Release and Dispersion Models uring an accident. Toxic release and dispersion models are an important part of the consequence modeling procedure shown in Figure 4-1. Serious accidents (such as Bhopal) emphasize the importance of planning for emergencies and of designing plants to minimize the occurrence and consequences of a toxic release. identifying the release incident (what process situations can lead to a release? This was described in sections 4-9 and 4-10). and 3. An excellent safety program strives to identify problems before they occur. Toxic release models are routinely used to estimate the effects of a release on the plant and community environments. . as discussed in section 5-4). estimating the downwind concentrations of the toxic material using a dispersion model (once the downwind concentrations are known. Chemical engineers must understand all aspects of toxic release to prevent the existence of release situations and to reduce the impact of a release if one occurs. and rupture of a train or truck transportation tank following an accident. developing a source model to describe how materials are released and the rate of release (this was detailed in chapter 4). process equipment can release toxic materials quickly and in significant enough quantities to spread in dangerous clouds throughout a plant site and the local community. A few examples are explosive rupture of a process vessel as a result of excessive pressure caused by a runaway reaction. rupture of a pipeline containing toxic materials at high pressure. These steps are D 1. rupture of a tank containing toxic material stored above its atmospheric boiling point. 2.

(2) developing engineering modifications to eliminate the source of the release. water. Sometimes an inversion occurs. During the day. ground conditions (buildings. atmospheric stability. the temperature increases with height. This most often occurs at night because the ground cools rapidly as a result of thermal radiation. as shown in Figure 5-1. resulting in less vertical motion. The air temperature difference does not influence atmospheric mechanical turbulence. or a puff. (4) reducing inventories of hazardous materials to reduce the quantity released. reducing the effect of solar energy input. momentum and buoyancy of the initial material released. For unstable atmospheric conditions the sun heats the ground faster than the heat can be removed so that the air temperature near the ground is higher than the air temperature at higher elevations. the substance is carried downwind faster but is diluted faster by a larger quantity of air. neutral. as might be observed in the early morning hours. The maximum concentration of toxic material occurs at the release point (which may not be at ground level).172 Chapter 5 Toxic Release and Dispersion Models Various options are available. A wide variety of parameters affect atmospheric dispersion of toxic materials: wind speed. height of the release above ground level. For neutral stability the air above the ground warms and the wind speed increases. At night the temperature decrease is less. Concentrations downwind are less. This influence of buoyancy enhances atmospheric mechanical turbulence. based on the predictions of the toxic release model. (3) enclosing the potential release and adding appropriate vent scrubbers or other vapor removal equipment. As the wind speed increases. Temperature profiles for day and night situations are shown in Figure 5-3. Atmospheric stability relates to vertical mixing of the air. This results in unstable stability because air of lower density is below air of greater density. therefore . These options are discussed in more detail in section 5-6 on release mitigation. the air temperature decreases rapidly with height. After a release the airborne toxic material is carried away by the wind in a characteristic plume. resulting in minimal vertical motion. encouraging vertical motions. (1) developing an emergency response plan with the surrounding community. and stable. or insolation. because of turbulent mixing and dispersion of the toxic substance with air. For stable atmospheric conditions the sun cannot heat the ground as fast as the ground cools. and (5) adding area monitors to detect incipient leaks and providing block valves and engineering controls to eliminate hazardous levels of spills and leaks. 5-1 Parameters Affecting Dispersion Dispersion models describe the airborne transport of toxic materials away from the accident site and into the plant and community. trees). as shown in Figure 5-2. During an inversion. Atmospheric stability is classified according to three stability classes: unstable. for example. the plume in Figure 5-1 becomes longer and narrower.

.

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Workbook of Atmospheric Dispersion Estimates (Cincinnati: US Department of Health. Adapted from D. Education. Trees and buildings increase mixing. OC Figure 5-3 Air temperature as a function of altitude for day and night conditions. Adapted from D. whereas lakes and open areas decrease it. the temperature near the ground is lower than the air temperature at higher elevations.5-1 Parameters Affecting Dispersion T e m p e r a t u r e . 2. 1970). p. Bruce Turner. and Welfare. Education. Figure 5-4 shows the change in wind speed versus height for a variety of surface conditions. Bruce Turner. This condition is stable because the air of higher density is below air of lower density. ' l W i n d G r a d i e n t s U r b a n S u b u r b s F l a t Figure 5-4 Effect of ground conditions on vertical wind gradient. (Cincinnati: US Department of Health. Ground conditions affect the mechanical mixing at the surface and the wind profile with height. The temperature gradient affects the vertical air motion. 1970). . 1. p. Workbook of Atmospheric Dispersion Estimates. The influence of buoyancy suppresses mechanical turbulence. and Welfare.

The distinction between the two . For all gases. resulting in a much higher effective release height. The puff model describes the temporal concentration of material from a single release of a fixed amount of material. typically in the parts per million range. then the released gas will initially be negatively buoyant and will slump toward the ground. The momentum of a high-velocity jet will carry the gas higher than the point of release. The plume model describes the steady-state concentration of material released from a continuous source. The temperature and molecular weight of the released gas determine the gas density relative to that of air (with a molecular weight of 28. As the release height increases. If the gas has a density less than air. Two types of neutrally buoyant vapor cloud dispersion models are commonly used: the plume and the puff models. Figure 5-6 demonstrates these effects.97). Figure 5-5 Increased release height decreases the ground concentration. a point will eventually be reached where the gas has been diluted adequately to be considered neutrally buoyant.176 Chapter 5 Toxic Release and Dispersion Models Continuous release source Wind direction I I I As release height increases. If the gas has a density greater than air. 5-2 Neutrally Buoyant Dispersion Models Neutrally buoyant dispersion models are used to estimate the concentrations downwind of a release in which the gas is mixed with fresh air to the point that the resulting mixture is neutrally buoyant. At this point the dispersion is dominated by ambient turbulence. Thus these models apply to gases at low concentrations. the released gas will initially be positively buoyant and will lift upward. The buoyancy and momentum of the material released change the effective height of the release. The release height significantlyaffects ground-level concentrations. as the gas travels downwind and is mixed with fresh air. this distance increases.The increased distance leads to greater dispersion and a lower concentration at ground level. ground-level concentrations are reduced because the plume must disperse a greater distance vertically. This is shown in Figure 5-5.

and 2 . the plume model is recommended because it is easier to use. The coordinate system is fixed at the source. Hanna and Peter J. 1987)._ _ .Dominance of / . The puff model can be used to describe a plume. \ ambient turbulence \ \ Release source Transition from dominance of internal buoyancy to dominance of ambient turbulence Figure 5-6 The initial acceleration and buoyancy of the released material affects the plume character. A large vapor cloud is formed that moves away from the rupture point. . into an infinite expanse of air (a ground surface will be added later). The dispersion models discussed in this chapter represent only ambient turbulence. . the concentration C of material resulting from this release is given by the advection equation where uj is the velocity of the air and the subscript j represents the summation over all coordinate directions x._ Wind . the effect on a plume of a change in wind direction). Guidelines for Use of Vapor Cloud Dispersion Models (New York: American Institute of Chemical Engineers. For the puff model a typical example is the sudden release of a fixed amount of material because of the rupture of a storage vessel. models is shown graphically in Figures 5-1 and 5-2. . we would find that the material disperses much faster than . / / . For the plume model a typical example is the continuous release of gases from a smokestack. Q. Drivas. If the velocity uj in Equation 5-1 is set equal to the average wind velocity and the equation is solved. .. \ \ \ \ \ \ Dominance of internal buoyancy . 6. the puff model must be used. a plume is simply the release of continuous puffs. if steady-state plume information is all that is required.. Assuming no reaction or molecular diffusion.5-2 Neutrally Buoyant Dispersion Models 177 Initial acceleration and dilution -. p. Adapted from Steven R. A steady-state plume is formed downwind from the smokestack. However.y. For studies involving dynamic plumes (for instance. . Consider the instantaneous release of a fixed mass of material.

(5-3) (C') = 0. If we could specify the wind velocity exactly with time and position. is An additional equation is required to describe the turbulent flux. Unfortunately.178 Chapter 5 Toxic Release and Dispersion Models predicted. This is due to turbulence in the velocity field. so C = (C) + C'. Because the fluctuations in both C and uj are around the average or mean values. is the stochastic fluctuation resulting from turbulence. Equation 5-1 would predict the correct concentration. It follows that the concentration C will also fluctuate as a result of the velocity field. but the turbulent = = flux term (u. As a result.) is the average velocity and u.)C1) (u. The usual approach is to define an eddy diffusivity K.)C1 and u. including the effects resulting from turbulence.(C)are zero when averaged (((u.C1) not necessarily zero and remains in the equation.)(C1r O). it follows that (u. an approximation is used. where (C)is the mean concentration and C' is the stochastic fluctuation. no models are currently available to adequately describe turbulence.) = 0. (with units of areahime) such that . Substituting Equations 5-2 and 5-3 into Equation 5-1 and averaging the result over time yields The terms ju. Let the velocity be represented by an average (or mean) and stochastic quantity where (u.

and the z axis is the elevation I Continuous Release o f Occurs Material / a t R a t e Q. Note the coordinate system: xis downwind direction. Here Wind Direction \ with Wind S p e e d . u Figure 5-7 Steady-state continuous point source release with wind.- .. y is off-wind direction. . The coordinate system used for the dispersion models is shown in Figures 5-7 and 5-8.- 5-2 Neutrally Buoyant Dispersion Models Substituting Equation 5-6 into Equation 5-5 yields If the atmosphere is assumed to be incompressible. then and Equation 5-7 becomes Equation 5-9 together with appropriate boundary and initial conditions forms the fundamental basis for dispersion modeling. and z is vertical direction. The x axis is the centerline directly downwind from the release point and is rotated for different wind directions. They axis is the distance off the centerline. This equation will be solved for a variety of cases.

above the release point. = K* in all directions). the puff moves with the wind.0) are along the centerline.) = 0).0) is at the release point. The point (x. For this case Equation 5-9 reduces to the form Equation 5-10 is more tractable by defining a radius as r2 = x2 + y 2 tion 5-10 in terms of r yields + z2.180 Chapter 5 Toxic Release and Dispersion Models Wind Direction Wind S p e e d . no wind ((u. After the initial instantaneous release. = constant). or x axis. steady state (d(C)ldt = 0). y.0.y. Case 1: Steady-State Continuous Point Release with No Wind The applicable conditions are constant mass release rate (Q. . 0) are level with the release point. and the coordinates (x. Transforming Equa- . z ) = (0. 0. and constant eddy diffusivity (K. The coordinates (x. u I n s t a n t a n e o u s Release o f Material Here a t t Q. Occurs 3 : L t Initial Puff at t = 0 P u f f Moves D o w n w i n d a t u Velocity = 0 z Puff at t = t 1 X Concentrations Are E q u a l o n B o t h " R o u g h " Surfaces Figure 5-8 Puff with wind.

This is represented mathematically by the following flux boundary condition: The remaining boundary condition is As r -+m.) = O). = K* in all directions). (C)-0. Equation 5-9 reduces for this case to . that is. no wind ((u. = m: (5-13) Equation 5-12 is separated and integrated between any point r and r Solving Equation 5-14 for (C)yields It is easy to verify by substitution that Equation 5-15 is also a solution to Equation 5-11 and thus a solution to this case. Equation 5-15 is transformed to rectangular coordinates to yield Case 2: Puff with No Wind The applicable conditions are puff release. instantaneous release of a fixed mass of material Q: (with units of mass). and constant eddy diffusivity (K.5-2 Neutrally Buoyant Dispersion Models 181 For a continuous steady-state release the concentration flux at any point r from the origin must equal the release rate Qm(with units of massltime).

Y . 2Carslaw and Jaeger. t ) = 0 at t = 0. C. 'H. p. Conduction of Heat in Solids (London: Oxford University Press. Jaeger. S. 261. = K* in all directions). The solution to Equation 5-17 in spherical coordinates1 is and in rectangular coordinates it is Case 3: Non-Steady-State Continuous Point Release with No Wind The applicable conditions are constant mass release rate (Q. (C)(x. Carslaw and J. no wind ((ui) O ) . For this case Equation 5-9 reduces to Equation 5-17 with the initial condition expressed by Equation 5-18 and the boundary condition expressed by Equation 5-13. Equations 5-21 and 5-22 reduce to the corresponding steady-state solutions (Equations 5-15 and 5-16). The solution is found by integrating the instantaneous solution (Equation 5-19 or 5-20) with respect to time. The result in spherical coordinates2 is and in rectangular coordinates it is Qm (C)(x. Conduction of Heat. = constant). p.182 Chapter 5 Toxic Release and Dispersion Models The initial condition required to solve Equation 5-17 is y. 1959). t ) = 4 r r K * d x 2 + y2 + z2 erfc ( ' x2 + Y 2 + z2 22/K*t (5-22) As t -+ oo. and = constant eddy diffusivity (K. z. . 256. 2 .

then by using . and K. wind blowing in x direction only ((u. The solution for the average concentration at any point3 is If a slender plume is assumed (the plume is long and slender and is not far removed from the x axis).) = (u. = K* in all directions).Equation 5-24 is simplified to Along the centerline of this plume. = constant).) = u = constant).). = constant).. p. y = z = 0. = 1 + aI2. The applicable conditions are 1 puff release (Q.5-2 Neutrally Buoyant Dispersion Models 183 Case 4: Steady-State Continuous Point Source Release with Wind This case is shown in Figure 5-7. 267. The applicable conditions are continuous release ( Q . K. no wind ((u. T a r s l a w and Jaeger. and Case 5: Puff with No Wind and Eddy Diffusivity Is a Function of Direction This case is the same as case 2 but with eddy diffusivity a function of direction.)= O).. and constant eddy diffusivity (K. that is. For this case Equation 5-9 reduces to Equation 5-23 is solved together with boundary conditions expressed by Equations 5-12 and 5-13. and each coordinate direction has a different but constant eddy diffusivity (K. Conduction of Heat. .

k "ees. ... steady-state (d(C)lat= 0). y = z = 0.. Figure 5-8 shows the geometry. and K. Loss Prevention. Equation 5-9 reduces to The solution is Along the centerline of this plume. p.).)= (u. and K. K. and each coordinate direction has a different but constant eddy diffusivity (K. 151107. 1996).p. 4 ~ r a n P.).- -- Chapter 5 Toxic Release and Dispersion Models Equation 5-9 reduces to the following equation for this case: The solution is4 Case 6: Steady-State Continuous Point Source Release with Wind and Eddy Diffusivity Is a Function of Direction This case is the same as case 4 but with eddy diffusivity a function of direction..) = u = constant). The applicable conditions are puff release (Q. 151106. The applicable conditions are continuous release (Q. = constant). and the average concentration is given by Case 7: Puff with Wind This case is the same as case 5 but with wind. = constant). = each coordinate direction has a different but constant eddy diffusivity (K. K. wind blowing in x direction only ((uj) (u. (London:Butterworths. Lees.. 2d ed. Loss Prevention in the Process Industries.) = u = constant). wind blowing in x direction only ((u. and slender plume approximation (Equation 5-25).

x . the solution to this case is found by replacing the existing coordinate x by a new coordinate system. As a result. transformed into this new coordinate system: Case 8: Puff with No Wind and with Source on Ground This case is the same as case 5 but with the source on the ground.(5-34) Case 9: Steady-State Plume with Source on Ground This case is the same as case 6 but with the release source on the ground. The solution to case 5 represents a puff fixed around the release point. The variable t is the time since the release of the puff. that moves with the wind velocity. u Figure 5-9 Steady-state plume with source at ground level. " ~ K Kz i)]. The solution is 2 times Equation 5-29: Qi (C)(x7 Y' z' ') = 4 ( ~ t 1 x2 y2 -+ -+ ) exp[-%~ ( K . The solution is 2 times Equation 5-31: z Wind Continuous Release of Material Direction with Wind Speed. The solution is simply Equation 5-29.ut. The ground represents an impervious boundary. the concentration is twice the concentration in case 6. As a result. The ground represents an impervious boundary. If the puff moves with the wind along the x axis. and u is the wind velocity. . The concentration is twice the concentration of a plume without the ground.5-2 Neutrally Buoyant Dispersion Models 185 The solution to this problem is found by a simple transformation of coordinates. the concentration is twice the concentration in case 5. as shown in Figure 5-9.

with the corresponding correlations given in Table 5-2. it is not convenient experimentally and does not provide a useful framework for correlation. shown in Table 5-1. increased wind speed results in greater atmospheric stability. The atmospheric conditions are classified according to six different stability classes. . the standard deviations of the concentration in the downwind. Although the eddy diffusivity approach is useful theoretically. above the Ground For this case the ground acts as an impervious boundary at a distance H from the source. 1953). Pasquill-Gifford Model Cases 1 through 10 all depend on the specification of a value for the eddy diffusivity K. The dispersion coefficients are a function of atmospheric conditions and the distance downwind from the release. In general. The dispersion coefficients a and a. .186 Chapter 5 Toxic Release and Dispersion Models Case 10: Continuous Steady-State Source with Source at Height H. wind velocity. for a continuous source are given in Figures 5-10 and . Micrometeorology (New York:McGraw-Hill.. G. Y. . and a. = 0. p. z ) directions. 5-11. and prevailing weather conditions. respectively. represent .Loss Prevention. Values for the dispersion coefficients are much easier to obtain experimentally than eddy diffusivities. Values for a are not provided 6Lees. 151107. a . The stability classes depend on wind speed and quantity of sunlight. and vertical (x. time. Kj changes with position. p. Sutton. This is due to a change in vertical temperature profiles from day to night. z ) = e m eXP(--) uy" 4pXw If H. whereas at night the reverse is true. Equation 5-36 reduces to Equation 5-35 for a source on the ground. 286. 70. . The solution is" fi)(x. crosswind. y . Sutton7 solved this difficulty by proposing the following definition for a dispersion coeficient: with similiar expressions given for a and uZ The dispersion coefficients a. During the day.

1 1 Distance downwind. I o4 A 1o3 Ei C 102 D E F 10' . neutrally stable E. A. for overcast conditions during day or night and for any sky conditions during the hour before or after sunset or sunrise. 6Theneutral category D should be used.1 1 Distance downwind. respectively. ." Nuclear Safety (1976).5-2 Neutrally Buoyant Dispersion Models 187 Table 5-1 Atmospheric Stability Classes for Use with the Pasquill-Gifford Dispersion Modell. Gifford. moderately unstable C. regardless of wind speed. 17(1): 68.A. 3Strong insolation corresponds to a sunny midday in midsummer in England. extremely unstable B. km 10 0. slightly stable E moderately stable IF. "Turbulent Diffusion-Typing Schemes: A Review. Gifford.- 0. Slight insolation to similar conditions in midwinter. slightly stable D. "Use of Routine Meteorological Observations for Estimating Atmospheric Dispersion.2 Nighttime conditions4 Surface wind speed (m 1s) <2 2-3 3-4 4-6 >6 Daytime insolation3 Strong Moderate A-B B B-C C-D D6 Slight B C C D6 D6 Thin overcast 5318 or >4/8 low cloud cloudiness A A-B B C C F5 E D D6 D F F E Dh D6 Stability classes: A. 4Night refers to the period 1 hour before sunset and 1 hour after dawn. km 10 Figure 5-1 0 Dispersion coefficients for . 2(4): 47. 2F." Nuclear Safety (1961). "These values are filled in to complete the table.Giffordplume model for rural releases.

Report ATDL-106 (Washington.1 1 10 Distance downwind. km -Giffordplume model for urban releases. 'R. A. 28(17):2861-2865." Atmospheric Environment (1994). km Figure 5-11 Distance downwind. Environmental Research Laboratories. Dispersion coefficients for Pasquill- Table 5-2 Recommended Equations for Pasquill-Gifford Dispersion Coefficients for Plume Dispersionl. 2G. Atmospheric Turbulence. 1974). Briggs.2 (the downwind distance x has units of meters) Pasquill-Gifford stability class (m) ffz(m) Rural conditions A B C D E F Urban conditions A-B D D E -F - A-F are defined in Table 5-1. DC: Air Resources. Diffusion Estimation for Small Emissions. . and Diffusion Laboratory.188 Chapter 5 Toxic Release and Dispersion Models A-B A-B C D E-F E n E-F 1 0.E Griffiths. "Errors in the Use of the Briggs Parameterization for Atmospheric Dispersion Coefficients.

release are given in Figure 5-12 and the equations are provided in Table 5-3. The puff dispersion coefficients are based on limited data (shown in Table 5-2) and should not be considered precise.18~~. Briggs. because it is reasonable to assume that a.'~ 0.'~ 0.60~O.05~'. 1 0 h5 ~ ~ 0. .5-2 Neutrally Buoyant Dispersion Models 189 0.04~O. Diffusion Estimation for Small Emissions.'~ 0.06x~.53x07" 0 .1~ x O . Griffiths. (m) U Z(m) 0." 0. F. Report ATDL-106 (Washington. The dispersion coefficients a and a.~' A-F are defined in Table 5-1. Atmospheric Turbulence. km 10 Figure 5-12 Dispersion coefficients for Pasquill-Giffordpuff model.34x0. 1974). for a puff .1 1 Distance downwind. km 10 0." Atmospheric Environment (1994). . 28(17): 2861-2865. andDiffusionLaboratory.'~ 0 . "Errorsin the Use of the Briggs ParameterizationforAtmospheric Dispersion Coefficients. 'R.14~O. ~ (the downwind distance x has units of meters) Pasquill-Gifford stability class A B C D E F a. (m) or a. DC: Air Resources. Table 5-3 Recommended Equations for PasquillGifford Dispersion Coefficients for Puff D i s p e r s i ~ n ~ . 'G. = a. 1 0 ~ ~ ~ ~ ~ 0. Environmental ResearchLaboratories.~" 0. ~ " 0. A.1 1 Distance downwind.

. The center of the cloud is found at coordinates (ut. (o. Q. The solution has a form similar to Equation 5-33: The ground-level concentration is given at z = 0: The ground-level concentration along the x axis is given at y = z = 0: (C)(x. These equations along with the correlations for the dispersion coefficients are known as the Pasquill-Gifford model. The concentration at the center of this moving cloud is given by The total integrated dose D. Case 11: Puff with Instantaneous Point Source at Ground Level.y.Pasquill. Atmospheric Diffusion (London: Van Nostrand.0. 1962).O).2 1.) 4 .Chapter 5 Toxic Release and Dispersion Models The equations for cases 1through 10 were rederived by Pasquills using expressions of the form of Equation 5-37.. 1 x-ut v2%-3'2ffxuy~. received by an individual standing at fixed coordinates (x.. Coordinates Fixed at Release Point.O. t ) = O. Constant Wind Only in x Direction with Constant Velocity u This case is identical to case 7. z ) is the time integral of the concentration: 8F.

The procedure is repeated for each value of t required. t ) along the x axis using Equation 5-40.u. Specify (C)*. t ) = (C)" in Equation 5-45. The line connecting points of equal concentration around the cloud boundary is called an isopleth. The solution has a form similar to Equation 5-35: . For a specified concentration (C)* the isopleths at ground level are determined by dividing the equation for the centerline concentration (Equation 5-40) by the equation for the general ground-level concentration (Equation 5-39). and t.y. Determine the concentrations (C)(x.0 . This equation is solved directly for y: The procedure is 1. 2. The result is The total integrated dose along the x axis on the ground is Frequently the cloud boundary defined by a fixed concentration is required. Set (C)(x. 0 . and determine the values of y at each centerline point determined in step 2.5-2 Neutrally Buoyant Dispersion Models The total integrated dose at ground level is found by integrating Equation 5-39 according to Equation 5-42. Define the boundary of the cloud along the x axis. Case 12: Plume with Continuous Steady-State Source at Ground Level and Wind Moving in x Direction at Constant Velocity u This case is identical to case 9. 0 . 3.

192 Chapter 5 Toxic Release and Dispersion Models The ground-level concentration is given at z = 0: The concentration along the centerline of the plume directly downwind is given at y = z = 0: The isopleths are found using a procedure identical to the isopleth procedure used for case 11. above Ground Level and Wind Moving in x Direction at Constant Velocity u This case is identical to case 10.. Case 13: Plume with Continuous Steady-State Source at Height H. is found using .. For continuous ground-level releases the maximum concentration occurs at the release point. The solution has a form similar to Equation 5-36: - The ground-level concentration is found by setting z = 0: The ground-level centerline concentrations are found by setting y = z = 0: The maximum ground-level concentration along the x axis (C).

The result is .5-2 Neutrally Buoyant Dispersion Models 193 The distance downwind at which the maximum ground-level concentration occurs is found from The procedure for finding the maximum concentration and the downwind distance is to use Equation 5-53 to determine the distance. followed by using Equation 5-52 to determine the maximum concentration. because their values change as the puff moves downwind from the release point. Equation 5-54 does not predict the correct result. and the concentration is computed using The concentration along the ground at the centerline is given at y = z = 0: The total integrated dose at ground level is found by applying Equation 5-42 to Equation 5-55. If wind is absent ( u = O). The average concentration is given by The time dependence is achieved through the dispersion coefficients. At ground level. z = 0. Case 14: Puff with Instantaneous Point Source at Height Hrabove Ground Level and a Coordinate System on the Ground That Moves with the Puff For this case the center of the puff is found at x = ut.

If weather conditions are not known or are not specified. and then decreases in diameter. that is. The EPA9suggests that F stability can exist with wind speeds as low as 1. 1996).Chapter 5 Toxic Release and Dispersion Models Case 15: Puff with Instantaneous Point Source at Height Hrabove Ground Level and a Coordinate System Fixed on the Ground at the Release Point For this case the result is obtained using a transformation of coordinates similar to the transformation used for case 7. It is typically valid only for a distance of 0. For a puff the maximum concentration is always found at the puff center. The weather conditions in the Pasquill-Gifford dispersion equations are included by means of the dispersion coefficients and the wind speed.5 m/s. The result is 'C)(x''' '' ') = system (Equations 5-54 through 5-56)] where t is the time since the release of the puff.1-10 km from the release point. then certain assumptions can be made to result in a worst-case result. R M P Offsite Consequence Analysis Guidance (Washington. the highest concentration is estimated. For a puff isopleth the isopleth is close to circular as it moves downwind. we can see that the smallest dispersion coefficients occur with F stability. If the release occurs above ground level. The diameter of the isopleth increases initially as the puff travels downwind. DC: US Environmental Protection Agency. By examining the Pasguill-Gifford dispersion equations for estimating the concentrations. For a release above ground level the puff center will move parallel to the ground and the maximum concentration on the ground will occur directly below the puff center. reaches a maximum. Thus the maximum concentration is estimated by selecting the weather conditions and wind speed that result in the smallest values of the dispersion coefficients and the wind speed. Clearly. the wind speed cannot be zero. By inspecting Figures 5-10 through 5-12. then the highest concentration on the ground is found at a point downwind from the release. Some risk analysts use a wind speed of 2 m/s. Limitations to Pasquill-Gifford Dispersion Modeling Pasquill-Gifford or Gaussian dispersion applies only to neutrally buoyant dispersion of gases in which the turbulent mixing is the dominant feature of the dispersion. The assumptions used in the calculation must be clearly stated. so a finite value must be selected. "PA. it is readily evident that the dispersion coefficients and wind speed are in the denominator. . Worst-Case Conditions For a plume the highest concentration is always found at the release point.

g is the acceleration due to gravity (length/time2).this might be important for emergency response. the duration of release. The initial cloud buoyancy is defined as where g.5-3 Dense Gas Dispersion 195 The concentrations predicted by the Gaussian models are time averages. The models presented here assume a 10-minute time average. Workbook on the Dispersion of Dense Gases (Sheffield. Thus the results are not applicable to areas where terrain effects are significant. p. and p. 5-3 Dense Gas Dispersion A dense gas is defined as any gas whose density is greater than the density of the ambient air through which it is being dispersed. The release is assumed to occur at ambient temperature and without aerosol or liquid droplet formation. The Britter and McQuaid10model was developed by performing a dimensional analysis and correlating existing data on dense cloud dispersion. Atmospheric stability was found to have little effect on the results and is not a part of the model. The model requires a specification of the initial cloud volume. Following a typical puff release. After sufficient dilution occurs. United Kingdom: Health and Safety Executive. This result can be due to a gas with a molecular weight greater than that of air or a gas with a low temperature resulting from autorefrigeration during release or other processes. Subsequently the cloud height increases because of further entrainment of air across both the vertical and the horizontal interfaces. Britter and J. and the initial gas density. Considerable initial dilution occurs because of the gravity-driven intrusion of the cloud into the ambient air. the initial plume volume flux. is the initial buoyancy factor (length/time2). The model is best suited for instantaneous or continuous ground-level releases of dense gases. normal atmospheric turbulence predominates over gravitational forces and typical Gaussian dispersion characteristics are exhibited. The first step is to determine whether the dense gas model is applicable. and the ambient gas density. 1°R. Also required is the wind speed at a height of 10 m. The dense cloud slumps toward the ground under the influence of gravity. is the density of ambient air (mass/volume). is the initial density of released material (mass/volume). a cloud having similar vertical and horizontal dimensions (near the source) may form. McQuaid. the distance downwind. Actual instantaneous concentrations may vary by as much as a factor of 2 from the concentrations computed using Gaussian models. increasing its diameter and reducing its height. 1988). Most of the data came from dispersion tests in remote rural areas on mostly flat terrain. . Thus it is possible for instantaneous local concentrations to exceed the average values predicted . E.

then Figures 5-13 and 5-14 are used to estimate the downwind concentrations.is the initial volume of released dense gas material (length3). dependent on the type of release. is the initial plume volume flux for dense gas dispersion (volume/time). q. and. Tables 5-4 and 5-5 provide equations for the correlations in these figures. is the characteristic source dimension for continuous releases of dense gases (length).196 Chapter 5 Toxic Release and Dispersion Models A characteristic source dimension. is the release duration (time) and x is the downwind distance in dimensional space (length). The criteria for determining whether the release is continuous or instantaneous is calculated using the following group: where R. If these criteria are satisfied.. and u is the wind speed at 10 m elevation (lengthltime). . The criteria for a sufficiently dense cloud to require a dense cloud representation are. for instantaneous releases. for continuous releases. For continuous releases where D. can also be defined. For instantaneous releases the characteristic source dimension is defined as where Di is the characteristic source dimension for instantaneous releases of dense gases (length) and V.

. - - 10' - - I 0.5-3 Dense Gas Dispersion 197 Figure 5-13 Britter-McQuaid dimensional correlation for dispersion of dense gas plumes.1 I Passive limit I data region Figure 5-14 Britter-McQuaid dimensional correlation for dispersion of dense gas puffs.

If the difference between the two calculations is small. If the group value is less than or equal to 0. which provides a limit to the effect of heat transfer. then the release is considered instantaneous. If the . then the concentrations are calculated using both continuous and instantaneous models and the maximum concentration result is selected. If the value lies in-between.Chapter 5 Toxic Release and Dispersion Models Table 5-4 Equations Used to Approximate the Curves in the Britter-McQuaidCorrelations Provided in Figure 5-13 for Plumes Concentration ratio (CmICo) Valid range for P = log [-I x (qo/u)'" If this group has a value greater than or equal to 2. For nonisothermal releases the Britter-McQuaid model recommends two slightly different calculations. If the two calculations are within a factor of 2. For gases lighter than air (such as methane or liquefied natural gas) the second calculation might be meaningless. For the first calculation a correction term is applied to the initial concentration (see Example 5-3). then the nonisothermal effects are assumed negligible. then the calculation providing the maximum. concentration is used.6. then the dense gas release is considered continuous. For the second calculation heat addition is assumed at the source to bring the source material to ambient temperature.5. or most pessimistic.

are overly conservative and are designed for worker exposures. not short-term exposures under emergency conditions. then the maximum. The model is also unable to account for the effects of parameters such as release height. These models are also capable of including the effects resulting from transient changes in toxic concentrations.5-4 Toxic Effect Criteria 199 Table 5-5 Equations Used to Approximate the Curves in the Britter-McQuaid Correlations Provided in Figure 5-14 for Puffs Concentration ratio (CmICo) Valid range for difference is very large (greater than a factor of 2). based on a correlation developed from experimental data. However. and wind speed profiles. ground roughness. discussed in chapter 2. One approach is to use the probit models developed in chapter 2. The Britter-McQuaid model is a dimensional analysis technique. concentration is selected. the model is based only on data from flat rural terrain and is applicable only to these types of releases. or most pessimistic. the question arises: What concentration is considered dangerous? Concentrations based on TLV-TWA values. but further investigation using more detailed methods (such as a computer code) may be worthwhile. Unfor- . 5-4 Toxic Effect Criteria Once the dispersion calculations are completed.

ERPGs are prepared by an industry task force and are published by the AIHA. These criteria and methods are based on a combination of results from animal experiments. and expanded by an AIHA peer review task force. and toxic endpoints promulgated by the EPA as part of the RMP. ERPG-3 is the maximum airborne concentration below which it is believed nearly all individuals could be exposed for up to 1hr without experiencing or developing life-threatening health effects (similar to EEGLs). including short-term exposure limits (TLV-STELs) and ceiling concentrations (TLV-Cs). ERPG-1 is the maximum airborne concentration below which it is believed nearly all individuals could be exposed for up to 1 hr without experiencing effects other than mild transient adverse health effects or perceiving a clearly defined objectionable odor. NIOSH publishes IDLH concentrations to be used as acute toxicity measures for common industrial gases. To date. and the data show wide variations from the correlations. PELS promulgated by OSHA. TLVs established by the ACGIH. One simplified approach is to specify a toxic concentration criterion above which it is assumed that individuals exposed to this value will be in danger. ERPG data are shown in Table 5-6. updated. ERPGs are becoming an acceptable industry1 government norm.200 Chapter 5 Toxic Release and Dispersion Models tunately.and short-term human exposures. observations of long. published correlations are available for only a few chemicals. toxicity dispersion (TXDS) methods used by the New Jersey Department of Environmental Protection. IDLH levels established by NIOSH. emergency exposure guidance levels (EEGLs) and short-term public emergency guidance levels (SPEGLs) issued by the National Academy of Sciences/National Research Council. 3. and expert judgment. 47 ERPGs have been developed and are being reviewed. An IDLH exposure condition is defined as a condition "that poses a threat of . Three concentration ranges are provided as a consequence of exposure to a specific substance: 1. Some of these criteria and methods include emergency response planning guidelines (ERPGs) for air contaminants issued by the American Industrial Hygiene Association (AIHA). The following paragraphs define these criteria and describe some of their features. ERPG-2 is the maximum airborne concentration below which it is believed nearly all individuals could be exposed for up to 1 hr without experiencing or developing irreversible or other serious health effects or symptoms that could impair their abilities to take protective action. Because of the comprehensive effort to develop acute toxicity values. 2. This approach has led to many criteria promulgated by several government agencies and private associations.

3-Butadiene n-Butyl acrylate n-Butyl isocyanate Carbon disulfide Carbon tetrachloride Chlorine Chlorine trifluoride Chloroacetyl chloride Chloropicrin Chlorosulfonic acid Chlorotrifluoroethylene Crotonaldehyde Diborane Diketene Dimethylamine Dimethylchlorosilane Dimethyl disulfide Epichlorohydrin Ethylene oxide Formaldehyde Hexachlorobutadiene Hexafluoroacetone Hexafluoropropylene Hydrogen chloride Hydrogen cyanide Hydrogen fluoride Hydrogen sulfide Isobutyronitrile 2-Isocyanatoethyl methacrylate Lithium hydride Methanol Methyl chloride Methylene chloride Methyl iodide ERPG-1 ERPG-2 ERPGQ 1000 3 750 75 300 1000 1000 25 5 5000 250 1 500 750 20 10 10 3 30 mg/m3 300 50 3 50 500 25 250 100 500 25 30 50 500 100 25 50 100 200 1 500 pglm3 5.000 1000 4000 125 (continued) .5-4 Toxic Effect Criteria Table 5-6 Emergency Response Planning Guidelines (ERPGs)l (all values are in ppm unless otherwise noted) Chemical Acetaldehyde Acrolein Acrylic acid Acrylonitrile Ally1 chloride Ammonia Benzene Benzyl chloride Bromine 1.

Because IDLH values were developed to protect healthy worker populations. all unprotected workers must leave the area immediately. that could prevent escape. such as older. (Fairfax. IDLH data are currently available for 380 materials."~] IDLH values also take into consideration acute toxic reactions. If IDLH values are exceeded. The IDLH level is considered a maximum concentration above which only a highly reliable breathing apparatus providing maximum worker protection is permitted. they must be adjusted for sensitive populations. or ill populations. 1994). An EEGL is defined as a concentration of a gas. Since the 1940s.202 Chapter 5 Toxic Release and Dispersion Models Table 5-6 Chemical (continued) ERPG-1 ERPG-2 ERPG-3 Methyl isocyanate Methyl mercaptan Methyltrichlorosilane Monomethylamine PerAuoroisobutylene Phenol Phosgene Phosphorus pentoxide Propylene oxide Styrene Sulfonic acid (oleum. such as severe eye irritation. For flammable vapors the IDLH concentration is defined as one-tenth of the lower flammability limit (LFL) concentration. or aerosol that is judged acceptable and that allows exposed individuals to perform specific tasks during emergency conditions lasting from 1to 24 hr. 1996). vapor. the National Research Council's Committee on Toxicology has submitted EEGLs for 44 chemicals of special concern to the Department of Defense. Also note that IDLH levels have not been peer-reviewed and that no substantive documentation for the values exists. and sulfuric acid) Sulfur dioxide Tetrafluoroethylene Titanium tetrachloride Toluene Trimethylamine Uranium hexafluoride Vinyl acetate - 'AIHA. Emergency Response Planning Guidelines and Workplace ~ivironmental Exposure Levels American Industrial Hygiene Association. disabled. NIOSH Pocket Guide to Chemical Hazards. sulfur trioxide. DC: US Department of Health and Human Services. Publication 94-116 (Washington. VA: exposure to airborne contaminants when that exposure is likely to cause death or immediate or delayed permanent adverse health effects or prevent escape from such an en~ironment. Exposure to concentrations at the EEGL may produce transient irritation or central nervous sys" N I O S H . .

such effects include irritation and narcosis." or "action levels" may be appropriate for use as benchmarks. These criteria are discussed in chapter 2. Certain (ACGIH) criteria may be appropriate for use as benchmarks. the most directly relevant toxicologic criteria currently available. The advantages of using EEGLs and SPEGLs rather than IDLH values are (1) a SPEGL considers effects on sensitive populations. (2) the median lethal concentration (LC50) value from animal test data multiplied by 0.TLV-STELs and TLV-Cs . An acute toxic concentration (ATC) is defined as the concentration of a gas or vapor of a toxic substance that will result in acute health effects in the affected population and 1fatality out of 20 or less (5% or more) during a 1-hr exposure. SPEGLs. defined as acceptable concentrations for exposures of members of the general public. In addition to EEGLs. The EPA has promulgated a set of toxic endpoints to be used for air dispersion modeling for toxic gas releases as part of the EPA RMP. in order of preference.1. For incidents involving substances for which no I2EPA. (2) EEGLs and SPEGLs are developed for several different exposure durations. The LOC is considered "the maximum concentration of an extremely hazardous substance in air that will not cause serious irreversible health effects in the general population when exposed to the substance for relatively short duration. These criteria can be used for toxic gas dispersion but typically produce a conservative result because they are designed for worker exposures. and EEGLs. OSHA-cited "acceptable ceiling concentrations. The PELS are promulgated by OSHA and have force of law. are estimated for 103 "extraordinarily hazardous substances" and are based on the lowest value of one of the following: (1) the lowest reported lethal concentration (LCLO) value for animal test data. SPEGLs are generally set at 10-50% of the EEGL and are calculated to take account of the effects of exposure on sensitive heterogeneous populations.5-4 Toxic Effect Criteria 203 tem effects but should not produce effects that are lasting or that would impair performance of a task. DC: US Environmental Protection Agency. as proposed by the New Jersey Department of Environmental Protection. These were developed specifically to apply to general populations and to account for sensitive populations and scientific uncertainty in toxicologic data. RMP Offsite Consequence Analysis Guidance (Washington. The ACGIH threshold limit values . These levels are similar to the ACGIH criteria for TLV-TWAs because they are also based on 8-hr time-weighted average exposures. (1) the ERPG-2 or (2) the level of concern (LOC) promulgated by the Emergency Planning and Community Right-to-Know Act. are ERPGs." Toxic endpoints are provided for 74 chemicals under the RMP rule and are shown in Table 5-8.are designed to protect workers from acute effects resulting from exposure to chemicals. or (3) the IDLH value. particularly for developing emergency response plans. 1996). . ATC values. In general. the National Research Council has developed SPEGLs." "excursion limits. EEGL and SPEGL values are shown in Table 5-7. The New Jersey Department of Environmental Protection uses the TXDS method of consequence analysis to estimate potentially catastrophic quantities of toxic substances.12 The toxic endpoint is. as required by the New Jersey Toxic Catastrophe Prevention Act (TCPA). and (3) the methods by which EEGLs and SPEGLs were developed are well documented in National Research Council publications.

2 2 mg/m3 10 1 mg/m3 200 200 ppm 1500 1500 .000 1 0.204 Chapter 5 Toxic Release and Dispersion Models Table 5-7 Emergency Exposure Guidance Levels (EEGLs) from the National Research Council (NRC) (all values are in ppm unless otherwise noted) - Compound Acetone Acrolein AIuminum oxide Ammonia Arsine Benzene Bromotrifluoromethane Carbon disulfide Carbon monoxide Chlorine Chlorine trifluoride Chloroform Dichlorodifluoromethane Dichlorofluoromethane Dichlorotetrafluoroethane l. 1-hr EEGL 24-hr EEGL Source NRC I NRC I N R C IV N R C VII NRC I N R C VI N R C 111 NRC I N R C IV N R C I1 N R C I1 NRC I N R C I1 N R C I1 N R C I1 NRC V N R C I1 N R C IV N R C VI NRC I NRC V N R C VII N R C IV N R C I1 N R C VII N R C VIII NRC I NRC I N R C IV NRC V N R C IV N R C IV NRC I N R C I1 N R C I1 N R C I1 NRC I N R C VII N R C VIII NRC T I N R C I1 N R C TI NRC T I 400 15 mglm" 100 pg lm" 200 0.l -Dimethylhydrazine Ethanolamine Ethylene glycol Ethylene oxide Fluorine Hydrazine Hydrogen chloride Hydrogen sulfide Isopropyl alcohol Lithium bromide Lithium chromate Mercury (vapor) Methane Methanol Methylhydrazine Nitrogen dioxide Nitrous oxide Ozone Phosgene Sodium hydroxide Sulfur dioxide Sulfuric acid Toluene Trichloroethylene Trichlorofluoromethane Trichlorotrifluoroethane Vinylidene chloride Xylene ISPEGL value.24 1' 10.

018 0.4-diisocyanate Toluene 2.6-diisocyanate Toluene diisocyanate (unspecified) Trimethylchlorosilane Vinyl acetate monomer - Toxic endpoint (mg/L) 0.0035 0.090 0.020 0.030 0.028 0.085 0. DC: US Environmental Protection Agency.050 0.0019 0.59 0.0070 0.042 0.010 0.0028 0.012 0. RMP Offsite Consequence Analysis Guidance (Washington.036 0.00066 0.023 0.0012 0.00025 0.0011 0.016 0.0027 0.00067 0.82 0.0018 0.0092 0.16 0.026 0.0030 0.00090 0.0012 0.0045 0.0011 0.10 0.011 0.031 0.029 'EPA.018 0.030 0.076 0.01 Chemical name Gases Ammonia (anhydrous) Arsine Boron trichloride Boron trifluoride Chlorine Chlorine dioxide Cyanogen chloride Diborane Ethylene oxide Fluorine Formaldehyde (anhydrous) Hydrocyanic acid Hydrogen chloride (anhydrous) Hydrogen fluoride (anhydrous) Hydrogen selenide Hydrogen sulfide Methyl chloride Methyl mercaptan Nitric oxide Phosgene Phosphine Sulfur dioxide (anhydrous) Sulfur tetrafluoride Liquids Acrolein Acrylonitrile Acrylyl chloride Allyl alcohol Allylamine Arsenuous trichloride Boron trifluoride compound with methyl ether (1 :1) Bromine Carbon disulfide Chloroform Chloromethyl ether Chloromethyl methyl ether Crotonaldehyde Chemical name Liquids (continued) Cyclohexylamine Dimethyldichlorosilane 1.049 0.012 0. pentacarbonylIsobutyronitrile Isopropyl chloroformate Methacrylonitrile Methyl chloroformate Methyl hydrazine Methyl isocyanate Methyl thiocyanate Methyltrichlorosilane Nickel carbonyl Nitric acid (100%) Peracetic acid Perchloromethylmercaptan Phosphorus oxychloride Phosphorus trichloride Piperidine Propionitrile Propyl chloroformate Propyleneimine Propylene oxide Sulfur trioxide Tetramethyllead Tetranitromethane Titanium tetrachloride Toluene 2.0040 0.0078 0.022 0.0019 0.0076 0.0070 0.0037 0.0065 0.16 0.14 0.0040 0.26 - 0.010 0.028 0.l-Dimethylhydrazine Epichlorohydrin Ethylenediamine Ethyleneimine Furan Hydrazine Iron.026 0.00081 0.010 0.5-4 Toxic Effect Criteria 205 Table 5-8 Toxic Endpoints Specified by the EPA Risk Management Plan1 Toxic endpoint (mg/L) 0.076 0.00044 0.0070 0.49 0.12 0.0032 0.0094 0.0039 0.0087 0.49 0. 1996) .14 0.011 0.

J. Petrocchi. such as sensory irritation or odor perception. K. "Alternative Guideline Limits for Chemicals without Environmental Response Planning Guidelines.5 ppm. J.Chapter 5 Toxic Release and Dispersion Models Table 5-9 Primary guideline ERPG-3 Recommended Hierarchy of Alternative Concentration Guidelines1 Hierarchy of alternative guidelines EEGL (30-minute) IDLH Source AIHA NRC NIOSH AIHA NRC EPAIFEMAIDOT OSHA ACGIH ACGIH AIHA OSHA ACGIH ACGIH ERPG-2 EEGL (60 minute) LOC PEL-C TLV-C 5 X TLV-TWA ERPG-3 PEL-STEL TLV-STEL 3 X TLV-TWA AIHA: American Industrial Hygiene Association NIOSH: National Institute for Occupational Safety and Health NRC: National Research Council Committee on Toxicology EPA: Environmental Protection Agency FEMA: Federal Emergency Management Agency DOT: US Department of Transportation OSHA: US Occupational Safety and Health Administration ACGIH: American Conference of Governmental Industrial Hygienists ID. R. J. D. J. Davis. DeVore. Powell. A. IDLH levels provide alternative criteria. This hierarchy is shown in Table 5-9. Petrocchi. The use of TLV-STELs and ceiling limits may be most appropriate if the objective is to identify effect zones in which the primary concerns include more transient effects. Effect zones resulting from the release of this gas are defined as any zone in which the concentration of chlorine dioxide is estimated to exceed 0. . 56. J. Craig. the approach is conservative and gives unrealistic results. because IDLH levels were not developed to account for sensitive populations and because they were based on a maximum 30-min exposure period. S. Hansen. 13D. the EPA suggests that the identification of an effect zone should be based on exposure levels of one-tenth the IDLH level. persons located outside the zone that is based on these limits can be assumed to be unaffected by the release. and T. However. "Alternative Guideline Limits for Chemicals without Environmental Response Planning Guidelines. Craig et al. R. J. Davis. Powell. D. and T.I3 provided a hierarchy of alternative concentration guidelines in the event that ERPG data are not available. K. Craig. SPEGLs or EEGLs are available. A. In general. S. Of course. DeVore. Hansen." AIHA Journal (1995)." AIHA Journal (1995). For example. 56. J. the IDLH level for chlorine dioxide is 5 ppm. J. a more realistic approach is to use a constant-dose assumption for releases less than 30 min using the IDLH level.

The location of the maximum concentration is found from Equation 5-53: . Good judgement should prevail. Example 5-1 On an overcast day a stack with an effective height of 60 m is releasing sulfur dioxide at the rate of 80 gls. b. The stack is located in a rural area. The location and value of the maximum mean concentration on ground level directly downwind. Determine a. Solution a. The mean concentration on the ground 500 m downwind and 50 m crosswind. The wind speed is 6 m/s. The mean concentration of SO2 on the ground 500 m downwind. Using Table 5-2: Substituting into Equation 5-51. The dispersion coefficients are obtained from either Figure 5-11 or Table 5-2. we obtain b. The ground concentration directly downwind is given by Equation 5-51: From Table 5-1 the stability class is D.5-4 Toxic Effect Criteria 207 These methods may result in some inconsistencies because the different methods are based on different concepts. The mean concentration 50 m crosswind is found by using Equation 5-50 and by setting y = 50. c. The results from part a are applied directly: c. This is a continuous release.

For a distance of 500 m and a wind speed of 2 m/s. a = 88 m. The maximum concentration of chlorine in the residential area.= ---. a has this value at about 1200 m downwind. 5-10 or Table 5-2. b. at a point 5 km directly downwind on the ground. From Figure .0 kg of chlorine will be released instantaneously.250 s = 4. based on the ERPG-1. This is for nighttime conditions with thin to light .2 min. Assume a wind speed of 2 mls. The concentration is given by Equation 5-41: The stability conditions are selected to maximize (C)in Equation 5-41. The release will occur at ground level.. u 2 m/s This leaves very little time for emergency warning. From Figure 5-12 the lowest value of either dispersion coefficient occurs with F stability conditions. What stability conditions and wind speed produces the maximum concentration? c.0 ppm. Use the conditions of part b. Compare this with an ERPG-1 for chlorine of 1. b. Assume the conditions of part b. Determine a. Determine the size of the cloud. A residential area is 500 m away from the chlorine source.208 Chapter 5 Toxic Release and Dispersion Models From Figure 5-10 for D stability. The maximum concentration is determined using Equation 5-52: Example 5-2 Chlorine is used in a particular chemical process. the time required for the center of the cloud to reach the residential area is t = x 500m . . This requires dispersion coefficients of minimum value. The maximum concentration occurs at the center of the cloud directly downwind from the release. The time required for the center of the cloud to reach the residential area. Solution a. Determine the distance the cloud must travel to disperse the cloud to a maximum concentration below the ERPG-I. Assume in all cases that the chlorine cloud released is neutrally buoyant (which might not be a valid assumption). A source model study indicates that for a particular accident scenario 1. d.

Thus From Equation 5-41 This is converted to ppm using Equation 2-6.a. From Table 2-7 the ERPG-1 of 1. t ) = Q: 1 x-ut f i ~ ~ ~ ~ aexp[-?(_) . d. The downwind centerline concentration is given by Equation 5-40: ( C ) ( x . c.0 mg/m3or 3. we obtain The distance downwind is solved using the equations provided in Table 5-3. we calculate .0 km downwind. This is much higher than the ERPG-1 of 1.0.0 ppm.0 X kg/m3. The concentration at the center of the cloud is given by Equation 5-41. Assuming a pressure of 1 atm and a temperature of 298 K.5-4 Toxic Effect Criteria 209 overcast and a wind speed less than 3 m/s. Any individuals within the immediate residential area and any personnel within the plant will be excessively exposed if they are outside and downwind from the source.0 ppm is 3. The maximum concentration in the puff also occurs at the closest point to the release in the residential area. Substituting the known values. This occurs at a distance of 500m.a. 1- The time required for the center of the plume to arrive is At a downwind distance of x = 5 km = 5000 m and assuming F stability conditions. 0. the concentration in ppm is 798 ppm. Thus for F stability Solving for x by trial and error results in x = 8.

5000 0.): 174 s. LNG vapor density at boiling point of -162°C: 1.23 m3/s. The quantity (x . Solution The volumetric discharge rate is given by The ambient air density is computed from the ideal gas law and gives a result of 1.8 m wide at this point. Assume ambient conditions of 298 K and 1atm.E. .2 ( 39. United Kingdom: Health and Safety Executive. An appropriate emergency procedure would be to alert residents to stay indoors with the windows closed and ventilation off until the cloud passes. 1988). Britter and J. An effort by the plant to reduce the quantity of chlorine released is also indicated.5000) represents the width of the plume. Thus from Equation 5-59: 14R. Workbook on the Dispersion of Dense Gases (Sheffield. LNG density: 425. Wind speed at 10 m above ground (u): 10.6 kg/m3.76 kg/m3. The following data are available: Spill rate of liquid: 0. Spill duration (R.9 mls. based on the ERPG-1 concentration. McQuaid.2m [ 11' The cloud is 87. At 2 m/s it will take approximately to pass.22 kg/m3.326 = exp -. Solving for this quantity.210 Chapter 5 Toxic Release and Dispersion Models Substituting the numbers provided gives where x has units of meters. Example 5-314 Compute the distance downwind from the following liquefied natural gas (LNG) release to obtain a concentration equal to the lower flammability limit (LFL) of 5% vapor concentration by volume. we obtain 1 x .

S t e p 4. Substituting the appropriate numbers gives and it is clear that the dense cloud model applies.05. Compute the dimensionless groups for Figure 5-13: and S t e p 5. S t e p 3. and the quantity must be greater than 2. the equation for Cgives an effective concentration of 0. = 0. For our required concentration of 0. For this case expression 5-64 applies.IC. Determine whether the release is considered continuous or instantaneous. and it follows that C. is essentially pure LNG. then the effective concentration is given by where Tais the ambient temperature and Tois the source temperature. From Figure 5-13. .019. Apply Figure 5-13 to determine the downwind distance. For this case Equations 5-60 and 5-62 apply. both in absolute temperature.019. Thus Co = 1. The Britter-MacQuaid model provides an adjustment to the concentration to account for nonisothermal release of the vapor.5-4 Toxic Effect Criteria 21 1 S t e p 1. If the original concentration is C*. S t e p 2. The initial concentration of gas C. Adjust the concentration for a nonisothermal release.5 for a continuous release.. Determine whether a dense cloud model applies.0.. Substituting the required numbers gives and it follows that for a continuous release The final distance must be less than this.

p. Thus the material continues to rise after its release from the stack. d is the inside stack diameter (in m). I5D. if the material is released above ground level. based on its upward velocity within the stack pipe. a release of vapor at a temperature higher than the ambient air temperature will rise because of buoyancy effects. increasing the effective height of the release. because its temperature is higher than the ambient temperature. u is the wind speed (in mls). The material released from the smokestack contains momentum. The initial momentum and buoyancy change the effective height of release. is the correction to the release height H.. . A release that occurs at ground level but in an upward spouting jet of vaporizing liquid has a greater effective height than a release without a jet.Chapter 5 Toxic Release and Dispersion Models and it follows that x = (2. This compares to an experimentally determined distance of 200 m. Similarly. The upward rise is slowed and eventually stopped as the released material cools and the momentum is dissipated. and it is also buoyant. 31. - For heavier-than-air vapors. and Welfare. Workbook of Atmospheric Dispersion Estimates (Cincinnati: U S Department of Health. then the material will initially fall toward the ground until it disperses enough to reduce the cloud density. 1970). This demonstrates that dense gas dispersion estimates can easily be off by a factor of 2. and Tais the air temperature (in K). Bruce Turner.26 m)(126) = 285 m. 5-5 Effect of Release Momentum and Buoyancy Figure 5-6 indicates that the release characteristics of a puff or plume depend on the initial release momentum and buoyancy. is the stack gas temperature (in K). Both effects are demonstrated by the traditional smokestack release shown in Figure 5-15. T. - usis the stack gas exit velocity (in mls). Education. For smokestack releases Turner suggested using the empirical Holland formula to compute the additional height resulting from the buoyancy and momentum of the release: where AH. P is the atmospheric pressure (in mb).

it is better to prevent the release in the first place. Guidelines for Vapor Release Mitigation (New York: American Institute of Chemical Engineers. Release mitigation is defined as "lessening the risk of a release incident by acting on the source (at the point of release) either (1) in a preventive way by reducing the likelihood of an event that could generate a hazardous vapor cloud or (2) in a protective way by reducing the magnitude of the release andlor the exposure of local persons or property. engineering design. a source model is used to determine either the release rate or the total quantity released. the effort might not be required. Both the consequence and the probability must be included to assess risk. reducing the time available for an emergency response procedure.5-6 Release Mitigation 213 Gases mix C O O cool as t h e y N e u t r a l Buoyancy and d i l u t e with l a i r . Johnson. 1988). and management should be the first issues considered in any release mitigation procedure. After selection of a release incident. Clearly. leading to extensive plant mitigation efforts to reduce the consequence. This is coupled to a dispersion model and subsequent models for fires or explosions. this impact can occur minutes after the initial release. 16Richard W. Thus an estimate of the consequences of a release provides only half the total risk assessment. 2. o f h o t gases Figure 5-15 Smokestack plume demonstrating initial buoyant rise o hot gases. if the probability is low. p. Prugh and Robert W. Inherent safety. Table 5-10 contains a number of measures to mitigate a release. f 5-6 Release Mitigation The purpose of the toxic release model is to provide a tool for performing release mitigation. In addition. It is possible that a particular release incident might have high consequences. The example problems presented in this chapter demonstrate that a small release can result in significant downwind impact. Finally." l 6 The release mitigation procedure is part of the consequence modeling procedure shown in Figure 4-1. . an effect model is used to estimate the impact of the release. Risk is composed of both consequence and probability. which is a measure of the consequence. However.

procedures. Suggested Reading Vapor Cloud Modeling Guidelines for Consequence Analysis of Chemical Releases (New York: American Institute of Chemical Engineers. and drills Major area Inherent safety Engineering design Management Early vapor detection and warning Countermeasures Emergency response 'Richard W. Johnson. 1988). . Guidelines for Vapor Cloud Dispersion Models. training. Guidelines for Vapor Release Mitigation (New York: American Institute of Chemical Engineers.Chapter 5 Toxic Release and Dispersion Models Table 5-10 Release Mitigation Approaches1 Examples Inventory reduction: Less chemicals inventoried or less in process vessels Chemical substitution: Substitute a less hazardous chemical for one more hazardous Process attentuation: Use lower temperatures and pressures Plant physical integrity: Use better seals or materials of construction Process integrity: Ensure proper operating conditions and material purity Process design features for emergency control: Emergency relief systems Spill containment: Dikes and spill vessels Operating policies and procedures Training for vapor release prevention and control Audits and inspections Equipment testing Maintenance program Management of modifications and changes to prevent new hazards Security Detection by sensors Detection by personnel Water sprays Water curtains Steam curtains Air curtains Deliberate ignition of explosive cloud Dilution Foams On-site communications Emergency shutdown equipment and procedures Site evacuation Safe havens Personal protective equipment Medical treatment On-site emergency plans. 2d ed. 1999). Prugh and Robert W. 1996). (New York: American Institute of Chemical Engineers.

The toluene is pumped from a 50-gal drum into a countercurrent centrifugal extractor. 1988). ch. 12. John H. Bruce Turner. 1999). (London: Butterworths. Lees. and 14.Problems 215 International Conference and Workshop on Modeling the Consequences of Accidental Releases of Hazardous Materials (New York: American Institute of Chemical Engineers. Loss Prevention in the Process Industries. 15 and 18. where it is burned. The propane-air mixture then arrives at the burner assembly. A backyard barbeque grill contains a 20-lb tank of propane. Atmospheric Chemistry and Physics ofAir Pollution (New York: Wiley.13. 1970). Contaminated toluene is fed to a water wash system shown in Figure 5-16. The propane leaves the tank through a valve and regulator and is fed through a 112-in rubber hose to a dual valve assembly. Education. The extractor W a t e r f r o m Supply a t 40 psig r Z Centrifugal Extractor C l e a n Toluene (50 Gallon Drum) Dirty W a t e r (50 G a l l o n Drum) Dirty Toluene (50 Gallon Drum) \ Figure 5-16 Toluene water wash process. 5-2. Guidelines for Vapor Release Mitigation (New York: American Institute of Chemical Engineers. After the valves the propane flows through a dual set of ejectors where it is mixed with air. Workbook of Atmospheric Dispersion Estimates (Cincinnati: US Department of Health. ch. D. 1986). Seinfeld. Johnson. 1996). and Welfare. Describe the possible propane release incidents for this equipment. Frank P. Prugh and Robert W. Problems 5-1. 2d ed. . Release Mitigation Richard W.

determine the location of the 5 mg/m3 ground-level isopleth. Estimate the amount of acrolein that must be instantaneously released at ground level to produce a concentration at the boundary of the residential area equal to the ERPG-1. and the wind speed is 18 kmlhr. A burning dump emits an estimated 3 g/s of oxides of nitrogen.1 ppm) is located 1500 m from a residential area. 5-5.- - - - - - 216 Chapter 5 Toxic Release and Dispersion Models 5-3. 5-9.0 X lops g/m3.? A storage tank containing acrolein (ERPG-1 = 0. Diborane is used in silicon chip manufacture.M. b. Consider again Problem 5-7. 5-7. The washed toluene and contaminated water flow into 50-gal drums. Reconsider Problem 5-10. The concentration at the center of the cloud. On a sunny day with a 2 mls wind the concentration of sulfur dioxide 200 m directly downwind is measured at 5. The cement plant releases fine particulates (less than 15 . 5-6. separates the water from the toluene by centrifugal force acting on the difference in densities.6 mg/m3. 5-11. Assume now that the bottle ruptures and that the entire contents of diborane are released instantaneously. One facility uses a 500-lb bottle. You have been suddenly enveloped by a plume of toxic material from a nearby chemical plant. What is the release rate required to produce an average concentration at the boundary to the residential area equal to the ERPG-I? The concentration of vinyl chloride 2 km downwind from a continuous release 25 m high is 1. . Assume that the release is at ground level. A trash incinerator has an effective stack height of 100 m. Also estimate the maximum sulfur dioxide concentration expected on the ground and its location downwind from the stack. Estimate the mass release rate (in gls) of sulfur dioxide from this stack.1 km perpendicular to the plume 2 km downwind. but assume a continuous release at ground level. Determine. It is a sunny day. The location of the 5 mg/m3 isopleth. The location of the vapor cloud. sunny day with a 5 mph wind. It is a clear. If the entire bottle is released continuously during a 20-min period. Determine a number of release incidents for this equipment. a. What is the concentration of particulates at the air sampling station when the wind is from 30" at 3 mls on a clear day in the late fall at 4:00 P. What is the average concentration of oxides of nitrogen from this source directly downwind at a distance of 3 km on an overcast night with a wind speed of 7 m/s? Assume that this dump is a point ground-level source. at 15 min after the release.urn diameter) at the rate of 750 lblhr from a 30-m stack. 5-10. The water enters the center of the extractor and flows to the periphery. Determine the average concentration 0. Which way should you run with respect to the wind to minimize your exposure? An air sampling station is located at an azimuth of 203" from a cement plant at a distance of 1500 m. The contaminated toluene enters the extractor at the periphery and flows to the center. 5-8. c. 5-4.

A study of various release scenarios indicates that a rupture of the reactor will spill the liquid into a boiling pool on the ground. 5-15. Determine which chemical presents the greater hazard to the community. nursing homes. f. Identify any special concerns (schools. About 20% by weight of the solid has a particle size less than 10 pm. The total dosage received by an individual standing on the downwind axis at the 15min downwind location. Without any additional information. g.4 mph on a clear night. For chlorine gas. They report the following chemicals and amounts: 100 lb of hydrogen chloride and 100 gal of sulfuric acid.You have been appointed emergency coordinator for the community of Smallville. Determine transportation routes that will be used to transport hazardous materials into or out of the facility. a.000 Ib of solid acrylamide stored in a large bin. and the like) that appear in the transportation route vulnerable zone. . e. Identify any high-risk intersections where accidents might occur. Identify locations that might be affected by a release incident at the plant or might contribute to the incident because of its proximity to the plant.Problems 217 d. determine the distance downwind that must be evacuated. shopping centers. How far and long the cloud will need to travel to reduce the maximum concentration to 5 mg/m3. estimate the area that must be evacuated. evacuation of the population must occur for areas where the vapor concentration exceeds the ERPG-1. 5-14. The boiling rate of MIC has been estimated to be 20 lblmin. shown in Figure 5-17. You are required to develop an emergency plan for the community. A scenario study indicates that all the fine particles could be airborne in a period of 10 min.5 mi on either side of the route. unless a smaller distance is indicated by part b. Assuming all of the chemical is released during a 10-min period. A study of the release scenarios indicates that the entire tank contents could be released as vapor in a period of 10 min. c. 5-12. If evacuation must occur in areas where the particle concentration exceeds 110 mg/m3. e. Use a distance of 0. Evacuation of the population must occur in areas where the vapor concentration exceeds ERPG-1. ABC Chemical Company is shown on the map.A chemical plant has 10. Determine evacuation routes for the areas surrounding the plant. estimate the distance downwind that must be evacuated. d. If the wind speed is 3. The liquid is near its boiling point.A reactor in a pesticide plant contains 1000 lb of a liquid mixture of 50% by weight liquid methyl isocyanate (MIC). 5-13. b. estimate the area downwind that must be evacuated. Determine the vulnerable zone along the transportation routes identified in part d.An 800-lb tank of chlorine is stored at a water treatment plant.

One response to a short-term release is to warn people to stay in their homes or offices with the windows closed and the ventilation off. j. 5-16. Derive an equation for the concentration of chemical vapor within the house based on a parameter. Determine the resources required to support the needs of parts g and h. h. an initial zero concentration of vapor within the house.Derive Equation 5-43. exchanges air with the surroundings equal to three times the volume of the house per hour (although wide variations are expected).Chapter 5 Toxic Release and Dispersion Models r Church MI 5 2 Mega Shopping Center Muddy River -- A Home ---. 5-17.H o s p i t a l MI 52 Little Railway -- Senior --citizens 7 City Hall -- ----- Picnic Area - Apple Road South Road Chemical Srnallville School 0 u in Miles 1 2 P r e v a i l i n g Wind Scale Figure 5-17 Map of Srnallville. Determine alternative traffic routes around the potential hazard. N. Assume wellmixed behavior for the air. Estimate the potential number of people evacuated during an emergency. i. An average house. and a constant external concentration during the exposure period. and describe the content of an example warning message that could be used in an emergency at the facility. 1 What other concerns might be important during a chemical emergency? . Determine how these people are to be moved and where they might be evacuated to. . Identify the means required to warn the area. k. a. equal to the number of volume exchanges per hour.. with the windows closed.

2S°C. 5-20. The toxic endpoint is specified in the RMP as 0.Problems 219 b. What is the maximum hole diameter (in mm) in this tank that will result in a downwind concentration equal to the ERPG-1 at a downwind distance of 300 m? Assume 1 atm. . a molecular weight of chlorine of 70. What does this imply about the size of chemical inventories for chemical plants? 5-21.016 mg/L. A vapor cloud with a maximum concentration of 20 ppm is moving through a community. Determine the distance downwind (in miles) to the toxic endpoint for an EPA worst-case release. Many plants have much larger vessels on site. with doors and windows closed.5 m/s wind speed. and that all the liquid chlorine vaporizes. 5-19. The emergency coordinator has decided that the appropriate emergency response to the immediate release of a toxic material is to alert people to stay in their homes. each facility must determine the downwind distance to a toxic endpoint. etc. A tank has ruptured and a pool of benzene has formed. wind speed. 5-22. until the cloud has passed. what is the maximum time available to the plant personnel to stop or reduce the release to ensure that the concentrations within the homes do not exceed the 10 ppm value? 5-18. If the supply line ruptures.9. b.000 Pa). The temperature is 90°F. A plant has a 100-lbtank of anhydrous hydrogen fluoride (molecular weight = 20). a.3 mglm3.10 mg/m3 of this material for any longer than 2 min. Comment on how a larger quantity would affect the downwind distance and how this might affect the public's perception of your facility. Define the plume boundary using the TLV-TWA of 10 ppm. A supply line (internal diameter = 0. One hundred pounds of HF is a small quantity. Determine the time before the vapor concentration within an average house reaches 10 ppm. If the wind is blowing at 2 mph and the plant is 1mi upwind from the community. The release is near ground level. Assume an overcast day with a 15 mph wind and a temperature of 80°F. The EPA Risk Management Plan (RMP) defines a worst-case scenario as the catastrophic release of the entire process inventory in a 10-min period (assumed to be a continuous release). Be sure to clearly state any assumptions about weather conditions. The dispersion calculations must be completed assuming F stability and 1. It is an overcast day with a 9 mph wind. Estimate the evaporation rate and the distance affected downwind. The pool is approximately rectangular with dimensions of 20 ft by 30 ft.493 in) containing chlorine gas is piped from a regulated supply at 50 psig. Estimate the maximum instantaneous release of material (in kg) allowed for these specifications. The coordinator has also indicated that homes 4000 m downwind must not be exposed to concentrations exceeding 0. As part of the RMP rule. Comment on the viability of using a continuous release model for a 10-min release period. c. These results must be reported to the EPA and to the surrounding community. estimate the distance the plume must travel to reduce the concentration to 7. A tank of chlorine contains 1000 kg of chlorine at 50 bar gauge (1 bar = 100. c.

It is estimated that ammonia will release at the rate of 10 lbls if this pipeline ruptures. What recommendation will you make as to the evacuation distance downwind? Assume that the wind speed is 6 mph and that the sun is shining brightly.76 kgls. Determine the maximum width of the plume (in ft) and the distance downwind (in mi) where it occurs. 5-24. Assume that evacuation must occur in any location that exceeds the OSHA PEL. molecular weight of the released material. Assume ambient conditions of 298 K and 1atm. Determine the distance downwind that must be evacuated (in km). The boiling point for the chlorine is -34"C. For this release the hydrogen sulfide in the tank is at a pressure of 1MPa absolute and 2S°C. You have decided that anyone exposed to more than 100 ppm of ammonia must be evacuated until repairs are made. and the density of the liquid at the boiling point is 1470 kg/m3. In this case the relief device has a 3-cm diameter. The wind speed at 10 rn height is 10 mls. It is decided that anyone exposed to potential concentrations exceeding 500 ppm must be evacuated. The spreadsheet output should include. All areas downwind with a concentration exceeding 4 times the PEL must be evacuated. Determine the distance downwind (in mi) that must be evacuated. Assume that the release occurs over a duration of 500 s with a volumetric release rate of 1 m3/s. b. 5-25. It is a cloudy night with a 5 mph wind. You are developing emergency evacuation plans for the local community downwind of your plant. c. Determine the evaporation rate from the dike (in lbls). One scenario identified is the rupture of an ammonia pipeline. downwind centerline concentrations (ppm). release height (m). both y and z dispersion coefficients (m). What evacuation distance downwind will you recommend? 5-26. at each point downwind. a. the release occurs at ground level. It is predicted that if a particular pipeline were to rupture. and isopleth locations (m). A tank containing hydrogen sulfide gas (molecular weight 34) has been overpressured and the relief device has been opened. 5-27.220 Chapter 5 Toxic Release and Dispersion Models 5-23. temperature (K). it would release ammonia at a rate of 100 Ibis. A pipeline carrying benzene has developed a large leak. A cloud of material has formed downwind of the release. pressure (atm). wind speed (mls). the leak occurred in a diked area and the liquid benzene is contained within the square 50 ft X 30 ft dike. and the flow through the relief is equivalent to the flow obtained through a 3-cm-diameter hole in the tank. and it is a clear night with a wind speed of 5. . Emergency plans are being formulated so that rapid action can be taken in the event of an equipment failure. The spreadsheet should have specific cell inputs for release rate (gls). Use a spreadsheet program to determine the location of a ground isopleth for a plume. The temperature is 80°F and the ambient pressure is 1 atm. In this case the flow of gas has been calculated to be 1. Fortunately. Use the Britter-McQuaid dense gas dispersion model to determine the distance to the 1% concentration for a release of chlorine gas. spatial increment (m). and isopleth concentration (ppm). 5-28.5 mls.

and plot the maximum puff width as a function of distance downwind from the release. release height (m). The spreadsheet output should include. all based on the isopleth values. total release (kg). Comment on the difference between the two cases. At what distance downwind does the puff reach its maximum width? b. . Your submitted work should include a brief description of your method of solution. Compare the plume width. both y and z dispersion coefficients. and downwind distance for each case. ambient temperature (K). The spreadsheet output should also include a graph of the isopleth location. Use the spreadsheet for the following case: Release mass: 0. at each point downwind. downwind centerline concentration. you will need a large number of cells. and plots of the isopleth locations. Answer the following questions: a. Otherwise. and isopleth distance off-center (+I-). At what distance and time does the puff dissipate? c. we suggest that you set up the cells to move with the puff center.Problems 221 The spreadsheet should also have cells providing the downwind distance. and isopleth concentration (ppm). Develop a spreadsheet to determine the isopleths for a puff at a specified time after the release of material. molecular weight of released gas. the total area of the plume. and the maximum width of the plume. area. Use the following two cases for computations. outputs from the spreadsheet. and assume worst-case stability conditions: Case a: Release rate: 200 g/s Release height: 0 m Molecular weight: 100 Temperature: 298 K Pressure: 1atm Isopleth concentration: 10 ppm Case b: Same as above. but release height = 10 m. 5-29. downwind location.5 kg Release height: 0 m Molecular weight of gas: 30 Ambient temperature: 298 K Ambient pressure: 1 atm Isopleth concentration: 1 ppm Atmospheric stability: F Run the spreadsheet for a number of different times. wind speed (mls). The spreadsheet should contain specific cells for user input of the following quantities: time after release (s). Estimate the total area swept out by the puff from initial release to dissipation. ambient pressure (atm). For your spreadsheet construction.

A fixed mass of toxic gas has been released almost instantaneously from a process unit. . C is the concentration in ppm.. a plot of maximum puff width as a function of downwind distance. This is the concentration recorded at a fixed location as the cloud passes. and T is the time interval (min).75 in the probit equation. a plot of the percentage of fatalities vs. and then decreases linearly to zero. The concentration increases linearly to a maximum concentration C. 5-31. Use the total release quantity as a parameter. quantity released. Record the results at enough points to provide an accurate plot of the percentage of fatalities vs. including the puff concentration profile and the percent fatalities. a plot of the concentration profile for the 5-kg case vs. and rerun your spreadsheet for a total release amount of 5 kg. 5-30. Prepare a spreadsheet to calculate the concentration profile around the center of the puff 2000 m downwind from the release.00 instead of 2. Your submitted work must include a single output of the spreadsheet for a total release of 5 kg. a single output of the spreadsheet for a 5-kg release with a probit exponent of 2. and the calculation of the total swept area.222 Chapter 5 Toxic Release and Dispersion Models Your submitted work should include a description of your method of solution. total quantity released. and a complete discussion of your method and your results. How sensitive are the results to this exponent? Hint: Assume that the puff shape and concentration profile remain essentially fixed as the puff passes. Determine the percentage of fatalities at the 2000-m downwind location as a result of the passing puff. the distance in meters from the center of the puff. a complete spreadsheet output at 2000 s after release. Supplemental information: Molecular weight of gas: 30 Temperature: 298 K Pressure: 1atm Release height: 0 Wind speed: 2 m/s Use a probit equation for fatalities of the form where Y is the probit variable. The release occurs at night with calm and clear conditions.00. You have been asked to determine the percentage of fatalities expected 2000 m downwind from the release. Vary the total release quantity to result in a range of fatalities from 0 to 100%. Change the concentration exponent value to 2. A particular release of chlorine gas has resulted in the concentration profile given in Figure 5-18 for the cloud moving downwind along the ground.

What conclusions can be drawn about the results? . 60. passing a fixed location. Time Figure 5-18 Concentration profile for a chlorine gas release. and 100 ppm.Problems 223 Duration cmax Conc. duration of exposure.80. Set up your spreadsheet to include input parameters of cloud duration and maximum concentration.70. The width of the cloud is represented by the duration or time to pass. 50. Draw a curve on the plot for each of the maximum concentrations of 40. Develop a spreadsheet to compute the percentage of fatalities expected as a result of this cloud. as shown. Use your spreadsheet to draw a plot of the percentage of fatalities vs. with this particular shape.

.

Chemical and hydrocarbon plant losses resulting from fires and explosions are substantial. To prevent accidents resulting from fires and explosions.' Additional losses in life and business interruptions are also substantial. with yearly property losses in the United States estimated at almost $300 million (1997 dollars). and procedures to reduce fire and explosion hazards. and an ignition source. Coco. the nature of the fire and explosion process.Organic solvents are the most common source of fires and explosions in the chemical industry. These elements are illustrated by the fire triangle. c 6-1 The Fire Triangle The essential elements for combustion are fuel. engineers must be familiar with the fire and explosion properties of materials. ed. an oxidizer. in that order (see chapter 1). The potential consequences of fires and explosions in pilot plants and plant environments are even greater. shown in Figure 6-1. . persons present may be killed. The combustion of one gallon of toluene can destroy an ordinary chemistry laboratory in minutes. We discuss procedures to reduce fire and explosion hazards in chapter 7. explosions. 1997)..Fires and Explosions hemicals present a substantial hazard in the form of fires and explosions. emphasizing definitions and calculation methods for estimating the magnitude and consequences of fires and explosions. IJames C. Marsh & McLennan. Large Property Damage Losses in the Hydrocarbon-Chemical1ndustry:A Thirty Year Review (New York: J. H. In this chapter we cover the first two topics. and toxic releases. The three most common chemical plant accidents are fires.

air. static electricity. and ignition sources common in the chemical industry are Fuels Liquids: gasoline. The combustion always occurs in the vapor phase. liquid. Two common examples of the three components of the fire triangle are wood. This means a fire will not occur if (1)fuel is not present or is not present in sufficient quantities. liquids are volatized and solids are decomposed into vapor before combustion. oxidizer. oxidizers. is the rapid exothermic oxidation of an ignited fuel. less obvious combinations of chemicals can lead to fires and explosions. air. carbon monoxide. Various fuels. acetone. \ Sides Ignition Source Fire. The fuel can be in solid. or burning. When fuel. but vapor and liquid fuels are generally easier to ignite. pentane Solids: plastics. ammonium nitrite Ignition sources Sparks. and a match. and (3) the ignition source is not energetic enough to initiate the fire. burning will occur. ether. flames. metal particles Gases: acetylene. and a spark. other. hydrogen Oxidizers Gases: oxygen. fibers. or vapor form. and gasoline. However. heat . propane. (2) an oxidizer is not present or is not present in sufficient quantities. chlorine Liquids: hydrogen peroxide. and an ignition source are present at the necessary levels. nitric acid. fluorine. perchloric acid Solids: metal peroxides. wood dust.226 Chapter 6 Fires and Explosions A \ Fire: When A l l Are Connected / N o Fire: + Figure 6-1 The fire triangle.

Fires can also result from explosions. The flash point generally increases with increasing pressure. Each method produces a somewhat different value. As a result. The open-cup flash point is a few degrees higher than the closed-cup flash point. the fire point temperature is higher than the flash point. If the tire ruptures suddenly and all the energy within the compressed tire releases rapidly. whereas explosions release energy rapidly. inadequate vapor is produced to maintain combustion. Flash point (FP):The flash point of a liquid is the lowest temperature at which it gives off enough vapor to form an ignitable mixture with air. the tire is harmlessly deflated. The compressed air within the tire contains energy. Firepoint: The fire point is the lowest temperature at which a vapor above a liquid will continue to burn once ignited. Practical experience has shown that this is not robust enough . Fires release energy slowly. 6-3 Definitions Some of the commonly used definitions related to fires and explosions are given in what follows. and explosions can result from fires.the ignition energies for most flammable materials are too low and ignition sources too plentiful. The two most commonly used methods are open cup and closed cup. At the flash point the vapor will burn but only briefly. depending on the physical configuration of the experimental equipment. If the energy is released slowly through the nozzle. A good example of how the energy release rate affects the consequences of an accident is a standard automobile tire. typically on the order of microseconds. There are several different experimental methods used to determine flash points. Autoignition temperature (AIT):A fixed temperature above which adequate energy is available in the environment to provide an ignition source. 6-2 Distinction between Fires and Explosions The major distinction between fires and explosions is the rate of energy release. current practice is to prevent fires and explosions by continuing to eliminate ignition sources while focusing efforts strongly on preventing flammable mixtures. . Part of the energy released is used to sustain the reaction. the result is a dangerous explosion. These definitions are discussed in greater detail in later sections. Ignition: Ignition of a flammable mixture may be caused by a flammable mixture coming in contact with a source of ignition with sufficient energy or the gas reaching a temperature high enough to cause the gas to autoignite.6-3 Definitions 227 In the past the sole method for controlling fires and explosions was elimination of or reduction in ignition sources. Combustion orfire: Combustion or fire is a chemical reaction in which a substance combines with an oxidant and releases energy.

Unconfined explosions are rarer than confined explosions because the explosive material is frequently diluted below the LFL by wind dispersion. Mechanical explosion: An explosion resulting from the sudden failure of a vessel containing high-pressure nonreactive gas. The subsequent BLEVE is the explosive vaporization of a large fraction of the vessel contents. the hot liquid volatilizes explosively. Dejlagration: An explosion in which the reaction front moves at a speed less than the speed of sound in the unreacted medium. the vapor pressure of the liquid within the tank increases and the tank's structural integrity is reduced because of the heating. As the tank contents heat. Many solid materials (including common metals such as iron and aluminum) become flammable when reduced to a fine powder. If the tgnk ruptures. the mixture is too lean for combustion. Unconfined explosion: Unconfined explosions occur in the open. The mixture will not burn when the composition is lower than the lower flammable limit (LFL). . Dust explosion: This explosion results from the rapid combustion of fine solid particles. Explosion damage is caused by the pressure or shock wave. This type of explosion occurs when an external fire heats the contents of a tank of volatile material. or it can be the result of a rapid chemical reaction. Detonation: An explosion in which the reaction front moves at a speed greater than the speed of sound in the unreacted medium. Explosion: An explosion is a rapid expansion of gases resulting in a rapidly moving pressure or shock wave. This type of explosion is usually the result of a flammable gas spill. The mixture is also not combustible when the composition is too rich. The expansion can be mechanical (by means of a sudden rupture of a pressurized vessel). Confined explosion: An explosion occurring within a vessel or a building. Commonly used units are volume percent fuel (percentage of fuel plus air).228 Chapter 6 Fires and Explosions Flammability limits: Vapor-air mixtures will ignite and burn only over a well-specified range of compositions. The gas is dispersed and mixed with air until it comes in contact with an ignition source. These are most common and usually result in injury to the building inhabitants and extensive damage. possibly followed by combustion or explosion of the vaporized cloud if it is combustible. that is. These explosions are destructive because large quantities of gas and large areas are frequently involved. when it is above the upper flammable limit (UFL). A mixture is flammable only when the composition is between the LFL and the UFL. Boiling-liquid expanding-vapor explosion (BLEVE):A BLEVE occurs if a vessel that contains a liquid at a temperature above its atmospheric pressure boiling point ruptures. Lower explosion limit (LEL) and upper explosion limit (UEL) are used interchangeably with LFL and UFL.

The autoignition temperature is actually the lowest temperature of an autoignition region. Shock wave: An abrupt pressure wave moving through a gas.. The flash point and flammability limits are not fundamental properties but are defined only by the specific experimental apparatus and procedure used. . Typically. although experimental data do not always agree with this. the combined shock wave and wind is called a blast wave. 6-4 Flammability Characteristics of Liquids and Vapors Flammability characteristics of some important organic chemicals (liquids and gases) are provided in appendix B. The pressure increase in the shock wave is so rapid that the process is mostly adiabatic. A shock wave in open air is followed by a strong wind. The behavior of the autoignition region and the flammability limits at higher temperatures are not known. The LFL theoretically intersects the saturation vapor pressure curve at the flash point. Figure 6-2 is a plot of concentration versus temperature and shows how several of these definitions are related. The exponential curve in Figure 6-2 represents the saturation vapor pressure curve for the liquid material. the UFL increases and the LFL decreases with temperature.- - 6-4 Flammability Characteristics of Liquids and Vapors Saturation vapor pressure curve \. Overpressure: The pressure on an object as a result of an impacting shock wave. Not flammable Mists 1 / Flammable ( 1 Lower flammability limit Not flammable I I 1 Flashpoint temperature 1 Autoignition temperature (AIT) Temperature 1 Figure 6-2 Relationships between various flammability properties.

called the fire point temperature. The liquid temperature is measured with a thermometer while a Bunsen burner is used to heat the liquid.230 Chapter 6 Fires and Explosions Liquids The flash point temperature is one of the major quantities used to characterize the fire and explosion hazard of liquids. Flash point temperatures are determined using an open-cup apparatus. most modern flash point methods employ a closed-cup procedure. To prevent this. Eventually a temperature is reached at which the liquid is volatile enough to produce a flammable vapor. shown in Figure 6-3. The temperature at which this first occurs is called the flash point temperature. During heating. The problem with open-cup flash point procedures is that air movements over the open cup may change the vapor concentrations and increase the experimentally determined flash point. is required to produce a continuous flame. Note that at the fla'sh point temperature only a momentary flame occurs. The test flame applicator is moved back and forth horizontally over the liquid sample. For Figure 6-3 Cleveland open-cup flash point determination. . The liquid to be tested is placed in the open cup. and a momentary flashing flame occurs. a higher temperature. the wand is slowly moved back and forth over the open liquid pool. A small flame is established on the end of a movable wand.

32: 81-85.1 264. Rao. this apparatus a small. G." Journal of Hazardous Materials (1992). a. and c are constants provided in Table 6-1 (K). The liquid is placed in a preheated cup and allowed to sit for a fixed time period.5 201. Satyanarayana and P.1 230.9 238. Closed-cup methods typically result in lower flash points.5 416.0 260.4 323.0 416. The shutter is then opened and the liquid is exposed to the flame.0 293. Rao. Satyanarayana and P. .9 b 537. Satyanarayana and Rao2 showed that the flash point temperatures for pure materials correlate well with the boiling point of the liquid.8 222.6 390.4 c 2217 1780 1900 2970 2879 2297 2217 1908 2154 1970 1666 1645 1807 lK.6 600. manually opened shutter is provided at the top of the cup.7 185. Flash points can be estimated for multicomponent mixtures if only one component is flammable and if the flash point of the flammable component is known. is the boiling point temperature of the material (K).1 700. 32: 81-85. Journal of Hazardous Materials (1992). and T. In this case the flash point temperature is estimated by determining the temperature at which the vapor pressure of the flammable component in the mixture is equal to the pure component vapor pressure at its 2K.2 275.9 449. G.7 237.5 262.0 334.2 296.0 577. b. "Improved Equation to Estimate Flash Points of Organic Compounds.1 432.8 260. is the flash point temperature (K). They were able to fit the flash point for over 1200 compounds with an error of less than 1%using the equation where T.0 414.6-4 Flammability Characteristics of Liquids and Vapors 231 Table 6-1 Constants Used in Equation 6-1 for Predicting the Flash Point Chemical group Hydrocarbons Alcohols Amines Acids Ethers Sulfur Esters Ketones Halogens Aldehydes Phosphorus-containing Nitrogen-containing Petroleum fractions a 225.

Example 6-1 Methanol has a flash point of 54"F. Experimentally determined flash points are recommended for multicomponent mixtures with more than o n e flammable component.34 3. the flash point of the solution is 20S°C. Using a graph of the vapor pressure versus temperature.73 Mole fraction 0.00 25 75 - Raoult's law is used to compute the vapor pressure (Pmt) pure methanol. Temperature ( *c) Figure 6-4 Saturation vapor pressure for methanol .39 2. or 68.63 = 98.g°F. shown in Figure 6-4.232 Chapter 6 Fires and Explosions flash point.37 0. we can construct the following: Pounds Water Methanol - Molecular weight 18 32 - Moles 1. based on the partial presof sure required to flash: p = xpsat PSt = PIX = 6210. What is the flash point of a solution containing 75% methanol and 25% water by weight? Solution The mole fractions of each component are needed to apply Raoult's law.63 1.4 mm Hg. and its vapor pressure at this temperature is 62 mm Hg. Assuming a basis of 100 lb of solution.

Investigation of Fire and Explosion Accidents in the Chemical. Kuchta.6-4 Flammability Characteristics of Liquids and Vapors 233 LFL \ & . 8. *a UFL Mashuga and Crowl Kuchta I l l ' l ' o l l l l r r l l l l r ' 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Methane volume % in air Figure 6-5 Maximum pressure for methane combustion in a 20-L sphere. Data from C. DC: US Bureau of Mines. The maximum explosion pressure is measured. Mashuga and D. 19: 388-395. V. M. Crowl. 17(3): 176-1 83. "Estimation of Firedamp by Flammability Limits. Figure 6-5 shows the results for methane. Process Safety Progress (1998). 3H. The flammability limits are defined at 1 psig maximum pressure. Mines (1891)." Ann. . US Bureau of Mines Report 680 (Washington. A. and J. Vapor Mixtures Frequently LFLs and UFLs for mixtures are needed. yi is the mole fraction of component i on a combustible basis. 1985). ser. Gases and Vapors Flammability limits for vapors are determined experimentally in a specially designed closed vessel apparatus (see Figure 6-14 on page 255). Le Chatelier. and n is the number of combustible species. Mining. and Fuel-Related Industries: A Manual. This test is repeated with different concentrations to establish the range of flammability for the specific gas. These mixture limits are computed using the Le Chatelier equation:3 where LFLi is the lower flammable limit for component i (in volume %) of component i in fuel and air. Vapor-air mixtures of known concentration are added and then ignited.

. "Derivation of Le Chatelier's Mixing Rule for Flammable Limits. Volume % Hexane Methane Ethylene Total combustibles Air 0. (2000). which may not be obvious to the user.24 0. Example 6-2 What are the LFL and UFL of a gas mixture composed of 0. with wide variability in the data.0% methane.15 UFLi (vol. %) 7. V. Combining data from these disparate sources may cause unsatisfactory results. Crowl. 19(2): 112-117." Process Safety Progress.61 0. The LFL and UFL data are obtained from appendix B. The combustion kinetics of the pure species is independent and unchanged by the presence of other combustible species. Also.1 4C. Mashuga and Crow14derived Le Chatelier's equation using thermodynamics.2 5.3 3.5 3. %) 0.5% ethylene by volume? Solution The mole fractions on a fuel-only basis are calculated in the following table.0 0.8% hexane. The adiabatic temperature rise at the flammability limit is the same for all species. These assumptions were found to be reasonably valid at the LFL and less so at the UFL. Proper usage of Le Chatelier's rule requires flammability limit data at the same temperature and pressure. The number of moles of gas is constant.5 15 32. The derivation shows that the following assumptions are inherent in this equation: The product heat capacities are constant.3 96. and 0.0 1. Le Chatelier's equation is empirically derived and is not universally applicable. flammability data reported in the literature may be from disparate sources. A.8 2. is the upper flammable limit for component i (in volume %) of component i in fuel and air. Mashuga and D. 2. where UFL.Chapter 6 Fires and Explosions Similarly.7 Mole fraction on combustible LFLi basis (vol.

Zabetakis. the flammability range increases with temperature. 484.6-4 Flammability Characteristics of Liquids and Vapors 235 Equation 6-2 is used to determine the LFL of the mixture: = 110. Lambiris. . Because the mixture contains 3. 1959). S.75% by volume total combustibles. Flammability Limit Dependence on Temperature In general. is the net heat of combustion (kcallmole) and T is the temperature ("C).5 The following empirically derived equations are available for vapors: where AH.363 = 2. p.3% total combustibles. S. 5M.G. and G. Equation 6-3 is used to determine the UFL of the mixture: = 12. Scott." in Seventh Symposium on Combustion (London: Butterworths. "Flame Temperatures of Limit Mixtures.9% by volume total combustibles. it is flammable.

= UFL + 20. The stoichiometric concentration for most organic compounds is determined using the general combustion reaction 6M. Extreme Cond.) of fuel: I I LFL = 0. Proc. pp." Chem. An empirical expression for the UFL for vapors as a function of pressure is a ~ a i l a b l e : ~ UFL. Jones. Chem." AICHE Inst.0% by volume at 0. is volume % fuel in fuel plus air.50Cs.. W. The UFL is determined using Equation 6-6: UFL. where flames do not propagate. Symp. ser... Zabetakis.. 99-104. Rev. experimental determination is always recommended. broadening the flammability range. Estimating Flammability Limits For some situations it may be necessary to estimate the flammability limits without experimental data. Symp. Example 6-3 If the UFLfor a substance is 11.2 MPa gauge? Solution The absolute pressure is P = 6. Engr. I 1 where C. Flammability limits are easily measured. Jones7 found that for many hydrocarbon vapors the LFL and the UFL are a function of the stoichiometric concentration (C. % fuel in air.6(log P + I).236 Chapter 6 Fires and Explosions Flammability Limit Dependence on Pressure Pressure has little effect on the LFL except at very low pressures ( 4 0 mm Hg absolute). "Inflammation Limits and Their Practical Application in Hazardous Industrial Operations. Chem.55CS. (1938). (1965). = UFL + 20. what is the UFL at 6.2 + 0.. 7G. . 2.0 MPa gauge. Engr.101 = 6. UFL = 3.6(log P + 1 ) = 48 vol. 22(1): 1-26. "Fire and Explosion Hazards at Temperature and Pressure Extremes. The UFL increases significantly as the pressure is increased.301 MPa. where P i s the pressure (megapascals absolute) and UFL is the upper flammable limit (volume % of fuel plus air at 1 atm). G.

nitrogen." Fire and Materials (1994).30AHC + 0 .569AHC + 0.76m + 1 .0538AHz + 1. The resulting correlations are LFL UFL =- -3. Koide. 1 9 ~ 2 .42 AH." Fire and Materials (1994). .~ bustion of the fuel. + 0. Additional stoichiometric and unit changes are required to determine C. 5 6 7 A ~ .5. and sulfur. oxygen. 23. 18: 333-336./mole fuel. Suzuki and K. as a function of z : cst = moles fuel moles fuel + moles air x 100 - 100 moles air moles fuel 100 1 - + (A) ( moles fuel O2 ) Substituting z and applying Equations 6-7 and 6-8 yields LFL = UFL = 3. 9T. hydrogen. (6-12 ) (6-13) = 6. Suzuki.. "Empirical Relationship Between Lower Flammability Limits and Standard Enthalpies of Combustion of Organic Compounds. A good fit was obtained for 30 organic materials containing carbon. 18: 393-397.50(100) 4. 3 8 ~+ 1 - Another m e t h ~ dcorrelates the flammability limits as a function of the heat of com~.80. + #T. "Correlation between Upper Flammability Limits and Thermochemical Properties of Organic Compounds.6-4 Flammability Characteristics of Liquids and Vapors 237 It follows from the stoichiometry that where z has units of moles O.

Example 6-4 Estimate the LFL and the UFL for hexane. is the heat of combustion for the fuel (in lo3 kJ/mol). 3. and y are found by balancing this chemical reaction using the definitions in Equation 6-9: The LFL and the UFL are determined by using Equations 6-10 and 6-11: LFL = 0. This is an especially useful result. 6-5 Limiting Oxygen Concentration and lnerting The LFL is based on fuel in air. oxygen is the key ingredient and there is a minimum oxygen concentration required to propagate a flame. % actual. % versus 1.5(100)/[4.5 vol. respectively.19(14) + 11 = 7. If the heat of combustion is provided in kcallmol. For methane and the higher hydrocarbons the results are improved.19 vol. Solution The stoichiometry is and z . x .9-23%.238 Chapter 6 Fires and Explosions where LFL and UFL are the lower and upper flammable limits (vol.184.76(6) = + 1. and AH. % versus 7.57 vol. For hydrogen the predictions are poor. and compare the calculated limits to the actual values determined experimentally. Thus these methods should be used only for a quick initial estimate and should not replace actual experimental data.76(6) UFL = + 1. it can be converted to kJ/mol by multiplying by 4. m.2 vol.55(100)/[4. because explosions and fires can be prevented by reducing the oxygen concentration regardless of the .19(14) + 11 1. % actual. The prediction capability of Equations 6-6 through 6-13 is only modest at best. However. Equation 6-13 is applicable only over the UFL range of 4. % fuel in air).

the LOC is estimated using the stoichiometry of the combustion rzaction and the LFL. MA: National Fire Protection Association. the maximum safe oxygen concentration (MSOC). Table 6-2 contains LOC values for a number of materials. This procedure works for many hydrocarbons. The LOC has units of percentage of moles of oxygen in total moles. The LOC has also been called the minimum oxygen concentration (MOC).5 11. The LOC depends on the inert gas species. 1994). If experimental data are not available.5 11. .5 12 10. Venting of Deflagrations (Quincy.5 N2/Air C02/Air Gas or vapor Kerosene JP-1 fuel JP-3 fuel JP-4 fuel Natural gas n-Butyl chloride Methylene chloride Ethylene dichloride Methyl chloroform Trichloroethylene Acetone t-butanol Carbon disulfide Carbon monoxide Ethanol 2-Ethyl butanol Ethyl ether Hydrogen Hydrogen sulfide Isobutyl formate Methanol Methyl acetate N2/Air C02/Air 'Data from NFPA 68.6-5 Limiting Oxygen Concentration and lnerting 239 Table 6-2 Limiting Oxygen Concentrations (LOCs) (volume percent oxygen concentration above which combustion can occur)l Gas or vapor Methane Ethane Propane n-Butane Isobutane n-Pentane Isopentane n-Hexane n-Heptane Ethylene Propylene 1-Butene Isobutylene Butadiene 3-Methyl-1-butene Benzene Toluene Styrene Ethylbenzene Vinyltoluene Diethylbenzene Cyclopropane Gasoline (731100) (1001130) (1151145) 10 11. concentration of the fuel. and other names. This concept is the basis for a common procedure called inerting (see chapter 7). Below the limiting oxygen concentration (LOC) the reaction cannot generate enough energy to heat the entire mixture of gases (including the inert gases) to the extent required for the self-propagation of the flame.

The tick marks on the scales show the direction in which the scale moves across the figure. or even water vapor until the oxygen concentration is below 12.4%. carbon dioxide. Because point A lies outside the flammable zone. oxygen.240 Chapter 6 Fires and Explosions Example 6-5 Estimate the LOC for butane (C4HI0). oxygen. and 20% nitrogen.9% by volume. The air line intersects the nitrogen axis at 79% nitrogen (and 21 % oxygen). Concentrations of fuel. however. 20% oxygen. The zone enclosed by the dashed line represents all mixtures that are flammable. Thus point A represents a mixture composed of 60% methane. which is the composition of pure air. moles 0. The UFL and the LFL are shown as the intersection of the flammability zone boundary with the air line. 6-6 Flammability Diagram A general way to represent the flammability of a gas or vapor is by the triangle diagram shown in Figure 6-6. and inert material (in volume or mole %) are plotted on the three axes. is not recommended because any condition that condenses water would move the oxygen concentration back into the flammable region. Solution The stoichiometry for this reaction is The LFL for butane (from appendix B) is 1. The addition of water. The air line in Figure 6-6 represents all possible combinations of fuel plus air. or nitrogen. The coml~ustion reaction can be written in the form Fuel + z 0 2 +combustion products. (6-14) . Each apex of the triangle represents either 100% fuel. The stoichiometric line represents all stoichiometric combinations of fuel plus oxygen. we obtain The combustion of butane is preventable by adding nitrogen. a mixture of this composition is not flammable. From the stoichiometry moles fuel (total = moles) moles 0. (moles fuel) = LFL( moles fuel ) By substitution.

pressure. A. temperature.6-6 Flammability Diagram 241 0 20 40 60 100 NITROGEN Figure 6-6 Flammability diagram for methane at an initial temperature and pressure of 25°C and 1 atm. Source: C. "Application of the Flammability Diagram for Evaluation of Fire and Explosion Hazards of Flammable Vapors. including fuel type. 17(3): 176-1 83. The LOC is also shown in Figure 6-6. where z is the stoichiometric coefficient for oxygen. and inert species. V. The intersection of the stoichiometric line with the oxygen axis (in volume % oxygen) is given by The stoichiometric line is drawn from this point to the pure nitrogen apex." Process Safety Progress (1998). . Thus the moles present are fuel (1 mole) plus oxygen (2 moles). Mashuga and D. and the mole or volume percent of oxygen is given by expression 6-15. Crowl. Expression 6-15 is derived by realizing that on the oxygen axis no nitrogen is present. The shape and size of the flammability zone on a flammability diagram change with a number of parameters. Thus the flammability limits and the LOC also change with these parameters. The total moles are thus 1 + z. Clearly. any gas mixture containing oxygen below the LOC is not flammable.

then the gas composition inside the vessel will follow the air line and finish at point A. the composition of gas within the vessel will follow the air line in Figure 6-7 until the vessel gas composition eventually reaches point B. Again. These results are useful for tracking the gas composition during a process operation to determine whether a flammable mixture exists during the procedure. the mixture composition follows along the straight line between points R and S on the flammability diagram. For this operation the methane must be removed from the vessel and replaced by air for the inspection workers to breathe. At this point the vessel contains 100% methane. If a mixture R is continuously diluted with mixture S. the mixture composition moves closer and closer to point S. Note that at some point in this operation the gas composition passes through the flammability zone. consider a storage vessel containing pure methane whose inside walls must be inspected as part of its periodic maintenance procedure. As the dilution continues. In this case the procedure begins at point B in Figure 6-7. These results show that: 1. Diagrams with experimental data . If the vessel is closed and methane is pumped in.242 Chapter 6 Fires and Explosions Appendix C derives several equations that are useful for working with flammability diagrams. the other two components are present in a fixed ratio along the entire line length. the final mixture point will lie closer to point S. 4. at infinite dilution the mixture composition is at point S. The procedure is reversed for placing the vessel back into service. Eventually. 2. For systems having composition points that fall on a straight line passing through an apex corresponding to one pure component. For example. If the vessel is opened and air is allowed to enter. The first step in the procedure is to depressurize the vessel to atmospheric pressure. If two gas mixtures R and S are combined. the resulting mixture composition lies on a line connecting the points R and S on the flammability diagram. This is identical to the lever rule used for phase diagrams. This is discussed in more detail in chapter 7. The determination of a complete flammability diagram requires several hundred tests using a specific testing apparatus (see Figure 6-14 on page 255). with the vessel containing air. 3. represented by point A in Figure 6-7. pure air. If an ignition source of sufficient strength were present. An inerting procedure can be used to avoid the flammability zone for both cases. This is equivalent to the equation LOC = z(LFL). The location of the final mixture on the straight line depends on the relative moles in the mixtures combined: If mixture S has more moles. the mixture is flammable as the gas composition moves through the flammability zone. then a fire or explosion would result. The LOC can be estimated by reading the oxygen concentration at the intersection of the stoichiometric line and a horizontal line drawn through the LFL (see appendix C).

the lower boundary of the flammability zone is mostly horizontal and can be approximated by the LFL. for methane and ethylene are shown in Figures 6-8 and 6-9. Data in the center region of the flammability zone are not available because the maximum pressure exceeds the pressure rating of the vessel or because unstable combustion or a transition to detonation is observed there. For most systems detailed experimental data of the type shown in Figure 6-8 or 6-9 are unavailable. First. respectively. Finally. This was done to obtain a more complete understanding of the pressure versus time behavior of the combustion over a wide range of mixtures.6-6 Flammability Diagram 243 A = Pure methane 100 NITROGEN Figure 6-7 Pure air: 79% N2 21% O2 = B The gas concentration during an operation to remove a vessel from service. This information is important for mitigation of the explosion. the flammability zone is much larger for ethylene than for methane. the UFL for ethylene is correspondingly higher. A number of important features are shown in Figures 6-8 and 6-9. Several methods have been developed to approximate the flammability zone: . the combustion produces copious amounts of soot in the upper fuel-rich parts of the flammability zone. For these data a mixture is considered flammable if the pressure increase after ignition is greater than 7% of the original ambient pressure. Note that many more data points are shown than required to define the flammability limits. Second. in accordance with ASTM E918.

69 psia Initial temperature: 25°C Reactor volume: 20 liters lgnitor type: 1 cm 40 AWG SnCu / 500VA lgnitor energy: 10 J Ignitor location: Center Figure 6-8 Experimental flammability diagram for methane. 1999). Use expression 6-15 to locate the stoichiometric point on the oxygen axis. and draw the stoichiometric line from this point to the 100% nitrogen apex. Draw a point at this intersection. and draw a line parallel to the fuel axis until it intersects with the stoichiometric line. (Source: C. and flammability limits in pure oxygen. 5. 3. dissertation (Michigan Technological University. Note that the lines defining the zone limits in Figures 6-8 and 6-9 are not exactly straight.Chapter 6 Fires and Explosions 0 20 40 60 NITROGEN 80 100 Experimental conditions Initial pressure: 14. Locate the LOC on the oxygen axis. The flammability zone derived from this approach is only an approximation of the actual zone. Method 1 (Figure 6-10): Given the flammability limits in air.D. the procedure is as follows: 1. V. Draw flammability limits in pure oxygen as points on the oxygen scale. Connect all the points shown. Draw flammability limits in air as points on the air line. the LOC. Ph. 4. This . Mashuga. 2.

Estimate the LOC using Equation 6-16. (Source: C. 1999). V. and 4 from method 1.6-6 Flammability Diagram 245 NITROGEN Experimental conditions lgnitor type: 1 cm 40 AWG SnCu 1500VA Initial pressure: 14.69 psia Initial temperature: 25°C Ignitor energy: 10 J Reactor volume: 20 liters Ignitor location: Center Figure 6-9 Experimental flammability diagram for ethylene. The lower boundary can also be approximated by the LFL. The flammability zone from the air line to the oxygen axis cannot be detailed without additional data. Ph. This is only an estimate. the procedure is as follows: Use steps 1 and 3 from method 1.3. . and usually (but not always) provides a conservative LOC. although it extends all the way to the oxygen axis and typically expands in size. Method 2 (Figure 6-11): Given the flammability limits in air and the LOC.In this case only the points at the nose of the flammability zone can be connected. Flammability limits in pure oxygen for a number of common hydrocarbons are provided in Table 6-3. method also requires flammability limits in pure oxygen . dissertation (Michigan Technological University. the procedure is as follows: Use steps 1.D.data that are not readily available. Method 3 (Figure 6-12): Given the flammability limits in air. Mashuga.

1987). 2The limits are insensitive to pHd. Lewis and G. and Explosions of Gases (New York: Harcourt Brace Jovanovich. von Elbe. . Combustion.246 Chapter 6 Fires and Explosions Flammability limits 100 0 NITROGEN Figure 6-10 Method 1 for the approximation of the flammability zone. Flames. Table 6-3 Flammability Limits in Pure Oxygen Limits of flammability in pure oxygen Compound Hydrogen Deuterium Carbon monoxide2 Ammonia Methane Ethane Ethylene Propylene Cyclopropane Diethyl ether Divinyl ether Formula Lower Upper 'Data from B.above a few mm Hg.

Only the area to the right of the air line can be determined.6-6 Flammability Diagram 247 NITROGEN LFL 100 Figure 6-1 1 Method 2 for the approximation of the flammability zone. NITROGEN LFL 100 Figure 6-12 Method 3 for the approximation of the flammability zone. Only the area to the right of the air line can be determined. .

the concentration. Combustion. contributing to plant explosions (see chapter 7).25 mJ. a static discharge of 22 mJ is initiated by walking across a rug. A few MIEs are given in Table 6-4. Experimental data indicate that the MIE decreases with an increase in pressure. the MIE of dusts is. Many hydrocarbons have MIEs of about 0. This is low compared with sources of ignition. The MIE depends on the specific chemical or mixture. also have energy levels exceeding the MIEs of flammable materials and can provide an ignition source.248 Chapter 6 Fires and Explosions Table 6-4 Chemical Minimum Ignition Energy for Selected Gases1 Minimum ignition energy (mJ) Acetylene Benzene 1. and an increase in the nitrogen concentration increases the MIE. in general. and temperature. Electrostatic discharges. pressure. All flammable materials (including dusts) have MIEs. at energy levels somewhat higher than combustible gases. (New York: Academic Press. 6-7 Ignition Energy The minimum ignition energy (MIE) is the minimum energy input required to initiate combustion. as a result of fluid flow. 3d ed. Glassman. For example. and an ordinary spark plug has a discharge energy of 25 mJ.3-Butadiene n-Butane Cyclohexane Cyclopropane Ethane Ethene Ethylacetate Ethylene oxide n-Heptane Hexane Hydrogen Methane Methanol Methyl acetylene Methyl ethyl ketone n-Pentane 2-Pentane Propane - 'Data from I. 1996). .

insulation on a steam pipe saturated with certain polymers. This is the cause of preignition knock in engines that are running too hot and too lean. For example. Composition affects the AIT. Larger system volumes decrease AITs. This strong dependence on conditions illustrates the importance of exercising caution when using AIT data. These examples illustrate why special precautions must be taken to prevent fires that can result from auto-oxidation and autoignition. sometimes leading to autoignition if the energy is not removed from the system. It is also the reason some overheated engines continue to run after the ignition is turned off. rich or lean mixtures have higher AITs. Liquids with relatively low volatility are particularly susceptible to this problem. 6-9 Auto-Oxidation Auto-oxidation is the process of slow oxidation with accompanying evolution of heat. allowing auto-oxidation and eventual autoignition). It is essential to experimentally determine AITs at conditions as close as possible to process conditions.6-10 Adiabatic Compression 249 6-8 Autoignition The autoignition temperature (AIT) of a vapor. referred to as spontaneous combustion. is the temperature at which the vapor ignites spontaneously from the energy of the environment. . The autoignition temperature is a function of the concentration of vapor. and filter aid saturated with certain polymers (cases have been recorded where 10-year-old filter aid residues were ignited when the land-filled material was bulldozed. Many fires are initiated as a result of auto-oxidation. an increase in pressure decreases AITs. Safeguards must be included in the process design to prevent undesirable fires that can result from adiabatic compression. Several large accidents have been caused by flammable vapors being sucked into the intake of air compressors. pressure of the system. subsequent compression resulted in autoignition. Liquids with high volatility are less susceptible to autoignition because they self-cool as a result of evaporation. A compressor is particularly susceptible to autoignition if it has a fouled after-cooler. Some examples of auto-oxidation with a potential for spontaneous combustion include oils on a rag in a warm storage area. and increases in oxygen concentration decrease AITs. gasoline and air in an automobile cylinder will ignite if the vapors are compressed to an adiabatic temperature that exceeds the autoignition temperature. AIT data are provided in appendix B. volume of vapor. presence of catalytic material. sometimes called the spontaneous ignition temperature (SIT). and flow conditions. 6-10 Adiabatic Compression An additional means of ignition is adiabatic compression.

P. and y for air is 1. Ti is the initial absolute temperature.3. The potential consequences of adiabatic temperature increases within a chemical plant are illustrated in the following two examples. compressor operations must always be maintained well below the AIT of the oil to prevent explosion. Solution Equation 6-17 applies. is the final absolute pressure. Solution From Equation 6-17 we have This temperature exceeds the AIT for hexane. Example 6-6 What is the final temperature after compressing air over liquid hexane from 14.7 psia) = 254 psia. .4. Assume an initial air temperature of 25°C and 1atm. Example 6-7 The lubricating oil in piston-type compressors is always found in minute amounts in the cylinder bore. A particular lubricating oil has an AIT of 400°C. The actual compression ratio or pressure should be kept well below this.7 psia to 500 psia if the initial temperature is 100°F? The AIT of hexane is 487°C (appendix B). is the final absolute temperature. Solving for the compression ratio.3)(14. Compute the compression ratio required to raise the temperature of air to the AIT of this oil. Pi is the initial absolute pressure. resulting in an explosion. This ratio represents an output pressure of only (17. we obtain = 17.250 Chapter 6 Fires and Explosions The adiabatic temperature increase for an ideal gas is computed from the thermodynamic adiabatic compression equation: where T.IC". and y = C.

Various ignition sources were tabulated for over 25. for example.000 fires by the Factory Mutual Engineering Corporation and are summarized in Table 6-5. Some special situations might occur in a process facility where it is impossible to avoid flammable mixtures.) Exposure (fires jumping into new areas) Incendiarism (fires maliciously set) Mechanical sparks (grinders. etc. crushers. heat.) Molten substances (hot spills) Chemical action (processes not in control) Static sparks (release of accumulated energy) Lightning (where lightning rods are not used) Miscellaneous 'Accident Prevention Manual for Industrial Operations (Chicago: National Safety Council. Combinations of sources must also be investigated.6-11 Ignition Sources 251 Table 6-5 Ignition Sources of Major Fires1 Electrical (wiring of motors) Smoking Friction (bearings or broken parts) Overheated materials (abnormally high temperatures) Hot surfaces (heat from boilers. etc. In these cases a thorough safety analysis is required to eliminate all possible ignition sources in each of the units where flammable gases are present.) Combustion sparks (sparks and embers) Spontaneous ignition (rubbish. . 6-11 Ignition Sources lo As illustrated by the fire triangle. because high-pressure process conditions are becoming more common in modern chemical plants. The elimination of the ignition sources with the greatest probability of occurrence (see Table 6-5) should be given the greatest attention. The goal is to eliminate or minimize ignition sources because the probability of a fire 1°Accident Prevention Manual for Industrial Operations (Chicago: National Safety Council. The sources of ignition are numerous. engineers must still continue to identify and eliminate them. etc. etc. lamps. and the need for periodic preventive maintenance programs when working with flammable gases and compressors. The main reason for rendering a flammable liquid inert. 1974). Although all sources of ignition are not likely to be identified. 1974) These examples illustrate the importance of careful design.) Cutting and welding (sparks. This is especially important today. fires and explosions can be prevented by eliminating ignition sources. consequently it is impossible to identify and eliminate them all. arcs. careful monitoring of conditions. etc. is to prevent a fire or explosion by ignition from an unidentified source.) Burner flames (improper use of torches.

2d ed. Many approaches to the problem have been undertaken.2 mm the LFL decreases as the drop diameter increases. explosion behavior is still not completely understood. the LFL is virtually the same as the substance in vapor form. 6-13 Explosions Explosion behavior depends on a large number of parameters. Borgoyne. In this situation. flame propagation is impossible. 2: 1. An explosion results from the rapid release of energy. and empirical studies. should use extrapolated results cautiously and provide a suitable margin of safety in all designs. For chemical plants much of the damage from explosions is due to this pressure wave.H. "The Flammability of Mists and Sprays. This is important when inerting in the presence of mists. (Boston: Butterworths. Despite these efforts. For mechanically formed mists with drop diameters between 0. forcing back the surrounding gas and initiating a pressure wave that moves rapidly outward from the blast source. Lees." Chemical Process Hazards (1965). The effort required increases significantly as the size of the plant increases. 1996). I1Frank P. If flammable vapors are present.252 Chapter 6 Fires and Explosions or explosion increases rapidly as the number of ignition sources increases. Loss Prevention in the Process Industries. including theoretical. The energy release must be sudden enough to cause a local accumulation of energy at the site of the explosion.01 mm. therefore. including formation of a pressure wave. semiempirical. 12J. the energy causes the gas to expand rapidly. potential ignition sources may be in the thousands. projectiles. When sprays have drop diameters between 0. we must understand the dynamics of the pressure wave.5 mm. Mists of this type are formed by condensation. If the explosion occurs in a gas. The pressure wave contains energy.12 For suspensions with drop diameters less than 0. thermal radiation.6 mm and 1. however. 6-12 Sprays and Mists l1 Static electricity is generated when mists or sprays pass through orifices. The damage from an explosion is caused by the dissipating energy. which results in damage to the surroundings. . In experiments with larger drop diameters the LFL was less than one-tenth of the normal LFL. Thus. A summary of the more important parameters is shown in Table 6-6. This is true even at low temperatures where the liquid is nonvolatile and no vapor is present. Explosion behavior is difficult to characterize. Mists and sprays also affect flammability limits. the presence of small drops andlor disturbances that shatter the larger drops may create a hazardous condition. a fire or explosion will occur. This energy is then dissipated by a variety of mechanisms. Practicing engineers. A charge may accumulate and discharge in a spark.01 mm and 0. in order to understand explosion impacts. and acoustic energy.

resulting in a reaction front and leading shock wave that propagates into the unreacted mixture at or above the sonic velocity. This is classified as a detonation. causing the reaction front to propagate at a speed less than the sonic velocity. but it can also occur from the sudden rupture of a pressure vessel. The maximum pressure over ambient pressure is called the peak overpressure. Fundamentally. This compression occurs rapidly. . For a deflagration the energy from the reaction is transferred to the unreacted mixture by heat conduction and molecular diffusion.6-13 Explosions 253 Table 6-6 Parameters Significantly Affecting the Behavior of Explosions Ambient temperature Ambient pressure Composition of explosive material Physical properties of explosive material Nature of ignition source: type. For ideal gases the speed of sound or sonic velocity is a function of temperature only and has a value of 344 m/s (1129 ft/s) at 20°C. energy. For a detonation the reaction front moves at a speed greater than the speed of sound. A shock wave is expected from highly explosive materials. resulting in an abrupt pressure change or shock in front of the reaction front. the sonic velocity is the speed at which information is transmitted through a gas. The reaction front provides the energy for the shock front and continues to drive it at sonic or greater speeds. A shock front is found a short distance in front of the reaction front. In some combustion reactions the reaction front is propagated by a strong pressure wave. such as TNT. Figure 6-13 shows the physical differences between a detonation and a deflagration for a combustion reaction that occurs in the gas phase in the open. Detonation and Deflagration The damage effects from an explosion depend highly on whether the explosion results from a detonation or a deflagration. The difference depends on whether the reaction front propagates above or below the speed of sound in the unreacted gases. A shock wave or shock front results if the pressure front has an abrupt pressure change. which compresses the unreacted mixture in front of the reaction front above its autoignition temperature. and duration Geometry of surroundings: confined or unconfined Amount of combustible material Turbulence of combustible material Time before ignition Rate at which combustible material is released A pressure wave propagating in air is called a blast wave because the pressure wave is followed by a strong wind. These processes are relatively slow.

--> DEFLAGRATION Reaction front In a deflagration. One way to conceptualize the resulting pressure front is to consider the reaction front as producing a series of individual pressure fronts. and total duration of typically less than 1ms. The explosion is initiated to the far left. a maximum pressure of greater than 10 atm. driving the shock front immediately preceding it. Both fronts move at the same speed. For a deflagration the reaction front propagates at a speed less than the speed of sound.-> Figure 6-13 Comparison of detonation and deflagration gas dynamics. A detonation produces a shock front. The pressure fronts produced by detonations and deflagrations are markedly different. These pressure fronts move away from the reaction front at the speed of sound and accumulate together in a main pressure front.254 Chapter 6 Fires and Explosions DETONATION ------- h Peak overpressure Reaction front Shock front lArnbient pressure In a detonation. Distance . while the pressure front moves away from the reaction front at the speed of sound. The main pressure front will continue to grow in size as additional energy and pressure fronts are produced by the reaction front. The pressure front resulting from a deflagration is characteristically wide (many milliseconds in duration). Distance . flat (without an abrupt . with an abrupt pressure rise. The pressure front moves at the speed of sound in the unreacted gas and moves away from the reaction front. the reaction front moves at a speed greater than the speed of sound. the reaction front moves at a speed less than the speed of sound.

Empirical studies have shown that the nature of the explosion is a function of several experimentally determined characteristics. and the maximum pressure after ignition. These characteristics depend on the explosive material used and include flammability or explosive limits. . Different behavior occurs if the fronts propagate in a closed vessel. This is called a deflagration to detonation transition (DDT). shown in Figures 6-14 and 6-17. The behaviors of the reaction and pressure fronts differ from those shown in Figure 6-13 depending on the local geometry constraining the fronts. Gas Manifold @ "8' I Figure 6-14 Magnetic Stirrer I Test apparatus for acquiring vapor explosion data. The two most common confined explosion scenarios involve explosive vapors and explosive dusts.6-13 Explosions 255 shock front). Confined Explosions A confined explosion occurs in a confined space. In a piping system energy from a deflagration can feed forward to the pressure wave. resulting in an increase in the adiabatic pressure rise. The gas dynamic behavior for complex geometries is beyond the scope of this text. The pressure builds and results in a full detonation. or through a congested process unit. These characteristics are determined using two similar laboratory devices. the rate of pressure rise after the flammable mixture is ignited. and with a maximum pressure much lower than the maximum pressure for a detonation (typically 1 or 2 atm). a pipeline. The transition is particularly common in pipes but unlikely in vessels or open spaces. A deflagration can also evolve into a detonation. such as a vessel or a building.

The test procedure includes (1)evacuating the vessel. as shown in Figure 6-15. Explosion Apparatus for Vapors The apparatus used to determine the explosive nature of vapors is shown in Figure 6-14. The rate of pressure rise is indicative of the flame front propagation rate and thus of the magnitude of the explosion. (2) adjusting the temperature. A typical pressure versus time plot is shown in Figure 6-15. the maximum pressure and pressure rates occur somewhere within the range of flammability (but not necessarily at the same concentration). Typically. By using this relatively simple set of experiments. The pressure within the vessel is measured by a transducer located on the external wall. Experiments of this type usuallyresult in a deflagration with a few atmospheres of pressure rise.024 s : V) = 316 bar/s - 0 0 I I I I I I I I 20 40 60 80 100 120 140 160 0 180 Time (ms) Figure 6-15 Typical pressure versus time data obtained from gas explosion apparatus shown in Figure 6-14. the reaction is terminated at the wall.60 F -.256 Chapter 6 Fires and Explosions - - - .P . (4) igniting the gas by a spark.120 - 3 .100 4 AP = 7. - .6 bar - .. in this example the flammability limits are between 2% and 8%. with the exception of a .-) ( I .80 . The pressure rate or slope is computed at the inflection point of the pressure curve.5 bar . The experiment is repeated at different concentrations. After ignition the pressure wave moves outward within the vessel until it collides with the wall. The pressure rate and maximum pressure for each run are plotted versus concentration.4 bar.the maximum pressure is 7. The maximum pressure and maximum rate of pressure rise are determined. The device is similar to the vapor explosion apparatus. and the maximum rate of pressure rise is 360 barls.- dP dt 7'6 bar 0. Explosion Apparatus for Dusts The experimental apparatus used to characterize the explosive nature of dusts is shown in Figure 6-17. (3) metering in the gases to obtain the proper mixture. as shown in Figure 6-16. and ( 5 ) measuring the pressure as a function of time. = 8. the explosive characteristics can be completely established.

Rate of Pressure Increase (bar/?.) Explosion Pressure (bar-gauge) .

discharged. or Halon) to stop the combustion process. Explosion Characteristics The explosion characteristics determined using the vapor and dust explosion apparatus are used in the following way: 1. The maximum rate is also used to design a vent for relieving a vessel during an explosion before the pressure ruptures the vessel or to establish the time interval for adding an explosion suppressant (water. The limits of flammability or explosivity are used to determine the safe concentrations for operation or the quantity of inert material required to control the concentration within safe regions. 2. as well as the flammability limits. Thus the explosive behavior of different materials can be compared on a relative basis. The computer measures the pressure as a function of time using high. The maximum rate of pressure increase indicates the robustness of an explosion. The air used to drive the dust into the sphere is carefully metered to ensure a pressure of 1 atm (0. A typical pressure versus time plot from the dust explosion apparatus is shown in Figure 6-18.258 Chapter 6 Fires and Explosions D i s t r i b u t i' o n Dust Sample Air I . The maximum pressure and the maximum rate of pressure increase are determined. I I lnput/Output Computer Devices I Figure 6-17 Test apparatus for acquiring dust explosion data. The data are collected and analyzed in the same fashion as for the vapor explosion apparatus. . carbon dioxide.and lowspeed pressure transducers.987 bar) within the sphere at ignition time.

.Hydrogen 1 0.. respectively.1 atm 0 0 50 150 100 Time (ms) 200 250 Figure 6-18 Pressure data from dust explosion device.0 10.. the deflagration indexes KG and Kst increase. A plot of the logarithm of the maximum pressure slope versus the logarithm of the vessel volume frequently produces a straight line of slope -113. are the deflagration indexes for gas and dust.... The cubic law states that ---. As the robustness of an explosion increases. ... 5..6-13 Explosions - - ------------- Peak pressure .. as shown in Figure 6-19. where KG and Ks..5 1O . This relationship is called the cubic law: (dPldt)m....0 Volume of vessel (m3) Figure 6-19 Typical explosion data exhibiting the cubic law.V1'3 = constant = KG.

5 55 75 104 100 94 7. Explosions-Schutz: Grundlagen und Anwendung (New York: Springer-Verlag.1 7.0 7.6 6.4 8. the pressure front takes longer to propagate through a larger vessel. as follows: .8 7.0 6.4 8.4 6.05 5.. These St classes are shown in Table 6-8.7 7." in 31st Loss Prevention Symposium (New York: American Institute of Chemical Engineers. depending on the value of the deflagration index.8 7.6 5. A. "KG:Data and Analysis.65 7. J. It is postulated that the KG values are sensitive to experimental configuration and conditions. such as a building or a vessel.5 7. 1997) W.0 92 7. Beaulieu. Senecal and P. Bartknecht.4 7. 1993). MA: National Fire Protection Association.. Venting ofDeflagrations (Quincy.4 106 96 550 78 8.0 6.2 171 638 67 46 94 7. A.8 7.8 7. P.9 7.9 NFPA 68 (1997) 109 10 92 105 115 106 78 94 659 45 64 5 104 96 8.9 7. 1997). respectively.8 7.260 Chapter 6 Fires and Explosions Table 6-7 Maximum Pressures and Deflagration Indexes for a Number of Gases and Vapors1 Maximum pressure Pmax g) (bar Senecal and Bartknecht Beaulieu (1993) (1998) Deflagration index KG(bar-m Is) Senecal and Bartknecht Beaulieu (1993) (1998) Chemical Acetylene Ammonia Butane Carbon disulfide Diethyl ether Ethane Ethyl alcohol Ethyl benzene Ethylene Hydrogen Hydrogen sulfide Isobutane Methane Methyl alcohol Methylene chloride Pentane Propane Toluene lData selected from: NFPA 68 (1997) 10.4 6. Equations 6-18 and 6-19 are used to estimate the consequences of an explosion in a confined space.2 76 NFPA 68. Table 6-7 shows that good agreement is found between different investigations for the maximum pressure but that only limited agreement is found for the KG values. and KG and Kst data for vapors and dusts are shown in Tables 6-7 and 6-8. Dusts are further classified into four classes.0 6.1 7.

2 8.9 10. resins.5 6.7 8.3 8.2 9.1 7.8 9.3 6.4 7.1 7.4 8. Ks. wood. auxiliary materials Adipinic acid Naphthalene Salicylic acid Median Minimum particle explosive dust size concentration P.0 5.4 - 112 90 57 - 8.3 - - 250 100 7 - 5.6-13 Explosions 261 Table 6-8 St Classes for Dusts and Combustion Data for Dust Clouds - Deflagration index. (~m) (g/m3) (bar g) 44 51 33 80 <10 80 200 400 80 165 - Kst (bar-rn Is) 24 66 18 18 27 - Minimum ignition energy (mJ) 100 60 - 7.4 7. rubber Polyacrylamide Polyester Polyethylene Polyethylene Polypropylene Polypropylene Polystyrene (copolymer) Polystyrene (hard foam) Polyurethane Intermediate products. coal products Activated carbon Bituminous coal Plastics.5 - 97 178 - - <1 - (continued) ..4 - 60 125 - - 180 >4000 - 50 10 18 <lo 10 <lo 72 280 25 162 155 760 3 60 60 60 60 60 - 9.8 75 44 55 12 194 67 20 101 38 110 23 156 75 >lo0 540 14 - 250 - - 30 200 30 - - <30 <10 95 - 60 15 30 8..(bar rn 1s) 0 1-200 200 -300 >300 St class St-0 St-1 St-2 St-3 Dust Cotton. food Dextrose Fructose Fructose Wheat grain dust Milk powder Rice flour Wheat flour Milk sugar Coal.3 8.7 4.0 8. peat Cotton Cellulose Wood dust Wood dust Paper dust Feed.

are not physical properties of the material because they are dependent on (1)the composition of the mixture. The constants KG and Ks. Equation 6-20 allows the experimental results from the dust and vapor explosion apparatus to be applied to determining the explosive behavior of materials in buildings and process vessels.. (2) the mixing within the vessel. Eckoff.5 4.Chapter 6 Fires and Explosions Table 6-8 (continued) Median Minimum particle explosive dust size concentration P. The dust particles can be either an unwanted by-product or the product itself. The subscript "in vessel" is for the reactor or building. (3) the shape of the reaction vessel.5% C) Sulfur Toner (bar-mIs) <lo <lo 52 <10 22 18 12 28 240 <lo <10 7 20 <lo - 50 60 60 30 750 500 30 500 125 250 <30 30 60 9.5 7. The spikes in the curves indicate a detonation.2 6. a point is reached where the deflagration turns into a detonation. As the initial pressure is increased. .0 10.2 11.7 5.9 73 249 237 515 110 31 50 508 12 126 125 71 151 196 - - - - 54 - - 4 'Data selected from R.2 9..0 11.1 5.8 11. The subscript "experimental" applies to data determined in the laboratory using either the vapor or dust explosion apparatus. It is therefore necessary to run the experiments as close as possible to the actual conditions under consideration. Dust explosions demonstrate unique behavior.8 8. (~m) (g/m3) (bar g) Minimum ignition energy (mJ) Kst Dust Other technical.9 6. Experimental studies indicate that the maximum explosion pressure is usually not affected by changes in volume. and (4) the energy of the ignition source. K. Dust Explosions in the Process Industries (Oxford: Butterworth-Heinemann. These explosions occur if finely divided particles of solid material are dispersed in air and ignited. and the maximum pressure and the maximum pressure rate are linearly dependent on the initial pressure. This is shown in Figure 6-20. 1997). This is discussed in more detail in chapter 9. chemical products Organic dyestuff (blue) Organic dyestuff (red) Organic dyestuff (red) Metals. alloys Aluminum powder Aluminum powder Bronze powder Iron (from dry filter) Magnesium Magnesium Silicon Zinc (dust from collector) Other inorganic products Graphite (99.2 17. as shown in Figure 6-21.

6-13 Explosions 263 Initial Pressure (bar) Figure 6-20 Effect of initial pressure on maximum explosion pressure and rate. and coal mining industries. Data from W. p. Accidents involving dust explosions can be quite substantial. 171266. grain storage. Bartknecht. Explosions involving dusts are most common in the flour milling. a series of grain silo explosions in Westwego near New Orleans in 1977 killed 35 people. Explosions (New York: Springer-Verlag.13 'Tees. . Loss Prevention in the Process Industries. 1981).

.264 Chapter 6 Fires and Explosions Propane Content (vol %) 1500 n = ~ - - - - I - - . The primary explosion sends a shock wave through the plant. Many times the secondary explosions are more damaging than the primary explosion. . ~ ' I " " 3 0 V cn n w 1000. stirring up additional dust. Explosions (New York: Springer-Verlag. . Data from W. Bartknecht.cn w - 2 3 cn V) 2 a C 500- 0 w + r Y 0 Propane Content in Air (vol %) Figure 6-21 Explosion data for propane showing peaks indicative of the onset of detonation. 1981). In this fashion the explosion leapfrogs its way through a plant. I ~ - - - I . An initial dust explosion can cause secondary explosions. possibly resulting in a secondary explosion.

For most of the underpressure period from t. t. however. is called the arrival time. the reaction front terminates. to t4 the blast wind reverses direction and flows toward the explosive origin. After attaining the maximum underpressure t. There is some damage associated with the underpressure period. the pressure will approach ambient pressure at t4. to t. the particle loading must be between certain limits. the shock front has arrived and a peak overpressure is observed. After the combustible material is consumed. A blast wave is composed of the pressure wave and subsequent wind. but the wind continues in the same direction for a short time. but the pressure wave continues its outward movement. It is the blast wave that causes most of the damage. The time period t. The shock duration is the period of greatest destruction to free-standing structures.There exists a small but finite time t. Blast Damage Resulting from Overpressure The explosion of a dust or gas (either as a deflagration or a detonation) results in a reaction front moving outward from the ignition source preceded by a shock wave or pressure front. a dust mixture must have the following characteristics: the particles must be below a certain minimum size.6-13 Explosions 265 Dust explosions are even more difficult to characterize than gaseous explosions. For most dustslqhe lower explosion limit is between 20 glm3 and 60 g/m%nd the upper explosion limit is between 2 kg/m%nd 6 kg/m3. immediately followed by a strong transient wind. For dust particles the particles are of varying size and many orders of magnitude larger than molecules.. the damage is much less than that of the overpressure period. At this time the blast wind and the direct destruction have terminated. 171265.. The explosion occurs at time to. before the shock front travels from its explosive origin to the affected location. Figure 6-22 shows the variation in pressure with time for a typical shock wave at a fixed location some distance from the explosion site. however. At t. p. . are powerful enough to destroy structures and kill or injure people. For a gas the molecules are small and of well-defined size.. 1981). so its value is important for estimating damage. The underpressure for large explosions and nuclear explosions. To be explosive. Gravity also affects dust particle behavior. I4Lees. the dust loading must be reasonably uniform. resulting in considerable damage.14 The pressure waves from dust deflagrations. 27. is called the shock duration.. can be quite large. This time. Loss Prevention in the Process Industries. p. The pressure quickly decreases to ambient pressure at time t.Bartknecht. but because the maximum underpressure is only a few psi for typical explosions. 15W. For dusts deflagrations appear to be much more common than detonations. Explosions (New York: Springer-Verlag. The decreasing pressure continues to drop below ambient pressure to a maximum underpressure at time t.

the damage is also a function of the rate of pressure increase and the duration of the blast wave. The reflected overpressure includes the side-on overpressure and the stagnation pressure. If the pressure transducer is at right angles to the blast wave. The reflected overpressure is a maximum when the blast wave arrives normal to the wall or object of concern and decreases as the angle changes from normal. are obtained using just the peak side-on overpressure. shown in Figure 6-22.266 Chapter 6 Fires and Explosions ti = arrival time t2 . Many references report overpressure data without clearly stating how the overpressure is measured. the side-on overpressure increases abruptly to its maximum value (peak side-on overpressure) and then drops off as the blast wave passes. In general. The stagnation pressure is due to deceleration of the moving gas as it impacts the pressure transducer. significant damage is expected for even small overpressures. Good estimates of blast damage. The reflected pressure for low side-on overpressures is about twice the side-on overpressure and can reach as high as 8 or more times the side-on overpressure for strong shocks. however. the overpressure measured is called the side-on overpressure (sometimes called the free-field overpressure).tl = shock duration t3 = maximum underpressure to ti t2 t3 Time t4 Figure 6-22 Blast wave pressure at a fixed location. As illustrated. . At a fixed location. If the pressure transducer is placed facing toward the oncoming shock wave. Blast damage is based on the determination of the peak side-on overpressure resulting from the pressure wave impacting on a structure. An important consideration is how the pressure is measured as the blast wave passes. Damage estimates based on overpressures are given in Table 6-9. overpressure implies the side-on overpressure and frequently the peak side-on overpressure. In general. then the measured pressure is the reflected overpressure.

8-20.9 6.2 20.-- - 6-13 Explosions Table 6-9 Damage Estimates for Common Structures Based on Overpressure (these values are approximation^)^ Pressure psig 0. very heavy machine tools (12.95 of no serious damage below this value).5-1.04 0.9 300 2068 IV.5 3 3-4 4 5 5 -7 7 7.0 1-2 2. 8-12 in thick. fail by shearing or flexure Loaded train boxcars completely demolished Probable total destruction of buildings.000 lb) in buildings slightly damaged Nearly complete destruction of houses Loaded train wagons overturned Brick panels.9-13.9 4.7 1. panels blow in Steel frame of clad building slightly distorted Partial collapse of walls and roofs of houses Concrete or cinder block walls. tall hydraulic presses (40.15 0. fastenings fail.8 9 10 9.03 0.8 6.0 0.03 2.76 3. heavy machine tools (7000 lb) moved and badly damaged. 1972).02 0. rupture of oil storage tanks Cladding of light industrial buildings ruptures Wooden utility poles snap. sonic boom. followed by buckling.7 15.5-48.3 2 2-3 2.7-27.69 1.6 34.8 17. 10-15 Hz) Occasional breaking of large glass windows already under strain Loud noise (143 dB).8 13.4-6. wood panels (standard housing). Clancey. made uninhabitable Corrugated asbestos shatters.3 2." paper presented at the Sixth International Meeting of Forensic Sciences (Edinburgh.21 0. not reinforced. . steel frame buildings distort and pull away from foundations Frameless.07 Damage Annoying noise (137 dB if of low frequency.8 1. occasional damage to window frames Minor damage to house structures Partial demolition of houses. projectile limit. shatter Lower limit of serious structural damage 50% destruction of brickwork of houses Heavy machines (3000 lb) in industrial buildings suffer little damage.28 0. glass failure Breakage of small windows under strain Typical pressure for glass breakage "Safe distance" (probability 0. 10% window glass broken Limited minor structural damage Large and small windows usually shatter.6 27. some damage to house ceilings. corrugated steel or aluminum panels.0 68.1 0. fastenings fail.000 lb) survive Limit of crater lip 0. "Diagnostic Features of Explosion Damage.2 48. not reinforced.2 48.5 34. self-framing steel panel buildings demolished.7 20.14 0. J.1 62.2-55.4 0.0 13.3 kPa 0.

. S..1 1 10 100 Scaled distance. Graham. Explosions in Air (Austin: University of Texas Press. z ( m ~ k ~ ' ' ~ ) . DC: U S Atomic Energy Commission. with units of m/kg"3. The Effects of Nuclear Weapons (Washington. Explosive Shocks in Air (Berlin: Springer-Verlag.. point of the explosion. versus scaled distance z. Experiments with explosives have demonstrated1* that the overpressure can be estimated using an equivalent mass of TNT. Glasstone.01 0. is given by 16W. Source: G. J. 1973). 1985). Kinney and K. and the distance from the ground-zero . Figure 6-23 provides a correlation for the scaled overpressure p. To convert ftllb"' to mlkgl''. Figure 6-23 Correlation between scaled distance and explosion peak side-on overpressure for a TNT explosion occurring on a flat surface. denoted m. denoted r. F. The empirically derived scaling law is The equivalent energy of TNT is 1120 callg.268 Chapter 6 Fires and Explosions 0. The scaled overpressure p. multiply by 0. Baker.E. 1962).3967.

6 kPa (0. Example 6-8 One kilogram of TNT is exploded. if the ambient pressure is 1 atm. is the peak side-on overpressure. p.81 psi).055. The approach is based on the assumption that an exploding fuel . the resulting overpressures from Figure 6-23 are multiplied by 0. For explosions occurring in the open air. and (4) use Table 6-9 to estimate the damage.0 kg)"" = 30 m kg-"" From Figure 6-23 the scaled overpressure is 0. Thus. TNT Equivalency TNT equivalency is a simple method for equating a known energy of a combustible fuel to an equivalent mass of TNT. Most explosions occurring in chemical plants are considered to originate on the ground. From Table 6-9 this overpressure will cause minor damage to house structures. then the resulting side-on overpressure is estimated at (0. (2) convert the energy to an equivalent amount of TNT. The data in Figure 6-23 are also represented by the empirical equation The procedure for estimating the overpressure at any distance r resulting from the explosion of a mass of material is as follows: (1) Compute the energy of the explosion using established thermodynamic procedures. Solution The value of the scaling parameter is determined using Equation 6-21: - 30 m (1. The data in Figure 6-23 are valid only for TNT explosions occurring on a flat surface.3kPa) = 5. is the scaled overpressure (unitless). and pais the ambient pressure.055)(101.5. Compute the overpressure at a distance of 30 m from the explosion. (3) use the scaling law and the correlations of Figure 6-23 to estimate the overpressure.6-13 Explosions 269 where p. well above the ground.

The heat of combustion for the flammable gas can be used in place of the energy of explosion for the combustible gas. Explosion efficiencies can also be defined for solid materials. 4. In addition. and calculate the equivalent mass of TNT using Equation 6-24. with most flammable cloud estimates varying between 1% and lo%. as reported by a number of sources. Determine the total quantity of flammable material involved in the explosion. The explosion efficiency is one of the major problems in the equivalency method. The TNT equivalency method also uses an overpressure curve that applies to point source detonations of TNT. Others have reported 5%. 7 is the empirical explosion efficiency (unitless). the overpressure curve for TNT tends to overpredict the overpressure near the VCE and to underpredict at distances away from the VCE. The procedure to estimate the damage associated with an explosion using the TNT equivalency method is as follows: 1. The advantage to the TNT equivalency method is that it is easy to apply because the calculations are simple. lo%. The explosion efficiency is used to adjust the estimate for a number of factors. The explosion efficiency is empirical. Estimate the explosion efficiency. including incomplete mixing with air of the combustible material and incomplete conversion of the thermal energy to mechanical energy. As a result. AHc is the energy of explosion of the flammable gas (energylmass). ~ is the equivalent mass of TNT (mass). and acetylene. m is the mass of hydrocarbon (mass). respectively. and ErnT is the energy of explosion of TNT. and 15% for flammable clouds of propane. the method is unable to consider the effects of flame speed acceleration resulting from confinement. such as ammonium nitrate. Use the scaling law given by Equation 6-21 and Figure 6-23 (or Equation 6-23) to estimate the peak side-on overpressure. 3. diethyl ether. A typical value for the energy of explosion of TNT is 1120 callg = 4686 kJ1kg = 2016 Btullb. The procedure can be applied in reverse to estimate the quantity of material involved based on damage estimates. The equivalent mass of TNT is estimated using the following equation: where r n . 2.- - - - 270 Chapter 6 Fires and Explosions mass behaves like exploding TNT on an equivalent energy basis. Vapor cloud explosions (VCEs) are explosions that occur because of the release of flammable vapor over a large volume and are most commonly deflagrations. . Use Table 6-9 to estimate the damage for common structures and process equipment.

and open buildings.5 x lo6~ I r n ~ (this value is typical for the heat of combustion of an average stoichiometric hydrocarbon-air mixture). culverts). Conduct a field inspection to identify the congested areas. Normally. 1994). assigns a relative degree of confinement. multistory parking garages). contribute to the blasts. bridges. Perform a dispersion model to determine the extent of the cloud. stacks of crates or pallets.6-13 Explosions 271 TNO Multi-Energy Method The TNO method identifies the confined volumes in a process. In general. and BLEVEs (New York: American Institute of Chemical Engineers. note that the flammable mixture may not fill an entire blast source volume and that the volume of equipment should be considered where it represents an appreciable proportion of the whole volume). sewage systems. Flash Fires. Identify potential sources of strong blast within the area covered by the flammable cloud. (b) assuming that the full quantities of fuel-air mixture present within the partially confined/obstructed areas and jets. however. and pipe racks. this is done by assuming that equipment and buildings are not present. 2. and then determines the contribution to the overpressure from this confined volume (TNO is the Netherlands Organization for Applied Scientific Research). Assign a number representative of the blast strength for each individual blast. 3. Potential sources of strong blast include congested areas and buildings. Estimate the energy of equivalent fuel-air charges by (a) considering each blast source separately. and (d) calculating the combustion energy E (J) for each blast by multiplying the individual volumes of the mixture by 3. Semi-empirical curves are used to determine the overpressure. identified as blast sources in the cloud. because of the limitations of dispersion modeling in congested areas. heavy vapors tend to move downhill. The basis for this model is that the energy of explosion depends highly on the level of congestion and depends less on the fuel in the cloud. 5. tunnels. for instance. (c) estimating the volumes of fuel-air mixture present in the individual areas identified as blast sources (this estimate can be based on the overall dimensions of the areas and jets. spaces between extended parallel planes (for example. The procedure for using the multi-energy model for a VCE is as follows:17 1. spaces within tubelike structures (for example. corridors. The remaining fuel-air mixture in the flammable cloud is assumed to produce a blast of minor strength. and an intensely turbulent fuel-air mixture in a jet resulting from release at high pressure. those beneath closely parked cars in parking lots. . such as process equipment in chemical plants or refineries. Some companies have defined procedures for this. many risk analysts use their own judgment. "Guidelines for Evaluating the Characteristics of Vapor Cloud Explosions. 4.

5 bar. Once the energy quantities E and the initial blast strengths of the individual equivalent fuel-air charges are estimated. assume a minimum strength of 1. is the side-on blast overpressure (Pa). which are in lowintensity turbulent motion (for instance. assume a strength of 3. a source strength of 7 seems to more accurately represent actual experience. For extended and quiescent parts. However. The overpressure is given by and the positive phase duration is given by where P. Furthermore. pa is the ambient pressure (Pa). no differences appear for source strengths ranging from 7 to 10. For more nonquiescent parts.is the Sachs-scaled side-on blast overpressure (dimensionless). . The blast peak side-on overpressure and positive-phase duration are calculated from the Sachs-scaled overpressure and the Sachs-scaled positive-phase duration. for side-on overpressures below about 0. 6. R is the distance from the charge (m). The blast resulting from the remaining unconfined and unobstructed parts of a cloud can be modeled by assuming a low initial strength.272 Chapter 6 Fires and Explosions A safe and most conservative estimate of the strength of the sources of a strong blast can be made if a maximum strength of 10 -representative of a detonation . because of the momentum of a fuel release). the Sachs-scaled blast side-on overpressure and positivephase duration at some distance R from a blast source is read from the blast charts in Figure 6-24 after calculation of the Sachs-scaled distance: where - R is the Sachs-scaled distance from the charge (dimensionless). E is the charge combustion energy (J). and Po is the ambient pressure (Pa). AP.is assumed.

used by permission. 1994). .C a .(I) 1 0. Source: Guidelines for Evaluating the Characteristics of Vapor Cloud Explosions.> . and BLEVEs (New York: American Institute of Chemical Engineers. Flash Fires.5 g - Ro Combustion energy-scaled distance (R) Po = atmospheric pressure co = atmospheric sound speed E = amount of combustion energy Ro = charge radius Combustion energy-scaled distance (R) Figure 6-24 Sachs-scaled overpressure and Sachs-scaled positive-phase duration for the TNO multi-energy blast model. .

and the number of moles on the righthand side is 25. Doolittle.A. (2) the flame expansion characteristics of the process unit (which relates to confinement and spatial configuration). Little guidance is provided for partial confinement geometries. the determination of a minimum distance between potential blast sources so that their individual blasts can be considered separately) is a factor in present research. is the ambient speed of sound (mls). "Recent Developments in the BakerStrehlow VCE Analysis Methodology. A complete description of the procedure is provided by Baker et al. although the TNO method tends to predict a higher pressure in the near field and the Baker-Strehlow method tends to predict a higher pressure in the far field. 17(4): 297. 18Q. G." Process Safety Progress (1998). and almost all the blast energy must be due to thermal energy release. is the Sachs-scaled positive-phase duration (dimensionless).274 Chapter 6 Fires and Explosions t. Energy of Chemical Explosions The blast wave resulting from a chemical explosion is generated by the rapid expansion of gases at the explosion site. A. This method is based on a flame speed.8. and the respective blasts should be added. The stoichiometric equation is The initial number of moles on the left-hand side is 24. C. . For example. Tang.8. The most conservative approach to this issue is to assume a maximum initial blast strength of 10 and to sum the combustion energy from each source in question. In this case only a small pressure increase is expected as a result of the change in the number of moles. Another popular method to estimate overpressures is the Baker-Strehlow method. is the positive-phase duration (s). consider the combustion of propane in air. they may be initiated almost simultaneously. t. Further definition of this important issue (for instance. it is not clear how the results from each blast strength should be combined. Baker. based on the degree of confinement. For most hydrocarbon combustion explosions in air the change in the number of moles is small. Both methods require more information and detailed calculations than the TNT equivalency method. and (3) the obstacle density within the process unit. and M. A set of semi-empirical curves is used to determine the overpressure. E is the charge combustion energy (J). M. Fitzgerald. Furthermore. J. If separate blast sources are located close to one another. which is selected based on three factors: (1)the reactivity of the released material. The major problem with the application of the TNO multi-energy method is that the user must decide on the selection of a severity factor.ls The TNO multi-energy and Baker-Strehlow methods are essentially equivalent. and c. This expansion can be caused by two mechanisms: (1) thermal heating of the reaction products and (2) the change in the total number of moles by reaction.

The released energy is equal to the work required to expand the gases. 1981). and explodes. . The energy of explosion for hexane is found in appendix B. Sussman20showed that the thermodynamic availability for a reacting system can be computed using the standard Gibbs energy of formation. . The thermodynamic availability is a state function used to determine the maximum mechanical energy extractable from a material as it moves into equilibrium with its surroundings. Thus the overpressure is This overpressure will demolish steel panel buildings. we obtain qmAH. Assume an explosion efficiency of 2%. M A : Mulliken House. Crowl also showed how the energy of explosion could be determined for materials exploding at different gas compositions and nonambient temperatures and pressures. mixes with air.7 kJ/mol) mTNT = = 218 kg TNT 4686 kJ/kg ETNT b. Example 6-9 One thousand kilograms of methane escapes from a storage vessel. Crowl19reasoned that this expansion work is a form of mechanical energy. However. Appendix B contains energy of explosion values based on thermodynamic availability.016 kg)(818. Crowl then concluded that the energy of explosion for a material exploding at room temperature and pressure is equal to the standard Gibbs energy of formation.6-13 Explosions 275 The energy released during a reaction explosion is computed using standard thermodynamics. as shown in appendix B. Crowl. For most practical purposes the two properties can be used interchangeably. Solution a. the scaled overpressure is 0. these adjustments are normally small. Determine (a) the equivalent amount of TNT and (b) the side-on peak overpressure at a distance of 50 m from the blast. Sussman. A. Substituting into Equation 6-24. 20M. Availability (Exergy) Analysis (Lexington.02)(1000 kg)(l moV0. Equation 6-21 is used to determine the scaled distance: From Figure 6-23 (or Equation 6-23).25.(0. Equation 6-24 applies. For many materials the heat of combustion and energy of explosion differ by less than lo%. S(2): 109-118.V." Journal of Loss Prevention in the Process Industries (1992). 19D. "Calculating the Energy of Explosion Using Thermodynamic Availability.

The concentration of vapor in the cloud is assumed to be at stoichiometric concentrations.L.3 kPa) = 13. 21H. The result is The curve labeled 7 in Figure 6-24 is used to determine the scaled overpressure value of about 0. Solution The heat of combustion of a stoichiometric hydrocarbon-air mixture is approximately 3. Determine the overpressure from this vapor cloud explosion at a distance of 100 m from the blast using the TNO multi-energy method. The resulting expression is where E is the energy of explosion (energy). Energy of Mechanical Explosions For mechanical explosions a reaction does not occur and the energy is obtained from the energy content of the contained substance. and thermodynamic availability. Examples of this type of explosion are the sudden failure of a tire full of compressed air and the sudden catastrophic rupture of a compressed gas tank. The resulting side-on overpressure is determined from Equation 6-26: po = AE. 2: 17. .2 kPa = 1. an explosion may result. To apply the TNO multi-energy method. Assume a cloud volume of 2094 m3. is the ambient pressure (forcelarea). Brode's method2I is perhaps the simplest approach.- - - 276 Chapter 6 Fires and Explosions Example 6-10 Consider the explosion of a propane-air vapor cloud confined beneath a storage tank.confined below the tank. the resulting total energy is (2094 m"(3. If this energy is released rapidly. isentropic expansion. representing the volume underneath the tank.13)(101. P. and by multiplying by the confined volume.5 ~ J l m ~ . pa This is adequate to shatter concrete or cinder block walls. = (0. Four methods are used to estimate the energy of explosion for a pressurized gas: Brode's equation.9 psi. a blast strength of 7 is chosen." Physics of Fluids (1959). Brode. isothermal expansion. The Sachs-scaled energy is determined using Equation 6-25.13. The tank is supported 1m off the ground by concrete piles. It determines the energy required to raise the pressure of the gas at constant volume from atmospheric pressure to the final gas pressure in the vessel. "Blast Waves from a Spherical Charge.5 MJ/m3) = 7329 MJ.

Crowl." . The final method uses thermodynamic availability to estimate the energy of explosion. This is represented by the following equation: where R. is the ambient temperature (degrees). The isentropic expansion method assumes that the gas expands isentropically from its initial to final state. "Calculating the Energy of Explosion.A. with the addition of a correction term. indicating that the energy is released to the surroundings during the vessel rupture. Thus thermodynamic availability predicts a maximum upper bound to the mechanical energy available to produce an overpressure. This correction term accounts for the energy lost as a result of the second law of thermodynamics. the energy calculated from Equation 6-28 is positive. Thermodynamic availability represents the maximum mechanical energy extractable from a material as it comes into equilibrium with the environment. Because P. is the burst pressure of the vessel (forcelarea). 22D.6-13 Explosions 277 P. V is the volume of expanding gas in the vessel (volume). >PI. is the ideal gas constant and T. 1 ~ batch thermodynamic availability resulted in the following An analysis by C r o ~ using ~ expression to predict the maximum explosion energy of a gas contained within a vessel: Note that Equation 6-31 is nearly the same as Equation 6-30 for an isothermal expansion. and y is the heat capacity ratio for the gas (unitless). The resulting overpressure from an explosion is a form of mechanical energy. The following equation represents this case: The isothermal expansion case assumes that the gas expands isothermally.

The question arises as to which method to use. Also. The isentropic method produces a low value for the energy of explosion. V. The gas expands into ambient air at 1 atm pressure.7 psia results in a final temperature of 254"R. The isothermal expansion method predicts a large value for the energy of explosion because it assumes that all the energy of compression is available to perform work. UnderstandingExplosions in the Process Industries (New York: American Institute of Chemical Engineers. in press). used by permission.Chapter 6 Fires and Explosions Isothermal 0 0 100 200 300 Gas pressure (psia) 400 0 500 Figure 6-25 The energy of explosion for a compressed inert gas. For estimation purposes it is not uncommon to subtract 50% of the total potential energy to calculate the blast pressure effects from vessel burst. .4. A. The isentropic expansion results in a gas at a very low temperature. or near field. Figure 6-25 presents the energy of explosion using all four methods as a function of initial gas pressure in the vessel. computed using four different methods. It is thought that the Brode equation more closely predicts the potential explosion energy close to the explosion source. a portion of the potential explosion energy of vessel burst is converted into kinetic energy of the vessel pieces and other inefficiencies (such as strain energy in the form of heat in the vessel fragments). the expansion of an ideal gas from 200 psia to 14. according to the second law of thermodynamics. some of the energy must be expelled as waste heat. Mashuga. or -205°F. or far field. and that the isentropic expansion method predicts better the effects at a greater distance. Source: D. In reality. However. All four methods continue to be used to estimate the energy of explosion for compressed gases. The calculation assumes an inert gas initially at 298 K with y = 1. Crowl and C. it is unclear where this transition occurs. This is thermodynamically inconsistent because the final temperature is ambient. The thermodynamic availability method accounts for this loss through the correction term in Equation 6-31.

" paper presented at Sixth International Meeting of Forensic Science (Edinburgh. discussed in section 2-6. resulting in the projection of debris over a wide area. or missiles. This debris.) Missile Damage An explosion occurring in a confined vessel or structure can rupture the vessel or structure. . Unconfined explosions also create missiles by blast wave impact and subsequent translation of structures. as illustrated in Figure 6-26. "Diagnostic Features of Explosion Damage. 2 " J. Blast damage effects are estimated using probit analysis. Data from V. resulting in secondary fires or explosions. A localized explosion in one part of the plant projects debris throughout the plant. This relationship is useful during accident investigations for calculating the energy level required to project fragments an observed distance. Clancey2"eveloped an empirical relationship between the mass of explosive and the maximum horizontal range of the fragments. Clancey. This debris strikes storage tanks." paper presented at the Sixth International Meeting of Forensic Sciences (Edinburgh. 1972. process equipment. 1972). "Diagnostic Features of Explosive Damage.6-13 Explosions 279 Distance (ft) Figure 6-26 Maximum horizontal range of blast fragments. can cause appreciable injury to people and damage to structures and process equipment. Clancey. Blast Damage to People People can be injured by explosions from direct blast effects (including overpressure and thermal radiation) or indirect blast effects (mostly missile damage). and pipelines. Missiles are frequently a means by which an accident propagates throughout a plant facility.

The probit equation for deaths resulting from lung hemorrhage is and the probit equation for eardrum rupture is where P is the overpressure in N/m2. This assumes complete conversion of explosion energy. If it explodes.000 Ib of TNT. Table 6-9 indicates that steel-panel buildings will be demolished at this location. Based on Figure 6-26.280 Chapter 6 Fires and Explosions Example 6-11 A reactor contains the equivalent of 10. The result shows that there are no deaths and that less than 10% of the exposed people suffer eardrum ruptures.21)(14.21 and the overpressure is (0. this explosion could project blast fragments a maximum distance of 6000 ft. resulting in probable injuries and damage as a result of blast fragments. estimate the injury to people and the damage to structures 500 ft away. Injury to personnel is determined using probit equations from Table 2-5. Solution The overpressure is determined using Equation 6-21 and Figure 6-23. The scaled distance is From Figure 6-23 the scaled overpressure is 0. Thus Substituting this value into the probit equations yields Table 2-4 converts the probit to percentages.1 psig.7 psia) = 3. .

probability of explosion rather than fire. dispersion of the vapor throughout the plant site while mixing with air. or high-pressure gases is considered a good candidate for a VCE.p. is a classic example of a VCE. 26Lees. Loss Prevention in the Process Industries. (3) the explosion efficiency is usually small (approximately 2% of the combustion energy is converted into a blast wave). Some of the parameters that affect VCE behaviorzs are quantity of material released. existence of a threshold quantity of material. 171156. The entire plant site was leveled and 28 people were killed. p. and (4) turbulent mixing of vapor and air and ignition of the cloud at a point remote from the release increases the impact of the explosion.6-13 Explosions 281 Vapor Cloud Explosions The most dangerous and destructive explosions in the chemical process industries are vapor cloud explosions (VCEs). "Evaluation of Unconfined Vapor Cloud Explosion Hazards.27 From a safety standpoint the best approach is to prevent the release of material. Accidents occur under uncontrolled circumstances. 713. VCEs are difficult to characterize. fraction of material vaporized. 714. volatile superheated liquid. time delay before ignition of cloud. containing a superheated and pressurized liquid.Loss Prevention in the Process Industries. primarily because of the large number of parameters needed to describe an event. "Evaluation of Unconfined Vapor Cloud Explosion Hazards. 2"rank P. Any process containing quantities of liquefied gases. England. A summary of 29 V C E Sover the period 1974-1986 shows property losses for each event ~~ of between $5." p.000 and $100.000 and 140 fatalities (an average of almost 13 per year)." International ConferW. 171155. p. efficiency of explosion. The accident at Flixborough. VCEs have increased in number because of an increase in inventories of flammable materials in process plants and because of operations at more severe conditions. A large cloud of combustible material is dangerous and almost impossible to control. Data collected from real events are mostly unreliable and difficult to compare. ence on Vapor Cloud Modeling (New York: American Institute of Chemical Engineers. ignition of the resulting vapor cloud. ruptures). A sudden failure of a 20-inch cyclohexane line between reactors led to vaporization of an estimated 30 tons of cyclohexane. 2. 1987). . sudden release of a large quantity of flammable vapor (typically this occurs when a vessel. 3. (2) vapor cloud fires are more common than explosions.000.000. Lees. distance traveled by the cloud before ignition. These explosions occur in a sequence of steps: 1. 27Pr~gh. 24Richard Prugh. despite any safety systems installed to prevent ignition. The vapor cloud dispersed throughout the plant site and was ignited by an unknown source 45 seconds after the release. and location of ignition source with respect to release. probability of ignition of the cloud. Qualitative studiesz6have shown that (1) the ignition probability increases as the size of the vapor cloud increases.

a large area might be subjected to toxic materials. explosively vaporizing its contents.p. 5. Industrial Explosion Prevention and Protection (New York: McGraw-Hill. The most common type of BLEVE is caused by fire. Bartknecht. using analyzers to detect leaks at low concentrations.1980). Industrial Explosion Prevention and Protection (New York: McGraw-Hill. W. If the flames reach the tank walls or roof where there is only vapor and no liquid to remove the heat. propelling vessel parts for great distances. Suggested Reading W. Bodurtha. 3. and installing automated block valves to shut systems down while the spill is in the incipient stage of development. the amount depends on the physical and thermodynamic conditions of the vessel contents. When a BLEVE occurs in a vessel. increasing the liquid temperature and the pressure in the tank. Bartknecht. Often. The fraction vaporized is estimated using the methods discussed in section 4-7. The tank walls below liquid level are cooled by the liquid. 28Lees. 2. pronounced blel-vee) is a special type of accident that can release large quantities of materials. The vapors might also be hazardous to personnel by means of skin burns or toxic effects. Protection (Berlin: Springer-Verlag. 4. flammable materials.282 Chapter 6 Fires and Explosions Methods that are used to prevent VCEs include keeping low inventories of volatile. 99. Bodurtha.1980). a VCE might result. For either situation the energy released by the BLEVE process itself can result in considerable damage. A fire develops adjacent to a tank containing a liquid. If the materials are flammable. BLEVEs are caused by the sudden failure of the container as a result of any cause. 1989). Prevention. Frank T. if they are toxic. The steps are as follows: 1. A BLEVE occurs when a tank containing a liquid held above its atmospheric pressure boiling point ruptures. using process conditions that minimize flashing if a vessel or pipeline is ruptured. the liquid may ignite as the tank ruptures. p. If the BLEVE is not caused by a fire. the boiling and burning liquid behaves as a rocket fuel. Explosions (Berlin: Springer-Verlag. The tank ruptures. The fire heats the walls of the tank. resulting in a VCE. . If the liquid is flammable and a fire is the cause of the BLEVE. only a fraction of the liquid vaporizes. a vapor cloud might form. Boiling-Liquid Expanding-Vapor E x p l o s i ~ n s ~ ~ A boiling-liquid expanding-vapor explosion (BLEVE. 171178. the tank metal temperature rises until the tank loses it structural strength. Dust Explosions: Course. 1980). resulting in the explosive vaporization of a large fraction of the tank contents.Loss Prevention in the Process Industries.

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D. A. Crow1 and C. V. Mashuga, Understanding Explosions in the Process Industries (New York: American Institute of Chemical Engineers, in press). Rolf K. Eckhoff, Dust Explosions in the Process Industries, 2d ed. (London: Butterworth-Heinemann, 1997). Guidelines for Evaluating Process Plant Buildings for External Explosions and Fires (New York: American Institute of Chemical Engineers, 1996). Guidelines for Evaluating the Characteristicsof Vapor Cloud Explosions, Flash Fires, and BLEVEs (New York: American Institute of Chemical Engineers, 1994). Gilbert F. Kinney and Kenneth J. Graham, Explosive Shocks in Air, 2d ed. (Berlin: Springer-Verlag, 1985). Frank P. Lees, Loss Prevention in the Process Industries, 2d ed. (London: Butterworth-Heinemann, 1996), ch. 16 and 17. Bernard Lewis and Guenther von Elbe, Combustion, Flames, and Explosions of Gases, 3d ed. (New York: Academic Press, 1987). Daniel R. Stull, Fundamentals of Fire and Explosion, AICHE Monograph Series, no. 10, v. 73 (New York: American Institute of Chemical Engineers, 1977).

Problems
6-1. Estimate the flash point of a solution of 50 mol % water and 50 mol % methanol. 6-2. Estimate the flash point of a solution of 50 mol % water and 50 mol % ethanol. 6-3. Estimate the LFL and the UFL of the following mixtures:
All in volume %

Hexane Methane Ethylene Acetone Ethyl ether Total combustibles Air

0.5 1. O 0.5 0.0 0.0 2.0 98.0

0.0 0.0 0.5 1.O 0.5 2.0 98.0

1.0 1O . 1. O 0.0 0.0 3.0 97.0

0.0 0.0 1.0 1.0 1.0 3.0 97.0

6-4. Estimate the LFL and the UFL of Problem 6-3a at 50°C, 75"C, and 100°C. 6-5. Estimate the UFL of Problem 6-3a at 1atm, 5 atm, 10 atm, and 20 atm of pressure. 6-6. Estimate the LFL and the UFL using the stoichiometric concentrations for methane, propylene, ethyl ether, and acetone. Compare these estimates to actual values. 6-7. Estimate the LOC of propane, hydrogen, and methane. 6-8. Determine the LOC of a mixture of 2% hexane, 3% propane, and 2% methane by volume. 6-9. Determine the minimum compression ratio required to raise the temperature of air over hexane to its AIT. Assume an initial temperature of 100°C. 6-10. What will be the LFL of hexane in the presence of hexane mists with drops larger than 0.01 mm'?

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6-11. Why do staged hydrogen compressors need interstage coolers? 6-12. Why do hot engines sometimes continue to run after the ignition is turned off? 6-13. A set of experiments is run on a flammable gas in a spherical vessel. The following data are obtained for two different vessel volumes. Estimate the value of KG for this combustible gas:

V = I m3
Time (s)

V = 20m3
Time (s)

P (bar)

P (bar)

-

-

-

-

-

-

6-14. Determine the energy of explosion for 1lb of gaseous n-butane. What is the TNT equivalent? 6-15. A gas cylinder contains 50 lb of propane. The cylinder accidentally falls over and ruptures, vaporizing the entire contents of the cylinder. The cloud is ignited and an explosion occurs. Determine the overpressure from this explosion 100 ft away. What type of damage is expected? 6-16. A VCE with methane destroyed a house structure 100 ft away from the ignition source. Estimate the amount of methane released. 6-17. A large cloud of propane is released and eventually ignited, producing a VCE. Estimate the quantity of propane released if the blast shattered windows 3 mi from the source of the ignition. 6-18. At 77°F gasoline has a vapor pressure of 4.6 psia. Why can gasoline be stored in vented storage vessels without the presence of flammable vapors above the liquid in the vessel? Comment on the EPA's effort to reduce gasoline volatility in order to reduce fugitive emissions. What will happen as the volatility is reduced?

Problems

285

6-19. An automobile assembly line includes an operation that involves filling the gas tanks with gasoline. Estimate the ventilation rate required to reduce the vapors from this operation to below the LFL for gasoline. Assume that each tank has a volume of 14 gal and that a tank can be filled in 3 min. Assume splash filling and that only one tank is filled at a time. The molecular weight of gasoline is about 94, and its vapor pressure at 77°F is 4.6 psia. Also, calculate the ventilation air required to reduce the concentration of the gasoline vapors to below the TLV-TWA. Which problem is more difficult? 6-20. A butane tank is located 500 ft from a residential area. Estimate the minimum instantaneous release of butane required to produce a vapor concentration in the residential area equal to the LFL for butane. What continuous release rate is required? Assume that the release occurs at ground level. Will the minimum amount increase, decrease, or stay the same if the release occurs above ground level? 6-21. Benzene is stored in an inside storage area, 15 ft long and 15 ft wide with an 8-ft ceiling. This storage area has a ventilation system that changes the air in the room completely six times per hour. The storage area is also equipped with a flammable vapor detector that sounds an alarm when the flammable vapor concentration reaches 25% of the LFL for benzene. What is the minimum benzene spill rate, in lblhr, that will set off the flammable vapor alarm in the room? Assume a pressure of 1 atm and a temperature of 80°F. Also assume average ventilation conditions. 6-22. A standard laboratory cylinder is about 5 ft high with an internal vessel diameter of about 6 in. Determine the total energy of explosion for this cylinder if it contains nitrogen compressed to 2500 psig. Assume initial and ambient conditions of 298 K and 1 atm. 6-23. Many chemical operators believe that the inerted vapors above a flammable liquid are not flammable when they mix with air. This is frequently not the case: If the inerted vapors escape from the vessel and mix with air or if the vessel is purged with air after emptying, the resulting mixture might be flammable. A storage vessel contains liquid benzene at 100°F. The vessel vapor space is inerted with pure nitrogen to a total pressure of 112-in of water gauge. Assume that the vapor space is saturated with benzene vapor. a. Determine the volume percent concentration of benzene in the vapor. b. Use a flammability diagram to show whether this mixture will become flammable or not when mixed with air. (Hint: 1 atm = 34.4 ft of water.) 6-24. An informal industry rule is to design occupied control rooms to withstand a 1-ton blast of TNT at 100 ft. a. What overpressure does this correspond to? b. What quantity (in pounds) of propane (C,H,) does this correspond to, based on an equivalent amount of energy? c. How far away (in ft) from this 1- ton blast must a residential home be in order to receive no more than minor damage to house structures?

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Chapter 6

Fires and Explosions

6-25. According to fire code, propane storage tanks cannot be closer than 10 ft from a house. This requirement is designed to prevent flammable vapors from entering the house, not to protect the house from a potential explosion. What quantity of propane (in lb,) can be stored under these conditions that will cause no more than minor damage to a house in the event of an explosion? Be sure to list any assumptions. 6-26. Fires and explosions are substantial hazards in many chemical plants. a. Describe with examples the three ingredients of any fire. b. Create a checklist with at least six items to identify fire hazards in any workplace. c. List six common fire preventionlprotection features for chemical plants, and describe when they would be appropriate. 6-27. The following liquids are stored in a storage vessel at 1 atm and 25°C. The vessels are vented with air. Determine whether the equilibrium vapor above the liquid will be flammable. The liquids are: a. Acetone b. Benzene c. Cyclohexane d. Ethyl alcohol e. Heptane f. Hexane g. Pentane h. Toluene 6-28. A natural gas wellhead is located 400 m from an instrument control room. The control room is a potential ignition hazard in the event of a leak of natural gas (essentially pure methane). Studies have shown that a suitable safety margin is imposed if the downwind gas concentration is determined using one-half the LFL. For methane this represents a concentration of 2.5 vol. %. a. What is the minimum release rate of methane (in kgls) that will result in a concentration at the control room equal to half the LFL? Be sure to state your assumptions clearly. Assume a temperature of 298 K and an ambient pressure of 1 atm. b. If the methane pressure in the wellhead is at 10 atm pressure, what hole size (in cm) will produce the release rate of part a? c. If the largest pipe Size in the wellhead is 4 cm (internal diameter), comment on the likelihood of an ignition hazard from the control room. 6-29. In the TWA Flight 800 tragedy the accident is blamed on explosion of fuel vapors in the central fuel tank. The volume of the central fuel tank is 18,000 gal. a. If, at the time of the explosion, the fuel concentration in the tank is 1% by volume and the pressure inside the tank is 12.9 psia, determine the equivalent energy of explosion for the vapor (in pounds of TNT). Assume a temperature of 80°F. Be sure to state carefully any assumptions.

Problems

287

b. Estimate the overpressure at a distance of 50 ft from the fuel tank explosion from the

explosion of the vapors in part a. c. Estimate the limiting oxygen concentration (LOC) for the jet fuel, given that the LFL is 0.6% by volume and the stoichiometric coefficient for oxygen in the combustion equation is 18.9. For jet fuel the energy of explosion is 18,590 Btullb and the molecular weight is 160. 6-30. You have decided to purchase a 500-gal tank of liquid propane (C,H,) to heat your house during the winter. You are concerned about tank rupture and the possibility of a vapor cloud explosion of all the propane. How far away (in ft) must the tank be from the house to ensure that your house will receive only minor damage from an explosion? The specific gravity of liquid propane is 0.500, and the energy of explosion for propane is 503.9 kcallg-mol. 6-31. A liquid mixture containing 0.50 mole fraction benzene-toluene is contained in a storage vessel at 25°C and 1atm. The vessel is vented to the atmosphere. a. Is the vapor in the vessel flammable? b. What are your resulting concerns about fire and explosion hazards with this storage vessel? Hint: Benzene-toluene can be assumed to be an ideal liquid-vapor system. 6-32. A tank containing liquid butane (C,H,,) is located 500 ft from an electrical substation. One of the scenarios we are considering is the breaking of a 1-in schedule 40 pipe (internal diameter = 1.049 in) with discharge of the liquid butane. We are concerned that this leak will cause flammable vapor concentrations at the substation. Assume that all the liquid flashes to vapor. a. Estimate the discharge rate (in lb,/s) of butane from the 1-in broken pipe. b. Estimate the butane vapor concentrations at the substation. Is this likely to be a flammable hazard? The temperature is 80°F and the ambient pressure is 1 atm. Make sure you clearly state any assumptions. The vapor pressure of liquid butane at 80°F is 40 psia, and the specific gravity of liquid butane at 80°F is 0.571. 6-33 Acetone is used as a solvent in a laboratory. There is some concern about the fire hazards associated with the acetone. One solution is to dilute the pure acetone with water, thus providing an increased flash point. What mole fraction of water in a water-acetone mixture is required to increase the flash point of the mixture to 100°F? Acetone is completely soluble in water. 6-34 You have been assigned the task of assisting in relocating the new control room for your process. The new control room will be designed to withstand an explosive overpressure of 2 psig. Your attention is focused on a propane storage tank located 100 m from the proposed site for the new control room. What is the maximum quantity of propane (in kg) that can be stored in this tank without exceeding the overpressure rating of the control room? Make sure you state any assumptions used in your calculation.

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6-35. Methyl alcohol liquid is stored in a vessel. Its vapor is inerted with nitrogen to a total pressure of 2 in of water gauge. Will the inerted vapor be flammable if it escapes the vessel? Assume a temperature of 25°C. 6-36. Draw a flammability diagram for n-butane. The experimentally reported LOC for n-butane is 12%. What must the oxygen concentration be reduced to before pumping in butane? What butane concentration must the vapor be reduced to before pumping air into the vessel before taking it out of service? 6-37. For flammable gases the minimum ignition energy is typically 0.1 mJ. The mass of a penny is typically 2.6 g. How far must this penny be dropped to contain the kinetic energy equal to 0.1 mJ? 6-38. During a particular accident, an estimated 39,000 kg of flammable material was released and ignited, resulting in an explosion and fireball and the subsequent fatalities and equipment damage. The publication Guidelines for Evaluating the Characteristics of Vapor Cloud Explosions, Flash Fires, and BLEVES (New York: American Institute of Chemical Engineers, 1994) provides a number of equations useful for estimating the effects of such an explosion. The heat radiation intensity (in kw/m2) from a ball of burning vapor is given by the empirical equation

The effective time duration (in seconds) of the burn is given by

The height of the center of the fireball (in meters) is assumed to be constant during the burn and is given by

Finally, the maximum diameter of the fireball (in meters) is given by

For these equations I, is the effective radiation intensity (kW/m2),m fis the mass of fuel (kg), L is the distance from the center of the fireball to the receptor (m), and t, is the effective time duration of the burn (s). Use a spreadsheet program (such as Quattro Pro or Excel) to estimate the total number of fatalities resulting from the burning fireball. Use the probit equations provided in the text. Assume that 400 people are distributed evenly at a distance of 75 m to 1000 m from the fireball center. Divide the distance interval into a number of small increments. Use a small enough distance increment so that the results are essentially independent of the increment size.

Problems

289

Your spreadsheet output should have designated columns for the distance from the fireball center, radiation intensity, probit values, and percentage and number of fatalities. You should also have a single designated spreadsheet cell providing the total number of fatalities. One way to simplify the procedure is to specify a threshold radiative flux. It is assumed that 100% fatalities will occur to anyone exposed to anything above this value. Anyone exposed to a lesser value will be unharmed. Estimate an approximate threshold radiative flux value that will result in the same number of fatalities as the detailed probit calculation. 6-39. The air in a 55-gal drum must be flushed and inerted with nitrogen before the drum is filled with a flammable liquid. This is accomplished by placing a nitrogen lance through the hole of the drum reaching to the bottom. A constant flow rate of nitrogen is used to achieve the inerting. a. Show that the concentration of oxygen in the drum is represented by

where C is the concentration of oxygen in the drum (mass/volume), k is the nonideal mixing factor (0.1 < k < I), and Q, is the volumetric flow of nitrogen (volume/time). b. Show that the time required to reach a target concentration Cf from an initial concentration C, is given by

c. Estimate the time it will take to inert a drum to 1% oxygen using 75 L/min of nitrogen. Use k as a parameter. 6-40. A container in a process using a flammable vapor has dimensions of 100 m by 100 m by 10 m high. Use the TNO multi-energy model to estimate the overpressure 100 m from the process resulting from the release and ignition of the flammable vapor. Assume that 20% of the process volume is moderately congested and that the remaining 80% is lightly congested. Be sure to state any additional assumptions.

Designs to Prevent Fires and Explosions

twofold strategy is used to limit the potential damage from fires and explosions: prevent the initiation of the fire or explosion and minimize the damage after a fire or explosion has occurred. This strategy is presented in this chapter. The specific topics include inerting, use of the flammability diagram introduced in chapter 6, static electricity, controlling static electricity, ventilation, explosion-proof equipment and instruments, sprinkler systems, and miscellaneous design features for preventing fires and explosions. For any fire or combustion explosion to occur, three conditions must be met (as shown in the fire triangle of Figure 6-1). First, a combustible or explosive material must be present. Second, oxygen must be present to support the combustion reaction. Finally, a source of ignition must be available to initiate the reaction. If any of the three conditions of the fire triangle is eliminated, the triangle is broken and it is impossible for a fire or combustion explosion to result. This is the basis for the first six design methods listed above. Damage resulting from fires and explosions is minimized by stopping fires or explosions as quickly as possible and also by designing the process equipment (and control centers) to withstand their effects. Miscellaneous design features are additional safety design methods that are usually included in the early design phases of new projects and are often the basis for safety improvements in existing plants.

A

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-

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Chapter 7

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7-1 lnerting
Inerting is the process of adding an inert gas to a combustible mixture to reduce the concentration of oxygen below the limiting oxygen concentration (LOC). The inert gas is usually nitrogen or carbon dioxide, although steam is sometimes used. For many gases the LOC is approximately lo%, and for many dusts it is approximately 8%. Inerting begins with an initial purge of the vessel with inert gas to bring the oxygen concentration down to safe concentrations. A commonly used control point is 4% below the LOC, that is, 6 % oxygen if the LOC is 10%. After the empty vessel has been inerted, the flammable material is charged. An inerting system is required to maintain an inert atmosphere in the vapor space above the liquid. Ideally this system should include an automatic inert gas addition feature to control the oxygen concentration below the LOC. This control system should have an analyzer to continuously monitor the oxygen concentration in relationship to the LOC and a controlled inert gas feed system to add inert gas when the oxygen concentration approaches the LOC. More frequently, however, the inerting system consists only of a regulator designed to maintain a fixed positive inert pressure in the vapor space; this ensures that inert gas is always flowing out of the vessel rather than air flowing in. The analyzer system, however, results in a significant savings in inert gas usage without sacrificing safety. Consider an inerting system designed to maintain the oxygen concentration below 10%. As oxygen leaks into the vessel and the concentration rises to 8%, a signal from the oxygen sensor opens the inert gas feed valve. Once again the oxygen level is adjusted to 6%. This closedloop control system, with high (8%) and low (6%) inerting set points, maintains the oxygen concentration at safe levels with a reasonable margin of safety. NFPA recommendations are described at the end of this section. There are several purging methods used to initially reduce the oxygen concentration to the low set point: vacuum purging, pressure purging, combined pressure-vacuum purging, vacuum and pressure purging with impure nitrogen, sweep-through purging, and siphon purging.

Vacuum Purging
Vacuum purging is the most common inerting procedure for vessels. This procedure is not used for large storage vessels because they are usually not designed for vacuums and usually can withstand a pressure of only a few inches of water. Reactors, however, are often designed for full vacuum, that is -760 mm Hg gauge or 0.0 mm Hg absolute. Consequently, vacuum purging is a common procedure for reactors. The steps in a vacuum purging process include (1) drawing a vacuum*on the vessel until the desired vacuum is reached, (2) relieving the vacuum with an inert gas, such as nitrogen or carbon dioxide to atmospheric pressure, and (3) repeating steps 1 and 2 until the desired oxidant concentration is reached.

7-1 lnerting

293

End of first vacuum purge

End of second vacuum purge

concentration is constant Time

Number of moles of oxygen is constant

Figure 7-1

Vacuum purge cycles.

The initial oxidant concentration under vacuum (yo)is the same as the initial concentraand initial low pressure or vaction, and the number of moles at the initial high pressure ( p H ) uum (PL)are computed using an equation of state. The process for vacuum purging is clarified using the stepwise procedure shown in Figure 7-1. A vessel of known size is vacuum-purged from an initial oxygen concentration yo to a final target oxygen concentration yi. The vessel is initially at pressure P, and is vacuum-purged using a vacuum at pressure PL. The objective of the following calculation is to determine the number of cycles required to achieve the desired oxygen concentration. Assuming ideal gas behavior, the total moles a t each pressure are

where nH and nL are the total moles in the atmospheric and vacuum states, respectively. The number of moles of oxidant for the low pressure PL and high pressure P, are computed using Dalton's law:

where 1L and 1H are the first atmospheric and first vacuum states, respectively.

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Chapter 7

Designs to Prevent Fires and Explosions

When the vacuum is relieved with pure nitrogen, the moles of oxidant are the same as in the vacuum state and the moles of nitrogen increase. The new (lower) oxidant concentration is

where y, is the oxygen concentration after the first purge with nitrogen. Substituting Equation 7-3 into Equation 7-5 gives

If the vacuum and inert relief process is repeated, the concentration after the second purge is

This process is repeated as often as required to decrease the oxidant concentration to a desired level. The concentration after j purge cycles, vacuum and relief, is given by the following general equation:

This equation assumes that the pressure limits P, and PL are identical for each cycle. The total moles of nitrogen added for each cycle is constant. For j cycles the total nitrogen is given by

Example 7-1
Use a vacuum purging technique to reduce the oxygen concentration within a 1000-gal vessel to 1ppm. Determine the number of purges required and the total nitrogen used. The temperature is 75"F,and the vessel is originally charged with air under ambient conditions. A vacuum pump is used that reaches 20 mm Hg absolute, and the vacuum is subsequently relieved with pure nitrogen until the pressure returns to 1 atm absolute.

Solution
The concentration of oxygen at the initial and final states is yo = 0.21 lb-mol 02/totalmol,
y,
=

1ppm

=

1x

1b-molO,/total mol.

7-1 lnerting

295

The required number of cycles is computed using Equation 7-6:

I

=

ln(10-610.21) = 3.37. ln(20 mm Hg/760 mm Hg)

Number of purges = j = 3.37. Four purge cycles are required to reduce the oxygen concentration to 1 ppm. The total nitrogen used is determined from Equation 7-7. The low pressure P, is

PI.=

20 (760mm Hg mm Hg

(14.7 psia) = 0.387 psia,

= =

4(14.7

-

0.387) psia
=

(1000 gal)(l ft3/7.48gal) (10.73 psia ft3/lb-mo1°~)(75 460)"R +

1.33 lb-mol

37.2 lb of nitrogen.

Pressure Purging
Vessels can be pressure-purged by adding inert gas under pressure. After this added gas is diffused throughout the vessel, it is vented to the atmosphere, usually down to atmospheric pressure. More than one pressure cycle may be necessary to reduce the oxidant content to the desired concentration. The cycles used to reduce the oxygen concentration to a target level are shown in Figure 7-2. In this case the vessel is initially at PL and is pressurized using a source of pure nitrogen at pH. The objective is to determine the number of pressure purge cycles required to reach the desired concentration. Because the vessel is pressurized with pure nitrogen, the number of moles of oxygen remains constant during pressurization, whereas the mole fraction decreases. During depressurization, the composition of the gas within the vessel remains constant, but the total number of moles is reduced. Thus the oxygen mole fraction remains unchanged. The relationship used for this purging process is identical to Equation 7-6, where nL is now the total moles at atmospheric pressure (low pressure) and n, is the total moles under pressure (high pressure). In this case, however, the initial concentration of oxidant in the vessel ( y o ) is computed after the vessel is pressurized (the first pressurized state). The number of moles for this pressurized state is n, and the number of moles for the atmospheric case is n ~ .

Determine the number of purges required to reduce the oxygen concentration to 1ppm using pure nitrogen at a pressure of 80 psig and at a temperature of 75°F. O n e practical advantage of pressure purging versus vacuum purging is the potential for cycle time reductions. Also. Also. Solution Equation 7-6 is used to determine the number of cycles required.7 psia [(80 + 14. The composition at the high-pressure condition is determined using the following equation: where Po is the starting pressure (here atmospheric). determine the total nitrogen required. .296 Chapter 7 Designs to Prevent Fires and Explosions End of first pressure purge End o second f pressure purge Oxygen concentration is constant Time Figure 7-2 Number of moles of oxygen is constant Pressure purge cycles. Substituting the numbers provided. Therefore the best purging process is selected based on cost and performance. we obtain yo = (0. uses more inert gas.0326.21) 14. Pressure purging.7) psia 1 = 0. The initial mole fraction of oxygen yo is now the concentration of oxygen at the end of the first pressurization cycle. Compare the quantities of nitrogen required for the two purging processes. Example 7-2 Use a pressure purging technique to reduce the oxygen concentration in the same vessel discussed in Example 7-1. The pressurization process is much more rapid compared to the relatively slow process of developing a vacuum. the capacity of vacuum systems decreases significantly as the absolute vacuum is decreased. however.

7-1 lnerting 297 The final oxygen concentration (y. the number of cycles j is the number of cycles after the initial pressurization. In this case the beginning of the cycle is defined as the end of the initial evacuation.T ) ~ = = 6(94.. The purging cycles for a pressure-first purge are shown in Figure 7-3.73 psia ft3/lb-mol0~)(53S0~) 11. However.2 lb of nitrogen for vacuum purging.21.) is specified to be 1ppm or number of cycles required is computed using Equation 7-6: lb-mol oxygenltotal lb-mol. Furthermore. = j(PH .14. The purging cycles for an evacuate-first purge are shown in Figure 7-4. The oxygen mole fraction at this point is the same as the initial mole fraction. the remaining cycles are identical to the vacuum purge operation and Equation 7-6 is directly applicable. Combined Pressure-Vacuum Purging In some cases both pressure and vacuum are available and are used simultaneously to purge a vessel. This result illustrates the need for a cost performance comparison to determine whether the time saved in pressure purging justifies the added cost for nitrogen.0326) ln[14. compared to four for the vacuum purge process. Pressure purging requires 6 purges and 311 Ib of nitrogen compared to 4 purges and 37.6. . the number of cycles j is the number of cycles after the initial evacuation.7 ft" (10.1 Ib-mol = 311 Ib of nitrogen. The quantity of nitrogen used for this inerting operation is determined using Equation 7-7: An. The j = 1n(10-~/0. However.7) psia] ' The number of purge cycles is j = 5.7) psia 133.P ~ R. The computational procedure depends on whether the vessel is first evacuated or pressurized.7 psiaI(80 + 14.7 . In this case the beginning of the cycle is defined as the end of the initial pressurization. Thus six pressure purges are required. the oxygen mole fraction at the end of this initial pressurization is given by At this point the remaining cycles are identical to pressure purging and Equation 7-6 applies. If the initial oxygen mole fraction is 0.

Many of the nitrogen separation processes available today do not provide pure nitrogen.Chapter 7 Designs to Prevent Fires and Explosions Time Figure 7-3 Vacuum-pressure purging with initial evacuation. Vacuum and Pressure Purging with Impure Nitrogen The equations developed for vacuum and pressure purging apply to the case of pure nitrogen only. Time Figure 7-4 Vacuum-pressure purging with initial evacuation. . they typically provide nitrogen in the 98% + range.

Vacuum purging uses less inert gas because the oxygen concentration is reduced primarily by vacuum. Advantages and Disadvantages of the Various Pressure and Vacuum lnerting Procedures Pressure purging is faster because the pressure differentials are greater.. however..7-1 lnerting 299 Assume that the nitrogen contains oxygen with a constant mole fraction of yo. When combining vacuum and pressure purging. Thus the mole fraction of oxygen at the end of this cycle is This result is generalized into the following recursive equation (Equation 7-11) and a generalized equation (Equation 7-12) for the oxygen concentration at the end of the jth pressure cycle: Equation 7-12 is used in place of Equation 7-6 for both pressure and vacuum purging. For a pressure purging procedure the total moles of oxygen present at the end of the first pressurization is given by the moles initially present plus the moles included with the nitrogen. This purging process is commonly used when the vessel or equipment is not rated for pressure or vacuum. it uses more inert gas than vacuum purging. the purge gas is added and withdrawn at atmospheric pressure. less nitrogen is used compared to pressure purging. This amount is The total moles in the vessel at the end of the first pressurization are given in Equation 7-1. especially if the initial cycle is a vacuum cycle. . Sweep-Through Purging The sweep-through purging process adds purge gas into a vessel at one opening and withdraws the mixed gas from the vessel to the atmosphere (or scrubber) from another opening.

assuming the nitrogen contains 0.t is determined using Equation 7-15: . The material balance around the vessel is where V is the vessel volume.Q. Example 7-3 A storage vessel contains 100% air by volume and must be inerted with nitrogen until the oxygen concentration is below 1. and it is determined using Equation 7-14: For many systems Co = 0.01% oxygen? Solution The volume of nitrogen required Q. Q. Equation 7-13 is rearranged and integrated: The volumetric quantity of inert gas required to reduce the oxidant concentration from C. C.is the inlet oxidant concentration (mass or volumetric units)...300 Chapter 7 Designs to Prevent Fires and Explosions Purging results are defined by assuming perfect mixing within the vessel.25% by volume. to C. constant temperature.t. The vessel volume is 1000 ft? How much nitrogen must be added.. and constant pressure. is the volumetric flow rate. is Q. C is the concentration of oxidant within the vessel (mass or volumetric units). and t is time. The mass or volumetric flow rate of oxidant into the vessel is C. and the flow rate of oxidant exiting is CQ. Under these conditions the mass or volumetric flow rate for the exit stream is equal to the inlet stream.

By using this method. The quantity of pure nitrogen required to reduce the oxygen concentration to 1. In this case the flammability zone is avoided and a safe vessel preparation procedure is ensured. One might suggest an even more optimized procedure. This involves first pumping air into the vessel until a point is reached on the air stoichiometric line above the UFL. the sweep-through process requires large quantities of nitrogen. The vessel is initially at point A and contains pure fuel. If air is used to purge the vessel. This could be expensive when purging large storage vessels.25% is Siphon Purging As illustrated in Example 7-3. the oxygen concentration is decreased to low concentrations with only a small added expense for the additional sweep-through purging. and the gas composition follows along the line SR in Figure 7-5. However. which crosses the flammability zone. A more robust design is to prevent the existence of flammable mixtures as the primary control. If nitrogen is first pumped into the vessel. Using the Flammability Diagram To Avoid Flammable Atmospheres The flammability diagram introduced in chapter 6 is an important tool to prevent the existence of flammable mixtures. One approach is to continue the nitrogen flow until the vessel contains pure nitrogen. A more efficient procedure is to inert with nitrogen until point S is reached. Then air can be introduced.01% oxygen). The purge gas is subsequently added to the vapor space of the vessel as the liquid is drained from the vessel. and the rate of purging is equivalent to the volumetric rate of liquid discharge. the composition follows line AR. The siphon purging process starts by filling the vessel with liquid .7-1 lnerting 301 This is the quantity of contaminated nitrogen added (containing 0. the elimination of ignition sources alone is not enough to prevent fires and explosions. ignition sources are too plentiful to use as the primary prevention mechanism. When using the siphon purging process. The flammability diagram is important for determining whether a flammable mixture exists and for providing target concentrations for inerting and purging procedures. This is followed . followed by the elimination of ignition sources as a secondary control. As previously stated. this requires a large amount of nitrogen and is costly. The procedure for taking a vessel out of service is illustrated in Figure 7-5. the gas composition follows along line AS. The volume of purge gas is equal to the volume of the vessel. as shown in Figure 7-5.water or any liquid compatible with the product. The objective is to avoid the flammable region. it may be desirable to first fill the vessel with liquid and then use the sweep-through purge process to remove oxygen from the residual head space. Siphon purging is used to minimize this type of purging expense.

Using nitrogen first avoids this problem. by pumping nitrogen into the vessel followed by air. When using the nitrogen purge process. Point S is approximated by a line starting at the pure air point R and connecting through a point M at the intersection of the LFL with the stoichiometric combustion line. This approach avoids the nose of the flammability zone and minimizes the consumption of nitrogen.A : A Chapter 7 Designs to Prevent Fires and Explosions Nitrogen pumped in 20 Flammability zone 100 / 20 v \ 40 v N 60 0 Nitrogen. is that the air forms a flammable mixture at the entry point as the pure air mixes with the fuel-rich gas mixture in the vessel. the composition at point S is determined graphically or with OSFC = . however. one must determine the location of point S in Figure 7-5. The approach is shown in Figure 7-6. Because the gas compositions at points R and M are known. The flammability diagram reflects only the average gas composition within the vessel. volume percent Figure 7-5 qRO 0 100 Pure air A procedure for avoiding the flammability zone for taking a vessel out of service. The problem with this approach.

7-1 lnerting 303 Figure 7-6 Estimating a target fuel concentration at point S for taking a vessel out of service. that is. The analytical result is OSFC = . where OSFC is the out-of-service fuel concentration. The derivation of Equation 7-16 is provided in appendix C. the fuel concentration at point S in Figure 7-6. Point M is the intersection of the LFL line with the stoichiometric line. and z is the stoichiometric oxygen coefficient from the combustion reaction given by Equation 6-9. LFL is the volume percent of fuel in air at the lower flammability limit. Another approach is to estimate the fuel concentration at point S by extending the line from point R though the intersection of the minimum oxygen concentration (M) and the stoichiometric combustion line.

17(3): 176. with a small margin of safety. Then fuel is pumped in. Equations 7-16 and 7-17 are approximations of the fuel concentration at point S. For all other species in Table 7-1. The problem is to determine the oxygen (or nitrogen) concentration at point S.304 Chapter 7 Designs to Prevent Fires and Explosions Table 7-1 Experimental In-Service Oxygen Concentrations (ISOCs) and Out-Of-Service Fuel Concentrations (OSFCs) l OSFC (vol. Crowl. less than the experimentally determined OSFC value. One approach is to use the intersection of the LFL with the stoichiometric combustion line.7% fuel. For instance. Nitrogen is pumped into the vessel until point S is reached. they are usually conservative. If a detailed flammability diagram is lacking. an OSFC value of 14% is determined. For ethylene. following line SR until point R is reached. % oxygen) OSFC (vol. 1.3-Butadiene Acetylene Benzene Chemical - ISOC (vol. A. The vessel begins with air. and hydrogen Equation 7-17 predicts a higher OSFC than the experimentally determined value. % Fuel) - Chemical Methane Ethane Propane Butane n-Pentane n-Hexane Natural gas Ethylene Propylene 2-Methylpropene 1-Butene 3-Methyl butene 1. where LOC is the limiting oxygen concentration (also called the minimum oxygen concentration) in volume percent of oxygen. This is closer to the experimental value but still conservative. Figure 7-7 shows the procedure for placing a vessel into service. The in-service oxygen concentration (ISOC) represents the maximum oxygen concentration at point S in Figure 7-7 that just avoids the flammability zone. shown as point A. By using an experimental LOC of 12%. V. "Application of the Flammability Diagram for Evaluation of Fire and Explosion Hazards of Flammable Vapors." Process Safety Progress (1998). % Fuel) ISOC (vol. Equation 7-16 estimates an OSFC that is less than the experimental value. then the ISOC is estimated. that is. A line is drawn . Fortunately.3-butadiene.3% and z is 2.51145) JP-4 Hydrogen Carbon monoxide 'C. % oxygen) Cyclopropane Methyl alcohol Ethyl alcohol Dimethyl ether Diethyl ether Methyl formate Isobutyl formate Methyl acetate Acetone Methyl ethyl ketone Carbon disulfide Gasoline (11. for methane the LFL is 5. This is compared to an experimentally determined OSFC of 14. Mashuga and D.5% (Table 7-1). Thus Equation 7-16 predicts an OSFC of 10. Equation 7-17 is derived in appendix C.

7-1 lnerting 305 Nitrogen. The composition at S is determined graphically or with -z-j ISOC = - (0 1) where ISOC is the in-service oxygen concentration in volume % oxygen. . volume percent ~ i i r o ~ pumped in en Figure 7-7 A procedure for avoiding the flammability zone for bringing a vessel into service. and LFL is the fuel concentration at the lower flammability limit. Equation 7-18 is derived in appendix C. in volume percent of fuel in air. z is the stoichiometric coefficient for oxygen given in Equation 6-9. from the top apex of the triangle (R) through this intersection to the nitrogen axis. This is shown in Figure 7-8.

A comparison of the estimates using Equations 7-18 and 7-19 with the experimental values in Table 7-1 shows that Equation 7-18 predicts a lower oxygen value than the experimental values for all species. with the exception of methyl formate. The nitrogen concentration at point S is equal to 100 .ISOC. The analytical result is .'fi ISOC = z-- where LOC is the minimum oxygen concentration in volume percent oxygen. volume percent Figure 7-8 Estimating a target nitrogen concentration at point S for placing a vessel into service. Point M is the intersection of the LFL line with the stoichiometric combustion line.306 Chapter 7 Designs to Prevent Fires and Explosions Nitrogen. Equation 7-19 predicts a lower . An expression to estimate ISOC using the intersection of the minimum oxygen concentration and the stoichiometric line is also found using a similar procedure.

1. If the oxygen concentration is not continuously monitored. 7-2 Static Electricity A common ignition source within chemical plants is sparks resulting from static charge buildup and sudden discharge. The clinging fabrics and sometimes audible sparks are the result of the buildup of static charge. one material becomes positively charged and the other negatively charged. . When different materials touch each other. and acetone. the charge buildup as a result of separation is small because the electrons are able to scurry between the surfaces. 3-methyl-1-butane.er. more of the electrons remain on one surface than on the other. however. For instance. serious explosions and fires caused by static ignition continue to plague the chemical process industry. removing a sweater. the electrons move across the interface from one surface to the oth.7-2 Static Electricity 307 oxygen concentration than the experimental value for all species in Table 7-1 with the exception of butane. lNFPA 69. MA: National Fire Protection Association. Static electricity is perhaps the most elusive of ignition sources. If. If the LOC is less than 5%. (Quincy. The calculated values are deliberately not shown in Table 7-1. Other methods are available to estimate the target gas concentration for placing a vessel into or out of service. For unavoidable static buildup design features are added to continuously and reliably inert the atmosphere around the regions where static sparks are likely. and combing hair.isobutyl formate. Standard on Explosion Prevention Systems. Direct and reliable experimental data under conditions as close as possible to process conditions is always recommended.3-butadiene. Fundamentals of Static Charge Static charge buildup is a result of physically separating a poor conductor from a good conductor or another poor conductor. NFPA 69 recommends a target oxygen concentration for storage vessels of no more than 2% below the measured LOC. The best design methods for preventing this type of ignition source are developed by understanding the fundamentals relevant to static charge and by using these fundamentals to design specific features within a plant to prevent the accumulation of static charge or to recognize situations where the buildup of static electricity is inevitable and unavoidable. placing different materials in a tumble dryer. or 40% of the LOC if the LOC is below 5 %. one or both of the materials are insulators or poor conductors. Upon separation. the target oxygen concentration is no more than 60% of the LOC. Household examples that result in a buildup of a static charge are walking across a rug. and the magnitude of the charge is much greater. 1997 ed. Despite considerable efforts. then the equipment must not operate at more than 60% of the LOC. 1997). If both the materials are good conductors. electrons are not as mobile and are trapped on one of the surfaces. if the oxygen concentration is continually monitored.

A. some of the charges remain separated. 2. Contact and frictional charging: When two materials. relaxation times.1 mJ is considered dangerous. The transferred charge is a function of the object's capacitance and of the conductivities of the droplet. 3. a charge separation occurs at the interface. Charge Accumulation There are four charge accumulation processes2 that are relevant to dangerous electrostatic discharges in a chemical plant: 1. 4. If the two objects are then separated. Double-layer charging: Charge separation occurs on a microscopic scale in a liquid at any interface (solid-liquid. Electrons in the person's body (head. Charging by transport: When charged liquid droplets or solid particles settle on an isolated object. and Applications (Bristol: Adam Higler. a pipe wall. creating a spark. and arms) migrate toward the positive charge of the vessel. and many more. (2) how charges discharge by means of charge transfer. it carries a charge and it leaves a charge of opposite sign on the other surface. This leaves the lower part of the body positively charged by induction. For industrial operations where flammable vapors may be present. the static buildup created by walking across a carpet averages about 20 mJ and exceeds several thousand volts. for example. and leaking steam that contacts an ungrounded conductor. In an explosive environment this sudden transfer of charges may be energetic enough to be an ignition source. When a metal object is touched. 1987). Electrostuti~~r: Principles. pneumatically conveying solids. . Basic electrostatic relationships are used to understand and investigate the sample situations. particle. are brought into contact. Induction charging: This phenomenon is applicable only to materials that are electrically conductive. with one being an insulator.308 Chapter 7 Designs to Prevent Fires and Explosions Common industrial examples are pumping a nonconductive liquid through a pipe. shoulders. and (3) how to estimate the resulting energy discharged in relation to the minimum ignition energy (MIE) of the explosive environment. Static charges of this magnitude are easy to generate. may approach an overhead vessel that is positively charged (previously filled with positively charged solids). gas-liquid. electrostatic potential. Subsequent grounding produces large and energetic sparks. one must understand (1) how charges accumulate on objects. currents and potentials in flow systems. capacitance. there is a transfer of the electrons. Cross. any charge accumulation exceeding 0. for example. Problems. An electrostatic discharge occurs when two materials at different potentials or polarities come close enough together to generate a charge transfer. mixing immiscible liquids. the object is charged. thus accumulating an equal quantity of positive charges on the opposite side of the body. As the liquid flows. The static charges in these examples accumulate to develop large voltages. These relationships may include field strengths produced by static charges. 2J. To prevent these ignitions. and interface. A person with insulated shoes. or liquid-liquid). giving the two materials opposite but equal charges.

This is therefore an energetic spark that can ignite a flammable dust or gas. A spark discharge (Figure 7-9) is a discharge between two metallic objects. Apropagating brush discharge (Figures 7-9 and 7-10) is a discharge from a grounded conductor when it approaches a charged insulator that is backed by a conductor. King. 1991). Electrostatic Discharges A charged object can be discharged to a ground or to an oppositely charged object when the field intensity exceeds 3 MVIm (breakdown voltage of air) or when the surface reaches a maximum charge density of 2. Jones and J. Powder Handling and Electrostatics (Chelsea.7 X lop5C/m2by six methods: (1) spark. grounds all metal \ Solids Lightning-like Propagating brush discharge .7-2 Static Electricity Grounded thermo well. lining 1 Tramp metal II A I L C Solids Metal shell and metal nozzle Figure 7-9 Common electrostatic discharges. discharge Nonconductive . M I : Lewis Publishers. L. the electrons move to exit at a single point of the charged object. and (6) corona discharges. Because both objects are conductive. Conical pile . and they enter the second object at a single point. (3) conical pile (sometimes known as Maurer discharge). These discharges 3T. . ( 5 ) lightning-like. (4) brush. (2) propagating brush. B.

30: 123-134. "Ignition Tests with Discharges from Bulked Polymeric Granules in Silos (Cone Discharge). Data show that propagating brush discharges are not possible if the breakdown voltage of the insulator is 4 kV or less4 A conicalpile discharge (Figure 7-9) is a form of a brush-type discharge that occurs at the conical surface of a pile of powder. Maurer. "Discharges Due to Electrostatic Charging of Particles in Large Storage Silos. 5M. Side view Grounded conductor Layer of dense charge (before .Grounded v conductor Figure 7-10 Propagating brush discharge. 3: 189-195. Glor and B. Maurer." German Chemical Engineering (1979). .t--z-." Journal of Electrostatic's (1993). are energetic. and they can ignite flammable gases and dusts.p~ Chapter 7 Designs to Prevent Fires and Explosions Top view of non-conductor brush discharge ------_------------------.5 The necessary conditions for this discharge are (1) a pow4B.

The electrode conductor has a sharp point. W. brush. This discharge is less intense compared with the point-to-point spark discharge. therefore they can ignite flammable gases and dusts. Maurer. Lightning-like discharges (Figure 7-9) are discharges from a cloud in the air over the powder. 3: 303-310. However. B. conical pile. Wider. and (4) filling rates above about 0. The discharge from such an electrode has sufficient energy to ignite only the most sensitive gases (for example. To ignite dusts. G. propagating 6P. Hilgner. brush discharges can ignite flammable gases.6 There is currently no physical evidence that lightning-like discharges have resulted in industrial deflagrations. It is known from experiments that lightning-like discharges do not occur in vessels with volumes less than 60 m3 or in silos with diameters less than 3 m. This discharge radiates from the conductor in a brush-like configuration. Boschung. charged by pneumatic transport). (2) a powder with coarse particles (>1mm in diameter). These are relatively intense discharges with energies up to several hundred millijoules. A corona discharge (Figure 7-11) is similar to a brush discharge. In general. the results illustrate that flammable gases and vapors can be ignited by spark. Energy from Electrostatic Discharges The energy generated in electrostatic discharges compared with the minimum ignition energies of gases and vapors and dusts is illustrated in Figure 7-12. der with a high resistivity (>lo1"ohm m).1-100 mm) and either another conductor or a charged insulated surface.7-2 Static Electricity 311 Corona discharge Conductor / (diameter < 5 mm) Figure 7-11 Corona discharge. A brush discharge (Figure 7-9) is a discharge between a relatively sharp-pointed conductor (radius of 0.5 kgls. hydrogen). Luttgens. and propagating brush discharges and that flammable dusts can be ignited only by sparks. "An Experimental Contribution to the Question of the Existence of Lightning-Like Discharges in Dust Clouds. and it is unlikely to ignite dusts. (3) a powder with a high charge to mass ratio (for example. ." Journal of Electrostatics (1977). and A. the coarse particles need a fraction of fines to give an explosive atmosphere.

Electrostatic Hazards in Powder Handling (New York: Wiley. "Ignition Tests with Discharges from Bulked Polymeric Granules in Silos (Cone Discharge). and the potential. Glor. The energy of a spark discharge is a function of the accumulated charge (Q in coulombs) on the object. or voltage (V in volts) of the object. 30: 123-134. and conical pile discharges. The regions enclosed by the dotted lines in Figure 7-12 indicate regions of uncertainty." Journal of Electrostatics (1993). Maurer. Adapted from M. 1988). A brush discharge is generated if the distance between the conductors is large compared to the radius of curvature of the conductor.312 Chapter 7 Designs to Prevent Fires and Explosions Energies to ignite Energies generated Figure 7-12 Minimum ignition energies compared to electrostatic discharge energies. brush. Energy of Electrostatic Ignition Sources A spark is generated between two conductors when the distance between the conductors is small compared to the diameter of the conductors and when the electric field intensity between the conductors is approximately 3 MVlm. These three variables are related by the expression C = QIV. and M. Glor and B. The actual energy (expressed in joules) associated with the discharge process is given by . the capacitance of the object (C in farads).

1999). pipe length.7-2 Static Electricity Equation 7-20 assumes a capacitance-type discharge (that is. fluid velocity. In an industrial setting. A precise experimental determination of the MIE is often required under the specific conditions of the system. The relation between a liquid streaming current and the pipe diameter. MIEs are shown in Table 6-4 for a number of flammable gases and in Table 6-8 for dusts. and fluid properties is given by where Is is the streaming current (amps). Britton. d is the pipe diameter (m). The static discharge energy is a function of the accumulated charge. an electrostatic charge develops on the streaming material. however. When a liquid or solid flows through a pipe (metal or glass). G. It is determined using 7L. this accumulated charge is usually the result of either contact or friction charging for flowing solids and double-layer charging for flowing liquids. a spark). The relaxation time is the time required for a charge to dissipate by leakage. This current is analogous to a current in an electrical circuit. . and r is the liquid relaxation time (seconds). L is the pipe length (m). Avoiding Static Ignition Hazards in Chemical Operations (New York: American Institute of Chemical Engineers. A criterion that is commonly used to estimate the potential hazard of a discharge is to compare the MIE of the fuel-air mixture to the equivalent energy of the discharge. u is the velocity (mts). Therefore Equation 7-20 is valid only for capacitive sparks. Streaming Current A streaming current Is is the flow of electricity produced by transfering electrons from one surface to another by a flowing fluid or solid. capacitance and voltage are not defined in nonconductive systems. In each case the charge (electrons) is transported with the material. The measure of this flow of electrons is a streaming current and is expressed in coulombs per second or amps. but it is used qualitatively for the other discharges.

Because solid geometries are almost always ill-defined.85 x 10-l~and N m2 ohm cm ' 8.0-7.0 x lo-14 10-l6 to 0.0 lJ. Chemical Engineers' Handbook. electrostatic calculations for solids are handled empirically.1 ~ 1. is the permittivity constant. H. . O 3. where T E.85 x lo-'' y. Perry. is the relaxation time (seconds). Charges also accumulate when solids are transported. coulomb2 s = 8. 3d ed. is the specific conductivity (mholcm). Specific conductivities and relative dielectric constants are listed in Table 7-2.0 x lo-s 0.8 1.5 2.2 X 10-l8 0.33 x 1 0 . 1734. that is. p.5 x 10-1' 10-10to 10-l3 1. 1950).0 x 1.5 4.9-2.9-7.0 6. is the relative dielectric constant (unitless).3 3. (New York: McGraw-Hill.0 3.314 Chapter 7 Designs to Prevent Fires and Explosions Table 7-2 Material Liquids Benzene Toluene Xylene Heptane Hexane Methanol Ethanol Isopropanol Water Properties for Electrostatic Calculations1 Specific conductivity2 (mholcm) Dielectric constant Other materials and air Air Cellulose Pyrex Paraffin Rubber Slate Teflon Wood 1. The buildup results from the separation of solid particle surfaces. 2Resistance = l/conductivity = l/(mho/cm) = ohm cm.

G.1 V .7-2 Static Electricity 315 Table 7-3 Process Charge Buildup for Various Operations1 Charge (coulomb/ kg) l0-"0 Sieving Pouring Grinding Micronizing Sliding down an incline Pneumatic transport of solids lo-" lo-7 to to lo-7 to lo-7 to to lo-7 lR. p. is coulombs1second or amps. Table 7-4 Accepted Electrostatic Values for Calculations1 14. as shown by where I.000 20 0. 1988) 7(1): 24. Some generally accepted guidelines for electrostatic calculations are shown in Table 7-4.1967). 163. "Electrostatics. 100 to 400 500 1000 100. "The Use (and Misuse) of Bonding for Control of Static Ignition A." Plant/Operations Progress (Jan." Chemical Engineering (March 13.01 mrn apart Maximum charge density before corona discharge Minimum ignition energies (mJ) Vapors in air Mists in air Dusts in air Approximate capacitances C (micro-microfarads) Humans Automobiles Tank truck (2000 gal) Tank ( 1 2 4 diameter with insulation) Capacitance between two 2-in flanges (118-in gap) Contact zeta potentials IF. Eichel. and kgls is the solids flow rate. Mancini. coulombslkg is given in Table 7-3. The streaming current that is generated while transporting solids is a function of the solids processing method (see Table 7-3) and the flow rate.01-0.65 X 1 0 ~ ~ o u l o m b / c m 2 Voltage to produce spark between needle points 112 in apart Voltage to produce spark between plates 0.000V 350 V 2. Hazards.

(in mholcm). where V is the potential difference and the charge is Q. Electrostatic Voltage Drops Figure 7-13 illustrates a tank with a feed line. the resistance decreases. and if the conductor length increases. the length of the conductor L (in cm). The streaming current builds up a charge and voltage in the feed line to the vessel and in the vessel itself. the integration gives Equation 7-20.316 Chapter 7 Designs to Prevent Fires and Explosions Glass Lined Pipe I Metal Pipe Wher esistance Glass Vessel Figure 7-13 Electrical charge accumulation in a feed line resulting from fluid flow. and the area A of the conductor (in cm2): This relationship shows that as the area of the conductor increases. Energy of Charged Capacitors The amount of work required to increase the charge on a capacitor from Q to Q + dQ is dl = V d Q . and substitutions give . Fluid flows through the feed line and drops into the tank. Because V = QIC. the resistance increases. The voltage from the electrical ground in the metal line to the end of the glass pipe is calculated using The resistance R (in ohms) is computed using the conductivity of the fluid y.

Equation 7-28 assumes that the system starts with no accumulation of charge. The units used in Equations 7-26 and 7-27 are usually C in farads.. is in amps and t is in seconds. Explain the potential hazards in this process for a flow rate of a. "The Use (and Misuse) of Bonding for Control of Static Ignition Hazards. and no current or charge loss terms (see the section "Balance of Charges" for a more complex system).7-2 Static Electricity Table 7-5 Object Capacitance of Various Objects1 Capacitance (farad) 5x 20 x 100 X 200 X 500 X 1000 x 10-l2 10-l2 10-l2 10-l2 10-l2 lo-'* Small scoop. A. Mancini. V in volts. Assuming a constant streaming current. beer can. and J in joules. tools Buckets. small drums 50-100-gal containers Person Automobile Tank truck lR. 150 gpm The data are: Hose length: 20 ft Hose diameter: 2 in . 7(1): 24. 1gpm b. as shown in Figure 7-14. Q in coulombs." Plant/Operations Progress (Jan. Charges can accumulate as a result of a streaming current dQldt = I. only one constant source of charge Is. where I. Also. 1988). compute the energy stored in the nozzle and the energy accumulated in the liquid. Example 7-4 Determine the voltage developed between a charging nozzle and a grounded tank. Capacitances of various materials used in the chemical industry are given in Table 7-5.

The average velocity in the pipe is .54cmlin)' = 20.54 cmlin) = 610 cm.The resistance is computed using Equation 7-25 for the conducting fluid with a resistance length equivalent to the hose length (from the ground near the pump to the nozzle) and a resistance area equivalent to the cross-sectional area of the conducting fluid: L = (20 ft)(12 in/ft)(2. we obtain = 3. Using Equation 7-25. Because the hose and nozzle are not grounded.88 g/cm3 Solution a.00 X lo9ohm. Liquid conductivity: mholcm Dielectric constant cr:25. the voltage generated at the nozzle tip is V = ZR. A = rrr2 = (3.14)(1 in)2(2.3 cm2.318 Chapter 7 Designs to Prevent Fires and Explosions I Non-Conducting Hose Steel Nozzle u S t o r a g e Vessel 300 G a l l o n S t e e l G r o u n d e d Vessel / Ground Figure 7-14 System for Example 7-4. The streaming current is a function of the velocity and the pipe diameter.7 Density: 0.

The voltage drop down the 20-ft line is the same as the voltage drop from the hose flange to the nozzle flange. - The capacitance between the two 1-in flanges is given in Table 7-4.48 X 10-'I amp.7-2 Static Electricity The relaxation time is estimated using Equation 7-22: 7=-= .074)' I = 5. Method 2: Compute the energy accumulated in the capacitor formed by the tank of liquid.1 = ] 2 X lo-')( - 12 X 3. Method 1: Compute the energy accumulated in the capacitor formed between the flanges at the nozzle.27 x (9.58X 10-')(I 2. The energy is determined using Equation 7-26: J = --.6 x 10-~)(2. such as a grounded thermocouple.0.102 x 2. C = 20 x 10-l2 farads = 20 X lo-'' coulomb/volt. A spark between the flanges may be an ignition source.1 mJ). assuming that the nozzle is grounded. - YC lo-' mholcm The streaming current is now determined using Equation 7-21: 10 X amp ( m / ~ ) ' ( m ) ~ [(3. therefore there is no hazard at the nozzle.074 volt.0 = X lo9ohm) .= 2 CV2 [20 X lO~'(O. The accumulated charge is computed using Equation 7-28: with the time equal to the filling time of the vessel: .49 X 10-l4 Joules.28 )]'[I 0) = - exp(. A brush discharge can jump from this liquid to a metal component. This is significantly lower than the energy required to ignite a flammable gas (0.48 X lo-'' amp)(3. 0.*that is. The voltage is therefore V = I R = (2.

that is.0) 8.99 mJ. This case is identical to case a except that the flow rate is higher. 3. This is greater than the energy required to ignite a ffammable gas (0.46 X 2C co~lomb)~ = 9.08 X amp)(3 X lo9ohm) = 2. = The capacitance of the liquid is estimated to be one-tenth of the capacitance of a 2000-gal vessel.27 X lo-' = 8.08 x amp.1)]'[1 (m/~)~(m)~ = amp - exp ( - 15.08 x 10-~(1. b.66. 150 gpm versus 1 gpm for case a: u = (0.320 Chapter 7 Designs to Prevent Fires and Explosions Substitution into Equation 7-28 gives Q = Ist = (2.46)(6. This exceeds the energy required to ignite a flammable gas (0.102 p)(lgprn) 150 gpm = 4.48 x lo-'' amp)(18.1 mJ). . Method 1: Compute the energy accumulated in the capacitor formed between the flanges at the nozzle: V = ZR = (8.46 x coulomb. and the accumulated energy is determined using Equation 7-20: J=-= e2 (4.42 X lo6)' 2 = 117 Joules..000 s) 4.9 X 2(100 X 10-12 farads) Joule = 0.3 X 2. therefore C = 100 X 10-l2 farads = 100 X coulomb/volt.1 mJ). In this situation the vessel should be purged with nitrogen to keep the concentration of the flammable vapor below the LFL. shown in Table 7-4.0 X lo9 ohm: The streaming current is 10 X ][(4. m The resistance is the same as for case a. The accumulated energy is again computed using Equation 7-26: J=-= cv2 2 (20 X 10-12)(2.42 X volts.

and C is the capacitance. It is relatively easy to build up energies that exceed 0. The capacitance C of a body is QIV.08 X 10-4)(160) = 0. For two parallel plates .1 mJ.t = (8.1 mJ. For a sphere with radius r the voltage developed when a charge Q is accumulated is derived with elementary physics: Therefore. Q = I. because C = QIV. In the chemical industry the properties of the developed capacitor are estimated by assuming parallel flat plate or spherical geometries.7-2 Static Electricity 321 Method 2: Compute the energy accumulated in the capacitor formed by the tank of fluid: t = 150gpm min 300 -(-)gal 60 s = 160s.13 coulombs.7 r is the sphere radius. Several examples are shown in Figure 7-15. EO X 10-l2 coulomb/volt ft).85 X 10-l2 coulomb2/N m2 = 2. E. Capacitance of a Body The buildup of a charge on one surface relative to another surface produces a capacitor. For example. and the capacitance of a person's shoe sole or of a noncorrosive tank lining is estimated assuming parallel flat plates. the capacitance for a spherical body is where is the relative dielectric constant (unitless). This energy exceeds 0. This problem illustrates the importance of inerting. the capacitance of a tank or a person is estimated by assuming spherical geometries. is the permittivity (8.

.l. t J Shoe Sole Ground Glass Lining ( ~ i e l e c t r i c ) Metal Vessel Person (Not rounded) Figure 7-15 Different types of industrial capacitors..322 Chapter 7 Designs to Prevent Fires and Explosions Flat Plates Condenser Shoe + Tank Gro Spheres Air (~ielectric) ++ Sphere (Not Grounded) Glass o r P l a s t i c T a n k (Air is Dielectric) + - 9er .ec .

7 = X coulomb) (6. that is.7-2 Static Electricity Therefore the capacitance between parallel plates is where A is the area of the surface and L is the thickness of the dielectric. the shoe sole is the dielectric of the capacitor.2 in Dielectric constant of shoe soles = 3. Example 7-6 Estimate the capacitance of a person standing on a conductive floor. which for flat parallel plates is (36)(2.4 ft2each) Shoe sole thickness = 0.5 Solution Use Equation 7-32. Given Shoe sole area (ft2) = 2 shoes (0. Solution This person's capacitance is estimated assuming that the person's shape is spherical and that the "sphere" is surrounded by air (E.54 x 10-lo farads.0 for air). 2 in tall) standing on a dry wooden floor. ft 10-l2 .volt ft ) 1.1. . Assume that the person's shoe soles separate the person from the floor.is 1.05 X 10-lo- coulomb volt ' The calculated capacitance is close to the value listed for a person in Table 7-5.7 X lo-"--- coulomb (0. we have 2. Example 7-5 Estimate the capacitance of a person (6 ft.8 n2) volt ft ) = 4. Using Equation 7-30 for a sphere.

324 Chapter 7 Designs to Prevent Fires and Explosions Example 7-7 Estimate the charge buildup.. Balance of Charges Some systems are more complex than those previously discussed.36 X 2(300 X J = . using Equation 7-20. An equal and opposite charge is also accumulated in the powder in the insulated drum.454 kg) lb = 1. The accumulated energy.36 X LO-' coulomh. is the current leaving through one specific outlet line j from a set of m lines...= coulomb^)^ 2C lo-'' = 30. a vessel may have several inlet lines and several outlet lines. Solution This operation is a sliding-contact type operation. as a result of a person (insulated from the floor) charging 30 lb of a dry powder. (Is). using a scoop.8 Joules. farad) These results illustrate that the energy exceeds the requirement for generating a spark capable of igniting a flammable gas. Assume that the person's capacitance is 300 X lo-'' farad. Therefore the charge buildup is c0u10mbs)(30 lb) (0. and accumulated energy. . From Table 7-3 this operation gives a charge of coulomb/kg.. Therefore the charged powder is another ignition source. for example. For example. The result is where is the streaming current entering the tank through a specific inlet line i from a set of n lines. an energetic spark could be generated. the charge carried away by flows going out. For this type of system a charge balance is required to establish the charge and accumulated energy as a function of time.. This spark would be discharged if the person approached a ground with a hand or with the scoop. into a 20-gal insulated drum. and charge loss resulting from relaxation. An example is illustrated in Figure 7-16. if a grounded object of any kind is placed close to the solids. The charge balance is developed by considering the currents streaming in. is Q2 (1.

Equation 7-35 is a linear differential equation that can be solved using standard techniques.ou. The result is . Q/Tis the charge loss resulting from relaxation. - - \ Figure 7-16 Any Vessel Vessel with multiple inlets and outlets. (ls)i. streaming currents. is a function of the charge accumulated in the tank and the rate of discharge F from the specific outlet nozzle j: where V . is the container or tank volume and Q is the total charge in the tank. Substituting Equation 7-34 into Equation 7-33 gives If the flows.7-2 Static Electricity 325 ( ' ( ' ~ IN ~ $-1 2 - - - ( ' S ) 1 OUT ( ' S 1 2 OUT ~ IN ~ - . and relaxation times are constant. and T is the relaxation time.

Therefore the hazards of relatively complex systems can be evaluated. In this case Q is computed for each step with the specified C (I.4. and (4) discharging the batch through a different line at a specified rate. and Dielectric constant = 2. These equations plus the equations described previously (equations for Is and J ) are used to compute Q and J as a function of time. Liquid conductivity = 10-l4 mho cm-l. rates. If the line sizes.5 X amp. the potential hazard of each step of the operation can be estimated.000 gal) and where F = 100 gpm.)&.000 gal) is being filled with toluene. Solution Because there is only one inlet line and no outlet lines. and C (FnIVc)for that particular step.326 Chapter 7 Designs to Prevent Fires and Explosions where Q. Compute Q and J during the filling operation when the vessel is half full (25. and materials of construction are known. Equation 7-33 reduces to . (3) holding the batch for a specified time. Example 7-8 A large vessel (50. and the initial Q. Equation 7-36 is also used when the filling and discharge rates are sequential. (2) charging methanol and toluene through two different lines at different rates. Is = 1. is the initial charge in the tank at t = 0. is the result from the previous step. An example of a sequential operation is (1)charging benzene to a vessel at a specific rate through a specific line of known size.

4)(8.0) 2.14)(1.2 s.7 3.19 X coulombs.5 X lo-'- coulomb S )(21. The relaxation time is computed using Equation 7-22: (2. r = 4(3. = 0. When the vessel contains 25. therefore the operating conditions for this vessel are extremely hazardous.000 gal.2 s)(l - e-1i21. The energy stored in this vessel (25. Therefore Q(15.000 gal of toluene) is computed using Equation 7-20: The minimum condition for an ignition is 0.000 s.10 mJ. Q.27 ft) = 10-In farads.48 gal ft-3 ) = 9. Using Equation 7-30 and assuming a dielectric of 1 for air. ~ . .e-'IT) = 1. = = YC ohm cm (10-l4 mho ~ m .14 X X 10-12- coulomb volt ft )(9.2). the elapsed time is 15.27 ft.7-2 Static Electricity 327 Therefore Because the vessel is initially empty.OOO s) = 3.000 gal 1 47~ 7.85 7 & Ell . The charge buildup as a function of time is Q(t) = lS7(1 . The capacitance of this vessel is estimated by assuming a spherical geometry surrounded by air: = ( 25.l ) X lo-"- = 21. we obtain C = 4 n e .

The time required to reduce the accumulated charge to half the equilibrium charge if the flows are stopped after equilibrium conditions are reached. Compute: a.00 s. d. Example 7-9 Figure 7-17 shows an in-line trap for removing water from a process stream. Q and J when the vessel fluid just reaches the overflow line (start with an empty vessel). b. c.4) (sss x lo-" .2 s. The relaxation time is determined using Equation 7-22: (2.328 Chapter 7 Designs to Prevent Fires and Explosions Overflow - P Toluene - 1 0 = 2x10 -'Coulomb in I n i t i a l (Charge Liquid a t T i m e = 0) Figure 7-17 Charge buildup with complex vessel system. The charge removed with the discharge under equilibrium conditions. Given: Volume of vessel = 5 gal Flow rate = 100 gpm toluene Streaming current I. Q and J under equilibrium conditions ( t = 0 ) 0.5 X amp (high value due to filter in line) Liquid conductivity = 10-14 mho/cm Dielectric constant = 2.~ m ) l ~ ~ - (s) = 3.ohm cm 10-14 -mh0 cm Er 80 7=-= = Yc 21.. = 1. The residence time of this vessel is Residence time = ( .4 Initial vessel charge = 2 X lo-' coulomb Solution a.o. .

the radius of this sphere is = 0.volt ft )(0.55 mJ.542 ft.2. Equations 7-35 and 7-36 reduce to Q(t) = I S r + (Q.IS7)e-'/' 1. ' 3. Equation 7-36 for this case reduces to (I(t = 00)= - - % ' = 3.84 X lo-" farads) The accumulated energy (9.93 x co~lomb)~ = 9." ~ ' . before the liquid level reaches the discharge line.r = 4 ~ ( 1 . 0 )2.5 X amp(21. with Q(t) in coulombs and tin seconds.542 ft) = lo-'' farads. The energy accumulated in this vessel is estimated using Equation 7-20: J=-= e2 2C (5.55 mJ) greatly exceeds the quantity required for ignition of flammable materials. This vessel will gradually level off to steady-state equilibrium conditions when the operating time significantly exceeds the relaxation time. Because 5 gal = 0.7 1.98 10-~e-"~'. b. .18 x lo-' . 2(1. This system is operating under hazardous conditions.94 X 1U-' coulomb.5 X = coulomb S (21.24 ~ ) ] e . The capacitance is estimated using Equation 7-30: C = 4~re.2 s) - + [ 2 x lo-' = coulomb X 1. therefore the exponential term of Equation 7-36 is 0.2 3 .e.~.84 X X coulomb 10-l2 . At 3 seconds This is the charge buildup just before reaching the overflow line.7-2 Static Electricity 329 During the filling operation. The vessel capacitance is calculated by assuming a spherical geometry with the surrounding air serving as the dielectric.668 ft3. 21.

are zero. d.. Q(t = co) = 3.330 Chapter 7 Designs to Prevent Fires and Explosions From part a the capacitance is C = 1. The examples and fundamentals developed in these sections were designed to emphasize the importance of this subject. The energy is determined by using Equation 7-20: Q~ 2C J=-= (3. and Equation 7-36 reduces to For QIQ. c.. and =-= Q coulomb 1. and the ignition of flammable materials is an inevitable event if control methods are not appropriately used.84 X lo-" farads.94 x Charge loss via relaxation coulomb. After the inlet flow is stopped. (I.22 mJ.. design engineers recognize .86 X lo-' . Under equilibrium conditions Equation 7-35 is set to zero: and from part b. Although there is an additional loss of charge with the overflowing liquid.5. Sparks resulting from static charge and discharge continue to cause major fires and explosions within the chemical industry. S F Charge loss via the overflow = -Q v c = 1. Therefore it only takes about 15 s to reduce the accumulated charge to one-half its original charge.). 7-3 Controlling Static Electricity Charge buildup.31 X coulomb S For this example the charge loss resulting from flow out of a system is greater than the loss resulting from relaxation. from the problem definition. = 0. Hopefully this emphasis on the fundamentals will make the subject less elusive and destructive. and (I.). resulting sparks. In practice. however.94 x 2(1. the system is still operating under hazardous conditions.84 coulomb^)^ X = lo-" farads) 4.

Brush discharges are prevented by keeping the nonconductive surfaces thin enough or conductive enough to have a breakdown voltage (U. For every charged object there exists its oppositely charged counterpart. General Design Methods To Prevent Electrostatic Ignitions The design objective is to prevent the buildup of charges on a product (liquid or powder) as well as on surrounding objects (equipment or personnel). Nonconductive coatings with a . Sparks are prevented by grounding and bonding. or by using containers with a volume less than 1m3. Conical pile discharges are prevented by increasing the conductivity (additives). Three methods are used to achieve this objective: 1. by decreasing the charge rate below 0. Prevent charges from accumulating to dangerous levels by designing the system to include charge reduction by means of low-energy discharges. Prevent charges from accumulating to dangerous levels by reducing the rate of charge generation and increasing the rate of charge relaxation. deflagration venting and explosion suppression). Measures to mitigate the consequences of an explosion are also options for consideration (for example. Methods for preventing charge buildup are described in the following paragraphs. Inerting (section 7-1) is the most effective and reliable method for preventing ignition. to eliminate the accumulation of a high-density charge on the metallic interface and a countercharge on the nonconductor surface.7-3 Controlling Static Electricity 331 this problem and install special features to prevent (1) sparks by eliminating the buildup and accumulation of static charge and (2) ignition by inerting the surroundings. It is always used when working with flammable liquids that are 5°C (or less) below the flash point (closed cup). 3. 2. Propagating brush discharges are prevented by keeping the nonconductive surfaces or coatings thin enough or conductive enough to have a breakdown voltage below 4 kV.The most effective way of preventing ignitions from conical pile discharges is inerting. Grounding and bonding are used especially to prevent the existence of isolated metal parts or objects. then prevent the possibility of an ignition by maintaining oxidant levels below the combustible levels (inerting) or by maintaining fuel levels below the LFL or above the UFL. This method is generally used when handling liquids. This procedure prevents two metallic objects (close to each other) from having different potentials. When dangerous discharges cannot be eliminated.5 kgls. These discharges are also prevented by keeping the metallic backings grounded.) of 4 kV. Isolated objects are notorious for building up large potentials and energetic sparks when they are approached by another conductor at a lower potential. The special design features for preventing electrostatic ignitions are described in the following paragraphs. This method is generally used when handling powders.

5 m2/s for road tanker filling and 0. a thickness of less than 2 mm is necessary. To prevent brush discharges. Bonding and grounding reduces the voltage of an entire system to ground level or zero voltage. 13. Examples of grounding and bonding are illustrated in Figures 7-18 and 7-19. of less than 0. . and Stray Currents (Washington. therefore. then the system needs to be inerted. from Equation 7-21. are capable of brush discharges even with a U . however. Protection Against Ignitions Arising Out of Static.G. The American Petroleum Institute9 recommends a ud. 9API RP 2003. The residence time in this relaxation section of pipe should be about twice the relaxation time determined from Equation 7-22. eliminating the potential for static sparks. the sets may have different voltages. This also eliminates the charge buildup between various parts of a system. DC: American Petroleum Institute. If this condition is not met. The "twice the relaxation time" rule. less than 4 kV." Chemical Engineering (Mar.8 m2/sfor rail car filling. Lightning. provides a safety factor of 4. that is. The voltage difference between sets is reduced to zero by bonding each set to ground. p.1967). Bonding and Grounding The voltage difference between two conductive materials is reduced to zero by bonding the two materials. Relaxation When pumping fluids into a vessel through a pipe on top of the vessel. This fixes the charges accumulated on the nonconductor. When comparing sets of bonded materials. This hold provides time for charge reduction by relaxation. and fixed charges cannot be transferred in a brush discharge. that is. 153. It is possible to substantially reduce this electrostatic hazard by adding an enlarged section of pipe just before entering the tank. by bonding one end of a conducting wire to one of the materials and bonding the other end to the second material. In actual practice: it was found that a hold time equal to or greater than one-half the calculated relaxation time is sufficient to eliminate charge buildup. The most effective way of preventing ignitions from brush discharges is inerting. the separation process produces a streaming current Is. 8F. by grounding.332 Chapter 7 Designs to Prevent Fires and Explosions thickness greater than 2 mm. Eichel. "Electrostatics. Brush discharges from nonconductive liquids are prevented by increasing the conductivity using conductive additives. which is the basis for charge buildup. 1991). Lightning-like discharges are prevented by keeping the vessel volume to less than 60 m" or the vessel diameter to less than 3 m.

(continued) Glass and plastic lined vessels are grounded using tantalum inserts or metal probes. sometimes called a dip leg or dip pipe.- - - 7-3 Controlling Static Electricity Charging f r o m D r u m Figure 7-18 Bonding and grounding procedures for tanks and vessels. however. to help eliminate the charge generation (and accumulation) resulting from separation during the filling operation. Another technique is to use an angle iron instead of a pipe and to let the liquid flow down the angle iron (see Figure 7-21). When using dip pipes." Chemical Engineering (Mar. however. p. 153. Also. "Electrostatics. . as illustrated in Figure 7-20. G. 1967). In this case the fill line should extend to the bottom of the vessel (see Figure 7-21). These methods are also used when filling drums. the inlet velocities should be low enough to minimize the charge generated by streaming current Is. reduces the electrical charge that accumulates when liquid is allowed to free fall. A commonly used method is to place a hole in the dip pipe near the top of the vessel. care must be taken to prevent siphoning back when the inlet flow is stopped. Eichel. Dip Pipes An extended line. is not effective when handling liquids with low conductivity. 13. This technique. Adapted from F.

/ + Conductive Hose i r e s Bonded to Metal Pipe 2 Drum Type " A " Clamp Type " B " Clamp Figure 7-18 (continued) .334 Chapter 7 Designs to Prevent Fires and Explosions Grounded Water Line Conductive Hose Metal Pipe Type " A " Clamp 1 L T "B" Clamp ~ ~ ~ Grounded W a t e r Line Bond --- Type ' Clamp -K NF: Vacuum Metal T--I.

7-3 Controlling Static Electricity

Grounded Water

Llne

amp or

Strap

Fill

Line

Type

Cla

Wire

Bonded Tank

to

Metal

Pipe

Car o r Truck

Unloading Tank

Trucks

or C a r s

Figure 7-18

(continued)

C l a m p o r S t r a p o n Metal Pipe J-- C o n d u c t i v e H o s e

&
# 4 Wire

Metal Pipe to Metal Pipe Metal

'Glass or Plastic Valve

Solder Wire t o I

O n e Brass Bolt, N u t a n d Washer ~ e F l a n a e r

-

Glass

Pipe Gasket

Solder Wire t o

Brass Bolt

Non-Conducting

Figure 7-19 Bonding procedures for valves, pipes, and flanges. Adapted from F. G. Eichel, "Electrostatics," Chemical Engineering (Mar. 13, 1967), p. 153.

336

Chapter 7

Designs to Prevent Fires and Explosions

Probe

a V e s s ie l s _ s n_

Tantalum Insert

-

-

Ground

Ground

Figure 7-20

Grounding glass-lined vessels.

Hole f o r Siphon

z . -

'

Break Dip Leg
-

-

- - - ---

-

Liquid

Figure 7-21

Dip legs to prevent free fall and accumulation of static charge.

Increasing Conductivity with Additives
The conductivity of nonconducting organic materials can sometimes be increased using additives called antistatic additives. Examples of antistatic additives include water and polar solvents, such as alcohols. Water is effective only when it is soluble in the offending liquid, because an insoluble phase gives an additional source of separation and charge buildup.

7-4 Explosion-Proof Equipment and Instruments

337

Permissible:

Vessel and Surrounding Area Must be Free from Flammable Vapors, Gases, and Liquids

Figure 7-22 Handling solids with no flammable vapors present. Adapted from Expert Commission for Safety in the Swiss Chemical Industry, "Static Electricity: Rules for Plant Safety," Plant/Operations Progress (January 1988), p. 19.

Handling Solids without Flammable Vapors
Charging solids with a nongrounded and conductive chute can result in a buildup of a charge on the chute. This charge can accumulate and finally produce a spark that may ignite a dispersed and flammable dust. Solids are transferred safely by bonding and grounding all conductive parts and/or by using nonconductive parts (drum and chute). See Figure 7-22.

Handling Solids with Flammable Vapors
A safe design for this operation includes closed handling of the solids and liquids in an inert atmosphere (see Figure 7-23). For solvent-free solids the use of nonconductive containers is permitted. For solids containing flammable solvents, only conductive and grounded containers are recommended.1°

7-4 Explosion-Proof Equipment and lnstruments
All electrical devices are inherent ignition sources. Special design features are required to prevent the ignition of flammable vapors and dusts. The fire and explosion hazard is directly proportional to the number and type of electrically powered devices in a process area.
l0Expert Commission for Safety in Swiss Chemical Industry, "Static Electricity: Rules for Plant Safety," Plant/Operations Progress (January 1988),7(1): 1.

338

Chapter 7

Designs to Prevent Fires and Explosions

Bonds a n d Ground

Valve

Valve Nitrogen

I
Nitrogen

Charge Container Closed a n d Purged with Nitrogen

0 . 0 0 0 . 00.0

before Opening Valve

Shutoff

Valve

..* .

B o n d All G a s k e t e d F l a n g e s

(e.g.: B r a s s B o l t s )

do

\

- - -

Ground

Figure 7-23 Handling solids with flammable vapors present. Source: Expert Commission for Safety in the Swiss Chemical Industry, "Static Electricity: Rules for Plant Safety," Plant/Operations Progress (January 1988), p. 19. Reprinted by permission of the American Institute of Chemical Engineers, New York.

7-4 Explosion-Proof Equipment and Instruments

339

Most safety practices for electrical installations are based on the National Electric Code (NEC)." Although states, municipalities, and insurance companies may have their own installation requirements, they are usually based on the NEC. Process areas are divided into two major types of environments: XP and non-XP. XP, for explosion proof, means flammable materials (particularly vapors) might be present at certain times. Non-XP means that flammable materials are not present, even under abnormal conditions. For non-XP designated areas open flames, heated elements, and other sources of ignition may be present.

Explosion-Proof Housings
In an XP area the electrical equipment and some instrumentation must have special explosion-proof housings. The housings are not designed to prevent flammable vapors and gases from entering but are designed to withstand an internal explosion and prevent the combustion from spreading beyond the inside of the enclosure. A motor starter, for example, is enclosed in a heavy cast walled box with the strength needed to withstand explosive pressures. The explosion-proof design includes the use of conduit with special sealed connections around all junction boxes.

Area and Material Classification
The design of electrical equipment and instrumentation is based on the nature of the process hazards or specific process classifications. The classification method is defined in the National Electrical Code; it is a function of the nature and degree of the process hazards within a particular area. The rating method includes Classes I, 11, and 111, Groups A-G, and Divisions 1 or 2. The classes are related to the nature of the flammable material: Class I: Locations where flammable gases or vapors are present. Class 11: Same for combustible dusts. Class 111: Hazard locations where combustible fibers or dusts are present but not likely to be in suspension. The groups designate the presence of specific chemical types. Chemicals that are grouped have equivalent hazards: Group A: acetylene Group B: hydrogen, ethylene Group C: carbon monoxide, hydrogen sulfide

''NFPA 70, The National Electrical Code Handbook (Quincy, MA: National Fire Protection Association,
1996).

Chapter 7

Designs to Prevent Fires and Explosions

Group D: butane, ethane, ethyl alcohol Group E: aluminum dust Group F: carbon black Group G: flour Division designations are categorized in relationship to the probability of the material being within the flammable or explosive regions: Division 1:Probability of ignition is high; that is, flammable concentrations are normally present. Division 2: Hazardous only under abnormal conditions. Flammable materials are normally contained in closed containers or systems.

Design of an XP Area
When designing an XP area, all pieces of electrical equipment and instrumentation are specified for the class, group, and division, as discussed previously. All pieces of equipment and instrumentation within an area must be appropriately specified and installed. The overall classification is only as good as the piece of equipment in an area with the lowest classification.

7-5 Ventilation
Proper ventilation is another method used to prevent fires and explosions. The purpose of ventilation is to dilute the explosive vapors with air to prevent explosion and to confine the hazardous flammable mixtures.

Open-Air Plants
Open-air plants are recommended because the average wind velocities are high enough to safely dilute volatile chemical leaks that may exist within a plant. Although safety precautions are always practiced to minimize leaks, accidental releases from pump seals and other potential release points.

Example 7-10
A plant handling substantial quantities of flammable toluene is located 1000 ft from a residential area. There is some concern that a sizable leak of flammable vapors will form a flammable cloud with subsequent ignition in the residential area. Determine the minimum mass flow rate of toluene leakage required to produce a vapor cloud in the residential area with a concentration equal to the LFL. Assume a 5 mph wind and D atmospheric stability.

7-5 Ventilation

341

Solution
Assume a continuous leak at ground level. The plume concentration directly downwind along the cloud centerline is given by Equation 5-48:

Solving for Q,, the mass flow rate from the leak, we obtain

The LFL for toluene is 1.4% in air (from appendix B). Converting the units, we obtain

0,014

m3 toluene

1 g-mol toluene 22.4 X lo-"' toluene

92 g toluene

=

57.5 g/m3.

The wind speed is 5 mph = 2.23 m/s. The distance downwind is 1000 ft u, = 22 m and u, = 12 m. Substituting, we obtain Qm = (49.3 g/m3)(3.14)(22m)(12 m)(2.23 mls)
=

=

304 m. From Figure 5-10,

9.11

X

lo4 gls

Any leak with a flow rate greater than 201 lb/s is capable of producing a flammable cloud in the residential area. Of course, the toxic effects of this cloud must also be considered. The LEL of 57.5 gim3 is much above the TLV of 0.188 g/m3.

Plants Inside Buildings
Frequently, processes cannot be constructed outside. In this case local and dilution ventilation systems are required. These ventilation systems were discussed in detail in chapter 3, section 3-4. Local ventilation is the most effective method for controlling flammable gas releases. Dilution ventilation, however, is also used because the potential points of release are usually numerous and it may be mechanically or economically impossible to cover every potential release point with only local ventilation. There are empirically determined design criteria for designing ventilation systems for flammable materials inside storage and process areas. These design criteria are given in Table 7-6. The effectiveness of a ventilation system is determined using material balance equations, described in chapter 3 in the section "Estimating Worker Exposures to Toxic Vapors," and as illustrated in the following example.

342

Chapter 7

Designs to Prevent Fires and Explosions

Table 7-6
Type of area

Ventilation Data for Handling Flammable Materials1
Rate
1ft?min/ft2 of floor area

Conditions
(a) System interlocked to sound an alarm when ventilation fails (b) Locate inlet and exhausts to provide air movement across entire area (c) Recirculation is permitted but stopped when air concentrations exceed 25% of LFL (a) to (c) as for inside storage areas (d) Design ventilation system to keep concentrations at a 5-ft radius from all sources to below 25% of LFL

Ventilation for inside storage areas

Ventilation for inside process areas

1 ft"min/ft2 of floor area or more; see (d)

Class I: Flash-point (closed cup) below 37.8"C (100°F) 1 Class 1 :Flash-point from 373°C to 60°C (100°F to 140°F) Class 111: Flash-point above 60°C (140°F) 'Data taken from NFPA 30, Flammables and Combustible Liquids Code, 1996 ed. (Quincy, MA: National Fire Protection Association, 1996).

Example 7-1 1
Determine the concentration of toluene over a diked area (100 ft2) that contains toluene as a result of a spill. Assume that the process area (2500 ft2) is designed to handle Class I flammable materials and that the liquid and air temperature is 65°F. The vapor pressure of toluene at 65'F is 20 mm Hg. The LEL is 1.4% by volume.

Solution
The source models for spills are described in chapter 3, Equations 3-14 and 3-18. The concentration of volatiles in a ventilated area resulting from the evaporation from a pool is given by Equation 3-14:

where

K is the mass transfer coefficient, determined using Equation 3-18, A is the area of the pool, PSat the saturation vapor pressure of the liquid, is k is the nonideal mixing factor, Q, is the volumetric ventilation rate, and P is the pressure.
The ventilation capacity for this process area is based on the design criterion of 1 ft"min/ft2 (Table 7-6); therefore
1 ft'

ft3 (2500 ft2) = 2500 7. min

7-6 Sprinkler Systems

Also,

M

=

92,

PS"' 20 mm Hg, =
A
=

100 ft2.

The mass transfer coefficient is computed using Equation 3-18 with M,,, and KOfor water, that is, 18 and 0.83 cmls, respectively:

The nonideal mixing factor k ranges between 0.1 and 0.5. Because no information is given about the ventilation, k is used as a parameter. Substituting into Equation 3-14, we obtain

-

(0.948 ft/min)(100 ft2)(20/760) atm (2500 ft3/min)(l atm)

X

lo6
=

998 ppm.

The concentration range is estimated to be

CpP,=1996ppm=0.1996%byvolume, C,,,
=

fork=0.5, fork = 0.1.

9980 ppm = 0.998% by volume,

These concentrations are considerably below the LFL of 1.4% by volume, which illustrates that the specified ventilation rate for Class I liquids is satisfactory for handling relatively large spills of flammable materials. The concentrations do, however, exceed the TLV for this substance.

7-6 Sprinkler Systems
Sprinkler systems are an effective way to contain fires. The system consists of an array of sprinkler heads connected to a water supply. The heads are mounted in a high location (usually near ceilings) and disperse a fine spray of water over an area when activated. The heads are activated by a variety of methods. A common approach activates the heads individually by the melting of a fusible link holding a plug in the head assembly. Once activated, the sprinklers cannot be turned off unless the main water supply is stopped. This approach is called a wet pipe system. These systems are used for storage areas, laboratories, control rooms, and small pilot areas. Another approach activates the entire sprinkler array from a common control point. The control point is connected to an array of heat andlor smoke detectors that start the sprinklers when an abnormal condition is detected. If a fire is detected, the entire sprinkler array within an area

344

Chapter 7

Designs to Prevent Fires and Explosions

Table 7-7

Fire Protection for Chemical Plants1

Sprinkler system types Antifreeze sprinkler system: a wet pipe system that contains an antifreeze solution and that is connected to a water supply. Deluge sprinkler system: open sprinklers and an empty line that is connected to a water supply line through a valve that is opened upon detection of heat or a flammable material. Dry pipe sprinkler system: a system filled with nitrogen or air under pressure. When the sprinkler is opened by heat, the system is depressurized, allowing water to flow into the system and out the open sprinklers. Wet pipe sprinkler system: a system containing water that discharges through the opened sprinklers via heat. Design densities (see NFPA documents for details) Source of fire: not less than 0.50 gpm/ft2 of floor area. Pumps and related equipment: 0.50 gpm/ft2 of projected area. Vessels: 0.25 gpm/ft2of exposed surface, including top and bottom. Vertical distance of nozzle should not exceed 12 ft. Horizontal structural steel: 0.10 gpm/ft2of surface area. This may not be necessary if the steel is insulated or designed to withstand the worse-case scenario. Vertical structural steel: 0.25 gpm/ft2of surface area. This may not be necessary if the steel is insulated or designed to withstand the worse-case scenario. Metal pipe, tubing, and conduit: Not less than 0.15 gpm/ft2of surface areaand directed toward the undersides. Cable trays: Not less than 0.3 gpm/ft2 of projected plane area (horizontal or vertical). Combined systems: The NFPA standards specify acceptable methods for combining the above requirements. Nominal discharge rates for 0.5-in orifice spray nozzles are: gPm: psi:
18 10

25 20

34 35

50 75

58 100

lData taken from NFPA 13, Installation of Sprinkler Systems (Quincy, MA: National Fire Protection Associates, 1999); and NFPA 15, Standards for Water Spray Fixed Systems for Fire Protection (Quincy, MA: National Fire Protection Association, 1996).

is activated, possibly in areas not even affected by the fire. This approach is called a deluge system. This system is used for plant process areas and larger pilot plants. Sprinkler systems can cause considerable water damage when activated, depending on the contents of the building or process structure. Statistically, the amount of water damage is never as great as the damage from fires in areas that should have had sprinklers. Sprinkler systems require maintenance to ensure that they remain in service and have an adequate and uninterrupted water supply. There are various fire classes that require different sprinkler designs. The detailed descriptions of these classes and sprinkler specifications are given inNFPA 13.12 average chemiAn cal plant is classified as an ordinary hazard (Group 3) area. Various sprinkler specifications for this type of area are given in Table 7-7.
I2NFPA 13, Iizstallation o f Sprinkler Systems (Quincy, MA: National Fire Protection Association, 1999).

7-6 Sprinkler Systems

345

Sometimes vessels need special water protection to keep the vessel walls cool during fires. High surface temperatures can result in metal failure at pressures far below the vessel's maximum allowable working pressure (MAWP) with potentially disastrous consequences. In hydrocarbon spill fires unprotected vessels (no insulation or water spray) can fail within minutes. A water spray protection system around vessels is recommended to prevent this type of failure. These water spray protection systems, commonly called deluge systems, are designed to keep the vessel cool, flush away potentially hazardous spills, and help to knock down gas clouds.13 Deluge systems can also provide enough time to transfer material out of a storage tank into another (safe) area. Vessel deluge systems are usually designed as open-head systems, which are activated when a fire is detected and/or a flammable gas mixture is detected. The deluge system is usually opened when the flammable gas concentration is a fraction of the LFL (approximately 25 %) or when a fire is detected through heat. Table 7-7 provides descriptions and design specifications for these systems. Monitors are fixed water hydrants with an attached discharge gun. They are also installed in process areas and storage tank areas. Fire hydrants and monitors are spaced 150-250 ft apart around process units, located so that all areas of the plant can be covered by 2 streams. The monitor is usually located 50 ft from the equipment being protected.14Fire monitors discharge water at a rate of 500-2000 gpm.

Example 7-12
Determine the sprinkler requirements for a chemical process area within a building with an area of 100 ft by 30 ft that handles reactive solvents. Determine the number of sprinkler spray nozzles and pump specifications. Assume 0.5-in orifice sprinklers with 35 psig at each nozzle, giving 34 gpm each, a 10-psig frictional loss within the system, and a 15-ft elevation of the sprinkler system above the pump.

Solution
Data for designing this system are found in Table 7-7. Total water requirement
= =

(0.50 gpm/ft2)(100ft)(30 ft) 1500 gpm, (1500 gpm) = 44.L, (34 gpm/nozzle)

Number of sprinkler nozzles =

which is rounded to the next even number for layout convenience, or 44. The pressure required at the pump is the sum of the minimum pressure at the nozzle (specified as 35 psi), the pressure loss resulting from friction (10 psi), and the pressure resulting from the

13D.C. Kirby and J. L. De Roo, "Water Spray Protection for a Chemical Processing Unit: One Company's View," Plant/Operations Progress (October 1984), 13(4). I40rville M. Slye, "Loss Control Association," Paper presented at AICHE Symposium, New Orleans, Louisiana, March 6-10,1988.

346

Chapter 7

Designs to Prevent Fires and Explosions

Table 7-8
Feature

Miscellaneous Designs for Preventing Fires and Explosions1
Explanation
The best way to prevent fires and explosions is to stop the release of flammable materials. Preventive maintenance programs are designed to upgrade system before failures occur. Insulate vessels, pipes, and structures to minimize damage resulting from fires. Add deluge systems and design to withstand some damage from fires and explosions; e.g., use multiple deluge systems with separate shutoffs. Design control rooms to withstand explosions. Provide supply for maximum demand. Consider many deluge systems running simultaneously. Diesel-engine pumps are recommended. Place shutoffs well away from process areas. Install hydrants, monitors, and deluge systems. Add good drainage. Separate (space) plants on a site, and separate units within plants. Provide access from two sides. Design steam, water, electricity, and air supplies to be available during emergencies. Place substations away from process areas. Locate personnel areas away from hazardous process and storage areas. Group units in rows. Design for safe operation and maintenance. Create islands of risk by concentrating hazardous process units in one area. Space units so hot work can be performed on one group while another is operating. Install isolation valves for safe shutdowns. Install in safe and accessible locations at edge of unit or group. Process equipment should be separated from flares and railroads. Place gas compressors downwind and separated from fired heaters. Locate flammable storage vessels at periphery of unit. Dike vessels to contain and carry away spills. Automated block valves should be placed to stop andlor control flows during emergencies. Ability to transfer hazardous materials from one area to another should be considered. Add appropriate on-line analyzers to (1) monitor the status of the process, (2) detect problems at the incipient stage, and (3) take appropriate action to minimize effects of problems while still in initial phase of development. All controls need to be designed to fail safely. Add safeguards for automated and safe shutdowns during emergencies.

Maintenance programs

Fireproofing

Control rooms Water supplies Control valves for deluge Manual fire protection Separate units Utilities Personnel areas Group units

Isolation valves Railroads and flares Compressors Dikes Block valves

On-line analyzers

Fail-safe designs

'John A. Davenport, "Prevent Vapor Cloud Explosions," Hydrocarbon Processing (March 1977), pp. 205-214; and Orville M. Slye, "Loss Prevention Fundamentals for Process Industry," Paper presented at AICHE Loss Prevention Symposium, New Orleans, LA, March 6-10,1988.

Suggested Reading

347

pipe elevation over the pump (15 ft water or 6.5 psi). Therefore the total pressure is 51.5 psi, which is rounded up to 52 psi. The pump power is now determined:

HP Horsepower = (25,029 ft-lbf/s)

Therefore this sprinkler requires a pump with a capacity of 1500 gpm and a 45.5-HP motor, assuming an efficiency of 100%. Actually, fire pumps are usually designed with discharge pressures of 100-125 psig so that the hose and monitor nozzle streams will have an effective reach. In addition, the size of the monitor is governed by requirements in the fire codes.15

7-7 Miscellaneous Designs for Preventing Fires and Explosions
The successful prevention of fires and explosions in chemical plants requires a combination of many design techniques, including those mentioned previously and many more. A complete description of these techniques is far beyond the scope of this text. A partial list, shown in Table 7-8, is given to illustrate that safety technology is relatively complex (the appropriate application requires significant knowledge and experience) and to serve as a checklist for engineers to help them include the critical features for preventing fires and explosions.

Suggested Reading
R. Beach, "Preventing Static Electricity Fires," Chemical Engineering (Dec. 21,1964), pp. 73-78; (Jan. 4, 1965), pp. 63-73; and (Feb. 2,1965), pp. 85-88. L. G. Britton, Avoiding Static Ignition Hazards in Chemical Operations (New York: American Institute of Chemical Engineers, 1999). H. Deichelmann, The Electrostatic Charge of Class-Lined Vessels and Piping, Pfaudler PWAG Report 326e. J.S. Dorsey, "Static Sparks: How to Exorcise the 'Go Devils,"' Chemical Engineering (Sept. 13,1976), pp. 203-205. Fire Protection Handbook, 14th ed. (Boston: National Fire Protection Association, 1976), ch. 5. S.K. Gallym, "Elements of Static Electricity," Gas (March 1949), pp. 12-46. M. Glor, Electrostatic Hazards in Powder Handling (New York: Wiley, 1988). H. Haase, Electrostatic Hazards (New York: Verlag Chemie-Weinheim, 1977). T. M. Kirby, "Overcoming Static Electricity Problems in Lined Vessels," Chemical Engineering (Dec. 27, 1971), p. 90.
l"ational Fire Codes, v. 1 (Quincy, MA: National Fire Protection Association, 1986).

1989). 101-106. Luttgens and M. Ethylene oxide is a flammable liquid having a normal boiling temperature below room temperature. 1. Include both inerting and purging as well as bonding and grounding procedures. 1959). 1972)." Industrial Engineering Chemistry (June 1942). T. Describe a system and a procedure for transferring ethylene oxide from a tank car through a pumping system to a storage tank. Electrostatic Ignitions of Fires and Explosions (Marietta. GA: Burgoyne. NFPA 77-1972(Boston: National Fire Protection Association.B. Describe an appropriate grounding and bonding procedure. 1942). "The Basic Mechanisms of Static Electrification. Use a vacuum purging technique to purge oxygen from a 150-ft3tank containing air.1945). W.B. a. b. Louvar. For the pressurization technique. 1985). The temperature is 80°F. Develop a list of steps needed to convert a common kitchen into an XP area. Because the tank's maximum allowable working pressure is 150 psia." Chemical Engineering Progress (1977). 1997). "Loss Prevention. H. Maurer. v. The tempera- . multiple pressurization cycles might be necessary. it is possible to use either the sweep-through or a pressurization technique. Static Electricity. MacKeown and V. 7-7. Pratt.L. DC: National Bureau of Standards. 1958). For the pressurization technique. Determine the volume of nitrogen required for each technique. Electrostatics in the Petroleum Industry (New York: Elsevier. pp. Kletz. What volume of nitrogen is required? Assume nitrogen with no oxygen and a temperature of 77°F. 7-5. pp. Wouk. 11. Bulletin 256 (Washington. 7-2. 573-576. Germany: Expert Verlag. F.348 Chapter 7 Designs to Prevent Fires and Explosions T. 1963). Klinkenberg and J. determine the number of cycles required if the pressure purge includes increasing the pressure to 140 psia with nitrogen and then venting to 0 psig. Using the sweep-through purging method. Pure nitrogen is available for the job. Circular C-438 (Washington. pp. Recommended Practice on Static Electricity. What Went Wrong? (Houston: Gulf Publishing. Problems 7-1. 75 -81. Saletan. and (Jun. 7-6. pp. "Tame Static Electricity. inert a 100-galvessel containing 100% air until the oxygen concentration is 1%. J. 29. with the tank being returned to atmospheric pressure at the end of each cycle. "Static Electricity Hazards. A. G. 7. B.I." Chemical Engineering (Jun." Science (Dec. Van der Mine. and G. pp. 7-4. Silsbee. What bonding and grounding procedures must be followed to transfer a drum of flammable solvent into a storage tank? 7-3. 99-102. Reduce the oxygen concentration to 1%using pure nitrogen as the inert gas. L.A. Static Electricity. Loeb. Boicourt. S." Chemical Engineering Progress (November 1994).S. D. Glor. Understanding and Controlling Static Electricity (Goethestrasse. A 150-ft3tank containing air is to be inerted to 1% oxygen concentration.1959). DC: US Department of Labor. Flammable liquid is being pumped out of a drum into a bucket using a hand pump. 659-664. "Electrical Charges Produced by Flowing Gasoline. F.

7-15. Include the following design features: a. part b.Problems 349 ture is 80°F. part b. . 7-11. 7-8. How long will it take to complete this purge process? 7-10. Vacuum and pressure purging. regulators. The powder is collected in an insulated vessel. b. 7-12. Assume that your vacuum system goes down to 20 mm Hg absolute. Determine the number of vacuum purges required to reduce a vessel's oxygen concentration from 21 % to 1% if the nitrogen contains: a.8 7-14. 9000 ppm of oxygen. Assume that the vacuum purge goes from atmospheric pressure to 20 mm Hg absolute. Repeat Problem 7-7 using a combined vacuum and pressure purge. Estimate the charge buildup and accumulated energy as a result of pneumatically conveying a dry powder through a Teflon duct. etc. Design a generalized pressure vessel storage tank for a flammable material. 7-16. Review Problem 7-13. Be sure to account for filling and emptying of the vessel. Repeat Example 7-2 with a 40. Design an inerting system for a pressure vessel to maintain the inert atmosphere at 40 psig. regulators. Draining the tank contents. to determine the hose diameter required to eliminate the potential hazard resulting from static buildup. b. 0 ppm of oxygen. 7-13. Determine the number of purge cycles required and the total moles of nitrogen used. Assume that the vessel height is equal to the diameter. Use a vacuum of 20 mm Hg absolute and a pressure of 200 psig.000-gal storage vessel. Vacuum charging of material from a 55-gal drum. 7-9. and process lines. Explain the potential hazard for cases a and b from the following table: Case a Case b Hose length (ft) Hose diameter (in) Flow rate (gpm) Liquid conductivity (mholcm) Dielectric constant Density (g/cm') 20 2 25 20 2 25 10-l8 2. Use the system $$$ described in Figure 7-14 to determine the voltage developed between the $$$ charging nozzle and the grounded tank. Use the sweep-through purging technique to reduce the concentration of toluene from an initial 20% to 1% in a room with a volume of 25.000 ft3.8 0. and the energy stored in the nozzle.Assume that the room is purged with air at a rate of 6 room volumes per hour. Use the system described in Problem 7-13.4 19 0. c. What is the most effective way to reduce the hazard of this situation? 7-17. Provide precise details on the location of valves. Indicate the precise location of valves. pipes.

7-29. 7-18. number of sprinkler heads. The vessel must be inerted with pure nitrogen before storage of the ace- . and assume that the vessel contains a reactive solvent.5-in orifice) are at 75 psig. 7-22.000 ft3) that will handle Class I liquids and gases. Repeat Problem 7-27 assuming that the nozzle pressure is 100 psig and that the rate is 58 gpm. Repeat the calculation for (a) a half full vessel. What electrical classification would be specified for an area that has Classes I and 11. 7-26. Determine the sprinkler requirements for a chemical process area 150 ft by 150 ft. Toluene leaks as large as 200 gprn have been recorded. describe what safety features should be added to this process area.350 Chapter 7 Designs to Prevent Fires and Explosions Repeat the calculation for a transport rate of 50 Iblmin and 100Iblmin for transport times of 1hr and 5 hr. Determine the water requirement (gprn) and number of nozzles for a deluge system required to protect a 10. Discuss ways to improve the safety of this situation. Determine the recommended ventilation rate for an inside process area (30.5-in orifice and that the nozzle pressure is 75 psig. Determine the number of sprinkler heads and the pump specifications for this system (HP and gprn). Groups A and E. Compute the accumulated charge and energy for a 100. and Divisions 1and 2 motors? 7-23. the floating head rises and falls within the cylindrical shell of the vessel. compute the accumulated charge and energy after 5 hr and after 20 hr. Assume that the sprinkler nozzles have a 0. a flat cover that floats on the liquid surface. if the inlet flow is stopped. Determine the recommended distance between a process area with toluene and an area with an open flame.Assume that the sprinkler nozzles have a 0. 7-27. (b) a full vessel. number of sprinklers. Acetone (C3H60)is to be stored in a cylindrical process vessel with a diameter of 5 ft and a height of 8 ft. and pump horsepower) to protect an inside process area of 200 ft2. and (c) a full vessel with an overflow line. Using the results of Problem 7-25. Assume an average wind speed of 5 mph and stability class D.000-galstorage tank that has a diameter of 15 ft. The temperature is 80°F. Assume that the friction loss from the last sprinkler head to the pump is 50 psi and that the nozzles (0. Use 0. Determine the fire water requirements (gpm. 7-30. 7-31. See chapter 4 for the appropriate source model and chapter 3 for material balance models. As the liquid volume increases and decreases. and the rate is 50 gpm. Discuss the consequences of these results. 7-24. For Problem 7-18. 7-28. 7-19. part c.000-galvessel being filled with a fluid at a rate of 200 gprn and having a streaming current of 2 X lop6amp. determine the concentration of propane in the area as a function of time if at t = 0 a 314-in propane line breaks (the propane main header is at 100 psig). the nozzle pressure is 75 psig. Some large storage vessels have a floating head.0. Make the calculation for a fluid having a conductivity of lo-'' mholcm and a dielectric constant of 2.5-in orifice. 7-25. For the process area described in Problem 7-24. and pump horsepower) to protect an inside process area of 2000ft2. 7-20. What are the reasons for this design? 7-21. Determine the fire water requirements (gpm.5-in nozzles with a nozzle pressure of 35 psig.

Determine the number of cycles required for your selected procedure. or a combination of both. A limited supply of pure nitrogen is available at 80 psig and 80°F. Decide whether a pressure or vacuum purge. . a. is the best procedure. A vacuum is available at 30 mm Hg absolute pressure. d. The ambient temperature is 80°F.Problems 351 tone. c. Determine the target oxygen concentration for the inerting procedure. b. The final pressure in the tank after the inerting procedure is atmospheric. Determine the total amount of nitrogen used.

.

A major effort is always directed toward controlling the process within safe operating regions.Introduction to Reliefs espite many safety precautions within chemical plants. scenarios are developed that describe the various ways in which a relief can occur. Second. and the relief is sized. The type depends mostly on the nature of the material relieved and the relief characteristics required. This can result in rupturing of process equipment. The motivation is to determine the material mass flow rate through the relief and the physical state of the material (liquid. Inherent safety. vapor. described in chapter 1. The defense against this type of accident is to prevent the accident in the first place. The second line of defense is better process control. D . they may exceed the maximum strength of pipelines and vessels. an error in any step of this procedure can result in catastrophic failures. Definitive guidelines are available. If pressures rise too high. including physical properties of the ejected material. is the first line of defense. Third. or two phases). The third line of defense against excessive pressures is to install relief systems to relieve liquids or gases before excessive pressures are developed. the worst-case scenario is selected and the final relief design is achieved. data are collected on the relief process. causing major releases of toxic or flammable chemicals. The relief system is composed of the relief device and the associated downstream process equipment to safely handle the material ejected. Dangerous high-pressure excursions must be prevented or minimized. The first step in the procedure is to specify where relief devices must be installed. the appropriate relief device type must be selected. Every step in this method is critical to the development of a safe design. equipment failures or operator errors can cause increases in process pressures beyond safe levels. Finally. Next. The method used for the safe installation of pressure relief devices is illustrated in Figure 8-1.

to minimize chemical losses during pressure upsets. 113-124. Relief sizing methods are covered in chapter 9. to prevent damage to equipment." Chemical Engineering (Feb. "Pressure Relief Systems. D e s i gn Rel i e f System Figure 8-1 Relief method.354 Chapter 8 Introduction to Reliefs I I L o c a t e Re1 i e f s I I u Choose e l i e f Types 0 Develop Re l i e f 5d Scenar ios Acquire Size Reliefs Size Rel iefs Sin l e Phase Two P h a s e s ( I Choose Worst Case Scenarios 1 I "Data may be simple physical properties or sophisticated calorimeter data to characterize two phase flow (including gassy systems and/or high viscosity laminar flow systems). 'Marx Isaacs. pp. In this chapter we introduce relief fundamentals and the steps in the relief design procedure. 8-1 Relief Concepts Pressure relief systems are required for the following reasons: to protect personnel from the dangers of overpressurizing equipment. .1971). 22.

or other scenario. . to reduce insurance premiums. Reaction runaways for large commercial reactors can occur in minutes. then the reactor temperature will rise. respectively. the pressure and temperature continue to rise until the reactants are completely consumed. As the temperature rises. the heat generation stops and the reactor cools. and to comply with governmental regulations. and (C) closed reaction vessel. as shown by curve C (Figure 8-2). failure of a valve. If cooling is lost because of a loss of cooling water supply. Assume that an exothermic reaction is occurring within a reactor. After the reactants are consumed. to prevent damage to adjoining property. with temperature and pressure increases of several hundred degrees per minute and several hundred psi per minute. (B) relieving froth (two-phase flow). If the reactor has no relief system. the reaction rate increases. This self-accelerating mechanism results in a runaway reaction. For the curves in Figure 8-2 the cooling is lost at t = 0. the pressure subsequently drops. Curve C assumes that the reactor is capable of withstanding the full pressure of the runaway reaction. Typical pressure versus time curves for runaway reactions are illustrated in Figure 8-2.8-1 Relief Concepts 355 i \ reactor (C) presrre Relief opening a AII vapbr (A) Time Figure 8-2 Pressure versus time for runaway reactions: (A) relieving vapor. leading to an increase in heat production. The pressure within the reactor increases because of increased vapor pressure of the liquid components and/or gaseous decomposition products resulting from the high temperature.

as the operating temperature decreases. It is expressed as a percentage of the MAWP. Set pressure: The pressure at which the relief device begins to activate. this pressure difference is called the blowdown. DC: American Petroleum Institute. Definitions that are commonly used within the chemical industry to describe reliefs are given in the following paragraphs. Curve A is for vapor or gas discharged through the relief valve. When froth is discharged (curve B in Figure 8-2). the nature of the relieved material must be known in order to design a proper relief. The pressure drops until the relief valve closes. Maximum allowable working pressure (MAWP): The maximum gauge pressure~ermissible at the top of a vessel for a designated temperature. The incremental pressure increase over the initial relief pressure is called overpressure. 4th ed. As the operating temperature increases. the MAWP decreases because of metal embrittlement at lower temperatures. Overpressure is equivalent to the accumulation when the set pressure is at the MAWP. .356 Chapter 8 Introductionto Reliefs If the reactor has a relief device. the MAWP decreases because the vessel metal loses its strength at higher temperatures. 1-3. Likewise. usually 10% below the MAWP. the pressure response depends on the relief device characteristics and the properties of the fluid discharged through the relief. (Washington. This is illustrated by curve A (Figure 8-2) for vapor relief only and by curve B for a two-phase froth (vapor and liquid). It is expressed as a percentage of the set pressure. 2API RP 521. Operating pressure: The gauge pressure during normal service. Accumulation: The pressure increase over the MAWP of a vessel during the relief process. Vessel failure typically occurs at 4 or 5 times the MAWP. The pressure will increase inside the reactor until the relief device activates at the pressure indicated. 1997). This is sometimes called the design pressure. Overpressure: The pressure increase in the vessel over the set pressure during the relieving process. the pressure continues to rise as the relief valve opens. Guide for Pressure-Relieving and Depressuring Systems. Because the relief character of two-phase vapor-liquid material is markedly different from vapor relief. The pressure drops immediately when the relief device opens because only a small amount of vapor discharge is required to decrease the pressure.pp. although vessel deformation may occur at as low as twice the MAWP.

Relief system: The network of components around a relief device. "Pressure-Relief Valves for Process Plants. . Figure 8-3 Backpressure: The pressure at the outlet of the relief device during the relief process resulting from pressure in the discharge system. . or other types of equipment that assist in the safe relief process. . or agitation? What happens if the process is contaminated or has a mischarge of a catalyst or monomer? 3Robert Kern. . at points where upset conditions create pressures that may exceed the MAWP. .. knockout drum. . Maximum allowable accumulated pressure: The sum of the MAWP and the allowable accumulation.. The engineer must anticipate the potential problems that may result in increased pressures. 8-3 Location of Reliefs3 The procedure for specifying the location of reliefs requires the review of every unit operation in the process and of every process operating step. . . The relationship between these terms is illustrated in Figures 8-3 and 8-4.. . pp. . including the pipe to the relief. It is expressed as a percentage of the set pressure. . . scrubber. discharge pipelines. MAWP Set pressure 4 . ... . ..... . 28." Chemical Engineering (Feb. . . 187-194. the relief device..8-3 Location of Reliefs 357 Overpressure (% of set pressure) Accumulation (% of set MAWP) ----f--+-L-\----. . . . Pressure relief devices are installed at every point identified as potentially hazardous. . that is. .... . . . 1977). Blowdown: The pressure difference between the relief set pressure and the relief reseating pressure. . ... The type of questions asked in this review process are What happens with loss of cooling.. flare. . \ \ Relief begins to open Description of overpressure and accumulation. .. . . heating.

Guide for PressureRelieving and Depressuring Systems.-.u L Y m D -n - - Max imum Re l i e v i n g Pressure for Process Multiple Valves Single Valves Overpressure (Maximum) Maximum A l l o u a b l e Working Pressure or Design Pressure (Hydrotest a t 150) - . .-. What happens if the operator makes an error? What is the consequence of closing valves (block valves) on vessels or in lines that are filled with liquids and exposed to heat or refrigeration? What happens if a line fails. a failure of a high-pressure gas line into a lowpressure vessel? What happens if the unit operation is engulfed in a fire? .-.x 0 . (Washington._ c D o 95 11 Blowdown ( T y p i c a l ) I - - L eseat Pressure ( T y p i c a l ) for Single Valve -a 90 r Standard Leak Test Pressure Figure 8-4 Guidelines for relief pressures...358 Chapter 8 Introduction to Reliefs Pressure Vessel Requirements Vessel Pressure Typical Characteristics o f Safety Rel i e f Valves Maximum R e l i e v i n g Pressure for F i r e Maximum A l l o u a b l e Accumulated Pressur Maximum A l l o w a b l e Accumulated Pressure for Multiple-valve Instal lation (Other Than F i r e Exposure) ' - .A D rn 2 116 . 4th ed. 30.W 9 Overpressure (Typical) 100 aximum A l l o w a b l e S e t P r e s s u r e or Single Valve (Average) S t a r t t o Open - U s u a l Maximum N o r m a l Operating Pressure .4 -r .. for example. 1997).. DC: American Petroleum Institute. p.. Adapted from API RP 521..* .

Heat exchanger (E-1): Heat exchanger tubes can rupture from excessive pressures when water is blocked in (V-10 and V-11 are closed) and the exchanger is heated (by steam. This hazard is eliminated by adding PSV-3. all process vessels need relief valves. Reactor (R-1): A relief is installed on this reactor because. Positive displacement pumps. V-5. and (4) stripping the residual monomer by means of a vacuum using valve V-15. PSV-4. pp. every process vessel needs a relief. 22. Vessel steam jackets are often rated for low-pressure steam. storage tanks. "Pressure-Relief Systems. Example 8-1 Specify the location of reliefs in the simple polymerization reactor system illustrated in Figure 8-5. Reliefs are installed in jackets to prevent excessive steam pressures due to operator error or regulator failure. overheated. b. and V-7 are closed) and the coil is heated with steam or even the sun.(3) adding monomer for a period of 3 hr. 'Marx Isaacs. towers. Reactor coil: This reactor coil can be pressure-ruptured when water is blocked in (V-4. and drums. d. in general. Solution The review method for specifying the location of reliefs follows. Positive displacement pump (P-1): Positive displacement pumps are overloaded. cooling during monomer addition with cooling water is necessary. and how are relief systems designed to handle the discharge as a result of runaway reactions? Some guidelines for locating reliefs are summarized in Table 8-1. and damaged if they are dead-headed without a pressure-relieving device (PSV-2). The reason for the two relief devices PSV-1A and PSV-1B is described in the next section. What conditions cause runaway reactions. The major steps in this polymerization process include (1) pumping 100 Ib of initiator into reactor R-1. 113-124. and turbines need reliefs on the discharge side. Blocked-in sections of cool liquid-filled lines that are exposed to heat (such as the sun) or refrigeration need reliefs. Because the reaction is exothermic. Refer to Figures 8-5 and 8-6 and Table 8-1 for relief locations. including reactors. Storage vessels need pressure and vacuum reliefs to protect against pumping in or out of a blocked-in vessel or against the generation of a vacuum by condensation. This completes the specification of the relief locations for this relatively simple process. Drum (D-1): Again. This type of relief discharge is usually recycled back to the feed vessel." Chemical Engineering (Feb. . This relief is labeled PSV-1 for pressure safety valve 1. c. (2) heating to the reaction temperature of 24OoF. for example). V-6. compressors. e. Add PSV-5 to this coil.1971).8-3 Location of Reliefs 359 Table 8-1 - Guidelines for Specifying Relief Positions1 All vessels need reliefs. a.

and the like). liquids and gases. and corrosive materials. the type of relief is chosen. Example 8-1 illustrates the engineering rationale for installing relief valves at various locations within a chemical plant. In engineering .360 Chapter 8 Introduction to Reliefs C o o l ing W a t e r O u t (10 g p m ) $.1 Spec ifi c a t ions Nitrogen 1 inch 0. depending on the specific application. they may be vented to the atmosphere or vented to containment systems (scrubber. 8-4 Relief Types Specific types of relief devices are chosen for specific applications. After the relief locations are specified. such as for liquids. flare. gases.5 i n c h Figure 8-5 Polymerization reactor without safety reliefs. condenser.-Il Monomer In ool ing W a t e r In Cooling Water Out (100 p s i g ) P. incinerator. solids.

1 Figure 8-6 Polymerization reactor with safety reliefs. the valve opens based on the pressure drop across the valve seat. the set pressure will increase and the valve may not open at the correct pressure. In addition. the flow through the balanced-bellows relief . the set pressure is proportional to the pressure drop across the seat. as illustrated in Figure 8-7. that is. the adjustable screw is covered with a threaded cap. if the backpressure downstream of the valve increases. The flow through the relief. therefore. Thus the balanced-bellows valve will always open at the desired set pressure. process conditions. is reduced as the backpressure increases. Thus. and physical properties of the relieved fluid. The relief set pressure is usually specified at 10% above the normal operating pressure.8-4 Relief Types 361 Cooling Water Out (10 gpm) Monomer ( 5 gpm) I n o o l i n g Water I n Steam (125 psig) C o o l i n g Water Cool ing Hate ( 2 0 0 gpm) Out Steam Trap P. For a conventional spring-operated relief. terms the type of relief device is specified on the basis of the details of the relief system. For the balanced-bellows design the bellows on the backside of the valve seat ensures that the pressure on that side of the seat is always atmospheric. There are two general categories of relief devices (spring-operated and rupture discs) and two major types of spring-operated valves (conventional and balanced-bellows). However. On spring-operated valves the adjustable spring tension offsets the inlet pressure. To avoid the possibility of an unauthorized person changing this setting. the flow through the conventional relief is proportional to the difference in pressure across the seat.

An important problem with rupture discs is the flexing of the metal as process pressures change. Another problem with rupture disc systems is that once they open. It may also allow air to enter the process.Chapter 8 Introduction to Reliefs S P ~ Seat. or in parallel to spring-loaded relief devices. including exotic corrosion-resistant materials. rupture discs are . To prevent this problem. Convent i ona l Spr i ng Operated Valve Rupture Disc and Assernbl y Bet low Balanced Bellows Figure 8-7 Major types of relief devices. Therefore the flow is reduced as the backpressure increases. They are used alone. This may lead to the complete discharge of process material. they remain open. Flexing could lead to premature failure at pressures below the set pressure. They usually consist of a calibrated sheet of metal designed to rupture at a well-specified pressure. For this reason some rupture disc systems are designed to operate at pressures well below the set pressure. is proportional to the difference in pressure between the inlet and the outlet of the valve. They can be made from a variety of materials. vacuum service may cause rupture disc failure if the relief system is not specifically designed for this service. in series. In some accidents discs were ruptured without the process operator being aware of the situation. Rupture discs are specially designed to rupture at a specified relief set pressure. leading to a possible fire and/or explosion. In addition.

This valve reaches full capacity when the pressure reaches 25% overpressure. the valve reseats at approximately 4% below the set pressure. Rupture discs are available in much larger sizes than spring-operated relief valves. The valve closes as the pressure returns to the set pressure. (3) to give absolute isolation when handling flammable gases.8-4 Relief Types 363 available with embedded wires that are cut when the disc ruptures. (2) to give absolute isolation when handling extremely toxic chemicals (spring-loaded reliefs may weep). this can activate an alarm in the control room to alert the operator. when rupture discs rupture. (4) to protect the relatively complex parts of a springloaded device from reactive monomers that could cause plugging. The failure can be the result of a pressure excursion or of a pinhole caused by corrosion. The safety relief valve is used for liquid and gas service. The relief valve (liquid only) begins to open at the set pressure. pieces of the disc may become dislodged. The safety valve is for gas service. 2. PSV-la is a rupture disc to protect PSV-lb from the reactive monomers (plugging from polymerization). . This telltale gauge is an indicator that shows when the disc ruptures. Rupture discs are frequently installed in series to a spring-loaded relief (1)to protect an expensive spring-loaded device from a corrosive environment. and (5) to relieve slurries that may plug spring-loaded devices. Rupture discs typically cost less than equivalently sized spring-operated relief valves. Also. After blowdown of the excess pressure. 3. the valve has a 4% blowdown. Safety relief valves function as relief valves for liquids and as safety valves for gases. a pressure gauge is installed between the two devices. Safety valves pop open when the pressure exceeds the set pressure. with commercial sizes available up to several feet in diameter. Example 8-2 Specify the types of relief devices needed for the polymerization reactor in Example 8-1 (see Figure 8-6). In all these examples the problems are eliminated if the rupture disc and system are specified and designed appropriately for the specific operating conditions of the process. There are three subcategory types of spring-loaded pressure reliefs: 1. The relief valve is primarily for liquid service. This is accomplished by using a discharge nozzle that directs high-velocity material toward the valve seat. Solution Each relief is reviewed in relation to the relief system and the properties of the relieved fluids: a. When rupture discs are used before a spring-loaded relief. In either case the telltale gauge indicates that the disc needs to be replaced. creating potential downstream plugging problems. Recent advances in rupture disc design have minimized this problem.

d. Because this vent will go to a scrubber with possibly large backpressures. A conventional valve is satisfactory. The same pump relief is in a line with a nitrogen regulator. A pump is dead-headed. the pump relief is sized to handle the full pump capacity at its rated pressure. c. The scenarios developed for the reactor system described in Figure 8-6 are summarized in Table 8-2. the relief scenarios are developed. The worst-case scenarios are identified later by means of the computed maximum relief area for each scenario and relief (see chapter 9). The relief vent area is subsequently computed for each event (scenario) and the worst-case scenario is the event requiring the largest relief vent area. Usually each relief has more than one relief event.- 364 Chapter 8 Introduction to Reliefs b. Examples of relief events are: 1. f. for example. 3. and pressures are increased inside the coil because of thermal expansion. the relief is sized to handle the nitrogen if the regulator fails. For each specific relief all possible scenarios are identified and cataloged. PSV-lb is a safety relief valve because a runaway reaction will give two-phase flow. 2. PSV-3 is a relief valve because it is for liquid only. the relief is sized to handle steam injected into the exchanger under uncontrolled conditions. In Table 8-2 only three reliefs have mul- . a balanced bellows is specified. This is a list of scenarios for one specific relief. and the worst-case scenario is the scenario or event that requires the largest relief vent area. e. PSV-2 is a relief valve because this relief is in a liquid service line. a steam regulator failure. A conventional relief device is satisfactory in this service. 8-5 Relief Scenarios A relief scenario is a description of one specific relief event. This step of the relief method is extremely important: The identification of the actual worst-case scenario frequently has a more significant effect on the relief size than the accuracy of relief sizing calculations. PSV-4 is a safety relief valve because liquid or vapor service is possible. The same pump is connected to a heat exchanger with live steam. The worst cases are a subset of the overall developed scenarios for each relief. PSV-5 is a relief valve for liquid service only. This relief provides protection for the following scenario: The liquid is blocked in by closing all valves. both liquid and vapor. the heat of reaction increases the temperature of the surrounding reactor fluid. After specifying the location and type of all relief devices.

as in a runaway reaction scenario. special methods have 4Harold G." Chemical Engineering Progress (August 1985). A runaway reaction is another scenario that requires special data. the entire contents of the bottle may be "relieved. The other three reliefs have only single scenarios. In the relief design. 8-6 Data for Sizing Reliefs Physical property data and sometimes reaction rate characteristics are required for making relief sizing calculations. (c) Nitrogen regulator fails. therefore they are the worst-case scenarios. When designing reliefs for gas or dust explosions. however. giving critical flow through 1-in line. giving critical flow through 0. Confined water line is heated with 125-psig steam. (b) Cooling coil is broken and water enters at 200 gpm and 50 psig. especially when conditions change rapidly. special deflagration data for the scenario conditions are required. (b) Note: The other R-1 scenarios will be relieved via PSV-1. Two-phase flow calculations are relatively complex.8-6 Data for Sizing Reliefs 365 Table 8-2 Relief Scenarios for Example 8-2 (See Figure 8-6) Scenarios (a) Vessel full of liquid and pump P-1 is accidentally actuated. V-1 is accidentally closed. If the champagne is heated before opening. It is known that runaway reactions nearly always result in two-phase flow reliefs4 The two phases discharge through the relief system similar to a champagne and carbon dioxide mixture exiting a freshly opened bottle. Data estimated using engineering assumptions are almost always acceptable when designing unit operations because the only result is poorer yields or poorer quality. (d) Loss of cooling during reaction (runaway). . system needs relief for 100 gpm at 50 psig. As a result of this complexity. and heat of reaction causes thermal expansion. "DIERS Research Program on Emergency Relief Systems. Fisher.5-in line. Relief identifications PSV-la and PSV-lb PSV-2 PSV-3 PSV-4 PSV-5 tiple scenarios that require the comparative calculations to establish the worst cases. these types of assumptions are not acceptable because an error may result in catastrophic and hazardous failures. (a) Nitrogen regulator fails. These data are acquired with the apparatus already described in section 6-13. 33-36.pp." This result has also been verified for runaway reactions in the chemical industry. Water blocked inside coil.

The data obtained from the calorimeters include maximum self-heat rate. The sample to be tested is heated by means of one of two modes. A small amount of the material to be tested (30-80 mg) is loaded into a thin-walled reactor vessel. Noronha. Muller. Tilley. J.366 Chapter 8 Introduction to Reliefs Nitrogen Adiabatic Heater / \Magnetic 'Stirrer Figure 8-8 Vent sizing package (VSP) for acquiring runaway reaction data. reaction onset temperature. Townsend and J. Emergency Relief System Design Using DZERS Technology (New York: American Institute of Chemical Engineers. Each calorimeter has a different sample size. J. A series of controlled 5D. Some calorimeters use a mix of the two modes. Grossel. . E. Fisher. A. 37: 1-30. G. container design. 6H. Huff. S. and B. If no reaction is detected. D. R. H. In the second heating mode the sample is heated at a fixed temperature rate and the calorimeter watches for a higher rate that identifies the initiation of the exothermic reaction." Thermochimica Acta (1980). S. In the first mode the sample is heated to a fixed incremental temperature. A. the automatic pressure-tracking adiabatic calorimeter (APTAC). "Thermal Hazard Evaluation by an Accelerating Rate Calorimeter. These include the accelerating rate calorimeter (ARC). 1992). data acquisition hardware. C. Forrest. and then the calorimeter maintains this temperature and waits a fixed time to determine whether an exothermic reaction occurs. The VSP (Figure 8-8) is essentially an adiabatic calorimeter. Several commercial calorimeters are available to characterize runaway reactions. then the temperature is increased by another increment. Shaw. J. S. been developed for acquiring the relevant data5 and for making the relief vent sizing calculations6 (see chapter 9). A. All of these calorimeters work essentially the same way. maximum pressure rate. the reactive system screening tool (RSST). and temperature and pressure as a function of time. I. and the vent sizing package (VSP). Tou. and data sensitivity.

During the runaway reaction. The data acquired with this calorimeter are shown in Figures 8-9 and 8-10. at the set Figure 8-10 Runaway reaction pressure data acquired using the vent sizing package. this prevents the thin-walled sample container from rupturing.8-6 Data for Sizing Reliefs 367 Time ( minutes ) Figure 8-9 Runaway reaction temperature data acquired using the vent sizing package (VSP). the VSP device tracks the pressure inside the can and maintains a similar pressure in the main containment vessel. heaters increases the sample temperature to the runaway conditions. . Results of particular importance for relief sizing calculations include the temperature rate (dTldt).

it is essential to understand this technology. design. industrial standards. Because the calorimeter starts with known weights and known compositions. The engineer must take the responsibility for adhering to standard practices. Other systems. a poor installation can result in completely unsatisfactory relief performance. the heat of reaction can also be determined from the Tversus t data (assuming that the heat capacities of the monomers and products are known). This same effort and creativity is essential when developing relief systems. To develop the necessary optimum and reliable relief systems.- - - - - - - - - - 368 Chapter 8 Introduction to Reliefs pressure and the temperature increase AT corresponding to the overpressure 4P. Codes of particular interest are published by the American Society of Mechanical Engineers. time. hopefully they will never need to operate. It is recommended that relief designers carefully consider all codes and. where feasible. usually evolve to their optimum performance and reliability. select the one that is most suited to the particular installation. and insurance requirements. This is particularly important because local government standards may vary. and process engineers. the engineer takes the responsibility for completing the design of the relief system. Some installation guidelines are illustrated in Figure 8-11. they must do so flawlessly. .During field construction. and tested. the American Petroleum Institute. specified. practical knowledge. Pressure-relieving systems are unique compared with other systems within a chemical plant. however. Relief Design Considerations A designer of relief systems must be familiar with governmental codes. and the cooperative efforts of the plant. in this case the relief system development must be optimally designed and demonstrated within a research environment before the plant start-up. sometimes expediency or construction convenience leads to modifications and deviations from acceptable practice. and the National Board of Fire Underwriters. This evolution requires creativity. such as extraction and distillation systems. 8-7 Relief Systems After the relief type has been chosen and the relief size computed. Relief Installation Practices Regardless of how carefully the relief is sized. but when they do. especially when installing relief systems. including deciding how to install the relief in the system and how to dispose of the exiting liquids and vapors. The objective of this section is to give students and design engineers the details necessary for understanding relief systems. Specific references have already been cited. hard work.

i n Extremely The 1 s t May P e r i o d i c a l l y Need t o be R e p l a c e d . 1963). u 9 23 T w o Rupture Discs Corrosive Service. The Rupture Toxicity or The S p r i n g Loaded R e l i e f C l o s e s and M i n i m i z e s Losses. R u p t u r e Disc and S p r i n g Loaded R e l i e f . T w o Rupture Discs with Special Valve W h i c h K e e p s One V a l v e A l w a y s D i r e c t l y Connected t o Vessel. M a t e r i a l s where Highly Toxic S p r i n g L o a d e d V a l v e M a y Weep. 19. I s Good f o r T h i s Type Design Polymerization Reactors Where P e r i o d i c C l e a n i n g I s N e c e s s a r y . Disc Protects Against Corrosion. 151-1 58. Adapted from Eric Jennett. N o r m a l R e l i e f M a y Go T h r o u g h S p r i n g and R u p t u r e D i s c I s Loaded Device. @ Two R e l i e f s i n S e r i e s . for Back-up L a r g e r Re l i e f s ." Chemical Engineering (Aug. "Components of PressureRelieving Systems. .8-7 Relief Systems 369 System Recommendations A Vesse l Rupture Disc O r for i n Corrosive Service. pp. Figure 8-11 Relief installation practices.

-A 1 t 4. C. Process L i n e s Should Not be Connected t o S a f e t y Valve I n l e t Piping. A. Vessel S h o u l d be S u p p o r t e d Below t h e Long Radius Elbow. Recommendations P r e s s u r e D r o p N o t M o r e T h a n 3% o f Set Pressure L o n g R a d i u s E l bow B ' I f D i s t a n c e i s G r e a t e r T h a n 10 Weight and R e a c t i o n F o r c e s Feet. A. Should N o t E x c e e d 2% o f t h e C r o s s Sectional Area o f t h e Protected Line. Device Causing Turbulence Regulator or Valve: 25 i n Same P l a n e : 2 0 2 E l l s o r Bends N o t 2 E l I s o r B e n d s i n Same P I a n e : 1 E l l o r Bend: P u l s a t i o n Damper: 15 18 16 Figure 8-11 (continued) . B.370 Chapter 8 Introduction t o Reliefs Ti T Jg System A. Turbulence Causing Device D i m e n s i o n ( B ) shown below: M i n i m u m Number o f S t r a i g h t Pipe Diameters B. M u l t i p l e Valves with Staggered S e t t i n g s May b e R e q u i r e d . L Pipe 8 O r i f i c e Area o f a S i n g l e Safety Relief i n Vapor Service.

this horizontal knockout drum system serves as a vapor-liquid separator as well as 'API 520. normal stress analysis is the recommended method.8-7 Relief Systems 371 To Condenser. flare. Horizontal Knockout Drum Knockout drums are sometimes called catch tanks or blowdown drums. 1994). . (Washington. Selection. and they are becoming an industrial standard. Another important consideration is the reaction forces generated when the relieved materials flow through the relief system at high speed. Blowdown Drum Figure 8-12 Relief containment system with blowdown drum. here the liquid is collected and the vapor is discharged to another treatment unit. scrubber. It is also important to recognize that company philosophy and the regulatory authorities have a significant influence on the design of the final disposal system. DC: American Petroleum Institute. 4th ed. The blowdown drum separates the vapor from the liquid. and Installation of Pressure-Relieving Devices in Refineries. As illustrated in Figure 8-12. Installation. or a combination of them. The API RP 5207has some guidelines. Sizing. For this reason reliefs are now rarely vented to the atmosphere. This type of system is called a total containment system. it may include a condenser. incinerator. In most cases a relief is first discharged to a knockout system to separate the liquid from the vapor. one is illustrated in Figure 8-12. Total containment systems are commonly used. however. primarily from the standpoint of pollution. 2. This subsequent vapor treatment unit depends on the hazards of the vapor. pt.

Grossel. with a vapor exit in the center to minimize vapor velocities. 63-67. pp. as shown in Figure 8-13. S. Guide for Pressure-Relievingatzd Depressurizing Systems.9The method is based on the maximum allowable velocity for minimizing liquid entrainment. 1997). "Design and Sizing of Knockout DrumsICatchtanks for Reactor Emergency Relief Systems. The two-phase mixture usually enters at one end.372 Chapter 8 Introduction to Reliefs Vent o r or t o Atmosphere F l a r e Stack Scrubber Long Knock-Out Radius Rupture L o c a t ed D i s c as s C lose t0 Vesse Poss l a i b le Figure 8-13 Tangential inlet knockout drum with separate liquid catch tank. The design method for sizing this type of system was published by Grosse18 and in API 521. 9API RP 521. 4th ed." Plant/Operations Progress (July 1986). DC: American Petroleum Institute. and the vapor leaves at the opposite end. When space within a plant is limited. The dropout velocity of a particle in a stream is 8S. a holdup vessel for the disengaged liquid. . a tangential knockout drum is used. (Washington. Inlets may be provided at each end.

is the vapor density. d. is the dropout velocity. is the particle diameter. 100 1 000 lb' 10" 1 b' C ( ~ e ) ~ Figure 8-14 Drag coefficient correlation. DC: American Petroleum Institute. Guide for Pressure-Relieving and Depressurizing Systems. (Washington.8-7 Relief Systems 373 10 . g is the acceleration due to gravity. . is the liquid density. p. 2d ed. p. where u. Data from API RP 521. The abscissa of Figure 8-14 is where pv is the vapor viscosity in centipoise and C(Re)2 is unitless. 1982). and Cis the drag coefficient given by Figure 8-14.

using Figure 8-14.01 centipoise.where Vapor rate = 170 lb/hr. and the general geometric configuration of the vessel. The graph abscissa is computed using Equation 8-2: X (0.3.2) Ibm/ft3 Using Figure 8-14.01 centipoise)' - 0. we find that C = 1.374 Chapter 8 Introduction to Reliefs - -- - Example 8-3 Determine the maximum vapor velocity in a horizontal knockout drum to dropout liquid particles with particle diameters of 300 pm.84X ft)"30 (0.20 lb/ft3. = 300 pm = 9. pv = 0. perpendicular to the vapor path. The dropout velocity is determined by using Equation 8-1: The required vapor space area. . pv = 0.84 x ft. Solution To determine the dropout velocity.2 lbmlft3)(9. p~ = 30 Iblft3. The entire vessel design is determined as a function of this vapor area plus the liquid hold volume. is subsequently computed using the velocity and the volumetric flow rate of the vapor. the drag coefficient is first determined. and d.

Tan. we know that the heat intensity q at a specific point is a function of the heat generated by the flame Q..000 Btullb. and a heating value of (in 20. l0Soen H.000 Iblhr. and the distance R from the flame: Assuming a flame height of 120df. Equation (8-3) can be algebraically modified to give the flare height Hi ft) as a function of the flare stack diameter df (in ft) and the desired heat intensity qf (in ~ t u / h r / f t ' ) at a distance Xf from the base of the flare (in ft) for a burning fuel with a molecular weight M and a vapor rate Q.8-7 Relief Systems 375 Flares l o Flares are sometimes used after knockout drums. the flare load is 970. The diameter of the flare must be suitable to maintain a stable flame and to prevent a blowout (when vapor velocities are greater than 20% of the sonic velocity). the emissivity E . The effects of thermal radiation are shown in the following table: Heat intensity (Btu/hr/ft2) 2000 5300 3000-4000 350 Effect Blisters in 20 s Blisters in 5 s Vegetation and wood are ignited Solar radiation Using the fundamentals of radiation. "Flare System Design Simplified. and the molecular weight of the vapor is 44. . an emissivity E = 0 . The flare diameter is 4 ft. The height of a flare is fixed on the basis of the heat generated and the resulting potential damage to equipment and humans. 0 4 8 m . (in lblhr): Example 8-4 Determine the stack height required to give a heat intensity of 1500Btu/hr/ft2at a distance of 410 ft from the base of the flare. The objective of a flare is to burn the combustible or toxic gas to produce combustion products that are neither toxic nor combustible. The usual design criterion is that the heat intensity at the base of the stack is not to exceed 1500 Btulhrlft2." Hydrocarbon Processing (January 1967).

ll Condensers A simple condenser is another possible alternative for treating exiting vapors. (New York: McGraw-Hill. S.Q. W. G. . This alternative should always be evaluated because it is simple and usually less expensive and because it minimizes the volume of material that may need additional post-treatment. 12D. Process Heat Transfer (New York: McGraw-Hill. they may be vented unless some regulation prohibits this type of discharge. If the vapors are nontoxic and nonflammable. (New York: McGraw-Hill. Liquids are subsequently collected and the vapors may or may not be vented. plate columns. Kern.12 Suggested Reading General Articles on Relief Valves and Systems Floyd E. 1980). Scrubber systems can be packed columns. "Pressure Relieving Devices. The units are consistent with those required: = 226 ft." Process Safety Progress (April 1995).376 Chapter 8 Introduction to Reliefs Solution The flare height is computed using Equation 8-4.E. 1958). Scrubbers The fluid from reliefs. sometimes two-phase flow. If the vapors are toxic. Louvar. Emergency Relief System Design (New York: American Institute of Chemical Engineers." in Safe and EfJicient Plant Operations and Maintenance. "R. Richard Greene. The design of condenser systems is covered by Kern. 207. Grossel and J. 1950). ed. a flare (described previously) or a scrubber system may be required. "Emergency Relief System (ERS) Design: An Integrated Approach Using DIERS Methodology. p. R. where the liquids and vapors are separated. 2000). Design for Overpressure and Underpressure Protection (New York: American Institute of Chemical Engineers. Treybal. Details of scrubber designs are covered by Treybal. Mass Transfer Operations. This alternative is particularly attractive if the vapors have a relatively high boiling point and if the recovered condensate is valuable. pp. Darby. S. 1997). Boicourt. 93-106. F. must first go to a knockout system. 3d ed. Anderson. or venturi-type systems.

Fisher. K. Referring to Problem 8-7. Review Figure 8-16 and Problem 8-10 to determine what types of relief devices should be used at each location. 113. Review Figure 8-16 and Problems 8-10 and 8-12. what design modifications would you make to this relief system? 8-6. Leung. Using the results of Problems 8-10 and 8-12. 8-9. and make recommendations for total containment systems. 8-16. PSV-2 of Figure 8-6 is a relief to protect the positive displacement pump P-1. "Simplified Vent Sizing Equations for Emergency Relief Requirements in Reactors and Storage Vessels. J. C. Review Figure 8-16. J. Review Figure 8-15 and Problems 8-9 and 8-11. p. Leung. C. 104: 13-29. Develop an example to illustrate the potential magnitude of the vacuum. 28. determine the relief scenarios for each relief device. Review Figure 8-15. 8-14. 8-12. 8-15. pp. G. If the fluid being handled is extremely volatile and flammable." Chemical Engineering (Feb. and determine the locations for relief devices. Can gate valves be placed between a vessel relief and its vessel? 8-2. and H. p. "Pressure-Relief Systems. Problems 8-1. One defense against runaway reactions is better process control. and make recommendations for total containment systems. Using the results of Problems 8-9 and 8-11. determine the relief scenarios for each relief device. Give four examples of situations requiring a combination of spring-operated reliefs in series with rupture discs. 8-3. 22. H. 8-10. In the future it is anticipated that insurance rates will be set as a function of the safety of a plant. what control features (safeguards) would you add to this reactor system? 8-7. 8-5. Review Figure 8-15 and Problem 8-9 to determine what types of relief devices should be used at each location. 1622-1634. how would this affect the size (qualitatively) of this relief system? 8-8.1971). 8-4. "Thermal Runaway Reactions in a Low Thermal Inertia Apparatus." Thermochimica Acta (1986). qualitatively describe the algorithm you would use to compute the relief size for this system. Robert Kern. Using the system illustrated in Figure 8-6. 1986). 187. Fauske. . 1977). 8-11." AICHE Journal (Oct. and determine the locations for relief devices. 8-13." Chemical Engineering (Feb. If a scrubber is installed after PSV-lb and it has a pressure drop of 30 psig. "Pressure-Relief Valves for Process Plants. Describe the process of creating a vacuum in a storage vessel as a result of condensation.Problems 377 Marx Isaacs. Illustrate the kinds of plant statistics that you would cite to reduce your insurance costs.

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05 50. Selection.01 350 8-19. See Grossel and Louvar (2000). Describe the advantages and disadvantages of a pilot-operated safety valve.01 300 0. for the following three cases: Case a - Case b 70. it is important to periodically check the pressure gauge to be sure that there is no pinhole leak in the rupture disc. Describe the advantages and disadvantages of a buckling pin relief valve. and Installation (1994). 8-21.03 64. what pressure losses are recommended? See API 520.5 0.000 10 3 Case c 80.04 64. 8-24.000 50 5 Vapor flow (lblhr) Molecular weight Heat intensity (~tu/hr/ft') Distance from base (ft) Stack diameter (ft) 60. Describe the advantages and disadvantages of a rupture disc followed by a springoperated relief valve. 8-23. Determine the vapor velocity inside a horizontal knockout drum for the following three systems: System System System b c a pv (lb/ft3) p~ (lb/ft3) Vapor viscosity (centipoise) Particle diameter (pm) 0.000 5 2 8-20. See Grossel and Louvar (2000).0 0. See Grossel and Louvar (2000).000 80 4.000 60 3.000 30 2.Chapter 8 Introduction to Reliefs 8-17. assuming various maximum heat intensities at ground level at the specified distances from the flare. Develop sketches of reactor vent systems for the following four cases: Case a Reactor relief is vapor only Reactor relief is two-phase flow Reactor contents are corrosive Reactor contents are plugging type Relieved vapors are toxic Relieved vapors are high boilers Vapors are low boilers Case b x x x Case c x Case d x x x x x x x x x 8-18.02 400 0.0 0. Determine the height of a flare. Describe several methods to satisfy this requirement. . When designing the inlet piping to a relief valve. When using a rupture disc followed by a spring-operated relief. 8-22. Sizing.

8-31. 8-29. Sometimes isolation valves are needed between the vessel and the relief." See Grossel and Louvar (2000). Describe a runaway that is a "hybrid. Identify the problems with the relief valve configurations shown in Figure 8-17. See Grossel and Louvar (2000). 8-27. Selection. What management system is recommended for isolation valves? See API 520. See Grossel and Louvar (2000). 8-26." See Grossel and Louvar (2000). and Installation (1994). What are these two stresses? See API 520. Sizing.Problems 381 Figure 8-17 Relief valve configurations: What's wrong? 8-25. 8-30. . Sizing. Describe a tempered runaway reaction. The outlet piping of a relief system is normally supported to resist two mechanical stresses. Selection. Describe a runaway that is "gassy. and Installation (1994). Describe a runaway reaction scenario that is the result of a sleeper reaction. 8-28.

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Spring relief devices require 25-30% of maximum flow capacity to maintain the valve seat in the open position. As shown in Figure 9-1." caused by rapid opening and closing of the valve disc. Experimental data at the actual relief conditions are recommended for sizing relief vents for runaway reaction scenarios. Lower flows result in "chattering. A relief device with an area that is too large for the required flow may chatter. the relief vent area is reduced substantially as the overpressure increases. The optimal vent area for a particular relief depends on the specific application. second. The relief sizing calculation procedure involves. manufacturers' technical specifications are used for selection. neither too small nor too large. R . using an appropriate equation based on fundamental hydrodynamic principles to determine the relief device vent area. The relief vent area calculation depends on the type of flow (liquid. As always. first. purchase. using an appropriate source model to determine the rate of material release through the relief device (see chapter 4) and. This is one example that illustrates this typical result.Relief Sizing elief sizing calculations are performed to determine the vent area of the relief device. depending on the requirements of the equipment protected and the type of material relieved. the relieving process begins at the relief set pressure with the pressure normally continuing to rise past the set pressure (see curve B in Figure 8-2). Normally. The overpressure specification is part of the relief design. These overpressures frequently exceed the set pressure by 25% or more. and installation. or two-phase) and the type of relief device (spring or rupture disc). For this reason reliefs must be designed with the proper vent area. A relief device designed to maintain the pressure at the set pressure could require an excessively large vent area. In chapter 8 we showed that for liquids and two-phase relief. relief devices are specified for overpressures from 10% to 25%. vapor. This can lead to destruction of the relief device and a dangerous situation.

An equation representing this flow is derived from the mechanical energy balance (Equation 4-1). except that the pressure is represented by a pressure difference across the spring relief: . The result is similiar to Equation 4-6. and reliefs for thermal expansion of process fluids. two-phase flow during runaway reactor relief. In this chapter we present methods for calculating the relief device vent areas for the following configurations: conventional spring-operated reliefs in liquid or vapor-gas service. 9-1 Conventional Spring-Operated Reliefs in Liquid Service Flow through spring-type reliefs is approximated as flow through an orifice. reliefs for fires external to process vessels." AlCHE Journal (1986). Leung. "Simplified Vent Sizing Equations for Emergency Relief Requirements in Reactors and Storage Vessels. reliefs for dust and vapor explosions. Data from J. rupture discs in liquid or vapor-gas service. C.384 Chapter 9 Relief Sizing Percent Overpressure Figure 9-1 Required vent area a s a function of overpressure for two-phase flow. 32(10). The vent area is decreased appreciably a s t h e overpressure increases.

is the discharge coefficient. 6th ed. Selection. DC: American Petroleum Institute. . increasing the discharge area and increasing the flow. A true orifice has a fixed area. of liquid is the product of the velocity times the area. is the discharge coefficient (unitless). The result is where A is the computed relief area (in2). flow through a spring-type relief is different from flow through an orifice. Many process fluids have high viscosities. is the volumetric flow through the relief (gpm).) and (2) making the appropriate substitutions for the unit conversions. As the pressure increases. or .9-1 Conventional Spring-Operated Reliefs in Liquid Service 385 where u is the liquid velocity through the spring relief.A. and p is the liquid density. and AP is the pressure drop across the spring relief (lbf/in2). Finally. (Washington. The relief vent area must increase as the fluid viscosity increases. C. Q. C. Equation 9-3 does not consider the special case of a balancedbellows-type relief. Equation 9-3 does not consider the viscosity of the fluid. Also. AP is the pressure drop across the relief. Equation 9-3 has been modified by the American Petroleum Institute to include corrections for the above situations. and Installation of Pressure Relieving Systems in Refineries. In reality. the relief spring is compressed. The result is API RP 520. 1993). (p/pref)is the specific gravity of the liquid (unitless). Recommended Practice for the Sizing.. Substituting Equation 9-1 and solving for the vent area A of the relief. The volumetric flow Q.. we obtain A working equation with fixed units is derived from Equation 9-2 by (1)replacing the density p with the specific gravity (pip.

is a function of the overpressure specified for the design. The required relief vent area becomes larger as the viscosity of the liquid increases (lower Reynolds numbers). K. Molavi. For most reliefs the Reynolds number is greater than 5000 and the correction is near 1. If this value is uncertain. This correction is given in Figure 9-3.Darby and K. Because the Reynolds number is required to determine the viscosity correction and because the vent area is required to calculate the Reynolds number. is the gauge set pressure (lbf/in2). includes the effect of discharge pressures greater than the set pressure. (p/pref) the specific gravity of the liquid (unitless). is the viscosity correction (unitless).25 times the set pressure." Process Safety Progress (1997). Equation 9-4 appears to assume a maximum pressure equal to 1. 16(2). corrects for the additional frictional losses rQulting from flow of high-viscosity material through the valve. Note that the A P term in Equation 9-3 has been replaced by a term involving the difference between the set pressure and the backpressure. The viscosity correction K. is the volumetric flow through the relief (gpm). This equation applies only to Reynolds numbers greater than 100: where K. C. the procedure is iterative. Discharge at other maximum pressures is accounted for in the overpressure correction term K. is the backpressure correction (unitless).and P. C.. This correction is given in Figure 9-2. Specific guidelines for the selection of an appropriate value are given in chapter 4. Darby and Molavi2 developed an equation to represent the viscosity correction factor shown in Figure 9-2. The overpressure correction K. 2R. . a conservative value of 0. As the specified overpressure becomes smaller. Q. K. is the gauge backpressure (lbf/in2). The overpressure correction K. is the viscosity correction factor (unitless) and Re is the Reynolds number (unitless). is the discharge coefficient.This assumption is frequently used as an initial estimate to begin the calculations.386 Chapter 9 Relief Sizing where A is the computed relief area (in2). section 4-2. is the overpressure correction (unitless). is P. is the discharge coefficient (unitless). K.61 is used to maximize the relief vent area. "Viscosity Correction Factor for Safety Relief Valves.

and lnstallation of Pressure-Relieving Systems in Refineries. Source: API RP 520. DC. ( 993).4 - e 8 0 ' l5 I I I I I I I I ' 45 I I 20 Overpressure (%) 25 30 35 40 50 . Selection. sion of the American Petroleum Institute. for spring-operated reliefs in liquid service.3 0. 6th ed.RecommendedPractice for the Sizing. Institute. 9 0. Source: API RP 520. (1993). V) V) $ 0.9-1 Conventional Spring-Operated Reliefs in Liquid Service 387 R = REYNOLDS NUMBER Figure 9-2 Viscosity correction factor K. 35. 37. O lo Figure 9-3 Overpressure correction K. 6th ed.Used by permisp. for conventional reliefs in liquid service.Used by permission of the American Petroleum 1 p. Washington.5 0. and Installationof PressureRelieving Systems in Refineries. Selection.2 01 . Washington.Recommended Practice for the Sizing. DC.

for 25% overpressure on balanced-bellows reliefs in liquid service. The set pressure is 200 psig. . Washington. The overpressure correction factor curve shown in Figure 9-3 shows that up to and including 25% overpressure. Above 25% the valve capacity is affected only by the change in overpressure because the valve discharge area is constant and behaves as a true orifice. 35. 'ItCK PRESSURE. This correction compensates for the absence of backpressure on the back of the relief vent disc. Solution a. assuming a backpressure of 20 psig and (a) a 10% overpressure and (b) a 25% overpressure. so overpressures less than 10% should be avoided. p. Recommended Practice for the Sizing. Designs incorporating less than 10% overpressure are not recommended. 6th ed. DC. resulting in a larger relief area. The backpressure correction K. Used by permission of the American Petroleum Institute. The backpressure is specified as 20 psig and the overpressure is 10% of the set pressure. is used only for balanced-bellows-type spring reliefs and is given in Figure 9-4. Because a deadheaded pump can be easily damaged. and Installation of Pressure Relieving Systems in Refineries. Example 9-1 A positive displacement pump pumps water at 200 gpm at a pressure of 200 psig. Source: API RP 520. or 20 psig. Selection. PSIG Figure 9-4 Backpressure correction K. and the change in overpressure. Valves operating at low overpressures tend to chatter. (1993).388 Chapter 9 Relief Sizing %GAGE BACK PRESSURE. compute the area required to relieve the pump. the change in the orifice discharge coefficient. the correction value decreases.PSIg1 ~ ) x SET PRESSURE. the relief device capacity is affected by the changing discharge area as the valve lifts.

Thus a selection must be made depending on relief device sizes available commercially.. Manufacturers do not provide relief devices to the nearest 0. For an overpressure of 25%. The Reynolds number through the relief device is not known.0 gpm (0.6. so Q. For all relief devices the manufacturers' technical specifications must be checked before selection and installation. However. and _ Jv = 0. Thus Kb = 1.61)(1.0 (Figure 9-3).0. As expected.851 in.. the downstream pressure must be checked to ensure that it is less than the choked pressure computed using Equation 4-49. = 1. K.9-2 Conventional Spring-Operated Reliefs in Vapor or Gas Service 389 The discharge coefficient C. These numbers are substituted directly into Equation 9-4: . K.0. However. K. Thus the viscosity correction is. The backpressure correction is not required because this is not a balanced-bellows spring relief.0) b. The overpressure correction K. 9-2 Conventional Spring-Operated Reliefs in Vapor or Gas Service For most vapor discharges through spring reliefs the flow is critical.0)(0. = 200 gpm.6)(1. from Figure 9-3.[in2(psi)'"] 200 gpm 38. from Figure 9-2. is not specified. The quantity of material relieved is the total flow of water. The next largest available size is normally selected.61 is used. the relief vent area decreases as the overpressure increases. Thus for an ideal gas Equation 4-50 is valid: .01 in. for a conservative estimate a value of 0. = 1. at 200 gpm the Reynolds number is assumed to be greater than 5000. Because the percentage of overpressure is lo%. However. = 0. is given in Figure 9-3.

A is the area of the discharge. and T is the absolute temperature of the discharge. M is the molecular weight of the gas. g. Equation 9-6 is simplified by defining a function X : Then the required relief vent area for an ideal gas is computed using a simplified form of Equation 9-6: For nonideal gases and real vents Equation 9-8 is modified by (1)including the compressibility factor z to represent a nonideal gas and (2) including a backpressure correction Kb.975 (unitless). and M is the average molecular weight of the discharge material. R.. is the ideal gas constant.: A=- . C.. K. is the discharge coefficient. . is the backpressure correction (unitless). P is the absolute upstream pressure. is the discharge mass flow. . usually 0. P is the maximum absolute discharge pressure. is the gravitational constant. Cois the effective discharge coefficient. z is the compressibility factor (unitless). T is the absolute temperature.390 Chapter 9 Relief Sizing where (Q. Qm / -- ygc[ TIM 2 )(~+l)'(~-l). Qmis the discharge flow. cop. y is the heat capacity ratio for the gas. The result is where A is the area of the relief vent.. Equation 4-50 is solved for the area of the relief vent given a specified mass flow rate Q.).

. It is given for the fixed-unit case by. 33.. Selection. " Y BACK PRESSURE. for conventional spring-type reliefs in vapor or gas service. 6th ed. and Installation of Pressure-RelievingSystems in Refineries. is the maximum gauge pressure in psig./hr.9-2 Conventional Spring-Operated Reliefs in Vapor or Gas Service 391 . The constant x is represented by Equation 9-7. Recommended Practice for the Sizing. PSIA % A B S O L U T E BACK PRESSURE= SET PRESSURE + PSIA X 100 = r X 100 Figure 9-5 Backpressure correction K. + 14.. Tin OR. P in psia... p. The area computed is in in2./lb-mol.. K. The pressure used in Equation 9-9 is the maximum absolute relieving pressure.. Equation 9-9 must have the following fixed units: Q. Washington. P. 1998). P = P..33PSfor piping. . Source: API RP 520. It is conveniently calculated using the following fixed-unit expression: If Equation 9-10 is used. is the backpressure correction and depends on the type of relief used. For vapor reliefs the following guidelines are recommended3: P. 1. (9-11) where P. Values are given in Figure 9-5 for conventional spring reliefs and in Figure 9-6 for balanced-bellows reliefs. = = 1.7.and M in lb. (1993). 3 A S M E Boiler and Pressure Vessel Code (New York: American Society of Mechanical Engineers. DC.2Psfor vessels exposed to fire. in lb. Used by permission of the American Petroleum Institute.

Recommended Practice for the Sizing. Because no other information on the piping system is provided. 6th ed. A relief vent must be installed to vent the nitrogen as fast as it is supplied through the 6-in line. the flow from the pipe is initially assumed to be represented by critical flow through an orifice.392 Chapter 9 Relief Sizing Figure 9-6 Backpressure correction K. The reactor relief is set at 50 psig. 29. (1993). The source of the nitrogen is at 70°F and 150 psig. must be estimated. . Example 9-2 A nitrogen regulator fails and allows nitrogen to enter a reactor through a 6-in-diameter line. p. Solution The nitrogen source is at 150 psig. Selection. The downstream pressure P i s now required. For vapor flows that are not choked by sonic flow the area is determined using Equation 4-48. If the regulator fails. Source: API RP 520. and the discharge coefficient C. and Installation of Pressure-Relieving Systems in Refineries. increasing the pressure to a point where the vessel will fail. Determine the diameter of a balanced-bellows spring-type vapor relief required to protect the reactor from this incident. for balanced-bellows reliefs in vapor or gas service. the nitrogen will flood the reactor. The API Pressure Vessel Code4 provides working equations that are equivalent to Equation 4-48. Recommended Practice. Assume a relief backpressure of 20 psig. Equation 4-50 describes this: 4API RP 520. Used by permission of the American Petroleum Institute. DC. Washington.

= (1. Thus psig (backpressure.. = l .975. The required quantities for Equation 4-50 are P = 150 + 14. Thus P = 69. l P . The maximum relief design pressure within the reactor during the relief venting is. The gas compressibility factor z is approximately 1at these pressures. Kb = 0.7 psia. The constant x is computed from Equation 9-10: . This is a 10% overpressure. we obtain = 3. For diatomic gases the choked pressure is given as (see chapter 4) Pchoked 0.40 for diatomic gases.7 psia.7 psia. however. determined from Figure 9-6. Substituting into Equation 4-50. y = 1. Thus the pressure in the reactor is less than the choked pressure. from Equation 9-12.528)(150 + 14. The effective discharge coefficient is assumed to be 0. X 1W = (z) x 100 = 40%.528P = = (0.- - 9-2 Conventional Spring-Operated Reliefs in Vapor or Gas Service First.psig ) set pressure..7 = 164.86 for an overpressure of 10%. T = 70°F + 460 = 530°R. P. The backpressure is 20 psig.1)(50 psig) = 55.7) = 87.0 psia. The pressure P is the maximum absolute pressure.0 psig = 69./ hr. the choked pressure across the pipe must be determined to ensure critical flow.82 x 10' lb. and the flow from the 6-in line will be critical. From Figure 9-6. The area of the relief vent is computed using Equations 9-9 and 9-10 with a backpressure correction K.

No corrections are suggested. p. The next largest diameter closest to the one required is selected.7psia) The required vent diameter is = (3. 9-4 Rupture Disc Reliefs in Vapor or Gas Service Flow of vapor through rupture discs is described using an orifice equation similar to Equation 9-9 but without the additional correction factors." Chemical Engineering (Feb. x . The procedure is iterative. Manufacturers provide relief devices only at convenient sizes.0. scrubbers.1971).125 in). The result is Equation 9-13 assumes a discharge coefficient C.14) 10.86)(69. a procedure similar to the procedure used for liquid reliefs through rupture discs is required./hr (0. Isaacs5 recommended assuming that the rupture disc is equivalent to 50 pipe diameters in the calculation.82 x 10' Ib. For rupture discs discharging into a relief system (which might include knockout drums. of 1. The calculation to determine the rupture disc area is iterative for this case. This would likely be 1@ in (10. 22.975)(356)(0. the rupture disc is considered a flow restriction. The calculation is performed identically to regular pipe flow (see chapter 4). If appreciable backpressures exist from downstream relief systems. 9-3 Rupture Disc Reliefs in Liquid Service For liquid reliefs through rupture discs without significantlengths of downstream piping the flow is represented by Equation 9-2 or by Equation 9-3 for flow through a sharp-edged orifice. Equations 9-2 and 9-3 apply to rupture discs discharging directly to the atmosphere. "Pressure Relief Systems. or flares). S ~ a rIsaacs.Chapter 9 Relief Sizing The required vent area is computed using Equation 9-9: - 3. and the flow through the entire pipe system must be considered. 113.1 in.

= [38.14) This compares to a spring relief vent area of 1. Solution The pressure drop across the rupture disc is AP = P. part a.Pb = 220 psig .gpm --.0.0 gpm] 0. The vent sizing package (VSP) laboratory apparatus described in chapter 8 provides the much needed temperature and pressure rise data for relief area sizing. . A conservative discharge coefficient of 0. with the exception of a deletion of the correction factor Kb. The solution is identical to Example 9-2.610 J z = The relief vent diameter is 0.. The specific gravity of the water (plp.61 is assumed. two-phase flow should be expected during the relief process. (3. Substituting into Equation 9-3. Solution The solution is provided by Equation 9-9.881 in. The area is therefore The rupture disc diameter is This compares to a spring relief diameter of 9. 9-5 Two-Phase Flow during Runaway Reaction Relief When a runaway reaction occurs within a reactor vessel.32 in.J is 1.10 in. we obtain = in2(psi)"2 200 . .9-5 Two-Phase Flow during Runaway Reaction Relief 395 Example 9-3 Determine the diameter of a rupture disc required to relieve the pump of Example 9-1. Example 9-4 Compute the rupture disc vent diameter required to relieve the process of Example 9-2.61 0.20 psig = 200 psig.

is the change of specific volume of the flashing liquid. The first step in the relief sizing calculation for two-phase vents is to determine the mass flux through the relief. and T. The energy terms include (1) energy accumulation resulting from the sensible heat of the reactor fluid as a result of its increased temperature due to overpressure and (2) the energy removal resulting from the vaporization of liquid in the reactor and subsequent discharge through the relief vent. representing choked two-phase flow through a hole: where. A is the area of the hole. This is computed using Equation 4-104. Figure 9-7 shows the most common type of reactor system.396 Chapter 9 Relief Sizing 2-Phase Flow Re l i e f Device Energy Loss by Vapor iz a t i o n o f Liquid Energy Generated by Reaction 1 I Energy Accumulated by Heating o f L i q u i d Beyond S e t Temperature Figure 9-7 A tempered reaction system showing the important energy terms. It is called "tempered" because the reactor contains a volatile liquid that vaporizes or flashes during the relieving process. is the mass flow through the relief.. . The runaway reactor is treated as entirely adiabatic. This vaporization removes energy by means of the heat of vaporization and tempers the rate of temperature rise resulting from the exothermic reaction. C. for this case. v. called a tempered reactor. is the heat capacity of the fluid. is the absolute saturation temperature of the fluid at the set pressure. Q. is the heat of vaporization of the fluid. The heat losses through the reactor walls are assumed negligible. AH.

Equation 9-14 is the so-called equilibrium rate model (ERM) for low-quality choked flow. "The Discharge of Two-Phase Flashing Flow in a Horizontal Duct. Fauske. Data from J. For a pipe of length 0." Plant Operations Progress (July 1985). 7J. A. The result should be generally applicable to homogeneous venting of a reactor (low quality." AICHE Journal (1987). "Flashing Flows or: Some Practical Guidelines for Emergency Releases." AICHE Journal (1986). "Simplified Vent Sizing Equations for Emergency Relief Requirements in Reactors and Storage Vessels. As the pipe length in- 6H. K. 33(3): 524-527. For two-phase flow through pipes an overall dimensionless discharge coefficient $ is applied. Leung. Grolmes. the value of $ decreases. Leung and M. = 1.9 to bring the value in line with the classic homogeneous equilibrium model (HEM).9-5 Two-Phase Flow during Runaway Reaction Relief Figure 9-8 Correction factor rC. . The mass flux GTis given by Equation 9-14 applies to two-phase relief through a hole. 32(10): 1622. $ creases.6Leung7 showed that Equation 9-14 must be multiplied by a factor 0. C. not restricted to just liquid inlet condition): Values for $ are provided in Figure 9-8. C. 4(3). correcting for two-phase flashing flow through pipes.

398 Chapter 9 Relief Sizing A somewhat more convenient expression is derived by rearranging Equation 4-102 to yield and substituting into Equation 9-15. ." . Details are provided e l s e ~ h e r eThe result is . is the total mass contained within the reactor vessel before relief. we obtain The exact derivative is approximated by a finite-difference derivative to yield where A P is the overpressure and AT is temperature rise corresponding to the overpressure. "Simplified Vent Sizing. q is the exothermic heat release rate per unit mass. V is the volume of the vessel. 8J. C. and C is the liquid heat capacity at constant volume.~ An alternative form is derived by applying Equation 4-102: For Equations 9-19 and 9-20 the following additional variables are defined: m. Leung. The required vent area is computed by solving a particular form of the dynamic energy balance.

uniform froth or homogeneous vessel venting occurs. AHv. 3. where the derivative.4"C = 482. The heat input q resulting from an exothermic reaction is determined using fundamental kinetic information or from the DIERS VSP (see chapter 8). corresponds to the temperature rise at the maximum turnaround pressure.): 209.6"Clmin = 0. and vfg are constant.662 Kls 'Leung. Both derivatives are determined experimentally using the VSP.7"CImin = 0. determine the relief vent diameter required. "Emergency Venting Requirements. Huff. = 29. For data obtained using the VSP. The first term in the denominator corresponds to the net heat removed by the liquid and vapor leaving the system.): 219.16 m3 Reaction mass (m. physical properties Cv. This applies to most reaction systems.4 bar absolute: Data Volume (V): 3500 gal = 13. Example 9-5 Leung9 reported on the data of Huff1O involving a 3500-gal reactor with styrene monomer undergoing adiabatic polymerization after being heated inadvertently to 70°C. The equations assume that 1. Units are a particular problem when using the two-phase equations. "Simplified Vent Sizing. the equation is applied. E.9-5 Two-Phase Flow during Runaway Reaction Relief 399 For both Equations 9-19 and 9-20 the relief area is based on the total heat added to the system (numerator) and the heat removed or absorbed (denominator)." Plant/Operations Progress (1982). The maximum allowable working pressure (MAWP) of the vessel is 5 bar.5"C = 492. l(4): 211 .5 K Data from VSP Maximum temperature (T. the system is a tempered reactor system.): 9500 kg Set temperature (T. 2. particularly when English engineering units are used. the reaction energy per unit mass q is treated as a constant." 1°J. the mass flux GTvaries little during the relief. 4.5 bar and a maximum pressure of 5. denoted by the subscript s. Given the following data.493 Kls (dTldt). = 39. and 5. Assume a set pressure of 4. corresponds to the heating rate at the set pressure and the derivative.7 K (dTldt). the second term corresponds to the heat absorbed as a result of increasing the temperature of the liquid because of the overpressure. denoted by the subscript m. The best procedure is to convert all energy units to their mechanical equivalents before solving for the relief area.

5 = 10.400 Chapter 9 Relief Sizing Physical Property Data 4.001388) m3/kg [ I (kg m/s2)/N] (2470 Jlkg KX482.9)(1.5 K)[1 (N m)/Jl The relief vent area is determined from Equation 9-19.600 J/kg)[l (N m)/J] X (0.482.4-bar peak Solution The heating rate q is determined using Equation 9-21: Assuming that C. The change in temperature AT is Tm.T.0: = (0. Assuming LID = 0.0.2 K: The required relief diameter is .7 .$ = 1. we have The mass flux is given by Equation 9-15. = 492.08553 . = C.5-bar set 5..0) (310.

32) [ I (kgm/s2)/~](104 kglkg-mol) This requires a relief device with a diameter of 0. the result would be physically incorrect and the reactor would be severely tested during this runaway event. a significantly smaller diameter than for two-phase flow.176 m. Then (8314 Pa m3/kg-mol K)(482.0. Fauske. if the relief were sized assuming all vapor relief." Plant/Operations Progress (1984). 3(4). = 1.600 Jlkg) Equation 9-6 provides the required relief area. At the set temperature the heat release rate q is The vapor mass flow through the relief is then - (1218 Jlkg s)(9500 kg) (310. Thus.9-5 Two-Phase Flow during Runaway Reaction Relief 401 Suppose that all vapor relief was assumed. Assume that y = 1. Simplified Nomograph Method Fauske l1 developed a simplified chart-driven approach to the two-phase reactor relief problem." Plant/Operations Progress (1984).32 and C. and "Generalized Vent Sizing Nomogram for Runaway Chemical Reactions. The size of the required vapor phase rupture disc is determined by assuming that all the heat energy is absorbed by the vaporization of the liquid.5 K)[1 (N/m2)/Pa) X d r (1. . He suggested the following equation for determining the relief area: "Hans K. The molecular weight of styrene is 104. "A Quick Approach to Reactor Vent Sizing. 3(3).

C. is the energy release rate per unit mass at the set pressure of the relief system. and q. Boyle Jr. and 9-23 yields Equation 9-24 provides a conservative estimate of the required vent area. is the heat capacity. and assuming a saturated water relationship.9-14. 63(8): 61. assuming a typical liquid heat capacity of 2510 J/kg K for most organic materials. By considering the case of 20% absolute overpressure.402 Chapter 9 Relief Sizing where A is the relief vent area. p is the density of the reactants. 6(2). K. The mass flux GTis given by Equation 9-15 or 9-18. . V is the reactor volume. GTis the mass flux through the relief. 135. Combining Equations 9-22. C.." Plant/Operations Progress (April 1987). and the venting time is given approximately by where AT is the temperature increase corresponding to the overpressure AP. T is the temperature. and Atvis the venting time. Leung and H." Chemical Engineering Progress (August 1967). Fauske. "Runaway System Characterization and Vent Sizing Based on DIERS Methodology. we can obtain the following equation 13: A = (m2/1000kg) = Ps(baI-1 "w. "Sizing Relief Area for Polymerization Reactors. Equation 9-22 was developed by Boylel"y defining the required vent area as the size that would empty the reactor before the pressure could rise above some allowable overpressure for a given vessel. J.

" Plant/Operations Progress (1984). requires a suitable correction. Fisher and J. as shown in the following example. and the mass of reactants. Used by permission of the American Institute of Chemical Engineers. . Recent studies14suggest that the nomograph data of Figure 9-9 apply for a discharge coefficient of = 0. The Fauske nomograph is useful for performing quick estimates and for checking the results of the more rigorous computation. C. Leung. K. 100 OC/min Figure 9-9 Nomograph for sizing two-phase reactor reliefs.9-5 Two-Phase Flow during Runaway Reaction Relief 403 I 1 0 SELF HEAT RATE. + 14H. the set pressure. 3(4). personal communication. The required vent area is determined simply from the heating rate. "Generalized Vent Sizing Nomogram for Runaway Chemical Reactions. Source: H. representing a discharge (LID) of 400. Fauske. G. A simple nomograph of the results can be plotted and is shown in Figure 9-9. January 1989. Use of the nomograph at other discharge pipe lengths and different rC.5.

as shown in Figure 9-10. Two-phase flow through reliefs is much more complex than the introduction provided here. This result compares to a more rigorously computed area of 0. = 1.9869bar/atm)(l4. Furthermore. they d o represent the most accepted method available today. The result can be adjusted for other overpressures by multiplying the area by a ratio of 20/(new absolute percentage of overpressure). A n uncontrolled dust explosion in a warehouse. substantial quantities of flammable dust are produced.- - - - 404 Chapter 9 Relief Sizing Example 9-6 Estimate the relief vent area using the Fauske nomograph approach for the reaction system of Example 9-5.Thus the From Figure 9-9 the vent area required per 1000 kg of reactant is about 1. the technology is still undergoing substantial development. m2/1000kg)(9500 kg) Figure 9-9 is applicable for 9 = 0. o r processing unit can eject high-velocity structural debris over a considerable area. The blowout panel is designed to have less strength than the walls .5 bar)(0. Solution The heating rate at the set temperature is specified as 29. However. for some situations hazards are unavoidable. The set pressure is 4.0 the area is adjusted linearly: This assumes a 20% absolute overpressure. The equations presented here are not universally applicable. propagating the accident and resulting in increased injuries. however. For IC. For example. during the milling process to make flour from wheat.6"C/min. = (4.3 psia.098 m2. so P.5 bar absolute. 9-6 Deflagration Venting for Dust and Vapor Explosions Loss prevention means preventing the existence of hazards.5.7 psialatm) = 65.03 X 0. The energy of the explosion is directed away from plant personnel and equipment. Deflagration venting in buildings and process vessels is usually achieved by using blowout panels.03 X total relief area is A = = (1. Deflagration venting reduces the impact of dust and vapor cloud explosions by controlling the release of the explosion energy. storage bin.084 m2. m2.

depending on a number of design factors. Damage to the remaining structure and equipment is minimized. of the structure. thermal insulation of panels is also required. the maximum overpressure allowable in the structure. Thus. and the volume of the structure. A detached blowout panel moving at high velocity can cause considerable damage. Construction details are available in manufacturers' literature. For particularly explosive dusts or vapors. . Guidefor Venting of Depagrations (Quincy. the blowout panels are preferentially detached and the explosive energy is vented. These include the explosive behavior of the dust or vapor. Blowout panels are designed to provide the proper relief area. Design standards are available. R e d u c i n g O v e r p r e s s u r e and R e s u l t i n g Damage Vent Figure 9-10 Deflagration vents for structures and process vessels. 1998). M A : National Fire Protection Association. during an explosion. The actual construction details of blowout panels is beyond the scope of the text.9-6 DeflagrationVenting for Dust and Vapor Explosions 405 n J D u s t o r Vapor Explosion Occurs Structure Attachment o f Vent P r e v e n t s P r o j e c t i o n o f Vent D e b r i s D e f l a g r a t i o n V e n t Opens. it is not unusual for the walls (and perhaps roof) of the entire structure to be constructed of blowout panels.'" l5 N F P A 68. Furthermore. Therefore a mechanism must be provided to retain the panel during the deflagration process.

and P i s the maximum internal pressure that can be withstood by the weakest member of the enclosure. .101. including many important combustion features: where A is the required vent area. p. ed. L. and so forth that are capable of withstanding pressures greater than 1. Low-pressure structures include structures with sheet metal sides and other lowstrength building materials. 16Richard R. Swift and Epstein17 presented a more detailed equation. Woodward. Vents for Low-Pressure Structures For low-pressure structures that are capable of withstanding pressures of not more than 1. is the inside surface area of the enclosure.1 bar gauge). is L. High-pressure structures include steel process vessels. 3." Plant/Operations Progress (April 1987). is the second smallest dimension of the enclosure to be vented.5 psig (0.Chapter 9 Relief Sizing Deflagration design is segregated into two categories: low-pressure and high-pressure structures. concrete buildings. "Performance of Low Pressure Explosion Vents. "Recent Developments in Deflagration Venting Design. is the smallest dimension of the rectangular building structure to be vented. 6(2).*.. A.1 bar gauge). John L. 1987). original design techniques were based on the Runes (pronounced Rooness) equation16: where A is the required vent area. 171an Swift and Mike Epstein..5 psig (0.1 bar gauge). Schwab. These structures are capable of withstanding not more than 1.5 psi (0." in Proceedings of the International Symposium on Preventing Major Chemical Accidents.a constant that depends on the nature of the combustible material. C. (New York: American Institute of Chemical Engineers.

51 INFPA.. is the laminar burning velocity. C. is the maximum unvented explosion pressure.10 0..17 0.3times that of propane. The liquids are expected to have fundamental burning velocities less than 1.14 Cvent (m) 0. Estimate the vent area required for this operation. M A : National Fire Protection Association. 1998). S . p. P. is the final peak pressure during the vent.13 0. The fourth and larger wall of the room is on the outer surface of the structure. is the density of the unburned gas.20 0.3 times that of propane St-1 dusts St-2 dusts St-3 dusts (m) 0. Three of the walls are shared with an adjoining structure.. G is the mass flux. P.30 0. These variables are regrouped to result in the following form: where P i s the maximum internal overpressure that can be withstood by the weakest structural element.05 bar.. Equation 9-28 is remarkably similar to the Runes equation (Equation 9-26). Many of the variables in Equation 9-27 can be estimated or assumed.Venting of Deflagrations (Quincy. The room is 9 m long by 6 m wide by 6 m in height.12 0.37 Gent 0. Pois the initial pressure. h is the turbulent augmentation factor. Values for the constant C.26 0. are given in Table 9-1. The three inside walls are capable of withstanding a pressure of 0.is the discharge coefficient.05 0.45 0. Example 9-7 A room is used for dispensing flammable liquids. and y is the heat capacity ratio.- - 9-6 Deflagration Venting for Dust and Vapor Explosions Table 9-1 Combustible Characteristic Constant for the Swift-Epstein Equation1 Combustible material Anhydrous ammonia Methane Aliphatic gases (excluding methane) or gases with a fundamental burning velocity less than 1.. .

1998).45 Equation 9-28 is used to estimate the required vent area. This would reduce the vent area required. is the maximum pressure increase. Kst is the deflagration index for dusts. The vent design is based on the definition of a deflagration index for gases or dusts: KG or Kst = (s) V113.18The length-to-diameter ratio LID of the enclosure determines the equation(s) used for calculating the necessary vent area.. MA: National Fire Protection Association. where A is the cross-sectional area normal to the longitudinal axis of the space. The venting constant for this flammable vapor is provided in Table 9-1 and has a value of 0. The total surface area of the room (including floor and ceiling) is m. For noncircular enclosures the value used for the diameter is the equivalent diameter given by D = 2 . max where KG is the deflagration index for gases and vapors.408 Chapter 9 Relief Sizing Solution The vent must be installed on the larger outer wall to vent the combustion away from the adjoining structure.5 psig (0. (dPldt). We discussed the experimental procedure used to determine the deflagration indexes for gases and dusts in chapter 6. The required vent area is This is larger than the area of the outer wall. .. and V is the volume of the vessel. One option is to strengthen the three inner walls to withstand a higher pressure. Extensive testing with dusts and vapors has resulted in a detailed set of empirical equations for the relief vent area (published as NFPA 68). Guidefor Venting of Deflagrations (Quincy. Tables of typical values were also provided. I8NFpA68.1 bar gauge). Vents for High-Pressure Structures High-pressure structures are capable of withstanding pressures of more than 1. determined experimentally.

Equation 9-30 has the following restrictions on its use: KG is less than 550 bar-mls. P.5 bar. P... and V is less than 1000 m3. is less than 2 bars.25. is the vent release pressure (bar).4. NFPA 68 must be consulted..1 bar to 0. initial pressure atmospheric.. is the vent area (m2). is less than 0. and 250 m3with an LID for all test vessels of approximately 1. ranging from 0. the following equation from NFPA 68 applies: where A. quiescent gas mixture at time of ignition with no turbulence inducers..- - - - 9-6 Deflagration Venting for Dust and Vapor Explosions For combusting vapors discharging through a low inertial vent and an enclosure LID of less than 2. For LID values greater than 5... The experimental conditions under which Equation 9-30 was developed are as follows: vessel volumes of 2. For enclosures with LID ranging from 2 to 5 the area calculated using Equation 9-30 is adjusted using where AA is the adjustment to the vent area of Equation 9-30 (m2)... and LID is the length to diameter ratio of the enclosure (unitless).. and P. .. and P. ignition energy of 10 J.5 bar. P.10. KG is the deflagration index for the combusting gas (bar-mls)... is the maximum pressure during venting (bar).. KG is the vapor deflagration index (bar-mls).

. 0. The following limitations apply to Equation 9-32: for Kst between 10 and 300 bar-mls..5 bars (22 psi). PI. is the vent release pressure (bar). For P. P.758)log -.1 and 10.) and that the KG of the vapor is 100 bar-mls.. Estimate the vent area required to protect this enclosure. and V is the volume of the enclosure (m3). NFPA 68 must be consulted. for Ks... must be between 5 and 12 bars. Example 9-8 Consider again the flammable liquid dispensing room of Example 9-7... P. low values of PI..000 m3. P.1 and 2 bars.. must be between 0.. the additional vent area is large. P...1 and 1bar. For long pipes and ducts where LID is greater than 6. is the maximum pressure reached during deflagration of an optimum mixture of combustible dust and air in a closed vessel (bar). The longitudinal axis runs the 9 m length of the room..305 log Pred+ 0. P..2 bar (P.4 bar (Pred). is the maximum pressure during venting (bar).(-4.. For LID values equal to or greater than 2 but less than 6 and for Predless than 1. the enclosure volume must be between 0. is the vent area (m2).. must be between 0. Thus D = .. In this case the walls have Assume that the vent will operate at been reinforced to withstand a pressure of 0. Solution The LID ratio must first be determined for this enclosure. the following equation from NFPA 68 applies: where A... the vent area of Equation 9-32 is increased by. D (9-33) For The adjusted vent area (Equation 9-33) is sensitive to Pred.410 Chapter 9 Relief Sizing For venting of combustible dusts through a low inertial vent and an enclosure LID of less than 2. Pmax must be between 5 and 10 bars. The cross-sectional area normal to this axis is (6 m)(6 m) = 36 m2. between 300 and 800 bar-m/s. values of 1. L AA = A. Kst is the dust deflagration index (bar-mls).5 bars and higher Equation 9-32 should be used alone.

as shown in Figure 9-11.2 .127 log 100 .4)-~. we obtain A. 9-7 Venting for Fires External to Process Vessels Fires external to process vessels can result in heating and boiling of process liquids. We discussed the experimental procedure to determine these values and also provided tables of typical values for gases and dusts in chapter 6. Venting is required to prevent explosion of these vessels. Two-phase flow during these reliefs is possible but not likely.4)-~. Two-phase flow during fire relief can therefore be prevented by providing a suitable vapor space above the liquid within the vessel. KG or Ks.0.~~~(0. The volume of the enclosure is (9 m)(6 m)(6 m) = 324 m3. Venting is required to f prevent vessel rupture. s . For runaway reactor reliefs the energy is generated by reaction throughout the entire reactor liquid contents. For heating caused by external fire the heating occurs only at the surface of the vessel. Substituting into Equation 9-30.3.1)](324)~'~ More than adequate area exists on the outer wall of the enclosure to accommodate this vent.77 m. = [(0. Both vent sizing methods for gases and dusts require values for the deflagration indexes. Then LID = 9 m16. Thus liquid boiling will occur only next to the wall. Pressure i n Vessel B u i l d s Due t o I n c r e a s e d r Pressure and/or rnposition Products Figure 9-11 Heating o a process vessel a s a result of an external fire. and it follows that Equation 9-30 applies without further correction.rr = 6.175(0.- - 9-7 Venting for Fires External to Process Vessels 21/(36 m2)/.~~~ + 0.77 m = 1.0567)(0.0. For most fires only a fraction of the external vessel i exposed to fire. and the resulting two-phase foam or froth at the liquid surface will not have a substantial thickness.

and NFPA 30. is the volume difference between the vapor and liquid phases. "Sizing Relief Valves for Fire Emergencies. 1 9 9 . (Washington.. is the liquid mass in the vessel.2~ analysis of the various standards." Chemical Engineering (Oct. This assumes a constant heat input rate Q: where T. is the heat of vaporization of the liquid. T.106 criterion20 is mandatory. . "Simplified Vent Sizing Equations. m. DC: US Department of Labor. ~ ~ ' 1000 < A < 2800. is the maximum temperature in the vessel. GTis the mass flux through the relief. A is the area of the relief. Flammable and Combustible Liquids Code (Quincy. A.For the special case of no overpressure. (9-36) I9Leung. Other standards are also a ~ a i l a b l eCro~ier.412 Chapter 9 Relief Sizing Two-phase fire relief equations are available for conservative design.OOOA for 20 < A < 200. 21API Standard 2000. Leung19presented an equation for the maximum temperature based on an energy balance around the heated vessel.106. T. MA: National Fire Protection Association. For regulated materials the OSHA 1910. 1996). and AH. is the set temperature corresponding to the set pressure. Flammable and Combustible Liquids (Washington. = T. Venting Atmospheric and Low-Pressure Storage Tanks (Nonrefrigerated and Refrigerated). ~ Q = 9 3 6 .. 28. The solution to Equation 9-34 for GTAis done by an iterative or trial-and-error technique. 4 0 0 ~ ~ . recom. In this case the correct solution is the minimum mass flux GT. Equation 9-34 is likely to produce multiple roots. v. 3 0 0 ~ ' . 2000). 22R..~~ after mended the following equations for determining the total heat input Q: Q Q = = 20. 1998. ~ ~for 200 < A < 1000. DC: American Petroleum Institute.1985).000~'. Cv is the heat capacity at constant volume.'~ for A > 2800.." ZOOSHA1910. and Equation 9-34 reduces to Various relationships have been recommended for computing the heat added to a vessel that is engulfed in fire. for Q = 21. Q is the constant heat input rate. Crozier. 5th ed. V is the volume of the vessel.

23APIR P 520. "Fires. 6th ed. API 52OZ3 suggests a slightly different approach to estimate the heat flux to process equipment as a result of a fire." Chemical Engineering (May 2000). 1993). WongZ4 mine this and provided a number of equations for various vessel geometries. (Washington. and Installation of Pressure-Relieving Devices in Refineries. and Q is the total heat input to the vessel (in Btulhr). A number of values for various insulation thicknesses are shown in Table 9-2. for horizontal tanks. Wong. 24W.9-7 Venting for Fires External to Process Vessels 413 Table 9-2 Environment factors F for Equations 9-37 and 9-38 Insulation thickness (in) Environment factor F where A is the area absorbing heat (in ft2) for the following geometries: for spheres. . DC: American Petroleum Institute. and the Pressure Relief Valve. F is an environment factor (unitless). If prompt fire fighting is available and if the flammable material is drained away from the vessel. The surface area A is the area of the vessel wetted by its internal liquid with a height less provided considerably more detail on how to deterthan 25 ft above the flame source. Vessels.Y. Selection. 75% of total exposed area. 55% of total exposed area. for vertical tanks. then the heat flux is estimated using If adequate fire fighting and drainage do not exist. Sizing. then the following equation is used: where Q is the total heat input through the surface of the vessel (Btuthr). 100% of total exposed area for first 30 ft. and A is the total wetted surface of the vessel (ft2). The mass flux GTis determined using Equation 9-15 or 9-18. The environment factor F is used to account for vessel protection from insulation.

The total heat input is found using Equation 9-36: If we use Equation 9-37 and assume that the vessel is full of liquid.55)(1121 ft2) = 616 ft2. The vessel has a volume of 100 m3 and contains 50. + 25Leung.82 6.5 K.14) ] = 5. This corresponds to a set temperature. The surface area of the sphere is The area exposed to heat is given by the geometry factors provided with Equation 9-36: A = (0.0.000)(1. The diameter of the sphere is d = (?)"'= [ (6)(100 m") (3.0)(1121ft2)0. A set pressure of 4. Then Q = 2 1 . The molecular weight of propane is 44.0. then the entire vessel surface area is exposed to the fire. From Equation 9-15 and assuming = 1.414 Chapter 9 Relief Sizing Example 9-9 Leung2"eported on the computation of the required relief area for a spherical propane vessel exposed to fire. then F = 1." . we obtain X lo6 Btulhr. Solution The problem is solved by assuming no overpressure during the relief.74 X 105J/kg. 0 0 0 ~ A ~ " (21.65 = ~ = which is close to the value estimated using Equation 9-36.76m. 3. = X 103 J/kg K.41 AH."Simplified Vent Sizing Equations. based on the saturation pressure. of 271.700 kg of propane. At these conditions the following physical property data are reported: Cp = CV= 2.5 bars absolute is required. If we also assume that no insulation is present. The relief vent area calculated is larger than the actual area required for a real relief device with overpressure.

Relief vents are installed in these systems to prevent damage resulting from liquid expansion. and repairs are time consuming. To size the relief for fire and a single-vapor phase. leading to damage to the cooling coils. shown in Figure 9-12. This assumes that all the heat input from the fire is used to vaporize the liquid. An alternative way to look at the problem might be to ask the question.9-8 Reliefs for Thermal Expansion of Process Fluids 415 The required vent area is determined from Equation 9-35: The required diameter is = 0.308 m = 12. Although this may appear to be a minor problem. A typical situation is thermal expansion of water in cooling coils in a reactor. What initial fill fraction should be specified in the tank to avoid two-phase flow during a fire exposure incident? No tested correlations are presently available to compute the height of a foam layer above the boiling liquid. p. and (4) large repair expenses. (2) subsequent corrosion problems. For fire reliefs with single-phase vapor flow the equations provided in sections 9-2 and 9-4 are used to determine the size of the relief. is defined as . The expansion will damage pipes and vessels if the pipe or vessel is filled completely with fluid and the liquid is blocked in.1 in. and determine the vapor mass flow rate through the relief by dividing the heat input by the heat of vaporization of the liquid. (3) substantial plant outages. the water will expand when heated by the reactor contents. As mentioned previously. A thermal expansion coefficient for liquids. use the heat input determined from Equations 9-36 to 9-38. If the coils are filled with water and are accidentally blocked in. The relief area is then determined using Equations 9-3 to 9-12. damage to heat exchange systems can result in (1) contamination of product or intermediate substances. two-phase flow discharges for fire scenarios are possible but not likely. Failure in heat exchange equipment is also difficult to identify. 9-8 Reliefs for Thermal Expansion of Process Fluids Liquids contained within process vessels and piping will normally expand when heated.

an energy balance on the fluid is given by mC. The volumetric expansion rate Q.416 Chapter 9 Relief Sizing Hot Proce L i q u i d I n Cool ing Water Cool ing Wa ter B o t h Wate Va I v e s C l o s e d Out In- A -Coo I i n g Co i l s F i l l e d with Liquid Heat Transfer from Hot Vessel F l u i d t o Cool ing L i q u i d Increases Cool ing L i q u i d Temperature Leading t o Thermal Expansion. through the relief resulting from thermal expansion is By applying the definition of the thermal expansion coefficient. . Coefficients for water are readily determined from the steam tables. we obtain For a pipe or process vessel heated externally by a hot fluid. given by Equation 9-39. Figure 9-12 Damage to cooling coils as a result of external heating of blocked-in cooling fluid. Table 9-3 lists thermal expansion coefficients for a number of substances. after which the thermal expansion coefficient increases with temperature.- dT dt = UA(T - T. Water behaves in an unusual fashion.). where V is the volume of the fluid and T is the temperature. The thermal expansion coefficient decreases with increasing temperature up to about 4"C.

UA is an overall heat transfer coefficient. = -UA(T - T. (Englewood Cliffs. sufficient for sizing a relief device. 1965).9-8 Reliefs for Thermal Expansion of Process Fluids 417 Table 9-3 Liquid Thermal Expansion Coefficients for a Variety of Liquids1 Density at 20°C (kg/m3) 791 792 877 1. . invoking the definition of the liquid density p. where T is the temperature of the fluid.= -(T dT dt UA mCp .). NJ: Prentice Hall. p. and. Cpis the heat capacity of the liquid.595 714 1. = -UA(T PV - ~ C P T. Shortley and D. Q. and T.261 13. ethyl Alcohol. 4th ed. changing the value of T However. is the ambient temperature. The volumetric expansion rate Q. when the fluid is initially exposed to the external temperature T.T.. we obtain Q. is subsequently used in an appropriate equation to determine the relief vent size. ethyl Glycerin Mercury Turpentine lo-5 lo-' lo-' lo-s lo-' lo-s lo-s 'G. Williams. 302. The heat transfer will increase the temperature of the liquid.).546 873 Thermal expansion coefficient ("C-') 112 x 120 x 124 X 124 x 166 X 51 X 18. Elements of Physics. it is apparent that Equation 9-45 provides the maximum thermal expansion rate.). It follows that . Equation 9-45 describes the fluid expansion only at the beginning of heat transfer.2 x 97 x Alcohol. Substituting into Equation 9-41. methyl Benzene Carbon tetrachloride Ether.

estimate the volumetric expansion rate of the water in the cooling coils in gpm. the steam tables do not provide liquid water specific volume data below 32°F.Given a heat transfer coefficient of 50 Btulhr-ft2-OF. A value between 32°F and some appropriate higher temperature will suffice. The relief device vent area must be designed to accommodate this volumetric flow.418 Chapter 9 Relief Sizing Example 9-10 The cooling coil in a reactor has a surface area of 10. Solution The expansion coefficient P for water at 32°F should be used. This is estimated using liquid volumetric data from the steam tables over a short range of temperatures around 32°F. Under the most severe conditions the coils can contain water at 32OF and can be exposed to superheated steam at 40OoF. Suggested Reading Deflagration Vents W." Plant/Operations Progress (October 1986). "Pressure Venting of Dust Explosions in Large Vessels. . From the steam tables: Temperature (OF) Specific volume (ft3/lb.) The expansion coefficient is computed using Equation 9-39: The volumetric expansion rate is given by Equation 9-45: = 102 ft3/hr = 12. 5(4): 196. However.000 ft2. Bartknecht.7 gpm.

H. "DIERS Research Program on Emergency Relief Systems. Huff. "Performance of Low Pressure Explosion Vents. ASME Boiler and Pressure Vessel Code (New York: American Society of Mechanical Engineers." Plant/Operations Progress (July 1985). G. . K. Ian Swift and Mike Epstein. NFPA 68. 32(10): 1743. 1990)." Chemical Engineering Progress (February 1999). Shaw. K. Boicourt." Chemical Engineering Progress (August 1985). Guide for Pressure-Relieving and Depressurizing Systems. Muller. DC: American Petroleum Institute. H. DC: American Petroleum Institute. K. p. C. (Washington. S. Fauske and J. (Washington. "Simplified Vent Sizing Equations for Emergency Relief Requirements in Reactors and Storage Vessels." AICHE Journal (October 1986). H. "Emergency Relief System (ERS) Design: An Integrated Approach Using DIERS Methodology. 6(2). 14(2). E. Noronha. Leung. 5th ed. S. H. H. "A Generalized Correlation for One-Component Homogeneous Equilibrium Flashing Choked Flow." Chemical Engineering Progress (August 1985). DC: American Petroleum Institute.Suggested Reading 41 9 Frank T. 1998). Bodurtha. C. Huff. K. R. "Generalized Vent Sizing Nomogram for Runaway Chemical Reactions. J. 32(10): 1622. API Standard 2000. "Flashing Flows or Some Practical Guidelines for Emergency Releases." Chemical Engineering Progress (February 2000). 3(4). A. Grossel. J. Fauske. J. 1998). "Properly Sized Vents for Nonreactive and Reactive Chemicals. 3d ed. Forrest. 6th ed. API RP 521. Recommended Practice for the Sizing. A. Venting Atmospheric and Low-Pressure Storage Tanks (Nonrefrigerated and Refrigerated). Fauske. "Design Charts for Two-Phase Flashing Flow in Emergency Pressure Relief Systems. "Determine Two-Phase Flows During Release. H. Fauske. 1992). MA: National Fire Protection Association. D. 33. Fauske. and R. Fauske. K. Fisher. "Emergency Relief System (ERS) Design. A. Industrial Explosion Prevention and Protection (New York: McGraw-Hill. Tilley. Selection. Two-Phase Flow G. and Installation of Pressure Relieving Systems in Refineries. (Washington. Leung. First and J." Plant/Operations Progress (April 1987)." Chemical Engineering Progress (August 1985). S." AICHE Journal (October 1986). H. 1998). "New Experimental Technique for Characterizing Runaway Chemical Reactions. H. Harold G." Plant/Operations Progress (October 1984). E. Fisher. 1993). W." Paper presented at 1988 AICHE Spring National Meeting. Relief Codes API RP 520. K. C. Guide for Venting of Deflagrations (Quincy. E. K. J. Leung. Emergency Relief System Design Using DIERS Technology (New York: American Institute of Chemical Engineers. 1980). J." Process Safety Progress (April 1995).

C. "A Generalized Correlation for Flashing Choked Flow of Initially Subcooled Liquid. A.420 Chapter 9 Relief Sizing J. 50 Set OverBackpressure pressure pressure (psig) (%I ("/. and the temperature is 100°F. 34(4): 688. C. Liquid flow (gpm) a. Determine the required diameter for rupture discs for the following conditions. C. A. Estimate the diameter of spring-type liquid reliefs for the following conditions: Pump capacity at AP (gpm) a. Leung and H." AICHE Journal (April 1988). Grolmes. 200 c. Determine the diameter of a spring-type vapor relief for the following conditions. "The Discharge of Two-Phase Flashing Flows in a Horizontal Duct.2 for all cases.I 9-3.I 50 100 50 20 20 10 10 30 40 Valve tY Pe Conventional Balanced-bellows Balanced-bellows (~I~ret) 1. Grolmes. 33(3): 524." AICHE Journal (March 1987).2 9-2. J. Problems 9-1.3. 100 Pressure drop (psi) 100 100 50 50 . O 1. Compressibility. Leung and M. J." Journal of Loss Prevention (April 1989).3 1. 1000 b. Leung and M. Assume a specific gravity of 1. the set pressure is 100 psia. "Two-Phase Flow Venting from Reactor Vessels. 2(2): 78. Molecular z weight Mass flow (Iblhr) Overpressure (%I Backpressure ("/. 1000 d. 100 b. Fisher. Assume for each case that y = 1. G. 100 c.

ft3 Set pressure.4 1.66 0..1 130 10. Determine the required diameter for rupture discs in vapor service for the following conditions.4 1. 200 Pressure (psi@ 100 100 50 50 9-5.52 .000 500 100 500 0.0 140 550 2. How is the overpressure included in the design of two-phase reliefs? 9-7. Determine the relief vent areas for the following two-phase fire scenarios. Assume that nitrogen is the vent gas and that the temperature is 100°F. ft3/lb Vapor specific volume. Ib Set pressure. 200 c.000 500 100 500 2. psia Set temperature.6 0. Assume a spherical vessel in each case.0 120 520 2. 100 d.02 1.000 100 220 150 275 150 1.4 1.000 500 100 500 2..6 0.1 130 10.2 1. O F Maximum pressure.. Assume in all cases that LID = 0. Reaction mass. Btullb "F 72 5000 30.. Molecular weight Volume.5 120 520 0.02 1.000 200 100 500 0. Btullb v.6 0.6 0. Determine the proper relief diameter for the following two-phase flow conditions.4 1.0. "Fls Maximum pressure. psia Maximum temperature. "F (dTldt).6 0.4 0. O F (dTldt). Ib Volume. ft" Initial mass. Gas flow (Iblhr) a.000 100 220 130 240 150 1.000 100 220 100 220 130 1.66 0. ftylb Heat capacity. 100 b..02 1.Problems 9-4.1 130 10.5 120 520 0.000 100 220 100 220 130 1. O F Heat of vaporization.40 86 5000 15. Btullb "F Heat of vaporization. psia Set temperature.40 72 5000 15.52 86 5000 15. "Fls Liquid specific volume.1 130 9-6. psia Maximum temperature. Btullb 10. ft"/lb C.

4 ft in diameter and 10 ft long.4 Volume. 9-11.000 550 70 75 10. If the heater is equipped with a 150-psia spring relief device. 9-13. part a.6 1000 1 16.7 29.7 17.422 Chapter 9 Relief Sizing 9-8. Assume no overpressure. Btulhr ft2O F 10. psia Gas Dusts - Methane a - Hydrogen b - Methane c - Hydrogen d - Volume.000 550 50 75 10.6 1000 3 16.7 29.7 20.000 800 32 75 10. A cylindrical tank.7 29. ft" Set pressure. Assume a set pressure of 500 psig. Also compute the relief vent size assuming all vapor relief.12 x 10-3/0C. ft3 Dust class Set pressure.6 c 1000 16. ft2 Maximum temperature. Home hot water heaters contain relief devices to provide protection in the event that the heater controls fail and the water is heated to a high temperature. is completely filled with water and blocked in. Estimate the thermal expansion rate of the water if the water is at 50°F and . and its density is 791 kg/m3. compute the area required for relief. This time use alcohol as a liquid medium with a thermal expansion coefficient of 1.The heat capacity of the alcohol is 0.000 Btulhr.7 20. Assume 20% backpressure. psia Maximum pressure. Determine the size of relief required to protect the following cooling coils against thermal expansion. Determine the relief size required. "F Heat transfer coefficient. A process vessel is equipped with a 2-in rupture disc set at 100 psig and designed for 10% overpressure. and no backpressure. Assume that the tubes can withstand a pressure of 1000 psig and that the normal operating pressure is 200 psig. 9-12.4 1000 3 16. Hint: Two-phase flow is expected.58 kcallkg "C.6 b 1000 16. Determine the relief size for spray dryers operating under the following conditions: Vapors a 1000 16. psia 1000 1 16. "F Minimum temperature. Blocked-in area. Water is used for each case.7 17.4 9-9. psia Maximum pressure. Consider Problem 9-9.4 d 1000 16.000 550 70 125 9-10. What size line would you select if the nitrogen is available from a 500-psig source? The temperature is 80°F. A nitrogen line must be added to the vessel to provide the capability of purging and/or pressure discharging liquids. an overpressure of 20%.7 29. A typical water heater contains 40 gal of water and has a heat input of 42.

A pressure relief system must be designed to protect the beverage bottle from overpressure.. 9-14. what is the required relief area? Assume no overpressure. A spray dryer is used to dry vitamins in powder form. Assume that the vent opens at 0. bottle. assuming a set pressure of 20 psig and an overpressure of 10%. Must two-phase flow be considered? c. 9-16. . One way to solve the problem is to install an orifice plate in the nitrogen line. A beverage dispensing system consists of a bottle of beverage. system to keep the beverage pressurized. b. Your calculations show that the maximum discharge rate of nitrogen through the existing relief system of the vessel is 0. and a 0. The cone is 5 ft long. and a CO.5 kgls. You are currently reviewing the scenario involving the failure of a nitrogen regulator that provides inert padding to the vapor space of the reactor. A 10-ft wide by 10-ft long by 10-ft high shed is used to store tanks of methane. 9-17. The tank MAWP is 200 psig.- - Problems 423 the steel shell of the tank is suddenly heated to 100°F by the sun.5-in (internal diameter) plastic hose connects the regulator to the beverage bottle.. Assume a heat transfer coefficient of 50 Btulhr ft2 "F and that only the top half of the tank is heated. system includes a small bottle of high-pressure liquefied CO.5 bar gauge. Also assume a spring-type relief. thus limiting the flow to the maximum of 0. The CO. Thus under the current configuration a failure of the nitrogen regulator will result in an overpressuring of the reactor. and a regulator to regulate the gas pressure delivery to the beverage. a. Assume a temperature of 80°F. Assume a nitrogen source supply pressure of 15 bar absolute.5 kg/s. The liquefied CO. The dryer consists of a cylindrical section 12. Determine the vent area required. However. The relief device will be installed in the C 0 2line where it enters the beverage container.1 psig. and a regulator set at 9 psig.2 bar gauge and that the maximum pressure is 0. If the tank is exposed to fire. a 5-lb bottle of liquefied CO. a dispensing hose with valve. The regulator is connected directly to the CO. What deflagration vent area is required? Assume a maximum internal overpressure of 0. If the deflagration index for the vitamin powder is 80 bar mls.75-gal beverage bottle. saturation vapor pressure is 800 psia.0 ft high and 5 ft in diameter. your calculations also show that the flow of nitrogen through the l-in supply pipe will be much greater than this. A typical beverage system contains a 7. determine the area required for a deflagration vent. The ambient temperature is 25°C and the ambient pressure is 1atm. You have been assigned the task of reviewing the relief scenarios for a specific chemical reactor in your plant. 9-15. Determine the most likely scenario contributing to overpressure of the beverage container. Attached to the bottom of the cylindrical section is a cone section for collecting the dried powder. Determine the orifice diameter (in cm) required to achieve this flow.

and a conventional spring-operated relief. 9-19. If the pump continues to operate. A 1-in (internal diameter) pipe is used to supply water to a low-pressure tank with an MAWP of 20 psig. 10 ft long and 3 ft in diameter. the reactor might be overfilled and overpressurized. MAWP of 200 psig. A batch chemical reactor contains 10. the heat of vaporization is 92.4 Btullb. The physical properties of the material are also reported: Heat capacity of liquid: 2. Assume that the discharge length is greater than 10 cm. and the heat capacity ratio of the vapor is 1. 9-23.5 kJ/kg K Heat of vaporization: 300 kJ/kg Molecular weight: 100 Vapor acts as an ideal triatomic gas. 9-20. Determine the maximum vaporization rate during a runaway reaction (in kgls). Determine the relief diameter (in m) required to vent the runaway reaction. conventional spring-operated relief. What rupture disc diameter is required to relieve the vessel properly? Assume a discharge pressure of 10 psig. A 500-gpm pump is used to provide water to a reactor vessel. The reactor system in a pilot plant contains stock tanks that are 24 in in diameter and 36 in high. calorimeter tests indicate that the maximum self-heat rate is 40°C/min. and that its molecular weight is 44. Determine the diameter of a conventional spring-operated relief required to protect the vessel from a regulator failure. its boiling point is 673"R. A relief device must be properly sized for a potential runaway reaction. Furthermore.2. What relief size is required to protect the vessel from fire exposure? Assume the following: vapor relief only. b. The water is supplied through a regulator from a source with a maximum pressure of 100 psig.30. The molecular weight of the liquid is 162.424 Chapter 9 Relief Sizing 9-18. A horizontal vessel. The MAWP of the vessel is 100 psig.000 kg of reacting liquid material. contains water. a. A relief system must be designed to protect the vessel in the event of fire exposure. Assume a MAWP of 7 bar gauge. b. Determine the relief diameter (in inches) required to protect the vessel. Please state clearly any additional assumptions required for your calculation. Assume a temperature of 200°C at the relief conditions. A laboratory test has shown that the reaction will not result in a two-phase relief. 9-22. Assume a 10% backpressure and a 10% overpressure in the relief system. Additional physical property data are: . 9-21. Calculate the mass flux (kg/m2s) of two-phase material through the same leak under the same conditions of part a. Be sure to state clearly any assumptions and your justifications for them. Thus a vapor relief system must be designed. Assume that the material is stored at 25OC. that it is discharged to 1 atm pressure. 10% backpressure. Calculate the mass flux (kg/m2s)of gaseous material through a leak assuming that the material is stored at its vapor pressure within the vessel (9. The vessel contains a flammable polymer material. a.5 x lo5 Pa abs).

with the test sample heated at a constant temperature rate until an exothermic reaction is encountered. a. Comment on the difference in flux rates between parts a and b. is the ideal gas constant (energylmol deg).. R. During an exothermic reaction. e.. Calculate the energy discharge rate for the discharge of part b. f. a plot of versus -10001T will produce a straight line of slope (El1000 R.23 X lo3 J/kg K Heat capacity of vapor: 1. In general. The RSST (reactive system screening tool) is a laboratory device used to characterize the reactive nature of liquid materials. where T is the absolute temperature (K). Assume that the energy is due to the sensible heat increase of the two-phase discharge stream and that the temperature of the discharge is 10 K higher.) and an intercept of In A. then. If the reaction is first order in concentration. Assume that the energy content of the vapor is due to the heat of vaporization of the liquid to gas. Is this consistent with the results of parts a and b? Why? d. It is essentially an adiabatic calorimeter. the increase in temperature will also be first order.Problems 425 Heat of vaporization: 3. relief systems designed for two-phase flow must be larger than those for all-vapor flow. Compare the results of parts d and e. Calculate the energy discharge rate for the discharge of part a. and A is the pre-exponential factor (time-'). Show that for a first-order system.70 X lo3Jlkg K c. if the heat of reaction is approximately constant. is the maximum temperature (K). E is the activation energy (energy/mol). How many times larger must the area of the twophase discharge be in order to remove energy at the same rate as the single-phase relief? Comment on the implications for relief systems on reactor vessels. It is also assumed that the reaction rate follows a typical Arrhenius function as follows: . T.: 0. Assume that a sample is being heated in the RSST. 9-24.33 X lo5 Jlkg vf. the energy of reaction heats the sample and increases its temperature. t is the time (s).048 m3/kg Heat capacity of liquid: 2.

The MAWP is 250 psig. The specific gravity of the oil is 0.928. and a maximum backpressure of 50 psig is expected. A relief device must be designed for a vessel to relieve 1800 gpm of crude oil liquid in the event that a discharge line is blocked. . Is the reaction first order? If so.426 Chapter 9 Relief Sizing b. determine the activation energy and the pre-exponential factor for the reaction. The following table provides a set of data collected from an RSST run.004 kglm s. and its viscosity is 0. Temperature Time (min) c'c) Pressure (psi4 9-25.

Is adequate wall area now available for the vent? 9-28.84. Determine the vent area required if the maximum pressure that the room can withstand is 1. a compressibility of 0. Determine the diameter of the relief. b. 9-30.672 ft2.3times that of propane.04 psi. 9-29. . What size nitrogen line would you select if the nitrogen is available from a 500-psig source? The ambient temperature is 80°F. What type of relief should be used: a rupture disc. Assume an overpressure of 10% and a backpressure of 0 psig. a. The relief must discharge 53. The hydrocarbon vapor has a molecular weight of 65. 9-27. Estimate the vent area required if the dryer is capable of withstanding a pressure of 0. b. Determine the vent area required if the maximum pressure that the room can withstand is 0. 30 ft wide. a conventional spring-operated relief. and the set pressure is 75 psig. A spray dryer is used to dry a dust with a Kst value of 230 bar mls. How does this area compare to the wall area available for the vent? b.2 bar gauge. Estimate the vent area required if the dryer is a low-pressure structure capable of withstanding 0. Assume a vent release pressure of 0. Determine the relief diameter required. One wall of the room is located against the wall of another structure and is thus not available for a vent.500 lblhr of hydrocarbon vapor. in inches. a.09. A relief device must be installed on a vessel to protect against an operational upset. The dryer is a vertical cylinder 2 m in diameter and 3 m high. A vent must be designed for a room that is 20 ft long. or a balanced-bellows relief? c. The room is used for dispensing flammable liquids.69 psi. A process vessel is equipped with a 2-in rupture disc set at 100 psig and designed for 10% overpressure.15 bar gauge. Determine the vent area required for this structure if the total internal surface area of the structure (including floor and roof) is 24. and 20 ft high. and a heat capacity ratio of 1. A nitrogen line must be added to the vessel to provide the capability of purging andlor pressure discharging liquids. Specify an appropriate set pressure and overpressure for this relief. The maximum pressure that this building can withstand is estimated at 0. The fundamental burning velocities of the liquid vapors are less than 1.5 psi.Problems 427 a. A pole barn with thin metal walls must be fitted with a vent to safely vent a hydrocarbon deflagration from the combustion of a hydrocarbon similar to propane. The relief temperature is 167"F.05 bar gauge. 9-26.

.

Risk assessment is sometimes called hazard analysis.C H A P T E R 1 0 Hazards Identification azards are everywhere. What are the consequences? The first question represents hazard identification. For each process in a chemical plant the following questions must be asked: H 1. It is essential to identify the hazards and reduce the risk well in advance of an accident. considered in detail in chapter 11. Unfortunately. After a description of the process is available. The last three questions are associated with risk assessment. the hazards are identified. whereas a procedure that determines probability and consequences is called quantitative risk analysis (QRA). What can go wrong and how? 3. Question 2 is frequently called scenario identification. The terminology used varies considerably.Risk assessment includes a determination of the events that can produce an accident. What are the chances? 4. the probability of those events. and the consequences. or loss of production and capital equipment. The various scenarios by which an accident can occur are then determined. a hazard is not always identified until an accident occurs. Figure 10-1 illustrates the normal procedure for using hazards identification and risk assessment. This is followed by a concurrent . The consequences could include human injury or loss of life. Hazard identification and risk assessment are sometimes combined into a general category called hazard evaluation. A risk assessment procedure that determines probabilities is frequently called probabilistic risk assessment (PRA). damage to the environment. What are the hazards? 2.

study of both the probability and the consequences of an accident. Risk determination I hazard acceptance Modify: Process or plant Process operation Emergency response Other I Yes Build and/or operate Figure 10-1 Hazards identification and risk assessment procedure.430 Chapter 10 Hazards Identification System description G Hazard identification I Scenario identification 1 J. Accident consequence I J. pp. 1985). If the risk is unacceptable. If the risk is acceptable. then the study is complete and the process is operated. 1-9. . then the system must be modified and the procedure is restarted. Adapted from Guidelines for Hazards Evaluation Procedures (New York: American Institute of Chemical Engineers. This information is assembled into a final risk assessment. Accident probability J.

2. If failure rate data on the applicable equipment are not available. No single approach is necessarily best suited for any particular application. Most companies use these methods or adaptations to suit their particular operation." This means that potentially unnecessary and expensive safety equipment and procedures are implemented.Chapter 10 Hazards Identification 431 The procedure described by Figure 10-1is frequently abbreviated based on circumstances. hazards with reasonable probability but minimal consequences are sometimes also neglected. Hazards and operability (HAZOP) studies: This approach allows the mind to go free in a controlled environment. An important part of the hazard identification procedure shown in Figure 10-1 is the risk acceptance step. What are the chances of their occurrence. or it can be as detailed as the Dow indexes. This enables modifications to be easily incorporated into the final design. 4. The Dow indexes are a formal rating system. For instance.l Only a few of the more popular approaches are considered here. much like an income tax form. 3. Each organization using these procedures must have suitable criteria. it should be done as soon as possible. The selection of the best method requires experience. The results are highly dependent on the experience and synergism of the group reviewing the process. Likewise. (New York: American Institute of Chemical Engineers. Process hazards checklists: This is a list of items and possible problems in the process that must be checked. . Safety review: An effective but less formal type of HAZOP study. 1992). then risk assessment procedures cannot be fully applied. Various events are suggested for a specific piece of equipment with the participants determining whether and how the event could occur and whether the event creates any form of risk. Guidelines for Hazard Evaluation Procedures. Hazards identification and risk assessment studies can be performed at any stage during the initial dcsign or ongoing operation of a process. Many methods are available for performing hazard identification and risk assessment. that provide penalties for hazards and credits for safety equipment and procedures. and what should be done about them? For most facilities the probability of these hazards is small: No steps are required for prevention. The hazard identification methods described in this chapter include the following: 1. Most plant sites (and even subunits within a plant) modify the procedure to fit their particular situation. However. flying aircraft and tornadoes are hazards to a chemical plant. Hazard identification can be performed independent of risk assessment. the best result is obtained if they are done together. 2d ed. If the study is performed with the initial design. Hazards surveys: This can be as simple as an inventory of hazardous materials. One outcome is that hazards of low probability and minimal consequences are identified and addressed with the result that the process is "gold-plated.

7th ed. 1994). The design of the checklist depends on the intent. Checklists should be applied only during the preliminary stages of hazard identification and should not be used as a replacement for a more complete hazard identification procedure. the effort expended in developing and using checklists can yield significant results. electrical systems. A checklist can be used during the design of a process to identify design hazards. A checklist intended for use during the initial design of the process will be considerably different from a checklist used for a process change. . The first column is used to indicate those areas that have been thoroughly investigated. The second column is used for those items that do not apply to the particular process. Check air pressure in tires. Checklists are most effective in identifying hazards arising from process design. and so forth. Check fluid level in radiator. The list reminds the reviewer or operator of the potential problem areas. Check air filter. Check fluid level in windshield washer tank. This checklist might contain the following items: Check oil in engine. A typical process design safety checklist is shown in Figure 10-2. The last column is used to mark those areas requiring further investigation. Check exhaust system for leaks. Check fluid levels in brake system. Checklists for chemical processes can be detailed. (New York: American Institute of Chemical Engineers. 10-2 Hazards Surveys A hazards survey can be as simple as an inventory of hazardous materials in a facility or as com)~ plicated as a rigorous procedure such as the Dow Fire and Explosion Index ( F ~ L E Iand the 2Dow's Fire and Explosion Index Hazard ClassiJicationCode. Some companies have checklists for specific pieces of equipment. storage of chemicals. as illustrated in the vacation example. Check gasoline level in tank. plant layout. Note that three checkoff columns are provided. involving hundreds or even thousands of items. But. or it can be used before process operation. Extensive notes on individual areas are kept separate from the checklist.432 Chapter 10 Hazards Identification 10-1 Process Hazards Checklists A process hazards checklist is simply a list of possible problems and areas to be checked. such as a heat exchanger or a distillation column. Check headlights and taillights. A classic example is an automobile checklist that one might review before driving away on a vacation.

Provisions for rapid disposal of reactants in an emergency? 0 9. Special fume or dust hoods required? 3.Clearance for overhead power lines? Buildings 1. Adequate ladders. Hazardous underground obstructions? 5. stairways and escapeways? 2. . Hazardous reactions possible due to mistakes or contamination? 7. Areas properly drained? 2." in Safe and Efficient Plant Operation and Maintenance. Need for fireproofed structural steel? 0 ' o 0 D 0 o 0 D 0 Process 1. Adapted from Henry E. Safety glass specified where necessary? 7. Consequences of exposure to. Failure of mechanical equipment possible cause of hazards? n o Figure 10-2 A typical process safety checklist. dikes and special guardrails needed? 4. Enough headroom? 8. Fire walls. Fire doors required? 3. Chemistry of processes completely understood and reviewed? 8. Ventilation adequate? 5. (New York: McGrawHill.10-2 Hazards Surveys 433 Further study required 1 Does not apply L Completed 1 General layout 1. Head obstructions marked? 4.adjacent operations considered? 2. A list of this type is frequently used before a more complete analysis.Hoists and elevators properly designed and safeguarded? 12. Unstable materials properly stored? 4. 1980). Hazardous overhead restrictions? 6.Adequate platforms for safe maintenance operations? 11. Provisions for protection from explosions? 6. ed. Safe storage space for raw materials and finished products? 10. Access for emergency vehicles? 9. Aisleways provided? 3. Emergency accesses and exits? 7. "What To Do When Disaster Strikes. Process laboratory checked for runaway explosive conditions? 5. Webb. Richard Greene. Need for ladder or stairway to roof? 6.

Designs correct for maximum operating pressure? 2.Public liability risks possible from sprays.Hazards possible from simultaneous loss of two or more utilities? 16.Provisions made for disposal of toxic materials? 13. Safety showers and eye baths required? 2.1 10. Provisions for thermal expansion? 4.Personnel protective insulation provided? 19.Drains to relieve pressure on suction and discharge of all process pumps? 16. Protection and identification of fragile pipe considered? 10.434 Chapter 10 Hazards Identification Further study required Does not apply L Completed .Hot steam lines insulated? Equipment 1. or combination of incidents. Washing-down hoses needed? 8. Sprinkler systems required? 3.Safety factors altered by design revisions? 17.Long and large vent lines supported? 13. mists or noise? 12.Material safety data sheets available for all chemical species? 15.Possible deterioration of exterior of piping by chemicals? 11. reviewed? 18.Relief valve piping designed to prevent plugging? 15.Process diagrams correct and up-to-date? Piping 1.Hazards involved in sewering material? 14.Emergency valves readily accessible? 12. Piping specifications followed? 7. All overflow lines directed to safe areas? 5. Vent lines directed safely? 6. Corrosion allowance considered? D 1 D 0 13 !J 0 0 o D D D D 0 0 0 0 0 0 0 0 D 0 0 D Figure 10-2 (continued) . fumes.Flammable fluids feeding production units shut off from a safe distance in case of fire or other emergency? 18.City water lines not connected to process pipes? 17.Hazards possible from gradual or sudden blockages in piping or equipment? 11.Steam condensate piping safely designed? 14. Check valves provided as needed? 9.Consequences of reasonably worst incident.

Materials of construction corrosion resistant? 3. Vents properly designed? (Size.10-2 Hazards Surveys 435 Further study required Does not apply 1 Completed I 3. sheaves and gears? 0 5. Telltale pressure gauges installed between rupture disks and relief valve? Instrument and Electrical 1. Guard rails for storage tanks? 8. Process safety affected by response lag? 7. Reclaimed and replacement equipment checked structurally and for process pressures? 10. Guards for belts.Breakers adequated for circuit protection? 13. showers and eyebaths? 12. Safeguards provided for process control when an instrument must be taken out of service? 6. Construction materials compatible with process chemicals? 9. as necessary? 11. Schedule for checking protective devices? 6. Tubing runs protected? 5. Labels for all start-stop switches? 8.Automatic lubrication of critical machinery? 12. Electrical failures cause unsafe conditions? 10. All controls fail safe? 2. configuration?) 4. Dikes for any storage tanks? 7. Flame arrestors required on vent lines? 5. direction. Dual indication of process variables necessary? 3. Special isolation for hazardous equipment? 4. Relief valves protected from plugging by rupture disks? 6. Equipment designed to permit lockout protection? 9.Sufficient lighting for both outside and inside operations? 1l. Relief valves or rupture disks required? 2.Emergency standby equipment needed? Venting 1. All equipment properly labelled? 4.Pipelines independently supported to relieve pumps and other equipment.All equipment grounded? o 1 o o 0 0 o o o o 0 o o Figure 10-2 (continued) .Lights provided for all sight glasses. pulleys.

Consequences of bad spills considered? 7.Emergency standby power on lighting equipment required? 16. Special emergency procedures and alarms required? 1 0 0 0 0 o o 0 0 Raw Materials 1. stability. Any raw materials and products affected by extreme weather conditions? 3. flammability. Proper containers being used? 5.Special interlocks needed for safe operation? 15. Special respiratory equipment required? 3. Special instructions needed for containers or for storage and warehousing by distributors? 8. etc? 6. Any products hazardous from a toxic or fire standpoint? 4.All necessary communications equipment provided? 18. Fire extinguishers required? 2. Colorimetric indicator tubes required? 5. Fire extinguishing materials compatible with process materials? 7. Any materials and products require special o handling equipment? 2. Flammable vapor detection apparatus required? 6. Does warehouse have operating instructions covering each product regarded as critical? o Figure 10-2 (continued) . Containers properly labelled for toxicity.436 Chapter 10 Hazards Identification Further study required Does not apply 1 Completed 1 14. Diking material required? 4.Emergency escape lighting required during power failure? 17.Special explosion proof electrical fixtures required? Safety Equipment 1.Emergency disconnect switches properly marked? 19.

Penalties for various unsafe situations are placed in this column. and processing of explosive and flammable materials. The resulting MF value for the process is written in the space provided at the top of the form in Figure 10-3. for determining the relative magnitude of flammable hazards in a chemical plant. The main idea of this procedure is to provide a purely systematic approach.10-2 Hazards Surveys 437 Dow-Chemical Exposure Index (CEI)3. These are formal systematized approaches using a rating form. The next step is to determine the material factor (MF) for use in the form shown in Figure 10-3. a reactor. shown in Figure 10-3. The Dow F&EI is designed for rating the relative hazards with the storage. A process safety checklist or hazards survey is frequently used to select the most hazardous units for further analysis. (New York: American Institute of Chemical Engineers. mostly independent of judgmental factors. If mixtures of materials are used. The final column is used for computation. In the event of uncertainty here. The first column is the penalty column. handling. the MF is determined from the properties of the mixture. similar to an income tax form. This factor is adjusted for general and special process hazards. 'Dow's Chemical Exposure Index Guide. This list also includes data on heat of combustion and flash and boiling point temperatures. the higher the value of the MF. In general. This allows for a reduction or increase in the penalty based on extenuating circumstances not completely covered by the form. 1994). The first step in the procedure is to conceptually divide the process into separate process units. the more flammable and/or explosive the material. A process unit is a single pump. The procedure begins with a material factor that is a function only of the type of chemical or chemicals used. A procedure is provided in the complete index for computing the material factor for other compounds not listed in Table 10-1 or provided in the Dow reference. A large process results in hundreds of individual units. These adjustments or penalties are based on conditions such as storage above the flash or boiling point. The form. The highest value of the MF under the complete range of operating conditions is suggested. 4th ed. It is not practical to apply the fire and explosion index to all these units. The F&EI also contains a mechanism for estimating the dollar loss in the event of an accident. The main forms used for the computations are shown in Figures 10-3 and 10-4.Table 10-1lists MFs for a number of important compounds. Credits for various safety systems and procedures are used for estimating the consequences of the hazard. endo. the complete penalty value from the first column is used. consists of three columns of numbers. or a storage tank.which are two popular forms of hazards survey. The usual approach is to select only the units that experience shows to have the highest likelihood of a hazard. The additional data are also used in the computation of the Dow F&EI. after the fire and explosion index has been determined. .or exothermic reactions. The final rating number provides a relative ranking of the hazard. The second column contains the penalty actually used. and fired heaters.

.... .... Pressure (See Figure 2) Operating Pressure psig or kPa gauge Retief Selling psig or kPa gauge F................ Liquids or Gases in Storage (See Figure 4) 3........... ............ .... Always in Flammable Range D.or kg ib Hc = B T U I b or kcallkg 1......10to 1. Use of Fired Equipment (See Figure 6) K..START UP ...20 to 0.. The figures and tables referenced in the form are provided in the index booklet........... ...nd...30 0...... I 5by MATERIALSIN PROQSS UNlT STATE OF OPERAllON BASK: MATERIAL(S)FOR MATERIAL FACTOR I I - - DESION .50 Special Process Hazards Factor (F2) Process Unit Hazards Factor (F1 x F2) . .438 Chapter 10 Hazards Identification FIRE & EXPLOSION INDEX AREA I O N R CUTY DIVISION I LOCATION I ME I Sm YANVACTURINO UNIT APPROVW P O E S UNrr R CS BUIWNO I PREPARED BY: REVIEWD I BY: (s. Corrosion and Erosion I... . Figure 10-3 Form used in the Dow Fire and Explosion Index.75 0.....nl) 1 L o n Pmv*ntlon) BY: ( .... 7th ed. = FQ. Combustible Solids in Storage.......... Reproduced by permission of the American Institute of Chemical Engineers.00 0. Rotating Equipment 0............. Quanliiy of FlammableNnstable Material: Quantity .1510 1......NDRMAL DPERATIDN ..win(... (1994).. Leakage Joints and Packing J... Hot Oil Heat Exchange System (See Table 5) L... Liquids or Gases in Process (See Figure 3) 2. Dust Explosion (See Table 3) E......10 to 0...... Low Temperature G.. Dust in Process (See Figure 5) H.........25 to 2........30 - 0..80 0. Source: Dow's Fire and Explosion Index Hazard Classification Guide..SHUTDOWN MATERIALF C O (See Table 1 w Appendices A w B) Note requiremernswhen tmit temperature over 140 O F (60 O C J ATR - 2...15 0.50 0........ Process upsetor Purge Failure 3.....) YI R W W D BY: (Tmchdwy Cmtmr) E E E I REVIEWED BY: ( ...

........ Maximum Probable Days Outage .... ................................ Drainage d. ......... Base Maximum Probable Property Damage ......96 Credit Factor Used(q c.......... $MM 7....... .....98 0.............. Damage Factor .....( 3.. Value of Area of Exposure................ Reproduced by permission of the American Institute of Chemical Engineers..................... (Figure 8) ...... (See Above) 8............ (See Front) ....... ........(Actual MPPD) [6 x 71 ... PROCESS UNIT RISK ANALYSIS SUMMARY 1.......... .91 to 0.......(MPDO) . (2) For no credit factor enter 1........96 to 0.....98 Feature a............ ...... I I I Actual Maximum Probable Property Damage ....... 1 6..... 9............................... ..................... fl or m ft2 or m2 Area of Exposure. Business Interruption . Source: Dowk Fire and Explosion lndex Hazard Classification Guide.................. Figure 7) 2..... 4................................. (Figure 9) days $MM 10.. (3) $MM Product of all factors used....................................... Radius of Exposure ..(Base MPPD) [4 x 51 .... Fire ProtectionCredit Factor (C3) n c3Value(3) 1 Loss Control Credit Factor = C1 X C2 X C3(3)= 7) on line below) (Enter 7 .00..(81) .... ..... Remote Control Valves b................. Figure 10-4 Form used for consequences analysis............... Interlock ~2 Credit Factor Use*L ~alue(3) 3................. Refer to Fire 8 Explosion Indew Hazard Classification Guide for details................ Dump/Blowdown Credit Factor Range 0..................... .............. 7th ed.....................10-2 Hazards Surveys 439 LOSS CONTROL CREDIT FACTORS 1................. Loss Control Credit Factor....... Process Control Credit Factor (C1) c1Vaiue(3) 2... Fire 8 Explosion Index (F8EI)..97 0......96 to 0........ ............ Material Isolation Credit Factor (C2) 1 7 Feature Credit Factor Range 0......... 1994........ ................. ...... $MM 5.....................

8 20. (New York: American Institute of Chemical Engineers.0 7.7 20.3 0.5 8.3-Butadiene Butane Calcium carbide Carbon monoxide Chlorine Cyclohexane Cyclohexanol Diesel fuel Ethane Ethylene Fuel oil #1 Fuel oil #6 Gasoline Hydrogen Methane Methanol Mineral oil Nitroglycerine Octane Pentane Petroleum (crude) Propylene Styrene Toluene Vinyl chloride Xylene Material factor 16 29 16 Heat of combustion (Btullb x 12.7 17.1 4.7 17.3 0.. The next step is to determine the general process hazards.7 9.7 18.0 18. exothermic reactions that might self-heat.0 19.2 19.3 20. 4.4 21.440 Chapter 10 Hazards Identification Table 10-1 - Selected Data for the Dow Fire and Explosion Index1 .108 77 -313 -29 179 322 315 -128 . Gas Gas -4 154 100-130 Gas Gas 100-162 100-270 -45 Gas Gas 52 380 56 <-40 20-90 .7 15.0 18.- . 2.400 -423 -258 147 680 258 97 - -54 293 232 7 279 'Selected from Dow's Fire and Explosion Index Hazard Classification Guide.4 20.162 88 40 .0 17.8 51. 3. 1994. including pumping and connection of transfer lines.155 304-574 100.4 17.3 19.7 18.4 8. .5 19. enclosed process units preventing dispersion of escaped vapors. 7th ed.6 17. Penalties are applied for the following factors: 1.6 21.8 18. material handling and transfer. endothermic reactions that could react because of an external heat source such as a fire.6 Flash point (OF) -4 Gas 12 - Boiling point (OF) 133 -118 176 - 1 24 21 24 21 1 16 10 10 21 24 10 10 16 21 21 16 4 40 16 21 16 21 24 16 24 16 -105 Gas - 24 31 - .- Compound Acetone Acetylene Benzene Bromine 1.

9. and 12. which could impede fire fighting. 11. 6. Table 10-2 Determining the Degree of Hazard from the Dow Fire and Explosion lndex Dow Fire and Explosion Index 1-60 61-96 97-127 128-158 159 and above Degree of hazard Light Moderate Intermediate Heavy Severe . 10. providing a ready ignition source. corrosion and erosion of process unit structures. Detailed instructions and correlations for determining the general and special process hazards are provided in the complete Dow F&EI. The consequences analysis is completed using the worksheet form shown in Figure 10-4. The Dow F&EI can be used to determine the consequences of an accident. dust explosion risks. poor drainage of flammable materials away from the process unit. leakage around joints and packings. toxic materials. 8. limited access for emergency equipment. The Dow F&EI is computed by multiplying the unit hazard factor by the MF. 4. and 6. higher than atmospheric pressure. 3. large rotating equipment. 7. The general process hazard factor (F1) and special process hazard factor (F. including pumps and compressors. 2. 5. less than atmospheric pressure operation with a risk of outside air entering.10-2 Hazards Surveys 441 5. This includes the maximum probable property damage (MPPD) and the maximum probable days outage (MPDO).). operation in or near the flammable limits. Table 10-2 provides the degree of hazard based on the index value. hot oil heat exchange systems where the hot oil is above its ignition temperature. quantity of flammable material. The computations are completed in the Risk Analysis Summary table at the bottom of the form.) are multiplied together to produce a unit hazard factor (F. Penalties for special process hazards are determined next: 1. use of fired heaters. low-temperature operation with potential embrittlement of carbon steel vessels.

442

Chapter 10

Hazards Identification

The damage radius is first estimated using a correlation published in the complete Dow index. This correlation is based on the previously determined F&EI. The dollar value of the equipment within this radius is determined. Next. a damage factor (based on a correlation provided) is applied to the fraction of the equipment actually damaged by the explosion or fire. Finally, a credit factor is applied based on safety systems. The final number, in dollars, is the MPPD value. This number is used to estimate the MPDO using a correlation. Details on the procedure are available in the complete Dow reference. The Dow indexes are useful for determining equipment spacing requirements. The F&EI uses an empirical correlation based entirely on the F&EI value to estimate the radius of exposure. It is assumed that any equipment located outside this distance would not be damaged by a fire or explosion. The CEI estimates the hazard distance for chemical exposure based on the emergency response planning guideline (ERPG) values for the particular material released.

Example 10-1
Your plant is considering the installation of a new railcar tank unloading facility. The facility will unload nominal 25,000-gal tank cars containing either pure butadiene or cyclohexane. The unloading system will be equipped with an emergency shutdown system with remotely operated block valves. The unloading operation will be done by computer control. The railcars are inerted with nitrogen to a pressure of 40 psig, and the railcar relief system has a set pressure of 75 psig. The unloading operating instructions are written and have been reviewed by the corporate technical staff. A reactive chemicals review has already been completed on the proposed facility. Combustible gas detectors will be located at the unloading station. A deluge system will be installed at the unloading site with an excellent water supply. A diking system will surround three sides of the facility, with any spills directed to a covered impounding area. Determine the Dow F&EI for this operation, and determine the minimum spacing from adjacent units.

Solution
The Dow Index contains most of the data required to complete the evaluation. The data for the chemical species used in this facility are:

Species
Butadiene Cyclohexane

NFPA Material factor health rating
24 16 2 1

Heat of combustion (Btullb)
19.2 x lo3 18.7 X lo3

Flash point
(OF)

-105 -4

Because the butadiene has the highest MF, it is the material we need to evaluate using the Dow F&EI. The completed F&EI form is shown in Figure 10-5. Each nonzero item on the form is discussed in what follows.

10-2 Hazar ds S u r v e y s

FIRE & EXPLOSION INDEX
-1

C N Y OU TR

OMSION

LOCATION

DATE

North America
SITE

North Central
MANUFACTURING UNIT

Arkansas
P O E S UNIT R CS

03/04/94
l eUliDlNC

No Loss
PEAE B: RPRD Y

Dow Polymer Alvin Doe

I APPROVED BY: (Superintendent)

Rail Car Unloading A-103
REVIEWED BY: (Safety L Loss Prevention)

John Smith
RMEWW

BY:(Y.nagement)

REVIEWEDBY:(TechnologyCenter)

Robert Big
MATEfUALS IN P OC S UNl R ES T

Bill Wright
BASIC MATER!AL(S)FOR MATERIAL FACTOR

Butadiene, Cyclohexane
S A E O OPERATION TT F

- DESIGN

- ST~VITw

-X-

NORMAL OPEFATION

- SHUTDOWN

I

Butadiene
I

MATERIAL FACTOR(See Table 1 or Appendices A or B) Note requirements

I General Process Hazards .

Penalty Fact o r Ranoe

Penalty Factor Usedri~

~~

- -

D.

Dust Explosion (See Table 3) Pressure (See Figure 2) Operating Pressure Relief Setting 40 75 psigpsig-

E.

I I

0.25 to 2.00

I

.28

F. Low Temperature G. Quantity of Flammable/UnstableMaterial:
1.

0.20 to 0.30 Quantity -130K- Ib-wkg -19.2K-BTUIlb or kcallkg

.76

Hc = Liquids or Gases in Process (See Figure 3) 2 Liquids or Gases in Storage (See Figure 4) 3. Combustible Solids in Storage, Dust in Process (See Figure 5) H. Corrosion and Erosion I. Leakage Joints and Packing J. Use of Fired Equipment (See Figure 6) K Hot Oil Heat Exchange System (See Table 5) L Rotating Equipment

-

-

0.10 to 0.75 O.1Oto 1.50 0.15to 1.15 0.50

. I .1

-

-

Special Process Hazards F a cto r (Fz) Process Unit Hazards Factor (FI

............................................................................................
=
F3

2.94 4.41 106.00

x Fp)

.............................................................................
..............................................................................

F i r e a n d Explosion Index (F3 x MF
FORU G D O RNlDi-04

=

FBEI)

(I) For no penalty use 0.00.

Figure 10-5 The Dow Fire and Explosion Index applied to the railcar unloading facility of Example 10-1.

-

-

-

444

Chapter 10

Hazards Identification

1.A. Exothermic chemical reactions: The reactive chemical review has determined that an exothermic chemical reaction here is not possible. The penalty is zero. 1.B. Endothermic chemical reactions: This penalty applies only to reactors, so the penalty is zero. 1.C. Material handling and transfer: The index documentation states: "Any loading and unloading operation involving Class I flammables or LPG-type materials where transfer lines are connected and disconnected receives a penalty of 0.50." 1.D. Enclosed or indoor process units: The unit is outdoors, so the penalty is zero. 1.E. Access: The unit will have emergency access from all sides, so the penalty is zero. 1.F. Drainage and spill control: No penalty is applied because the dike and impounding system is present. 2.A. Toxic materials: The index suggests using a penalty value of 0.20 X NFPA Health Rating. Because the rating is 2, the penalty value is 0.4. 2.B. Subatmospheric pressure: The operation is pressurized, so no penalty is applied here. 2.C. Operation in or near flammable range 1. Tank farms storage flammable liquids: The tanks are inerted with a closed vapor recovery system, so the penalty here is zero. 2. Process upset or purge failure: The unit relies on inert purging to keep it out of the flammable range, so a penalty of 0.30 is applied. 3. Always in flammable range: The process is not in the flammable range during normal operation, so the penalty is zero. 2.D. Dust explosion: No dusts are involved, so the penalty is zero. 2.E. Pressure: The Dow index provides a detailed procedure for determining this penalty. The operating pressure penalty is determined from Figure 2 in the Dow index booklet using the operating pressure. In this case the operating pressure of 40 psig results in a penalty of 0.24. Second, a penalty is determined at the relief set pressure (75 psig), again using Figure 2 in the Dow index booklet. This value is 0.27. The operating pressure penalty is then divided by the set pressure penalty to get a final pressure penalty adjustment. In this case the adjustment is 0.2410.27 = 0.8889. This is multiplied by the operating pressure penalty to obtain 0.24(0.8889) = 0.2133. Finally, this is multiplied by a correction factor of 1.3 because this is a liquefied flammable gas. The final penalty is 0.2133(1.3) = 0.28. 2.F. Low temperature: Low-temperature operating is not expected, so the penalty is zero. 2.6. Quantity of flammablelunstable material 1. Liquids or gases in process: This is not part of the process, so the penalty is zero. 2. Liquids or gases in storage: The total energy contained within the storage inventory is estimated in order to determine the penalty. This requires the specific gravity of butadiene, which can be found on the MSDS sheet or other reference. This value is 0.6263. Thus the total energy is (25,000 ga1)(8.345 lb/ga1)(0.6263) = 130,662 lb, (1.30
X

10" lb)(19.2

X

lo3 Btullb)

=

2.51

X

lo9 Btu.

From Figure 4, curve B, in the Dow index booklet, the penalty is 0.76. 3. Combustible solids in storage, dust in process: No solids are present here, so the penalty is zero.

10-2 Hazards Surveys

445

2.H. Corrosion and erosion: Corrosion and erosion is expected to be less than 0.5 millyr. Thus the penalty is 0.10. 2.1. Leakage -joints and packing: The pump and gland seals are expected to have some small but minor leakage. Thus the penalty here is 0.10. 2.5. Use of fired equipment: No fired equipment is present, so the penalty is zero. 2.K. Hot oil heat exchange system: Not present, so the penalty is zero. 2.L. Rotating equipment: No large rotating equipment is present, so the penalty is zero.
These penalties and factors are summarized in Figure 10-5. The resulting calculation shows an F&EI value of 106, which means that this unloading station is an intermediate hazard. Figure 7 in the Dow index booklet provides the radius of exposure based on the F&EI value. For this case the radius is 90 ft. Thus the unloading station must be located a minimum of 90 ft from any other equipment or processes.

The Dow CEI is a simple method of rating the relative acute health hazard potential for people in neighboring plants or communities arising from possible chemical release incidents. To use the CEI, the following items are required: an accurate plot plan of the plant and the surrounding area, a simplified process flow sheet showing the containment vessels, major piping, and chemical inventories, physical and chemical properties of the materials investigated, ERPG values, from Table 5-7, the CEI guide, and the CEI form shown in Figure 10-6.
A flowchart of the CEI procedure is shown in Figure 10-7. The procedure begins with a definition of possible release incidents. This includes releases from pipes, hoses, pressure relief devices relieving directly to the atmosphere, vessels, and tank overflows and spills. The CEI guide has detailed guidelines for these incidents, as shown in Table 4-5. The incidents are used with a number of simplified source models provided in the Dow guide4 to estimate the release rate of material. The ERPGs are then used with a simplified dispersion model to determine the CEI value and downwind hazard distances resulting from the release. Hazards surveys are suitable for identifying hazards associated with equipment design, layout, material storage, and so forth. They are not suitable for identifying hazards resulting from improper operation or upset conditions. On the other hand, this approach is fairly rigorous, requires little experience, is easy to apply, and provides a quick result.

4Dow's Chemical Exposure Index Guide.

CHEMICAL EXPOSURE INDEX SUMMARY
Plant Chemical Largest Single Containment Pressure Of Containment
1. Scenario Being Evaluated

Location Total Quantity In Plant

Temperature Of Containment

2. Airborne Release Rate from Scenario

kg/sec lblmin

3. Chemical Exposure Index
Concentration PPM
Hazard Distance meters feet

mghn3

ERPG- l/EEF'G- 1 ERPG-2/EEF'G-2 ERPG-3/EEPG-3

---meters
feet

5. Distances to:
Public (generally considered property line) Other in-company facility Non-company plant or business 6. The CEI and the Hazard Distance establish the level of review needed. 7. If further review is required, complete Containment and Mitigation Checklist (Chemical Exposure Index Guide, 2nd Edition -Appendix 2, page 26) and prepare Review Package.
8. List any sights, odors or sounds that might come from your facility and cause public concern or inquiries (e.g., smoke,large relief valves, odors below hazardous levels such as mercaptans or amines, etc.)

Prepared by: Reviewed by:
Date

Plant Superintendentor Manager Site Review Representative Additional Management Review (if required)

Figure 10-6 Form used for the Dow Chemical Exposure Index. Source: Dow's Chemical Exposure Index Guide (New York: American lnstitute of Chemical Engineers, 1994). Reproduced by permission of the American lnstitute of Chemical Engineers.

10-2 Hazards Surveys

447

i

Define possible chemical incidents

Determine the Airborne Quantity (AQ) for each scenario

Select the scenario with the largest Airborne Quantity (AQ)

Obtain ERPG-2 or ERPG3 values

I

Calculate the CEI

I

Calculate the hazard distance

Complete CEI summary sheets

Figure 10-7 Procedure for calculating the Chemical Exposure lndex (CEI). Source: Dow's Chemical Exposure lndex Guide (New York: American Institute of Chemical Engineers, 1994).

448

Chapter 10

Hazards Identification

10-3 Hazards and Operability Studies
The HAZOP study is a formal procedure to identify hazards in a chemical process fa~ility.~ The procedure is effective in identifying hazards and is well accepted by the chemical industry. The basic idea is to let the mind go free in a controlled fashion in order to consider all the possible ways that process and operational failures can occur. Before the HAZOP study is started, detailed information on the process must be available. This includes up-to-date process flow diagrams (PFDs), process and instrumentation diagrams (P&IDs), detailed equipment specifications, materials of construction, and mass and energy balances. The full HAZOP study requires a committee composed of a cross-section of experienced plant, laboratory, technical, and safety professionals. One individual must be a trained HAZOP leader and serves as the committee chair. This person leads the discussion and must be experienced with the HAZOP procedure and the chemical process under review. One individual must also be assigned the task of recording the results, although a number of vendors provide software to perform this function on a personal computer. The committee meets on a regular basis for a few hours each time. The meeting duration must be short enough to ensure continuing interest and input from all committee members. A large process might take several months of biweekly meetings to complete the HAZOP study. Obviously, a complete HAZOP study requires a large investment in time and effort, but the value of the result is well worth the effort. The HAZOP procedure uses the following steps to complete an analysis:

'

1. Begin with a detailed flow sheet. Break the flow sheet into a number of process units. Thus the reactor area might be one unit, and the storage tank another. Select a unit for study. 2. Choose a study node (vessel, line, operating instruction). 3. Describe the design intent of the study node. For example, vessel V-1 is designed to store the benzene feedstock and provide it on demand to the reactor. 4. Pick a process parameter: flow, level, temperature, pressure, concentration, pH, viscosity, state (solid, liquid, or gas), agitation, volume, reaction, sample, component, start, stop, stability, power, inert. 5. Apply a guide word to the process parameter to suggest possible deviations. A list of guide words is shown in Table 10-3. Some of the guide word process parameter combinations are meaningless, as shown in Tables 10-4 and 10-5 for process lines and vessels. 6. If the deviation is applicable, determine possible causes and note any protective systems. 7. Evaluate the consequences of the deviation (if any). 8. Recommend action (what? by whom? by when?) 9. Record all information.
SGuidelinesfor Hazard Evaluation Procedures, 2d ed. (New York: American Institute of Chemical Engineers, 1992).

-

-

-

-

10-3 Hazards and Operability Studies

Table 10-3
Guide words
NO, NOT, NONE

Guide Words Used for the HAZOP Procedure
Meaning
The complete negation of the intention Quantitative increase Quantitative decrease Qualitative increase

Comments
No part of the design intention is achieved, but nothing else happens. Applies to quantities such as flow rate and temperature and to activities such as heating and reaction. Applies to quantities such as flow rate and temperature and to activities such as heating and reaction. All the design and operating intentions are achieved along with some additional activity, such as contamination of process streams. Only some of the design intentions are achieved, some are not. Most applicable to activities such as flow or chemical reaction. Also applicable to substances, for example, poison instead of antidote. No part of the original intention is achieved - the original intention is replaced by something else. Applies to process steps or actions. Applies to process steps or actions. Applies to process locations, or locations in operating procedures.

MORE, HIGHER,

GREATER LESS, LOWER

AS WELL AS

PART O F

Qualitative decrease The logical opposite of

REVERSE

OTHER THAN

Complete substitution Too early or in the wrong order Too late or in the wrong order In additional locations

SOONER THAN

LATER THAN

WHERE ELSE

Table 10-4 Valid Guide Word and Process Parameter Combinations for Process Lines (x's represent valid combinations)
Process parameters
Flow Temperature Pressure Concentration pH Viscosity State

NO, More, not, higher, Less, none greater lower x x x x x x x x
X

As well as x x x

Part Other Sooner, Later, Where of Reverse than faster slower else x x x

x
x x x
X

x
x x x
X

x

x
X

x

x

x

x x

x

x

x

x

450

Chapter 10

Hazards Identification

Table 10-5 Valid Guide Word and Process Parameter Combinations for Process Vessels (x's represent valid combinations)
Process Parameters NO, More, not, higher, Less, none greater lower As well as Part Other Sooner, Later, Where of Reverse than faster slower else

Level Temperature Pressure Concentration pH Viscosity Agitation Volume Reaction State Sample

10. Repeat steps 5 through 9 until all applicable guide words have been applied to the chosen process parameter. 11. Repeat steps 4 through 10 until all applicable process parameters have been considered for the given study node. 12. Repeat steps 2 through 11 until all study nodes have been considered for the given section and proceed to the next section on the flow sheet.
The guide words AS WELL AS, PART OF, and OTHER THAN can sometimes be conceptually difficult to apply. As WELL AS means that something else happens in addition to the intended design intention. This could be boiling of a liquid, transfer of some additional component, or the transfer of some fluid somewhere else than expected. PARTOF means that one of the components is missing or the stream is being preferentially pumped to only part of the process. OTHER THAN applies to situations in which a material is substituted for the expected material, is transferred somewhere else, or the material solidifies and cannot be transported. The guide words SOONER THAN, LATER THAN, and WHERE ELSE are applicable to batch processing. An important part of the HAZOP procedure is the organization required to record and use the results. There are many methods to accomplish this and most companies custon~ize their approach to fit their particular way of doing things. Table 10-6 presents one type of basic HAZOP form. The first column, denoted "Item," is used to provide a unique identifier for each case considered. The numbering system used is a number-letter combination. Thus the designation "1 A" would designate the first study node and the first guide word. The second column lists the study node considered. The third column lists the process parameter, and the fourth column lists the deviations or guide words. The next three columns are the most important results of the analysis. The first column lists the possible

Table 1 0 - 6

HAZOP Form for Recording Data

Hazards and Operability Review

Chapter 10

Hazards Identification

Reactor
Monomer feed Cooling coils

\

Thermocouple

Figure 10-8

An exothermic reaction controlled by cooling water

causes. These causes a r e determined by t h e committee and a r e based on t h e specific deviation-guide word combination. T h e next column lists t h e possible consequences of t h e deviation. T h e last column lists t h e action required t o prevent t h e hazard from resulting in an accident. Notice that t h e items listed in these three columns a r e numbered consecutively. T h e last several columns a r e used t o track t h e work responsibility and completion of t h e work.

Example 10-2
Consider the reactor system shown in Figure 10-8.The reaction is exothermic, so a cooling system is provided to remove the excess energy of reaction. In the event that the cooling function is lost, the temperature of the reactor would increase. This would lead to an increase in reaction rate, leading to additional energy release. The result would be a runaway reaction with pressures exceeding the bursting pressure of the reactor vessel. The temperature within the reactor is measured and is used to control the cooling water flow rate by a valve. Perform a HAZOP study on this unit to improve the safety of the process. Use as study nodes the cooling coil (process parameters: flow and temperature) and the stirrer (process parameter: agitation).

Solution
The guide words are applied to the study node of the cooling coils and the stirrer with the designated process parameters. The HAZOP results are shown in Table 10-7, which is only a small part of the complete analysis.

Table 10-7

HAZOP S t u d y A p p l i e d t o t h e E x o t h e r m i c R e a c t o r of E x a m p l e 10-2.

Hazards and Operability Review
Project name: Example 10-2 Process: Reactor of Example 10-2 Section: Reactor shown in Example 10-2
Item Study node
1A Cooling coils

Date: 1/1/93

Page

1

of

2

Completed: No action: Reply date:

I
1
DAC 1/93 DAC 1/93 DAC 2/93 DAC 2/93 DAC 2193 DAC 1193 JFL 1/93

1

Reference drawing: Figure 10-8 Possible causes Possible consequences
1. Loss of cooling, possible runaway ,, 2.

Process parameters
Flow

Deviations (guide
No

Action required

to:

1. Control valve fails closed 2. Plugged cooling coils

3. Cooling water service failure 4. Controller fails and closes valve

3.
4.
5.

R o

1B

5.Air pressure fails, closing valve
High 1. Control valve fails open 2. Controller fails and opens valve 1. Partially plugged cooling line 2. Partial water source failure 3. Control valve fails to respond

1C

Low

1. Reactor cools, reactant conc. builds, possible runaway on heating 2. 1. Diminished cooling, possible runaway 2. 3. 1. Not possible here 1. Loss of cooling, possible runaway 2. 1. None 1. Temperature rises, possible runaway 1. None-controller handles 1. Cooling system capacity limited, temp, increases 1. No mixing, possible accumulation of unreacted materials 2. Monomer feed continues, possible accumulation of unreacted materials 1. None

1. Select valve to fail open 2. Install filter with maintenance procedure Install cooling water flow meter and low flow alarm Install high temperature alarm to alert operator 3. Check and monitor reliability of water service 4. Place controller on critical instrumentation list 5. See l A . l 1. Instruct operators and update procedures
2. See 1A.4 1. See 1A.2

1D 1E
1F

As well as, part of, reverse

1G 1H 1I 1J 1K 1L 2A Stirrer Temp. Agitation

1. Contamination of water supply 1. Covered under 1C 1. Failure of water source resulting in backflow 2. Backflow due to high backpressure Other than, 1. Not considered possible sooner than, 1. Cooling normally started early later than 1. Operator error Where else Low High No 1. Not considered possible 1. Low water supply temperature 1. High water supply temperature 1. Stirrer motor malfunction 2. Power failure

2. See 1A.2 3. Place valve on critical instrumentation list 1. None 1. See 1A.2 2. Install check valve

JFL 1193
X X

JFL 2193
X X

1. Interlock between cooling flow JW and reactor feed 1. None 1. Install high flow alarm andlor JW cooling water high temp. alarm 1. Interlock with feed line JW 2. Monomer feed valve must fail closed on power loss JW

1/93
X X

1193 1193 2/93
X

26

More

1. Stirrer motor controller fails,

resulting in high motor speed

454

Chapter 10

Hazards Identification

The potential process modifications resulting from this study (Example 10-2) are the following: install a high-temperature alarm to alert the operator in the event of cooling function loss, install a high-temperature shutdown system (this system would automatically shut down the process in the event of a high reactor temperature; the shutdown temperature would be higher than the alarm temperature to provide the operator with the opportunity to restore cooling before the reactor is shutdown), install a check valve in the cooling line to prevent reverse flow (a check valve could be installed both before and after the reactor to prevent the reactor contents from flowingupstream and to prevent the backflow in the event of a leak in the coils), periodically inspect the cooling coil to ensure its integrity, study the cooling water source to consider possible contamination and interruption of supply, install a cooling water flow meter and low-flow alarm (which will provide an immediate indication of cooling loss). In the event that the cooling water system fails (regardless of the source of the failure), the high-temperature alarm and emergency shutdown system prevents a runaway reaction. The review committee performing the HAZOP study decided that the installation of a backup controller and control valve was not essential. The high-temperature alarm and shutdown system prevents a runaway reaction in this event. Similarly, a loss of coolant water source or a plugged cooling line would be detected by either the alarm or the emergency shutdown system. The review committee suggested that all coolant water failures be properly reported and that if a particular cause occurred repeatedly, then additional process modifications were warranted. Example 10-2 demonstrates that the number of suggested process changes is great, although only a single process intention is considered. The advantage to this approach is that it provides a more complete identification of the hazards, including information on how hazards can develop as a result of operating procedures and operational upsets in the process. Companies that perform detailed HAZOPs studies find that their processes operate better and have less down time, that their product quality is improved, that less waste is produced, and that their employees are more confident in the safety of the process. The disadvantages are that the HAZOP approach is tedious to apply, requires considerable staff time, and can potentially identify hazards independent of the risk.

10-4 Safety Reviews
Another method that is commonly used to identify safety problems in laboratory and process areas and to develop solutions is the safety review. There are two types of safety reviews: the informal and the formal.

Example 10-3 Consider the laboratory reactor system shown in Figure 10-9.5-1 ppm.8"F. This system is designed to react phosgene (COCI.10-4 Safety Reviews VENT f COCI. Its TLV is 2 ppm. well above the TLV. The idea is to provide a lively dialogue where ideas can be exchanged and safety improvements can be developed. It includes the individual responsible for the process and one or two others not directly associated with the process but experienced with proper safety procedures. The informal safety review procedure usually involves just two or three people. and its odor threshold is 0. The isocyanate is used for the production of foams and plastics.1 ppm. The TLV for phosgene is 0. The improvements must be implemented before the process is operated. Phosgene is a colorless vapor with a boiling point of 46. Figure 10-10 Reaction stoichiometry for phosgene reactor. r U def lu-x Scrubber (NaOH) REACTOR Figure 10-9 Original design of phosgene reactor before informal safety review. The reaction is shown in Figure 10-10. Significant improvements should be summarized in a memo for others to reference in the future. Thus it is normally stored as a liquid in a container under pressure above its normal boiling point temperature.) with aniline to produce isocyanate and HCl. It is absorbed through the skin. The reviewers simply meet in an informal fashion to examine the process equipment and operating procedures and to offer suggestions on how the safety of the process might be improved. The informal safety review is used for small changes to existing processes and for small bench-scale or laboratory processes. Aniline is a liquid with a boiling point of 364°F. .

pail of caustic is added (the phosgene cylinder would be dumped into this pail in the event of a cylinder or valve leak. room. A caustic scrubber is used to remove the phosgene and HCl vapors from the exit vent stream. relief system is added with an outlet to a scrubber to prevent hazards resulting from a plugged fritted glass bubbler. flow indicator provides visual indication of flow.456 Chapter 10 Hazards Identification Vacuum NaoH C NH. bubblers are used instead of scrubbers because they are more effective. and processes that need an updated review. the caustic would absorb the phosgene). The final process design is shown in Figure 10-11. In addition. the reviewers recommended the following: (1) Hang phosgene indicator paper around the hood. In the process shown in Figure 10-9 the phosgene is fed from the container through a valve into a fritted glass bubbler in the reactor. before the process is started.OH REACTOR Figure reactor Figure 10-11 Final design of phosgene reactor after informal safety review. 4.1 ppm of phosgene). (2) use a safety checklist. The complete process is contained in a hood. and operating areas (this paper is normally white but turns brown when exposed to 0. trap catches liquid phosgene. The formal safety review is a three-step pro- . substantial changes in existing processes. The changes and additions to the process are as follows: 1. 5. 2. 3. and (3) post an up-to-date process sketch near the process. daily. ammonium hydroxide bubbler is more effective for absorbing phosgene. 7. 6. Conduct an informal safety review on this process. The reflux condenser condenses aniline vapors and returns them to the reactor. The formal safety review is used for new processes. Solution The safety review was completed by two individuals. vacuum is added to reduce boiling temperature.

B. pressures. Material safety data sheets: Provided for each hazardous material used. . 3. having a committee review the report and inspect the process. Equipment description: Describes the configuration of the equipment. Introduction A. C. and loss of electricity. such as loss of steam. Emergency shutdown: Describes the procedure used to shut down the equipment if an emergency should occur. C. Sketches of the equipment are provided. 111. D. Normal operating procedures: Describes how the process is operated. 2. This is done after the formal safety review is complete. Reactions and stoichiometry: Provides the chemical reaction equations and stoichiometry. B. 1V. water. handled. This consists in preparing a detailed formal safety review report. Raw materials and products: Refers to specific hazards and handling problems associated 1 with the raw materials and products. Fail-safe procedures: Examines the consequences of utility failures. Cleanup procedures: Describes how to cleatt the process after use. Waste disposal procedure: Describes how toxic or hazardous materials are collected. 1 . reactor runaway. and air pressure. Process overview or summary: Provides a brief description of the process with an emphasis on the major hazards in the operation. VI. air pressure. This checklist is used before every startup. B. D. electricity. Procedures A. This includes major leaks. Provides the physical data and design information associated with the equipment.10-4 Safety Reviews 457 cedure. Safety checklist: Provides the complete safety checklist for the operator to complete before operation of the process. Major release procedures: Describes what to do in the event of a major spill of toxic or flammable material. Safety procedures: Provides a description of the unique concerns associated with the equipment and materials and specific procedures used to minimize the risk. Discusses procedures to minimize these hazards. water. This includes: 1. Equipment setup A. and implementing the recommendations. and relevant physical property data for the materials used. The formal safety review report includes the following sections: I. Overview or summary: Provides a brief summary of the results of the formal safety review. V. Engineering data: Provides operating temperatures. Equipment specifications: Identifies the equipment by manufacturer name and model number. and disposed. or inert padding. Describes what to do for each case so that the system fails safely.

provide a vacuum connection to the dirty toluene storage for charging. 5. add inerting and purging to all drums. 3. Both phases are mixed within the centrifuge and separated countercurrently. or Pod. The heavy phase (water) is fed to the center and travels countercurrent to the toluene to the periphery of the centrifuge. Figure 10-13shows the modified process after the formal safety review has been completed. The heavy liquid out (contaminated water) is sent to waste treatment and the light liquid out (clean toluene) is collected in a 55-gal drum. 4. inerting. because of a difference in densities. add a charge drum with grounding.458 I I TOLUENE Chapter 10 Hazards Identification DIRTY TOLUENE STORAGE Figure 10-12 Toluene water wash process before formal safety review. add heat exchangers to all outlet streams to cool the exit solvents below their flash point (this must include temperature gauges to ensure proper operation). 6. add a relief valve to the dirty toluene storage tank. and . . The separation is achieved with a Podbielniak centrifuge. This process is used to clean water-soluble impurities from contaminated toluene. add elephant trunks at all drums to provide ventilation. bonding. provide dip legs in all drums to prevent the free fall of solvent resulting in the generation and accumulation of static charge. Example 10-4 A toluene water wash process is shown in Figure 10-12. and ventilation. 7. The light phase (contaminated toluene) is fed to the periphery of the centrifuge and travels to the center. Perform a formal safety review on this process. The extraction is conducted at 190°F. Solution The complete safety review report is provided in appendix D. 8. 2. The contaminated toluene is fed from a storage tank into the Pod. The significant changes or additions added as a result of the review are as follows: 1 add grounding and bonding to all collection and storage drums and process vessels.

9. . is relatively easy to apply. 10-5 Other Methods Other methods that are available for identifying hazards are the following: 1. For instance. They included 1. What if the flow stops? The analysis team then decides what the potential consequences might be and how to solve any problems. "What if" analysis: This less formal method of identifying hazards applies the words "what if" to a number of areas of investigation. the committee participants must be experienced in identifying safety problems.9 ~Vacuu - 77°F T POD DIRTY TOLUENE STORAGE 7 WATER "-? F DIRTY TOLUENE CHARGE Figure 10-13 Toluene water wash process after formal safety review. (b) increasing the ventilation to high speed. provide a waste water collection drum to collect all waste water that might contain substantial amounts of toluene from upset conditions. and (c) throwing the sewer isolation switch to prevent solvent from entering the main sewer lines. The formal safety review can be used almost immediately. and is known to provide good results. However. Additional changes were made in the operating and emergency procedure. the question might be. checking the room air periodically with colorimetric tubes to determine whether any toluene vapors are present and 2. changing the emergency procedure for spills to include (a) activating the spill alarm.10-5 Other Methods 459 an°F . For less experienced committees. a more formal HAZOP study may be more effective in identifying the hazards.

1996). The quench reaction is The quenching reaction also forms acetic acid. H A Z O P and H A Z A N . Lees. 8. effects. (London: Butterworths. Guidelines for Hazard Evaluation Procedures. Control panel layout is an excellent application for human error analysis because a control panel can be designed in such a fashion that human error is inevitable. it is necessary to quench the hydrolysis reaction as soon as the sample is taken.COOH). Loss Prevention in the Process Industries. 3d ed. England: Institution of Chemical Engineers. Human error analysis: This method is used to identify the parts and the procedures of a process that have a higher than normal probability of human error. A temperature controller in the water bath maintains the temperature to within 1°Fof the desired temperature. 1992). In this reaction acetic anhydride [(CH. The concentration of acetic anhydride at any time in the CSTR is determined by titration with sodium hydroxide. 1994). Problems 10-1. 3. Suggested Reading Dow's Fire and Explosion Index Hazard Classification Guide. . 2d ed.460 Chapter 10 Hazards Identification 2. The water is mixed with the acetic anhydride just before it enters the reactor. 1992). Kletz. Frank P. (New York: American Institute of Chemical Engineers. (New York: American Institute of Chemical Engineers. Water is also circulated by a centrifugal pump from the temperature bath through coils in the reactor vessel.CO)20] reacts with water to produce acetic acid (CH. This maintains the reactor temperature at a fixed value. Trevor A. The initial experimental design is shown in Figure 10-14. The quenching is achieved by adding an excess of aniline to the sample. ch. 2d ed. The effect of a particular failure is considered with respect to the process. but in a different stoichiometric ratio than the hydrolysis reaction. Failure mode. 7th ed. Water and acetic anhydride are gravity-fed from reservoirs and through a set of rotameters. Because the titration procedure requires time (relative to the hydrolysis reaction time). The hydrolysis of acetic anhydride is being studied in a laboratory-scale continuously stirred tank reactor (CSTR). and criticality analysis (FMECA): This method tabulates a list of equipment in the process along with all the possible failure modes for each item. (Warwickshire. Thus it is possible to determine the acetic anhydride concentration at the time the sample was taken.

b.-. v1 I v2 -----i --- a II R l [ R2 - . Consider the intention "reactant flow to reactor" for your analysis. b. Develop a safety checklist for use before operation of this experiment. Identify the study nodes of the process. Perform a HAZOP study on the intention "hot solvent from heat exchanger. 10-2. Perform a HAZOP study on the laboratory process of Problem 1. as shown in Figure 10-15.- h c z . I I . Samples are withdrawn from the point shown and titrated manually in a hood. Suggest modifications to improve the safety. Perform an informal safety review on the experiment. and a controller valve manipulates the amount of steam to the heat exchanger to achieve the desired set point temperature. ~3 Sample V5 I------- W--c P o i n t C i r c u l a t i n g Water Thermocouple Bath Figure 10-14 Acetic anhydride reactor system.A + . volatile solvents.. a. What safety equipment must be available? c. a. A heat exchanger is used to heat flammable..Problems 461 Acet ic Water 7 F Anhydr ide 7 F - -." Recommend possible modifications to improve the safety of the process.. What specific recommendations can you make to improve the safety of this experiment? 10-3. The temperature of the outlet stream is measured by a thermocouple. .

. 10-4. The hot combustion gases pass through a heat exchanger to heat fresh air for space heating. A gas-fired furnace is shown in Figure 10-16. A high-temperature switch shuts off all gas in the event of high temperature in the fresh air plenum.462 Chapter 10 Hazards Identification le a m /Control Valve i l e Solvent Condensate v G h Heat Exchanger Figure 10-15 Volatile solvent heating system. The gas is ignited by a pilot light flame. Chimney Heat Exchanger Cold Air I Burner I rmostat: n Valve Heat Close Valve Figure 10-16 if T > THish Furnace control system. The gas flow is controlled by an electric solenoid valve connected to a thermostat.

resulting in flooding of the torpedo room and possible sinking of the sub. 10-5. and the torpedo launched. and beverage (composed of syrup and water) in a sequential order. Beverage dispensers are notorious for either taking one's money or not delivering the proper beverage. ice. Determine the various ways in which this system can fail. b. Can you identify the hazard? A similar layout led to a serious accident by a maintenance P r o c e s s Pumps Figure 10-17 Pump layout. The presence of pressurized water was a direct indication that the outer door was open. Before opening the inner door. Suggest at least two ways to prevent this problem. 10-6. The inner door was then closed. What type of valve (normally open or normally closed) is recommended for the gas supply? c. Because no direct visible check was possible. A problem can also arise because of failure of the pilot light. Identify as many failure modes as possible. 10-7. The machine also makes change. Consider a beverage dispenser that delivers a paper cup. the outer door opened. Five process pumps are lined up in a row and numbered as shown in Figure 10-17. . One problem was ensuring that the outer door was closed before the inner door was opened. Use the HAZOP guide words to identify additional possibilities. Determine a failure mode for this system. leading to excessive heating of the plenum and possible fire. the valve was opened momentarily to check for the presence of pressurized water in the tube. The torpedo was loaded into the tube from the torpedo room using the inner door. leading to combustible gases in the furnace. What is the most likely failure mode? d. heat exchanger. leading to the inner door being opened when the outer door was open. a small pipe and valve were attached to the top of the torpedo tube in the torpedo room. and chimney. World War I1 submarines used torpedo tubes with outer and inner doors.Problems 463 a.

The foreman recognized a possible hazard from flammable vapor escaping from the vent pipe and igniting on the sparks from the welding operation. A welding operation was to occur on the roof of a storage vessel. An accident like this might be attributed to human error but is really a hazard resulting from poor layout.5 in of water gauge vacuum (0. 10-8. The roof was equipped with a vent pipe with a flame arrestor.2 psi). Standard storage tanks are designed for a maximum of 2. He connected a hose to the vent at the top of the tank and ran the hose down to the ground. The tank contained a flammable. Can you explain why? . both with independent level controllers. he stuck the end of the hose in a drum full of water. Figure 10-20 shows two tanks in series. Can you suggest a much simpler system? 10-9. an accident occurred.1 psi) and about 6 in of water gauge pressure (0. This configuration resulted in an explosion and fire because of loss of inert material. Figure 10-18 shows a sump designed to collect process fluids. volatile liquid. Complicated designs are almost always more hazardous than simple ones. Can you explain why? 10-11. Because the flammable vapors were water soluble. Figure 10-19 shows a storage tank blanketed with nitrogen.464 Chapter 10 Hazards Identification Figure 10-18 Sump level control system. During a subsequent operation that involved emptying the tank. Storage tanks typically are not capable of withstanding much pressure or vacuum. worker who was sprayed by hot solvent when he disconnected a pump line on the wrong pump. This configuration will result in the lower tank inevitably overflowing. The level controller and pump ensure that the sump level is maintained below a maximum height. A good acronym in chemical plant design is KISS -Keep It Simple. Can you explain what happened and how? 10-10. Stupid! This also applies to hazards.

.. the valve supplying cooling water to a chemical reactor would fail in the open position ("fail open") in the 1 Figure 10-20 Level tanks in series.. . . .. .. Develop a safety checklist for the system described in Example 10-3 and shown in Figure 10-11.:-:. "Fail-safe" is a concept used to specify the position of process instrumentation in the event of power.. .. .... . The intention of the checklist is to ensure the system is safe before operation. . . . i q u i d :::::. . . .. .. . . . . .. ... 10-16.. . .Problems 465 S t o r a g e Tank . 10-13. ... H y d r o c a r ban:.. .. . . . ... . Nitrogen L 40 p s i Figure 10-19 Nitrogen padding system for a storage tank. . identify the study nodes of the reactor process. . . . . . . . . . . ... 10-15. as shown. . or other utility failures. In Figure 10-8. 10-14. Prepare a formal safety review memo for the gas-fired furnace described in Problem 104 and shown in Figure 10-16. . . Review up to the reactor only. . .. Describe an informal safety review process for using a cylinder of phosgene to charge gaseous phosgene to a reactor.. . 10-12. . . . .. . . .... . . . . ... . . . ..... . . . .. . ... . . . . . .. . . .:-:.. .. . . This memo will be given to each committee member before the formal safety review committee meeting. . . . .. .. ... . . . . . air pressure. .:. . . . ... . .. . For instance.. . . . . . . . . . . . .

Feed to a reactor cannot be started until the reactor vessel stirring motor is activated. This led to an accidental release of toxic and flammable material. 10-17. raking in billions of dollars each year. c. you are in charge of ensuring the safety of all operations. A valve must be closed before a pump is started. Lalone is expected to be a blockbuster drug.466 Chapter 10 Hazards Identification event of a power failure. A remotely operated valve is used to fill a tank from a supply line. Two valves cannot both be closed at the same time. La La Pharmaceuticals has recently discovered a new drug. One chemical plant had some thermocouples that did not have sheaths. A valve controls combustion air to a furnace. 10-18. Lalone. b. in their chemical laboratories. d. The valve controls the flow of steam to the exchanger. h. d. This would provide maximum cooling to the reactor and prevent dangerous high temperatures in the vessel. These sheaths protect the thermocouple and also allow the thermocouple to be removed and replaced without shutting down the process. In many cases they can be as simple as a lock and key. A valve controls the flow rate of reactant to a reactor vessel. Interlocks can be mechanical or electronic. Why? 10-21. although they looked like the sheathed type. b." Determine at least 15 ways in which the operator might fail to perform the instructions correctly. a. f. A process operator is given the following instructions: "Charge 10 lb of catalyst into batch reactor A at 3 hr into the cycle. A valve controls the pressure in a steam header. A flammable solvent is heated by steam in a heat exchanger. e. In one such tank the material stored in the tank was changed and an overflow resulted. 10-19. Specify the simplest mechanical interlock capable of achieving the following functions: a. Interlocks are used to ensure that operations in a chemical plant are performed in the proper sequence. The reaction is endothermic. Liquid levels in storage tanks are frequently determined by measuring the pressure at the bottom of the tank. For the next stage of clinical studies over 50 kg of Lalone is required. c. A valve cannot be closed until a furnace is shut down. A remotely operated valve is connected to a drain on a storage tank. Specify either fail open or fail close. As the safety director for the pilot plant operations. The reaction is exothermic. Thermocouples in chemical plants are usually found in sheaths. g. Can you explain why? 10-20. Specify the proper fail-safe positions for the valves in the following equipment. . and La La Pharmaceuticals has decided to produce this in their existing pilot plant operations in Lala Land. A valve controls the flow rate of reactant to a reactor vessel. A valve controls the flow of natural gas to a utility furnace in a power station.

A small heater percolates the water up to the top of the coffee maker. Liquid was discharged and injured the operator. for example. where it drips down through the coffee grounds and filter assembly. This gauge was accidentally overpressured. A pneumatic pressure gauge was designed to operate in the range of 3-15 psig. (3) the chemical reactions are not fully understood. (2) Lalone is synthesized by a batch process through a series of four major steps . and the plant exploded. followed by drying to produce Lalone (all reactions are carried out in the liquid phase and require acetone as a solvent). (This problem requires student access to the Dow Fire and Explosion Index manual. a solvent (60% cyclohexane and 40% pentane) is removed from a . corresponding to the actual process pressures. Lalone has been manufactured only in the laboratory and in small quantities (less than 50 g). (4) so far. However. Describe how you would structure a hazard study for the Lalone manufacturing process. Perform a HAZOP study on a common coffee maker. Pneumatic process equipment operates in the range of 3-15 psig. An operator was told to control the temperature of a reactor at 60°C. corresponding to the pneumatic signal sent from the plant. and identify the study nodes. Draw a sketch of the coffee machine. b. you have learned the following: (1)Lalone is a fine. The coffee product is collected in the coffee pot.Problems 467 During a meeting with the chemist who synthesized Lalone in the laboratory. a. white powder. As the safety director of the pilot plant: a.) In a devolatilizer. a signal of 3 psig might represent 0 psig in the process and 15 psig might represent 1200 psig in the process.three sets of reactions to produce intermediates. He set the set point of the temperature controller at 60. Why? How would you prevent this problem? 10-25. What happened? 10-24. Based on your safety knowledge and experience. A coffee maker has a reservoir where a quantity of clean water is poured. and (6) the Engineering Division has already started writing the operating procedures for the eventual process. the scale printed on the gauge read 0 to 1200 psig. In reality it indicated only the status of the signal being sent to the valve. fresh-brewed coffee in the coffee pot. c. identify the major hazards in this process that you would be concerned about. A light in the control room of a chemical plant indicated whether a valve was closed or not. b. The scale actually indicated 0-100% of a temperature range of 0-200°C. What additional information will you need to conduct the hazard analysis study? 10-22. The valve did not close when it should have. (5) management wants the pilot plant operations to be started as soon as possible. This caused a runaway reaction that overpressured the vessel. 10-26. and most physical and chemical properties are not known. Thus. resulting in an accident. What was the set point temperature the operator actually set? 10-23. Use as a design objective hot.

000gal. The process has several interlocks to prevent polymerization. A water deluge system has been installed around the storage tank and transfer pump. Assuming an equipment value within the radius of exposure of $1 million. estimate the maximum probable property damage. Diesel-powered fire water pumps can provide a maximum fire water demand for 4 hr. Assuming a product value of $1. Operating instructions are current.) Consider a butadiene storage vessel in a tank farm area containing butadiene.4 X 103B ~ U J I ~ . and up-to-date operating instructions. The plant is also under computer control with emergency shutdown based on redundant inputs. 10-27. c. and portable dry chemical extinguishers are in the process area.468 Chapter 10 Hazards Identification polymer and sent to the solvent recycle section of the plant for treatment and recovery. a. and a water deluge system. estimate the business interruption loss. and the system has been through a recent reactive chemicals review. Backflow protection has been installed and is tested to prevent backflow into the transfer line and storage. b. Loss control features include combustible gas detectors installed around the containment area and transfer system. Vacuum is always broken with nitrogen. The storage area has the required drainage to direct a spill away from the tank. The process area has a 1% sloping concrete surface with a remote impounding area capable of handling all of a spill and 30 min of fire water. The plant has a diesel emergency power generator with an emergency cooling system. The process is run above the flash point of the solvent at 300 mm Hg. The process has complete. fireproofing. Cable trays are protected with deluge. The devolatilizer is located in an open structure with good access for fire fighting. The vapor space in the vessel is inerted. The vessel has a relief device set at 50 psig. . written. The butadiene storage is diked separately from the other materials. The transfer operations in and out of storage are monitored by computer control with emergency shutdown capability. The specific gravity of the butadiene is 0. styrene. The process unit has many loss control features. with the relief valve set at 50 psig. The process area has combustible gas detectors. The butadiene storage area is equipped with a chilled glycol cooling system that can be operated from an emergency generator if necessary. (This problem requires student access to the Dow Fire and Explosion Index manual.6263. The storage system has remotely operated emergency block valves on all transfer lines into and out of the tank. and isopropene. A diesel-driven fire pump is capable of handling the emergency demand for 4 hr. Assume a potential spill of 8000 lb of flammable material with a heat of combustion of 19.50 per pound and an annual plant production rate of 35 million lb. cyclohexane. A reactive chemicals review was completed recently. The maximum butadiene storage capacity is 100. The normal pressure of the butadiene storage vessel is 15 psig. Determine the Dow F&EI value for this process to estimate the relative degree of hazard. isopentane.

the temperature can rise quickly. estimate the business interruption loss. the reactor temperature rises. with the weakest part of the vessel being the welded seam between the roof and the vertical wall of the tank. Cooling coils are provided in batch reactors to remove the energy of reaction.00 per pound for this plant and an annual production rate of 10 million Ib. One vessel is called a weak seam roof tank. Assuming a product value of $2. 10-29. Which tank is the best choice for storing this material? 10-30. with the weakest part being the seam along the bottom of the tank.Problems 469 a. Your manufacturing plant has purchased a number of robots to facilitate production. estimate the maximum probable property damage. 10-28. A flammable liquid is to be stored in a large storage vessel. The other vessel is a domed roof tank. In the event of a cooling water failure. resulting in dangerous pressures within the reactor and a possible explosion. Determine the Dow F&EI value for this process to estimate the relative degree of hazard. What are the main hazards associated with robots? What are some effective safeguards against these hazards? . resulting in a higher reaction rate and higher energy generation. by the time the alarm sounds. Design a better instrumentation and alarm configuration to detect loss of cooling more directly. Frequently. The result is a runaway reaction. Draw the instrumentation diagram. Exothermic chemical reactions are frequently dangerous because of the potential for a runaway reaction. it is too late. c. Assuming an equipment value within the radius of exposure of $1million. During a runaway reaction. Loss of cooling can be detected by measuring the temperature within the reactor and sounding an alarm. Two vessels are available. b.

.

This is a form of consequences analysis. Consequence analysis describes the expected damage. It should be emphasized that the teachings of this chapter are all easy to use and to apply. Hazard and operability (HAZOP) studies provide information on how a particular accident occurs. No probabilities or numbers are used with the typical HAZOP study. and days outage. describe two probabilistic methods (event trees and fault trees). although the experience of the review committee is used to decide on an appropriate course of action. LOPA is a simplified QRA. This is a form of incident identification. these numbers are obtained by some rather simple calculations involving published correlations.C H A P T E R 1 1 Risk Assessment isk assessment includes incident identification and consequence analysis. However. Incident identification describes how an accident occurs. The last two sections show how the frequencies are used in QRA and LOPA studies. This includes loss of life. It frequently includes an analysis of the probabilities. The hazards identification procedures presented in chapter 10 include some aspects of risk assessment. show how the failure probabilities of individual hardware components contribute to the failure of a process. and describe the relationship between quantitative risk analysis (QRA) and LOPA. The Dow F&EI includes a calculation of the maximum probable property damage (MPPD) and the maximum probable days outage (MPDO). including the mathematics of equipment failure. We focus on determining the frequency of accident scenarios. describe the concepts of layer of protection analysis (LOPA). and the results R . In this chapter we will review probability mathematics. damage to the environment or capital equipment.

With adequate data it can be shown that. 11-1 Review of Probability Theory Equipment failures or faults in a process occur as a result of a complex interaction of the individual components. Control. Equation 11-1assumes a constant failure rate p. the faster the reliability decreases. The complement of the reliability is called the failure probability (or sometimes the unreliability). As t +oo. Other and more complex distributions are available. The overall probability of a failure in a process depends highly on the nature of this interaction. on average. 1982). ) = 1. 381. the component fails after a certain period of time.the reliability goes to 0. . and it is given by The failure density function is defined as the derivative of the failure probability: The area under the complete failure density function is 1. p. The higher the failure rate. This is called the average failure rate and is represented by p with units of faultsltime. Process Dynamics. +l . Data are collected on the failure rate of a particular hardware component. The failure density function is used to determine the probability P of at least one failure in the time period to to tl: P(r. E. MI: Ann Arbor Science. In this section we define the various types of interactions and describe how to perform failure probability computations. This simple exponential distribution is the one that is used most commonly because it requires only a single parameter. t) is given by a Poisson distribution1: where R is the reliability. The speed at which this occurs depends on the value of the failure rate p. (11-4) lB. The probability that the component will not fail during the time interval (0. Rijnsdorp. P. and Protection (Ann Arbor.472 Chapter 11 Risk Assessment are often the basis for significantly improving the design and operation of chemical and petrochemical plants. f1 f1 f (t) dt = p/ I.> e-@ dt = e-"' - ~ " 1 . Roffel and J. p.

and (d) the reliability R(t). and R are shown in Figure 11-1. p (faults/time) 0 Period of Approximately Constant 1. Failure Rate. Equations 11-1 through 11-5 are valid only for a constant failure rate p. The integral represents the fraction of the total area under the failure density function between time to and tl.- 11-1 Review of Probability Theory Failure Rate Failure Density Failure Probability Reliability Figure 11-1 Typical plots of (a) the failure rate p. shown in Figure 11-2. The time interval between two failures of the component is called the mean time between failures (MTBF) and is given by the first moment of the failure density function: E ( t ) = MTBF = 1 Typical plots of the functions p. The failure rate is approximately constant over the midlife of the component.1 -- Infant Mortality 4 Old Age D 0 P Time Figure 11-2 A typical bathtub failure rate curve for process hardware. The failure rate is highest when the component is new (infant mortality) and when it is old (old age). . f . the failure rate is reasonably constant and Equations 11-1 through 11-5 are valid. P. (c) the failure probability P(t). Many components exhibit a typical bathtub failure rate. Between these two periods (denoted by the lines in Figure 11-2). (b) the failure density f(t).

Equation 11-9 is expanded to The cross-product term P ( A ) P ( B )compensates for counting the overlapping cases twice. For series components the overall process reliability is found by multiplying the reliabilities for the individual components: The overall failure probability is computed from For a system composed of two components A and B. This rule is easily memorized because for parallel components the probabilities are multiplied. This means that the failure probabilities for the individual components must be multiplied: where n is the total number of components and P. The total reliability for parallel units is given by where Ri the reliability of an individual process component.474 Chapter 11 Risk Assessment Interactions between Process Units Accidents in chemical plants are usually the result of a complicated interaction of a number of process components. This parallel structure is represented by the logical AND function. The logical OR function represents this case. is the failure probability of each component. The overall process failure probability is computed from the individual component probabilities. Consider the example of tossing a single die and determining the probability that the number of points is even or divisible by 3. is Process components also interact in series. Process components interact in two different fashions. In this case . In some cases a process failure requires the simultaneous failure of a number of components in parallel. This means that a failure of any single component in the series of components will result in failure of the process.

Actual values would Table 11-1 Failure Rate Data for Various Selected Process Components1 Instrument Controller Control valve Flow measurement (fluids) Flow measurement (solids) Flow switch Gas-liquid chromatograph Hand valve Indicator lamp Level measurement (liquids) Level measurement (solids) Oxygen analyzer pH meter Pressure measurement Pressure relief valve Pressure switch Solenoid valve Stepper motor Strip chart recorder Thermocouple temperature measurement Thermometer temperature measurement Valve positioner Faultslyear 0. the term P(A)P(B) is negligible.13 0.75 1. .29 0. 313. Loss Prevention in the Process Industries (London: Butterworths. Lees.11-1 Review of Probability Theory 475 P(even or divisible by 3 ) = P(even) + P(divisib1e by 3) - P(even and divisible by 3 ) .88 1. 1986).044 0.44 'Selected from Frank P.14 0. These are average values determined at a typical chemical process facility. If the failure probabilities are small (a common situation). and Equation 11-10 reduces to This result is generalized for any number of components.41 0. For this special case Equation 11-9 reduces to Failure rate data for a number of typical process components are provided in Table 11-1.52 0.86 5.027 0.12 30.14 3.22 0.6 0. The last term subtracts the cases in which both conditions are satisfied.70 6.60 1. p.42 0.022 0.65 5.044 1.

A summary of computations for parallel and series process components is shown in Figure 11-3.(1 RIJq-~ F:=P Rz - Pl)(l - P2) R = R1R2 P P = = PI+ P. and not intermittent and that the failure of one device does not stress adjacent devices to the point that the failure probability is increased. .L n R ) / t Tpi n R = 1 . 1 = :I 3 . and the MTBF for this system. materials of construction. .476 Chapter 11 Risk Assessment Failure Probability Reliability F a i l u r e Rate p p1 z P = P 1 . there Note t h a t i s n o c o n v e n i e n t way t o c o m b i n e the failure rate. hard. and other factors.(1 .) P = ( . Determine the overall failure rate.( n 1 . 1 n !Pi S e r i e s L i n k o f Components: The f a i l u r e o f e i t h e r component a d d s t o the t o t a l system f a i l u r e . Figure 11-3 Computations for various types of component linkages. The flow is measured by a differential pressure (DP) device.T(I i = l Ri) P a r a l l e l L i n k o f Components: The f a i l u r e o f t h e s y s t e m r e q u i r e s t h e f a i l u r e o f b o t h components. depend on the manufacturer.2 i = 1 P = 1 - 1 i : 1 Pi) R =TR~ i . Example 11-1 The water flow to a chemical reactor cooling coil is controlled by the system shown in Figure 11-4. and the control valve manipulates the flow of coolant. P P = PIP2 P = i . the environment. the reliability. = 1 . the design. Assume a 1-yr period of operation. = . The assumptions in this analysis are that the failures are independent. the controller decides on an appropriate control strategy. the unreliability.

if any one of the components fails.45 0.25 0. The failure rates are from Table 11-1.10 = 0.10 = e-'' p = -ln(0.43 yr.The result is The failure probability is computed from P = 1. on average.76 The overall reliability for components in series is computed using Equation 11-8. The reliability and failure probability are computed for each component using Equations 11-1 and 11-2.30 failureslyr.10) = 2. The overall failure rate is computed using the definition of the reliability (Equation 11-1): 0. once every 0.11-1 Review of Probability Theory 477 Controller Control Flow Figure 11-4 Flow control system.0.55 0. The components of the control system are linked in series. Thus.R = 1 . The results are shown in the following table. This system is expected to fail. Solution These process components are related in series.901yr. The MTBF is computed using Equation 11-5: MTBF =-= 1 P 0.29 1.24 Failure probability P=1-R 0.75 0.60 0.43 yr. Component Control valve Controller DP cell Failure rate p (faultslyr) 0. the entire system fails.41 Reliability R = e-Pt 0. .

It consists of a pressure switch within the reactor connected to an alarm light indicator. 4. The alarm and feed shutdown systems are linked in parallel. and the MTBF for a high-pressure condition.66 Failure probability P=1-R 0. 2..14 0. The automatic system stops the flow of reactant in the event of dangerous pressures. . the reliability.--- - I Valve .96 0..87 0._ .044 0. Also. This reactor contains a high-pressure alarm to alert the operator in the event of dangerous reactor pressures. Assume a I-yr period of operation. Solution Failure rate data are available from Table 11-1.--.I . For additional safety an automatic high-pressure reactor shutdown system is installed. This system is activated at a pressure somewhat higher than the alarm system and consists of a pressure switch connected to a solenoid valve in the reactor feed line.u Figure 11-5 A chemical reactor with an alarm and an inlet feed solenoid.04 0. Compute the overall failure rate.. the failure probability.- u2L._ . Example 11-2 A diagram of the safety systems in a certain chemical reactor is shown in Figure 11-5.The reliability and failure probabilities of each component are computed using Equations 11-1 and 11-2: Component 1.-. Pressure switch 1 Alarm indicator Pressure switch 2 Solenoid valve Failure rate p (faultslyr) 0.34 ... ..14 0...478 Chapter 11 Risk Assessment Pressure k/ A larm Switch I .87 0.42 Reliability R = e-" 0.. 3.13 0. develop an expression for the overall failure probability based on the component failure probabilities.13 0.

MTBF = - 1 = 1.87)(0. a failure is expected once every 1.80 yr.5 yr.56 yr.11-1 Review of Probability Theory 479 A dangerous high-pressure reactor situation occurs only when both the alarm system and the shutdown system fail. The overall failure probability is given by where P ( A ) is the failure probability of the alarm system and P ( S ) is the failure probability of the emergency shutdown system. These two components are in parallel.835 = 0. For the alarm system the components are in series: R P = = n 2 i=l R. p = -In R = -1n(0.7 yr. with both systems in parallel the MTBF is significantly improved and a combined failure is expected every 13. For the alarm system .165. Similarly.R -1n R 1 = = 1 . P For the alarm system alone a failure is expected once every 5.0.574 = 0.555 faultslyr. 1 MTBF = .835) = 0. However.R = 1 .0.073 faultslyr.7 yr. for a reactor with a highpressure shutdown system alone.930) = 0. 1.80 yr.426.= 13.835.96) = 0. An alternative procedure is to invoke Equation 11-9 directly. = (0.574) = 0. p = -1n(0.180 faultslyr. P The two systems are combined using Equation 11-6: p = -In R = -ln(0. For the shutdown system the components are also in series: P = 1. MTBF = -= P 5.

and P. as shown. we obtain This is the same answer as before. Revealed and Unrevealed Failures Example 11-2 assumes that all failures in either the alarm or the shutdown system are immediately obvious to the operator and are fixed in a negligible amount of time. It is possible for the equipment to fail without the operator being aware of the situation.3%.480 Chapter 11 Risk Assessment For the shutdown system The overall failure probability is then Substituting the numbers provided in the example. After a failure occurs. The difference between this answer and the answer obtained previously is 14.). However. Without regular and reliable equipment testing. the spare tire in the trunk might also be flat without the driver being aware.. then P ( A ) = PI P ( S ) = P. . Figure 11-6 shows the nomenclature for revealed failures. Failures that are immediately obvious are called revealed failures.of the problem until the spare is needed. The time that the component is operational is called the period of operation and is denoted by T. + P..P4 are assumed to be small. called the period of inactivity or downtime (T. The MTBF is the sum of the period of operation and the downtime. a period of time. Emergency alarms and shutdown systems are used only when a dangerous situation occurs. and + P2. The component probabilities are not small enough in this example to assume that the cross-products are negligible. is required to repair the component. If the products PIP. This is called an unrevealed failure. A flat tire on a car is immediately obvious to the driver. alarm and emergency systems can fail without notice.

11-1 Review of Probability Theory 481 Component Repoired V] Component Fails Component Repoired 3 I.. For revealed failures the period of inactivity or downtime for a particular component is computed by averaging the inactive period for a number of failures: where n is the number of times the failure or inactivity occurred and T . I -t I I I I I Time Figure 11-6 Component cycles for revealed failures. . The MTBF is the sum of the period of operation and the repair period: MTBF =-=T . . is the period for repair for a particular failure. Similarly. 11 Operotionol 1 m w I ---q _O I I I I T - MTBF Tr . 1 I" + 7. the time before failure or period of operation is given by where rq is the period of operation between a particular set of failures. A failure requires a period of time for repair.

we can write the equations for the availability and unavailability for revealed failures: For unrevealed failures the failure becomes obvious only after regular inspection.we obtain . + 7. This situation is shown in Figure 11-7. The unavailability U is the probability that the component or process is found not functioning. It is obvious that The quantity 7. then The average period of unavailability is computed from the failure probability: P ( t ) dt. similarly. By definition. represents the period that the process is in operation. The availability A is simply the probability that the component or process is found functioning. If 7. 7" = Combining with Equation 11-19.482 Chapter 11 Risk Assessment It is convenient to define an availability and unavailability. and the total time. the unavailability is By combining Equations 11-16 and 11-17 with the result of Equation 11-14. it follows that the availability is given by 7. represents and. is the average period of unavailability during the inspection interval and if ri is the inspection interval.

. The result is u=1 An expression for the availability is - -(I P7i 1 - p T 8 ) . for unrevealed failures the process or component is unavailable during a period equal to half the inspection interval. (11-23) If the term PT. (11-24) and Equation 11-21 is integrated to give. K I I I 0 a Failed I I I I 0 I I I I iQ----I -+ + I I T~ i 7. This is substituted into Equation 11-23 and integrated. This is a useful and convenient result.11-1 Review of Probability Theory Component Repoired Component Foils Failure not Noticed i n f. on average. 1 Time Figure 11-7 Component cycles for unrevealed failures. 3 Operational I 1 until inspection I I I I I i 5 w C a. for unrevealed failures.egT1). < 1. (11-22) A = 1 -(I P7i . A decrease in the inspection interval is shown to increase the availability of an unrevealed failure. then the failure probability is approximated by < P(t) - Pt. The failure probability P(t) is given by Equation 11-2. It demonstrates that.

484 Chapter 11 Risk Assessment Equations 11-19 through 11-25 assume a ndgligible repair time. This is usually a valid assumption because on-line process equipment is generally repaired within hours.083 yr. The danger results only when a process upset occurs and the emergency system is unavailable. This is every p. times in a time interval Ti.55 faultslyr. . Thus The shutdown system is available 97. The inspection period is 1/12 = 0. For the shutdown system p = 0.2% of the time. Assume that a dangerous process episode occursp. Probability of Coincidence All process components demonstrate unavailability as a result of a failure. This requires a coincidence of events. Assume that a maintenance inspection occurs once every month and that the repair time is negligible. Example 11-3 Compute the availability and the unavailability for both the alarm and the shutdown systems of Example 11-2.18 faultslyr. a dangerous situation will occur only when the process episode occurs and the emergency system is unavailable. whereas the inspection intervals are usually monthly. The unavailability is computed using Equation 11-25: The alarm system is available 99. For the alarm system the failure rate is p = 0.U episodes. The frequency of this episode is given by For an emergency system with unavailability U. Solution Both systems demonstrate unrevealed failures. For alarms and emergency systems it is unlikely that these systems will be unavailable when a dangerous process episode occurs.7% of the time.

The unavailability is computed from Equation 11-25: The average frequency of dangerous coincidences is given by Equation 11-27: The MTBC is (from Equation 11-29) 1 1 MTBC = . .11-1 Review of Probability Theory 485 The average frequency of dangerous episodes Ad is the number of dangerous coincidences divided by the time period: For small failure rates U = $p7iandp. Solution The frequency of process episodes is given by Equation 11-26: A = 1 episode/[(l4 months)(l yr112 months)] = 0. This is a significant improvement and shows why a proper and timely maintenance program is important. Compute the MTBC for a high-pressure excursion and a failure in the emergency shutdown device..50 yr. Ad 0. If the inspection interval T~ is halved. = 0. and the resulting MTBC is 100 yr.= ---.020 It is expected that a simultaneous high-pressure incident and failure of the emergency shutdown device will occur once every 50 yr. = ATi. Assume that a maintenance inspection occurs every month.023.010. A. Substituting into Equation 11-27 yields The mean time between coincidences (MTBC) is the reciprocal of the average frequency of dangerous coincidences: Example 11-4 For the reactor of Example 11-3 a high-pressure incident is expected once every 14 months.8571yr. then U = 0.

identify an initiating event of interest. This is used effectively to determine the probability of a certain sequence of events and to decide what improvements are required. 2S. This increases the failure rate substantially. 2. and actuator (for example. An example of a redundant temperature measurement is an additional temperature probe. describe the resulting accident event sequences. Guidelines for Hazard Evaluation Procedures. . Handbook of Highly Toxic Materials Handling and Management (New York: Marcel Dekker. one needs to deliberately design the systems to minimize common cause failures. various safety systems come into play to prevent the accident from propagating. Grossel and D. 1995). This approach is inductive. An example of a redundant temperature control loop is an additional temperature probe. Crowl. If appropriate data are available.486 Chapter I 1 Risk Assessment Systems are designed to function normally even when a single instrument or control function fails. The method provides information on how a failure can occur and the probability of occurrence. 11-2 Event Trees Event trees begin with an initiating event and work toward a final result. When working with control systems. processing paths. construct the event tree. 1992). cooling water control valve). The event tree approach includes the effects of an event initiation followed by the impact of the safety systems. Common Mode Failures Occasionally an incident occurs that results in a common mode failure. identify the safety functions designed to deal with the initiating event. (New York: American Institute of Chemical Engineers. This is achieved with redundant controls. consider several flow control loops similar to Figure 11-4. The utility is connected to these systems via OR gates. The typical steps in an event tree analysis are3 1. These safety systems either fail or succeed. and actuators that ensure that the system operates safely and reliably. eds. 3. the procedure is used to assign numerical values to the various events. controller. This is a single event that affects a number of pieces of hardware simultaneously. 2d ed. and 4. 264. A common mode failure is the loss of electrical power or a loss of instrument air. S. When an accident occurs in a plant. The degree of redundancy depends on the hazards of the process and on the potential for economic losses. A. For example. including two or more measurements. p. A utility failure of this type can cause all the control loops to fail at the same time.

the horizontal line is continued through the safety function without branching. the upper branch continues through the second function. If the high-temperature alarm operates properly. Horizontal lines are drawn from these two states to the next safety function. A line is drawn from the initiating event to the first safety function. The second safety function is the operator noticing the high reactor temperature during normal inspection. and the circles with the crosses represent unsafe conditions. the operator will already be aware of the high-temperature condition. Four safety functions are identified. The open circles indicate safe conditions. By convention. The sequence description and consequences are indicated on the extreme right-hand side of the event tree. If a safety function does not apply. At this point the safety function can either succeed or fail. where the operator notices the high temperature. 1 g Q G I ing 1 C o i Is Nat i COO e r n Out Cool i n Water I I Alarm ' Therrnocoup High Temperature A larm Figure 11-8 Reactor with high-temperature alarm and temperature controller. The first safety function is the high-temperature alarm. For this example.. The initiating event is written first in the center of the page on the left. a successful operation is drawn by a straight line upward and a failure is drawn downward. These are written across the top of the sheet.11-2 Event Trees Reactor Feed . The final safety function is invoked by the operator performing an emergency shutdown of the reactor. The event tree for a loss-of-coolant initiating event is shown in Figure 11-9.This system is identical to the system shown in Figure 10-6. The third safety function is the operator reestablishing the coolant flow by correcting the problem in time. Consider the chemical reactor system shown in Figure 11-8. . except that a high-temperature alarm has been installed to warn the operator of a high temperature within the reactor. These safety functions are written across the page in the order in which they logically occur. The event tree is written from left to right.

Figure 11-9 Event tree for a loss-of-coolantaccident for the reactor of Figure 11-8.0000625 = 0.0075 Shu 0 .02500 occurrtnccS/yr.01 0.2250 o c c u r r c n c e ~ / y r .0025 Shu Run Shutdown Runaway : 0.H i a h Temp Operator Notices H i g h Temp Operator Re-starts Cool ins Operator S h u t s Donn Reactor Saf c ty Func t ion: Alarm R l e r t s Operator R Ident if ier: B C D E A 0.02975 + + 0. . 0.02't75 fl 1 I n .2227 = 0. t i a t ing Event: Run Con Loss o f Cool ing 1 Occurrcnce/y~.0001875 + + 0.001688 0. 0.7't25 I Con 0.0005625 = 0. 0 0 1 8 7 5 RBOE Run Con 0.

it is estimated that the operator successfully shuts down the system 9 out of 10 times. represents a successful safety function and the lower branch represents a failure.025 failure per year (sum of failures ADE. Figure 11-10 The computational sequence across a safety function in an event tree.10 failureldemand. The event tree can be used quantitatively if data are available on the failure rates of the safety functions and the occurrence rate of the initiation event.25 failureldemand. Also assume that the operator will notice the high reactor temperature 3 out of 4 times and that 3 out of 4 times the operator will be successful at reestablishing the coolant flow. The letters indicate the sequence of failures of the safety systems. The failure rates for the safety functions are written below the column headings. or 0. ABDE.495 Failure o f 0. The computational sequence performed at each junction is shown in Figure 11-10.01 *0. For this example the net frequency is estimated at 0. the upper branch. Finally. The lettering notation in the sequence description column is useful for identifying the particular event. This is a failure rate of 0. An event tree for a different initiating event in this study would use a different letter. The initiating event is always included as the first letter in the notation. This is a failure rate of 0. For this example assume that a loss-of-cooling event occurs once a year. the lettering sequence ADE represents initiating event A followed by failure of safety functions D and E. A possible solution is the inclusion of a high-temperature reactor shutdown system.005 Safety Function Occurrences/yr. and ABCDE). by convention. The net frequency associated with the event tree shown in Figure 11-9 is the sum of the frequencies of the unsafe states (the states with the circles and x's).5 = 0. Let us also assume that the hardware safety functions fail 1%of the time they are placed in demand. Both of these cases represent a failure rate of 1time out of 4.01 Failures/Dernand Initiating Event 5 ~ u c c e s so f safety Function Occurrences/yr. This control . (1 -0. This event tree analysis shows that a dangerous runaway reaction will occur on average 0.01 failureldemand.11-2 Event Trees 489 Safety Function 0. or once every 40 years. This is considered too high for this installation.01 )*0.025 time per year. Again.5 = 0. For the example here. The frequency associated with the upper branch is computed by subtracting the failure rate of the safety function from 1 (giving the success rate of the safety function) and then multiplying by the frequency of the incoming branch. The occurrence frequency for the initiating event is written below the line originating from the initiating event. The frequency associated with the lower branch is computed by multiplying the failure rate of the safety function times the frequency of the incoming branch.

Operator ~ l ~ r t ~ s. 2Lt50 S h u t Oonn 1 0.001875 ABCD t r n t i n u t Oprrmtisa 8.25 8-81 8. t i t r s Safety Func t ion: Hilh Temp I d e n t i f i e r : B C 0.00001688 0.01 0.8025 0.000001875 Shu t Down Rvnowoy RBC 0.1 0.001875 0.00750 0.25 ling Rear t e r 0 E F -r ROE Fo i lure~/Demond: R0 0.800625 0.H i g h Ttmp O p t r a t Re-stgrts Cee Shutdonn S h u t s Oena Optrater H i g h Temp Optrator RIor. This includes a high-temperature shutdown system .001856 RBDE 1 Occurrencc/yr. I 0.8006187 S h u t Oonn S h u t Oonn Runaney Figure 11-11 Event tree for the reactor of Figure 11-8.002228 S h u t Down R 1 ABD S h u t Oonn I n i t i a t i n g Event: LOSS o f Cooling 0.

This is perhaps the major disadvantage of event trees. In one case the flat is due to driving over debris on the road. A fault tree for anything but the simplest of plants can be large. Fault trees are a deductive method for identifying ways in which hazards can lead to accidents. If a probabilistic computation is attempted. The additional safety function provides a backup in the event that the high-temperature alarm fails or the operator fails to notice the high temperature. The emergency shutdown temperature would be higher than the alarm value to provide an opportunity for the operator to restore the coolant flow. The flat tire example is pictured using a fault tree logic diagram. The event tree is useful for providing scenarios of possible failure modes. 11-3 Fault Trees Fault trees originated in the aerospace industry and have been used extensively by the nuclear power industry to qualify and quantify the hazards and risks associated with nuclear power plants. or top event. and intermediate events are events that can. the tire failure is caused by either a defective tire or a worn tire. The basic events are events that cannot be defined further. The fishlike symbol represents the OR logic function. The other possible cause is tire failure. It means that either of the input events will cause the output state to occur. driving over the road debris is a basic event because no further definition is possible. and works backward toward the various scenarios that can cause the accident. . this approach lends itself to computerization. data must be available for every safety function in the event tree. Fortunately. involving thousands of process events. there is no certainty that the consequence of interest will actually result from the selected failure. The two contributing causes are either basic or intermediate events. The difficulty is that for most real processes the method can be extremely detailed. If an engineer is concerned about a particular consequence. Similarly. An event tree begins with a specified failure and terminates with a number of resulting consequences.the flat tire is caused by either debris on the road or tire failure. As shown in Figure 11-12. shown in Figure 11-12. a flat tire on an automobile is caused by two possible events.11-3 Fault Trees 491 system would automatically shut down the reactor in the event that the reactor temperature exceeds a fixed value.00025 time per year. resulting in a huge event tree. The flat tire is identified as the top event. with a variety of computer programs commercially available to draw fault trees based on an interactive session. an estimate can be made of the failure frequency. This approach is becoming more popular in the chemical process industries. The tire failure is an intermediate event because it results from either a defective tire or a worn tire. The circles denote basic events and the rectangles denote intermediate events. This is a substantial improvement obtained by the addition of a simple redundant shutdown system. or once every 400 years. The event tree for the modified process is shown in Figure 11-11. The runaway reaction is now estimated to occur 0. For this example. This is used most successfully to modify the design to improve the safety. The approach starts with a well-defined accident. For instance. If quantitative data are available. such as a nail. mostly as a result of the successful experiences demonstrated by the nuclear industry.

tornadoes. This means that the output state of the AND logic function is active only when both of the input states are active. Define the unallowed events. This could include wiring failures.Chapter 11 Risk Assessment +0 Tire Failure Debr is r? Flat Tire Top E v e n t Figure 11-12 A fault tree describing the various events contributing to a flat tire. whereas an event such as "leak in valve7'is too specific. a number of preliminary steps must be taken: 1. Before the actual fault tree is drawn. 4. and environmental factors. For instance. lightning. driving over debris in the road does not always lead to a flat tire. For reasonably complex chemical processes a number of additional logic functions are needed to construct a fault tree. 2. human. The INHIBIT function is useful for events that lead to a failure only part of the time. and hurricanes. Events in a fault tree are not restricted to hardware failures. The AND logic function is important for describing processes that interact in parallel. These are events that are unlikely or are not under consideration at the present. Events such as "high reactor temperature" or "liquid level too high" are precise and appropriate. Define the physical bounds of the process. Events such as "explosion of reactor" or "fire in process" are too vague. What components are to be considered in the fault tree? . The INHIBIT gate could be used in the fault tree of Figure 11-12 to represent this situation. Define the existing event. A detailed list is given in Figure 11-13. Define precisely the top event. They can also include software. What conditions are sure to be present when the top event occurs? 3.

11-3 Fault Trees 493 AND G a t e : The r e s u l t i n g requires the output event simultaneous input events. draw the top event at the top of the page. 0 INTERMEDIATE E v e n t : An e v e n t that results from t h e o f other i n t e r a c t i o n o f a number events. Define the equipment confiGration. occurrence o f a l l 6 OR G a t e : The resulting output event o f any requires the individual occurrence event. . 0 0 UNDEVELOPED E v e n t : An event that due t o cannot be developed suitable further lack o f informat ion. input OO 0 ~ ~ h i b Condition iI N H I B I T E v e n t : ~ The the output input event occurs w i l l occur if and t h e inhibit event BASIC E v e n t : occure. or will it be necessary to consider the valve components? The next step in the procedure is to draw the fault tree. Will the analysis consider just a valve. What valves are open or closed? What are the liquid levels? Is this a normal operation state? 6. 5. Label it as the top event to avoid confusion later when the fault tree has spread out to several sheets of paper. First. EXT ERNAL E v e n t : An e v e n t condition that i a a boundary fault tree. Define the level of resolution. event that needs no A fault further definition. t o the TRANSFER S y m b o l s : Used t o t r a n e f e r i n t o and out o f the f a u lt o f tree paper. a sheet Figure 11-13 The logic transfer components used in a fault tree.

The complete fault tree is shown in Figure 11-14. 4. What events must occur to contribute to this single event? Write these down as either intermediate. tornadoes. wiring failures. If the new events cannot be related to the top event by a single logic function. 3. electrical storms. the purpose of the fault tree is to determine the individual event steps that must occur to produce the top event. Solution The first step is to define the problem. Remember. Draw a fault tree for this system. If these events are related in parallel (all events must occur in order for the top event to occur). The emergency shutdown system can fail by a failure of either pressure switch 2 or the solenoid valve. The minimal cut sets are . These events must occur together so they must be connected by an AND function. Two events must occur for overpressuring: failure of the alarm indicator and failure of the emergency shutdown system. Continue developing the fault tree until all branches have been terminated by basic. determine the major events that contribute to the top event. undeveloped. These must also be connected by an OR function. 2. a number of computations can be performed. Determining the Minimal Cut Sets Once the fault tree has been fully drawn. Physical bounds: The equipment shown in Figure 11-5. they must be connected by an OR gate. Unallowed events: Failure of mixer. 6.494 Chapter 11 Risk Assessment Second. undeveloped. These must be connected by OR functions. Example 11-5 Consider again the alarm indicator and emergency shutdown system of Example 11-2. Top event: Damage to reactor as a result of overpressuring. undeveloped. or external events on the sheet. Now consider any one of the new intermediate events. Write these down as intermediate. the new events are probably improperly specified. electrical failures. The top event is written at the top of the fault tree and is indicated as the top event (see Figure 11-14). Then decide which logic function represents the interaction of these newest events. basic. reactor feed flowing. Equipment configuration: Solenoid valve open. they must be connected to the top event by an AND gate. basic. The first computation determines the minimal cut sets (or min cut sets). 1. All intermediate events must be expanded. or external events. 5. If these events are related in series (any event can occur in order for the top event to occur). Existing event: High process pressure. hurricanes. The alarm indicator can fail by a failure of either pressure switch 1or the alarm indicator light. Level of resolution: Equipment as shown in Figure 11-5. or external events on the tree.

. the minimal cut sets are ordered with respect to failure probability. 15." Transactions of the American Nuclear Society (1972). the top event could occur through a variety of different combinations of events. Similarly. Vesely.11-3 Fault Trees 495 Overpressur ing o f Reactor T~~ E~~~~ P = 0. the various sets of events that could lead to the top event. a set involving just two events is more likely than a set involving three. The higher probability sets are examined carefully to determine whether additional safety systems are required. ~ The procedure is best described using an example. B. Fussell and W. For instance. The different unique sets of events leading to the t event are the minimal cut sets. a set involving human interaction is more likely to fail than one involving hardware alone.0702 I F a i l u r e o f Alarm Indicator I F a i l u r e o f Emergency Shutdown P = 0. The minimal cut sets are determined using a procedure developed by Fussell and V e ~ e l y .1648 R = 0. Some of the mimimal cut sets have a higher probability than others. "A New Methodology for Obtaining Cut Sets for Fault Trees. E.8352 P 0. In general.4258 w w w w Figure 11-14 Fault tree for Example 11-5. Based on these simple rules. "% 4J. The mi imal cut sets are useful for determining the various ways in which a top event could occur.

whereas OR gates lead to more sets. Copy into this new row all the entries in the remaining column of the first row: Note that the C in the second column of the first row is copied to the new row. replace gate C in the second row by its inputs. Be sure to copy the 1 from the other column of the first row: Finally. . replace gate B by one of the inputs. First. gate B is replaced by adding an additional row below the present row. and then create a second row below the first. Solution The first step in the procedure is to label all the gates using letters and to label all the basic events using numbers. Because gate C i s also an O R gate. replace C by basic event 3 and then create a third row with the other event.496 Chapter 11 Risk Assessment Example 11-6 Determine the minimal cut sets for the fault tree of Example 11-5. Because gate B is an OR gate. replace gate C in the first row by its inputs. This is shown in Figure 11-14. gate A is replaced by gates B and C: Gate B has inputs from event 1 and event 2. This generates a fourth row: The cut sets are then This means that the top event occurs as a result of any one of these sets of basic events. Logic gate A in Figure 11-14 has two inputs: one from gate B and the other from gate C. The first logic gate below the top event is written: AND gates increase the number of events in the cut sets. Next. Because gate A is an AND gate.

consider The second and third sets are supersets of the first basic set because events 1 and 2 are in common. Sometimes a set might be of the following form: 1.04)(0.13) = 0.0442 P(2 AND 4 ) = (0. The failure probabilities for the basic events were obtained from Example 11-2. the probabilities from the cut sets are added together. The minimal cut sets represent the various failure modes.0052 P(l AND 4 ) = (0.1 1 -3 Fault Trees 497 The procedure does not always deliver the minimal cut sets. INHIBIT gates are considered a special case of an AND gate. In general.04)(0. This approach assumes that the probability crossproduct terms shown in Equation 11-10 are negligible.34) = 0. For instance. With the first approach the computations are performed using the fault tree diagram itself. Then the necessary computations are performed across the various logic gates.0136 Total 0. The supersets are eliminated to produce the minimal cut sets. and undeveloped events are written on the fault tree.13)(0. For Example 11-6 events 1 . This procedure approaches the exact result only if the probabilities of all the events are small.0169 P(2 AND 3 ) = (0.2. Quantitative Calculations Using the Fault Tree The fault tree can be used to perform quantitative calculations to determine the probability of the top event. This is accomplished in two ways.2 This is reduced to simply 1.13)(0.13) = 0. On other occasions the sets might include supersets.34) = 0.4 or 2. The failure probabilities of all the basic. Remember that probabilities are multiplied across an AND gate and that reliabilities are multiplied across an OR gate.3 or 1. 3 or 2. The results of this procedure are shown in Figure 11-14. The computations are continued in this fashion until the top event is reached. For this case 4 P ( l AND 3 ) = (0.0799 . For this example there are no supersets. The symbol P represents the probability and R represents the reliability. The other procedure is to use t e minimal cut sets. this result provides a number that is larger than the actual probability. To estimate the overall failure probability. external. 2.4 could cause the top event.

to complete. Also. More complete fault trees are usually developed by more experienced engineers. Software is available for graphically constructing fault trees. Fault trees developed by different individuals are usually different in structure. determining the minimal cut sets. The minimal cut sets provide enormous insight into the various ways for top events to occur. Fault trees of this size require a considerable amount of time. If the fault tree is used to compute a failure probability for the top event. This is opposed to the event tree approach. the approach assumes that a failure of one component does not stress the other components. Fault trees are also used to determine the minimal cut sets. increases the reliability of the system significantly. Reference libraries containing failure probabilities for various types of process equipment can also be included. A leaking valve is a good example of a partial failure. the entire fault tree procedure enables the application of computers. Furthermore. For Example 11-6 all the cut set probabilities were added. of course.- 498 Chapter 11 Risk Assessment This compares to the exact result of 0. Finally. Fault trees also assume that failures are "hard. because the cross-product terms were neglected. This inexact nature of fault trees is a considerable problem." that aparticular item of hardware does not fail partially.0702 obtained using the actual fault tree. measured in years. Advantages and Disadvantages of Fault Trees The main disadvantage of using fault trees is that for any reasonably complicated process the fault tree will be enormous. Fault trees involving thousands of gates and intermediate events are not unusual. These probabilities are not usually known or are not known accurately. This top event is selected by the user to be specific to the failure of interest. Fault trees begin with a top event and work backward toward the initiating events (deduction). and calculating failure probabilities. For small probabilities the cross-product terms are negligible and the addition will approach the true result. the developer of a fault tree can never be certain that all the failure modes have been considered. A major advantage of the fault tree approach is that it begins with a top event. Some companies adopt a control strategy to have all their minimal cut sets be a product of four or more independent failures. Relationship between Fault Trees and Event Trees Event trees begin with an initiating event and work toward the top event (induction). as shown by Equation 11-10. The different trees generally predict different failure probabilities. This. then failure probabilities are needed for all the events in the fault tree. resulting in a change in the component failure probabilities. where the events resulting from a single failure might not be the events of specific interest to the user. This is an approximate result. The cut sets are related to each other by the OR function. .

11-4 QRA and LOPA 499 Not acceptable Frequency Figure 11-15 of risk. 2000). Both are used together to produce a complete picture of an incident. from its initiating causes all the way to its final outcome. 11-4 QRA and LOPA Risk is the product of the probability of a release. engineering. The complexity of a QRA depends on the objectives of the study and the available information. th&obability of exposure. Q R A and LOPA are the methods that are most commonly used. The actual risk of a process or plant is usually determined using quantitative risk analysis (QRA) or a layer of protection analysis (LOPA). (New York: Center for Chemical Process Safety. . or an appropriate adaptation. Other methods are sometimes used. In both methods the frequency of the release is determined using a combination of event trees. General description The initiating events are the causes of the incident. Guidelines for Chemical Process Quantitative Risk Analysis. Quantitative Risk Analysis5 Q R A is a method that identifies where operations. fault trees. and the top events are the final outcomes. Risk is usually described graphically. however. and the consequences of the exposure. All companies decide their levels of acceptable risk and unacceptable risk. as shown in Figure 11-15. The two methods are related in that the top events for fault trees are the initiating events for the event trees. Maximum benefits result when QRAs are used at the beginning "CPS. 2d ed. or management systems can be modified to reduce risk. Probabilities and frequencies are attached to these diagrams. AICHE.

then a full QRA may be justified. The approximate values and categories are selected to provide conservative results. . The combined effects of the protection layers and the consequences are then compared against some risk tolerance criteria. the results of QRA and LOPA studies are especially satisfactory when comparing alternatives. The criteria may include frequency of fatalities. D. If the LOPA results are unsatisfactory or if there is any uncertainty in the results. The major steps of a QRA study include 1. such as relief valves. estimating the potential incident frequencies using event trees and fault trees. then the application of LOPA methods may be more appropriate. Layer of Protection Analysis: Simplified Process Risk Assessment. In general. ed. The protection layers may include inherently safer concepts. to lower the frequency of the undesired consequences. (New York: Center for Chemical Process Safety. QRA is a relatively complex procedure that requires expertise and a substantial commitment of resources and time. QRA is especially effective for evaluating alternative risk reduction strategies. The QRA method is designed to provide managers with a tool to help them evaluate the overall risk of a process. and required number of independent layers of protection for a specific consequence category. estimating the risk by combining the impacts and frequencies. 3. Crowl. estimating the incident impacts on people. Various layers of protection are added to a process. and 5. and recording the risk using a graph similar to Figure 11-15. This method includes simplified methods to characterize the consequences and estimate the frequencies. and human intervention. the frequencies are estimated. safety instrumented functions. Thus the results of a LOPA should always be more conservative than those from a QRA. This concept of layers of protection is illustrated in Figure 11-16. QRAs are used to evaluate potential risks when qualitative methods cannot provide an adequate understanding of the risks. In LOPA the consequences and effects are approximated by categories. passive devices. for example. defining the potential event sequences and potential incidents.- - - - - - - 500 Chapter 11 Risk Assessment of a project (conceptual review and design phases) and are maintained throughout the facility's life cycle. Individual companies use different criteria to establish the boundary between acceptable and unacceptable risk. AICHE. 6CCPS. A. frequency of fires. However. The results of both methods need to be used cautiously. active devices. maximum frequency of a specific category of a consequence. and the effectiveness of the protection layers is also approximated. such as dikes or blast walls. evaluating the incident consequences (the typical tools for this step include dispersion modeling and fire and explosion modeling). and property. Layer of Protection Analysis6 LOPA is a semi-quantitative tool for analyzing and assessing risk. environment. 2001) (in press). the basic process control system. 2. 4. In some instances this complexity may not be warranted.

many types of protective layers are possible. 3. identifying a single consequence (a simple method to determine consequence categories is described later). Figure 11-16 does not include all possible layers of protection. 2. A scenario may require one or many layers of protection.11-4 QRA and LOPA 501 Figure 11-16 Layers of protection to lower the frequency of a specific accident scenario. The primary purpose of LOPA is to determine whether there are sufficient layers of protection against a specific accident scenario. As illustrated in Figure 11-16. The major steps of a LOPA study include 1. Because no layer is perfectly effective. however. sufficient layers must be added to the process to reduce the risk to an acceptable level. . identifying the initiating event for the scenario and estimating the initiating event frequency (a simple method is described later). depending on the process complexity and potential severity of an accident. Note that for a given scenario only one layer must work successfully for the consequence to be prevented. identifying an accident scenario and cause associated with the consequence (the scenario consists of a single cause-consequence pair).

3.Table 11-2 Consequence size - Semi-Quantitative Consequences Categorization 1-10-lb release Category 3 Category 2 Category 2 Category 1 Category 1 Category 2 Category 1 Category 2 Category 1 Category 2 Category 3 Category 4 Category 3 Category 2 Category 4 Category 3 Category 5 Category 4 Category 5 Category 5 10-100-lb release 100-1.000 gal.000-10.000 Category 3 Plant outage 1-3 months Plant outage >3 months Category 4 Category 4 $1.000100.000 gal. >10.000-lb release 1.000$10.000-lb release Category 5 Category 5 Category 5 Category 4 Category 2 10.000.000 Category 4 Vessel rupture.000-lb release >100. . atmospheric boiling point.000-lb release Category 5 Category 5 Category 5 Category 5 Category 3 Release characteristic Extremely toxic above BP1 Extremely toxic below BP or highly toxic above BP Highly toxic below BP or flammable above BP Flammable below BP Combustible liquid Spared or nonessential equipment Plant outage <1 month Category 3 Category 2 $10. 100-300 psig >300 psig Category 4 Category 4 >$10. Vessel rupture.000 Category 2 Category 2 Category 2 $0 -$10.000 Category 1 Category 4 Category 3 $100.000$1.000$100.000.000.00010.000 Category 5 Category 5 Category 5 Consequence characteristic Mechanical damage to large main product plant Mechanical damage to small by-product plant Consequence cost (US dollars) Categories 'BP.000.

This can occur through a variety of incidents. as shown in Table 11-2. If. a reactor failure frequency is divided by 12 if the reactor is used only 1 month during the entire year. combining the initiating event frequency with the probabilities of failure on demand for the independent protection layers to estimate a mitigated consequence frequency for this initiating event. a control system is given preventive maintenance 4 times each year. such as a leak from a vessel. explosions. One of the less rigorous methods includes the following steps: 1. Consequence The most common scenario of interest for LOPA in the chemical process industry is loss of containment of hazardous material. then its failure frequency is divided by 4. The frequencies are also adjusted (reduced) to include the benefits of preventive maintenance. and (3) quantitative estimates with human harm. which may be deemphasized because the consequences are insignificant. . It also identifies problems. additional layers of protection are required). the quantity of the release is estimated using source models. Adjust this frequency to include the demand. In a LOPA study the consequences are estimated using one of the following methods: (1) semi-quantitative approach without the direct reference to human harm. (2) qualitative estimates with human harm. 2.and 7. and the consequences are characterized with a category. In a QRA study the consequences of these releases are quantified using dispersion modeling and a detailed analysis to determine the downwind consequences as a result of fires. See footnote 6 for the detailed methods. for example. 3. Determine the failure frequency of the initiating event. or release from a relief valve. for example. 5. Frequency When conducting a LOPA study. 6.1 1 -4 QRA and LOPA 503 4. This procedure is repeated for other consequences and scenarios. it clearly identifies problems that may need additional work. such as a QRA. When using the semi-quantitative method. plotting the consequence versus the consequence frequency to estimate the risk (the risk is usually shown in a figure similar to Figure 11-15). Adjust the failure frequency to include the probabilities of failure on demand (PFDs) for each independent layer of protection. Although the method is easy to use. several methods can be used to determine the frequency. a ruptured pipeline. identifying the protection layers available for this particular consequence and estimating the probability of failure on demand for each protection layer. or toxicity. This is an easy method to use compared with QRA. a gasket failure. A number of variations on this procedure are used. evaluating the risk for acceptability (if unacceptable.

100 rn. Failure rates can also be greatly affected by preventive maintenance routines. consistent with the degree of conservatism or the company's risk tolerance criteria. 2. well trained. not fatigued) to 10-4/lift 10-3 to 10-2 to 1 to 10-2 lo-' to 10-2 1 to 10-2 1 to 10-2 1 to lo-' lo-' to 10-2 to lo-" 10-QO opportunity 10-1 to 10-31 opportunity 1 X 10-4(/lift) 1 x lo-" 1x 1 x lo-' 1 x 10-I 1 x 10-I 1 x lo-' 1 x 10-I 1 x lo-' 1 x 10-2 1 x lo-" (/opportunity) 1 x 10-2 (Iopportunity) IIndividual companies choose their own values. 100 m Atmospheric tank failure Gasket /packing blowout Turbineldiesel engine overspeed with casing breach Third-party intervention (external impact by backhoe. The IPL is auditable. and documentation. 3.504 Chapter 11 Risk Assessment Table 11-3 Typical Frequency Values Assigned to lnitiating Events' Example of a Frequency range value chosen by a from literature company for use in LOPA (per yr) (per yr) Initiating event Pressure vessel residual failure Piping residual failure. There are three rules for classifying a specific system or action of an IPL: 1. The failure frequencies for the common initiating events of an accident scenario are shown in Table 11-3. testing. unstressed. The IPL is effective in preventing the consequence when it functions as designed.full breach Piping leak (10% section). vehicle. The common practice is to use a PFD of lo-' unless experience shows it to be higher or lower. the PFD of the IPL must be capable of validation including review. respectively. The IPL functions independently of the initiating event and the components of all other IPLs that are used for the same scenario. The PFD for each independent protection layer (IPL) varies from 10-' to for a weak IPL and a strong IPL. Some PFDs recommended by CCPS (see footnote 6) for screening are given in Tables 11-4 and 11-5. . etc.) Crane load drop Lightning strike Safety valve opens spuriously Cooling water failure Pump seal failure Unloading/loading hose failure BPCS instrument loop failure Regulator failure Small external fire (aggregate causes) Large external fire (aggregate causes) L O T 0 (lock-out tag-out) procedure failure (overall failure of a multiple element process) Operator failure (to execute routine procedure. that is.

The frequency of the consequence is subsequently determined using .1 1 -4 QRA and LOPA 505 Table 1 1-4 PFDs for Passive lPLs Comments (assuming an adequate design basis. f! is the initiating event frequency for the initiating event i. Preventsoverpressure Reduces rate of heat input and provides additional time for depressurizing. etc Reduces the frequency of large consequences (widespread spill) of a tank overfill. (New York: American Institute of Chemical Engineers. inspections. Reduces the frequency of large consequences of an explosion by confining blast and by protecting equipment. etc. 2001) (in press). If properly implemented. When there are multiple scenarios with the same consequence. and maintained. as described previously. A. etc. spill. can eliminate scenarios or significantly reduce the consequences associated with a scenario If properly designed. each scenario is evaluated individually using Equation 11-30. etc. can eliminate the potential for flashback through a piping system or into a vessel or tank Passive lPLs Dike PFDs from industry' 1 X lo-z to 1 x lo-' 1X to 1 x lo-3 1X 1x 1X 1x 1X 1x PFDs from CCPS1 1X Underground drainage system Open vent (no valve) Fireproofing Blast wall or bunker Inherently safer design Flame or detonation arrestors 1 X lo-z to lo-3 lo-' to lo-3 lo-' to 1X 1 X lo-' 1X lo-3 1 X lo-z 1 x lo-' to 1 x lo-6 1 x 10-I to 1 x lo-3 1x 'CCPS. The PFD is usually lo-'. Crowl. ed. Simplified Process Risk Assessment: Layer of Protection Analysis. fire fighting. rupture. and maintenance procedures) Reduces the frequency of large consequences (widespread spill) of a tank overfill. buildings. The frequency of a consequence of a specific scenario endpoint is computed using where ff is the mitigated consequence frequency for a specific consequence C for an initiating event i. rupture. spill. D. installed. and PFDij is the probability of failure of the jth IPL that protects against the specific consequence and the specific initiating event i.

The consequence frequency is found using Equation 11-30: . The PFDs are estimated from Tables 11-4 and 11-5. IEC 61508. 2001) (in press). See IEC 1X (1998. The IPLs are human interaction with 10-min response time and a basic process control system (BPCS). 1998) and IEC 6151 1 (IEC. (Draft in Process). 'IEC (1998). 1 to 1 X 10-' 1 x lo-' 1 X 10-' to 1X 1 X lo-2 'CCPS. that is. Geneva: International Electrotechnical Commission. 1 X 10-' 1 X lo-' to Can be credited as an IPL if not associated with the initiating event being considered. 1 x lo-' to 1x Prevents system from exceeding specified overpressure. Effectiveness of this device can be 1 x lo-' sensitive to service and experience.506 Chapter 11 Risk Assessment Table 11-5 PFDs for Active lPLs and Human Actions Comments [assuming an adequate design basis. D. where f: is the frequency of the Cth consequence for the ith initiating event and I is the total number of initiating events for the same consequence. A. inspections. training. Example 11-7 Determine the consequence frequency for a cooling water failure if the system is designed with two IPLs. Effectiveness of this device is sensitive to service and experience.The human response PFD is lo-' and the PFD for the BPCS is 10-I. f : = lo-'. 2001). ed. Geneva: International Electrotechnical Commission. Simplified Process Risk Assessment: Layer of Protection Analysis. and maintenance procedures PFDs (active IPLs) and adequate documentation.' See IEC 61508 (IEC. Functional Safety of ElectricaNElectronic/Programmable Electronic Safety-related Systems." Simple well-documented action with clear and reliable indications that the action is required.2. IEC 61511. Parts 1-3. and testing procedures from (human action)] industry Active IPL or human action Relief valve PFDs from CCPS1 Rupture disc Basic process control system (BPCS) Safety instrumented functions (interlocks) Human action with 10 min response time Human action with 40 min response time 1 x 10-I to 1 x lo-2 Prevents system from exceeding specified over1 x lo-5 pressure. 'IEC (2001). Parts 1-7. Solution The frequency of a cooling water failure is taken from Table 11-3. Simple well-documented action with clear and reliable indications that the action is required. Functional Safety Instrumented Systems for the Process Industry Sector. 2001) for life-cycle requirements and additional disc~ssion. Crowl. (New York: American Institute of Chemical Engineers.~.

F. D. ch. 15.Suggested Reading 507 As illustrated in Example 11-7. and using a deenergized trip system (i. including the sensor. Louvar and B.e.the failure frequency is determined easily by using LOPA methods. 19. There are three safety integrity levels (SILs) that are generally accepted in the chemical process industry for emergency shutdown systems: 1. "A New Methodology for Obtaining Cut Sets for Fault Trees. . Louvar. A SIF achieves low PFD figures by using redundant sensors and final redundant control elements. 2d ed. The concept of PFD is also used when designing emergency shutdown systems called safety instrumented functions (SIFs). MI: Ann Arbor Science. J. 1998). Roffel and J. B. Vesely. Guidelines for Consequence Analysis of Chemical Releases (New York: American Institute of Chemical Engineers. Fussell and W. Process Dynamics. including the sensor. and Protection (Ann Arbor. Health and Eizvironmental Risk Analysis: Fundamentals with Applications (Upper Saddle River. Control. 1982). Many companies find that they have a limited number of SIL3 systems because of the high cost normally associated with this architecture. F. logic solver. 1999). 2. a single logic solver. Lees. NJ: Prentice Hall PTR. J. Guidelines for Hazard Evaluation Procedures." Transactions ofthe American Nuclear Society (1972).. and requires periodic proof testing. P. 1992). Rijnsdorp. and final control element. and the system requires careful design and frequent validation tests to achieve the low PFD figures. using multiple sensors with voting systems and redundant final control elements. a single final control element. SIL3 (PFD = loe3to lop4):SIL3 systems are typically fully redundant. Suggested Reading CCPS. testing the system components at specific intervals to reduce the probability of failures on demand by detecting hidden failures. logic solver. E. Loss Prevention in the Process Industries. 3. E. SILl (PFD = lo-' to lop2):These SIFs are normally implemented with a single sensor. final control element. B. (London: Butterworths. 1996). (New York: American Institute of Chemical Engineers. SIL2 (PFD = to These SIFs are typically fully redundant. and requires periodic proof testing. 2d ed. a relayed shutdown system).

the storage tank is equipped with a high-level alarm and a high-level shutdown system. estimate the number of overflows expected per year. Determine an expression for the probability of the top event in terms of the component failure probabilities. The storage tank system shown in Figure 11-18is used to store process feedstock. Determine the minimal cut sets. Given that the level indicator fails 4 timeslyr. The high-level shutdown system is connected to a solenoid valve that stops the flow of input stock. Compute a value for the failure probability of the top event. Overfilling of storage tanks is a common problem in the process industries. a.508 Chapter 11 Risk Assessment Figure 11-17 Fault tree gates. Given the fault tree gates shown in Figure 11-17 and the following set of failure probabilities: Component Failure probability a. Use both the expression of part a and the fault tree itself. 11-2. c. Use the following data: . b. Develop an event tree for this system using the "failure of level indicator" as the initiating event. To prevent overfilling. Problems 11-1.

Develop a fault tree for the top event of "storage tank overflows. the reliability. 11-8. Show that for a process protected by two independent protection systems the frequency of dangerous coincidences is given by 11-7. and the MTBC.01 0. what is the new probability of the top event? 11-5. assuming that a high-level episode occurs once every 6 months. . Compute the availability of the level indicator system and flow shutdown system for Problem 11-2. A reactor experiences trouble once every 16 months. Determine the minimal cut sets. Determine the overall failure frequency. A starter is connected to a motor that is connected to a pump. The starter fails once in 50 yr and requires 2 hr to repair. Inspection takes place once every month. and the unavailability for this system.01 b. Calculate the unavailability. System High-level alarm Operator stops flow High-level switch system Failuresldemand 0.1 0. 11-4. Compute the MTBC for a high-level episode and a failure in the shutdown system. Derive Equation 11-22. What are the most likely failure modes? Should the design be improved? 11-3. The problem of Example 11-5 is somewhat unrealistic in that it is highly likely that the operator will notice the high pressure even if the alarm and shutdown systems are not functioning. the probability that the system will fail in the coming 2 yr. Draw a fault tree using an INHIBIT gate to include this situation. 11-6.Problems 509 Solenoid Flow meter Chart Valve Figure 11-18 Level control system with alarm." Use the data in Table 11-1 to estimate the failure probability of the top event and the expected number of occurrences per year. Determine the minimal cut sets. Assume a 1-month maintenance schedule. The motor fails once in 20 yr and requires 36 hr to repair. The pump fails once per 10 yr and requires 4 hr to repair. the frequency of dangerous coincidences. The protection device fails once every 25 yr. If the operator fails to notice the high pressure in 1 out of 4 occasions.

1 faultlyr I I Flammable vapor 0. .3 Figure 11-19 Determine the failure characteristics of the top event. I Explosion I Chemical deflagration p = 0.4 P = 0.2 P = 0.E Top event 5 6 P = 0.1 P = 0.2 faultlyr flame p = 10 faultlyr p = Figure 11-20 Determine the MTBF of the top event.

Also list the minimal cut sets. failure rate. 11-10. reliability. Compute the MTBF. 11-11. and probability of failure of the top event of the system shown in Figure 11-19. p. Determine P. Also show the minimal cut sets. Determine the MTBF of the top event (explosion) of the system shown in Figure 11-20. -7 Overflow A Figure 11-21 Determine the failure characteristics of the top event.Problems 511 11-9. and the MTBF for the top event of the system shown in Figure 11-21. . R.

512 Chapter 11 Risk Assessment Y Reactor explosion (T) Figure 11-22 Determine the failure characteristics of a reactor explosion. and SIL3 ratings with PFDs of lop3. that is. someone turns off valve 7. 11-14. Using the system shown in Figure 11-23. SIL2. when the alarm sounds. what will be the frequency if this regulator is given preventive maintenance once per month? . Using the system shown in Figure 11-24. Determine the expected failure rates and MTBFs for control systems with SIL1. 11-13. If a regulator has a consequence frequency of lop1failurelyr.respectively. 11-12. draw the fault tree and determine the failure characteristics of the top event (vessel overflows). 11-15. 11-16. 11-17. Determine the failure characteristics and the minimal cut sets for the system shown in Figure 11-22.and lop4. draw the fault tree and determine the failure characteristics of the top event (vessel pressure exceeds MAWP). Determine the consequence frequency for a regular failure if the system is designed with three IPLs. In this problem you have human intervention.

Overflow I I I I 1 2 5 Worker closes valve 7 when level goes up Figure 11-24 Control system to prevent vessel overflow. .Problems 513 Valve 8 opens at high pressure Valve 4 closes at high level Top event = vessel pressure exceeds MAWP Figure 11-23 A control system to prevent the pressure from exceeding the MAWP.

how many IPLs are needed to reduce this frequency to 11-22. a.000. what steps would you take to improve the performance? 11-29. If you have a plant with poor safety performance. Release of 1000 pounds of phosgene. What would you do to move the unacceptable scenarios into the acceptable region? b. per opportunity. If you have a complex and dangerous plant. What redundant components should be added to a critical measurement and controller? 11-30. describe what you would do to establish which parts of the plant need special attention. Are the following scenarios acceptable or not: a. Release of 1000 pounds of isopropanol at 75OF. 11-24. list four protective layers that are clearly IPLs. Determine the consequence frequency of a cooling water system if it is used only 2 months every year and if it is given preventive maintenance each month of operation. Using the results of Problem 11-19. Was the analysis of Problem 11-19 acceptable? 11-21. describe the process for determining the frequency of this specific event.514 Chapter 11 Risk Assessment 11-18. Category 2 every 50 years.000. 11-26. What consequence categories do the following scenarios have? a. b. Assume that a company decides to characterize an acceptable risk as a Category 1 failure every 2 years and a Category 5 failure every 1000 years. If a specific consequence has two initiating events that give the same consequence. If a plant has a consequence frequency of lo-'. b. c. if they have PFDs of lo-'. Potential facility damage of $1. 11-20. 11-23.) 11-27. 11-19. and respectively. What steps should be taken to decrease the MTBF of a critical control loop? . 11-28. If your lock-outltag-out procedure has a failure frequency of what measures could be taken to reduce this frequency? 11-25. Using the rules for IPLs. Determine the MTBF for SIL1-3 systems. lo-'. Category 4 every 100 years. (Note: This is not the same as Problem 11-15.

An important principle in safety states that the causes of accidents are visible the day before the accident. investigation summary.C H A P T E R 1 2 Accident Investigations he investigation of accidents and near misses (that is. close calls) provides opportunities to learn how to prevent similar events in the future. Accident investigations. T 12-1 Learning from Accidents Every member of an investigation team learns about problems that precipitate accidents. including detailed descriptions and recommendations. This vision (knowledge or awareness) is developed by the study and development of accident and nearmiss investigations. This new knowledge helps every team member avoid similar situations in the future. In this chapter we cover the more important techniques. Many professionals believe that this sharing of information about accidents has been a major contributor to the steady improvement in safety performance. In recent years important techniques have been developed for improving the effectiveness of investigations. . layered investigations. aids for diagnosis. These causes are visible to professionals who "see" deficiencies. many others will also benefit. and aids for recommendations. If the investigation is appropriately reported. the investigation process. are commonly shared within the chemical industry. including learning from accidents.

(3) analyzing the facts and developing potential causes of the accident. Kletz. (2) accumulating relevant facts. Their evidence supported their conclusions.516 Chapter 12 Accident Investigations This concept is also important for reporting minor accidents or near misses. 1988). . faultfinding creates an environment that is not conducive to learning. The newer and better method includes a deeper analysis of the facts and additional levels or layers of recommendations. pp. this older method developed recommendations that were relatively superficial. This deeper analysis is. similar to a brainstorming session to develop new applications for a common house brick. (6) developing recommendations to eliminate recurrence of this type of accident. and (7) using an investigation style that is fact-finding and not faultfinding. for example. "Layered Accident Investigations. most accidents are investigated in this style." Hydrocarbon Processing (November 1979). Good investigations help organizations use every accident as an opportunity to learn how to prevent future accidents. It is much easier to correct minor problems before serious accidents occur than to correct them after they are manifested in major losses. and T. The fundamental steps in an investigation include (1) developing a detailed description of the accident. Kletz. Investigation results are used to change hazardous practices and procedures and to develop management systems to use this new knowledge on a long-term and continuous basis. Unfortunately. 'T. often leads to new conclusions and recommendations. Accident investigations are designed to enhance learning. (4) studying the system and operating methods relevant to the potential causes of the accident. Further investigation usually cannot uncover additional facts. Kletz emphasized an extra effort to generate three levels of recommendations for preventing and mitigating accidents: First layer: immediate technical recommendations. New and interesting applications will continue to surface. This recommended deeper analysis identifies underlying causes of the accident that are analyzed to develop a multilayered solution to the problem layered recommendations. According to Kletz. 373-382. however. Learning from Accidents in Industry (Boston: Butterworths.' It is a technique that significantly improves the commonly used older methods. A deeper analysis of the facts. Second layer: recommendations to avoid the hazards. 12-2 Layered Investigations The important concept of layered investigations is emphasized by T. ( 5 ) developing the most likely causes. The number of relevant facts accumulated in an accident investigation is usually limited. and one or two technical recommendations resulted. Minor accidents and near misses are excellent opportunities to obtain "free chances" to prevent larger accidents from occurring in the future. Kletz. Third layer: recommendations to improve the management system. Older investigation methods identified only the relatively obvious causes of an accident.

3.12-2 Layered Investigations 517 To fully utilize this layered technique. such as paint pool depths at the edges of the pool and add more lifeguards. 7. The pool was relatively crowded. Third layer recommendations: Improving the management system 1. An older child unknowingly pushed a 5-year-old into the deep water. 5. the older child was engaged in horseplay. 6. Approximately 100 children. 3. An old-style accident investigation report would include only one or two recommendations. the younger child did not know how to swim. ranging between 5 and 16 years old. Second layer recommendations: Avoiding the hazard 1. and the 5-year-old slipped under the water without being noticed by others. Add a roving lifeguard to monitor and control pool behavior. Add more lifeguards. 2. 3. 2. Paint pool depths at the pool edges. and the pool did not offer swimming lessons. Add swimming lessons for all age groups. Give all new swimmers (especially young children) a pool orientation. Assign the supervisor to make formal (documented) audits on a regular basis. 4. 2. 2. the lifeguard had many blind fields of vision. ~ Example 12-1 Illustrate the layered investigation process to develop underlying causes of a municipal pool accident. Layered recommendations are the result of uncovering the underlying causes of the accident: First layer recommendations: Immediate technical recommendations 1. Train lifeguards to alert supervision of observed potential problems. These technical improvements and new management systems will prevent future drown- . almost all recommendations can be implemented without difficulty. Reduce the number of swimmers. the pool was overly crowded. were in and around a pool (3 ft to 9 ft deep). A drowning accident occurred during an open swim period. including the lifeguard. 4. In this particular example. Facts about the accident that support conclusions at all three levels are accumulated. the investigation process is conducted with an open mind. the pool did not have deep and shallow markings. the pool did not have an orientation program. Prohibit horseplay. 5. Solution The facts uncovered by an investigation team are 1. Zone pool to keep smaller children at shallow end of pool.

This example also illustrates the value of having an open mind during the investigation. etc.)? How can leaks (etc. C r a ~ e n . One approach that can be used for most accidents is described here and shown in Table 12-2. Safety and Accident Prevention in Chemical Operations (New York: Wiley. decomposed. . 1982). 153.518 Chapter 12 Accident Investigations Table 12-1 Questions for Layered Accident Investigations1 (1) What equipment failed? How can failures be prevented or made less likely? How can failures or approaching failure be detected? How can failures be controlled or consequences minimized? What does the equipment do? What other equipment can be used instead? What could we do instead? (2) What material leaked (exploded. A set of questions designed to help accident investigators find less obvious ways to prevent accidents is shown in Table 12-1. Learning from Accidents in Industry (Boston: Butterworths. 1988).. ~ 2Howard H. 659-680. eds. it is an adaptation of a process recommended by A.) be prevented? How can leaks or approaching leak be detected? What does material do? Can volumes of material be reduced? What materials can be substituted? What could we do instead? (3) Which people could have performed better? What could they have done better? How can we help them to perform better? (4) What is the purpose of the operation involved in the accident? Why do we do this? What could we do instead? How else could we do it? Who else could do it? When else could we do it? - 'Trevor Kletz. and feedback approach by team members gives results that are always greater than the sum of the parts. Fawcett and William S. D. The team approach of questioning and answering is especially important because the supportive. pp. which is a requirement for uncovering underlying causes. ings and also prevent other types of accidents in this pool environment. Wood. synergistic.p. 12-3 Investigation Process Different investigators use different approaches to accident investigations.

Do not smother key results. which is the major purpose of the investigation. Items 5-7 appropriately contain the opinions of the authors (investigation team). however. Items 1-4 are objective and should not include the authors' opinions. The accident investigation report is written using the principles of technical documentation. photographs. (3) incident description.12-4 Investigation Summary 519 Table 12-2 Step Accident lnvestigation Process Purpose Choose team as quickly as possible. Make overview survey (maximum of 1 hr) to understand the type and value of the information needed to derive causes of the accident. Establish origin of accident and facts relevant to layered causes and recommendations. concise. accurate. Study (2) to (6) to develop conclusions and layered recommendations. and data (interviews or recorded data) are used. and hypothesize the sequence of events. (2) process description (equipment and chemistry). This technical style allows readers to develop their own independent conclusions and recommendations. It includes comprehensive details that are of particular interest to specialists. procedures. Delegate responsibilities to team members with suggested completion times. the accident investigation report is a learning tool. and analyze facts to clarify perplexing evidence. and recommendations (8) Report The accident investigation report is the major result of the investigation. (6) conclusions. Based on (1) and (2). As a result of these criteria. . Gather and organize preincident facts. Keep report clear. Experience and affiliation are proportional to the magnitude of the accident. and technical. Record extent of damage. These details. are too focused for an average inquirer. and interviews. inspections. Resist development of potential causes to maintain momentum and objectivity while collecting data. (1) Investigation team (2) Brief survey (3) Set objectives and delegate responsibilities (4) Preincident facts (5) Accident facts (6) Research and analyses (7) Discussion. Make detailed examinations with photos. define the objectives and subobjectives of the investigation (the investigation team does this). (5) discussion. the format should be flexible and designed specifically to best explain the accident. In general. The format may include the following sections: (1) introduction. (4) investigation results. 12-4 lnvestigation Summary The previously described accident investigation report is a logical and necessary result of an investigation. Flow sheets. Initiate research-type experiments. and (7) layered recommendations. Develop accident investigation report. conclusions.

. or change methods (layers 2 & 3) * * * * * Management influences (Decisions and practices) * * * * * Physical and management events to give preaccident conditions * * * * * * * Recommendations (and events) may address historical events. p. The third-layer recommendations shown in Figure 12-1emphasize the importance of management systems for preventing accidents. Kletz. and on a long-term basis. to break the link in the chain of events that led to the accident. that is. These concepts are described in Example 12-2. This type of summary is shown in Figure 12-1. It emphasizes underlying causes and layered recommendations. Management systems are designed to continuously. either prevent the accident or eliminate the hazardous conditions. Examples may be (1) a quar3T. inspect. for example. Kletz3 used a report format that summarizes the events and recommendations in a diagram. Learning from Accidents in Industry. The illustrated format is similar to the one used by Kletz.520 Chapter 12 Accident Investigations Accident Summary Accident title: Major damage: Date: Location: Recommendations for ~reventiodmitiaation lst layer: Immediate technical recommendation 2nd layer: Recommendations for avoiding hazard 3rd layer: Recommendations for improving the management systems Events Major accident Events which precipitate accident Recommendations * * * * * Recommendations which will break the chain of events (layers 1. plant design procedures * Figure 12-1 Accident report summary. 22.2 & 3 Preaccident conditions Sequence of operations or steps to derive accident conditions * Recommendations to train.

. 5-year-oldfatality. Add roving lifeguard. Example 12-2 Use the investigation described in Example 12-1to develop an investigation summary Solution Accident title: Major damage: Date: Location: Drowning in municipal pool. o r (3) a checklist that is initiated by management and checked by operations on a daily basis. Layered events and recommendations are developed primarily by experienced personnel. p. Train lifeguards to watch for safety problems. Safety and Accident Prevention. eds. 668. 12-5 Aids for Diagnosis The data collected during an investigation are studied and analyzed to establish the causes of the accident and to develop recommendations to prevent a recurrence. Recommendations for preventionlmitigation ~~~~~~ 1st layer: Immediate technical recommendation 2nd layer: Recommendations for avoiding hazard 3rd layer: Recommendations for improving the management systems Events Recommendations Drowning (5-yr-old) Child knocked in pool Crowded pool Horseplay Pool depth not marked No swimming lessons Add more lifeguards. Paint pool depths at edges of pool. . Initiate rule to keep small children away from the deep region of the pool. the evidence needs added 4Fawcettand Wood. and often they also make significant contributions through an open and probing discussion. For this reason some experienced personnel are always assigned to investigation teams. Inexperienced team members learn from the experienced personnel. (2) a semiannual orientation program to review and study accident reports. Initiate periodic audit program to monitor adherence to rules and regulations. Limit number of swimmers to improve visibility and control. Sometimes. Give periodic pool orientation and prohibit running and horseplay. Park Z.12-5 Aids for Diagnosis 521 terly audit program t o ensure that recommendations are understood and used. Initiate swimming lessons for all levels. xx /xx /xx Detroit municipal pool. I n most cases the evidence clearly supports one o r more causes. however.

then the region of the origin can be approximated. Loss Prevention in the Process Industries (Boston: Butterworths. In this regard observations around the charred remains are helpful.Because pure copper melts at 1080°C. If copper beads are found around electrical equipment. Therefore. Deflagrations Breaks in pipes or vessels resulting from deflagrations or simple overpressurizations are usually tears with lengths no longer than a few pipe diameters. it may not be the primary source of the fire. For example. Although this type of evidence indicates a source of ignition. . if the time of extinguishment is known and if the depth of char at various locations is known.= 8 for hydrocarbon-air mixtures. Sometimes pits at the ends of conductors indicate high temperatures and vaporization of copper while arcing. Aluminum and alloys of aluminum have very low melting points (660°C).16 for hydrocarbon-oxygen mixtures. This evidence together with steelwork distortions is not useful. Fires The identification of the primary source of ignition is one of the major objectives of investigations. Iron and steel have high melting points (1300 -1 500°C) compared to fire temperatures. 567. and most woods burn at a rate of 1. plastic.522 Chapter 12 Accident Investigations analysis to uncover explanations. The integrity of steelwork is not very useful evidence. All aluminum products will therefore melt during fires. The fire temperature for various materials. "rank P. as shown in the following discussion. is approximately 1000°C. Lees. Further searching in this region may reveal possible causes of the fire. 1983).5 inlhr. However. therefore steelwork may be completely distorted. the depth of wood charring is proportional to the duration of burning. and deeper analysis in this regard should be avoided. and solvents. copper wire usually survives fires. steel weakens at approximately 575°C. P2 P 2 P1 PI (12-1) . This phase of the investigation may require special techniques or aids to diagnosis to relate the evidence to specific causes. Explosions The classification of the explosion as either a deflagration or a detonation and the magnitude of the explosion may be useful for developing causes and recommendations during accident investigations. The pressure increases during deflagrations are approximately5 . it may indicate that electrical arcs created temperatures greater than those observed in fires. p. such as wood.

and the point of ignition has no relationship to the ultimate point of failure. = p. . Therefore. In a single vessel detonations increase pressures significantlyh: When a pipe network is involved. therefore. therefore p. 6Lees. Rapidly expanding gases give large tears and can propel missiles. With pressure piling. Detonation failures in pipe networks are always downstream from the ignition source. Pressure Effects When pipe or vessel ruptures are investigated. p2 = p. 569. Loss Prevention. Blast pressures can shatter an elbow into many small fragments. In pipe systems explosions can initiate as deflagrations and the Aame front may accelerate to detonation speeds. X 16 X 16 for Equations 12-1 and 12-2. They usually occur at pipe elbows or other pipe constrictions. The downstream pressure may be 8 to 16 times greater than the original upstream pressure. Hydraulic and Pneumatic Failures Hydraulic high-pressure failures also give relatively small tears compared to pneumatic failures. it is important to know the pressures required to create the damage and ultimately to determine the magnitude and source of energy.12-5 Aids for Diagnosis 523 For pipe networks the pressure will increase in front of the flame front as the flame travels through the network. if the vessel parts are reconstructed. The damage is manifested as tears (detonations give shearing failures). may increase by as much as another factor of 20. Detonations As described in chapter 6. the pressure is uniform throughout the vessel. the source of ignition is at the point with the thinnest walls. the source of ignition is usually coincident with the point of maximum vessel thinning resulting from expansion. such as valves. the downstream p . which are destructive. detonations have a rapidly moving flame andlor pressure front. A detonation in light-gauge ductwork can tear the duct along seams and can also produce a large amount of structural distortion in the torn ducts. increases because of pressure piling. During deflagrations in vessels. x 8 x 8 andp. drums. Sources of Ignition in Vessels When a vessel ruptures because of a deflagration. Detonation failures usually occur in pipelines or vessels with large length-to-diameter ratios. respectively. and vessels great distances. therefore the failure occurs at the vessel's weakest point. This concept is called pressure piling. p.

385 times the mechanical strength of the material SM where p is the internal gauge pressure. the vessel diameter. and r is the inside radius of the vessel.Strength of material data are provided in Table 12-3. and the mechanical properties of the vessel walL7 For cylindrical vessels with the pressure p not exceeding 0. For cylindrical vessels and pressures exceeding 0. S . .They are also used to determine the pressures required to produce failures by using tensile strengths for S M . "Designing Pressure Vessels.385SM.665SM the equation is For spherical vessels and pressures exceeding 0. t. is the wall thickness of the vessel.the following equation applies: For spherical vessels with pressures not exceeding 0. 'Samuel Strelzoff and L.524 Chapter 12 Accident Investigations The pressure necessary to produce a specific stress in a vessel depends on the thickness of the vessel." ChemicalEngineering (Nov. p.665SM the equation is These formulas are also used to determine the pressure required to produce elastic deformations by using yield strengths for SM. 4.1968). C. Pan. 191. is the strength of the material.

The maximum internal pressure for pipes is calculated using Equations 12-4 and 12-5. using Equation 6-29. and (6) signs of eye irritation. ( 5 ) principles of grounding . the explosive energy is computed.12-5 Aids for Diagnosis 525 Table 12-3 Strength of Materials1 Tensile strength (psi) Yield point (psi) Material Borosilicate glass Carbon Duriron Hastelloy C Nickel Stainless 304 Stainless 316 Stainless 420 'Robert H.). A brief review of safety fundamentals before the investigation is helpful. and they must also make supporting calculations to evaluate various hypotheses. During an accident investigation. 6-96 and 6-97. for example. (3) type of poisoning (carbon monoxide. After the energy and ignition sources are identified. pp. (4) dispersion of vapors outside or inside plants. The ultimate source of this explosion energy is found by developing various reaction or mechanical hypotheses and comparing the reaction energy to the explosion energy until the most likely hypothesis is identified. High-pressure failures are as likely to occur in a pipe or pipe system as they are in vessels. eds.. Medical Evidence Medical examinations of the accident victims result in evidence that may be useful for identifying the source of the accident or for identifying some circumstances that may help to uncover underlying causes. (4) signs of suffocation. This includes. attention is placed on developing conditions to prevent the source of failure. After the maximum internal pressure is computed. (1) toxicity of chemicals or combinations of chemicals. Perry and Cecil H. etc. Chilton. The types of medical data that help accident investigations include (1) type and level of toxic or abusive substances in the blood. toluene. the investigation team must watch for visible evidence. 1973). (3) magnitude of leaks depending on the source. Miscellaneous Aids to Diagnosis Other aids for identifying underlying causes of accidents are found throughout this text. (5) signs of heat exposure or heat exhaustion. Chemical Engineers' Handbook (New York: McGraw-Hill. (2) location and magnitude of injuries. (2) explosion limits.

5 in) . has a radius of 3 ft.526 Chapter 12 Accident Investigations and bonding. and (8) methods for performing accident investigations.013 in) + 0. Equation 12-6 is applicable if the pressure is less than 0. Solution Because the pressure is unknown.200 psi. From Table 12-3 the tensile strength SMfor stainless 316 is 85. we obtain = S.000) = 53.5 in) - = 1170 psi.385SM = 32.75 in) = 1990 psi. and was it a deflagration or a detonation that caused this rupture? Solution A 4-in schedule 40 pipe has an outside diameter of 4.75 in. and r = 3 ft = 36 in and t.5 in.237 in) . Equation 12-4 for cylinders is used to compute the pressure necessary to rupture this pipe: = y SM~" (85. and has a wall thickness of 0.5 in. By substituting into Equation 12-4 for cylindrical vessels. (7) design concepts for handling flammable materials. Deflagration tests in a small spherical vessel indicate a deflagration pressure of 500 psi. we obtain = y 2tvS~ - 2(0. and a pressure of 1170 psi is required to rupture this vessel.6653.000 psi.237 in. a wall thickness of 0.000 psi)(0. (85.237 in) - = 9348 psi. Therefore Equation 12-4 is applicable.6(0.(36 in) + 0. Example 12-5 During an accident investigation.Because SM (from Table 12-3) is 85. Using Equation 12-6 for spherical vessels. and an inside diameter of 4.026 in.6(0. it is found that the source of the accident was an explosion that ruptured a 4-in-diameter stainless 316 schedule 40 pipe. .(2. It is hypothesized that a hydrogen and oxygen deflagration or a detonation was the cause of the accident.385SM. Equation 12-4 is applicable for pressures below 0.5 in. or 0. (6) principles of static electricity.000 psi. and has a wall thickness of 0.t. has a radius of 5 ft.75 in)(80. The pressure criteria is met for this equation. 0.700 psi. Example 12-3 Determine the pressure required to rupture a cylindrical vessel if the vessel is stainless 316.000 psi)(0. This knowledge and information will be useful during an investigation. = 0.000psi) (5 ft)(12 inlft) + 0. The pressure required to rupture this vessel is 1990 psi. Example 12-4 Determine the pressure required to rupture a spherical vessel if the vessel is stainless 304. Solution This problem is similar to Example 12-3.665(80.2(0. Equation 12-4 or 12-5 is used by trial and error until the correct equation is identified. What pressure ruptured the pipe.

= = 1. or is the explosion the result of some other process? Solution From Equation 6-29. representing the energy contained in a compressed gas. therefore. using Equation 12-2: p. A small vessel could be used as a test. and assuming pressure piling. y = 1.13 X 10" g TNT 249 lb of TNT. Site damage indicates that the windows in a structure 100 yards away are shattered. Is the mechanical explosion of this compressed air tank consistent with the damage reported. of 500 psi.4. A 1000-ft3tank containing compressed air at 100 atm is suspected.700 psi. we can estimate the deflagration pressure in the pipe using Equation 12-2: p. we obtain The equivalent amount of TNT is m . A detonation with pressure piling is now computed using Equation 12-3: p. = 500116 = 31. = 500 X 16 = 8000 psi. we estimate the original deflagration test pressure p. For air.3 X 20 X 20 = 12.385SM= 32. is 9348 psi. .500 psi. To estimate pressures resulting from a detonation and pressure piling. = 31.3 psi. which gave a p. Using the deflagration test data. The pressure required to rupture this pipe. Substituting the known quantities. This pipe rupture was therefore due to a detonation. The next step in the investigation would include searching for a chemical reaction that would give a detonation.12-5 Aids for Diagnosis 527 Equation 12-4 is applicable because the pressure is less than 0. Example 12-6 An explosion rips through a chemical plant.27 X 10' call(ll20 callg TNT) = 1.

They are made to prevent a recurrence of the specific accident. All the fundamentals described in this text are commonly used to develop recommendations. 3. If the designer is not careful. Develop recommendations to improve the management and staff support of safety with the same enthusiasm. One good accident investigation can prevent hundreds of accidents. 4.we obtain z. checklists.3psia. Many accidents are the result of plant modifications.66 ftllb"' = 18. Make safety investments on a basis of cost and performance. plans.528 Chapter 12 Accident Investigations From Equation 6-21 the scaling factor is Substituting.9 mlkg"' From Figure 6-23 the overpressure is estimated at 1. changes to the system or new procedures may add complexities that result in a more hazardous situation rather than in an improvement. The ultimate result of accident investigations is the elimination of the underlying causes of entire families of accidents. and in these situations all efforts are directed toward a quick restart. Some aids to recommendations are covered in the following sections. and audits. Develop recommendations to improve the management system to prevent the existence of safety hazards. From the data provided in Table 6-9 the estimated damage is consistent with the observed damage. they are sometimes the result of mechanical problems that shut the plant down. In addition. Control Plant Modifications Modifications to plants are often not given the same attention and concern as a new plant design. and organization as used in production programs. including training. but they are also made to prevent similar accidents within the company and within the industry. quality. 12-6 Aids for Recommendations Recommendations are the most important result of an accident investigation. inspections. Develop layered recommendations with an appropriate emphasis on recommendations to eliminate underlying causes of accidents. = (249 lb)"" 300 ft = 47. . Evaluate each investment (money and time) to ensure that there is a true safety improvement proportional to the investment. There are four overriding principles that are used to influence accident investigation recommendations: 1. safety reviews. 2. attention.

changes are difficult and costly to make. / Block Valves Block valves are installed throughout plants to return a process to a safe condition under unusual circumstances. Once the system is constructed. For example. Examples of friendly designs include using nontoxic and nonflammable solvents when possible. operators. p. If the hose breaks. 2. sewer analyzers for detecting high concentrations of contaminants. Authorization: All modifications must be authorized by several levels of management. economically sound. the process shown in Figure 12-2 detects a hose leak by comparing flow rates at both ends of the hose. 148. Audit: Every plant modification needs periodic audits to be sure that the modifications are made and maintained as designed.to tolerate departures from the norm without creating hazardous conditions. 3. Block valves are often controlled on the basis of analyzer results. These five requirements are all part of the OSHA q'ocess Safety Management regulation discussed in chapter 3. 4. Learning from Accidents in Industry. and designing for safe shutdowns during emergency situations (expect the unexpected). 8Kletz. Training: Engineers and operators need sufficient training to understand and appreciate the modified operation. . and vent analyzers to detect high levels of contaminants. the leak is detected and the block valves on the reactor and sewer are immediately closed. such as area monitors for detecting solvent leaks. and design specialists while the modification project is in the design phase. Design: The modification designs must be mechanically constructed with the same quality of equipment and pipes as the original design. Safety reviews: A safety review (HAZOP study or equivalent study for hazardous operations) must be conducted by engineers. plausible. User-Friendly Designs8 New plants or modifications to existing plants must be designed to be friendly . 5. The designers must appreciate that for every problem there are many interesting.12-6 Aids for Recommendations 529 Recommendations are especially designed to prevent this kind of problem: 1. This allows (and encourages) safety changes to be made with minimum effort. Original designs should be studied so that the consequences of any change are understood. and wrong solutions. keeping temperatures below the flash point and below the boiling point at atmospheric conditions. reactor analyzers for detecting runaway reactions (a block valve can be opened to add a reaction inhibitor or to turn on a deluge system). keeping inventories low.

This system prevents the reactor contents from siphoning back into the monomer storage vessel. . the block valves are open and the bleed line is closed. Double Block and Bleed A special double block and bleed system. During normal operating conditions. If the flow at both ends of the hose is not identical.is added to every feed line to a reactor. A little neglect can cause serious property damage and may be the genesis of serious accidents. even if the block valves leak. especially those owning automobiles or homes.530 Chapter 12 Accident Investigations Hose Reactor Solvent Storage Sewer Curbs a n d Sump for Spill Control Figure 12-2 A block valve arrangement used to prevent leakage from the connecting hose.anywhere a positive break in a line is desired. Preventive Maintenance Most engineers are aware of the importance of preventive maintenance programs. poorly maintained brake systems have inevitable consequences. Figure 12-3is a relatively simple example of a particularly important application of double block and bleed systems. When the feed pump is shut off. for example. the block valves are closed and the bleed line is open. These systems are also commonly used for reactive intermediates and analyzer systems . the block valves are closed. shown in Figure 12-3. This prevents an unexpected chemical reaction in the storage tank.

Preventive maintenance programs must be organized. action can be taken to return the system to safe operating regions with no adverse consequences. instruments. it is found that protective equipment failed because it was neglected. but bad results are apparent when plants are not appropriately maintained. there was no preventive maintenance program. In this case new procedures or new equipment is not needed. and fully supported by management. and deluge systems. when evaluating underlying causes of accidents. Analyzers Chemical analysis of reactor contents and of the surrounding environment is an important way to understand the status of a plant and to identify problems at the incipient state of development.12-6 Aids for Recommendations Double Block Pipe L Controller Figure 12-3 A double block and bleed arrangement used to prevent reactant from entering reactor vessel. In plants one major cause of accidents is the failure of emergency protection equipment such as cooling water pumps. Good results may not be immediately apparent. When problems are identified at an early stage. The only improvement needed is upgrading the existing maintenance program. The maintenance schedule is subsequently changed if more frequent maintenance is required. adding more protective equipment or procedures might increase the likelihood of accidents. . Every maintenance job requires a feedback mechanism based on the inspection of parts while conducting the maintenance. Many times. Good maintenance programs include scheduled maintenance and a system to keep an inventory of critical maintenance parts. managed.

11th ed. Use the Bhopal accident and the investigation developed in Problem 12-3to develop an investigation summary similar to Example 12-2. (New York: American Institute of Chemical Engineers. Include layered recommendations. Use the Seveso. Include layered recommendations to cover the accident causes and underlying causes.532 Chapter 12 Accident Investigations In recent years new and better analyzers have been developed. 1996). Large Property Damage Losses in the Hydrocarbon-Chemical Industries: A Thirty-Year Review. Use the Flixborough Works accident and the investigation developed in Problem 12-1 to develop an investigation summary similar to Example 12-2. Kletz. Plant Guidelines for Technical Management of Chemical Process Safety (New York: American Institute of Chemical Engineers. Problems 12-1. A Thirty Year Review of One Hundred ofthe Largest Property Damage Losses in the Hydrocarbon-Chemical Industry. 1996). particularly in regard to safety. Chemical Process Safety: Learning from Case Histories. CCPS. 1994). Use the Flixborough Works accident described in chapter 1to develop an investigation similar to Example 12-1. 1988). 12-6. quality. CCPS. Roy E. Design engineers should always search for new opportunities to use process analyzers to improve operations and safety within plants. India. Use the Bhopal. pp. and yield improvements. . What Went Wrong? Case Histories of Process Plant Disasters (Houston: Gulf Publishing. 1985). Chemical Process Safety: Learningfvom Case Histories (Boston: Butterworth-Heinemann. 373382. 1992).. Trevor A. As the reliability and applicability of analyzers are improved. 1992). Kletz. "Layered Accident Investigations. 12-2. Suggested Reading CCPS. Use the Seveso." Hydrocarbon Processing (November 1979). (Boston: Butterworth-Heinemann. 2d ed. 12-4. Sanders. Italy. 18th ed. accident described in chapter 1 to develop an investigation similar to Example 12-1. Kletz. accident described in chapter 1 to develop an investigation similar to Example 12-1. Trevor A. 12-5. 12-3. (Chicago: J&H Marsh & McLennan Inc. Inherently Safer Chemical Processes (New York: American Institute of Chemical Engineers. CCPS. 1998). Italy. Include layered recommendations. Learning from Accidents in Industry. Guidelines for Investigating Chemical Process Accidents (New York: American Institute of Chemical Engineers. 1999). (Chicago: Marsh and McLennan Protection Consultants. they will become the key control elements in chemical plants. 2d ed. Trevor A. accident and the investigation developed in Problem 12-5 to develop an investigation summary similar to Example 12-2.

12-21. 12-11. 12-12. Describe a preventive maintenance program that is designed to prevent automobile accidents. Using the data and results of Example 12-6. Describe why the second vessel requires a greater wall thickness. An accident occurs that ruptures a high-pressure spherical vessel. Compute the theoretical maximum pressure obtained after igniting a stoichiometric quantity of methane and oxygen in a spherical vessel that is 1. Assume that the vessel's cylindrical wall height is equal to the vessel's diameter. is made of stainless 304. The system has two vessels that are connected with a 4-in vapor line.5 ft in diameter. In the 1930s there were many accidents in homes because of the explosion of hot water heaters. Create your own brief accident scenario for this problem.determine the vessel wall thickness required to contain an explosion in another vessel that is physically connected to the first vessel with a 1-in pipe. Describe why accident investigation recommendations must include recommendations to improve the management system. The spherical vessel is 1. assuming that stoichiometric quantities of hydrogen and air explode.5 ft in diameter. . The vessel is 1. A cloud of hydrogen gas is released and subsequently explodes. 12-20. The normal operating pressure is 2 atm. Determine the required thickness of a reactor with cylindrical walls that must be designed to safely contain a deflagration (hydrocarbon plus air). Using the results of Problem 12-11. Determine the vessel wall thickness required to contain an explosion of 2 lb of TNT. Describe the concept of using block valves to prevent detonation accidents in a system handling flammable gases.Problems 533 12-7. Determine the pressure required for a pipe to swell and the pressure required for a pipe failure. The pipe is 3-in stainless 316 schedule 40 pipeline for transporting a gas mixture that is sometimes within the explosive composition range. Determine the pressure required to cause this failure. 12-9.5 ft in diameter.determine the required vessel wall thickness to contain this explosion if the vessel is made of stainless 316. 12-10. 12-15. Develop some hypotheses regarding the causes of this accident. and the walls are 0. 12-19. 12-16. 12-17.5 ft in diameter and is constructed with stainless steel 316. Describe what features are added to water heaters to eliminate accidents. Assume that the initial pressure is 1atm. 12-14. 12-13. Develop an investigation similar to Example 12-1 and an investigation summary for an automobile accident that occurred as a result of a brake failure. Glass is shattered 500 ft away. Compute the theoretical maximum pressure obtained after igniting a stoichiometric quantity of methane and air in a spherical vessel that is 1.25 in thick. 12-18. 12-8. determine the wall thickness required to eliminate future failures. Using the results of Problem 12-13. Estimate the quantity of hydrogen gas initially released. The vessel has a diameter of 4 ft and is constructed with stainless steel 304. Assume an initial pressure of 1 atm.

and develop three layers of recommendations.chernsafety. Summarize the findings of these accidents and develop a few management system recommendations for these industries. Compare your answer to CCPS's (1992. 12-28. epa. See http:15/ www. 239). A management system for accident investigations includes good communications. The US Chemical Safety and Hazard Investigation Board investigated an accident at the Morton Specialty Chemical Company in 1998. p. Plant Guidelines for Technical Management of Chemical Process Safety (1992). and break them down into three layers of recommendations. An accident investigation at the Tosco Refinery Company emphasized the importance of a management system. 12-27. What facts should a near-miss accident report include? Compare your answer to CCPS's (1992.htm. As stated in section 12-4. p. and compare it to CCPS's definition. p.gov/ceppo/pubs/lodiintr. Describe the accident.epa. See http://www. Evaluate the board's recommendations. included previous industrial accidents with sodium hydrosulfite and aluminum.chernsafety . Develop a definition for a major incident. 12-29. developed the root causes and recommendations to address the root causes. See CCPS. and develop layered recommendations for this specific accident. See http://www. New Jersey. New Jersey. Near-miss (close-call) accident investigation reports are also important. Describe the accident. What are the tangible benefits of a good communications system? Compare your answer to CCPS's (1992. htm. in Lodi. 12-30. The accident investigation at Lodi.gov/ceppo/pubs/lodirecc. 12-23. 238). 238. 12-26. 12-24. This management system includes the delegation of responsibilities and followup.gov/. 12-25. An EPA-OSHA accident investigation at Napp Technologies Inc. 240). . the three layers of recommendations for accident investigations include management systems to prevent similar accidents or to eliminate the hazardous conditions.gov/.534 Chapter 12 Accident Investigations 12-22. See http:// www. Define nearmiss accidents. 236. What are the benefits of followup? Compare your answer to the benefits described in the CCPS (1992) reference on p. p.

anyone working in the chemical industry can learn from case histories and avoid hazardous situations or ignore history and be involved in potentially life-threatening accidents. the ones who know and appreciate the accident and accident prevention methods. References are provided for more thorough studies. The study of case histories is important in the area of safety. Each of these sections includes descriptions of several accidents and a summary of the lessons learned. These are the people with the hands-on experience. In this chapter we cover case histories as reported in the literature. through actual case histories. and procedures. To paraphrase G.C H A P T E R 1 3 Case Histories ase histories are written descriptions of accidents. These accidents actually occurred. The cause of a specific accident frequently places it in more than one category. They are descriptions written by plant managers and operating personnel. and methods required to prevent similar events. Anyone familiar with the specific equipment or procedures will appreciate the lessons learned. . system design. This is especially true for safety. Santayana. The objective of this chapter is to illustrate. consequences. The following statements place the case histories into perspective: c 1. including the causes. the importance of applying the fundamentals of chemical process safety. one learns from history or is doomed to repeat it. These case histories are categorized into four sections: static electricity. chemical reactivity.

Accidents occur rapidly and unexpectedly. Case Histories of Accidents in the Chemical Industry. the contents of the tank exploded. The accident investigation indicated that the explosion was caused by a static spark that jumped from the steel nozzle to the tank car. Those who believe that they can successfully control accident deviations manually are doomed to repeat history. The operator on top of the tank was thrown to the ground. July 1962). p. There is usually inadequate time to manually return a situation back into control after a significant deviation from the norm is observed. The following series of case histories is given to illustrate the complexity of this topic and to give some important design requirements for preventing future accidents involving static electricity. 2 (Washington. . 13-1 Static Electricity A large proportion of the reported fires and explosions are the result of a flammable mixture being ignited by a spark caused by static electricity. The fill line from the reactor to the centrifuge was Teflon-lined steel. 2Case Histories of Accidents in the Chemical Industry. The foreman's hand was burned. DC: Manufacturing Chemists' Association. he sustained a fractured skull and multiple body burns and died from these injuries. One operator was on the ground. 231. The lid was lifted and a flame was released between the centrifuge and the lid. The nozzle was not bonded to the tank car to prevent static accumulation. A few seconds after the loading operation started. running to a point 3 S from the centrifuge where there was a rubber sleeve connector. and the other was on top of the car with the nozzle end of a loading hose. January 1966). v. Many of these accidents are repeats of previously recorded accidents. The short line from the t sleeve to the centrifuge was steel. 1 (Washington. The use of a nonmetallic hose probably also contributed. Tank Car Loading Explosion Two plant operators were filling a tank car with vinyl acetate. A foreman was about to look into the centrifuge when it exploded. p. engineers are missing some of the important aspects of this subject. DC: Manufacturing Chemists' Association. 106. v. Explosion in a Centrifuge2 A slurry containing a solvent mixture of 90% methylcyclohexane and 10% toluene was being fed into a basket centrifuge.536 Chapter 13 Case Histories 2. The centrifuge was lined.

which was grounded. The other system was being charged through a funnel with a dry organic intermediate. p. This accident points out the need for carefully reviewing systems before. "Tame Static Electricity. A spark jumped from the tramp metal to the grounded wall. A piece of tramp metal entered the hopper with the solids. v a s e Histories of Accidents in the Chemical Industry. Maurer. v. for example. 4J. Boicourt. proper grounding and bonding techniques must be used to prevent static buildup. Fortunately. The transportation of the intermediate dust through the glass and plastic line generated a static charge and spark. The spark was energetic compared to the minimum ignition energy of the dust. Conductor in a Solids Storage Bin4 A dry organic powder was collected in a hopper. dryers. 95. F. One system was recently repaired and left open. and after modifications are made. 3 (Washington. Because the storage hopper's atmosphere was air (plus the dust). Open lines should be blanked-off when the discharge of flammable vapors is possible. The lined centrifuge was the source of ignition as a result of static accumulation and discharge. The open system emitted some methanol vapors. B. Also. An additional safeguard would be the addition of an inerting gas. a magnetic trap or a screen. DC: Manufacturing Chemists' Association. the dust exploded and the storage hopper ruptured. . The charge line consisted of a new glass pipe and a 6-ft section of plastic pipe. As it rolled down the solids. Later (and successful) processing was conducted in a grounded stainless steel centrifuge that was inerted with nitrogen. and G. pp. and the explosion initiated other fires. Several explosion vents were ruptured. April 1970). no one was seriously injured. At some point in the operation the tramp metal approached the metal wall of the hopper. 75-81. The duct system that was being charged exploded violently. and hoppers. it accumulated a charge by the charging method called separation. W. during. This explosion could have been prevented with a tramp metal collector. The ignition source created violent explosions in both systems.13-1 Static Electricity 537 The accident investigation indicated that a flammable atmosphere had developed because of an air leak. Duct System Explosion Two duct systems in the same vicinity contained dust transport lines. The accident investigation indicated that methanol vapors entered the second charging system. Louvar. and a building blowout panel also ruptured." Chemical Engineering Progress (November 1994).

The helper walked through a cloud of steam before handing the tool to his boss.538 Chapter 13 Case Histories Pigment and Filter5 A low-flash-point solvent containing pigment was pumped through a bag filter into an open drum. the grounding rod was placed closer to the filter than previously. It is hypothesized that one of two scenarios could have created the ignition. giving the conditions for a brush discharge between the filter and the grounding rod. some important lessons were identified: (1) A built-in ground line is rendered nonconductive by the use of a nonconductive pipe dope. Lessons Learned Case histories involving static electricity emphasize the importance of understanding and using the fundamentals described in chapter 7. This system was modified to include an inerting system and a dip pipe charging line. In reviewing approximately 30 additional case histories regarding static electricity. (4) free-fall filling generates static charge and discharge. "Tame Static Electricity. for example. it became charged as it exited a manifold. (6) large voltages are generated when crumpling and shaking an empty polyethylene bag.. "Tame Static Electricity. It is also possible that the grounding rod wire was closer to the isolated drum than previously. The pigment drum was grounded by means of a grounding rod. during an emergency situation. The problem was the steam. and (7) a weak grounding clamp may not penetrate the paint on a drum adequately to provide a good electrical contact. ( 2 )clothing that generates static electricity must be prohibited. (3) recirculation lines must be extended 5 ~ o u v aet al. and all metal parts were bonded." r h ~ o u v aet al. ( 2 ) a potential is generated between two vessels that are not bonded. Charge loss was prevented because the helper was wearing insulated shoes. resulting in static buildup. This example may have been a disaster if the pipefitter was repairing a flammable gas leak. Subsequent operations were incident-free. Possibly.. Then the charge was transferred to the helper and to the tools when the helper passed through the steam cloud. The boss was grounded because he was kneeling on a damp grounded grating." r . the boss received a rather large shock. ( 3 ) leather arch supporters make shoes ineffective against static. in this case a spark could have jumped between the drum and the grounding wire. Upon each transfer. ( 5 ) the use of nonmetallic hoses is a source of static buildup. A number of recommendations are also developed: (1) Operators must be cautioned against drawing pipes or tubing through their rubber gloves. Pipefitter's Helper6 Apipefitter's helper was transporting tools to the boss. Using conductive shoes and changing the location of the toolbox solved this problem. Although the operation ran successfully for some time. one day there was a fire.

(10) Spring-loaded grounding or bonding clips should be replaced with screw type C-clamps. Initiate an immediate inspection of all loading and unloading operations. 2. no inspection or safety review procedure was in place to identify problems of this kind. 4. Solution The facts uncovered by the investigation are 1. and ground tank car and hose. or combinations are recommended when static electricity is a fire hazard. Use a conductive metal hose for transferring flammable fluids. and 5. (8) drums. First-layer recommendations: immediate technical recommendations 1. contents at the top of vessel were flammable. a policy to give all new loading and unloading applications a safety review. 5.13-1 Static Electricity 539 into the liquid to prevent static buildup. Provide a means to nitrogen-pad the tank car during the filling operation. 4. (7) inert gas blankets must b e used when handling flammable materials. 3. the charging line was a nonconductive hose. 2. scoops. (5) bonding. 3. 2. Develop tank car loading procedures. develop the underlying causes of the tank car loading explosion discussed earlier in this section. Third-layer recommendations: improving the management system 1. 3. Provide dip pipe design for charging tank cars. and bags should b e physically bonded and grounded. (9) ground connections must be verified with a resistance tester. and (14) flanges in piping and duct systems must be bonded. Develop and give operators special training so the hazards are understood for every loading and unloading operation. Bond hose to tank car. a spark probably jumped between the charging nozzle and the tank car. (12) sodium hydride must be handled in static-proof bags. (11) conductive grease should be used in bearing seals that need to conduct static charges. (4) shoes with conductive soles are required when handling flammable materials. (6) a small water spray will rapidly drain electrical charges during chopping operations. Second-layerrecommendations: avoiding the hazard 1. ionization. the explosion knocked the man off the tank car (the fatal injury was probably the fractured skull sustained in the fall). Initiate a periodic (every six months) audit to ensure that all standards and procedures are effectively utilized. Add guardrails to charging platforms to prevent accidental falls from the top of the tank car to the ground. Layered recommendations are the result of uncovering the underlying causes of the accident. . (13) stainless steel centrifuges must be used when handling flammable materials. humidification. Initiate. Example 13-1 Using the layered accident investigation process discussed in chapter 12. 2. grounding. as a standard practice. Include engineers and operators in this review.

Only small quantities should be purchased. coherently described how the accident happened. including potential side reactions. Case Histories. in fact. v. The reactor was designed to contain 60 gal of sulfuric acid and nitrobenzene sulfonic acid. When working with chemicals. v. Light. p. especially isopropyl ether. so he grasped the bottle in one hand. unexpected. 6. and often injurious to personnel. The following case histories illustrate the importance of understanding the complete chemistry of a reaction system. or the wrong temperature). decomposition reactions. the potential for unwanted. resulting in the tank being driven through the floor. Inhibitors should be used whenever possible. Containers should be labeled and dated upon receipt. All work with ethers should be done behind safety shields. wrong concentrations. It is hypothesized that some of the peroxides crystallized in the threads of the cap and exploded when the cap was turned. which formed in the ether while the bottle sat in storage. 111 . 2. The victim remained conscious and. the bottle exploded. He found a pint glass bottle. An accident investigation identified the cause of the accident to be the rapid decomposition of peroxides. the consequences are dramatic. The cap appeared to be stuck tightly. He unsuccessfully tried to open the bottle over a sink. p. which was known to decompose at 200°C. These materials are unstable. and opened containers should be discarded after 3 months. As ethers age. Just as the cap broke loose. 3. and reactions resulting from the accidental and wrong combination of chemicals or reaction conditions (wrong type. they form peroxides.540 Chapter 13 Case Histories 13-2 Chemical Reactivity Although accidents attributable to chemical reactivity are less frequent compared to fires and explosions. destructive. and heat accelerate the formation of peroxides. Nitrobenzene Sulfonic Acid DecompositionX A 300-gal reactor experienced a violent reaction. Bottle of lsopropyl Ether7 A chemist needed isopropyl ether. 8Case Histories. Ethers should be stored in metal containers. out the wall of the building. practically disemboweling the man and tearing off several fingers. and hazardous reactions must always be recognized. The peroxides react further to form additional hazardous by-products. pressed it to his stomach and twisted the cap with his other hand. The man was taken to a hospital and died within 2 hr of the accident of massive internal hemorrhage. such as triacetone peroxide. and through the roof of an adjoining building. Ethers should not be kept over 6 months. air.

One operator went to find a thermometer. Without agitation. This type of problem is currently preventable through better operator training and installation of electronic safeguards to prevent operators from making this mistake. 3. the hotter chemicals mix and react violently. experimental testing is necessary. With good data. Cuse Histories. If data are not available. The accident investigation stated that the agitator should never be turned off for this type of reaction. Although previous tests indicated decomposition at 200°C. subsequent tests showed exothermic decomposition above 145°C. cooling is no longer efficient. At this point the material in the kettle erupted through the manhole.p. The two operators turned the agitator off and also shut off the steam. so heat-up occurs. Lessons Learned Case histories regarding reactive chemicals teach the importance of understanding the reactive properties of chemicals before working with them. . The two operators were drenched and both died from these injuries. Approximately 1 hour later. Organic Oxidation Chemical operators were preparing for an organic oxidation. and flash point. This is achieved by adding redundant and remote temperature sensors and by adding electronic interlocks to prevent the agitator from being turned off while the reaction is still exothermic. engineers can design safeguards to absolutely prevent accidental heat-up.13-2 Chemical Reactivity 541 The investigation indicated that the vessel contents were held for 11hr. He turned on the agitator. The underlying cause of this accident was the lack of precise reaction decomposition data. The best source of data is the open literature. 121. rate of reaction or activation energy. Functional Groups A preliminary indication of the potential hazards can be estimated by knowing something about the chemical structure. Specific functional groups that contribute to the explosive properties of a chemical through rapid combustion or detonation are illustrated in Table 13-1. the operator was ready to take a temperature reading through the manhole. Without agitation. When the agitator is subsequently activated. v. segregation of chemicals also occurs. A steam leak into the jacket brought the temperature to about 150°C. Steam was applied to the reactor jacket to heat the sulfuric acid and an organic material to a temperature of 70°C. The rate of heating was slower than normal. Data of special interest include decomposition temperatures. impact shock sensitivity.

ed. Structures of peroxidizable compounds are shown in Table 13-2." in Safety in the Chemical Industry. (Easton." in Safety in the Chernicul Industry. Steere. Jackson et al. PA: Division of Chemical Education. Norman V. "Linking Thermodynamic and Kinetics to Predict Real Chemical Hazards. Norman V. L. American Chemical Society. pp. 3. American Chemical Society. v. the solution is hazardous..1° Reaction Hazard Index D. 114 -1 17. . 3. ed." in Safety in the Chemical Laboratory. Peroxides Peroxides and peroxidizable compounds are dangerous sources of explosions. pp. 22-25. "Control of Peroxidizable Compounds. (Easton. Stull. 1974). "D. the rating is called the reaction hazard index (RHI). When peroxide concentrations increase to 20 ppm or greater. PA: Division of Chemical Education. 106 -1 10. Steere.Chapter 13 Case Histories Table 13-1 Azide Diazo Diazonium Nitro Nitroso Nitrite Nitrate Fulminate Peroxide Peracid Hydroperoxide Ozonide Reactive Functional Groups1 N3 -N=N-N2+X- -NO2 -NO -O N 0 -ON02 -O N C -0-o-C 0 3 H -0-0-H 0 3 -N-Cl Amine oxide Hypohalites Chlorates Acetylides of heavy metals X =NO - I ox C103 -C=CM 'Conrad Schuerch. R. 1974). Jackson et al. R. It is defined as RHI = 'OH. v. Some examples of peroxidizable compounds are given in Table 13-3. pp. Methods for detecting and controlling peroxides are outlined by H. L. The RHI is related to the maximum adiabatic temperature reached by the products of a decomposition reaction. "Safe Practice in the Chemistry Laboratory: A Safety Manual. Stullll developed a rating system to establish the relative potential hazards of specific chemicals.

Viele. 28-36. C. . Rondestvedt. Norman V. lactones: 7. W. 1974). American Chemical Society. Dienes. ed. McCormack. 2R. Smeltz. terpenes. v. particularly potassium 2. vinyl acetylenes: and 4. Alkali metal alkoxides and amides 3. acetals: 2. K. pp. amides. including vinyl halides. methacrylates. Aldehydes: I H 0 6. Ureas. 114-117. Kelly.13-2 Chemical Reactivity 543 Table 13-2 Peroxidizable corn pound^^^^ Organic material and structure H -C-0- 1. J. and I. pp. Steere. 3. C. Organometallics 'H. "Review of Safety Guidelines for Peroxidizable Organic Chemicals. Jackson. particularly those with tertiary hydrogen: I I I >C=C-C=C< >C=C-CGCH >C- I H -C=O 5. S. (Easton. Vinyl monomers. Ethers. vinyl esters: H 11 -C-N-C I I / > C=C-C-C< 8. E. Ketones having an alpha-hydrogen: 11 0 I H Inorganic materials 1.and fluoroolefins." Chemical Health and Safety (September-October 1996). Alkali metals. "Control of Peroxidizable Compounds. tetrahydronaphthalene: I > C=C < 3. Paraffins and alkyl-aromatic hydrocarbons. Olefins with allylic hydrogen. PA: Division of Chemical Education. chloro." in Safety in [he Chemical Industry. B. acrylates. L.

. ed. where T. v. is the decomposition temperature (K) and E. . PA: Division of Chemical Education.544 Chapter 13 Case Histories Table 13-3 Examples of Peroxidizable Compounds Peroxidizable hazard on storage Isopropyl ether Divinyl acetylene Vinylidene chloride Potassium metal Sodium amide Peroxidizable hazard on concentration Diethyl ether Tetrahydrofuran Dioxane Acetal Methyl i-butyl ketone Ethylene glycol dimethyl ether (glyme) Vinyl ethers Dicyctapentadiene Diacetylene Methyl acetylene Cumene Tetrahydronaphthalene Cyclohexane Methylcyclopentane Hazardous when exposed to oxygen due to peroxide formation and subsequent peroxide initiation of polymerization Styrene Butadiene Tetrafluoroethylene Chlorotrifluoroethylene Vinyl acetylene Vinyl acetate Vinyl chloride Vinyl pyridine Chloroprene H. 3. Jackson et al. is the Arrhenius activation energy (kcallmol)." in Safety in the Chemrcal Industry. "Control of Peroxidizable Compounds. 1974). Norman V. 114-117. Steere. American Chemical Society. L. (Easton. The RHI relationship (Equation 13-1) has a low value (1 to 3) for relatively low reactivities and higher values (5 to 8) for high reactivities. pp. Some RHI data for various chemicals are provided in Table 13-4.

Norman V.5 85 67.5 79.0 C8H8 N2H4 C2H40 C4H4 C12H~6N40~~ C2H2 C3H5N309 C4H~002 ID.4 19. and compare the result to that shown in Table 13-4. Steere.5 78 63. PA: Division of Chemical Education.5 40.38 2.5) which is the same as the value given in Table 13-4.0 46.64 C7H8 C2H402 C3H6 C~HI~O C2H4 C4H6 C4H.25 3.05 7." in Safety in the Chemical Industry. 106-110.52 2.33 6. Explain why the RHI is relatively low. However.70 2.5 57.4 28.5 46. Stull. R. "Linking Thermodynamics and Kinetics to Predict Real Chemical Hazards. Substituting.19 2. (Easton.26 1. is 712°K and E. T. v.98 6. isopropyl ether is a peroxidizable compound.33 4. 1974). American Chemical Society. we obtain RHI = (10)(712) (712) + (30)(63. where. Solution The RHI is computed using Equation 13-1: RHI = 10T.3 Number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Formula CHC1.2 60.12 7. 3.81 7. C2H6 Compound chloroform ethane toluene acetic acid propylene isopropyl ether ethylene 1. + 30Ea' T. from Table 13-4.. If we assume .94 3. as indicated in Table 13-3.05 4.82 2. This RHI indicates a chemical with low reactivity. Example 13-2 Compute the RHI for isopropyl ether. The units are compatible with Equation 13-1.3-butadiene vinyl ethyl ether styrene hydrazine ethylene oxide vinylacetylene cellulose nitrate acetylene nitroglycerine diethyl peroxide RHI 3. ed.3 37.5 kcallmol.13-2 Chemical Reactivity 545 Table 13-4 Reaction Hazard Index Data1 Decomposition Activation temperature energy (K) (kcallmol) 683 597 859 634 866 712 1005 991 880 993 1338 1062 2317 2213 2898 2895 968 47 89.72 4.4 44. is 63. pp.7 40.

" Chemical Engineering Progress (September 1977). '%avenport.30 ton of TNT. A vapor cloud was formed and almost immediately exploded. About 200 gal of butadiene spilled 12J. resulting in an accumulation of flammable vapors."A Survey of Vapor Cloud Incidents. This accident was attributed to the lack of design protection to prevent the backup of ammonia into this storage tank. (2) installation of pipe in trenches. Ethylene Explosion l3 Failure of a 3/8-in compression fitting on a 1000-2500-psi ethylene line in a pipe trench resulted in a spill of 200-500 lb of ethylene. It also appears that mitigation techniques were not part of the system (deluge systems. The probable causes of this accident include (1)use of nonwelded pipe. and the like).64). and (3) lack of automated vapor detection analyzers and alarms. Davenport. the hazards of handling isopropyl ether are high even with peroxide concentrations as low as 20 ppm. Butadiene Explosionl4 A valve on the bottom of a reactor accidentally opened because of an air failure. "A Survey of Vapor Cloud Incidents. The tank ruptured and dispersed ethylene oxide into the air. "A Survey of Vapor Cloud Incidents.5 million. giving a partially confined vapor cloud explosion. One person was killed and nine were injured. pp. The following case histories emphasize the importance of these special safety design features. Ethylene Oxide Explosion l 2 A process storage tank contained 6500 gal of ethylene oxide. 54-63. 13-3 System Designs When new plants are constructed or when modifications are needed in existing plants. dikes.12-0.A. It created an explosive force equivalent to 18 tons of TNT. property losses exceeded $16. detailed process designs are required. A cloud was formed and ignited. property loss was $6." I4Davenport. as evidenced by the damage. The events happened so rapidly that personnel could not take appropriate cover. This example illustrates the importance of understanding the chemistry of the entire system. It was accidentally contaminated with ammonia.5 million. giving an explosion equivalent to 0.546 Chapter 13 Case Histories an RHI equivalent to diethyl peroxide (RHI = 4. This accident took place in a courtyard." . These designs must include special safety features to protect the system and operating personnel. Two people were killed and 17 were injured. The spill generated a vapor cloud that was ignited 50 ft from the source.

Plant damage totaled over $15 million. "A Survey of Vapor Cloud Incidents. (2) improved deluge system design. as the following shows. A pump roller bearing failure in a crude oil refinery initiated the fracture of the motor shaft and the pump bearing bracket.5-1 psi were estimated. Three people were killed and two were injured. Significant damage resulted from the subsequent fires. One Hundred Largest Losses:A Thirty-Year Review ofproperty Damage Losses in the Hydrocarbon Chemical Industries. and deluge systems. Because the pump was equipped only with manually operated suction-side valves. Potential design improvements include vibration detectors. Overpressures of 0. p. (Chicago: Marsh & McLennan Protection Consultants. 9th ed. This accident could have been prevented by a good inspection and maintenance program. the valves could not be reached during the fire. One Hundred Largest Losses. which autoignited. 7. . An explosion ruptured other process pipes. "Garrison. and (4) failure to eliminate ignition sources in this operating region. A vapor cloud developed and ignited. Light Hydrocarbon Explosion l5 A pipe failed and resulted in a spill of 16. adding fuel to the original fire. Pump Vibration I h Vibration from a bad pump bearing caused a pump seal to fail in a cumene section of a phenol acetone unit.800 lb of light hydrocarbons. 1986). Probable causes of this accident include (1)installation of a fail-open valve instead of a fail-closed valve.6 million. (3) backup or more secure electrical supply. 7. The explosion knocked out the deluge systems and electrical supplies to the fire pumps. This accident had two fatalities and nine injuries. and (4) installation of detection analyzers and block valves. The maximum overpressure was estimated from the damage to be 3. block valves." IhWilliarnG. Pump Failure17 Numerous accidents are unfortunate duplicates of previous accidents. (2) lack of vapor detectors.- 13-3 System Designs 547 before ignition. The pump casing then broke. The released flammable liquids and vapors ignited. Damage to the plant exceeded $23 million. An equivalent of 1ton of TNT was estimated. p. The magnitude of this accident could have been reduced with (1) improved pipe design. giving an explosion yield of approximately 1%of the total energy source. releasing hot oil. (3) lack of a block installed as a mitigating device. Garrison. The total damage was estimated to be $15. gas analyzers. I5Davenport.5 psi at 120 ft. Secondary pipe and flange failures contributed fuel to the fire..

in the layout design it should have been noticed that the compressor needed special consideration to eliminate this ignition source. Gaseous compositions are controlled carefully to keep the concentrations outside the explosion limits. and this explosion ignited the rest of the vapors. The ethylene detonated in the engine. and recycled carbon dioxide to a continuous reactor. Twelve buildings were destroyed. Ethylene ExplosionlY Ethylene was accidentally released from a 118-in stainless steel instrument tubing line leading to a gauge from a main line on a compressor system. The ethylene cloud drifted and entered the intake system of an engine that was driving one of the compressors. This accident could have been mitigated if the gas detection analyzers alarmed at lower concentrations. Ethylene Oxide E x p l o ~ i o n ~ ~ ) Ethylene oxide is produced by adding ethylene. I9Garrison. This accident caused $21. "Instrument-Connected Losses in the CPI. but not before 45011. The tubing failed as a result of transverse fatigue caused by vibration from the reciprocating compressor. One Hundred Largest Losses. A good inspection and maintenance program would have prevented the accident. p. H. The explosions were felt 6 miles away. Also. The leak was too large for the spray system to handle." Instrument Technology (October 1972).One Hundred Largest Losses. IXGarrison. However.000 lb of gas had already escaped. a methane diluent. 20W. p. This accident emphasizes the importance of adding gas detectors that measure flammable gases at low concentrations so that alarms and block valves can be actuated before large quantities of gas are released. Doyle. which was designed to wash the ethylene from the atmosphere. allowing ethylene to escape. 8. The unmanned compressor building was equipped with a combustible gas detection system. pp. blocking-in the flow of ethylene. it failed to sound an alarm because of a faulty relay in the control room. Ethylene Explosion ls A drain fitting in a high-pressure (40 kpsi) compressor line broke. oxygen. Ignition may have been by static electricity.8 million in damage. 38-42. 3. .548 Chapter 13 Case Histories Automated block valves would have minimized damage in this fire. and fire and explosion damage occurred throughout the polyethylene plant. Automatic fail-safe valves functioned properly. The damage was estimated at over $15 million. Automatic equipment promptly detected the hazardous vapor and operated the automatic high-density water-spray system.

p. Learning from Accidents in Industry (Boston: Butterworths. requiring only minor process changes. usually with inadequate time to manually return the system to control once the accident scenario is in progress. A flange leak will douse the cables with liquid. Lessons Learned The case histories related to system design emphasize that (1) accidents occur rapidly. welds) meets the required specifications. The emergency procedures specified: Close the oxygen feed valve. (2) the system designs required for preventing accidents or mitigating the consequences of accidents are frequently subtle. and (3) the time and effort required to develop a safe system design is justified: An engineer is hired for a fraction of the cost of most accidents. 1988). Do not secure pipes too rigidly. "Process Safety Technology and the Responsibilities of Industry. resulting in several injuries and significant plant damage. The air. Trevor KletzZ1and Walter B.13-3 System Designs 549 One plant experienced an emergency situation. A violent explosion occurred. Pipes must be free to expand so that they will not damage other parts of the system. Check all purchased instruments and equipment for integrity and functionality. In addition. Be sure that the quality of construction (for example. r 22Walter B. It is now an industrial standard to use positive identification of the valve position on all important safety valves -limit switches that are tripped when the valve is open or shut. 143. Although the vent valve was open. Howard. . all valve vent lines are now covered with bug screens to prevent blockage." Chemical Engineering Progress (September 1988). the air could not escape. pp. Howard22 have emphasized the special design features for safer plants. however. especially when using old systems for new applications. The following recommendations also include design features from our own experiences: Use the appropriate materials of construction. The gases in the ethylene oxide reactor moved into the explosive region while being above the autoignition temperature. as indicated on the control panel. Do not install liquid-filled flanges above electrical cables. 2 1 T r e v ~Kletz. The bleed line was opened and was noted on the control panel. In this particular case the accident could also have been prevented with appropriate inspection and maintenance procedures. Do not install pipes underground. The oxygen control valve was normally closed by bleeding air out of the valve bonnet diaphragm (air to open). 25-33. did not bleed off through the bonnet vent because a mud dauber wasp constructed mud cells over the vent hole.

Design systems for easy operation and easy maintenance. Do not install relief tailpipes too close to the ground where ice blockage may make them inoperable. nipples. for example. Add interlocks to decrease pressure before the doors can be opened. Safety technology must work right the first time. and design pipe networks for easy maintenance or with easy access to equipment requiring maintenance. If required. Provide hand-operated or automatic block valves. not glass sight glasses. Do not use screwed joints and fittings when handling hazardous chemicals. or equivalent valves. ensure that trapped air can escape through a vent during heating. Do not let pipes touch the ground. Make structural analyses of relief systems to avoid structural damage during emergency reliefs. Remove all temporary startup or checkout branches. and replace them with properly designed welded plugs. . Also.550 Chapter 13 Case Histories Provide adequate supports for equipment and pipes. trenches. for emergency shutdowns. Add fail-safe block valves with a positive indication of the valve position (limit switches). Install bug screens on vent lines. Remove all temporary supports after construction is completed. Critical safety instruments must have backups. Bellows should be used cautiously. Example 13-3 Analyze the first ethylene explosion example (318-in fitting failure) to determine the percentage of fuel that actually exploded compared to the quantity of ethylene released in a vapor cloud. Make static and dynamic analyses of pipe systems to avoid excessive stresses or excessive vibrations. Design doors and lids so that they cannot be opened under pressure. there is no opportunity to adjust or improve its operation. Check to ensure that all equipment is assembled correctly. or depressions where water can accumulate. Install bellows carefully and according to manufacturers' specifications. When welding reinforcement pads to pipes or vessels. Usually. and plugs. Be sure that all tracing is covered. Do not install traps in lines where water can collect and develop a corrosion problem. inspect frequently and replace when necessary before they fail. Use electronic or mechanical level gauges. Be sure that all lines that can catch water can be appropriately drained. Do not allow spring supports to be completely compressed. install manual valves within easy reach of the operators. add visible pressure gauges at the doors. Do not install pipes in pits.

The tons of TNT based on this heat of combustion are calculated using Equation 6-24.2% is considerably higher than the 2% normally observed (see section 6-13) for unconfined vapor cloud explosions.2%. Therefore the fraction of energy manifested in the explosion is 0. 13-4 Procedures An organization can develop a good safety program if it has personnel who can identify and eliminate safety problems. the explosive energy was equivalent to 0.69 = 11.69 ton of TNT m . The management systems commonly used in industry include safety reviews. . operating procedures. is developed by implementing management systems to prevent the existence of safety problems in the first place. and maintenance procedures. This 11. however.017 X 1OYcal/ton 2.3 ton TNT. = Based on the accident investigation.13-4 Procedures 551 Solution The total energy contained in the vapor cloud is estimated by assuming the heat of combustion (appendix B). one must recognize that the existence of procedures is not enough. The higher energy conversion is a result of the explosion occurring in a partially confined area.2 kJ/mol = 12046 callg. In the study of these case histories. vm AHc ~ T N = T ETNT where Therefore (1)(227. An even better safety program. The combustion reaction is Therefore the theoretical energy is AHc = 1411. Case histories that especially demonstrate this problem are illustrated in this section.000 g)(12.312.046 callg) ~ I N = T 1. The causes of all accidents can ultimately be attributed to a lack of management systems.

another operator on an adjoining floor pushed. e . v. A short time later. with the key in the mechanics pocket. 2. The foreman and three employees set to work 23 Case Histories. Pipefitters were given the job of checking the welds for leaks.and used effectively. 113. prevents this type of accident. 186. p. A padlocked switch at the starter box disconnect. Fortunately. As one mechanic was completing his work inside the mixer. the mixer was stopped with one of three start-stop buttons. and the two fitters escaped injury. The mixer started. In addition. the mechanic should also verify the dead circuit by testing the push-button at all switches. 225. one of the other start-stop buttons. The gauge was incorrectly chosen for vacuum service and not pressure because the vacuum identifier was small. there was no fragmentation of the metal. as the fitters were carrying out the tests. Lock-tag-and-try procedures were developed to prevent accidents of this kind. The main switch was left energized. by mistake. After the switch gear lockout. and reactor 4 was nearly full of monomer and in the polymerization phase. 2. the fitters should have taken more time to check out the gauge to ensure that it was correct for this application. Man Working in Vessel24 Two maintenance workers were replacing part of a ribbon in a large ribbon mixer. Vinyl Chloride E x p l o s i ~ n ~ ~ Two vinyl chloride polymerization reactors were being operated by the same team of operators. Reactor 3 was in the cool down and dump phase of the process.552 Chapter 13 Case Histories There must also be a system of checks in place to ensure that the procedures are actually used . v. They were instructed to use 5 psi of air pressure and a soap solution to identify the leaks. the float ruptured violently. v. p. 2. this is the "try" part of the lock-tag-and-try procedure. A busy instrument worker gave them a gauge. p. They clamped a 100-psi air hose to a nipple on the tank. killing the mechanic between the ribbon flight and the shell of the vessel. The accident investigation found that the leak test should have been conducted with a hydraulic procedure and not air and that the vessel should have been protected with a relief device. Leak Testing a Vessel23 A 2-ft-diameter float was fabricated using stainless steel and welded seam construction. 2 5 C a ~Histories. 24CaseHistories.

for example.gov/ceppo/. relief valves should also be installed to mitigate these events. Flashing steam surged upward through the tower. HOW to Prevent Runaway Reactions. 1984). contrary to standard operating procedures. This accident. that the second valve created a dead space between the two block valves and that water was trapped between them. The gaseous vinyl chloride monomer just in the process of polymerization burst out of the vessel. the tower was destroyed by this accident. Phenol-Formaldehyde Runaway Reaction27 A plant had a runaway reaction with a phenol-formaldehyde polymerization reaction. A valve at the bottom of the tower was opened to initiate the transfer of heavy hot oil to a process pump. It was not realized. A bleed line and possibly a nitrogen blow-out line would have prevented the accumulation of this water. presumably ignited by a spark from an electric motor or by static electricity generated by the escaping gas. In this case the pressure luckily did not exceed the vessel rupture pressure. The result was one fatality and seven injuries and environmental damage. but in error they opened vessel 4 instead. a double block valve arrangement was installed in the bottom discharge line. Although no injuries were sustained. This accident resulted in four fatalities and ten injuries in and around the plant. The runaway reaction was triggered when.13-4 Procedures 553 to discharge the contents of reactor 3. all the raw materials and 26Hazards of Water. or adequate safeguards should be added to the system to prevent the specific hazard scenario. The accident could have been prevented with better operating procedures and better training to make the operators appreciate the consequences of mistakes. Dangerous Water E x p a n ~ i o n ~ ~ A hot oil distillation system was being prepared for operation. 20. If these scenarios are possible. however. Modern plants use interlocks or sequence controllers and other special safeguards to prevent this type of error. The steam created excessive pressures at the bottom of the tower. . could have been prevented if the plant had used a safety review procedure during the design phase of this plant modification. booklet 1 (Chicago: Amoco Oil Company. and all the trays dropped within the tower. The temperature was gradually raised to 500°F. Available at www.epa . Report 550-F99-004 (August 1999). p. and shortly afterward exploded violently. Before this particular start-up. *'EPA. Consequences of contaminating hot and high boiling liquids with low boilers can be estimated using thermodynamics. When the bottom valve was opened. filled the room. Problems similar to this are usually identified in safety reviews. the pocket of water came in contact with the hot oil.

such as the possibility of a runaway reaction and the specific steps to be taken to avoid or recover from such deviations.u. The other root causes were (1) the poor understanding of the chemistry. The resulting high temperature led to a secondary runaway decomposition reaction. The investigation team found that the reaction accelerated beyond the heat-removal capacity of the reactor. and it proceeds rapidly at 75°C. Available at http://www. Conditions and Secondary Reaction Cause Expl0sion2~ A plant manufactured a dye by mixing and reacting two chemicals. (2) an inadequate risk analysis. This company's initial research for the process identified and described two exothermic chemical reactions: (1) The desired exothermic reaction is initiated at an onset temperature of 38"C. The recommendations from the investigation included (1) revalidating the safety data for all reactive chemicals. (2) an undesirable decomposition (the dye) reaction has an onset temperature of 195°C.chemsufety. ortho-nitrochlorobenzene (0-NCB) and 2-ethylhexylamine (2-EHA). The root cause of this accident was poor operating procedures and poor process info\r mation. but they did not include information on the undesirable decomposition reaction. (2) the steam used to initiate the reaction was left on for too long. causing an explosion that blew the hatch off the reactor and allowed the release of the contents from the vessel. (2) evaluating relief requirements using the appropriate technology published by the Design Institute for Emergency Relief Systems (DIERS) (see details in chapters 8 and 9).htm. . The plant's operating and process information described the desired exothermic reaction. Chemical Manufacturing Incident. followed by the addition of heat. and (3) no safeguard controls to prevent runaway reactions. The operating procedure. Information on their MSDS was also misleading (mentioning a lower reactivity and a much lower boiling point than the actual values). and (3) the use of cooling water to control the reaction rate was not initiated soon enough. (3) installing the appropriate controls and safety features to safely manage these reactive chemicals. did not cover the safety consequences of deviations from the normal operating conditions. The primary reason for this accident was the lack of administrative controls to ensure that the standard operating procedures were used appropriately and that the operators were trained. A runaway reaction caused an explosion and flash fires that injured nine workers. The runaway reaction was the result of the following factors: (1) The reaction was started at a temperature higher than normal. (4) revising the operating procedures and training for handling these reactive chemicals to include descriptions of the possible consequences of deviations from normal 2XCSB. The operating plant was not aware of the decomposition reaction. Report 1998-06-I-NY. This EPA case history also summarized seven similar accidents with phenol-formaldehyde reactions during a 10-year period (1988-1997). for example.554 Chapter 13 Case Histories catalyst were charged to the reactor at once.gov/ reports/2000/rnorton/inde.

and explosions. engulfing one employee. and chlorates. and (6) revising the MSDSs and distributing them to anyone needing this information. Prevention of Reactive Chemical Explosions. Available at www. The potential consequences of mixing such incompatible materials are violent reactions. and (6) ensuring that all employees understand the hazards of the chemical process. The flammable vapor exploded. and nitrites. This facility had two 1000-galblend tanks to blend waste solvents. (5) implementing a program to investigate and document safety incidents.epa. Chlorates. two workers poured four drums of liquid waste into the blending vessel . and other flammable and combustible wastes. On the day of the accident. One worker was killed and two others were injured.gov/ ceppoL . Then they added solids into the top of the tank: about 2 lb each of chlorates. including perchlorates. Before this accident the operating procedures included (1) adding about 500 gal of solvent before starting the agitator. nitrites. perchlorates. (4) It was known that the addition of oxidizers could be hazardous if the oxidizers were added without a large quantity of liquid fuel in the blend tanks. (2) No inert gas blanketing was used to lower the vapor concentration to below the LFL. and other strong oxidizers are potentially incompatible with alcohols. liquid suddenly erupted out of the vessel manway. including emergency response action. (3) properly training employees in the processes they work on using the standard operating procedures for the processes and job tasks. Fuel-Blending Tank Explosi0n2~ An accident occurred in a fuel-blending facility that provided a way to reuse flammable and hazardous wastes. The EPA's recommendations for the prevention of this type of accident included (1) establishing standard operating procedures that are essential for safe operation. (4) ensuring that the chemicals and reaction mechanisms associated with the substances mixed or blended are well understood and documented. perchlorates. "EPA. and a small quantity of oxidizers. Report 550-F00-001. who died. cleaners.13-4 Procedures 555 operating conditions and the steps taken to correct the resulting problems. (5) ensuring that chemical and process hazards are understood and addressed. The explosion and resulting fire caused extensive damage to the facility. and injuring two others. In the EPA's report of the investigation it was stated that strong oxidizers are generally considered incompatible with many organic substances because of the potential for dangerous reactions. (3) Oxidizers were added only after the vessel was three-quarters full of solvent and the agitator was running. Thirty to 60 seconds after the oxidizers were added and while a fifth drum of solvent was being dumped into the top of the reactor. other organic compounds and solvents. (2) evaluating the chemical and process hazards before starting a process or procedure that has been changed or modified.about half the amount needed to reach the agitator. halogenated hydrocarbons. according to an unwritten procedure. fires.

compute the approximate pressures that were developed in the bottom of this column. If the tray vapor paths are small openings. 182-188. and (3) maintain steady progress. emergency. vessel entry.- 556 Chapter 13 Case Histories Lessons Learned Procedures are sometimes incorrectly perceived as bureaucratic regulations that impede progress. Use procedures effectively (lock-tag-and-try. including new installations or modifications to existing systems. Solution The areas of the column trays are 3. and used appropriately.14 ft2. 1985). (2) minimize incapacitating damage to facilities. There is significant information in the open literature. hot work. a water slug of 1gal.14 ft'. Kletz. . Assume a column diameter of 2 ft. and a column pressure of 10 psia. Make periodic and precise audits of procedures and equipment. Assuming a tray spacing of 1 ft. What Went Wrong? Case Histories of Process Plant Disasters (Houston: Gulf Publishing. additional lessons are identified3? Use a permit procedure for opening vessels that are normally under pressure. Communicate operating changes to other operations that may be affected by the change. we obtain = 1522 psia if all the water vaporized. Train operators and maintenance personnel to understand the consequences of deviations from the norm. The references provide excellent information for more studies. the worst-case scenario assumes that all the water vapor collects beneath the bottom tray. the volume under the first tray is 3. Use safety review procedures during the design phases of projects. In the review of case histories relevant to procedures. Example 13-4 Using the dangerous water expansion example. When reviewing case histories it is apparent that safety procedures and standard operating procedures are needed to help the chemical industry (1)eliminate injury to personnel. 13-5 Conclusion This chapter on case histories is brief and does not include all the lessons relevant to accidents. understood. pp. Using an equation of state. However. Never use gas to open plugged lines. and the like). 30T.A. case histories and safety literature are of no value unless they are studied.

Kletz. T. DC: Manufacturing Chemists' Association. 1996). 13-2. 13-4. 1985). v. Repeat Problem 13-1for the bottle of isopropyl ether accident described in section 13-2. Repeat Problem 13-1 for the vinyl chloride explosion described in section 13-4. the stress on each bolt is Assuming a tensile strength of 85. 3.Problems 557 At 500°F the vapor pressure of water is 680 psia. Frank P. The force on the bottom tray