Guidelines for Chemical Reactivity Evaluation and Application to Process Design

by CCPS (Center for Chemical Process Safety)

Overview

This book contains guidelines for companies to improve their process safety performance through the proper identification and mitigation of chemical reactivity hazards. Extensive use of case histories is made throughout the text to illustrated key points and learnings. By using the CCPS RBPS framework for reactive assessments, the reader is guided in how to design and implement a reactive chemistry management framework. Topics concerning the use of published data, open source screening and evaluation software allow the reader to focus the scope of further quantitative evaluation efficiently. Detailed discussion (with applicable example evaluations and case histories) of testing methodologies, both historic and cutting-edge, fill in the Process Knowledge gaps concerning reactive hazards, and allow for design and engineering of specific prevention, control and mitigation methods to manage chemical reactivity risk.

Finally, using the well-established RBPS framework puts chemical reactivity evaluation into perspective relative to other process safety hazards and activities, and provides a means to effectively incorporate evaluation results into Hazard Identification and Risk Assessment (HIRA), Operating and Maintenance Procedures, Asset Integrity and Reliability programs, Conduct of Operations and Operational Readiness evaluations, each of which have unique chemical reactivity-related requirements in addition to their more general application to process safety risks.

Product Details

ISBN-13:	9781394164936
Publisher:	Wiley
Publication date:	08/11/2026
Edition description:	2nd ed.
Pages:	352
Product dimensions:	6.50(w) x 1.50(h) x 9.50(d)

About the Author

The CENTER FOR CHEMICAL PROCESS SAFETY (CCPS), an industry technology alliance of the American Institute of Chemical Engineers (AIChE), has been a world leader in developing and disseminatinginformation on process safety management and technology since 1985. CCPS has published over 80 books in its process safety guidelines and process safety concepts series. For more information, visit www.ccpsonline.org.

Table of Contents

List of Tables.

List of Figures.

Preface.

Acknowledgments.

Glossary.

List of Symbols.

Chapter 1. Introduction.

1.1. General.

1.2. Chemical Reactivity.

1.3. Detonations, Deflagrations, and Runaways.

1.4. Assessment and Testing Strategies.

Chapter 2. Identification of Hazardous Chemical Reactivity.

2.1. Summary/Strategy.

2.1.1. Introduction.

2.1.2. Hazard Identification Strategy.

2.1.3. Exothermic Reactions.

2.1.4. Experimental Thermal and Reactivity Measurements.

2.1.5. Test Strategies.

2.1.6. Overview of Thermal Stability Test methods.

2.1.7. Examples of Interpretation and Application of Test Data.

2.2. Technical Section.

2.2.2. Identification of High Energy Substances.

2.2.3. Hazard Prediction by Thermodynamic Calculations.

2.2.3.1. Oxygen Balance.

2.2.3.2. Calculation of the Reaction Enthalpy.

2.2.3.3. Application of Computer Programs.

2.2.4. Instability/Incompatibility Factors.

2.2.4.1. Factors Influencing Stability.

2.2.4.2. Redox Systems.

2.2.4.3. Reactions with Water.

2.2.4.4. Reactions between Halogenated Hydrocarbons and Metals.

2.3. Practical Testing.

2.3.1. Screening Tests.

2.3.1.1. Thermal Analysis.

2.3.1.2. Isoperibolic Calorimetry.

2.3.2. Thermal Stability and Runaway Testing.

2.3.2.1. Isothermal Storage Tests.

2.3.2.2. Dewar Flask Testing and Adiabatic Storage Tests.

2.3.2.3. Accelerating Rate Calorimeter (ARC).

2.3.2.4. Stability Tests for Powders.

2.3.3. Explosibility Testing.

2.3.3.1.Detonation Testing.

2.3.3.2. Deflagration Testing and Autoclave Testing.

2.3.3.3. Mechanical Sensitivity Testing.

2.3.3.4. Sensitivity to heating Under Confinement.

2.3.4. Reactivity Testing.

2.3.4.1. Pyrophoric Properties.

2.3.4.2. Reactivity with Water.

2.3.4.3. Oxidizing Properties.

2.3.5. Flammability Testing.

Chapter 3. Chemical Reactivity Considerations in Process/Reactor Design and Operation.

3.1. Introduction.

3.1.1. Thermal Hazards: Identification and Analysis.

3.1.1.1. Cause, Definition, and Prevention of a Runaway.

3.1.1.2. Some Simple Rules for Inherent Safety.

3.1.1.3. Strategy for Inherent Safety in Design and Operation.

3.1.1.4. Equipment to be Used for the Analysis of Hazards.

3.2. Reactor, Heat and Mass Balance Considerations.

3.2.1. Heat and Mass Balances, Kinetics, and Reaction Stability.

3.2.1.1. Adiabatic Temperature Rise.

3.2.1.2. The Reaction.

3.2.1.3. Reaction Rate.

3.2.1.4. Reaction Rate Constant.

3.2.1.5. Concentration of Reactants.

3.2.1.6. Effect of Surrounding Temperature on Stability.

3.2.1.7. Effect of Agitation and Surface Fouling on Stability.

3.2.1.8. Mass Balance.

3.2.2. Choice of Reactor.

3.2.3. Heat Transfer.

3.2.3.1. Heat Transfer in Nonagitated Vessels.

3.2.3.2. Heat Transfer in Agitated Vessels.

3.3. Acquisition and Use of Process Design data.

3.3.1. Introduction.

3.3.2. Bench-Scale Equipment for Batch/Tank Reactors.

3.3.2.1. Reaction Calorimeter (RC1).

3.3.2.2. Contalab.

3.3.2.3. CPA ThermoMetric Instruments.

3.3.2.4. Quantitative Reaction Calorimeter.

3.3.2.5. Specialized Rectors.

3.3.2.6. Vent Size Package (VSP).

3.3.2.7. Reactive System Screening Tool (RSST).

3.3.3. Process Safety for Reactive Systems.

3.3.3.1. Test Plan.

3.3.3.2. System Under Investigation.

3.3.3.3. Test Results.

3.3.3.4. Malfunction and Process Deviation Testing.

3.3.3.5. Pressure Effect.

3.3.3.6. Results from the ARC, RSST, and VSP.

3.3.4. Scale-up and Pilot Plants.

3.3.4.1. General Remarks.

3.3.4.2. Chemical Kinetics.

3.3.4.3. Mass Transfer/Mixing.

3.3.4.4. Heat Transfer.

3.3.4.5. Self-Heating.

3.3.4.6. Scale-Up of Accelerating Rate Calorimeter (ARC) Results.

3.3.4.7. Scale-Up of Vent Size Package (VSP) Results.

3.3.5. Process Design Applications.

3.3.5.1. Batch and Semi-Batch Processing Plants.

3.3.5.2. An Example Involving Peroxides.

3.3.5.3. An Example Involving a Continuous Nitration.

3.3.5.4. A Self-Heating Example.

3.3.5.5. Batch-to-Continuous Example

3.3.5.6. Integrated Relief Evaluation.

3.3.6. Storage and Handling.

3.3.6.1. Scale-Up Example for Storage.

3.3.6.2. Peroxides.

3.3.6.3. Passive Means to Prevent Explosions.

3.3.7. Dryers and Filters.

3.4. Protective Measures.

3.4.1. Containment.

3.4.1.1. Introduction.

3.4.1.2. Determination of Gas-Vapor Release.

3.4.1.3. Laboratory Scale.

3.4.1.4. Full-Scale Example.

3.4.2. Instrumentation and Detection of Runaways.

3.4.2.1. Methods of On-Line Detection.

3.4.2.2. Methods of Noise Suppression.

3.4.3. Mitigation Measures.

3.4.3.1. Reaction Quenching Methods.

3.4.3.2. An Example Involving a Sulfonation.

3.4.3.3. Relief Disposal.

3.4.3.4. Dispersion, Flaring, Scrubbing, and Containment.

3.4.3.5. Venting.

Chapter 4. Management of Chemical Process Safety.

4.1. Hazard Identification and Quantification.

4.2. Hazard Evaluation Procedures.

4.3. Chemical Process Safety Management.

4.4. Future Trends.

References.

References Cited.

Selected Additional Readings.

Index.