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Table 4.1 Gap Analysis: Chemical Reactivity Hazard Management System

Table 4.1 Gap Analysis: Chemical Reactivity Hazard Management System

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ESSENTIAL PRACTICES FOR



Managing

Chemical

Reactivity

Hazards

ROBERT W. JOHNSON

STEVEN W. RUDY

STEPHEN D. UNWIN



Center for Chemical Process Safety



of the

American Institute of Chemical Engineers



3 Park Avenue, New York, NY 10016-5991



Copyright © 2003

American Institute of Chemical Engineers

3 Park Avenue

New York, New York 10016-5991

All rights reserved. No part of this publication may be reproduced, stored in a

retrieval system, or transmitted in any form or by any means, electronic,

mechanical, photocopying, recording, or otherwise without the prior

permission of the copyright owner. AIChE™and CCPS® are trademarks

owned by the American Institute of Chemical Engineers. These trademarks

may not be used without the prior express written consent of the American

Institute of Chemical Engineers. The use of this product in whole or in part for

commercial use is prohibited without prior express written consent of the

American Institute of Chemical Engineers. To obtain appropriate license and

permission for such use contact Scott Berger, 212-591-7237, scotb@AIChE.org.

Library of Congress Cataloging-in-Publication Data:

CIP data applied for

ISBN 0-8169-0896-6

CCPS Publication G-81

It is sincerely hoped that the information presented in this document will lead to an even

more impressive safety record for the entire industry; however, neither the American

Institute of Chemical Engineers, its consultants, CCPS Technical Steering Committee and

Subcommittee members, their employers, their employers’ officers and directors, nor

Unwin Company and its employees warrant or represent, expressly or by implication,

the correctness or accuracy of the content of the information presented in this document.

As between (1) American Institute of Chemical Engineers, its consultants, CCPS Technical

Steering Committee and Subcommittee members, their employers, their employers’

officers and directors, and Unwin Company and its employees, and (2) the user of this

document, the user accepts any legal liability or responsibility whatsoever for the

consequence of its use or misuse.



This book is available at a special discount when ordered

in bulk quantities. For information, contact the Center for

Chemical Process Safety at the address shown above.

PRINTED IN THE UNITED STATES OF AMERICA

10 9 8 7 6 5 4 3 2 1



Preface



For over 40 years, the American Institute of Chemical Engineers (AIChE)

has been involved with process safety and loss prevention in the chemical,

petrochemical, hydrocarbon processing and related industries. AIChE

publications are information resources for chemical engineers and other

professionals to better understand the causes of process incidents and offer

ways to prevent them. The Center for Chemical Process Safety (CCPS), a

directorate of AIChE, was established in 1985 to develop and disseminate

information for use in promoting the safe operation of chemical facilities

and processes with the objective of preventing chemical process incidents.

CCPS activities are supported by the funding and technical expertise of

over 80 corporations. Several government agencies and nonprofit and academic institutions also participate in CCPS endeavors.

With the support and direction of its advisory and management

boards, CCPS established a multifaceted program to address the need for

process safety technology and management systems to reduce potential

exposures to the public, the environment, personnel and facilities. Over

the past several years, CCPS has extended its publication program to

include a “Concept Series” of books. These books are focused on more specific topics than the longer, more comprehensive Guidelines series and are

intended to complement them. With the issuance of this title, CCPS has

published 80 books.

In 1989, CCPS published the landmark Guidelines for the Technical Management of Chemical Process Safety. This publication, Essential Practices for

Managing Chemical Reactivity Hazards, has been developed to provide companies, organizations and individuals guidance relating to management

systems and hazard assessment protocols. This guidance is directed

toward the safe handling, processing and storing of chemicals that might

become involved in uncontrolled chemical reactions, either in fixed facilities or in transport containers. This publication provides some examples

vii



viii



Managing Chemical Reactivity Hazards



and recommendations for effective methods and practices for managing

the hazards related to uncontrolled chemical reactions. The objective of the

publication is to provide guidance, to any facility with chemical reactivity

hazards, on ways to effectively address the difficult challenge of preventing loss, injury or environmental harm from uncontrolled chemical reactions. This publication is not intended to provide the only guidance on how

to safely manage chemical reactivity hazards, but it does represent the

result of a consensus of the development committee representing a

number of chemical companies and consulting organizations.



Acknowledgments



This publication was written by Robert W. Johnson, Steven W. Rudy and

Stephen D. Unwin of Unwin Company, Columbus, Ohio. This project was

initiated and guided by the CCPS Reactive Chemicals Subcommittee.

The American Institute of Chemical Engineers and the Center for

Chemical Process Safety express their gratitude to all the members of the

Reactive Chemicals Subcommittee for their generous efforts and technical

contributions in the preparation of this Concept Series publication.

Reactive Chemicals Subcommittee Chair:

Peter N. Lodal of Eastman Chemical Company

Members of the Reactive Chemicals Subcommittee

contributing to this project:

J. S. (Steve) Arendt of ABS Consulting

Donald J. Connolley of Akzo Nobel Chemicals

John Ferris of the U.S. Environmental Protection Agency

Walter L. Frank of ABS Consulting

Dennis C. Hendershot of Rohm and Haas Company

John W. Herber of 3M Company

Gregory L. Keeports of Rohm and Haas Company

David J. Leggett of Baker Engineering and Risk Consultants

John F. Murphy of the U.S. Chemical Safety and Hazard Investigation Board

Milton L. (Mickey) Norsworthy of Arch Chemicals Inc.

Gary Pilkington of Abbott Laboratories

Seshu Dharmavaram of E. I. du Pont de Nemours and Company, Inc.

Dennis Waibel of Degussa Corporation

Jan Windhorst of NOVA Chemicals

Gary York of Rhodia Inc.

ix



x



Managing Chemical Reactivity Hazards



The Subcommittee acknowledges the support and contributions of

their employer organizations in completing this project.

CCPS Staff Consultants:

John S. Bresland, now on the U.S. Chemical Safety and Hazard

Investigation Board

Gary C. Phillips, formerly of Dow Chemical Company

Scott Berger of CCPS sponsored and supported this project and provided access to the resources of CCPS and its sponsoring organizations.

CCPS staff members Shami Nayak and Clare Bennett also provided project

support.

Before publication, all CCPS books are subjected to a thorough peer

review process. CCPS also gratefully acknowledges the thoughtful comments and suggestions of the peer reviewers. Their work enhanced the

accuracy and clarity of the publication.

Peer Reviewers:

Chris Bagley of DanChem Technologies, Inc.

Reginald Baldini of New Jersey Department of Environmental Protection

Michael P. Broadribb of BP America

J. Wayne Chastain of Eastman Chemical Company

J.G. Hansel of Air Products

Thomas Hoppe of Ciba Specialty Chemicals

Peter Howell of Mark V, Inc.

Harold Johnstone of The Dow Chemical Company

Ronald Kersten of TNO Prins Maurits Laboratory, The Netherlands

Marc E. Levin of Shell Global Solutions (US)

J. Paul Lieck of Clariant Corporation (representing SOCMA)

Sam Mannan of Mary Kay O’Connor Process Safety Center,

Texas A&M University

Janet Rose of Bayer Corporation

Irv Rosenthal of the U.S. Chemical Safety and Hazard Investigation Board

Kenan Stevick of The Dow Chemical Company

Tony Thompson of Monsanto Company

Edward R. Zamejc of BP America



Abbreviations and

Acronyms



ACC

AIChE

APTAC

ARC®

ARSST

ASTM

CANUTEC

CAS

CCPS

CDC

CFR

CHEMTREC®

CHETAH

CIRC

CSB

DCS

DIERS

DOT

DPT

DSC

DTA

EPCRA



American Chemistry Council

American Institute of Chemical Engineers

Automatic Pressure Tracking Adiabatic Calorimeter

Accelerating Rate Calorimeter; Accelerating Rate

Calorimetry

Advanced Reactive Systems Screening Tool

American Society for Testing and Materials

Canadian Transportation Emergency Centre

Chemical Abstracts Service

Center for Chemical Process Safety

Centers for Disease Control and Prevention (U.S.)

Code of Federal Regulations (U.S.)

Chemical Transportation Emergency Center

Chemical Thermodynamic and Energy Release Program

Chemical Incidents Report Center

U.S. Chemical Safety and Hazard Investigation Board

Distributed Control System

Design Institute for Emergency Relief Systems

Department of Transportation

Decomposition Pressure Test

Differential Scanning Calorimeter; Differential Scanning

Calorimetry

Differential Thermal Analysis

Emergency Planning and Community Right to Know Act

xi



xii

EPA

HarsNet

HAZOP

HSE

IChemE

ICSC

IET

IPL

IPCS

ISO

LEPC

LOPA

MIC

MIE

MOC

MSDS

NA

NACD

NFPA

NIOSH

NIST

NOAA

OSHA

PHA

PSI

PSM

RCRA

RMP

RSST

SADT

SETIQ

SOCMA



Managing Chemical Reactivity Hazards



U.S. Environmental Protection Agency

Thematic Network on Hazard Assessment of Highly

Reactive Systems

Hazard and Operability [Study]

UK Health and Safety Executive

Institution of Chemical Engineers (UK)

International Chemical Safety Card

Insulated Exotherm Test

Independent Protection Layer

International Programme on Chemical Safety

International Organization for Standardization (Geneva,

Switzerland)

Local Emergency Planning Committee

Layer of Protection Analysis

Methyl Isocyanate

Minimum Ignition Energy

Management of Change

Material Safety Data Sheet

Not Applicable

National Association of Chemical Distributors

National Fire Protection Association (U.S.)

National Institute for Occupational Safety and Health

(U.S.)

National Institute of Standards and Technology

National Oceanic and Atmospheric Administration (U.S.)

U.S. Occupational Safety and Health Administration

Process Hazard Analysis

Process Safety Information

Process Safety Management

Resource Conservation and Recovery Act

Risk Management Plan/Program

Reactive System Screening Tool

Self-Accelerating Decomposition Temperature

Sistema de Emergencias en Transporte para la Industria

Quimica (Mexico)

Synthetic Organic Chemical Manufacturers Association



Abbreviations and Acronyms



UK

UN

U.S.

VSP

VSP2



United Kingdom

United Nations

United States [of America]

Vent Sizing Package

Vent Sizing Package, version 2



xiii



Contents



Preface



vii



Acknowledgments



ix



Abbreviations and Acronyms



xi



1



Introduction and Overview

1.1.

1.2.

1.3.

1.4.

1.5.



Purpose

Need

Unintentional/Intentional Chemistry Incidents

How to Use This Publication

Related Resources



2



Chemical Reactivity Hazard Management

2.1. Key Considerations for Managing

Chemical Reactivity Hazards

2.2. Life Cycle Issues

2.3. Existing Management Systems

2.4. Product Stewardship



1



3

4

6

11

13



17

17

19

25

29



3



Preliminary Screening Method for

Chemical Reactivity Hazards



3.1. Intentional Chemistry

3.2. Mixing and Physical Processing

3.3. Storage, Handling, and Repackaging



31



37

41

43

v



vi



Managing Chemical Reactivity Hazards



4



Essential Management Practices



4.1. Put into Place a System to Manage

Chemical Reactivity Hazards

4.2. Collect Reactivity Hazard Information

4.3. Identify Chemical Reactivity Hazards

4.4. Test for Chemical Reactivity

4.5. Assess Chemical Reactivity Risks

4.6. Identify Process Controls and Risk Management Options

4.7. Document Chemical Reactivity Risks

and Management Decisions

4.8. Communicate and Train on Chemical Reactivity Hazards

4.9. Investigate Chemical Reactivity Incidents

4.10. Review, Audit, Manage Change, and Improve

Hazard Management Practices and Program



5



Worked Examples

5.1.

5.2.

5.3.

5.4.

5.5.

5.6.



Intentional Chemistry Example

Combustor Example

Repackaging Example

Physical Processing Example

Mixing Example

Oxygen System Example



6



65

65

71

78

84

90

96

101

107

110

113



119



119

120

124

128

128

133



Future Work on Chemical Reactivity Hazards



135



Glossary

References

A-1. Case Histories

A-2. An Inherently Safer Process Checklist

A-3. Executive Summary of CSB Investigation Report

Contents of CD-ROM

Index



139

149

155

167

173

185

187



6.1. Inform

6.2. Communicate



135

137



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