Chemical Re Activity Hazard Management

Introduction to Chemical Reactivity Hazard Management
Mikal Shabazz U.S. Environmental Protection Agency Mid-Atlantic Region, Office of Enforcement Oil and Prevention Branch
Overview
What is Chemical Reactivity? What are its Hazards? Challenges in Managing Reactive Hazards Examples of Facilities with Reactive Chemistry Hazards Screening Example using Case History Principles of Reactive Hazard Management Tools and Resources
Uses of Reactive Chemistry
What energy/products will be released? Initial conditions Reaction path Reaction thermodynamics Reaction kinetics AND How will the released energy/products interact with the environment? Environmental conditions Process equipment & controls Heat & mass transfer People/property/environment response
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Types of Chemical Reactivity

Main Category Readily SelfReacts Readily Reacts with Common Environmental Substances Readily Reacts with Other Chemicals
10
Subcategory
Polymerizes Decomposes Rearranges Condenses Reacts with Nitrogen Reacts with Oxygen Reacts with Water Reacts with Ordinary Combustibles Reacts with Metals Reacts with Acids Reacts with Bases Reacts with Hydrogen
The Problem
Chemical Safety Board Report 167 incidents in a 21 year period 108 fatalities Significant property damage Data are incomplete, and certainly underestimate the magnitude of the problem
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The Problem
In 90% + of all incidents studied, the information necessary to have prevented the incident was documented and publicly available.
12
Groups that Use Reactive Chemistry

No Chemistry Users Unintentional Chemistry Users Intentional Chemistry Users Or, stated another way Storage, Handling and Repackaging Mixing and Physical Processing Chemical Manufacturing
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Preliminary Screening Method Management System Framework
Concept Book(~ 200 pages) FREE DOWNLOAD http://www.aiche.org/ccps/resources.htm

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Guiding Principles
1. 2.
Use existing information Apply appropriate levels of technology to the level of the problem Identify areas requiring additional testing, data generation Use existing management systems/ structures to the maximum extent possible
3.
4.
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Recommended Approach
Preliminary Screening Method Management System Framework
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Preliminary Screening for Chemical Reactivity Hazards
Summary Flowchart
Preliminary Screening: Summary Flowchart
Summary Flowchart (continued)
Table 3.1 Example Form to Document Screening of Chemical Reactivity Hazards

FACILITY: COMPLETED BY: YES, NO or NA COMPLETION DATE: APPROVED BY:
Do the answers to the following questions indicate chemical reactivity hazard(s) are present? _____________
AT THIS FACILITY: BASIS FOR ANSWER; COMMENTS
Is intentional chemistry performed? 2. Is there any mixing or combining of different substances? 3. Does any other physical processing of substances occur? 4. Are there any hazardous substances stored or handled? 5. Is combustion with air the only chemistry intended? 6. Is any heat generated during the mixing or physical processing of substances? 7. Is any hazardous material identified as spontaneously combustible? 8. Is any hazardous material identified as peroxide forming? 9. Is any hazardous material identified as water reactive? 10. Is any hazardous material identified as an oxidizer? 11. Is any hazardous material identified as self-reactive? 12. Can incompatible materials coming into contact cause hazardous consequences, based on the following analysis?
Question 1.
Example Form for Documenting Chemical Reactivity Hazard Screening

R, NR or ?** INFORMATION SOURCES; COMMENTS
SCENARIO
CONDITIONS NORMAL?*
1 2 3
*Does the contact/mixing occur at ambient temperature, atmospheric pressure, 21% oxygen atmosphere, and unconfined? (IF NOT, DO NOT ASSUME THAT PUBLISHED DATA FOR AMBIENT CONDITIONS APPLY) **R = Reactive (incompatible) under the stated scenario and conditions NR = Non-reactive (compatible) under the stated scenario and conditions ? = Unknown; assume incompatible until further information is obtained
An Example
Simplified retrospective of 1995 explosion / fire at Napp Technologies, Lodi, New Jersey Intent: Illustrate the Preliminary Screening Method for the type of process involved in the incident
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Mixing Example
A toll manufacturer is contracted to prepare one 8100 lb batch of a gold precipitating agent.
Ingredients mixed in a 125 ft3 (6 m3) cone blender Blender is insulated and has a steel jacket to allow cooling and heating with a water/glycol mixture Dry ingredients blended: ~ 66% sodium hydrosulfite, 22% aluminum powder and 11% potassium carbonate by weight Small amount of benzaldehyde added for odor control Product blend packaged into eighteen 55 gal drums for shipment
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Table 3.1 Example Form to Document Screening of Chemical Reactivity Hazards

FACILITY: COMPLETED BY:
Mixing Example Documentation APPROVED BY:

YES, NO or NA BASIS FOR ANSWER; COMMENTS
COMPLETION DATE:
Do the answers to the following questions indicate chemical reactivity hazard(s) are present? _____________
AT THIS FACILITY:
Is intentional chemistry performed? 2. Is there any mixing or combining of different substances? 3. Does any other physical processing of substances occur? 4. Are there any hazardous substances stored or handled? 5. Is combustion with air the only chemistry intended? 6. Is any heat generated during the mixing or physical processing of substances? 7. Is any hazardous material identified as spontaneously combustible? 8. Is any hazardous material identified as peroxide forming? 9. Is any hazardous material identified as water reactive? 10. Is any hazardous material identified as an oxidizer? 11. Is any hazardous material identified as self-reactive? 12. Can incompatible materials coming into contact cause hazardous consequences, based on the following analysis?
Question 1.
SCENARIO
CONDITIONS NORMAL?*
R, NR or ?**
INFORMATION SOURCES; COMMENTS
1 2 3
Sources of Information
Here are some key sources of reactivity information, if you know what chemicals are being handled.
International Chemical Safety Cards - accessible from CDC website at http://www.cdc.gov/niosh/ipcs/icstart.html) NIOSH Pocket Guide to Chemical Hazards - online version available at http://www.cdc.gov/niosh/npg/npg.html) NFPA Fire Protection Guide to Hazardous Materials [NFPA 2002] Bretherick's Handbook of Reactive Chemical Hazards [Urben 1999] Coast Guard Hazardous Information System http://www.chrismanual.com NOAA Chemical Reactivity Worksheet - discussed later in this session - http://response.restoration.noaa.gov/chemaids/react Sax's Dangerous Properties of Industrial Materials [Lewis and Irving 2000] Data from manufacturers/suppliers, including Material Safety Data Sheets (MSDSs)
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Material Safety Data Sheets Basic reactivity hazards of each chemical used should be included the Material Safety Data Sheet provided by your chemical supplier. In the U.S., the OSHA HAZCOM Standard says what must be included in an MSDS, but does not give a required format.
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Material Safety Data Sheets

The widely used ANSI Standard Z400.1 gives a consistent format for MSDSs. Reactivity information might be found in:
Section 5: Fire-Fighting Measures Look for water reactivity and the consequences of heating the material in a fire situation, including decomposition, polymerization, and the generation of gaseous reaction products. Section 10: Stability and Reactivity The primary section for reactivity hazards. Look for information on chemical stability, conditions to avoid, incompatibility with other materials, hazardous decomposition, and hazardous polymerization. Section 14: Transport Information Look for the hazardous material description, the hazard class, and the UN/NA identification number. One place to look up what the classes and numbers mean is in the DOT Emergency Response Guidebook. Section 16: Other Information Look for hazard ratings (such as the NFPA instability rating) and other possible clues such as how the material is prepared.
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Material Safety Data Sheets WARNING:

MSDSs often contain incomplete or contradictory information. The U.S. EPA issued a Safety Alert warning not to rely on a single data source in emergency situations. The same is true when attempting to identify reactivity hazards that need to be avoided or managed. Other MSDS limitations are listed in Section 4.2 of the CCPS Essential Practices book.
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Screening Question 1
Question 1
Is intentional chemistry performed at your facility?
Mixing Example Documentation

AT THIS FACILITY: YES, NO or NA BASIS FOR ANSWER; COMMENTS
Question 1. Is intentional chemistry performed?
NO
Loading, blending, and packaging only
Question 2
Is there any mixing or combining of different substances?

Question 1. Is intentional chemistry performed? 2. Is there any mixing or combining of different substances?
NO YES
Loading, blending, and packaging only Blending of ingredients in cone blender
Question 6
Is any heat generated during the mixing or physical processing of substances?

Question 1. Is intentional chemistry performed? 2. Is there any mixing or combining of different substances? 3. Does any other physical processing of substances occur? 4. Are there any hazardous substances stored or handled? 5. Is combustion with air the only chemistry intended?
NO YES NA NA NA

Question 1. Is intentional chemistry performed? 2. Is there any mixing or combining of different substances? 3. Does any other physical processing of substances occur? 4. Are there any hazardous substances stored or handled? 5. Is combustion with air the only chemistry intended? 6. Is any heat generated during the mixing or physical
NO YES NA NA NA NO
processing of substances?
No indication of heat generation from previous batch or from nature of blend
Question 7
Is any substance identified as spontaneously combustible?
Do the answers to the following questions indicate chemical reactivity hazard(s) are present?
AT THIS FACILITY: YES, NO or NA

NO YES NA NA NA NO YES
YES
BASIS FOR ANSWER; COMMENTS
processing of substances? 7. Is any substance identified as spontaneously combustible?
No indication of heat generation from previous batch or from nature of blend Sodium hydrosulfite is DOT/UN Hazard Class 4.2, Spontaneously Combustible Material; finely divided aluminum powder is pyrophoric without oxide coating
Expect chemical reactivity hazard(s) to be present; Go to Chapter 4 for information on identifying and managing hazards

YES

YES
8. Is any substance identified as peroxide forming? 9. Is any substance identified as water reactive?
10. Is any substance identified as an oxidizer? 11. Is any substance identified as self-reactive?
12. Can incompatible materials coming into contact cause
undesired consequences, based on the following analysis?

YES
NO
No indication of heat generation from previous batch or from nature of blend Sodium hydrosulfite is DOT/UN Hazard Class 4.2, Spontaneously Combustible Material; finely divided aluminum powder is pyrophoric without oxide coating No indication from MSDS or literature

YES
NO YES
No indication of heat generation from previous batch or from nature of blend Sodium hydrosulfite is DOT/UN Hazard Class 4.2, Spontaneously Combustible Material; finely divided aluminum powder is pyrophoric without oxide coating No indication from MSDS or literature Sodium hydrosulfite is water reactive; uncoated aluminum powder is DOT/UN Hazard Class 4.3, Dangerous when Wet

YES
NO YES
NO
No indication of heat generation from previous batch or from nature of blend Sodium hydrosulfite is DOT/UN Hazard Class 4.2, Spontaneously Combustible Material; finely divided aluminum powder is pyrophoric without oxide coating No indication from MSDS or literature Sodium hydrosulfite is water reactive; uncoated aluminum powder is DOT/UN Hazard Class 4.3, Dangerous when Wet No indication from MSDS or literature

YES
NO YES
NO YES
No indication of heat generation from previous batch or from nature of blend Sodium hydrosulfite is DOT/UN Hazard Class 4.2, Spontaneously Combustible Material; finely divided aluminum powder is pyrophoric without oxide coating No indication from MSDS or literature Sodium hydrosulfite is water reactive; uncoated aluminum powder is DOT/UN Hazard Class 4.3, Dangerous when Wet No indication from MSDS or literature Heating of sodium hydrosulfite can initiate self-sustaining exothermic decomposition

YES
8. Is any substance identified as peroxide forming? peroxide forming? 9. Is any substance identified as water reactive? water reactive?
NO YES
10. Is any substance identified as an oxidizer? oxidizer? 11. Is any substance identified as self-reactive? self-reactive?
NO YES

YES
NO YES
NO YES
12. Can incompatible materials coming into contact cause incompatible materials coming into contact
undesired consequences, based on the following analysis? cause undesired consequences?
Chemical Compatibility Determinations Public literature (e.g., Sax, Brethericks, MSDS, etc.) Chemical Compatibility Charts (ASTM E 2012-00 Standard Guide for the Preparation of a Binary Chemical Compatibility Chart, Coast Guard chart, etc.) NOAA Chemical Reactivity Worksheet
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NOAA Chemical Reactivity Worksheet

The Chemical Reactivity Worksheet is a PC Application written by the National Oceanic and Atmospheric Administration (NOAA). It is included on the CD available at this session, or as a free download from the NOAA website. The page which contains the download link as well as other information on the worksheet is:
http://response.restoration.noaa.gov/chemaids/react.html
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NOAA Chemical Information
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NOAA Compatibility Chart
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NOAA Compatibility Chart
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FACILITY:
Mixing Example Documentation Napp Technologies, Inc., Lodi, New Jersey

YES, NO or NA
(continued)
Do the answers to the following questions indicate chemical reactivity hazard(s) are present? 1 ___YES____
AT THIS FACILITY:
Question 1. Is intentional chemistry performed? cause 12. Can incompatible materials coming into contact
2. Is thereconsequences,combining thedifferent substances? undesired any mixing or based on of following analysis? 3. Does any other physical processing of substances occur? CONDITIONS SCENARIO 2 handled? 4. Are there any hazardous substances stored or NORMAL? No 1 Vacuum seal coolingair the only chemistry intended? N2 5. Is combustion with water enters blender, reacts with aluminum powder and sodium atmosphere, 6. Is any heat generated during the mixing or physical hydrosulfite, and initiates confinement processing of substances? exothermic decomposition in blender 7. Is any substance identified as spontaneously combustible? No N2 2 Glycol/water mixture leaks from jacket into blender, reacts with aluminum powder and atmosphere, sodium hydrosulfite, and initiates confinement exothermic decomposition in blender 8. Is any substance identified as peroxide forming?
NO YES YES NA R, NR 3 or ? NA R NA NO
Loading, blending, See analysis belowand packaging only below Blending of ingredients in cone blender
INFORMATION SOURCES; COMMENTS
Both aluminum powder and sodium hydrosulfite are watergeneration from No indication of heat reactive
previous batch or from nature of blend Sodium hydrosulfite is DOT/UN Hazard YES NOAA Worksheet indicates combining R Class 4.2, Spontaneously Combustible sodium hydrosulfite with ethylene glycol Material; finely divided aluminum powder is explosive without oxide coating is pyrophoric due to vigorous reaction or reaction products may produce NO No indication from MSDS or literature detonation, may cause fire, and Sodium hydrosulfite is water reactive; 9. Is any substance identified as water reactive? YES indicates flammable gas generation uncoated aluminum powder is DOT/UN and heat generation by chemical Hazard Class 4.3, Dangerous When Wet reaction, may cause pressurization NO No indication from MSDS or literature 10. Is any substance identified as an oxidizer? 1 Use Figure 3.1 with answers to Questions 1-12 to determine if answer is YES or NO Heating of sodium hydrosulfite can 11. Is any substance identified as self-reactive? YES 2 Does the contact/mixing occur at ambient temperature, atmospheric pressure, 21% oxygen atmosphere, and initiate self-sustaining exothermic unconfined? (IF NOT, DO NOT ASSUME THAT PUBLISHED DATA FOR AMBIENT CONDITIONS APPLY) 3 decomposition R = Reactive (incompatible) under the stated scenario and conditions NR Can incompatible materials coming into contact cause See analysis below 12.= Non-reactive (compatible) under the stated scenario and conditions YES ? = Unknown; assume incompatible until further information is obtained undesired consequences, based on the following analysis?
An Example
For this retrospective example: Preliminary Screening Method would indicate that chemical reactivity hazards need to be managed at this facility Multiple indicators present Individual chemicals are spontaneously combustible, water reactive, thermally sensitive Interaction scenarios indicate potential incompatibilities
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Preliminary Screening for Chemical Reactivity Hazards
Summary Flowchart
Incident
April 21, 1995 5 worker fatalities ~300 evacuated Facility destroyed Surrounding businesses damaged
Ed Hill, The Bergen Record Used with permission
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Appropriate Management Systems

Identification of the reactive nature and interaction of the materials Use of a compatible heating / cooling medium Mechanical integrity program to decrease the likelihood of leaks Training of personnel (operations and emergency response) on possible upset situations and appropriate response
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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
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Essential Management Practices

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
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Summary
Preliminary screening method Useful for identifying where chemical reactivity hazards are likely to exist Management system framework Applicable to all levels of complexity and sophistication Builds on existing management systems Supplemented with tools appropriate for chemical reactivity hazards
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Ongoing Reactivity Initiatives

OSHA Chemical Reactivity Hazards Management Alliance
http://www.osha.gov/SLTC/reactivechemicals/
Reactivity Management Roundtable

http://www.aiche.org/CCPS/ActiveProjects/RMR/ index.aspx
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Reactive Hazard Resources CD

The CD available at this session includes the following: Complete text of CCPS concept book CSB reactive hazards investigation reports and alerts NOAA Reactivity Worksheet Collection of reactive chemical MSDSs EPA chemical reactivity safety alerts This presentation
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Introduction to Chemical Reactivity Hazard Management

Uses of Reactive Chemistry

Types of Chemical Reactivity

Groups that Use Reactive Chemistry

Preliminary Screening Method Management System Framework

Concept Book(~ 200 pages) FREE DOWNLOAD http://www.aiche.org/ccps/resources.htm

Preliminary Screening for Chemical Reactivity Hazards

Preliminary Screening: Summary Flowchart

Summary Flowchart (continued)

Table 3.1 Example Form to Document Screening of Chemical Reactivity Hazards

Example Form for Documenting Chemical Reactivity Hazard Screening

Table 3.1 Example Form to Document Screening of Chemical Reactivity Hazards

Mixing Example Documentation APPROVED BY:

INFORMATION SOURCES; COMMENTS

Material Safety Data Sheets

Material Safety Data Sheets WARNING:

Mixing Example Documentation

Question 1. Is intentional chemistry performed?

Loading, blending, and packaging only

Is there any mixing or combining of different substances?

Mixing Example Documentation

Loading, blending, and packaging only Blending of ingredients in cone blender

Is any heat generated during the mixing or physical processing of substances?

Mixing Example Documentation

Loading, blending, and packaging only Blending of ingredients in cone blender

Mixing Example Documentation

Loading, blending, and packaging only Blending of ingredients in cone blender

No indication of heat generation from previous batch or from nature of blend

Is any substance identified as spontaneously combustible?

Mixing Example Documentation

BASIS FOR ANSWER; COMMENTS

Loading, blending, and packaging only Blending of ingredients in cone blender

processing of substances? 7. Is any substance identified as spontaneously combustible?

Mixing Example Documentation

BASIS FOR ANSWER; COMMENTS

Loading, blending, and packaging only Blending of ingredients in cone blender

processing of substances? 7. Is any substance identified as spontaneously combustible?

Mixing Example Documentation

BASIS FOR ANSWER; COMMENTS

Loading, blending, and packaging only Blending of ingredients in cone blender

processing of substances? 7. Is any substance identified as spontaneously combustible?

12. Can incompatible materials coming into contact cause

undesired consequences, based on the following analysis?

Mixing Example Documentation

BASIS FOR ANSWER; COMMENTS

Loading, blending, and packaging only Blending of ingredients in cone blender

processing of substances? 7. Is any substance identified as spontaneously combustible?

12. Can incompatible materials coming into contact cause

undesired consequences, based on the following analysis?

Mixing Example Documentation

BASIS FOR ANSWER; COMMENTS

Loading, blending, and packaging only Blending of ingredients in cone blender

processing of substances? 7. Is any substance identified as spontaneously combustible?

12. Can incompatible materials coming into contact cause

undesired consequences, based on the following analysis?

Mixing Example Documentation

BASIS FOR ANSWER; COMMENTS

Loading, blending, and packaging only Blending of ingredients in cone blender

processing of substances? 7. Is any substance identified as spontaneously combustible?

12. Can incompatible materials coming into contact cause