Introduction to Chemical Reactivity Hazard Management

1. Introduction to Chemical Reactivity Hazard Management Mikal Shabazz U.S. Environmental Protection Agency Mid-Atlantic Region, Office of Enforcement Oil and Prevention Branch

2. 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

4. Uses of Reactive Chemistry

9. 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

10. Types of Chemical Reactivity

11. 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

12. The Problem • In 90% + of all incidents studied, the information necessary to have prevented the incident was documented and publicly available.

13. 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

14. Concept Book(~ 200 pages) FREE DOWNLOAD http://www.aiche.org/ccps/resources.htm • Preliminary Screening Method • Management System Framework

15. Guiding Principles • 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

16. Recommended Approach • Preliminary Screening Method • Management System Framework

17. Summary Flowchart Preliminary ScreeningforChemical ReactivityHazards

18. Preliminary Screening: Summary Flowchart

19. Summary Flowchart (continued)

20. ExampleForm forDocumentingChemicalReactivityHazardScreening

21. 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

22. 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

23. Mixing Example Documentation

24. 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)

25. 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.

26. 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 InformationLook 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.   

27. 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.

28. Is intentional chemistry performed at your facility? Question 1 Screening Question 1

29. Mixing Example Documentation NO Loading, blending, and packaging only YES, NO or NA BASIS FOR ANSWER; COMMENTS AT THIS FACILITY: Question 1. Is intentional chemistry performed?

30. Question 2 Is there any mixing or combining of different substances?

31. Mixing Example Documentation YES NO Blending of ingredients in cone blender Loading, blending, and packaging only YES, NO or NA BASIS FOR ANSWER; COMMENTS AT THIS FACILITY: Question 1. Is intentional chemistry performed? 2. Is there any mixing or combining of different substances?

32. Question 6 Is any heat generated during the mixing or physical processing of substances?

33. Mixing Example Documentation YES NO NA NA NA Blending of ingredients in cone blender Loading, blending, and packaging only YES, NO or NA BASIS FOR ANSWER; COMMENTS AT THIS FACILITY: 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?

34. Mixing Example Documentation NA NA NO NA YES NO No indication of heat generation from previous batch or from nature of blend Blending of ingredients in cone blender Loading, blending, and packaging only YES, NO or NA BASIS FOR ANSWER; COMMENTS AT THIS FACILITY: 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 processing of substances?

35. Question 7 Is any substance identified as spontaneously combustible?

36. Do the answers to the following questions indicate chemical reactivity hazard(s) are present? YES Mixing Example Documentation Do the answers to the following questions indicate chemical reactivity hazard(s) are present? YES NA NA NO NA YES NO Sodium hydrosulfite is DOT/UN Hazard Class 4.2, Spontaneously Combustible Material; finely divided aluminum pow-der is pyrophoric without oxide coating No indication of heat generation from previous batch or from nature of blend Blending of ingredients in cone blender Loading, blending, and packaging only YES, NO or NA BASIS FOR ANSWER; COMMENTS AT THIS FACILITY: 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 processing of substances? 7.Is any substance identified as spontaneously combustible?

37. Expect chemical reactivity hazard(s) to be present; Go to Chapter 4 for information on identifying and managing hazards

38. Mixing Example Documentation Do the answers to the following questions indicate chemical reactivity hazard(s) are present? YES YES NA NA NO NA YES NO Blending of ingredients in cone blender Sodium hydrosulfite is DOT/UN Hazard Class 4.2, Spontaneously Combustible Material; finely divided aluminum pow-der is pyrophoric without oxide coating Loading, blending, and packaging only No indication of heat generation from previous batch or from nature of blend YES, NO or NA BASIS FOR ANSWER; COMMENTS AT THIS FACILITY: 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 processing of substances? 7.Is any substance identified as spontaneously combustible?

39. Mixing Example Documentation Do the answers to the following questions indicate chemical reactivity hazard(s) are present? YES NA NA NA YES NO NO YES No indication of heat generation from previous batch or from nature of blend Blending of ingredients in cone blender Loading, blending, and packaging only Sodium hydrosulfite is DOT/UN Hazard Class 4.2, Spontaneously Combustible Material; finely divided aluminum pow-der is pyrophoric without oxide coating YES, NO or NA BASIS FOR ANSWER; COMMENTS AT THIS FACILITY: 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 processing of substances? 7.Is any substance identified as spontaneously combustible? 8. Is any substance identified as peroxide forming? 8. Is any substance identified as peroxide forming? 9. Is any substance identified as water reactive? 9. Is any substance identified as water reactive? 10. Is any substance identified as an oxidizer? 10. Is any substance identified as an oxidizer? 11. Is any substance identified as self-reactive? 11. Is any substance identified as self-reactive? 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis? 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis?

40. Mixing Example Documentation Do the answers to the following questions indicate chemical reactivity hazard(s) are present? YES NO NO NO YES YES NA NA NA No indication from MSDS or literature Loading, blending, and packaging only 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 pow-der is pyrophoric without oxide coating Blending of ingredients in cone blender YES, NO or NA BASIS FOR ANSWER; COMMENTS AT THIS FACILITY: 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 processing of substances? 7.Is any substance identified as spontaneously combustible? 8. Is any substance identified as peroxide forming? 8. Is any substance identified as peroxide forming? 9. Is any substance identified as water reactive? 9. Is any substance identified as water reactive? 10. Is any substance identified as an oxidizer? 10. Is any substance identified as an oxidizer? 11. Is any substance identified as self-reactive? 11. Is any substance identified as self-reactive? 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis? 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis?

41. Mixing Example Documentation Do the answers to the following questions indicate chemical reactivity hazard(s) are present? YES NO YES NA NO YES YES NO NA NA Loading, blending, and packaging only No indication from MSDS or literature Sodium hydrosulfite is water reactive; uncoated aluminum powder is DOT/UN Hazard Class 4.3, Dangerous when Wet Blending of ingredients in cone blender 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 pow-der is pyrophoric without oxide coating YES, NO or NA BASIS FOR ANSWER; COMMENTS AT THIS FACILITY: 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 processing of substances? 7.Is any substance identified as spontaneously combustible? 8. Is any substance identified as peroxide forming? 8. Is any substance identified as peroxide forming? 9. Is any substance identified as water reactive? 9. Is any substance identified as water reactive? 10. Is any substance identified as an oxidizer? 10. Is any substance identified as an oxidizer? 11. Is any substance identified as self-reactive? 11. Is any substance identified as self-reactive? 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis? 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis?

42. Mixing Example Documentation Do the answers to the following questions indicate chemical reactivity hazard(s) are present? YES NA YES NA YES NO YES NO NO NA NO No indication of heat generation from previous batch or from nature of blend No indication from MSDS or literature No indication from MSDS or literature Sodium hydrosulfite is water reactive; uncoated aluminum powder is DOT/UN Hazard Class 4.3, Dangerous when Wet Loading, blending, and packaging only Blending of ingredients in cone blender Sodium hydrosulfite is DOT/UN Hazard Class 4.2, Spontaneously Combustible Material; finely divided aluminum pow-der is pyrophoric without oxide coating YES, NO or NA BASIS FOR ANSWER; COMMENTS AT THIS FACILITY: 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 processing of substances? 7.Is any substance identified as spontaneously combustible? 8. Is any substance identified as peroxide forming? 8. Is any substance identified as peroxide forming? 9. Is any substance identified as water reactive? 9. Is any substance identified as water reactive? 10. Is any substance identified as an oxidizer? 10. Is any substance identified as an oxidizer? 11. Is any substance identified as self-reactive? 11. Is any substance identified as self-reactive? 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis? 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis?

43. Mixing Example Documentation Do the answers to the following questions indicate chemical reactivity hazard(s) are present? YES NA YES NO YES NO NO YES NO YES NA NA Loading, blending, and packaging only 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 pow-der is pyrophoric without oxide coating Blending of ingredients in cone blender No indication from MSDS or literature No indication from MSDS or literature Sodium hydrosulfite is water reactive; uncoated aluminum powder is DOT/UN Hazard Class 4.3, Dangerous when Wet Heating of sodium hydrosulfite can initiate self-sustaining exothermic decomposition YES, NO or NA BASIS FOR ANSWER; COMMENTS AT THIS FACILITY: 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 processing of substances? 7.Is any substance identified as spontaneously combustible? 8. Is any substance identified as peroxide forming? 8. Is any substance identified as peroxide forming? 9. Is any substance identified as water reactive? 9. Is any substance identified as water reactive? 10. Is any substance identified as an oxidizer? 10. Is any substance identified as an oxidizer? 11. Is any substance identified as self-reactive? 11. Is any substance identified as self-reactive? 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis? 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis?

44. Mixing Example Documentation Do the answers to the following questions indicate chemical reactivity hazard(s) are present? YES NA YES NO YES NO NO YES NO YES NA NA Blending of ingredients in cone blender 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 pow-der is pyrophoric without oxide coating Loading, blending, and packaging only No indication from MSDS or literature No indication from MSDS or literature Heating of sodium hydrosulfite can initiate self-sustaining exothermic decomposition Sodium hydrosulfite is water reactive; uncoated aluminum powder is DOT/UN Hazard Class 4.3, Dangerous when Wet YES, NO or NA BASIS FOR ANSWER; COMMENTS AT THIS FACILITY: 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 processing of substances? 7.Is any substance identified as spontaneously combustible? 8. Is any substance identified as peroxide forming? 8. Is any substance identified as peroxide forming? 9. Is any substance identified as water reactive? 9. Is any substance identified as water reactive? 10. Is any substance identified as an oxidizer? 10. Is any substance identified as an oxidizer? 11. Is any substance identified as self-reactive? 11. Is any substance identified as self-reactive? 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis?

45. Mixing Example Documentation Do the answers to the following questions indicate chemical reactivity hazard(s) are present? YES NA YES NO YES NO NO YES NO YES NA NA Loading, blending, and packaging only 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 pow-der is pyrophoric without oxide coating Blending of ingredients in cone blender No indication from MSDS or literature No indication from MSDS or literature Sodium hydrosulfite is water reactive; uncoated aluminum powder is DOT/UN Hazard Class 4.3, Dangerous when Wet Heating of sodium hydrosulfite can initiate self-sustaining exothermic decomposition YES, NO or NA BASIS FOR ANSWER; COMMENTS AT THIS FACILITY: 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 processing of substances? 7.Is any substance identified as spontaneously combustible? 8. Is any substance identified as peroxide forming? 8. Is any substance identified as peroxide forming? 9. Is any substance identified as water reactive? 9. Is any substance identified as water reactive? 10. Is any substance identified as an oxidizer? 10. Is any substance identified as an oxidizer? 11. Is any substance identified as self-reactive? 11. Is any substance identified as self-reactive? 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis? 12.Can incompatible materials coming into contact cause undesired consequences?

46. 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

47. 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

48. NOAA Chemical Information

49. NOAA Compatibility Chart

50. NOAA Compatibility Chart