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1 Best viewed by selecting the Fit Page icon from the toolbar, then (if in Internet Explorer) selecting menu item View/Full Screen and typing Ctrl-L to enlarge. Use Ctrl-(right arrow) to page forward. 1 1

2 Chemical Reactivity Hazard Management: A Problem in Search of a Solution Peter N. Lodal Senior Technical Associate Plant Protection Technical Services, Tennessee Operations Eastman Chemical Company Kingsport TN Robert W. Johnson Principal Consultant Unwin Company Integrated Risk Management 1920 Northwest Blvd, Suite 201 Columbus OH Bob Johnson presented a paper by this title at the 2003 AIChE Spring National Meeting, as part of the Process Plant Safety Symposium. Pete Lodal made the same presentation to the Society for Chemical Hazard Communication and to the American Industrial Hygiene Association. This file shows their presentation slides and script. Contact one of the authors for the full paper. 2

3 A World Without Reactive Chemistry Imagine, if you can, a world with no chemical reactions. On the surface, it would seem an ideal situation: no losses, injuries or harm to the environment by uncontrolled chemical reactions, fires or explosions. Sounds pretty good, doesn't it? 3

4 A World Without Reactive Chemistry However, this world would also have no living organisms, since all of life depends on chemical reactions of extreme complexity and sophistication. 4

5 A World Without Reactive Chemistry Even if we take this to a less dramatic level, there would be no plastics,... 5

6 A World Without Reactive Chemistry... no antibiotics, no paints and coatings, and less clean water, just to name a few of the benefits of modern chemistry. 6

7 A World Without Reactive Chemistry So while we obviously want to avoid reactive incidents, we do not want to give up the many and significant benefits associated with reactive chemistry. Chemical Reactivity Hazard Management strives to solve this problem. 7

8 Presentation Problem Project Preliminary Screening Method Proof of Concept Practices Essential to Managing Chemical Reactivity Hazards 8 I hope you don t mind some alliteration for the organization of our presentation. 8

9 Presentation Problem 9 First, a statement of the problem addressed by our paper. 9

10 The Problem CSB Report 167 incidents in a 21 year period 108 fatalities Significant property damage 10 As a nation, we continue to have chemical reactivity incidents that cause harm to people, property and the environment. The U.S. Chemical Safety Board s hazard investigation on Improving Reactive Hazard Management analyzed 167 incidents from that resulted in a total of 108 fatalities and significant property damage. 10

11 The Problem CSB Report 167 incidents in a 21 year period 108 fatalities Significant property damage Data are incomplete, and certainly underestimate the magnitude of the problem 11 While this number may seem small in comparison to, say the number of automobile related fatalities annually in the US, it is significant for two reasons: First, the data used are admittedly incomplete, leading to the expectation that the "true" impact of chemical reactivity incidents is much higher. 11

12 The Problem In 90% + of all incidents studied, the information necessary to have prevented the incident was documented and publicly available. 12 And second, according to the CSB report, in a vast majority of these cases, the information needed to properly assess (and therefore, control) these hazards was known prior to the incident. 12

13 Presentation Problem Project 13 Any effort that can prevent 108 fatalities is worth pursuing. Therefore, the Center for Chemical Process Safety, or CCPS, undertook a new project in early 2002, forming a multi-company committee of reactive chemistry experts. 13

14 Reactive Chemicals Subcommittee Pete Lodal Steve Arendt Don Connolley Seshu Dharmavaram John Ferris Walt Frank Dennis Hendershot John Herber Greg Keeports Dave Leggett John Murphy Mickey Norsworthy Gary Pilkington Dennis Waibel Jan Windhorst Gary York 14 Eastman Chemical (Chair) ABS Consulting Akzo Nobel Chemicals Du Pont U.S. EPA ABS Consulting Rohm & Haas 3M Rohm & Haas Baker Risk Chemical Safety Board Arch Chemicals Abbott Labs Degussa NOVA Chemicals Rhodia Sixteen members of CCPS Reactive Chemicals Subcommittee, representing fourteen different companies, contributed to this project. Pete Lodal chaired the Subcommittee s efforts. 14

15 Project Timeline 1/02 Project Started by Subcommittee 4/02 Writing Started by Unwin Company 10/02 Peer Review 3/03 Publication 15 The three principals of Unwin Company--Bob Johnson, Steve Rudy, and Steve Unwin--authored the text on a fast-track schedule, with guidance and feedback from the Subcommittee as the writing progressed. 17 persons from 15 different industry and governmental organizations peer-reviewed the manuscript in October and November of last year. Over 500 peer review comments were received and evaluated for incorporation into the document before it was sent to the publisher in December. 15

16 Presentation Problem Project Probable audiences Guiding principles Proposed solution 16 First a few words about the expected audiences for this book and the guiding principles behind its development, before we take a look at the proposed solution to the problem that was posed earlier. 16

17 Probable Audiences No Chemistry Users 17 As a starting point, three distinct audiences, or levels of application, were identified within the universe of those involved with reactivity hazards. First: what was called No Chemistry Users. These would include warehousers and those who simply store prepackaged chemicals, never intending the material to be removed from its original packaging while under their control. It would also include industries where the use of chemicals is for non-chemistry applications, such as for refrigeration systems. 17

18 Probable Audiences No Chemistry Users Unintentional Chemistry Users 18 Second: what might be called Unintentional Chemistry Users, including operations where materials are processed but there is no intentional chemical reactions, such as the physical processes of mixing, blending, distillation, and drying. Users in this category may be a part of a large chemical manufacturer, but are not involved in traditional reactive chemistry issues. 18

19 Probable Audiences No Chemistry Users Unintentional Chemistry Users Intentional Chemistry Users 19 And third: The Intentional Chemistry Users. These users include what would traditionally be considered chemical producers, but would also include pharmaceutical and other industries such as semiconductor manufacturers who practice chemistry in a more nontraditional setting. This project had no intention of trying to develop a resource that would be sufficient for all the complexities of intentional chemistry processes. 19

20 20 Other resources, such as the three books shown here, more fully deal with chemical reactivity in an intentional setting. 20

21 Probable Audiences No Chemistry Users Unintentional Chemistry Users Intentional Chemistry Users 21 As the project progressed, the three original audiences were slightly modified to what you find in the book... 21

22 Probable Audiences Storage, Handling and Repackaging Mixing and Physical Processing Intentional Chemistry 22 as these three general situations that may involve chemical reactivity hazards but require somewhat different organizational structures to identify and manage those hazards. 22

23 Guiding Principles Use existing information Apply appropriate levels of technology to the different audiences Identify areas requiring additional testing, data generation Use existing management systems/ structures 23 Several principles guided the Subcommittee as the Concept Book was developed: Use existing chemical reactivity information to the maximum extent possible, Apply appropriate levels of technology to the three different audiences, Identify areas where additional testing and data generation are required, and Use existing management systems/structures to the maximum extent possible. 23

24 Proposed Solution Preliminary Screening Method Management System Framework 24 The goal of the CCPS effort was two-fold: Develop a simple screening method to identify chemical reactivity hazards, and Create a management system framework for preventing and mitigating uncontrolled chemical reactions. 24

25 Proposed Solution Preliminary Screening Method Management System Framework 25 The screening tool would allow all kinds of facilities to use existing information as a means to identify where chemical reactivity hazards are likely to exist. The management system would allow facilities to incorporate the results of a systematic identification of hazards and development of reactivity data into a comprehensive framework to prevent, control and mitigate chemical reactivity risks. 25

26 Preliminary Screening Method Management System Framework Concept Book ~ 200 pages Published 3/03 26 The approach the Subcommittee settled upon has been developed by its contract author and published by CCPS as a 200-page Concept Book entitled Essential Practices for Managing Chemical Reactivity Hazards. (The book is now available from CCPS.) Our paper provides a brief description of the tools developed. 26

27 Presentation Problem Project Preliminary Screening Method 27 The first goal of the CCPS effort was to develop a simple screening tool. This preliminary screening method is not intended to be capable of identifying all chemical reactivity hazards. Systematic identification of all hazards is part of the essential practices that will be discussed at the end of this presentation. 27

28 Presentation Problem Project Preliminary Screening Method 28 The screening method is intended to give a preliminary indication of whether any kind of fixed facility is likely to have chemical reactivity hazards that will need to be managed. The question to be addressed is: Are we likely to have one or more chemical reactivity hazards that must be managed at our facility? 28

29 Preliminary Screening for Chemical Reactivity Hazards Summary Flowchart The preliminary screening method is comprised of 12 questions, with a one-page flowchart tying them together. 29

30 Preliminary Screening: Summary Flowchart The first few questions, at the top of the flowchart, address what is intended to take place in the facility. We ll take a closer look at these questions in just a minute. 30

31 Summary Flowchart (continued) The latter questions address different kinds of reactive materials and reactive interactions. Definitions and examples for each question are given in the text of the CCPS Concept Book. 31

32 FACILITY: COMPLETED BY: COMPLETION DATE: APPROVED BY: Do the answers to the following questions indicate chemical reactivity hazard(s) are present? 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 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? SCENARIO CONDITIONS NORMAL? *, NO or NA R, NR or? ** BASIS FOR ANSWER; COMMENTS Example Form for Documenting Chemical Reactivity Hazard Screening INFORMATION SOURCES; COMMENTS *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 A suggested form is also provided for documenting the decisions that are made as you work your way through the screening questions. 32

33 Chemical Reactivity Hazard A situation with the potential for an uncontrolled chemical reaction that can result directly or indirectly in serious harm to people, property or the environment. 33 By way of definition, the CCPS Concept Book intentionally uses the term chemical reactivity hazard rather than reactive hazard, reactive chemical hazard, or chemical reaction hazard. A chemical reactivity hazard is defined as a situation with the potential for an uncontrolled chemical reaction that can result in serious harm or loss. 33

34 Presentation Problem Project Preliminary Screening Method Proof of Concept 34 Several worked examples are given in the Concept Book. They show how the preliminary screening method might apply to different kinds of facilities. In Attachment 1 of our paper, we summarize one of these worked examples. 34

35 Proof of Concept: Worked 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 35 This Attachment presents a simplified retrospective of the process involved in the 1995 Napp Technologies explosion and fire, for the purpose of illustrating the Preliminary Screening Method for a mixing and blending facility. 35

36 Mixing Example A toll manufacturer is contracted to prepare one 8100 lb batch of a gold precipitating agent. Ingredients mixed in a 125 ft 3 (6 m 3 ) 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 36 The process involved a blending operation in a jacketed cone blender to produce a gold precipitating agent. The ingredients included sodium hydrosulfite, aluminum powder, and potassium carbonate, with a small amount of benzaldehyde added before packaging the product blend in 55 gallon drums. 36

37 Other Worked Examples Batch Reactors, Waste Treatment (Intentional chemistry) Incinerator (Combustion; incompatibility) Repackaging (Material of construction incompatibility) Physical Processing (Heat generation, thermal decomposition) Gas Distribution System (Oxidizer; incompatibility) 37 Five additional worked examples, each covering a different type of facility, are also included in the CCPS Concept Book. We will only have time to look at the one mixing example. 37

38 FACILITY: COMPLETED BY: COMPLETION DATE: Mixing Example Documentation APPROVED BY: Do the answers to the following questions indicate chemical reactivity hazard(s) are present? 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 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? SCENARIO Mixing Example Documentation CONDITIONS NORMAL? *, NO or NA R, NR or? ** BASIS FOR ANSWER; COMMENTS INFORMATION SOURCES; COMMENTS The Example Documentation Form will be used, along with the Preliminary Screening Method flowchart, to see how the Screening Method might address the type of process encountered at the toll blending facility. 38

39 Question 1 Screening Question 1 Is intentional chemistry performed at your facility? Question 1, Is intentional chemistry performed at your facility?, would be answered NO for the mixing example, since the operation consists only of loading, blending, and packaging, with no intended chemical reactions. 39

40 AT THIS FACILITY: Mixing Example Documentation Question 1. Is intentional chemistry performed?, NO or NA NO BASIS FOR ANSWER; COMMENTS Loading, blending, and packaging only The NO answer and its basis would then be entered on the documentation form for Question 1. 40

41 Question 2 Is there any mixing or combining of different substances? Question 2, Is there any mixing or combining of different substances?, would obviously be answered, since the blending operation involves mixing of the ingredients. 41

42 AT THIS FACILITY: Mixing Example Documentation Question 1. Is intentional chemistry performed? 2. Is there any mixing or combining of different substances?, NO or NA NO BASIS FOR ANSWER; COMMENTS Loading, blending, and packaging only Blending of ingredients in cone blender would then be entered for Question 2. 42

43 Question 6 Is any heat generated during the mixing or physical processing of substances? The flowchart would then take us down to Question 6, Is any heat generated during the mixing or physical processing of substances? 43

44 AT THIS FACILITY: Mixing Example Documentation 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 or NA NO NA NA NA BASIS FOR ANSWER; COMMENTS Loading, blending, and packaging only Blending of ingredients in cone blender Since the flowchart bypassed Questions 3, 4 and 5 for this operation, these questions would all be documented as Not Applicable on the form. 44

45 AT THIS FACILITY: Mixing Example Documentation 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?, NO or NA NO NA NA NA NO BASIS FOR ANSWER; COMMENTS Loading, blending, and packaging only Blending of ingredients in cone blender No indication of heat generation from previous batch or from nature of blend Assuming no indication of heat generation is reported for the blending operation, Question 6 would be answered NO. 45

46 Question 7 Is any substance identified as spontaneously combustible? This would bring us to Question 7, Is any substance identified as spontaneously combustible? 46

47 AT THIS FACILITY: Mixing Example Documentation 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?, NO or NA NO NA NA NA NO BASIS FOR ANSWER; COMMENTS Loading, blending, and packaging only 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 powder is pyrophoric without oxide coating Transport containers of sodium hydrosulfite must be labeled as Spontaneously Combustible Material ; this is a real good hint that Question 7 should be answered. 47

48 AT THIS FACILITY: Mixing Example Documentation Do the answers to the following questions indicate chemical reactivity hazard(s) are present? 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?, NO or NA NO NA NA NA NO BASIS FOR ANSWER; COMMENTS Loading, blending, and packaging only 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 powder is pyrophoric without oxide coating A answer to Question 7 is sufficient to indicate that a chemical reactivity hazard is likely to be present at this facility. 48

49 Expect chemical reactivity hazard(s) to be present; Go to Chapter 4 for information on identifying and managing hazards The flowchart would also point the user to Chapter 4 of the CCPS Concept Book, where essential practices are given for identifying and managing chemical reactivity hazards. 49

50 AT THIS FACILITY: Mixing Example Documentation Do the answers to the following questions indicate chemical reactivity hazard(s) are present? 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?, NO or NA NO NA NA NA NO BASIS FOR ANSWER; COMMENTS Loading, blending, and packaging only 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 powder is pyrophoric without oxide coating We would not need to go any further with the Preliminary Screening, since we have the answer to our basic question of whether chemical reactivity hazards will likely need to be managed at this facility. However, for completeness sake,... 50

51 Do the answers to the following questions indicate chemical reactivity hazard(s) are present? AT THIS FACILITY: 8. Is any substance identified as peroxide forming? 9. Is any substance identified as water reactive? Mixing Example Documentation 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?, NO or NA NO NA NA NA NO BASIS FOR ANSWER; COMMENTS Loading, blending, and packaging only 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 powder is pyrophoric without oxide coating 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? we may want to go ahead and document answers to the remaining five screening questions. 51

52 Do the answers to the following questions indicate chemical reactivity hazard(s) are present? AT THIS FACILITY: 8. Is any substance identified as peroxide forming? 9. Is any substance identified as water reactive? Mixing Example Documentation 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?, NO or NA NO NA NA NA NO NO BASIS FOR ANSWER; COMMENTS Loading, blending, and packaging only 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 powder is pyrophoric without oxide coating No indication from MSDS or literature 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? No substance was identified as peroxide forming. 52

53 Do the answers to the following questions indicate chemical reactivity hazard(s) are present? AT THIS FACILITY: 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? Mixing Example Documentation 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?, NO or NA NO NA NA NA NO NO BASIS FOR ANSWER; COMMENTS Loading, blending, and packaging only 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 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 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis? Sodium hydrosulfite will react with water. Uncoated aluminum powder is also water-reactive. So Question 9 gets a answer. 53

54 Do the answers to the following questions indicate chemical reactivity hazard(s) are present? AT THIS FACILITY: 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? Mixing Example Documentation 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?, NO or NA NO NA NA NA NO NO NO BASIS FOR ANSWER; COMMENTS Loading, blending, and packaging only 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 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 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis? None of the blended materials were identified as oxidizers. 54

55 Do the answers to the following questions indicate chemical reactivity hazard(s) are present? AT THIS FACILITY: 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? Mixing Example Documentation 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? 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis?, NO or NA NO NA NA NA NO NO NO BASIS FOR ANSWER; COMMENTS Loading, blending, and packaging only 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 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 Self-reactivity can be by decomposition, polymerization, or rearrangement. Sodium hydrosulfite is self-reactive by exothermic decomposition when it is heated. So Question 11 also gets a answer. 55

56 Do the answers to the following questions indicate chemical reactivity hazard(s) are present? AT THIS FACILITY: 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? Mixing Example Documentation 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? 12. Can incompatible materials coming into contact cause undesired consequences, based on the following analysis?, NO or NA NO NA NA NA NO NO NO BASIS FOR ANSWER; COMMENTS Loading, blending, and packaging only 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 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 So far, we have looked at the reactivity hazards of each individual substance, either in terms of its selfreactivity, or its reactivity with ubiquitous substances such as air, water and ordinary combustibles, in addition to intentional chemistry. 56

57 Do the answers to the following questions indicate chemical reactivity hazard(s) are present? AT THIS FACILITY: 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? Mixing Example Documentation 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? 12. Can incompatible materials coming into into contact contact cause cause undesired undesired consequences, consequences? based the following analysis?, NO or NA NO NA NA NA NO NO NO BASIS FOR ANSWER; COMMENTS Loading, blending, and packaging only 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 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 Question 12 considers whether an unintended combination of incompatible materials could result in undesired consequences. 57

58 ASTM E Standard Guide for the Preparation of a Binary Chemical Compatibility Chart Define scenario Define incompatibility Compile chart 58 The approach taken for this screening question has similarities to a relatively recent ASTM standard for preparing binary compatibility charts. The ASTM Standard emphasizes that chemical compatibility depends heavily on the mixing scenario, Factors that should be considered when specifying the mixing scenario 58

59 ASTM E Standard Guide for the Preparation of a Binary Chemical Compatibility Chart Define scenario Quantities Temperatures Confinement Atmosphere (air, nitrogen, inerted) Contact time 59 Factors that should be considered when specifying the mixing scenario include material quantities and temperatures, degree of confinement, atmosphere, and the maximum time the materials may be in contact. 59

60 FACILITY: Mixing Example Documentation (continued) Napp Technologies, Inc., Lodi, New Jersey Do the answers to the following questions indicate chemical reactivity hazard(s) are present? 1 AT THIS FACILITY:, NO or NA BASIS FOR ANSWER; COMMENTS 12. Question Can incompatible 1. Is intentional materials chemistry coming performed? into into contact cause cause NO Loading, See analysis blending, belowand packaging only undesired 2. Is there consequences, any mixing or combining based on on of the different following substances? analysis? Blending of ingredients in cone blender 3. Does any other physical processing of substances CONDITIONS occur? R, NA NR SCENARIO 4. Are there any hazardous substances stored or NORMAL? handled? or NA? INFORMATION SOURCES; COMMENTS 5. 1 Vacuum Is combustion seal cooling with air water the only enters chemistry blender, intended? No N2 NA R Both aluminum powder and sodium reacts 6. Is any with heat aluminum generated powder during and the sodium mixing or physical atmosphere, NO No hydrosulfite indication are of water heat generation reactive from hydrosulfite, and initiates exothermic confinement processing of substances? previous batch or from nature of blend decomposition in blender 7. Is any substance identified as spontaneously combustible? Sodium hydrosulfite is DOT/UN Hazard 2 Glycol/water mixture leaks from jacket into No N2 R Class NOAA 4.2, Worksheet Spontaneously indicates Combustible combining blender, reacts with aluminum powder and atmosphere, Material; sodium hydrosulfite finely divided with aluminum ethylene powder glycol sodium hydrosulfite, and initiates confinement is pyrophoric explosive due without to vigorous oxide coating reaction or exothermic 8. Is any substance decomposition identified as peroxide forming? in blender NO No reaction indication products from may MSDS produce or literature detonation, may cause fire, and 9. Is any substance identified as water reactive? Sodium indicates hydrosulfite flammable is gas water generation reactive; uncoated and heat aluminum generation powder by chemical is DOT/UN Hazard reaction, Class may 4.3, cause Dangerous pressurization When Wet Is any substance identified as an oxidizer? NO No indication from MSDS or literature Use Figure 3.1 with answers to Questions 1-12 to determine if answer is or NO Does Is any the contact/mixing substance identified occur as at ambient self-reactive? temperature, atmospheric pressure, Heating 21% oxygen of sodium atmosphere, hydrosulfite and can unconfined? (IF NOT, DO NOT ASSUME THAT PUBLISHED DATA FOR AMBIENT initiate self-sustaining CONDITIONS exothermic APPLY) 3 R = Reactive (incompatible) under the stated scenario and conditions decomposition 12. NR = Can Non-reactive incompatible (compatible) materials under coming the into stated contact scenario causeand conditions See analysis below? = Unknown; assume incompatible until further information is obtained undesired consequences, based on the following analysis? At the bottom of the documentation form, identified mixing scenarios can be described, along with an indication of whether or not a chemical reaction will take place. 60

61 FACILITY: Mixing Example Documentation (continued) Napp Technologies, Inc., Lodi, New Jersey Do the answers to the following questions indicate chemical reactivity hazard(s) are present? 1 AT THIS FACILITY:, NO or NA BASIS FOR ANSWER; COMMENTS Question 12. Can incompatible 1. Is intentional materials chemistry coming performed? into contact cause NO Loading, See analysis blending, belowand packaging only 2. undesired Is there consequences, any mixing or combining based on the of different following substances? analysis? Blending of ingredients in cone blender 3. Does any other physical processing of substances CONDITIONS occur? R, NA NR SCENARIO 4. Are there any hazardous substances stored or NORMAL? handled? or NA? INFORMATION SOURCES; COMMENTS 5. 1 Vacuum Is combustion seal cooling with air water the only enters chemistry blender, intended? No N2 NA R Both aluminum powder and sodium 6. reacts Is any with heat aluminum generated powder during and the sodium mixing or physical atmosphere, NO No hydrosulfite indication are of water heat generation reactive from processing hydrosulfite, of substances? and initiates exothermic confinement previous batch or from nature of blend decomposition in blender 7. Is any substance identified as spontaneously combustible? Sodium hydrosulfite is DOT/UN Hazard 2 Glycol/water mixture leaks from jacket into No N2 R Class NOAA 4.2, Worksheet Spontaneously indicates Combustible combining blender, reacts with aluminum powder and atmosphere, Material; sodium hydrosulfite finely divided with aluminum ethylene powder glycol sodium hydrosulfite, and initiates confinement is pyrophoric explosive due without to vigorous oxide coating reaction or 8. exothermic Is any substance decomposition identified as peroxide forming? in blender NO No reaction indication products from may MSDS produce or literature detonation, may cause fire, and 9. Is any substance identified as water reactive? Sodium indicates hydrosulfite flammable is gas water generation reactive; uncoated and heat aluminum generation powder by chemical is DOT/UN Hazard reaction, Class may 4.3, cause Dangerous pressurization When Wet Is any substance identified as an oxidizer? NO No indication from MSDS or literature Use Figure 3.1 with answers to Questions 1-12 to determine if answer is or NO Is any substance identified as self-reactive? Heating of sodium hydrosulfite can 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 initiate self-sustaining CONDITIONS exothermic APPLY) 3 R = Reactive (incompatible) under the stated scenario and conditions decomposition 12. NR = Can Non-reactive incompatible (compatible) materials under coming the into stated contact scenario causeand conditions See analysis below? = Unknown; assume incompatible until further information is obtained undesired consequences, based on the following analysis? One scenario for our mixing example would be for vacuum seal cooling water to leak into the blender and react with the water-reactive components of the mixture. Under the conditions specified, a chemical reaction would be expected to occur, so the scenario should be designated R for Reactive. 61

62 FACILITY: Mixing Example Documentation (continued) Napp Technologies, Inc., Lodi, New Jersey Do the answers to the following questions indicate chemical reactivity hazard(s) are present? 1 AT THIS FACILITY:, NO or NA BASIS FOR ANSWER; COMMENTS Question 12. Can incompatible 1. Is intentional materials chemistry coming performed? into contact cause NO Loading, See analysis blending, belowand packaging only 2. undesired Is there consequences, any mixing or combining based on the of different following substances? analysis? Blending of ingredients in cone blender 3. Does any other physical processing of substances CONDITIONS occur? R, NA NR SCENARIO 4. Are there any hazardous substances stored or NORMAL? handled? or NA? INFORMATION SOURCES; COMMENTS 5. 1 Vacuum Is combustion seal cooling with air water the only enters chemistry blender, intended? No N2 NA R Both aluminum powder and sodium 6. reacts Is any with heat aluminum generated powder during and the sodium mixing or physical atmosphere, NO No hydrosulfite indication are of water heat generation reactive from processing hydrosulfite, of substances? and initiates exothermic confinement previous batch or from nature of blend decomposition in blender 7. Is any substance identified as spontaneously combustible? Sodium hydrosulfite is DOT/UN Hazard 2 Glycol/water mixture leaks from jacket into No N2 R Class NOAA 4.2, Worksheet Spontaneously indicates Combustible combining blender, reacts with aluminum powder and atmosphere, Material; sodium hydrosulfite finely divided with aluminum ethylene powder glycol sodium hydrosulfite, and initiates confinement is pyrophoric explosive due without to vigorous oxide coating reaction or 8. exothermic Is any substance decomposition identified as peroxide forming? in blender NO No reaction indication products from may MSDS produce or literature detonation, may cause fire, and 9. Is any substance identified as water reactive? Sodium indicates hydrosulfite flammable is gas water generation reactive; uncoated and heat aluminum generation powder by chemical is DOT/UN Hazard reaction, Class may 4.3, cause Dangerous pressurization When Wet Is any substance identified as an oxidizer? NO No indication from MSDS or literature Use Figure 3.1 with answers to Questions 1-12 to determine if answer is or NO Is any substance identified as self-reactive? Heating of sodium hydrosulfite can 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 initiate self-sustaining CONDITIONS exothermic APPLY) 3 R = Reactive (incompatible) under the stated scenario and conditions decomposition 12. NR = Can Non-reactive incompatible (compatible) materials under coming the into stated contact scenario causeand conditions See analysis below? = Unknown; assume incompatible until further information is obtained undesired consequences, based on the following analysis? Another scenario might be for a glycol/water mixture to leak from the jacket into the blender. Not only could the water be expected to react with the dry ingredients, but ethylene glycol may also react. One useful tool for identifying potential incompatibilities is a computerized Chemical Reactivity Worksheet, available free of charge from the U.S. National Oceanic and Atmospheric Administration, or NOAA. 62

63 NOAA Chemical Information 63 The NOAA Worksheet not only indicates the hazards of individual substances, such as shown here for sodium hydrosulfite,... 63

64 NOAA Compatibility Chart 64 it also predicts the consequences of mixing two materials at a time, based on reactive groups. 64

65 NOAA Compatibility Chart 65 Combining an inorganic reducing agent such as sodium hydrosulfite with an alcohol or polyol such as ethylene glycol is predicted to have the very significant effects shown here. 65

66 FACILITY: Mixing Example Documentation (continued) Napp Technologies, Inc., Lodi, New Jersey Do the answers to the following questions indicate chemical reactivity hazard(s) are present? 1 AT THIS FACILITY:, NO or NA BASIS FOR ANSWER; COMMENTS Question 12. Can incompatible 1. Is intentional materials chemistry coming performed? into contact cause NO See Loading, analysis blending, belowand packaging only 2. undesired Is there consequences, any mixing or combining based on the of different following substances? analysis? Blending of ingredients in cone blender 3. Does any other physical processing of substances CONDITIONS occur? R, NA NR SCENARIO 4. Are there any hazardous substances stored or NORMAL? handled? or NA? INFORMATION SOURCES; COMMENTS 5. 1 Vacuum Is combustion seal cooling with air water the only enters chemistry blender, intended? No N2 NA R Both aluminum powder and sodium 6. reacts Is any with heat aluminum generated powder during and the sodium mixing or physical atmosphere, NO No hydrosulfite indication are of water heat generation reactive from processing hydrosulfite, of substances? and initiates exothermic confinement previous batch or from nature of blend decomposition in blender 7. Is any substance identified as spontaneously combustible? Sodium hydrosulfite is DOT/UN Hazard 2 Glycol/water mixture leaks from jacket into No N2 R Class NOAA 4.2, Worksheet Spontaneously indicates Combustible combining blender, reacts with aluminum powder and atmosphere, Material; sodium hydrosulfite finely divided with aluminum ethylene powder glycol sodium hydrosulfite, and initiates confinement is pyrophoric explosive due without to vigorous oxide coating reaction or 8. exothermic Is any substance decomposition identified as peroxide forming? in blender NO No reaction indication products from may MSDS produce or literature detonation, may cause fire, and 9. Is any substance identified as water reactive? Sodium indicates hydrosulfite flammable is gas water generation reactive; uncoated and heat aluminum generation powder by chemical is DOT/UN Hazard reaction, Class may 4.3, cause Dangerous pressurization When Wet Is any substance identified as an oxidizer? NO No indication from MSDS or literature Use Figure 3.1 with answers to Questions 1-12 to determine if answer is or NO Is any substance identified as self-reactive? Heating of sodium hydrosulfite can 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 initiate self-sustaining CONDITIONS exothermic APPLY) 3 R = Reactive (incompatible) under the stated scenario and conditions decomposition 12. NR = Can Non-reactive incompatible (compatible) materials under coming the into stated contact scenario causeand conditions See analysis below? = Unknown; assume incompatible until further information is obtained undesired consequences, based on the following analysis? Thus, Question 12 of the screening method should be answered as a result of potential incompatibilities. 66

67 Proof of Concept 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 67 So, for this mixing example, the Preliminary Screening Method would have multiple indicators pointing to a need for managing chemical reactivity hazards at such a facility. 67

68 Mixing Example Documentation FACILITY: Napp Technologies, Inc., Lodi, New Jersey Do the answers Mixing to the following questions Example indicate chemical Documentation reactivity hazard(s) are present? 1, NO AT 7. THIS Is FACILITY: any substance identified as spontaneously BASIS FOR ANSWER; COMMENTS or NA combustible? Question 1. Is intentional chemistry performed? NO Loading, blending, and packaging only 2. Is there any mixing or combining of different substances? Blending of ingredients in cone blender 3. Does any other physical processing of substances occur? NA 4. Are there any hazardous substances stored or handled? NA 5. Is combustion with air the only chemistry intended? NA Is any Is heat any generated substance during the identified mixing or physical as peroxide NO forming? No indication of heat generation NO from processing of substances? previous batch or from nature of blend 9. Is any identified as water reactive? 7. Is any substance identified as spontaneously combustible? Sodium hydrosulfite is DOT/UN Hazard Class 4.2, Spontaneously Combustible Material; finely divided aluminum powder is pyrophoric without oxide coating 8. Is any substance identified as peroxide forming? NO No indication from MSDS or literature 10. Is any substance identified as an oxidizer? NO 9. Is any substance identified as water reactive? Sodium hydrosulfite is water reactive; 11. Is any substance identified as self-reactive? uncoated aluminum powder is DOT/UN Hazard Class 4.3, Dangerous When Wet 10. Is any substance identified as an oxidizer? NO No indication from MSDS or literature 11. Is any substance identified as self-reactive? Heating of sodium hydrosulfite can initiate self-sustaining exothermic 12. Can incompatible materials coming into contact decomposition cause 12. Can incompatible materials coming into contact cause See below undesired consequences, consequences, based the following based analysis? on the following analysis? Four of the screening questions gave answers that would indicate... 68

69 Preliminary Screening for Chemical Reactivity Hazards Summary Flowchart that chemical reactivity hazards should be expected, and steps should be taken to identify and manage the hazards. 69

70 Incident April 21, worker fatalities ~300 evacuated Facility destroyed Surrounding businesses damaged Ed Hill, The Bergen Record Used with permission 70 An uncontrolled chemical reaction did occur at the Napp Technologies facility. The incident resulted in multiple fatalities and extensive property damage. (But again, the purpose of this retrospective example was only to illustrate the preliminary screening method for this type of operation, and show that a probable need for managing reactivity hazards at similar facilities would be indicated.) 70