ADVANCES IN CHEMICAL REACTIVITY

EVALUATION AT DOW
MARABETH HOLSINGER, PH.D
GLOBAL TECHNOLOGY LEADER,
REACTVE CHEMICALS / ANALYTICAL SCIENCES

Our intent is that by sharing enhanced practices for identifying and managing
uncontrolled chemical reactions, the chemical process industries can realize
benefits from improved reliability of operations, fewer incidents over the life of
a process, and reduced consequences of any incidents that occur.

P2SAC - Purdue Process Safety and Assurance Center – Fall Conference

West Lafayette, IN Nov 10, 2016
 Dow Business and Market Focus
2

Delivering Customer Solutions

Performance
Agricultural Consumer Infrastructure Performance Performance
Materials
Sciences Solutions Solutions & Chemicals Plastics Silicones
 Dow Electronic  Dow Coating  Chlor Alkali and Vinyl  Dow Packaging and
 Seeds Materials Materials  Polyurethanes Specialty Plastics
 Crop Protection  Dow Automotive  Performance Mon.  Industrial Solutions  Dow Elastomers
Systems  Dow Building &  Dow Electrical and
 Consumer Care Construction Telecommunications MOLYKOTE®
 Energy & Water Soln.  Energy Lubricants &
Silastic®
 Hydrocarbons Elastomers
VORALUX™ Specialty
Flex Foams
Dow
AR™ Fast-Etch Corning®
Organic BARC FORMASHIELD™ 3901 Liquid
Technology Satin

100% PE PacXpert™
Stand-up Packaging Dow Corning®
ENFORCER™ Polyurethane
BETAMATE™ Structural Pouch Technology Façade
FR63 Polymeric Flame for Artificial Turf
Adhesives Solutions
Retardant Burj Khalifa
Ema\ar
Properties

Syl-Off®
INFUSE™ Olefin Block Release
ECOSURF™ Nonionic Copolymers for Athletic
POLYOX™ Polymers FILMTEC™ RO Surfactants Coatings
Shoe Midsoles

Revenue: $6.4B Revenue: $4.4B Revenue: $7.4B Revenue: $12.0B Revenue: $18.4B Revenue: $4.7B‡

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Preventing Reactive Chemicals Incidents
3

 Dow has a wide variety of chemical processes

―
Different types of chemistries and operations in different businesses
―
The scope of hazard scenarios is wide and complicated
―
From R&D labs to pilot plants and full-scale manufacturing

 To effectively eliminate potential incidents in our processes at all scales,

Dow relies on its strong Reactive Chemicals Program:
―
Based on three key principles:
 To know how much inherent energy is present in every process step or unit operation
 To know the conditions under which this energy can be released such that adequate

controls can be put in place to manage the risks

 To hold the owner (of a process, lab, or plant) responsible to ensure that reactive

chemicals hazards are identified, adequate layers of protection are in place, and
formalized and documented periodic reviews are conducted
―
Evolved into a recognized industry model leveraged through CCPS1

―
1. Frurip, D.J.; The Essential Elements of a Successful Reactive Chemicals Program, Chemical Engineering Transactions, 26, (2012), pp. 1-
6
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 Dow’s Reactive Chemicals Program
4

 Dow’s Reactive Chemicals Program was established after an incident

happened in Dow in 1966.
 The purpose of Dow’s Reactive Chemicals Program is to prevent
uncontrolled or unexpected chemical reactions that have the potential
to result in injury, property damage or environmental harm.
O

N O

Br Cl

Cl Cl

Propargyl bromide + Chloropicrin

Dec 1966 - Three craters left by

explosions caused by mixing of
materials that formed a shock
sensitive material using 2 railcars
and a tank truck (3 fatalities).
from The Dow Chemical Company
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 Formalized and Documented Hazard Reviews
5

 An essential aspect of a strong Reactive Chemicals Program involves

periodic Reactive Chemicals/Process Hazard Analysis (RC/PHA) and
Laboratory Hazard Analysis (RC/LHA) reviews for new and existing Dow
facilities, new leaders, and capital projects.
―
Multi-disciplinary review teams are formed from employees with broad technical
expertise and backgrounds. Typically includes representatives from the facility, the
Technology Center, EH&S, and Process Safety and Reactive Chemicals (RC) functions,
along with “outside-in” expertise from R&D, engineering, and manufacturing.
―
The review team’s goal - to provide a company-wide, consistent, and as accurate as
currently available perspective on hazard identification and the evaluation of adequacy
of hazard controls, reaching consensus on whether additional controls are needed, or if
additional hazard or risk evaluation is warranted.
―
Using provided documentation and Dow’s RC/PHA Questionnaire as a guide, they
 Identify and document potential hazards for every unit operation, including conditions leading
to such hazards
 Capture follow-up actions for items not resolved at the meeting
 May perform a walk through inspection of the facility
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 Dow’s Process Safety Performance, 2005-2015
6

Dow’s goal is to
eliminate all
major process
safety events
that impact our
people, our
communities
and the
environment

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Process Safety Performance Goals, 2015-2025
The Sustainability of Dow’s Reactive Chemical’s
7
Program:

2025 Sustainability Goals

We have embarked on the

third stage of our
sustainability journey with
our ambitious 2025
Sustainability Goals.
Through these Goals, we
are collaborating with like-
minded partners to advance
the well-being of humanity
by helping lead the
transition to sustainable
planet and society

Source: www.dow.com
PSCE: Process Safety & Containment Event

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Dow – A Safe Place to Work
8

Dow is committed
to providing a safe
work environment
to its employees

Source: 2011 industry OSHA rates from US Bureau of Labor Statistics at http://www.bls.gov/iif/oshsum.htm
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 Dow’s Reactive Chemicals Capability
9

 Member of Dow’s Analytical Sciences Organization

 Strategic Focus:
• Technical problem solving utilizing reactive chemicals (RC) technologies for
complex issues at all scales
• New technology and application development
• Advanced solutions ensuring safe operating limits, operational reliability,
process development and optimization.
• 24/7 Immediate Response and Incident Investigations
• Reactive Chemicals Process Hazard Analysis (RC/PHA, RC/LHA) and New
Leader Reviews (NLR)
• Compliance testing for REACH, MSDS, NFPA, DOT etc.
• Understanding reactive chemicals issues through deep knowledge of
business chemistries and process technologies (RC Business focal points)
• Increase awareness of RC hazards through training to labs, plants, Tech
Centers and business/functional stakeholders (RCaPS Network /Webinars)
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 Reactive Chemicals Hazard Evaluation Tools
10

• The types of testing and calculations, and the amount of effort we spend,
depends on the type of operation, the scale of the process, the conditions of
the process, the amount of energy release, and the potential for gas and
pressure generation.

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Thermal Screening Tools
11

 Desktop methods or literature

• Heat of reaction and adiabatic temperature rise calculations
• Dow’s internal database
• CHETAH calculations
• Bretherick’s Handbook of Reactive Chemical Hazards
• Chemical Reactivity Worksheet (CRW) TA Instruments

• High energy functional groups

HEL
• MSDS, hazard statements (R and H phrases)
 Heat of mixing calorimetry (HOM)
 Differential Scanning Calorimetry (DSC)
 Thermal Screening Unit (TSU)
• Temperature ramp or isothermal mode
• Accurate measurement of pressure and detected onset
• Can detect exotherm and endotherm
• Disadvantage – Heat data is not quantitative
• Disadvantage – Data cannot be modeled
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 Heat of Reaction Calculations
12

 For early stage of process development, small scale

 Start from a balanced equation for the reaction
 Using simplified analog reactions if needed
 Find or estimate enthalpies formation for the reactants and products
involved in the reaction
• Phase correction, concentration effect
 Liquid, gas, solid, aqueous solutions
• Data from literature, compilations and handbooks
 NBS Tables, NIST WebBook, Pedley, DIPPR, Cox and Pilcher…
 Dow’s internal database and tools
 Adiabatic temperature rise calculations
• Need heat capacity data
 CHETAH calculations
• Most recent version: CHETAH 10.0 was released in January 2016

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Chemical Reactivity Evaluation – Desktop Methods
13

CHETAH 10.0 (Chemical Thermodynamic and Energy Release) Program:

 A unique tool for predicting both thermochemical properties
and certain ”reactive chemicals” hazards associated with a pure
chemical, a mixture of chemicals, or a chemical reaction.
 Requires only knowledge of the molecular structure(s) of the
components involved, then implements Benson's method of
group additivity.
 Useful for classifying materials for their ability to decompose
with violence, for estimating heats of reaction or combustion,
and for predicting lower flammable limits.
(Britton and Harrison, 2014)

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Chemical Reactivity Evaluation – Desktop Methods
14

CHETAH 10.0 (Chemical Thermodynamic and Energy Release) Program:

 What’s new in 10.0 ?
• New interface
• Expanded ideal gas Benson groups database (now1060 groups)
• Updated thermodynamic values provided for 20 Benson groups based on latest best
values in the literature.
• Entropy values were predicted and added to the database for many missing ideal
gas Benson groups
• Various property databases reviewed for consistency and accuracy
• Improved accuracy of mixture flammability calculations (Britton, 2002; Britton and Frurip,
2003)
• Change in programming language for CHETAH makes the program more
compatible and seamless with the current versions of the Microsoft Windows OS
• Output reports have been improved for clarity of presentation.
• Maintains a clear record of use with past sessions - easily be modified and reused
• Easier to establish and maintain a user database of proprietary data
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 Chemical Reactivity Evaluation – Desktop Methods
15

Chemical Reactivity Worksheet (CRW4) - *NEW* (CCPS, 2016)

 Predicts potential hazards from the unintentional mixing of chemicals with other chemicals,
with absorbents, and with materials of construction.
 Free software
 One of the most comprehensive tools available for identifying and managing chemical reactions
with the potential to release heat or toxic gaseous byproducts.
 Co-developed by Dow, NOAA, CCPS, and others from the chemical industry and academia
Key features of CRW include: New features of CRW4
Compatibility determinations based on Reactive Training videos
Groups and Special Hazard Codes
Extensive database of specific chemicals (~5200) Materials of Construction section
Ability to input data and add custom chemicals Refinement of Reactive Groups (68 total)
Common absorbent guidance Improved file sharing and chart display
Ability to display/print charts (up to 100x100)

Limitation - The CRW only accounts for reactions between two chemicals at a time (i.e. pair-wise
reactions). Reactions involving more than two reactants may not be accurately predicted – Use test
methods to validate.
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 Chemical Reactivity Evaluation – Desktop Methods
16

• CRW4 is used in Dow to generate

compatibility charts
• Hazard potential if accidentally mixed
• LOPA Scenarios
• Verify with measurements when needed

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Chemical Reactivity Evaluation – Desktop Methods
17

Yoshida’s Correlation - to screen for potential impact sensitivity hazards by DSC

 Strictly empirical method derived from a series of ~35 sealed-cell DSC (Differential
Scanning Calorimetry) tests on known high energy materials in the powder form,
mainly nitro compounds (Yoshida, 1987).
• Predicts a material’s hazard potential when subjected to low-to-moderate energy
forces (e.g. crushing, scraping with a spatula, dropping containers, hitting with a
hammer, puncturing with a fork truck tine)
• Conservative, since the original test data materials were all classified for their
ability to propagate an explosion under high energy stimulus. Some of these did
not propagate an explosion at BAM (German Republic Materials Testing Lab.)
• DSC test data are plotted as the log10 of the integrated energy of the exothermic
decomposition versus the log10 (Tonset, extrapolated°C - 25°C).
• Typically, materials having a DSC decomposition energy below -250 cal/g
(-1046 J/g) will not be an explosion hazard when subjected to low-to-moderate
energy forces.
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 Chemical Reactivity Evaluation – Desktop Methods
18

Example: DSC of an unknown

material in a sealed-N2 capillary.
A large exotherm is detected at
205oC with a reported enthalpy
of -450 cal/g (-1883 J/g).

Note: Within Dow, we enter the

DSC detected onset temperature
instead of the extrapolated onset
temperature (easy to obtain,
more conservative)

Limitations:
 Use caution when applying to liquids and non nitro-containing compounds
 Work to improve this correlation not incorporated here (Oxley et al., 1999, 2010; Chervin and
Bodman, 2003; and Bodman and Chervin, 2004) .
 If result is “above the line”, consider testing, especially if material contains known
energetic functional groups.
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 Advancements in Heat of Mixing Calorimetry
19

Heat of Mixing Calorimetry –

• The “2-drop” was invented at Dow to measure
heats of solution, absorption, reaction, gas
evolution; excellent for assessing chemical
compatibility
• To obtain DHrxn, must measure % conversion
Dow evaluated and selected Thermal Hazard
Technology’s (THT) micro reaction calorimeter (mRC)
• Higher temperature range -5 to 170ºC
• Rapid equilibration, easy to use, portable, and
small sample sizes
• More operating modes: titration calorimetry,
isothermal calorimetry and differential scanning
calorimetry for applications in hazard analysis,
thermal stability, Cp determination, rxn kinetics
• Higher pressure- withstands160 psi (vs. Dow’s
2-drop cell at 30 psi) making it less prone to
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 Improved Instrumentation for DSC (Differential Scanning
Calorimetry)
20

Measures heat generation (exotherm) and absorption

(endotherm) during a temperature scan

• No pressure measurements
• Small changes in composition can have a big impact on results
• Low activation energy kinetic reactions may be missed >200 oC

Ampoule, glass, 20uL

Max press. = 1,000 psig
Capillary, glass, 3 uL
0.5
Max press. = 3000psig
0.45

0.4

0.35

0.3
dQ/dT

0.25

Autocatalytic Reaction
0.2

0.15
Zero Order Reaction
0.1 Isothermal DSC may be utilized to
0.05

0
nth Order Reaction verify autocatalytic reaction kinetics
64 114 164 214 264
time (min)

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Advancements in Thermal Hazard Evaluation Testing and
Methods
21

Thermal Screening Unit (TSu)

20% DTBP in
 Provides an accurate measurement toluene (Singh and Simms,
of pressure 2001)

 Accurate measurement of detected

onset temps for low and high
activation energy materials
 Uses the same sample container as
the ARC (i.e. universal consumable
parts): (1-7g)
 Not a true calorimeter
• Non adiabatic; kinetics cannot be
modeled
• Cannot quantify heat generation

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Advancements in Thermal Hazard Evaluation Testing and
Methods
22

 Within Dow, we utilize the TSu:

• For screening worst-case pressure scenarios for relief design (i.e. VSP test pre-screen)
• For quantifying non-condensable gases under isothermal conditions
• In combination with DSC to obtain both thermokinetics (from DSC) and pressure
data (from Tsu)
• To generate results fast and economically. If no significant exothermic and pressure
generation events, then no need to get more tests.
 Advantages over the ARC:
• A test in the ARC may take up to three days longer to complete.
• DSC and TSu are cheaper and less costly to maintain (than an ARC)
• Using these instruments can save wear and tear on the ARC.
• Can be set up for injection runs
• Easier to recover after a ruptured sample sphere in TSU than ARC
• Returning an ARC to service can take up to two weeks longer than returning a TS U to
service (considering repair, calibration, and performance validation).
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 More Advanced Calorimetric Testing Tools
23

 Accelerating Rate Calorimetry (ARC)

• Measures heat (exotherm only) and pressure under
adiabatic conditions
• More sensitive than DSC
• Data suitable for modeling (with Phi correction)

NETZSCH

 Microcalorimeters
• C80, TAM III…
• Very sensitive

• Can confirm ARC kinetic extrapolation to lower

temperatures
• Long-term storage stability testing
TA Instruments
• Self accelerating decomposition temperature (SADT)
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 ARC (Accelerating Rate Calorimeter)
24

Invented at Dow in the 1970’s, became the industry standard for adiabatic calorimetry
and hazard evaluation. “Work-horse” for runaway reaction modeling!

Rate = r0 (1-c)n e (DE/R) (1/T –1/T) 0

ARC Plot
100

Key Kinetic Parameters: Initial Slope = DE/R

 Heat of Reaction per mass, DHR, 10

Self Heat Rate (Deg C/min)

determines maximum temperature rise
and reaction end point
1
 Activation Energy, DE, determines
the slope of reaction rate with
temperature 0.1

 Initial Temperature-Rate Pair (T0,

R0) determines a starting point for the 0.01
0 20 50 100 150 200 250 300 350
model representing near zero conversion Temperature (deg C)

of reactants.
R is the Gas Law Constant Initial Temperature-
Cp is Heat Capacity Rate Pair Total Temperature Rise
= DHRR / Cp
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 Open Cup ARC Testing
25

 Air is circulated through a preheater and purged

through a sample (powder, granules, liquid, or
liquid soaked insulation etc.) through a dip tube
 A thermocouple is placed in the sample adjacent to
the air outlet
 Heat-Wait-Search, and detection of exotherm
 Excellent for quantifying oxidative runaway
potential of high surface area materials soaked with
organic fluids to determine conditions resulting in a
fire….

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Open Cup ARC Testing
26

Excellent for quantifying the oxidative runaway potential of high surface area
materials soaked with organic fluids to determine conditions resulting in a fire

Insulation

Column packing

(Hofelich et al, 2001)

Powdery solids,
Absorbents
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 Advancements in Thermal Hazard Evaluation Testing and
Methods
27

Microcalorimetry
 At Dow, many types of micro-calorimeters (e.g. TAM III, C-80) are utilized for
validating extrapolated kinetic models from ARC data to lower temperatures.
 Example: Using ARC and micro-calorimetric data with known ambient heat losses
from piles of powdery solids (Frank-Kamenetskii Method), estimate how thick a layer
of powdery product “X” must be before the heat gains will outpace the heat losses

At 100°C we predict that “X” will run away at thicknesses

greater than 4 inches, and as small as 1 inch at 110°C

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Scalable Testing Tools and Modeling
28

 Vent Sizing Package (VSP)

• Phi factor is close to 1
• Primary tool for relief sizing
 Reaction Calorimetry (RC1)
• Can simulate process conditions
Fauske
• Can get kinetics of desired reactions
 Modeling
• Development of detailed kinetic
models for the process/chemistry
• Time to Maximum Rate (TMR)
• Heat gain and heat loss evaluation for
determination of Temperature of No Mettler Toledo

Return (TNR)
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 VSP – Vent Sizing Package
29

 Primary tool for relief/vent sizing

• Light-weight test cell (Phi close to 1)
• VSP data can be used for pressure
relief design without Phi correction
• VSP data is scalable to large reactors
 Key features and capabilities
• Fast adiabatic tracking of exotherm
• Pressure compensation
• Magnetic or mechanical stirring
• Injection of liquid under pressure
• Can simulate process upset scenarios
 Loss of cooling
 Loss of agitation Fauske

 Mischarge of reactants
 Accumulation of reactants
 Contamination
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 VSP (Vent Sizing Package)
30

Case Study:
Studying decomposition kinetics for producing/drying product in a Littleford Dryer

Self-heat rate profile is significantly different when mixing is involved. Clumped material in
front of a plow blade might act like the material not being mixed (D - “Quiescent Dry”)

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Flammability and Dust Explosion Testing
31
 Flammability testing
• Flash point (FP)
• Flammable limits (LFL and UFL)
• Limiting oxygen concentration (LOC)
• Autoignition temperature (AIT)
• Electrical conductivity
MIKE3
 Dust explosion testing*
• Particle size distribution (PSD)
• Minimum ignition energy (MIE)
• Dust explosion severity (Kst/Pmax)
• Minimum ignition temperature of dust
cloud (MAIT) and dust layer (MIT)
• Minimum explosive concentration (MEC)
*Internal and external labs 20 Liter Sphere

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Energetic Materials Testing
32

 Explosivity, UN/DOT classification

• At Dow, we occasionally encounter chemicals in our
processes that contain high energy functional groups
and/or may have explosive properties
 Internal testing capabilities
• Thermal stability (DSC)
• Impact sensitivity (drop weight test)
 Work with external labs on UN/DOT explosivity
testing for transportation classification
• Friction sensitivity
• Card gap tests
• Koenen tube tests
• Time/pressure tests
BAM Friction Apparatus BAM Fallhammer
UN: United Nations; DOT: US Department of Transportation
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 Advances in Thermochemical Modeling – Tools at
33
Dow
“CRISIS” Spread sheet for Immediate Response

• Kinetic parameters Ea and A are from other tabs

in CRISIS
• Need physical parameters
• Only considers heat losses to environment

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Advances in Thermochemical Modeling – Tools at
Dow
34

Basis for TMR in Dow’s “CRISIS” Spread sheet for Immediate Response
Time to maximum rate using ARC data (Townsend and Tou, 1980)
 With an activation energy Ea, one can define the thermokinetics (zeroth
order kinetics assumed)
Temperature early Temperature at
In Exotherm Maximum Rate

Temperature Rate
Corresponding to Maximum Rate
•Very useful if ARC data exist Temp. in numerator
•If TMR’s from worst case operating T’s are days, weeks, months, then risk is probably low
•Use a good Cp (lower is more conservative)
•Do NOT drop second term in TMR if activation energy is below 20 kcal/mol
•Does not apply for autocatalytic reactions
P2SAC – Purdue Process Safety Conference 9-Nov-2016
 Advances in Thermochemical Modeling – Tools at
35
Dow
“CRISIS” Spread sheet for Immediate Response: Temperature Limit from DSC
 Estimates the adiabatic Time to Maximum Rate (TMR) using dynamic DSC experimental
data
 Detected onset temperature (T) defines a data point of heat rate based on the detection
limit of the DSC (45 µW/g)
 Assuming a reasonable activation energy (Ea) and heat capacity (Cp), one can estimate the
temperature limit (T) for a desired TMR, or for a TMR at T, assuming zeroth order kinetics.

 Very useful at early stages (R&D)

 Use a good Cp (lower is more conservative)
 Use a conservative Ea (50 kJ/mol)
 If TMR’s from worst case operating T’s are days, weeks, months, then risk is probably low

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Example: Temperature Limit from ARC
36

 At what temperature can a product be safely stored during a turnaround ?

Normal residence times in the tank are <3 days. The turnaround will take
about 7 days. Because the product is viscous, it is normally stored at a
temperature of 450C.
• Available data: ARC Detected onset Temp: 124 oC @ 0.03 oC/min
• PHI factor: 1.91

Temp Limit
is 6700C at
TMR(ad) =
10 days (240
hrs)

P2SAC – Purdue Process Safety Conference 9-Nov-2016

 Summary and Conclusions
37

 Dow continues to be a strong leader in Process Safety and Reactive Chemicals

to advance best practices and develop new technologies for identifying and
managing process hazard risks.
 This is demonstrated by the diversity of innovative test methods and modeling
approaches which Dow employs to gather critical information to quantity
potential hazards for our operations and help to determine that we have
adequate protection to prevent incidents and to mitigate the consequences.
 As part of our commitment to Responsible Care, we have also continued to
leverage key aspects of Dow’s Reactive Chemicals Program, including hazard
review protocols.
 Our intent is that by sharing Dow’s practices for identification, assessment and
management of reactive chemicals hazards, the chemical process industries
can realize benefits from improved reliability of operations, fewer incidents
over the life of a process, and reduced consequences of any incidents that may
occur.
Thank you!
P2SAC – Purdue Process Safety Conference
Questions ? 9-Nov-2016
 References
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with Overpressure Protection By System Design, 2007
ASME Boiler and Pressure Vessel Code, Section VIII
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Britton and Frurip, 2003 L.G. Britton, D.J. Frurip
“Further Uses of the Heat of Oxidation in Chemical
Hazard Assessment “, Proc. Saf. Prog. 22 (2003), pp. 1–
19
Britton and Harrison, 2014 L.G. Britton, B.K. Harrison,
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(1995). Experimental approaches to testing in the VSP
for different types of reactions for emergency relief
design by simplified equations. United States.
P2SAC – Purdue Process Safety Conference
CCPS, 1995 “Guidelines for Chemical Reactivity
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and Bulk Solids”, Center for Chemical Process Safety,
New Jersey: John Wiley & Sons (2010). See section 4.3.3
– Laboratory Test Methods for Chemical Incompatibility
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Ryan, D. Sliva, D. Viveros, “Chemical Reactivity
Worksheet Version 4 (CRW4)“, Center for Chemical
Process Safety at
http://www.aiche.org/ccps/resources/chemical-reactivity-w
orksheet-40
CEFIC, 2012 Bulk Storage Guideline of Hydrogen
Peroxide, CEFIC, March 2012
Chervin and Bodman, 2003 S. Chervin and G.T.
Bodman ,“Method for Estimating Decomposition
Characteristics of Energetic Chemicals “, Proc. Saf. Prog.,
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