SAFETY IN AN INDUSTRIAL LABORATORY - Michigan State University · SAFETY IN AN INDUSTRIAL LABORATORY Jordan Reddel and Matt Belowich The Dow Chemical Company. October 22, 2019

SAFETY IN AN INDUSTRIAL LABORATORY

Jordan Reddel and Matt BelowichThe Dow Chemical Company

October 22, 2019Chemical Safety

Michigan State University

Acknowledgments

• MSU Chemistry Department

• Our colleagues and leadership at Dow

• Lori Seiler, Associate Director for Global R&D EH&S Delivery

MRosen & MBelowich, 11/29/2018 Page 2

Outline

1. Introductions

2. Hazards of Laboratory Research

3. Approaching Research in Industry: How Does Dow Do Research Safely?

4. Q&A


• 2007 – 2011: University of New Hampshire – Undergraduate Research

• 2011 – 2016 : Northwestern University – Ph.D. (Regan Thomson)– Total synthesis of lignan natural products and method development

• 2016 – present: The Dow Chemical Company – Chemical Science (Core R&D)

– Organic Synthesis– Homogeneous catalysis, new catalyst development

Jordan’s Background

Page 4JReddel & MBelowich, 10/22/2018

– Bioinorganic chemistry: Design and synthesis of copper (II) ligands for ratiometric metal-ion sensors

Matt’s Background


• 2011: Northwestern University – Ph.D. (Fraser Stoddart)– Supramolecular chemistry– Mechanically-interlocked molecules– Organic synthesis

• 2012: Princeton University – Post-doc (David MacMillan)– Synthetic methodology– α-Arylation of carbonyls

• 2012: The Dow Chemical Company – Coating Materials– Polymer chemistry– Emulsion polymerization

• 2016: The Dow Chemical Company – Chemical Science (Core R&D)– Organic synthesis– Polymer chemistry– Organometallic chemistry

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Positioned to Capitalize on Global Growth Trends

High-Throughput Research

Polymer Science

Material Science

Formulation Sciences

Process Engineering

Target MarketsBuilding Blocks Product Development

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High-PerformanceComputer Modeling

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Catalyst Discovery & Ligand Synthesis

Application Development

Packaging

Infrastructure

Consumer

Urbanization Digitalization SustainabilityGlobalization

Cellulosics

Acrylics

Olefin Building Blocks

Ethylene Oxide

Propylene Oxide

Silicones

Various Others

Chemical Science Core Capability


POLYMERCHEMISTRY

Controlled architecture synthesisPolymer modification

Novel polymer additives

Electronic structure methodsMolecular dynamicsStructure-activity relationships

COMPUTATIONALCHEMISTRY

PROCESSCHEMISTRY

Atom economyRoute optimizationMaterials processingScale-up troubleshooting

ORGANIC & INORGANIC SYNTHESIS

HTR enabledCatalytic coupling chemistriesLigand design and inorganic

materials synthesis

Structure-property relationshipsHTR screening

Synthesis of homogeneous &heterogeneous catalysts

PHYSICAL CHEMISTRY

Reaction kineticsReaction thermodynamics

Phase behavior analysis

SKILL SETSORGANOMETALLIC CHEMISTRY

Hazards of Laboratory Research

Overview of Process Hazards


• Chemical Hazards Examples– Toxicity– Flammability– Shock sensitivity– Reaction exothermicity

• Physical Hazard Examples– Mechanical– Thermal– Pressure– Electrical– Ergonomics

• Work Area Hazard Examples– General housekeeping– Location and amount of

flammable materials

Engineering controls, administrative controls, and personal protective equipment (PPE) can keep you safe!

Rupture disc: Pressure Relief Device

Sign to Warn Others of Thermal Hazard

Sign and Physical Shield to Mitigate

Mechanical Hazards

Hidden Hazards of “Common” Reactions

• Hazards– Toxicity of NaN3: equivalent to NaCN– NaN3 can be explosive – even using a metal spatula can cause decomposition!– Changing the solvent from DMF can to dichloromethane (CH2Cl2) can lead to an explosive

chemical incompatibility!MRosen & MBelowich, 11/29/2018 Page 10

Macromolecules, 2018, 51, 2969

• Azide-Alkyne ‘Click Chemistry’is commonly used to makevarious polymer architectures.

R LG

LG = -Cl, -Br -OMs

NaN3+ Solvent

R N3

Sodium Azide CH2Cl2

HIGHLY EXPLOSIVE!

R LG NaN3+ R N3

DMF

+ N3

H2C N3

Diazidomethane

R N3

Hazards of Literature Prep Modification

• Modifications to literature procedures, and the procedures themselves need to be considered carefully

• In Dec. 2010, a reaction mixture detonated in a lab in the chemistry department at Northwestern University and a researcher was seriously injured

– Deviations to literature procedures were made:• Higher H2O2/iodobenzene ratio (25 instead of 2.8)• 35 wt% freshly opened H2O2 instead of 30 wt% H2O2

– Cause of explosion is unknown, but it is thought that the modified reaction conditions may allow the formation of diacetyl peroxide, a shock-sensitive explosive


1) H2O2/Ac2O

2) NaOH

ISO2

IOSO2

2-(t-butylsulfonyl)iodosylbenzene

C&EN News, Jan 10, 2011 Letters

OO

O

ODiacetyl peroxide

http://cen.acs.org/articles/89/i2/Chemical-Safety-Synthesis-Procedure.html

Work Area Hazards


• Poor housekeeping can lead to hazardous situations!– Ex: One student put a 1-L bottle of HCl on a high shelf, and later that day a different

student put a 1-L bottle of KCN on the same shelf hazardous situation!• Numerous hazards in messy hoods

Example from academia

Approaching Research in Industry: How Does Dow Do Research Safely?

Two Types of Chemistry Environments

1. Plant-Scale Reactors– Large reactor vessels (hundreds to thousands of gallons)– Materials transferred from large holding tanks– Chemistry is well-established and reaction process/products are fully

characterized and understood

2. The Research Laboratory– Small scale glassware and reactors– Material synthesis usually gram-scale– Exploratory chemistry and reactions


Safety in this environment will be the focus of our talk today!

The Move to Industry

• Disclaimer: The approach to safety that we take at Dow works well for us. However, each program and organization is unique, and the techniques that work for us may not work for your organization. Your organization should ensure that the safety program you use matches your needs!

Safety is the foundation for everything we do

Safety is collaborative Proactive about safety Safety is equally as important as generating results (scientific success)


Collaboration: The Cornerstone of Safety

• The key to our safety program is that we actively work with each other to share information and have lots of eyes on our chemistry!

• We have different communication options and tools to emphasize safety

– CHAT (Continuous Hazard Awareness Tool) Meetings: informal discussion about tasks planned for the day and the hazard control steps to be used

– WAG (Work Area Group) Meetings: discussion of chemistry occurring in the hoods in our immediate work area

– Safe-Operation Cards (SOC): reactions and processes we plan to perform are reviewed by a colleague for potential hazards

– Safety Moments: start a meeting with a “lesson learned”, may be work-related or even personal examples


Preparing to be safe: The SOC card• Before we do ANY process, we prepare an “SOC Card”

– SOC card posted on the hood or outside the area where process is being conducted– Consider worst-case scenarios: “If this happens, am I still safe?”– Provides others with quick reference to ongoing processes– In case of emergency, others can rapidly identify components/hazards of process

• Key components of a Safe Operation Card (SOC)– Process owner and contact info– Experimental section

• Description of chemistry• Reagent hazards (use SDS!) • Procedure for experiment

– Order of addition, reaction time, workup, and purification

• Acceptable operating parameters– Temperature, pressure, etc.

– Emergency procedures• Proper PPE for Chemistry• Emergency shutdown• Spill cleanup procedures


http://safety.dow.com/en/safety-courses/plan-evaluate-execute/safe-operation-card

Preparing to be safe: The SOC card


(SLOW DOWN!)

S S

Br

x yS S

N3

x y

NaN3

THF

The alkyl bromide is dissolved in anhydrous THF under an atmosphere of nitrogen behind ablast shield. NaN3 is added in one portion and the solution is heated to 70 C for 16 hr. Thereaction mixture is then poured into methanol to precipitate the polymer and filtered.

CAS #’s: Sodium Azide (26628-22-8), Tetrahydrofuran (109-99-9), Methanol (67-56-1)

In the event of a chemical exposure immediately enter safety shower and havesomeone call emergency services.

• Goggles• Fire-retardant lab coat• 2 layers of nitrile gloves• polyethylene sleeves for wrist protection

Sweep up and dispose of material in appropriate waste stream. Do NOT use water asit may generate toxic gas.

Sodium Azide: H310 Fatal if in contact with skin H373 May cause damage to organs (brain)H410 Very toxic to aquatic life with long lasting effectsTetrahydrofuran: H225 Highly flammable liquid H302 Harmful if swallowed H319 Causesserious eye irritation H335 May cause respiratory irritation H351 Suspected of causing cancerMethanol: H225 Highly flammable liquid H301/H311/H331 Toxic if swallowed, in contact withskin, or inhaled H370 Causes damage to organs

Marie Curie, (917) 123-7654Irene Joliot-Curie, (917) 456-0987

Taking Your Safety Personally• Levels of Control

– Engineering Controls• Fume Hoods (ventilation and fume hood sash)• Blast Shields

– Administrative Controls• Training• Procedures

– Personal Protective Equipment• Gloves, Goggles, Lab Coat, etc.• Should be treated as a LAST LINE OF DEFENSE


Most Effective

Least Effective

Example from academia

PPE should never be used in place of engineering controls

• Trends at Dow:– Relatively few injuries involve reactive/toxic chemistry issues– Routine tasks/ergonomics lead to most injuries!

• Examples of Low Risk, High Frequency Tasks:– Glassware handling: NMR tube insertion into spinner, washing dishes, etc– Walking– Driving– Ergonomic

• SOC cards force one to think about thehazards of chemistry and anticipatepotentially dangerous scenarios.

“Sleeper” Hazards


High Risk, Low Frequency Tasks

High Risk, High Frequency Tasks

Low Risk, Low Frequency Tasks

Low Risk, High Frequency

Tasks

62%

Frequency

Perc

eive

d R

isk

Reaction Example

• Olefin Polymerization in a 2-L Semi-Batch Parr Reactor

• Some chemistry and process hazards:– Ethylene polymerization is a highly exothermic reaction (ΔH = -22 kcal/mol)

• Is the reactor properly equipped to dissipate the heat of reaction?– Variables: temperature, pressure, scale, catalyst loading

• Low temperatures: more ethylene is in solution, high temperatures: more active catalyst• High pressures and larger scales: more ethylene in the reactor• High catalyst loading: potential exotherm is higher

– Flammability of ethylene, 1-octene, and reaction solvent• Is the reactor free of leaks?


H2C CH2 CH2 CH2 n CH CH2

C6H13

CH CH2

C6H13

m+ catalyst

1-OcteneLiquid (bp = 121 °C)

EthyleneGas (bp = -104 °C)

PolyethyleneSolid (mp > 120 °C)

Summary

Safety is the foundation for everything we do

Safety is collaborative Proactive about safety Safety is equally as important as generating results (scientific success)

No experiment is worth pursuing without understanding the hazards

• At Dow, safety is our primary focus whenever we consider doing work– The activities that we use to ensure a safe work environment vary from process

to process or reaction to reaction but it is always a priority.


Dow Lab Safety Academy

http://safety.dow.com/en

LaunchedMay 2013

Earned the 2013 Safety Investment Award from ChemInnovations


Earned the 2018 Howard Fawcett Chemical Health & Safety Award from ACS

75,000 + enrolled viewers

>550,000 views >180 universities >500 Government

Agencies, National Labs & Companies

>150 countries

http://safety.dow.com/en

Thanks for your attention!

Questions?

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SAFETY IN AN INDUSTRIAL LABORATORY - Michigan State University · SAFETY IN AN INDUSTRIAL LABORATORY Jordan Reddel and Matt Belowich The Dow Chemical Company. October 22, 2019