New Technologies in ONG

Fire Protection and Related

Environmental Regulations

Mark L. Robin, PhD

DuPont Chemicals & Fluoroproducts

mark.l.robin@dupont.com

Oil Industry Safety Directorate Annual Seminar

Kolkata, India

February 15th, 2013

Traditional Fire Protection

in the Oil & Gas Industry

Onshore and Offshore Oil & Gas Operations

• Water

• Foam

• Dry Chemical

• Halons

• Power production facilities

• Process control rooms

• Computer rooms

• Communication centers

• Turbine generators

• Switch gear rooms

• Storage tanks

Leave residues

Require cleanup

Business interruption

Halons = Clean Agents

No residue

No to minimal cleanup

No to minimal business

interruption

Ozone Depletion

New Technologies: Halon Replacements

Halon 1301 Replacements:

Total Flooding Halon 1211 Replacements:

Potables, Local Applications

Properties of the Ideal Halon Replacement • Clean

• Efficient fire suppression

• Chemically inert Long term storage stability

No chemical reactions with water, fuels, assets

• Electrically non-conducting

• Low toxicity

• Zero ODP

• Zero GWP

• Reasonable manufacturing cost

Properties of the Ideal Halon Replacement • Clean

• Efficient fire suppression

• Chemically inert Long term storage stability

No chemical reactions with water, fuels, assets

• Electrically non-conducting

• Low toxicity

• Zero ODP

• Zero GWP

• Reasonable manufacturing cost

No replacement has been

found which satisfies ALL of

the requirements of the ideal

Halon replacement

• Hydrofluorocarbons (HFCs) HFC-227ea: FM-200® CF3CHFCF3

HFC-125: FE-25TM CF3CF2H

HFC-23: FE-13TM CF3H

• Hydrochlorofluorocarbons (HCFCs) HCFC Blend A: NAF-S-III

• HCFC-22/HCFC-123/HCFC-124/d-limonene

• Inert Gases IG-541: InergenTM Ar/N2/CO2

IG-55: ArgoniteTM Ar/N2

• Perfluorinated Ketones FK-5-1-12: NovecTM 1230 CF3CF2C(O)CF(CF3)2

Halon 1301 Replacements

8

• Hydrofluorocarbons (HFCs) HFC-227ea: FM-200® CF3CHFCF3

HFC-125: FE-25TM CF3CF2H

HFC-23: FE-13TM CF3H

• Hydrochlorofluorocarbons (HCFCs) HCFC Blend A: NAF-S-III

• HCFC-22/HCFC-123/HCFC-124/d-limonene

• Inert Gases IG-541: InergenTM Ar/N2/CO2

IG-55: ArgoniteTM Ar/N2

• Perfluorinated Ketones FK-5-1-12: NovecTM 1230 CF3CF2C(O)CF(CF3)2

Halon 1301 Replacements

HCFCs subject to phaseout

Ideal Halon 1301 Replacement Halon 1301 HFCs Inert Gases Perfluoroketones High weight efficiency √√ √

Gas at ambient temperature √ √ √

Low chemical reactivity √ √ √

Electrically nonconducting √ √ √ √

Low toxicity √ √ √

Lack of metabolism √ √ √

Low agent cost √ √ √

Low system cost √ √ √

Low number agent cylinders √ √ √

Low storage volume √ √ √

Low system footprint √ √ √

Low cylinder pressure rating √ √ √

Low manifold pressure rating √ √ √

Low negative pressures during discharge √ √ √

Low positive pressures during discharge √ √ √

Slow stratification √ √ √

Zero ODP (ozone depletion potential) √ √ √

Zero GWP (global warming potential) √

VOC exempt (no contribution to smog) √ √ √

Comparison of Halon Replacements = provides desired property

HFCs offer the best overall combination of the

properties desirable in a Halon replacement

Worldwide Clean Agent Market

Number of Installed Systems

HFCs are the most widely employed

Halon 1301 alternatives

HFCs (70%)

Inert Gases (20%)

Other (10%)

A Closer Look at Halon Replacements:

Inert Gases vs Halocarbons

Comparison of Inert Gas and

Halogenated Systems

Inert Gas Agents

• Cannot be compressed to liquid – stored as high pressure gas

• Require high pressure cylinders, piping

• Require large number of cylinders – large footprint

• Cost increases more rapidly with increasing system size

• High MDC – need for venting

Halogenated Agents

• Stored as liquid

• Large mass of agent can be stored in small volume

• Standard cylinders, piping

• Small number of cylinders required – small footprint

Halocarbon vs Inert Gas System:

1000 m3 Enclosure, Class A Hazard

Agent

Design

Conc., %

v/v

Agent, kg

No.

Cylinders

FM-200®

7.0 548 2

InergenTM

(300 bar) 40.0 724 22

FM-200®

Inergen®

A Closer Look at Halon Replacements:

HFCs vs Perfluoroketones

Physical &

Chemical

Properties

Novec 1230TM Differs From All Other

Clean Agents in Three Important Aspects

Property

HFC and Inert

Gas Clean

Agents

NovecTM 1230

Chemical

Reactivity

Very Low

High – reacts

with water,

alcohols, amines

Interaction in

human body

No reaction to

form toxic

products

Hydrolyzes in

lungs to form

F-propionic acid

Physical State Gas Liquid

CF3CF2C(O)CF(CF3)2 + H2O CF3CF2COOH + CF3CHFCF3

Novec 1230 Water Perfluoropropionic acid HFC-227ea

This same reaction occurs when NovecTM 1230

crosses the lung-air interface b

NovecTM 1230 Chemical Reactivity &

Interaction in the Human Body

NovecTM 1230 is chemically reactive with water, alcohols

and amines, and is incompatible with hydrocarbon

and polar solvents a

a "Contact with water or solvents either polar or hydrocarbon could render Novec 1230 fluid ineffective.“

Sapphire Pre-Engineered Clean Agent Fire Suppression Systems, Installation Operation Inspection and

Maintenance Manual, Page 1 (Ansul/Tyco)

b Novec 1230 Fire Protection Fluid Safety Assessment (3M)

A Closer Look at Halon Replacements:

HFCs vs Perfluoroketones

Efficiency

FM-200® & NovecTM 1230: Efficiency

25% More NovecTM 1230 by mass required

Agent

Class C

Design Conc.,

% v/v

kg Agent

Required to

Protect

100 m3

Mass

Efficiency

FM-200® 7.0 55 1.00

NovecTM 1230 4.7 69 1.25

Example: IT/Telco Facility Protection

Per NFPA 2001 (2012)

FM-200® & NovecTM 1230: Cost Effectiveness

• 25% more NovecTM 1230 required by weight

• NovecTM 1230 price per kg > FM-200®

• NovecTM system design more complex

o Lower area coverage per nozzle vs FM-200 ®

o More nozzles, piping required with NovecTM 1230

Agent

Max Nozzle

Coverage

length x width

Max Nozzle

Coverage Area,

m2

Area Coverage

Efficiency

FM-200® 19.5 m x 19.5 m 380 2.7

NovecTM 1230 11.9 m x 11.9 m 142 1.0

3 fold increase in area coverage

achievable with FM-200®

System Design Example

IT Facility

38 m x 38 m x 3 m

Class A and Class C Hazards

Agent

Design

Concentration

% v/v

kg Agent

Required

Number of

Nozzles

Required

FM-200® 7.0 2375 4

NovecTM 1230 4.7 2972 16

25% more agent by weight, 4 x number

nozzles required for NovecTM 1230

A Closer Look at Halon Replacements:

HFCs vs Perfluoroketones

Toxicology

• HFCs • Chemically unreactive

• Toxicology of HFCs well-established

• FM-200 tested in humans, approved as

propellant for medicaments in metered

dose inhalers

• Perfluoroketones • Very reactive chemically

• Very little toxicological data available on perfluoroketones

• Perfluoroacetone extremely toxic

• Novec 1230 hydrolyzed when crossing air-lung interface to Perfluoropropionic acid (CF3CF2COOH)

Chemical Reactivity: Impact on Toxicology

A Closer Look at Halon Replacements:

HFCs vs Perfluoroketones

Environmental

Properties

Agent ODP GWP

Inert Gases 0 0

FM-200® 0 3500

NovecTM 1230 0 1

Environmental Properties

ODP = 0 no depletion of stratospheric ozone

GWP = 3500 release of 1 kg of FM-200® has

same impact on global warming as

the release of 3500 kg CO2

…..but there is more to the story

The Rumor:

“HFCs have a large

impact on climate

change/global

warming because they

have a high GWP

value”

What are the Facts?

Global Warming/Climate Change 101

Impact on Global Warming

Does not depend only on GWP value

Does not depend only emissions level

The impact on global warming depends on both

the GWP of the gas released and the amount

of the gas released

Impact on Global Warming = Emissions x GWP

Imp

act o

n G

lob

al W

arm

ing

, T

g C

O2

Impact on Global Warming

CO2 GWP = 1

FM-200 GWP = 3500

0.9

5,706

Source: Inventory of US GHG Emissions & Sinks: 1990-2010 (US EPA, 4/15/2012)

Imp

act o

n G

lob

al W

arm

ing

, T

g C

O2

Impact on Global Warming

CO2 GWP = 1

FM-200 GWP = 3500

0.6

5,706

The GWP Value by Itself Does Not Indicate the

Impact of an Agent on Global Warming

Source: Inventory of US GHG Emissions & Sinks: 1990-2010 (US EPA, 4/15/2012)

Impact of HFC Emissions from Fire Suppression Tg of CO2 Equivalents

Impact of HFC Emissions from

Fire Suppression, 0.01%

Impact of all GHG Emissions

except HFCs from Fire

Suppression, 99.99%

Impact of HFC emissions from fire suppression applications

on climate change represents 0.01% of the

total impact of all GHG emissions

Inventory of US GHG Emissions & Sinks: 1990-2010 (US EPA, 4/15/2012)

30

Impact of HFC Emissions from Fire Suppression Tg of CO2 Equivalents

Impact of HFC Emissions from

Fire Suppression, 0.01%

Impact of all GHG Emissions

except HFCs from Fire

Suppression, 99.99%

Impact of HFC emissions from fire suppression applications

on climate change represents 0.01% of the

total impact of all GHG emissions

Inventory of US GHG Emissions & Sinks: 1990-2010 (US EPA, 4/15/2012)

HFCs in fire suppression

applications have essentially no

affect on global warming/climate change

The Rumor:

“FM-200® and other HFCs

used in fire suppression

are having a large impact

on climate change….and

that impact has been

increasing rapidly over

time”

What are the Facts?

32

2005 2006 2007 2008 2009 2010

Refrigeration/AC 87.9 90.1 90.3 90.4 91.3 97.6

Aerosol 7.3 7.7 8.2 8.6 9.1 9.3

Foam 1.9 2.1 2.3 2.5 3.9 5.4

Solvent 1.3 1.3 1.3 1.3 1.3 1.3

Fire Protection 0.5 0.6 0.7 0.7 0.8 0.9

Semiconductor manufacture 0.2 0.3 0.3 0.3 0.3 0.3

R-22 manufacture 15.8 13.8 17 13.6 5.4 8.1

Total HFCs 114.9 115.9 120.1 117.4 112.1 123.0

Total All GHGs 7204.3 7159.2 7252.8 7048.4 6608.3 6821.7

Contribution to climate change

from HFCs in fire extinguishing

applications

0.01% 0.01% 0.01% 0.01% 0.01% 0.01%

Tg of Carbon Dioxide Equivalents

Impact of Emissions of HFCs from Fire Suppression

Applications on Climate Change: Historical

Source: Inventory of US GHG Emissions & Sinks: 1990-2010 (US EPA, 4/15/2012)

mlr _1_2013

Emissions of HFCs in fire protection

are NOT rapidly increasing

The Rumor:

“FM-200® has been or

will be banned

from use in fire

suppression”

What are the Facts?

Regulatory Status of HFCs in Fire Extinguishing

No regulatory proposals targeting ban or

phaseout of HFCs in Fire Protection

Montreal Protocol

Relates to ODSs ; HFCs have zero ODP so not subject to

Montreal Protocol

Kyoto Protocol

Relates to reduction of emissions

No bans, restrictions on HFCs in fire protection

F-Gas Regulations

Relates to reduction of emissions

No bans, restrictions on HFCs in fire protection

Recent proposals do not restrict use of FM-200®

Regulatory Status of HFCs in

Fire Extinguishing

• When encountered with an allegation of the

banning of FM-200® in fire suppression

applications…..

Ask two simple questions:

1. What document indicates this?

2. Where in the document does it

specifically indicate the banning of

FM-200® in fire suppression applications?

The Montreal Protocol: India’s

Success Story

• “The Montreal Protocol: India’s Success Story”

• Published 2012 by the Ozone Cell, Ministry of

Environment and Forests, Government of India, New

Delhi, India

• Identifies FM-200® and HFCs as viable alternatives to

Halons 1301, 1211 and 2402 (page 12)

Halon 1211 Replacements

Commercialized Agents

• PFC-5-1-14

• Halotron® I

• Saclon II

• NAF-P-IV

• AF11E

• HFC-236fa

Commercialized Agents

• PFC-5-1-14

• Halotron® I

• Saclon II

• NAF-P-IV

• AF11E

• HFC-236fa

ODP≠ 0

ODP≠ 0

ODP≠ 0

HCFCs subject to Phaseout

under the Montreal Protocol

Halon 1211 Replacements

PFC

Performance: UL Ratings

UL Rating FE-36TM

kg

Halotron® I

kg

Saclon II

NAF P-IV

Halon 1211

kg

1BC - 0.64 No UL listings -

2BC 1.1 1.13 No UL listings 0.6

5BC 2.2 2.27 No UL listings 1.1

1A 10BC 4.3 5.0 No UL listings 4.1

2A 10BC 6.0 7.03 No UL listings -

Performance/Efficiency FE-36TM Halotron® I

FE-36TM Toxicity << Halotron® I

FE-36TM : Superior Material Compatibility

FE-36TM ODP = 0

CF3I

• Excellent fire suppressant

• equal to Halon 1301 on mass basis

• Sensitive to water, light – tends to produce iodine

• High toxicity

• Very high cost

• No large commercial suppliers

• No UL listings, no FM approvals

CF3I FM-200® FE-36TM

CS NOAEL 0.2 % 9.0 % 10 %

CS LOAEL 0.4 % 10.5 % 15 %

4h LC50 27.4 % (15 min) a > 80 % b > 45.7 % b

a 50% of test animals died b no test animals died

A Selection of Recent

FM-200® Clean Agent Installations

National Security Agency (NSA) Comprehensive

National Cybersecurity Initiative

Camp Williams, Utah

$1.5 billion

Completion in 2013

Protection of the USA’s most critical

data related to national security

FM-200® System

Notable FM-200® Projects in Asia

Mumbai Metro

New Delhi Metro

Chennai Metro

Mumbai Stock Exchange

Tata Communications

Samsung Korea

Metros – HK, Singapore, Bangkok, Taiwan

Airports – India, Korea, Thailand,

Singapore, Vietnam, Indonesia,

Philippines, Malaysia,

Mecca Railway

Dubai Metro

Burj Khalifa

Qatari Telecom

DOKAAE Project

du Telecom

Dubai Int’l Airport

EMEA: Some notable FM-200® projects

FM-200®: Oil & Gas Industry Installations

Saudi Aramco Unical

Amoco YPF

Amerada Hess Schlumberger

Burlington Resources SOCO Offshore

Texaco PDVSA

Caltex Ecopetrol

BP Chevron USA

Reliance Petroleum China Petroleum

BHP Petroleum Mobil

PetroCanada Lyondell-Citgo

Petronas Exxon

Shell PEMEX

Solar Turbines Phillips Petroleum

Computer rooms, critical records, control rooms,

critical processes, telco equipment

FE-36TM : Applications

Crew & Engine Portable Extinguishers

Healthcare: MRI

Floating Roof Tanks Motorsports Aviation Lavex

Summary • There are no halon replacements which satisfy all of the

requirements of a ideal halon replacement

• The HFC clean agents provide the best overall combination

of the properties desired in an ideal halon replacement,

followed by the inert gases

• There are no proposed bans or phaseout of HFCs in fire

protection applications

• Environmentally acceptable under SNAP

• US EPA, EU-27 data indicates minuscule impact on

global warming

• International regulatory bodies understand the essentially

no-emissive nature of clean agent systems