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 Leave residues
• Dry Chemical Require cleanup
Business interruption
• Halons
• Power production facilities
• Process control rooms
• Computer rooms Halons = Clean Agents
• Communication centers No residue
• Turbine generators No to minimal cleanup
• Switch gear rooms No to minimal business
• Storage tanks interruption
Ozone Depletion
New Technologies: Halon Replacements

Halon 1301 Replacements: Halon 1211 Replacements:

Total Flooding 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
No
 Long replacement
term storage stability has been
 No
found
chemicalwhich
reactionssatisfies ALL
with water, fuels, of
assets
• Electrically non-conducting
the requirements of the ideal
• Low toxicity
• Zero ODP Halon replacement
• Zero GWP
• Reasonable manufacturing cost
Halon 1301 Replacements
• 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
• 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
HCFCs subject to phaseout
• 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

8
 Comparison of Halon Replacements
 = provides desired property
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) √ √ √

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%)
Other (10%)

Inert Gases (20%)

A Closer Look at Halon Replacements:
Inert Gases vs Halocarbons
 Comparison of Inert Gas and
Halogenated Systems
Inert Gas Agents Halogenated Agents
• Cannot be compressed to liquid – • Stored as liquid
stored as high pressure gas • Large mass of agent can be stored
• Require high pressure cylinders, in small volume
piping • Standard cylinders, piping
• Require large number of cylinders – • Small number of cylinders
large footprint required – small footprint
• Cost increases more rapidly with
increasing system size
• High MDC – need for venting
 Halocarbon vs Inert Gas System:
1000 m3 Enclosure, Class A Hazard

Agent Design Agent, kg No.

Conc., % Cylinders
v/v
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
HFC and Inert
Property Gas Clean NovecTM 1230
Agents
High – reacts
Chemical Very Low with water,
Reactivity alcohols, amines

No reaction to Hydrolyzes in
Interaction in form toxic lungs to form
human body products F-propionic acid

Physical State Gas Liquid

 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

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
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

Example: IT/Telco Facility Protection
Class C kg Agent
Agent Design Conc., Required to Mass
% v/v Protect Efficiency
100 m3
FM-200® 7.0 55 1.00

NovecTM 1230 4.7 69 1.25

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

Max Nozzle Max Nozzle Area Coverage

Agent Coverage Coverage Area, Efficiency
length x width m2
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
Design kg Agent Number of
Agent Concentration Required Nozzles
% v/v 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
Chemical Reactivity: Impact on 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)
A Closer Look at Halon Replacements:
HFCs vs Perfluoroketones

Environmental
Properties
 Environmental Properties
Agent ODP GWP

Inert Gases 0 0

FM-200® 0 3500

NovecTM 1230 0 1

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

Impact on Global Warming, Tg CO2
Impact on Global Warming
5,706
CO2 GWP = 1
FM-200 GWP = 3500

0.9

Source: Inventory of US GHG Emissions & Sinks: 1990-2010 (US EPA, 4/15/2012)
Impact on Global Warming, Tg CO2
Impact on Global Warming
5,706
CO2 GWP = 1
FM-200 GWP = 3500

The GWP Value by Itself Does Not Indicate the

Impact of an Agent on Global Warming

0.6

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

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

Impact of all GHG Emissions Impact of HFC Emissions from

except HFCs from Fire Fire Suppression, 0.01%
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
 Impact of HFC Emissions from Fire Suppression
Tg of CO2 Equivalents

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

Impact of all GHG Emissions Impact of HFC Emissions from

except HFCs from Fire Fire Suppression, 0.01%
Suppression, 99.99% HFCs
in fire suppression
applications have essentially no
affect on global warming/climate change

Impact of HFC emissions from fire suppression applications

on climate change represents 0.01% of the
total impact of all GHG emissions

30
 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?

 Impact of Emissions of HFCs from Fire Suppression
Applications on Climate Change: Historical
Tg of Carbon Dioxide Equivalents
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 0.01% 0.01% 0.01% 0.01% 0.01% 0.01%
applications
Source: Inventory of US GHG Emissions & Sinks: 1990-2010 (US EPA, 4/15/2012)

Emissions of HFCs in fire protection

are NOT rapidly increasing
32

mlr _1_2013
 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
Halon 1211 Replacements
Commercialized Agents

• PFC-5-1-14 PFC
• Halotron® I ODP≠ 0
• Saclon II
• NAF-P-IV ODP≠ 0
• AF11E ODP≠ 0
• HFC-236fa
HCFCs subject to Phaseout
under the Montreal Protocol
 Performance: UL Ratings
FE-36TM Halotron® I Saclon II Halon 1211
UL Rating kg kg NAF P-IV 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
Protection of the USA’s most critical
data related to national security Camp Williams, Utah
$1.5 billion
Completion in 2013
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,
 EMEA:
Some notable FM-200® projects
Mecca Railway
Dubai Metro
Burj Khalifa
Qatari Telecom
DOKAAE Project
du Telecom
Dubai Int’l Airport
FM-200®: Oil & Gas Industry Installations
Computer rooms, critical records, control rooms,
critical processes, telco equipment

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
 FE-36TM : Applications

Healthcare: MRI
Portable Extinguishers Crew & Engine

Floating Roof Tanks Aviation Lavex

Motorsports
 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