Low Global Warming Potential Alternatives for the Foam Sector

Helen Walter-Terrinoni

2

Program Status

• The role of hydrocarbons in foam

• Options for different market spaces

• Life Cycle Analysis

• DuPont™ Formacel® 1100

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The Role of Hydrocarbons (HCs) in FoamKey HCFC uses: • Rigid polyurethane (PU) &

polyisocyanurate (PIR) insulating foams• Extruded polystyrene (XPS) foam

~2/3 of solution in non-Article V countries: • Non-Spray foam • Medium and Large Enterprises• Lower energy efficiency requirements• No concerns about flammability

Some Key Exceptions: • Flammability concerns (like spray foam)• High energy efficiency requirements

(like domestic appliances) • Different countries have different

energy efficiency requirements• HFCs, HFOs, HFCOs or blends w

HCs improve foam thermal performance.

• Small Enterprises: Capital cost for safe use of HCs is prohibitive/not cost effective.

TEAP May 2013 Decision XXIV/7 Task Force Report (vo lume 2) –2013 Section 4.1 ODS Alternatives

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HCFC-141b Alternatives HCFC-141b:

+ Thermal Performance & Cost

- Environmental

� Single Solution for many applications

HFCs, HFOs, HCFOs:

+ Good Thermal Performance

+ Environmental

+ Low to Medium conversion cost

- Product cost higher than HCs

HCs, methyl formate, water (CO2), methylal:

- Thermal performance- Foam can have physical property challenge

+/- +GWP/ODP/-VOC

+ Lower product cost - Higher conversion cost

FEAs

Zero ODP GWP FlammabilityLambda @ 25 oC

(mW/mK)

Boiling Point

(oC)

Conversion Cost

HCFC-141b no 725 a No flashpoint 9.7 32 NA

HFC-245fa yes 1030 a No 12.7 15

Medium

(High vapor pressure)

HFC-365mfc-227 yes 794 a No 10.5 40 Low

Cyclopentane yes 11 b Yes 13

b 49 High (Flammability)

CO2/ water yes 1 No 16.3b -139 Low

Methylal yes <25g Yes 42 High (Flammability)

Methyl Formate yes <25g Yes 10.7

b 32 High (Flammability)

HCFO-1233zd nof

<7 f No 19

d

Low - Medium

(Potential high vapor

pressure)

AFA-L1 noe

<15 d No 9

d 15 - 30

d

Low - Medium

(Potential high vapor

pressure)

HFO-1336mzz-Z yes 8.9c No 10.7 33 Low

a: IPCC/TEAP (2005)

b: UNDP, Phaseout Technologies for PU Foams, June 2010;

c: NOAA(2010)

d: Proceedings of Polyurethanes 2012 Technical Conference

e: Indian Polyurethane Association, Alternative Blowing Agent Options for HCFC 141b , June 2010

f: Federal Register, Volume 77 Issue 155

g: Transitioning to Low-GWP Alternatives in Building Constructino Foams US EPA-430-F-11-005

Environmental & Safety Thermal performance & Cost

� Unlike HCFC-141b, No single solution for all applications

� How to decide?

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Overview of Alternatives to Ozone Depleting Substanc es for Various Sectors

TEAP May 2013 Decision XXIV/7 Task Force Report (vo lume 2) – 2013 Section 4.1 ODS Alternatives

http://ozone.unep.org/new_site/en/assessment_panels_bodies.php?committee_id=6

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Example of Detail for HCFC Replacement Options: Pro s and Cons

TEAP May 2013 Decision XXIV/7 Task Force Report (vo lume 2) – 2013 Section 4.2.2 Commercially available alternatives to Ozone Depleting Substances

http://ozone.unep.org/new_site/en/assessment_panels_bodies.php?committee_id=6

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For DuPont Use Only

Life Cycle Assessment – Green house Gas Burdens

Preliminary results

Greenhouse GasFrom Manufacture

GWP – Assumes all FEA released

Relative Greenhouse Gas Burden

0

500

1000

1500

2000

2500

3000

3500

FEA-1100 HFC-245fa cyclopentane HFC-134a

Cra

dle

& G

rave

Gre

enho

use

Gas

Foo

tprin

t

Usage/End-of-Life(100% FEA Emitted)Foam Expansion AgentProductionPolyurethaneProduction

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Greenhouse Gas from Energy Consumption

19500

20000

20500

21000

21500

22000

22500

23000

23500

FEA-1100 HFC-245fa cyclopentane HFC-134a

Cra

dle

& G

rave

GH

G F

ootp

rint

kg C

o2 e

quiv

alen

t uni

ts

For DuPont Use Only

Life Cycle Assessment – Greenhouse Gas from Energy

Preliminary results

Product Use: Greenhouse Gas from ENERGY Consumption

14 year life of refrigerator

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20 yr life Greenhouse Gas Burden and Emissions

0

5000

10000

15000

20000

25000

30000

35000

40000

FEA-1100 HFC-245fa cyclopentane HFC-134a

Cra

dle

to G

rave

GH

G F

ootp

rint

kg C

O2

equi

vale

nt u

nits CO2 from energy

consumptionUsage/End-of-Life (100%FEA Emitted)Foam Expansion AgentProductionPolyurethane Production

For DuPont Use Only

Preliminary results

Greenhouse GasFrom Manufacture

Product Use: Greenhouse Gas from ENERGY Consumption

GWP

Life Cycle Assessment – Greenhouse Gas – Complete Pic ture

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Key Needs

Chlorine High Less No No

ODP High Lower No NoDouble bond No No No Yes

GWP(100yr ith) High Less Less Low

Key Criteria for New FEAs

�Environmental Sustainability (ODP, GWP, VOC..)

�Safety (Toxicity, Flammability, Pressure..)

�Performance (Stability, Energy Efficiency, Foam Properties..)

�Cost Effective (Efficiency, Compatibility, Handling…)

HCFC-141b

(CCl2FCH3)

HFC-245fa

(CF3CH2CHF2)

CFC-11

(CFCl3)Formacel® 1100

(CF3CH=CHCF3)

11

CF3CH=CHCF3

Formacel® 1100 (HFO-1336mzz)

• ODP = 0

• GWP 100 yr ITH = 8.9 (NOAA)

• ATM lifetime = 22 days (NOAA)

• Nonflammable (ASTM E 681 at 60oC &

100oC)

• MIR of Formacel®1100 is 86% less than

ethane b.p = 33 oC

• λ= 10.7 mW/mK @ 25 oC

• AEL = 500 ppm 8hr / 12hr

Conversion Cost is Low:

Formacel ® 1100 does NOT require investment for:

• higher gauge tanks, piping or containers for transportation or storage

• changes in materials of construction

• Flammability or explosion proofing equipment

Ease of Conversion:

• Vapor Pressure Curve similar to other FEA ’s

• Non-Flammable ASTM E-681 (60C and 100C)

• Material and Ingredient Compatibility

• Metals, Elastomers, Plastics

• Other raw materials

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Formacel® 1100 vs Other Zero ODP Options

[1] Based on low MIR number[2] AEL is DuPont Allowable Exposure Limits (8-12 hr TWA)[3] HCFC-141b LFL - vol% in air and (kg/m3) at 23ºCf - ISO/DIS 817:2009 - Refrigerants -Designation and Safety Classification

Formacel® 1100 - the only zero ODP option that also provides low GWP, non-VOC, low

toxicity, non-flammability , low thermal conductivity and suitable boiling point .

Property HCFC-141b Formacel® 1100 HFC-245fa HFC-365mfc Cyclopentane Methyl Formate

ODP 0.12 0 0 0 0 0GWP(100yr ITH) 725 8.9 1030 794 11 <25VOC No No [1] No No Yes NoToxicity – OEL, TLV or AEL (ppm)

500 500 [2] 300 1000 600 100

Flammability LFL 9.0 (0.431) No No Yes Yes Yes

Lambda @ 25 oC (mW/mK)

9.7 10.7 12.7 10.5 13 10.7

Boiling Point (oC) 32 33 15 40 49 32

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Assessment of Formacel® 1100 (FEA-1100) Blowing Age nt in Rigid Polyurethane Insulating Foams for Domestic Appliance (Melissa Rose The Dow Chemical Company; Vanni Parenti, Rosella Riccio Dow Italia S.r.l.; Paulo Altoe’ Dow Brasil Sudeste Industrial)

Dow - DuPont Appliance Trial - Formacel® 1100 vs Cyclopentane (Cp)

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73 mole%

Cp

73 mole% Formacel

® 1100

40 mole%

Formacel® 1100

60:40 Formacel®

1100:Cp blend(39 mole% Formacel®

1100)

60:40 Formacel®

1100:Cp blend(29 mole% Formacel®

1100)

Relative k-factor vs Cp

k-factor (mW/mK) at 10 oC Control -9% -11% -13% -7%

Relative Formacel® 1100 Usage

Relative Formacel ® 1100 Control -45% -47% -61%

DuPont Lab Study - Formacel® 1100 – Cyclopentane (Cp) blends

Formacel® 1100 in blends w HCs or water can

provide improved insulation performance.

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Summary

• There is no single best solution for HCFC-141b replacement due to issues of

flammability, cost, energy efficiency needs

• Life cycle analysis can help to define lowest greenhouse gas impact

[1] Environmentally sustainable is based on zero ODP, low GWP, low MIR & POCP values

• Formacel® 1100 provides zero ODP and low GWP while maintaining desired

characteristics: non-VOC, suitable boiling point, low vapor thermal conductivity and

nonflammability

• Customer evaluations demonstrate that Formacel® 1100 is a viable foam expansion

agent for various type foams, improving performance compared to current options

• DuPont is committed to provide an environmentally sustainable [1] FEA with

significantly improved insulation performance and cost effectiveness to the foam

industry

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DISCLAIMER

The information set forth herein is furnished free of charge and based on technical data that

DuPont believes to be reliable. It is intended for use by persons having technical skill, at their own

risk. Since conditions of use are outside our control, we make no warranties, expressed or

implied and assume no liability in connection with any use of this information. Nothing herein is to

be taken as a license to operate under, or a recommendation to infringe any patents or patent

applications.

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Comparison of Formacel® 1100 at 40 mole% vs HCFC-141b at 73 mole%

Initial Foam Properties73 mole % HCFC-

141b

40 mole % Formacel ®

1100

Density (kg/m 3) 28.8 28.5

k-factor (mW/mK) at 24 oC 20.1 20.3

k-factor (mW/mK) at 10 oC 19.5 19.4

k-factor (mW/mK) at 1.7 oC 19.3 19.2

Relative k-factors k-factor at 24 oC Control 1.0%k-factor at 10 oC Control -0.2%

k-factor at 1.7 oC Control -0.4%

Relative FEA ChangesFEA (weight) Control -23%

• Reduced Formacel® 1100 usage by 23 wt%

• Equivalent k-factor performance at all temperatures

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Assessment of Formacel® 1100 (FEA-1100) Blowing Age nt in Rigid Polyurethane Insulating Foams for Domestic Appliance (Melissa Rose The Dow Chemical Company; Vanni Parenti, Rosella Riccio Dow Italia S.r.l.; Paulo Altoe’ Dow Brasil Sudeste Industrial)

Dow Lab Study - Formacel® 1100 blended w Cyclopentane (Cp)

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Comparison of k-factor Improvement from Customer Evaluations

• Formacel® 1100 showed improved k-factors in all 3 cases

• FEA level and B-side formulations affect the amount of improvement

*Reference: Proceedings of Utech Europe 2012

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Performance Demonstration from Customer Evaluations

• Drop-in performance for various applications

• Physical stability (up to 9 months)

• Chemical stability (up to 9 months)

• Insulation performance (initial & aged k-factors)

• Energy efficiency (appliance test)

• Other foam properties (dimensional stability, mechanical properties..)

• Use in blends to balance insulation performance & cost