Low Global Warming Potential Alternatives for the Foam Sector Helen Walter-Terrinoni.pdf · Helen...
Transcript of Low Global Warming Potential Alternatives for the Foam Sector Helen Walter-Terrinoni.pdf · Helen...
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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)
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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