45
z Enovate TM (HFC-245fa) Blowing Agent Solstice TM Liquid Blowing Agent Solstice TM Gaseous Blowing Agent Technical Update

Enovate (HFC-245fa) Blowing Agent Solstice Liquid Blowing ... · z Enovate TM (HFC-245fa) Blowing Agent Solstice TM Liquid Blowing Agent Solstice TM Gaseous Blowing Agent Technical

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Page 1: Enovate (HFC-245fa) Blowing Agent Solstice Liquid Blowing ... · z Enovate TM (HFC-245fa) Blowing Agent Solstice TM Liquid Blowing Agent Solstice TM Gaseous Blowing Agent Technical

z

EnovateTM (HFC-245fa) Blowing AgentSolsticeTM Liquid Blowing Agent

SolsticeTM Gaseous Blowing AgentTechnical Update

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Honeywell – a History of Innovation

HCFC

Phase-out

CFC

Phase-out

F-Gas Regulation

MONTREAL PROTOCOL EU LEGISLATION

KYOTO PROTOCOL

Innovating to enable industries’ compliance

CFCs OlefinsHCFCs HFCs

Ozone Depletingand Very High Global

Warming Potential

Non-Ozone Depleting but High Global Warming

Potential

Low-Global-Warming Potential and No Ozone

Depletion Effect

22

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Solstice Liquid Blowing Agent: 1233zd(E)

CC

HCl

• (E) 1-chloro-3,3,3-trifluoropropene

• (E) CHCl=CH-CF3

• Trans or E (entgegen) isomer

Physical Properties

Solstice LBA 141b Enovate

Mol. Wt. 130 117 134

Boiling Point, oC 19 32 15

Flame Limits, % by volume in air

None 7.6-17.7 None

Flash Point None None None

Environmental Properties

3

CF3H

Short Life = Ultra Low Environmental

Impact

Environmental Properties

Solstice LBA

141b Enovate

Atmospheric Life 26 days 9.3 yr 7.6 years

ODP ~0* 0.11 ~ 0*

GWP100 < 7 725 1030

VOC, USA reg No (est.) No No

Toxicity / OEL 300ppm** 500ppm 300ppm

*No impact on depletion of ozone layer and is commonly referred to as zero (0)

(Wuebbles , Private Communication)

** Internal HON OEL

Solstice LBA: Short Lifetime in Atmosphere � Ultra Low Environmental Impact

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Solstice Gas Blowing Agent: 1234ze(E)

CC

HCl

• (E) 1,3,3,3-trifluoropropene

• (E) CHF=CHCF3

• Trans or E (entgegen) isomer

Physical Properties

Solstice GBA 134a

Mol. Wt. 114.0 102.0

Boiling Point -19oC (-3oF) -26oC (-15oF)

Flame Limits None None

Flash Point None None

Environmental Properties

F

CF3H

Short Life = Ultra Low Environmental

Impact

Environmental Properties

Solstice GBA 134a

Atmospheric Life 14 days 7.6 years

ODP ~0* ~ 0*

GWP100 < 6 1030

VOC No (est.) No

Toxicity / OEL 1000ppm** 300ppm

*No impact on depletion of ozone layer and is commonly referred to as zero (0)

(Wuebbles , Private Communication)

** Internal HON OEL

Solstice GBA: Short Lifetime in Atmosphere � Ultra Low Environmental Impact

5

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Appliance Foam Evaluations

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Commercial Appliance Trial Results

�Trial run with major global OEM and major global systems house

– Commercially manufactured household refrigerator

– 32 complete units

– Conventional foam equipment, existing in the factory

• No modifications to the process or equipment

�Solstice LBA processed very similarly to Enovate (245fa)

– Comparable in all aspects to world scale processing parameters

6

– Comparable in all aspects to world scale processing parameters

– Foam density: nearly identical

– Minimum fill weights: nearly identical

– Demold time: equal / improved

– HIPS Liner compatibility excellent even after 2 years

Solstice LBA processes similar to Enovate in refrigerator/freezer applications

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Solstice LBA PUR Cabinet Lambda Data

7

Solstice LBA optimized: 8% improvement over Enovate baseline

EnovateEnovate EnovateEnovate

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DOE Energy Performance Assessment

• DOE Energy Test Method

• Sets of 5 refrigerators: Solstice LBA and Enovate Blowing Agent baseline

Enovate Enovate

8

Solstice LBA Refrigerators: DOE Standard minus 29.5% Energy RatingSolstice LBA Refrigerators: 4% system energy improvement over baseline Enovate

2%

29.5%

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23

Solstice LBA versus 141b

Foam performance of Solstice LBA

• Polyol miscibility equal to 141b, improved compared to Enovate Blowing Agent

• Similar strength properties to Enovate, improved compared to 141b at equal density

• Improved k-factor than Enovate foams

• Improved k-factor compared to c-pentane foams

8

10

% C

han

ge i

n E

nerg

y

141b

Lambda Performance Energy Performance

Solstice LBA foam

15

16

17

18

19

20

21

22

-20 -10 0 10 20 30 40 50

Enovate

c-Pentane

HCFC-141b

Solstice LBA

La

mb

da

, m

W/m

K

Mean Temperature, oC

Lambda and Energy Performance Superior to 141b, CP, and Enovate

Source: AHAM 3rd Gen BA study plus Hon data on Solstice LBA

13

-4

-2

0

2

4

6

8

Solstice LBA Enovate c-Pentane

% C

han

ge i

n E

nerg

y

Co

nsu

mp

tio

n v

s141b

Solstice LBA foam- 3% improved vs 141b- 4% improved vs 245fa- 12% improved vs cyclopentane

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Blowing Agents ComparisonEnovate Enovate

Blowing AgentSolstice LBA

Energy Efficiency

Lower Cost/Unit

Adoption Capital/ Ease

Co

st

eff

ecti

ve

Perf

orm

an

ce HydroHydro

CarbonsHCFCHCFC141b

In-Place λλλλ

(mW/mK @ 24°C)

• 141b 17

• c-pentane 20-21

• Enovate 18-

19

• Solstice 17-18

Flammability

Toxicity

En

vir

on

men

tC

ost

eff

ecti

ve

Safe

ty

Ozone Depletion Impact

Global Warming Impact(Direct)

Volatile Organics

* Specifics will vary by energy efficiency standards and type of refrigerator

Solstice LBA: application economics, most efficient & environmentally-superior

15

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Spray Foam Evaluations

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Spray Trial Formulation

ComponentsEnovate

phpSolstice LBA

php

Mannich polyether polyol 40.0 40.0

Aromatic polyester polyol 60.0 60.0

Silicone Surfactant 2.0 2.0

Amine catalysts 2.0 2.0

Solstice LBA used in existing generic industry formulation

Amine catalysts 2.0 2.0

Metal catalysts 4.1 4.1

Flame retardant 20.0 20.0

Water 2.0 2.0

Enovate Blowing Agent 20.0 -

Solstice LBA - Equal molar

Index 130 130

12

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Formulation Properties - Vapor Pressure

80

100

120

140

160

180

Pre

ssu

re, kp

a

Lower Vapor Pressure Means:

• Less potential for bulging drums

• Potential to use lower - 41%

- 31%

- 26%Enovate Blowing Agent

Solstice LBA

0

20

40

60

80

22 33 43 54

Pre

ssu

re, kp

a

Temperature, °C

Solstice LBA formulation has significantly lower vapour pressure at all temperatures

• Potential to use lower

gauge drums

• Less potential for blowing

agent loss from system

- 59%

13

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Formulation Properties - Stability

15

20

25

30

Solstice LBA Formulation Stability @ 54 °C

Enovate Blowing Agent

Solstice LBA

Gel T

ime, S

ec

Solstice LBA Formulation Stability @ 23C• Solstice LBA

formulation shows acceptable gel time variation at 54 °C

0

5

10

0 1 2 4Time @ 54 °C, Weeks

Gel T

ime, S

ec

Solstice LBA formulation has acceptable stability

• Solstice LBA formulation shows no gel time variation at RT

4 Weeks 8 Weeks

Time @ 23C

0 Weeks

14

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Lambda of Foam Sprayed @ 25°C Room Temperature

• Initial lambda• Solstice LBA 5 to 8%

lower than Enovate

• Aged lambda• Solstice LBA 4 to 8%

lower than Enovate

24

26

28

30

32

Lam

bd

a, m

W/m

K

Solstice LBA produces spray with improved lambda vs Enovate

16

18

20

22

4 24 33

Lam

bd

a, m

W

Mean Temperature , oC245fa Initial Solstice LBA Initial

245fa 28 Day Solstice LBA 28 Day

Initial Aged Initial Aged Initial Aged

15

Enovate Initial

Enovate 28 days

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Solstice LBS Versus 141b in Spray Foam

Initial Thermal Conductivity

19,0

19,2

19,4

19,6

19,8

20,0L

am

bd

a, m

W/m

K

Solstice LBA shows superior performance to 141b and Enovate Blowing Agent

18,0

18,2

18,4

18,6

18,8

19,0

141b 245fa Solstice LBA

Lam

bd

a, m

W/m

K

16

Enovate

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Panel Foam Evaluations

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Polyol Blend (B-side)

Components (php) Solstice LBA Enovate cyclopentane 141b

Polyether Polyol 65.0

Polyester Polyol 35.0

Catalyst 2.0

Chinese Generic Discontinuous Panel Formulations

Surfactant 1.5

Flame Retardant 22.0

Water 2.0

Blowing Agent 23.3 24.0 12.5 21.0

Isocyanate (A-side)

PMDI 143.6

A Blowing Agent “Drop-in” Replacement Study was Conducted

18

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Cold (-29oC), 28 days

Hot (90oC), 28 days

Hot/Humid (70oC/95%RH), 28 days

Dimensional Stability

Comparison of Physical Properties

Parallel Perpendicular

Comparable Properties to Enovate, Better Properties than Cyclopentane

Compressive StrengthSolstice LBA

Cyclopentane

141b

Enovate

19

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Initial Thermal Conductivity

0,15

0,16

0,17

0,18

Th

erm

al C

on

du

cti

vit

y/f

t2.h

.oF

)

Th

erm

al C

on

du

ctiv

ity(m

W/

21.6

23.1

24.5

26.0

Cold Chain Applications 4%

8%

Cyclopentane

0,11

0,12

0,13

0,14

20 40 60 80 100 120

Temperature (°F)

Th

erm

al C

on

du

cti

vit

y(B

tu.i

n/f

t

Th

erm

al C

on

du

ctiv

ity/m

K)

15.9

17.3

18.7

20.2

oF oF-6.7 oC 4.4 oC 15.6 oC 26.7 oC 37.8 oC 48.9 oC

Temperature

Best Thermal Insulation Performance for Cold Chain Applications

oF oF oF oF

Enovate

Solstice LBA

Cyclopentane

141b

20

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28 Day Aged Thermal Conductivity

0,15

0,16

0,17

0,18

Th

erm

al C

on

du

cti

vit

y/f

t2.h

.oF

)

Th

erm

al C

on

du

ctiv

ity(m

W/

21.6

23.1

24.5

26.0

6%

10%

21%

Enovate

Cyclopentane

141b6%

0,11

0,12

0,13

0,14

20 40 60 80 100 120

Temperature (°F)

Th

erm

al C

on

du

cti

vit

y(B

tu.i

n/f

t

Th

erm

al C

on

du

ctiv

ity/m

K)

15.9

17.3

18.7

20.2

oF oF-6.7 oC 4.4 oC 15.6 oC 26.7 oC 37.8 oC 48.9 oC

Temperature

Cold Chain Applications

oF oF oF oF

Best Thermal Insulation Retention at All Evaluated Temperatures

Enovate

Solstice LBA

6%

21

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Solstice LBA in Panel Foam

Initial Thermal Conductivity Vs Temperature

18

20

22

La

mb

da

, m

W/m

K

HBA-2 shows superior performance to 141b and Enovate

12

14

16

13 24Mean Temperature, oC

141b Enovate Solstice LBA

La

mb

da

,

22

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Solstice LBA / Cyclopentane Blends

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Comparison of Physical Properties

Cold (-29oC), 28 days

Hot (90oC), 28 days

Hot/Humid (70oC/95%RH), 28 days

Dimensional Stability

Solstice GBA/C-C5 Blend: Balanced Solution for Cost and Physical Properties

Parallel Perpendicular

Compressive Strength

100/075/25

0/10050/50

Solstice LBA/Cyclopentane Mol. Ratio

24

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Solstice LBA/Cyclopentane Blends

Initial Thermal Conductivity

0,15

0,16

0,17

0,18

Th

erm

al C

on

du

cti

vit

yB

tu.i

n/f

t2.h

.oF

)

Th

erm

al C

on

du

ctiv

ity(m

W/

21.6

23.1

24.5

26.0

Cold Chain Applications

0/100Mol. Ratio

0,11

0,12

0,13

0,14

20 40 60 80 100 120

Temperature (°F)

Th

erm

al C

on

du

cti

vit

y(B

tu.i

n

Th

erm

al C

on

du

ctiv

ity/m

K)

15.9

17.3

18.7

20.2

oF oF-6.7 oC 4.4 oC 15.6 oC 26.7 oC 37.8 oC 48.9 oC

Temperature

Solstice LBA/Cyclopentane Blend: Balanced Solution of Cost and k-factors

oF oF oF oF

100/0

0/100

75/2550/5025/75

25

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28 Day Aged Thermal Conductivity

0,15

0,16

0,17

0,18

Th

erm

al C

on

du

cti

vit

yB

tu.i

n/f

t2.h

.oF

)

Th

erm

al C

on

du

ctiv

ity(m

W/

21.6

23.1

24.5

26.0

0/100

50/50

25/75

75/25

Solstice LBA/Cyclopentane Blends

0,11

0,12

0,13

0,14

20 40 60 80 100 120

Temperature (°F)

Th

erm

al C

on

du

cti

vit

y(B

tu.i

n

Th

erm

al C

on

du

ctiv

ity/m

K)

15.9

17.3

18.7

20.2

oF oF-6.7 oC 4.4 oC 15.6 oC 26.7 oC 37.8 oC 48.9 oC

Temperature

Addition of Solstice LBA Enhanced Thermal Insulation Retention

Cold Chain Applications

oF oF oF oF

100/0

50/5075/25

Mol. Ratio

26

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Foam Flammability Evaluations

DIN 4102-1:Class B2

15

20

Fla

me

He

igh

t, c

m

Fail

Solstice LBA: Enhanced Foam Fire Retardancy

0

5

10

100/0 75/25 50/50 25/75 0/100

Fla

me

He

igh

t, c

m

Pass

Solstice LBA/Cyclopentane Blend, Mol. Ratio

37

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Gas Blowing Agent EvaluationsSolstice GBA in Panel Applications

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Comparison of Physical Properties

Cold (-29oC), 28 days

Hot (90oC), 28 days

Hot/Humid (70oC/95%RH), 28 days

Dimensional Stability

Compressive Strength

Solstice GBA

FlexuralStrength

Solstice GBA: Similar Physical Properties to 134a in Commercial Formulation

134a

29

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0,15

0,16

0,17

0,18

Initial Thermal ConductivityT

herm

al C

on

du

cti

vit

yB

tu.i

n/f

t2.h

.oF

)

Th

erm

al C

on

du

ctiv

ity(m

W/

21.6

23.1

24.5

26.0

5%

134a

Solstice GBA

0,11

0,12

0,13

0,14

20 30 40 50 60 70 80

Temperature (°F)

Th

erm

al C

on

du

cti

vit

y(B

tu.i

n

Th

erm

al C

on

du

ctiv

ity/m

K)

15.9

17.3

18.7

20.2

oF oF

-6.7 oC -1.1 oC 10.0 oC

Solstice GBA: 4% - 5% Better Thermal Insulation Value

oF oF oF oF oF

4.4 oC 15.6 oC 21.1 oC 26.6 oC

Temperature

4%

41

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Toxicity / Registration / Commercialization Status

Solstice LBA

• Toxicity – nearly complete

• Global Registrations– U.S.: SNAP / PMN applications filed

with U.S. EPA � under review

– EU: REACH registration in-process

• Current REACH registration to 10 tonnes

– Japan: Registration complete

Solstice GBA

• Toxicity – Complete

• Global Registrations• U.S.: SNAP / PMN approvals complete –

commercial sales can commence

• EU: REACH registration process underway

– Current REACH registration to 10 tonnes– Japan: Registration complete �commercial sales can commence

• Japan Chemical Substances Control

Law

– ROW Registrations to meet regional commercialization needs

• Solstice LBA registration complete:

Mexico and India

• Commercialization– Semi-commercial – late 2012

– Commercial - 2013

– Current REACH registration to 10 tonnes

• Japan: Registration complete �commercial sales can commence

– Japan Chemical Substances Control Law

• ROW Registrations to meet regional commercialization needs

– Solstice LBA registration complete: Mexico

and India

• Commercialization– Semi-commercial - NOW

– Commercial - 2013Low environmental impact solutions will meet regulatory needs timing

31

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Conclusions

• In foams, both molecules perform better than third generation benchmarks

• Solstice GBA

• 5% better thermal conductivity than 134a

• Comparable physical properties

• A environmentally sustainable and safe product

• Low GWP: Solstice GBA is < 6; Solstice LBA is < 7

• Both are not flammable

• Comparable physical properties

• Solstice LBA

• Lowest thermal conductivity and best thermal insulation retention

• Comparable dimensional stability to Enovate and better than cyclopentane

• Solstice LBA/Cyclopentane Blend

• A solution for formulation flexibility, but the blowing agent blend is most likely flammable

• Commercialization Status

• Solstice GBA is commercialized, Solstice LBA will be commercialized in late 2012

Solstice LBA or GBA: The Best Choices for Panel Foams

43

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z

Enovate™ blowing agent HFC-245fa blending solutions

Shanghai Lab

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Technical development background

• China updated energy efficiency standards,

– China appliance OEMs to face technical limits with CP system

• 245fa/CP technology is becoming a major solution for China appliance industry

• 245fa/CP technology provides an optimal combination of performance and cost

• Honeywell is the leader in 245fa/CP blend development and has IP for 245fa/CP applicationapplication

• Honeywell has comprehensive technology solution for 245fa/CP application

- Strong development capability

- Good relationship with system house and equipment supplier

- Offers refrigerator OEMs with tailor made solution for 245fa/CP blend technology

- Offers excellent service

Honeywell is the leadership for 245fa application

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Boiling point of 245fa/CP blend

• 245fa/CP is an Azeotrope-like Blend

Blowing agent (wt%)

Boiling point at 745mmHg (°C)

245fa CP

100 0 14.6

Lower boiling point, better flowability

100 0 14.6

95~40 5~60 11.7±1

0 100 49

• The Boiling Point of Blend is Lower than 245fa and CP

* Honeywell Patent US 5,677,358

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Thermal conductivity of 245fa/CP blown foam

1.10

1.15

1.20

Relative K-factor

7 days. Foam Density ~ 32kg/m3

-fa

cto

r Solo

245fa

blown

245fa/CP

blend

blown

0.95

1.00

1.05

100 90 75 50 40 30 25 20 10

Re

lative

K-

0 25 50 60 75 90

% 245fa in blowing agent blend

% CP in blowing agent blend

10 70 80

Better K-factor as 245fa Levels Increase

* Honeywell Patent US 5,677,358

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Dimensional stability of 245fa/CP co-blown foam

0.4

0.6

0.8

1

Dimensional stability, -20°C after 22 days. Foam Density ~ 2.0lb/ft3 (32kg/m3)V

olu

me

Ch

an

ge

, %

Better Dimension Stability as 245fa Portion Increases

-0.2

0

0.2

0.4

100 50 30 25 20 10

Vo

lum

e C

ha

ng

e,

%

0 50 70 75 80 90

% 245fa in blowing agent blend

% CP in blowing agent blend

* Honeywell Patent US 5,677,358

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245fa in Spray Applications

• Major challenges in 141b phase-out

• Cost sensitive segment (Construction)

• HC and HFC 365mfc will not be an option due to safety concerns

• Water: poor thermal insulation and adhesion

• Blowing agent comparison:

++-++-price

-++++adhesion

++-+++handling

--++++Foam cell

++

-

+

365mfc

++-++ODP

-++++insulation

++

245fa

++

HCFC-141b

++

Water

Flammable

• Blowing agent comparison:

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Spray system development

Wall system Roof system

Test Item Unit Standard Requirement 245fa foam Requirement 245fa foam

Density kg/m3 GB/T 6343 ≥35.0 37.0 ≥55.0 55.5

Thermal conductivity W/m·k GB 3399 ≤0.024 0.0208 ≤0.024 0.022

Compressive strength kPa GB/T 8813 ≥150 240 ≥300 340

Dimensional stability•-30℃•48h•

% GB/T 8811 ≤1 0.8 ≤1 ≤1

Flammability cm GB/T 8624 ≤15 12 ≤15 13

Dimensional stability

•70℃•48h•% GB/T 8811 ≤5 3.7 ≤5 3.7

Closed cell content % GB/T 10799 ≥90 93 ≥90 95

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HFC 245fa advantages in spray application

- Quicker rise

- Larger application window

- Lower operating temperature

- Less shrinkage - reversion

- Easily applies on cold surfaces

- Equivalent or better yield

- Drums used for 141b systems can be used for

systems with ~10% of 245fa

- Minimal 245fa loss during blending- Confirmed by calculation and experimentation

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245fa in Panel Applications

• Some continuous panel manufacturers switching to HC and water from 141b

• Almost all discontinuous panel manufacturers are using 141b

• Major challenges in 141b phase-out

• Water: poor thermal insulation and adhesion

• HC: high capital investment; safety

•Blowing agent comparison:

• HC: high capital investment; safety

245fa HCFC-141b 365mfc Cyclopentane

insulation ++ ++ + +

flowability ++ ++ + +

Demouldability ++ + + +

Polyol compatibility ++ ++ + -

Foam cell ++ ++ - -

Flammability ++ ++ - -

Handling + ++ - -

Adhesion ++ + + -

Price - ++ - ++

++ best + average - worst

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Panel application

HCFC-141b 245fa/HCFC-141b 245fa

A 100 100 100

B 92 92 92

CT 22 17 27

GT 67 66 73

TFT 105 105 115

FRD 26.7 25.3 27.5

filling W 500 452 437 420 454filling W 500 452 437 420 454

CD 42.2 42.6 40.8 42.8 44.8

K factor 21.69 21.52 21.45

Compressive strength122 143 124 202 194

161 186 164 244 290

Demoudability

30 min 10.5 9.9

NA

3.13

NA

33min 12.1 11.76 4.51

36min 12.43 11.57 4.46

39min 12.16 11.25 4.32

42min 11.95 10.96 4.18

Dimensional stability

-30 • -0.90% -1.11% -1.47% -1.17%

70 • 1.39% 1.30% 1.63% 0.17%

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Transitioning from Blowing Agent 141b

Cyclo-pentane

Performance

Cost-effective

Environment

Safety

Performance

Cost-effective

• May not meet emerging energy standards and may require a 2nd transition to 245fa or Solstice LBA

Current: Transition to: Assessment Future Impact

• Solution available today

• Will meet energy efficiency

Today

141b

Cost-effective

Environment

Safety

Performance

Cost-effective

Environment

Safety

245fa &

Blends

Solstice

LBA&

Blends

245fa and LBA & Blends: Low Capital and Cost Transitions

• Will meet energy efficiency standards

• Can transition to HBA2 in future to meet GWP standards

• Most energy efficient blowing agent with very low GWP (7) puts you in the best position now and in the future

2013+

Today

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Transitioning from Cyclopentane

245fa &

Blends

Performance

Cost-effective

Environment

Safety

Current: Transition to:

• While better positioned to meet new energy standards, GWP may be an issue down the road

Assessment Future Impact

Today

Cyclo-pentane

Solstice LBA & Blends

Performance

Cost-effective

Environment

Safety

• Most energy efficient blowing agent with very low GWP (7) puts you in the best position now and in the future

245fa and LBA & Blends Offer Better Solutions Than Cyclopentane

2013+

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responsibility of carrying out its own tests and experiments, and the user assumes all risks and liability for use of the information

and results obtained. Statements or suggestions concerning the use of materials and processes are made without representation

or warranty that any such use is free of patent infringement and are not recommendations to infringe on any patents. The user

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