Hydrofluoro-olefinsLow-GWP Refrigerants

A Primer on HFOs

January 30, 20112011 ASHRAE Winter ConferenceLas Vegas, NV

Brett Van Horn, PhDArkema Inc.

ASHRAE is a Registered Provider with The American Institute of Architects Continuing Education Systems. Credit earned on completion of this program will be reported to ASHRAE Records for AIA members. Certificates of Completion for non-AIA members are available on request.

This program is registered with the AIA/ASHRAE for continuing professional education. As such, it does not include content that may be deemed or construed to be an approval or endorsement by the AIA of any material of construction or any method or manner of handling, using, distributing, or dealing in any material or product. Questions related to specific materials, methods, and services will be addressed at the conclusion of this presentation.

• Describe the climate change issue and associated with high GWP refrigerants and the leading low GWP options available

• Explain the refrigerant thermophysical property requirements needed for new low GWP refrigerants and how property data may be used

• Be able to explain the challenges with measuring the flammability properties of refrigerants that are only marginally flammable and options to make these measurements

• Explain the development history of hydrofluoro-olefin low GWP refrigerants such as HFO-1234yf

• Describe the codes and regulations in the US, Europe and Japan that govern the use of low GWP refrigerants such as CO2, ammonia, hydrocarbons and HFOs and the barriers in current standards for their potential use

• Apply learnings from this seminar to begin selecting low GWP refrigerants for specific applications and begin designing new HVAC&R systems with these refrigerants

Learning Objectives for this Session

SafetyFlammability

Toxicity

EnvironmentalSustainabilityODP, GWP, LCCP

PerformanceEfficiencyCapacity

SupplyCost, Availability

NASA-GSFC, 2002

Drivers for Refrigerant Selection

Refrigerant Timeline

1748: William Cullen: mechanical refrigeration1805: Oliver Evans : concepts of mechanical refrigeration1824: Nicolas Léonard Sadi Carnot: Carnot Cycle 1834: Jacob Perkins: refrigerating device1844: John Gorrie: first “practical” refrigerator 1857: James Harrison: refrigerator

Feasibility

U.S. Patent 8,080

Ethyl EtherNH3CO2

CH3ClSO2CCl4Etc.

1930 20101950 19901970

Refrigerant Timeline

FeasibilityFeasibilityFeasibility Safety & Efficiency

Ethyl EtherNH3CO2

CH3ClSO2CCl4Etc.

CFCsCFCsHCFCsHCFCs

1930 20101950 19901970

1928: Midgley, Henne, McNary (GM): CFC refrigerants1931: R-121932: R-111933: R-1141934: R-1131936: R-22

Refrigerant Timeline

FeasibilityFeasibilityFeasibility Safety & EfficiencySafety & EfficiencySafety & Efficiency Ozone Protection

Ethyl EtherNH3CO2

CH3ClSO2CCl4Etc.

CFCsCFCsHCFCsHCFCs

1930 20101950 19901970

1985: Vienna Convention1987: Montreal Protocol1996: CFC phase-out

HFCsHFCs

NASA-GSFC, 2002

Refrigerant Timeline

FeasibilityFeasibilityFeasibility Safety & EfficiencySafety & EfficiencySafety & Efficiency Ozone ProtectionOzone ProtectionOzone Protection Climate Change

Next Generation: HFO RefrigerantsCan offer balance among:

Environmental profileSafety and DurabilityPerformance

Ethyl EtherNH3CO2

CH3ClSO2CCl4Etc.

CFCsCFCsHCFCsHCFCs HFOsHFOs

1930 20101950 19901970

HFCsHFCs

HFO: Nomenclature

HFO – 1 2 3 4 y f

# of fluorine atoms# of hydrogen atoms + 1

# of carbon atoms - 1 # of unsaturated bonds Substitution on central carbon:

x: -Cl, y: -F, z: -H

Substitution on terminal methylene carbon:a: =CCl2c: =CF2e: =CHF

Hydro-Fluoro-Olefin

Propene Series

2,3,3,3-tetrafluoroprop-1-ene

b: =CClFd: =CHClf: =CH2

Toxicity

Flammability

Tb = -29°CTb = -19°CTb = -29°CTb = -22°CTb = -48°C

R-1216R-1234ze(E)R-1234yfR-1243zfR-1270

nc AAncA

1*#F = 6

2L#F = 4

2L#F = 4

2*#F = 3

3#F = 0

Toxicity

Flammability

Tb = -29°CTb = -19°CTb = -29°CTb = -22°CTb = -48°C

R-1216R-1234ze(E)R-1234yfR-1243zfR-1270

nc AAncA

1*#F = 6

2L#F = 4

2L#F = 4

2*#F = 3

3#F = 0

^

^

Propylene Series: examples

*: estimated. ^: as submitted to ASHRAE. nc: not classified by ASHRAE

Refrigerant Timeline: Introduction of Propenes

Ethyl EtherNH3CO2

CH3ClSO2CCl4Etc.

CFCsCFCsHCFCsHCFCs HFOsHFOs

1930 20101950 19901970

HFCsHFCs

Refrigerant Timeline: Introduction of Propenes

R-1270

Ethyl EtherNH3CO2

CH3ClSO2CCl4Etc.

CFCsCFCsHCFCsHCFCs HFOsHFOs

1930 20101950 19901970

HFCsHFCs

Refrigerant Timeline: Introduction of Propenes

R-1270

Ethyl EtherNH3CO2

CH3ClSO2CCl4Etc.

CFCsCFCsHCFCsHCFCs

HFCsHFCsHFOsHFOs

1930 20101950 19901970

R-1243zf

Refrigerant Timeline: Introduction of Propenes

R-1270 Fluoropropenes (1243zf, 1234yf, 1234ze, 1216 . . .)

Ethyl EtherNH3CO2

CH3ClSO2CCl4Etc.

CFCsCFCsHCFCsHCFCs

HFCsHFCsHFOsHFOs

1930 20101950 19901970

R-1216R-1243zf

Refrigerant Timeline: Introduction of Propenes

R-1270 R-1234yf

Ethyl EtherNH3CO2

CH3ClSO2CCl4Etc.

CFCsCFCsHCFCsHCFCs

HFCsHFCsHFOsHFOs

1930 20101950 19901970

R-1216R-1243zf

Fluoropropenes (1243zf, 1234yf, 1234ze, 1216 . . .)

Refrigerant Selection

Many factors are important for selecting arefrigerant for any particular application

The approach is to find the best balancebetween refrigerant properties, system

architecture, and application environment.Advances in refrigeration technology can affect refrigerant selection.

EnvironmentalOzone DepletionGlobal Warming

SafetyFlammability

Toxicity, Pressure

ThermodynamicsBoiling Point, Critical Point

P-H, T-S , . . .

DurabilityStability

Material Compatibility

Physical PropertiesDensity, Thermal Conductivity,

Pressure, Viscosity, . . .

PerformanceEfficiency, Capacity

Flow Rate, Pressure Ratio,…

RefrigerantSelection

Refrigerant Volumetric Capacities (CAP)

1

10

100

1000

0.01 0.1 1 10

Evaporator Pressure (bar)

Rel

ativ

e V

olum

etric

Cap

acity

(%)

R-123

R-11

R-365mfc

R-113

R-22

R-152a

R-245fa

R-32R-410A

R-125

R-12

R-134a

R-404A

Water

R-114

R-290

R-600a

1

10

100

1000

0.01 0.1 1 10

Evaporator Pressure (bar)

Rel

ativ

e V

olum

etric

Cap

acity

(%)

R-123

R-11

R-365mfc

R-113

R-22

R-152a

R-245fa

R-32R-410A

R-125

R-12

R-134a

R-404A

Water

R-114

R-290

R-600a

1

10

100

1000

0.01 0.1 1 10

Evaporator Pressure (bar)

Rel

ativ

e V

olum

etric

Cap

acity

(%)

R-123

R-11

R-365mfc

R-113

R-22

R-152a

R-245fa

R-32R-410A

R-125

R-12

R-134a

R-404A

Water

R-114

R-290

R-600a

1

10

100

1000

0.01 0.1 1 10

Evaporator Pressure (bar)

Rel

ativ

e V

olum

etric

Cap

acity

(%)

R-123

R-11

R-365mfc

R-113

R-22

R-152a

R-245fa

R-32R-410A

R-125

R-12

R-134a

R-404A

Water

R-114

R-290

R-600a

Refrigerant Volumetric Capacities (CAP)

R-1234yf is a close match to R-134a

R-1234yf

R-1234ze

R-1243zf

R-1234yf R-134a

CF3-CF=CH2 Formula CF3-CFH2

0 ODP 0 4 GWP 1430

11 days Atm. Lifetime 13.8 years

114 mw (g/mol) 102 -29 Bp (°C) -26 95 Tc (°C) 102

A Toxicity A

2 L Flammability 1 6.5% / 12.3% LFL/UFL (v/v) none

R-1234yf – Properties SummaryLow Toxicity

Low Flammability

Performance similar to R-134aPure component, no glide

Similar coefficient of performance and capacity

Good thermal stability and material compatibility

Atmospheric chemistry is publishedSame breakdown products as R-134a

No high-GWP breakdown products

LCCP R-1234yf < LCCP R-134a

R-290

R-152a

R-1234yfR-32, NH3

BV ≤ 10cm/s

BV > 10cm/s

R-134a

0

18

0.1

1

10

100

1000

0

18

0

50

0

50

10

0

0.35

ΔFL(v%)(v%)

HoC (MJ/kg)

BV(cm/s)

MIE(mJ)

mor

e fla

mm

able

(kg/m3)LFL

0

18

0.1

1

10

100

1000

0

18

0

50

0

50

10

0

0.35

ΔFL(v%)(v%)

HoC (MJ/kg)

BV(cm/s)

MIE(mJ)

mor

e fla

mm

able

(kg/m3)LFL

R-1234yf – FlammabilityClass

1

2L

3

2

R-1234yfLow Flammable Range

High LFLNarrow flammable window

Difficult to igniteHigh Min. Ignition Energy

Low impact of ignitionLow Burning VelocityLow Heat of Combustion

LFL > 0.1 kg/m3and

HOC < 19 MJ/kg

LFL ≤ 0.1 kg/m3or

HOC ≥ 19 MJ/kg

No flamepropagation

Blend R-1234yf with other refrigerants to reduce the GWP and adjust refrigerant properties for market segments

Tailor blend compositions for target applications & system architectures

HVAC / RPerspective on HFO Blends

10

100

1000

1.0 10.0

R-134a

R-410A R-32

R-404A

R-22R-407C

HFO-1234yf

Evaporator Pressure (bar)

Rel

ativ

e V

olum

etric

Cap

acity

(%)

R-152aR-12

10

100

1000

1.0 10.0

R-134a

R-410A R-32

R-404A

R-22R-407C

HFO-1234yf

Evaporator Pressure (bar)

Rel

ativ

e V

olum

etric

Cap

acity

(%)

R-152aR-12

Refrigerant Blends: Volumetric Capacities

Refrigerant Blends: Volumetric Capacities

10

100

1000

1.0 10.0

R-134a

R-410A R-32

R-404A

R-22R-407C

HFO-1234yf

Evaporator Pressure (bar)

Rel

ativ

e V

olum

etric

Cap

acity

(%)

R-152aR-12

10

100

1000

1.0 10.0

R-134a

R-410A R-32

R-404A

R-22R-407C

HFO-1234yf

Evaporator Pressure (bar)

Rel

ativ

e V

olum

etric

Cap

acity

(%)

R-152aR-12

ARM01ARM02ARM03

ARM04ARM05

ARM06

ARM BlendsGWP < 1000

Refrigerant Blends: Conclusions

Refrigerant Properties

&

Refrigeration Technology

Environmental

Safety

Thermodynamics

Durability

Physical Properties

Performance

RefrigerantSelection

HFO-based blends allow for the development of reduced GWP solutions for various market segments of HVAC & Refrigeration

Blend compositions are adapted for applications & systems architectures

New technical challenges are ahead in the coming decades

Other considerations for refrigerant blendsSafety classification, glide, application range, performance, . . .

HVAC & R

Applications

Performance – Environmental Impact

Thank you!