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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!
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