1. Zero-ODP, Low GWP
Non-Flammable
Working Fluids for
High Temperature Heat Pumps
June 7th, 2013
Kostas Kontomaris, Ph.D.
DuPont Fluorochemicals R&D
HFO-Based
Increasing Energy prices
Climate Protection
CSG
Latest Technology in Refrigeration and Air Conditioning
XV EUROPEAN CONFERENCE, MILANO 7th-8th JUNE 2013
“Big energy savings have been achieved
by seemingly minor technological changes
such as moving from gas boilers
for space heating to heat pumps.”
Financial Times, June 4th, 2013

2. Heat Uplifting:
Mechanical Compression Heat Pumps
Evaporator
Condenser
Expansion
Valve
Compressor  Power
Low Temp Heat
T<100-120 oC
Waste Heat
Geothermal Heat
Solar Heat
High Temp Heat
T: 80-160 oC
Reverse
Rankine
Cycle
May not be of adequate quality for
direct heating or mechanical power generation

3. Hydro-Fluoro-Olefins
CFCs  HCFCs  HFCs  HFOs
CFC-12 HFC-134a DR-14
CFC-114 HFC-245fa DR-12
CFC-11 HCFC-123 DR-2
Less Chlorine No Chlorine Double Bond
Conventional Wisdom:
Unsaturated fluorocarbons are
not sufficiently stable to be
used as refrigerants!
Paradigm Shift:
Unsaturated fluorocarbon refrigerants
decompose rapidly in the atmosphere
but can remain stable in a system!

4. Developmental Refrigerant: DR-14
HFC-134a DR-14
Chemical Formula CH2FCF3 Azeotrope
Flam Class
(ASHRAE Std 34)
1 1(*)
ODP None None
GWP100 1,430 ~375
Tcr [oC] 101.1 111.6
Pcr [MPa] 4.06 3.96
Tb [oC] -26.1 -20.5
Glide [oC] N/A Negligible
(*) Expected

5. Developmental Refrigerant: DR-12
(*) Expected
HFC-245fa DR-12
Flam Class
(ASHRAE Std 34)
1 1(*)
ALT [yrs] 7.6 0.24 (~90 Days)
ODP none none
GWP100
1,030 32
Tb [oC] 15.1 <10
Tcr [oC] 154 137.7
Pcr [MPa] 3.65 ~3.0
Very Low GWP AND Non-Flammable

6. Developmental Refrigerant: DR-2
(*) Expected
HFC-245fa DR-2
Flam Class
(ASHRAE Std 34)
1 1(*)
ALT [yrs] 7.6 0.0658 (24 days)
ODP none None
GWP100
1,030 9
Tb [oC] 15.1 33.4
Tcr [oC] 154 171.3
Pcr [MPa] 3.65 2.9
Very Low GWP AND Non-Flammable

7. DR-14, DR-12, DR-2 Components:
Stable At Least Up to 250 oC
Even After 2 Wks @ 250 oC:
Clear Fluid, Clean Coupons
Negligible formation of decomposition products
Sealed tube
testing
based on
ASHRAE-ANSI
STD 97
IN SUMMARY(*):
High Thermal Stability
Attractive Safety, Health and Environmental Properties
Range of Favorable Thermodynamics vs Incumbents:
Higher Critical Temperatures, Lower Vapor Pressures
(*) Based on testing to date

8. 0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
4.50
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190
VaporPressure,MPa
Temperature, oC
Vapor Pressure
HFC-134a DR-14
DR-12
HFC-
245fa
DR-2
HFC-134a DR-14 DR-12 HFC-245fa DR-2
Tcr, oC 101.1 111.6 137.7 154.0 171.3

9. 0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
4.50
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190
VaporPressure,MPa
Temperature, oC
HFC-134a DR-14
DR-12
HFC-
245fa
DR-2
Maximum Condensing Temperature
HFC-134a DR-14 DR-12 HFC-245fa DR-2
T2.5, oC 77.5 87.8 125.4 133.5 162.8

10. 4.50
5.00
5.50
6.00
6.50
7.00
50 60 70 80 90 100 110 120 130 140 150 160 170 180
COPh
Condenser Temperature, oC
Predicted Heating Performance: COPh
DTLIFT= 40 oC
HFC-134a
DR-14
DR-12 HFC-
245fa
DR-2
DTsuperh, oC 11
DTsubc, oC 5
EFFcompr 0.8
ATTRACTIVE COPh
UNDER ALL FEASIBLE CONDITIONS
DR-2: Highest COPh

11. 0
1,000
2,000
3,000
4,000
5,000
6,000
7,000
8,000
9,000
50 60 70 80 90 100 110 120 130 140 150 160 170 180
VolumetricHeating
Capacity,kJ/m3
Condenser Temperature, oC
HFC-134a
DR-14
DR-12
HFC-
245fa
DR-2
DTsuperh, oC 11
DTsubc, oC 5
EFFcompr 0.8
Predicted Heating Performance: CAPh
(*)
DTLIFT= 40 oC
DR-14: Highest CAPh Among Low GWP Fluids)

12. 2.50
3.00
3.50
50 60 70 80 90 100 110 120 130 140 150 160 170 180
COPh
Condenser Temperature, oC
HFC-134a
DR-14
DR-12 HFC-
245fa
DR-2
DTsuperh, oC 20
DTsubc, oC 5
EFFcompr 0.8
Predicted Heating Performance: COPh
DTLIFT= 70 oC
COPh: Decreases with Increasing Lift But …

13. 2.50
3.00
3.50
50 60 70 80 90 100 110 120 130 140 150 160 170 180
COPh
Condenser Temperature, oC
HFC-134a
DR-14
DR-12 HFC-
245fa
DR-2
DTsuperh, oC 20
DTsubc, oC 5
EFFcompr 0.8
Predicted Heating Performance: COPh
DTLIFT= 70 oC
COPh: Still Attractive Under Broad Conditions

14. 0
500
1,000
1,500
2,000
2,500
3,000
3,500
4,000
4,500
50 60 70 80 90 100 110 120 130 140 150 160 170 180
VolumetricHeatingCapacity
kJ/m3
Condenser Temperature, oC
DTsuperh, oC 20
DTsubc, oC 5
EFFcompr 0.8
HFC-134a
DR-14
DR-12
HFC-
245fa
DR-2
Predicted Heating Performance: CAPh
DTLIFT= 70 oC
CAPh: Decreasing with Increasing Lift But …

15. 0
500
1,000
1,500
2,000
2,500
3,000
3,500
4,000
4,500
50 60 70 80 90 100 110 120 130 140 150 160 170 180
VolumetricHeatingCapacity
kJ/m3
Condenser Temperature, oC
DTsuperh, oC 20
DTsubc, oC 5
EFFcompr 0.8
HFC-134a
DR-14
DR-12
HFC-
245fa
DR-2
Predicted Heating Performance: CAPh
DTLIFT= 70 oC
CAPh: Still Practical Under Broad Conditions…

16. Summary-Conclusions
HFOs: Rich class of zero-ODP, low GWP
compounds each with its own characteristics;
pipeline of candidates tailor-made for various
applications emerging
Non-flammable, HFO-based, developmental fluids
DR-14, DR-12, and DR-2 could enable high
temperature heat pumps over wide ranges of
condensing temperatures and volumetric
heating capacities with attractive energy
efficiencies
DR-2: Could enable condensing temperatures up
to 160oC

17. Thank you!
Email:
konstantinos.kontomaris@dupont.com
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.
Claus-Peter Keller
Fluorochemicals Business Development EMEA
Du Pont de Nemours (Deutschland) GmbH
Tel: ++49 (0) 6102 / 18-2806
Mobile: ++49 (0) 175 573 0043
e-mail: claus-peter.keller@dupont.com