DuPont Fluorochemicals. Athens, Greece May 23 rd, 2015

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Zero-ODP, Lower GWP, Non-lammable Refrigerants for Marine Applications: R-452A, R-449A, R-513A, R-1336mzz(Z) for improved sustainability and energy savings Konstantinos (Kostas)

1 Zero-ODP, Lower GWP, Non-lammable Refrigerants for Marine Applications: R-452A, R-449A, R-513A, R-1336mzz(Z) for improved sustainability and energy savings Konstantinos (Kostas) Kontomaris, Ph.D. DuPont luorochemicals Athens, Greece May 23 rd, 2015 EEinS International Conference ENVIRONMENT & ENERGY in SHIPS 2015

2 Cooling, Heating & Power Generation: On-Board & On-Shore Applications Refrigeration Air Conditioning Water Heating/Steam Generation Mechanical or Electrical Power Generation

3 Cooling, Heating & Power Generation: On-Board & On-Shore Applications Refrigeration Air Conditioning Water Heating/Steam Generation Power Generation rom Low Temperature Waste Heat?

4 Cooling, Heating & Power Generation: On-Board & On-Shore Applications Refrigeration Air Conditioning Water Heating/Steam Generation Power Generation HIGH ENERGY USE HIGH ENVIRONMENTAL IMPACT (including CO 2 & Refrigerant Emissions)

5 The Rankine Cycle Q in Evaporator Condenser Expa nder P out POWER Pump Q out Organic Rankine Cycle (ORC)

6 The Rankine Cycle Q in Evaporator Condenser Expa nder P out POWER Pump Q out Organic Rankine Cycle (ORC) Reject Heat to Sea Water

Evaporator Comp ressor Pump Q out Q in Air Conditioning

7 The Rankine Cycle Q in Q out Heat Pump HEATING Evaporator P out Condenser P in Condenser Expa nder POWER Valve Evaporator Comp ressor Pump Q out Q in Air Conditioning Refrigeration COOLING Organic Rankine Cycle (ORC) Reverse Rankine Cycle

8 The Rankine Cycle Q in Q out Heat Pump HEATING Evaporator P out Condenser P in Condenser Expa nder POWER Valve Evaporator Comp ressor Pump Q out Q in Air Conditioning Refrigeration COOLING Organic Rankine Cycle (ORC) Reverse Rankine Cycle Working luid?

9 Working luids Requirements High energy efficiency High volumetric capacity for cooling, heating or power generation Low or no temperature glide Low toxicity Low or no flammability High chemical and thermal stability Compatibility with commercially available lubricants Compatibility with common materials of equipment construction Short atmospheric life time No ozone depletion potential Acceptable atmospheric breakdown products Acceptable performance in existing equipment with no or little modification Low fluid cost and low total cost of ownership AND LOW GLOBAL WARMING IMPACT

10 Working luids Requirements High energy efficiency High volumetric capacity for cooling, heating or power generation Low or no temperature glide Low toxicity Low or no flammability High chemical and thermal stability Compatibility with commercially available lubricants Compatibility with common materials of equipment construction Short atmospheric life time No ozone depletion potential Acceptable atmospheric breakdown products Acceptable performance in existing equipment with no or little modification Low fluid cost and low total cost of ownership AND LOW GLOBAL WARMING IMPACT Threading The Needle! Optimal Balance of Properties for Each App

11 Working luids Transitions

12 Working luids Transitions

13 Working luids Transitions

14 Hydro-luoro-Olefins (HOs) Next: HO-Based luids for Current and Emerging Applications

15 % Transport Refrigeration: Lower GWP Replacements for R-404A 0 R-404A GWP=3922 GWP Reduction -45% 452A -64% 449A -84% 404A XP44 XP40 XP10 R-452A (GWP=2140) (HO-1234yf/HC-32/HC-125) Close performance with 45% lower GWP than R-404A Nonflammable; ideal for marine transport refrigeration New and retrofit with no equipment or oil change Energy Efficiency is comparable to R-404A Compliance With -Gas Regulation

16 R-452A for Truck & Trailer Refrigeration: Test Results Minor & Gerstel - Chillventa, 2014 Compressor Discharge Temperature with R-452A within 1K vs. R-404A

17 % Transport Refrigeration: Lower GWP Replacements for R-404A 0 R-404A GWP=3922 GWP Reduction -45% 452A -64% 449A -84% 404A XP44 XP40 XP10 Compliance With -Gas Regulation R-452A (GWP=2140) (HO-1234yf/HC-32/HC-125) Close performance with 45% lower GWP than R-404A Nonflammable; ideal for transport refrigeration New and retrofit with no equipment or oil change Energy Efficiency is comparable to R-404A or use where lowest discharge temperature required

18 % Refrigeration: Lower GWP Replacements for R-404A R-404A GWP=3922 GWP Reduction -45% -64% -84% R-449A (GWP=1397 ) (HO-1234yf/HC-32/HC-125/HC-134a) Close performance with 64% lower GWP than R-404A Nonflammable; ideal for on-board applications New and retrofit with no equipment or oil change 0 452A 449A 404A XP44 XP40 XP10 Compliance With -Gas Regulation

19 % Refrigeration: Lower GWP Replacements for R-404A 0 R-404A GWP=3922 GWP Reduction -45% 452A -64% 449A -84% 404A XP44 XP40 XP10 Compliance With -Gas Regulation R-449A (GWP=1397 ) (HO-1234yf/HC-32/HC-125/HC-134a) Close performance with 64% lower GWP than R-404A Nonflammable; ideal for on-board applications New and retrofit with no equipment or oil change Potential energy efficiency benefit based on system tests: 8-12% MT and ~ 3% LT

20 Chillers: Lower GWP Replacement for HC-134a Chemical ormula GWP (100 yr) AR4 (AR5) R-134a C 3 CH (1300) R-513A HC-134a/HO-1234yf (44/56 wt%) 631 (573) Boiling Point C Critical Point C Temp Glide (K) 0 0 (Azeotrope) Tox/lamm A1 A1 R-513A: Near Drop-In Replacement for HC-134a in Chillers Kontomaris et. al, HVAC & R Research, Vol. 19, Issue 7, , 2013

21 R-513A: Lower GWP Replacement for HC-134a Chemical ormula GWP (100 yr) AR4 (AR5) R-134a C 3 CH (1300) R-513A HC-134a/HO-1234yf (44/56 wt%) 631 (573) Boiling Point C Critical Point C Temp Glide (K) 0 0 (Azeotrope) Tox/lamm A1 A1 Also for Refrigeration!

22 Improve uel Efficiency to Reduce: uel Costs Environmental Impact Power from Engine Waste Heat: R-1336mzz(Z)

23 Novel Working luid: HO-1336mzz(Z) Chemical ormula HO- 1336mzz(Z) H H C 3 CH=CHC 3 (Z)

24 Novel Working luid: HO-1336mzz(Z) Chemical ormula HO- 1336mzz(Z) OEL [ppm] 500 lammabilty ODP Non-lam None GWP T cr [ o C] P cr [MPa] 2.90 T b [ o C] 33.4 R-1336mzz(Z) recommended for a safety classification of A1 (low toxicity, no flammability) with an OEL of 500 ppm by ASHRAE Standing Standard Project Committee 34, pending public review H C 3 CH=CHC 3 (Z) H

25 Novel Working luid: HO-1336mzz(Z) Chemical ormula HO- 1336mzz(Z) OEL [ppm] 500 lammabilty ODP Non-lam None GWP T cr [ o C] P cr [MPa] 2.90 T b [ o C] 33.4 Very Low GWP And Non-lammable H C 3 CH=CHC 3 (Z) H

26 Novel Working luid: HO-1336mzz(Z) Chemical ormula HO- 1336mzz(Z) H H C 3 CH=CHC 3 (Z) No Chlorine: Dramatically Increased Chemical Stability to Various Transformation Mechanisms at High Temps 1 1 Kontomaris, K.: 15 th Inter. Refrig. & Air Cond. Conf. at Purdue, West Lafayette, IN, USA, July 14-17, 2014.

27 DR-2 vs. HC-245fa Reference luid: HC-245fa HC-245fa HO-1336mzz(Z) Chemical ormula C 3 CH 2 CH 2 cis-c 3 CH=CHC 3 OEL/AEL [ppm] lammabilty Non-lam Non-lam ASHRAE Std 34 Safety Class B1 A1 ODP None None GWP ALT [yrs] (22 days) T cr [ o C] P cr [MPa] T b [ o C] T freez [ o C]

28 Vapor Pressure, MPa HO-1336mzz(Z): Vapor Pressure HC-245fa HO-1336mzz(Z) Temperature, o C HC-245fa HO-1336mzz(Z) T cr [ o C]

29 0 Pressure (MPa) 10 Heat Source Temp>T cr DR-2 HO-1336mzz(Z) o C Expander Inlet: T high =225 C Enthalpy (kj/kg)

30 0 Pressure (MPa) Representative Cycle Conditions DR-2 HO-1336mzz(Z) o C Expander Inlet: T high =225 C Condenser: T cond =75 C Enthalpy (kj/kg)

31 0 Pressure (MPa) Representative Cycle Conditions DR-2 HO-1336mzz(Z) o C Expander Inlet: T high =225 C Condenser: T cond =75 C T cond =20 C Enthalpy (kj/kg) 0.1 See Written Paper in Proceedings

32 0 Pressure (MPa) Representative Cycle Conditions DR-2 HO-1336mzz(Z) o C Expander Inlet: T high =225 C Condenser: T cond =75 C 50 Subcooling: DT subc =5 K Enthalpy (kj/kg)

33 0 Pressure (MPa) 10 Representative Cycle Conditions DR-2 HO-1336mzz(Z) o C Expander Inlet: T high =225 C Condenser: T cond =75 C 50 Subcooling: DT subc =5 K Enthalpy (kj/kg) 0.1 h exp =0.75 h pump =0.50

34 0 Pressure (MPa) Optimization of High-Side Pressure DR-2 HO-1336mzz(Z) P high < P cr o C Expander Inlet: T high =225 C Condenser: T cond =75 C 50 Subcooling: DT subc =5 K Enthalpy (kj/kg) 0.1 h exp =0.75 h pump =0.50

35 0 Pressure (MPa) 10 High-Side Pressure: Upper Limit DR-2 HO- 1336mzz(Z) P high > P cr o C Expander Inlet: T high =225 C Condenser: T cond =75 C 50 Subcooling: DT subc =5 K Enthalpy (kj/kg) 0.1 h exp =0.75 h pump =0.50

36 Net Cycle Thermal Efficiency HO-1336mzz(Z): Maximization of Thermal Efficiency P high [MPa] Net Cycle Efficiency Exhibits Maximum

37 Net Cycle Thermal Efficiency HO-1336mzz(Z): Maximization of Thermal Efficiency P cr P high [MPa] Maximum Efficiency at P high >P cr 10-15% Higher Than Subcritical Cycle Efficiency

38 Net Cycle Thermal Efficiency HO-1336mzz(Z): Maximization of Thermal Efficiency P cr P high [MPa] P high [MPa] 4 PR 10.7

39 Net Cycle Thermal Efficiency HO-1336mzz(Z) vs. HC-245fa: Cycle Efficiency HO- 1336mzz(Z) 8 Basic ORC (No Recuperator) T high C 225 T cond C 75 DT subc K 5 h exp 0.75 h pump HC-245fa P high [MPa]

40 Net Cycle Thermal Efficiency HO-1336mzz(Z) vs. HC-245fa: Cycle Efficiency HO- 1336mzz(Z) Basic ORC (No Recuperator) T high C 225 T cond C 75 DT subc K 5 h exp 0.75 h pump HC-245fa +16.5% P high [MPa] HO-1336mzz(Z): 99.8% Lower GWP and 16.5% Higher Efficiency!

41 HO-1336mzz(Z) Heat Pump Steam Generator Use heat from engine jacket cooling water to generate steam? Valve Q out Condenser Evaporator Q in o C Comp ressor o C P in Reverse Rankine Cycle

42 HO-1336mzz(Z) Heat Pump Steam Generator Energy Efficiency Metric: COP h =Q out /P in Coefficient of Performance for Heating Valve Q out Condenser Evaporator Q in o C Comp ressor o C P in Reverse Rankine Cycle

43 HO-1336mzz(Z) High Temp Heat Pump: Predicted Simple Cycle Performance TEMP LIT= 35 o C COP h T evap = T cond 35 o C; DT superh = 11 o C; DT subc = 5 o C; Compressor Efficiency=0.8 HC-245fa HO-1336mzz(Z) Condensing Temperature, o C ATTRACTIVE COP h

44 HO-1336mzz(Z) High Temp Heat Pump: Predicted Simple Cycle Performance TEMP LIT= 35 o C COP h T evap = T cond 35 o C; DT superh = 11 o C; DT subc = 5 o C; Compressor Efficiency=0.8 HC-245fa HO-1336mzz(Z) Condensing Temperature, o C ATTRACTIVE COP h

45 Summary Newly Registered Non-lammable, Lower GWP ASHRAE Refrigerants: R-452A: R-404A replacement with lower compressor discharge temperature R-449A: R-404A replacement with lower GWP and energy consumption R-513A: Near drop-in replacement for HC-134a R-1336mzz(Z): Unique combination of properties for power and heating from low temp waste heat for increased fuel efficiency and reduced environmental impacts

Zero-ODP, Lower GWP, Non-lammable Refrigerants and Working luids for Cooling, Heating and Power Generation Konstantinos Kontomaris Konstantinos.Kontomaris@DuPont.

It is intended for use by persons having technical skill, at their own risk.

46 Zero-ODP, Lower GWP, Non-lammable Refrigerants and Working luids for Cooling, Heating and Power Generation Konstantinos Kontomaris 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, DuPont 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

Zero-ODP, Low GWP, Non-Flammable Working Fluid for Organic Rankine Cycles: HFO-1336mzz-Z

Zero-ODP, Low GWP, Non-Flammable Working Fluid for Organic Rankine Cycles: HFO-1336mzz-Z Reduce: Primary Energy Use Environmental Impact Zero-ODP, Low GWP, Non-lammable Working luid for Organic Rankine Cycles: HO-1336mzz-Z Kostas Kontomaris, Ph.D. DuPont luorochemicals Kobe, Japan November