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. Konstantinos.Kontomaris@DuPont.com DuPont luorochemicals Athens, Greece May 23 rd, 2015 EEinS2015 - International Conference ENVIRONMENT & ENERGY in SHIPS 2015
Cooling, Heating & Power Generation: On-Board & On-Shore Applications Refrigeration Air Conditioning Water Heating/Steam Generation Mechanical or Electrical Power Generation
Cooling, Heating & Power Generation: On-Board & On-Shore Applications Refrigeration Air Conditioning Water Heating/Steam Generation Power Generation rom Low Temperature Waste Heat?
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)
The Rankine Cycle Q in Evaporator Condenser Expa nder P out POWER Pump Q out Organic Rankine Cycle (ORC)
The Rankine Cycle Q in Evaporator Condenser Expa nder P out POWER Pump Q out Organic Rankine Cycle (ORC) Reject Heat to Sea Water
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
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?
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
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
Working luids Transitions
Working luids Transitions
Working luids Transitions
Hydro-luoro-Olefins (HOs) Next: HO-Based luids for Current and Emerging Applications
% 100 80 60 40 20 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
R-452A for Truck & Trailer Refrigeration: Test Results Minor & Gerstel - Chillventa, 2014 Compressor Discharge Temperature with R-452A within 1K vs. R-404A
% 100 80 60 40 20 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
% 100 80 60 40 20 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
% 100 80 60 40 20 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
Chillers: Lower GWP Replacement for HC-134a Chemical ormula GWP (100 yr) AR4 (AR5) R-134a C 3 CH 2 1430 (1300) R-513A HC-134a/HO-1234yf (44/56 wt%) 631 (573) Boiling Point C -26.1-29.2 Critical Point C 101 97 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, 857-864, 2013
R-513A: Lower GWP Replacement for HC-134a Chemical ormula GWP (100 yr) AR4 (AR5) R-134a C 3 CH 2 1430 (1300) R-513A HC-134a/HO-1234yf (44/56 wt%) 631 (573) Boiling Point C -26.1-29.2 Critical Point C 101 97 Temp Glide (K) 0 0 (Azeotrope) Tox/lamm A1 A1 Also for Refrigeration!
Improve uel Efficiency to Reduce: uel Costs Environmental Impact Power from Engine Waste Heat: R-1336mzz(Z)
Novel Working luid: HO-1336mzz(Z) Chemical ormula HO- 1336mzz(Z) H H C 3 CH=CHC 3 (Z)
Novel Working luid: HO-1336mzz(Z) Chemical ormula HO- 1336mzz(Z) OEL [ppm] 500 lammabilty ODP Non-lam None GWP 100 2 T cr [ o C] 171.3 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
Novel Working luid: HO-1336mzz(Z) Chemical ormula HO- 1336mzz(Z) OEL [ppm] 500 lammabilty ODP Non-lam None GWP 100 2 T cr [ o C] 171.3 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
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.
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] 300 500 lammabilty Non-lam Non-lam ASHRAE Std 34 Safety Class B1 A1 ODP None None GWP 100 858 2 ALT [yrs] 7.7 0.060274 (22 days) T cr [ o C] 154 171.3 P cr [MPa] 3.65 2.90 T b [ o C] 15.1 33.4 T freez [ o C] -107-90.5
Vapor Pressure, MPa HO-1336mzz(Z): Vapor Pressure 4.00 3.50 HC-245fa 3.00 2.50 2.00 1.50 1.00 HO-1336mzz(Z) 0.50 0.00 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 Temperature, o C HC-245fa HO-1336mzz(Z) T cr [ o C] 154.0 171.3
0 Pressure (MPa) 10 Heat Source Temp>T cr 200 250 300 350 400 450 500 550 600 650 10 DR-2 HO-1336mzz(Z) 150 175 200 225 250 275 o C Expander Inlet: T high =225 C 1 125 1 100 75 50 0.1 0.1 25 200 250 300 350 400 450 500 550 600 650 Enthalpy (kj/kg)
0 Pressure (MPa) Representative Cycle Conditions 10 200 250 300 350 400 450 500 550 600 650 10 DR-2 HO-1336mzz(Z) 150 175 200 225 250 275 o C Expander Inlet: T high =225 C 1 75 100 125 1 Condenser: T cond =75 C 50 0.1 0.1 25 200 250 300 350 400 450 500 550 600 650 Enthalpy (kj/kg)
0 Pressure (MPa) Representative Cycle Conditions 10 200 250 300 350 400 450 500 550 600 650 10 DR-2 HO-1336mzz(Z) 150 175 200 225 250 275 o C Expander Inlet: T high =225 C 1 75 100 125 1 Condenser: T cond =75 C T cond =20 C 0.1 25 50 200 250 300 350 400 450 500 550 600 650 Enthalpy (kj/kg) 0.1 See Written Paper in Proceedings
0 Pressure (MPa) Representative Cycle Conditions 10 200 250 300 350 400 450 500 550 600 650 10 DR-2 HO-1336mzz(Z) 150 175 200 225 250 275 o C Expander Inlet: T high =225 C 1 75 100 125 1 Condenser: T cond =75 C 50 Subcooling: DT subc =5 K 0.1 0.1 25 200 250 300 350 400 450 500 550 600 650 Enthalpy (kj/kg)
0 Pressure (MPa) 10 Representative Cycle Conditions 200 250 300 350 400 450 500 550 600 650 10 DR-2 HO-1336mzz(Z) 150 175 200 225 250 275 o C Expander Inlet: T high =225 C 1 75 100 125 1 Condenser: T cond =75 C 50 Subcooling: DT subc =5 K 0.1 25 200 250 300 350 400 450 500 550 600 650 Enthalpy (kj/kg) 0.1 h exp =0.75 h pump =0.50
0 Pressure (MPa) Optimization of High-Side Pressure 10 200 250 300 350 400 450 500 550 600 650 10 DR-2 HO-1336mzz(Z) P high < P cr 150 175 200 225 250 275 o C Expander Inlet: T high =225 C 1 75 100 125 1 Condenser: T cond =75 C 50 Subcooling: DT subc =5 K 0.1 25 200 250 300 350 400 450 500 550 600 650 Enthalpy (kj/kg) 0.1 h exp =0.75 h pump =0.50
0 Pressure (MPa) 10 High-Side Pressure: Upper Limit 200 250 300 350 400 450 500 550 600 650 10 DR-2 HO- 1336mzz(Z) P high > P cr 150 175 200 225 250 275 o C Expander Inlet: T high =225 C 1 75 100 125 1 Condenser: T cond =75 C 50 Subcooling: DT subc =5 K 0.1 25 200 250 300 350 400 450 500 550 600 650 Enthalpy (kj/kg) 0.1 h exp =0.75 h pump =0.50
Net Cycle Thermal Efficiency HO-1336mzz(Z): Maximization of Thermal Efficiency 11 10 9 8 7 6 5 0 1 2 3 4 5 6 7 8 9 10 P high [MPa] Net Cycle Efficiency Exhibits Maximum
Net Cycle Thermal Efficiency HO-1336mzz(Z): Maximization of Thermal Efficiency 11 10 9 8 7 6 5 P cr 0 1 2 3 4 5 6 7 8 9 10 P high [MPa] Maximum Efficiency at P high >P cr 10-15% Higher Than Subcritical Cycle Efficiency
Net Cycle Thermal Efficiency HO-1336mzz(Z): Maximization of Thermal Efficiency 11 10 9 8 7 6 5 P cr 0 1 2 3 4 5 6 7 8 9 10 P high [MPa] P high [MPa] 4 PR 10.7
Net Cycle Thermal Efficiency HO-1336mzz(Z) vs. HC-245fa: Cycle Efficiency 11 10 9 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 0.50 7 6 5 HC-245fa 0 1 2 3 4 5 6 7 8 9 10 P high [MPa]
Net Cycle Thermal Efficiency HO-1336mzz(Z) vs. HC-245fa: Cycle Efficiency 11 10 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 0.50 9 8 7 6 5 HC-245fa +16.5% 0 1 2 3 4 5 6 7 8 9 10 P high [MPa] HO-1336mzz(Z): 99.8% Lower GWP and 16.5% Higher Efficiency!
HO-1336mzz(Z) Heat Pump Steam Generator Use heat from engine jacket cooling water to generate steam? Valve Q out Condenser Evaporator Q in 100-150 o C Comp ressor 50-100 o C P in Reverse Rankine Cycle
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 100-150 o C Comp ressor 50-100 o C P in Reverse Rankine Cycle
HO-1336mzz(Z) High Temp Heat Pump: Predicted Simple Cycle Performance 8.00 7.50 TEMP LIT= 35 o C COP h 7.00 6.50 6.00 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) 5.50 60 70 80 90 100 110 120 130 140 150 160 170 180 Condensing Temperature, o C ATTRACTIVE COP h
HO-1336mzz(Z) High Temp Heat Pump: Predicted Simple Cycle Performance 8.00 7.50 TEMP LIT= 35 o C COP h 7.00 6.50 6.00 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) 5.50 60 70 80 90 100 110 120 130 140 150 160 170 180 Condensing Temperature, o C ATTRACTIVE COP h
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.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, 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