Zero-ODP, Low-GWP, Nonflammable Working Fluids for High Temperature Heat Pumps

Transcription

1 Seminar 35 - Advances in Low Global Warming Potential Refrigerants Zero-ODP, Low-GWP, Nonflammable Working Fluids for High Temperature Heat Pumps Kostas Kontomaris, Ph.D. Global Technology Leader, Working Fluids DuPont Fluorochemicals 2014 ASHRAE Annual Conference, Seattle, Washington July 1 st, 2014 Reduce: Primary Energy Use Environmental Impact

2 LEARNING OBJECTIVES: Explain recent development activities related to low GWP refrigerants including air conditioning alternatives to R-410A and R-22 and refrigeration alternatives, including recent drivers in Europe requiring the development of these refrigerants. Describe new low GWP fluids under development for high temperature heat pump applications which have excellent thermal stability and cooling/heating performance at high temperatures. Share refrigerant/lubricant property data and trends including miscibility, solubility and viscosity date for low GWP refrigerants with lubricants Describe results for thermodynamic cycle modeling and system performance testing of several low GWP refrigerants in various applications. 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.

3 PROSPECTIVE APPLICATIONS T cond [ o C] CAP h [kw] ,000 1,000-10, Steam Generation Evaporation Distillation DHW-JPN DHW-xJPN Clothes Steam Generation Evaporation Distillation District Heating District Heating

4 PROSPECTIVE APPLICATIONS T cond [ o C] CAP h [kw] ,000 1,000-10, Steam Generation Evaporation Distillation DHW-JPN DHW-xJPN Clothes Steam Generation Evaporation Distillation District Heating District Heating

5 PROSPECTIVE APPLICATIONS T cond [ o C] CAP h [kw] ,000 1,000-10, Steam Generation Evaporation Distillation DHW-JPN DHW-xJPN Clothes Steam Generation Evaporation Distillation District Heating District Heating

6 PROSPECTIVE APPLICATIONS T cond [ o C] CAP h [kw] ,000 1,000-10, Steam Generation Evaporation Distillation DHW-JPN DHW-xJPN Clothes Steam Generation Evaporation Distillation District Heating District Heating Large Untapped Potential for Industrial/Process Heating

7 PROSPECTIVE APPLICATIONS T cond [ o C] CAP h [kw] ,000 1,000-10, Steam Generation Evaporation Distillation DHW-JPN DHW-xJPN Clothes Steam Generation Evaporation Distillation District Heating District Heating Replacement of Fossil Fuel Steam Boilers By Heat Pumps

8 PROSPECTIVE APPLICATIONS T cond [ o C] CAP h [kw] ,000 1,000-10, Steam Generation Evaporation Distillation DHW-JPN DHW-xJPN Clothes Steam Generation Evaporation Distillation District Heating District Heating

9 PROSPECTIVE APPLICATIONS T cond [ o C] CAP h [kw] ,000 1,000-10, Steam Generation Evaporation Distillation DHW-JPN DHW-xJPN Clothes Steam Generation Evaporation Distillation District Heating District Heating Diverse Markets: Segments, Temp and Capacity Ranges, Equipment Technologies, Fluid Specifications Comprehensive Fluid Portfolio Needed

10 HFO-Based Developmental Fluids Chemical Formula DR-14A Azeotropic Blend GWP 100 ~415 T cr [ o C] P cr [MPa] 3.96 T b [ o C] Temp Glide [K] (@ P=1 atm) In order of increasing T cr (& NBP) 0.04

11 HFO-Based Developmental Fluids Chemical Formula DR-14A Azeotropic Blend GWP 100 ~415 T cr [ o C] P cr [MPa] 3.96 T b [ o C] Temp Glide [K] (@ P=1 atm) 0.04 Negligible Temperature Glide Suitable for Large Heat Pumps (and Chillers) with Flooded Heat Exchangers

12 HFO-Based Developmental Fluids Chemical Formula DR-14A Azeotropic Blend DR-12 Confidential GWP 100 ~ T cr [ o C] P cr [MPa] T b [ o C] Temp Glide [K] (@ P=1 atm) 0.04 N/A

13 HFO-Based Developmental Fluids DR-12: Very Low GWP and Non-Flammable Chemical Formula DR-14A Azeotropic Blend DR-12 Confidential GWP 100 ~ T cr [ o C] P cr [MPa] T b [ o C] Temp Glide [K] (@ P=1 atm) 0.04 N/A

14 HFO-Based Developmental Fluids Chemical Formula DR-14A DR-12 DR-40A Azeotropic Blend Confidential Near-Azeo Blend GWP 100 ~ <170 T cr [ o C] P cr [MPa] T b [ o C] Temp Glide [K] (@ P=1 atm) 0.04 N/A 0.86

15 HFO-Based Developmental Fluids Chemical Formula DR-14A DR-12 DR-40A DR-2 Azeotropic Blend Confidential Near-Azeo Blend GWP 100 ~ <170 2 T cr [ o C] P cr [MPa] T b [ o C] Temp Glide [K] (@ P=1 atm) 0.04 N/A 0.86 N/A

16 HFO-Based Developmental Fluids Chemical Formula DR-14A DR-12 DR-40A DR-2 Azeotropic Blend Confidential Near-Azeo Blend HFO- 1336mzz(Z) GWP 100 ~ <170 2 T cr [ o C] P cr [MPa] T b [ o C] Temp Glide [K] (@ P=1 atm) 0.04 N/A 0.86 N/A F F F F F F H H CF 3 CH=CHCF 3 (Z)

17 HFO-Based Developmental Fluids DR-2: Very Low GWP and Non-Flammable Chemical Formula DR-14A DR-12 DR-40A DR-2 Azeotropic Blend Confidential Near-Azeo Blend HFO- 1336mzz(Z) GWP 100 ~ <170 2 T cr [ o C] P cr [MPa] T b [ o C] Temp Glide [K] (@ P=1 atm) 0.04 N/A 0.86 N/A

18 HFO-Based Developmental Fluids Chemical Formula DR-14A DR-12 DR-40A DR-2 Azeotropic Blend Confidential Near-Azeo Blend HFO- 1336mzz(Z) GWP 100 ~ <170 2 T cr [ o C] P cr [MPa] T b [ o C] Temp Glide [K] (@ P=1 atm) 0.04 N/A 0.86 N/A No Chlorine (*) : -Zero ODP -Dramatically Increased Chemical Stability at High Temps (*) or other halogen atoms other than fluorine

19 DR-2: Unique Combination of Attributes Very Low GWP No Flammability

20 DR-2: Unique Combination of Attributes Very Low GWP No Flammability Surprisingly High Chemical Stability at High Temperatures (to Polymerization, Decomposition/De-hydrofluorination, Oxidation and Hydrolysis)

21 DR-2: High Chemical Stability 250 o C w/ Metals; Air: 7.6 mmhg; Moisture: 200 ppm Sealed tube testing based on ASHRAE-ANSI STD 97 Fluoride Ion Concentration After Aging [ppm] AGING [DAYS] HFO DR-2 HFC-245fa DR-2 as Stable as a Saturated HFC Widely Used in High Temp Apps

22 DR-2: Stereo-Isomerization Stability Aging in the Presence of Metals for 14 Days Aging Temp [ o C] Un-aged Stock HFO- 1336mzz-E [ppm] Not Present ,023 HFO-1336mzz(E) F F F H F H F F DR-2 Stable to Stereo-Isomerization Despite Thermodynamic Driving Force!

23 DR-2: Unique Combination of Attributes Very Low GWP No Flammability Surprisingly High Chemical Stability at High Temps Compatible with Many Plastics and Elastomers

24 DR-2 Compatibility with Plastics & Elastomers: (I) Weight changes of polymeric specimens after exposure to HFO-1336mzz-Z/POE Lubricant blends for 14 days at 100 o C Immediately after Exposure Twenty Four Hours after Exposure Material % % Neoprene EPDM Polyester Resin Nylon Resin Epoxy Polyester PET Polyester PBT Polycarbonate Polyimide Teflon PTFE Teflon FEP Tefzel ETFE Phenolic PVC PEEK Mild Interactions between HFO-1336mzz-Z and Many Plastics and Elastomers

25 DR-2 Compatibility with Plastics & Elastomers: (II) Hardness changes of polymeric specimens after exposure to HFO-1336mzz-Z/POE Lubricant blends for 14 days at 100 o C Immediately after Exposure Twenty Four Hours after Exposure Material % % Neoprene EPDM Polyester Resin Nylon Resin Epoxy Polyester PET Polyester PBT Polycarbonate Polyimide Teflon PTFE Teflon FEP Tefzel ETFE Phenolic PVC PEEK Mild Interactions between HFO-1336mzz-Z and Many Plastics and Elastomers

26 DR-2: Unique Combination of Attributes Very Low GWP No Flammability Surprisingly High Chemical Stability at High Temps Compatibility with Many Common Plastics and Elastomers Attractive Thermodynamic Properties for High Temperature Applications High Critical Temperature Low, Easy to Confine Vapor Pressure High Cycle Efficiency

27 Vapor Pressure Vapor Pressure, MPa HFC- 134a DR-14A DR-12 HFC- 245fa DR-40A DR No Suitable Reference Fluid for DR Temperature, o C HFC-134a DR-14A DR-12 HFC-245fa DR-40A DR-2 T cr, o C

28 Vapor Pressure Vapor Pressure, MPa P max =2.5 MPa HFC- 134a DR-14A DR-12 HFC- 245fa DR-40A DR Temperature, o C HFC-134a DR-14A DR-12 HFC-245fa DR-40A DR-2 T 2.5MPa, o C

29 Vapor Pressure Vapor Pressure, MPa P max =2.5 MPa HFC- 134a DR-14A DR-12 HFC- 245fa DR-40A DR Temperature, o C HFC-134a DR-14A DR-12 HFC-245fa DR-40A DR-2 T 2.5MPa, o C o C

30 Vapor Pressure Vapor Pressure, MPa P max =2.5 MPa HFC- 134a DR-14A DR-12 HFC- 245fa DR-40A DR Temperature, o C HFC-134a DR-14A DR-12 HFC-245fa DR-40A DR-2 T 2.5MPa, o C o C

31 Vapor Pressure Vapor Pressure, MPa P max =2.5 MPa HFC- 134a DR-14A DR-12 HFC- 245fa DR-40A DR Temperature, o C HFC-134a DR-14A DR-12 HFC-245fa DR-40A DR-2 T 2.5MPa, o C o C

32 Predicted Simple Cycle Performance DT superh = 11 o C; DT subc = 5 o C; Compressor Efficiency= TEMP LIFT= 35 o C COP h HFC-134a DR-14A DR-12 HFC- 245fa Condensing Temperature, o C DR- 40A DR-2 T evap = T cond 35 o C

33 Predicted Simple Cycle Performance DT superh = 11 o C; DT subc = 5 o C; Compressor Efficiency= TEMP LIFT= 35 o C COP h HFC-134a DR-14A DR-12 HFC- 245fa Condensing Temperature, o C DR- 40A DR-2 COP h DECREASES CLOSE TO T cr

34 Predicted Simple Cycle Performance DT superh = 11 o C; DT subc = 5 o C; Compressor Efficiency= TEMP LIFT= 35 o C COP h HFC-134a DR-14A DR-12 HFC- 245fa Condensing Temperature, o C DR- 40A DR-2 COP h DIFFERENCES AMONG FLUIDS MAGNIFIED AT HIGHER TEMPS

35 Predicted Simple Cycle Performance DT superh = 11 o C; DT subc = 5 o C; Compressor Efficiency= TEMP LIFT= 35 o C COP h HFC-134a DR-14A DR-12 HFC- 245fa Condensing Temperature, o C DR- 40A DR-2 ATTRACTIVE COP h UNDER ALL FEASIBLE CONDITIONS

36 Predicted Performance: COP h at High Temp Lift DT superh = 20 o C; DT subc = 5 o C; Compressor Efficiency=0.8 COP h HFC-134a DR-14A DR-12 HFC- 245fa Condensing Temperature, o C TEMP LIFT=70 o C DR- 40A COP h LOWER AT HIGHER LIFT BUT STILL ATTRACTIVE UNDER BROAD CONDITIONS DR-2

37 Predicted Performance: COP h at High Temp Lift DT superh = 20 o C; DT subc = 5 o C; Compressor Efficiency=0.8 COP h HFC-134a DR-14A DR-12 HFC- 245fa Condensing Temperature, o C TEMP LIFT=70 o C DR- 40A DR-2 DR-40A: HIGHEST COP h FOR T cond < ~140 o C

38 Predicted Performance: CAP h at High Temp Lift CAP h, kj/m 3 5,000 4,500 4,000 3,500 3,000 2,500 2,000 1,500 1, DT superh = 20 o C; DT subc = 5 o C; Compressor Efficiency=0.8 HFC-134a DR-14A HFC-245fa DR-40A DR-12 DR Condensing Temperature, o C TEMP LIFT= 70 o C In Inverse Order to COP h Practical Under Broad Conditions Even at the Higher Lift

39 Summary Efforts to increase energy efficiency and reduce environmental impacts from the use of fossil fuels could encourage wider adoption of heat pumps for heating including at higher temperatures than it has been common in the past Non-flammable, HFO-based, developmental fluids DR-14A, DR-12, DR-40A and DR-2 could enable heat pumps delivering condensing temperatures up to 160 o C with attractive energy efficiencies

40 Questions? Kostas Kontomaris Thank you! 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.