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Framtidens köldmedier Pavel Makhnatch, KTH Svenska Kyl & Värmepumpdagen 2016. 21 oktober 2016

"It is not often you get a chance to have a 0.5-degree centigrade reduction by taking one single step together as countries - each doing different things perhaps at different times, but getting the job done, said US Secretary of State John Kerry.

Adopted in 1987, the Montreal Protocol on Substances that Deplete the Ozone Layer is the most successful UN environmental agreement in history. Ratified by 197 parties, it has led to a 98 per cent decrease in the production and use of ozonedamaging chemicals, helping the ozone layer to start recovering, saving an estimated two million people each year by 2030 from skin cancer and contributing to mitigating climate change. /UNEP.ORG

Source: UNEP 2011 Global consumption of CFCs, HCFCs and HFCs

New refrigerants screening Filtering step Applied filter Constraint Resulting compound count 0 56,203 1 GWP (100yr time GWP<200 52,565 horizont) 2 Toxicity Obviously toxic compounds eliminated 3 Flammability LFL > 0.1 kg m -3 (ASHRAE Class 2 flammability) 30,135 20,277 4 Critical temperature 300 K < T c <550 K 1,728 5 Stability 1,234 Source: Kazakov et al. 2014, Computational Design of New Refrigerant Fluids Based on Environmental, Safety, and Thermodynamic Characteristics

Source: McLinden et al. 2014, A thermodynamic analysis of refrigerants: Possibilities and tradeoffs for Low-GWP refrigerants

New single component refrigerants listed in ASHRAE 34 R1234yf A2L, NBP=-29,4 C R1234ze(E) A2L, NBP=-19,0 C R1336mzz(Z) - A1, NBP=33.4 C R1233zd(E) A1, NBP=18.1 C R1130(E) B2 NBP=47.7 C R152a A2, NBP=-24.0 C Not yet designated by ASHRAE: HFO1123 HFO1234ze(Z)

New refrigerants trans-1,2- dichloroethene ODP n/a R1234yf A2L, NBP=-29,4 C R1234ze(E) A2L, NBP=-19,0 C R1336mzz(Z) - A1, NBP=33.4 C R1233zd(E) A1, NBP=18.1 C R1130(E) B2 NBP=47.7 C R152a A2, NBP=-24.0 C Not yet designated by ASHRAE: HFO1123 HFO1234ze(Z) trans-1-chloro- 3,3,3- trifluoropropene ODP from 0.00024 to 0.00034

Refrigerant mixtures (azeotropes (no glide), no ODP) 507A R-125/143a (50.0/50.0) 508A R-23/116 (39.0/61.0) 508B R-23/116 (46.0/54.0) 510A R-E170/600a (88.0/12.0) 511A R-290/152a (95.0/5.0) 512A R-134a/152a (5.0/95.0) 513A R-1234yf/134a (56.0/44.0) 513B R-1234yf/134a (58.5/41.5) 514A R-1336mzz(Z)/1130(E) (74.7/25.3) 515A R-1234ze(E)/227ea (88.0/12.0)

Refrigerant mixtures (zeotropes (with glide), no ODP) 404A R-125/143a/134a (44.0/52.0/4.0) 422B R-125/134a/600a (55.0/42.0/3.0) 407A R-32/125/134a (20.0/40.0/40.0) 422C R-125/134a/600a (82.0/15.0/3.0) 407B R-32/125/134a (10.0/70.0/20.0) 422D R-125/134a/600a (65.1/31.5/3.4) 407C R-32/125/134a (23.0/25.0/52.0) 422E R-125/134a/600a (58.0/39.3/2.7) 407D R-32/125/134a (15.0/15.0/70.0) 424A R-125/134a/600a/600/601a (50.5/47.0/0.9/1.0/0.6) 407E R-32/125/134a (25.0/15.0/60.0) 426A R-125/134a/600/601a (5.1/93.0/1.3/0.6) 407F R-32/125/134a (30.0/30.0/40.0) 427A R-32/125/143a/134a (15.0/25.0/10.0/50.0) 407G R-32/125/134a (2.5/2.5/95.0) 428A R-125/143a/290/600a (77.5/20.0/0.6/1.9) 407H R-32/125/134a (32.5/15.0/52.5) 429A R-E170/152a/600a (60.0/10.0/30.0) 438A R-32/125/134a/600/601a (8.5/45.0/44.2/1.7/0.6) 439A R-32/125/600a (50.0/47.0/3.0) 440A R-290/134a/152a (0.6/1.6/97.8) 441A 442A R-170/290/600a/600 (3.1/54.8/6.0/36.1) R-32/125/134a/152a/227ea (31.0/31.0/30.0/3.0/5.0) 443A R-1270/290/600a (55.0/40.0/5.0) 444A R-32/152a/1234ze(E) (12.0/5.0/83.0) 445A R-744/134a/1234ze(E) (6.0/9.0/85.0) 447B R-32/125/1234ze (E) (68.0/8.0/24.0) 410A R-32/125 (50.0/50.0) 430A R-152a/600a (76.0/24.0) 449C R-32/125/1234yf/134a (20.0/20.0/31.0/29.0) 410B R-32/125 (45.0/55.0) 431A R-290/152a (71.0/29.0) 452B R-32/125/1234yf (67.0/7.0/26.0) 413A R-218/134a/600a (9.0/88.0/3.0) 432A R-1270/E170 (80.0/20.0) 452C R-32/125/1234yf (12.5/61.0/26.5) 417A R-125/134a/600 (46.6/50.0/3.4) 433A R-1270/290 (30.0/70.0) 454C R-32/1234yf (21.5/78.5) 417B R-125/134a/600 (79.0/18.3/2.7) 433B R-1270/290 (5.0/95.0) 455A R-744/32/1234yf (3.0/21.5/75.5) 417C R-125/134a/600 (19.5/78.8/1.7) 433C R-1270/290 (25.0/75.0) 456A R-32/134a/1234ze(E) (6.0/45.0/49.0) 419A R-125/134a/E170 (77.0/19.0/4.0) 434A R-125/143a/134a/600a 457A R-32/1234yf/152a (18.0/70.0/12.0) 419B R-125/134a/E170 (48.5/48.0/3.5) 435A R-E170/152a (80.0/20.0) 458A R-32/125/134a/227ea/236fa (20.5/4.0/61.4/13.5/0.6) 421A R-125/134a (58.0/42.0) 436A R-290/600a (56.0/44.0) 459A R-32/1234yf/1234ze(E) (68.0/26.0/6.0) 421B R-125/134a (85.0/15.0) 436B R-290/600a (52.0/48.0) 459B LTR 11: R-32/1234yf/1234ze(E) (21.0/69.0/10.0) 422A R-125/134a/600a (85.1/11.5/3.4) 437A R-125/134a/600/601 (19.5/78.5/1.4/0.6) 460B LTR4X10: R-32/125/134a/1234ze(E) (28.0/25.0/20.0/27.0)

Glide 6.6 K 5.9K 0.8K 8.1K 8.4K 3.7K 6.6K 0.2K 1.2K 21.5K 7.2K 3.6K 10K 26,8K Source: ASHRAE standard 34

Selected nonflammable R404A alternative mixtures R449A Chemours R449B Arkema R449C Chemours R448A Honeywell R32 R125 R1234yf R134a R1234ze(E) 24.3 (+0.2, 1.0) 25,2 (+0.3, 1.5) 20.0 (+0.5, 1.5) 26.0 (+0.5, -2.0) 24.7 (+1.0, 0.2) 24,3 (+1.5, 0.3) 20.0 (+1.5, 0.5) 26.0 (+2.0, 0.5) 25.7 (+1.0, 0.2) 23,2 (+0.3, 1.5) 31.0 (+0.5, 1.5) 20.0 (+0.5, 2.0) 25.3 (+0.2, 1.0) - 27,3 (+1.5, 0.3) - 29.0 (+1.5, 0.5) - 21.0 7.0 (+2.0, 1.0) (+0.5, 2.0)

Selected nonflammable R134a alternative mixtures R513A Chemours R513B Daikin R1234yf R134a R1234ze(E) 56.0 (±1.0) 58,0 (±1.0) 44.0 (±1.0) - 42,0 (±1.0) - R450A Honeywell - 42.0 58.0

Source: Bitzer, 2016, Refrigerant report 19 Commercially available alternatives

Combustion of different refrigerants 18

P08 Köldmedier med låg växthuseffekter (P08) Pavel Makhnatch, Adrián Mota Babiloni Rahmatollah Khodabandeh NOWAB

Recent publications in Kyla+ Värmepumpar Ett alternativ för att ersätta R404A i små kylsystem, KYLA+ Värmepumpar, nr 07, 2016. Senaste nytt från Gustav Lorentzen Natural Working Fluids Conference i Edinburgh UK, KYLA+ Värmepumpar, nr 06, 2016. Möjligheter och utmaningar för R152a. Del 2., KYLA+ Värmepumpar, nr 05, 2016. Möjligheter och utmaningar för R152a. Del 1, KYLA+ Värmepumpar, nr 04, 2016. Miljöindikatorer TEWI och LCCP, KYLA+ Värmepumpar, nr 03, 2016. Källor för köldmediers termodynamiska egenskaper, KYLA+ Värmepumpar, nr 02, 2016. Några frågor från våra läsare, KYLA+ Värmepumpar, nr 01, 2016.

R404A replacement field tests 2 representative supermarkets 4 refrigeration systems

MT system layout Evaporator secondary fluid W Condenser secondary fluid T P P T T expansion valve compressor T T evaporator sight glass T filter condenser magnetic valve subcooler

1 h R404A operation 1 h R449A operation

LT system layout

2.5 h R404A operation 1 h R449A operation

kwh LT R404A LT R449A 110 100 90 80 88,8 95,2 91,0 95,7 90,3 95,4 88,3 93,5 88,4 92,7 89,7 94,1 88,4 94,6 70 60 50 40 30 20 10 0 Måndag Tisdag Onsdag Torsdag Fredag Lördag Söndag

R449A as a replacement to R404A results Not a drop-in replacement Suitable to replace R404A (comparable COP, slightly lower capacity) Suitability should be assessed prior to replacement Significantly higher discharge gas temperature (especially important for LT systems and/or high superheat) Lower massflow

Selected nonflammable R134a alternative mixtures

Refrigerant R134a R513A Composition pure R134a/1234yf 44/56 ASHRAE safety classification A1 A1 ODP 0 0 GWP 100-yr 1300 572-56% Critical temperature (K) 374.2 370.8-2.1% Critical pressure (kpa) 4059.3 3855.3-5.6% NBP (K) 246.8 243.3-1.9% Glide (K) at 100kPa 0.1 Liquid density a (kg m -3 ) 1295.3 1222.4-2.5% Vapor density a (kg m -3 ) 14.35 17.14 23.2% Liquid c a p (kj kg -1 K -1 ) 1.341 1.313-1.2% Vapor c a p (kj kg -1 K -1 ) 0.897 0.920 3.1% Liquid thermal conductivity a (W m -1 K -1 ) 92.08 79.26-7.0% Vapor thermal conductivity a (W m -1 K -1 ) 11.50 11.72 0.2% Liquid viscosity a (Pa s -1 ) 267.0 227.5-11.9% Vapor viscosity a (Pa s -1 ) 10.7 10.5-5.8%

Total emissions of GHG Direct/indirect Indirect/direct

Source: IIR, available online at goo.gl/fvi9pd

LCCP of a heat pump kg CO 2e 10000 9000 8000 7000 6000 5000 4000 3000 2000 1000 0 R290 R152a R1234yf R134a Indirect Direct

LCCP of a heat pump including uncertainties kg CO 2 e 10000 9000 8000 7000 6000 5000 4000 3000 2000 1000 0 R290 R152a R1234yf R134a Indirect Direct

Final remarks International regulations have set clear environmental targets for refrigeration industry The development path will depend on upcoming standards and regulations Effsys Expand P08 will continue to compile and generate knowledge in the field and update Swedish industry We have reached the limits of chemistry in terms of new refrigerants Selection of refrigerants is still a trade-off, but environmental properties are given very high weight now