Next Generation Refrigerants

November 7 th, 2016 Okinawa Professional Engineers Symposium 1 Next Generation Refrigerants Yukihiro Higashi Research Center for Next Generation Refrigerant Properties (NEXT-RP) International Institute for Carbon-Neutral Energy Research (I 2 CNER) WPI-I 2 CNER, Kyushu University

Research Center for Next Generation Refrigerant Properties (NEXT-RP) WPI-I 2 CNER, Kyushu University 2 International Institute for Carbon-Neutral Energy Research 1 Research Center for Next Generation Refrigerant Properties (NEXT-RP)

Research Center for Next Generation Refrigerant Properties (NEXT-RP) WPI-I 2 CNER, Kyushu University 3 Founded April 1, 2016 Research Center for Next Generation Refrigerant Properties (NEXT-RP), International Institute for Carbon-Neutral Energy Research (I²CNER), Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395 JAPAN TEL: +81-92-802-6704 FAX: +81-92-802-6728 EMAIL: next-rp@i2cner.kyushu-u.ac.jp

Research Center for Next Generation Refrigerant Properties (NEXT-RP) WPI-I 2 CNER, Kyushu University 4 Mission Determine thermophysical properties of next generation refrigerants and thermal science and engineering to help enable the most effective use of these refrigerants in carbon-neutral energy technologies. Research new thermal energy heat pump and refrigeration systems which are focused on the use of new refrigerants and which will result in improved overall energy efficiencies and reduced CO 2 emissions. Organize an international collaboration network in order to obtain reliable information on thermophysical properties and to establish the worldwide standard for next generation refrigerant properties.

Research Center for Next Generation Refrigerant Properties (NEXT-RP) WPI-I 2 CNER, Kyushu University 5 (1) Division for Thermophysical Properties and Transfer Processes of Next Generation Refrigerants Thermodynamic and transport properties of next generation refrigerants are essential for the design and development of new refrigerators and heat pumps. We measure the reliable thermophysical properties for new refrigerants and mixtures thereof, and propose highly accurate equations of state and correlations for use in the analysis of the transfer process.

Research Center for Next Generation Refrigerant Properties (NEXT-RP) WPI-I 2 CNER, Kyushu University 6 (2) Division for Heat Pump and Refrigeration Cycles In order to adapt next generation refrigerants for use in heat pumps and refrigeration instruments, we carry out analysis, not only of heat transfer for several types of heat exchangers, but also of the cycle performance of heat pumps and refrigeration that uses pure refrigerants and mixtures thereof. MF48 d i MF58 MF64

Research Center for Next Generation Refrigerant Properties (NEXT-RP) WPI-I 2 CNER, Kyushu University 7 (3) Division for Refrigerant Property Information and Academia-Industry Collaboration Data obtained by divisions (1) and (2) are compiled into a database, and the data are transferred using userfriendly software. International collaboration is established amongst Japanese researchers and other researchers at international universities and institutes.

Research Center for Next Generation Refrigerant Properties (NEXT-RP) WPI-I 2 CNER, Kyushu University 8 International Collaboration

Beginning in the 1930s, Appearance of novel refrigerants, CFC (ChloroFluoroCarbon) and HCFC (Hydrochlorofluorocarbon) 9 Problem: (1980s) Ozone Layer Depletion Solution: Appearance of non-chlorine fluorocarbons HFC (HydroFuoroCarbon) refrigerants and their mixtures Problem: (2000s) Global Warming Solution: Appearance of Low GWP Refrigerants HFO (HydroFluoroOlefin) refrigerants and their mixtures Problem: Flammability and Safety At the present, our task is to find out the following next generation refrigerants: (1) Low ODP (Ozone Depletion Potential) (2) Low GWP (Global Warming Potential) (3) Non-flammable or Mild flammable (4) No toxicity

Refrigerants 10 CFC (Chlorofluorocarbon) is made of C, F, and Cl. R11, R12, R113, R114, R115 HCFC (Hydrochlorofluorocarbon):is made of C, F, Cl, and H. R21, R22, R123, R124, R141b, R142b, R225 HFC (Hydrofluorocarbon):is made of C, F, and H. R23, R32, R125, R134a, R143a, R152a, R245fa HC (Hydrocarbon):is made of C and H. R290, R600, R600a, R1270 HFO (Hydrofluoroolefin):is made of C, F, and H. and it has a double bond. R1234yf, R1234ze(E), R1234ze(Z), R1243zf

11 Prediction of pressure enthalpy diagram for HFOs. J. S. Brown, ASHRAE Journal, August, 2009, pp. 22-29. HFOs

HFOs C 3 H 2 F 4 12 R1234yf R1234ze(E) R1234ze(Z) CF 3 F C C H H CF 3 H C C H F CF 3 H C C F H Group substitution First appended letter Group substitution Second appended letter -Cl x =CCl 2 a -F y =CClF b -H z =CF 2 c =CHCl =CHF =CH 2 d e f

13 Categoly of next generation refrigerants R410A alternative (= R12, R22, R134a alternative) R404A alternative (= R502 alternative) Working fluids for ORC (= R600a, R245fa alternative)

14 R410A alternatives For room air-conditioners and refrigerators Before Montreal Protocol R12, R22 After Montreal Protocol R134a, R410A (R32+R125) Global warming = Kyoto Protocol R32, R1234yf, R290, R600a (Hydrocarbons) Risk R32 higher GWP (Global warming potential) R1234yf (GWP=1 以下 ) expensive Flammable

15 R404A alternatives Lower temperature than R410A Before Montreal Protocol R502 (azeotropic mixture of R22+R115) After Montreal Protocol R404A (R125+R134a+R143a mixture) Risk R502 includes R115 (CFC) R404A has high GWP = 4200

16 Working fluid for ORC Organic Rankine Cycle is expected as the energy reuse system because we are afraid of the future of Japanese energy after the accident of nuclear power plant on 3.11. ORC is considered as an expecting new energy without fossil fuel with the combination of renewable energy. Previously R114 (CFC), R245fa (HFC but high GWP), R600a (HC) was considered as the ORC working fluids. New candidates of R245fa alternative are: R1234ze(Z), R1233zd(E), R1336mzz(Z), R1224yd(Z) etc.

17 R1224yd(Z) : C 3 HClF 4 CF 3 H C C F Cl R1234ze(Z) CF 3 F C C H H Group substitution First appended letter Group substitution Second appended letter -Cl x =CCl 2 a -F y =CClF b -H z =CF 2 c =CHCl =CHF =CH 2 d e f

Experimental apparatus in NEXT-RP 18 Critical point measurements critical parameters, Tc and rc saturated liquid and vapor densities PrT properties measurements PrT properties along isochors saturation pressure and Pc Vapor-liquid equilibrium measurements VLE properties saturation pressure Surface tension measurements by differential capillary rise method

(Experiment 1) Critical point measurements critical parameters, Tc and rc saturated liquid and vapor densities 19 Expansion Vessel Supplying Vessel A: supplying vessel, B: expansion vessel, C: optical cell, D1, D2: thermometer bridge, E:digital multimeter, F: voltage converter, G: PID controller, H: rocking stage, I, J: 25Ω platinum resistance thermometer, K: stirrer, L: 300W heater, M: 1.5 W heater, N: voltage transformer, O: Computer, P: vacuum pump Optical Cell

Temperature Phenomena of meniscus disappearance 20 Temperature r << r c r < r c r = r c r > r c r >> r c Density

21 In the case of saturated vapor density Coexistence curve Phenomena of meniscus disappearance

22 In the case of saturated liquid density Coexistence curve Phenomena of meniscus disappearance

23 In the case of the critical density Coexistence curve Phenomena of meniscus disappearance

24 Criteria for determining the T c and r c from the experiment 1. Meniscus locates the center level at the vapor-liquid coexistence state 2. Meniscus level is kept unchanged in spite of increasing temperature 3. Critical opalescence is observed 4. The intensity of the critical opalescence in the vapor phase is the same as that in the liquid phase 5. Meniscus disappears at the center in the cell 6. Meniscus reappears at the center in the cell Determination of the P c from the experiment 1. Vapor-pressures on the critical isochore are measured. 2. Calculate the P c on the critical isochore at T c. (as a fitting parameter of vapor pressure correlation)

25 Vapor pressure of R1224yd(Z) T Ps Deviation from Fukushima s Ps Correlation (K) (kpa) (kpa) (%) 310.00 224.4 2.34 1.05 315.00 262.1 1.94 0.75 320.00 304.9 2.00 0.66 325.00 352.7 1.80 0.51 330.00 406.1 1.71 0.42 335.00 465.6 1.69 0.36 340.00 531.2 1.90 0.26 345.00 604.0 1.45 0.24 350.00 683.5 0.99 0.14 355.00 771.3 1.09 0.14 360.00 866.5 0.30 0.03 365.00 971.3 0.46 0.05 370.00 1084.1-0.72-0.07 375.00 1208.2-0.40-0.03 380.00 1340.3-2.42-0.18 385.00 1484.9-2.89-0.19 390.00 1640.0-4.59-0.28 395.00 1807.7-6.03-0.33 400.00 1988.9-7.10-0.36 405.00 2184.1-8.18-0.37 410.00 2392.5-11.02-0.46 415.00 2618.1-12.78-0.49 420.00 2860.1-15.75-0.55 425.00 3122.7-17.57-0.56 428.69 => Pc

Vapor pressure correlation of R1224yd(Z) 26 lnp = lnp c +(T c /T)(Aτ + Bτ 1.5 + Cτ 2.5 + Dτ 5 ) T c (K) 428.69 P c (kpa) 3332 A -7.6437 Present Correlation B 1.93439 C -2.94503 D 1.27199 Average deviation 0.25 kpa: 0.02 % Standard deviation 0.34 kpa: 0.03 %

27 Critical parameters of R1224yd(Z) Critical Temperature: 428.69 ± 0.02 K Critical Density: 535 ± 5 kg/m 3 Critical Pressure: 3332 ± 3 kpa Researchers T c (K) r c (kg/m 3 ) P c (kpa) Fukushima et al. * 429.18 530 3379 Present work 428.69 535 3332 (*) Fukushima, M., Hayamizu, H. and Hashimoto, M., Thermodynamic properties of low-gwp refrigerant for Centrifugal Chiller, Proc. 16 th International Refrigeration and Air Conditioning Conference, Purdue University, July (2016), #2151.

Saturated Densities and Critical Parameters 28 Refrigerant T c K P c kpa r c kg/m 3 R245fa 427.01 3651 522 R1234ze(Z) 423.27 3533 470 R600a 407.795 3628.2 229 R1234ze(E) 382.51 3632 486 R1243zf 376.93 3517 414 R134a 374.11 4048 511 R290 369.818 4246.5 227 R1234yf 367.85 3382 478 R32 351.26 5780 428 R404A 345.27 3735 487 R410A 344.49 4901 459 R125 339.17 3618 572 R1123 331.73 4546 504

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30 Next Generation Refrigerants Components Composition(mass%) Bubble point ( C) Safety group R444A R32/R152a/R1234ze(E) (12.0/5.0/83.0) -25 A2 R444B R32/R152a/R1234ze(E) (41.5/10.0/48.5) -44.6 A2L R445A R744/R134a/R1234ze(E) (6.0/9.0/85.0) -24 A2 R446A R32/R1234ze(E)/R600 (68.0/29.0/3.0) -47.2 A2L R447A R32/R125/R1234ze(E) (68.0/3.5/28.5) -47.6 A2L R448A R32/R125/R1234yf/R134a/R1234ze(E) (26.0/26.0/20.0/21.0/7.0) -45.9 A1 R449A R32/R125/R1234yf/R134a (24.3/24.7/25.3/25.7) -46.0 A1 R449B R32/R125/R1234yf/R134a (25.2/24.3/23.2/27.3) -46.1 A1 R450A R134a/R1234ze(E) (42.0/58.0) -23.4 A1 R451A R1234yf/R134a (89.8/10.2) -30.8 A2L R451B R1234yf/R134a (88.8/11.2) -31.0 A2L R452A R32/R125/R1234yf (11.0/59.0/30.0) -47.0 A1 R452B R32/R125/R1234yf (67.0/7.0/26.0) -51.0 A2L R452C R32/R125/R1234yf (12.5/61.0/26.5) -47.5 A1 R454A R32/R1234yf (35.0/65.0) -48.4 A2L R454B R32/R1234yf (68.9/31.1) -50.9 A2L R454C R32/R1234yf (21.5/78.5) -46.0 A2L R455A R744/R32/R1234yf (3.0/21.5/75.5) -51.6 A2L R456A R32/R134a/R1234ze(E) (6.0/45.0/49.0) -30.4 A1 R457A R32/ R1234yf/R152a (18.0/70.0/12.0) -42.7 A2L R513A R1234yf/R134a (56.0/44.0) -29.2 (NBP) A1 R513B R1234yf/R134a (58.5/41.5) -29.2 (NBP) A1 R515A R1234ze(E)/R227ea (88.0/12.0) -18.9 (NBP) A1

31 Binary mixtures and multi-component mixture Components Composition(mass%) Bubble point ( C) Safety group R444A R32/R152a/R1234ze(E) (12.0/5.0/83.0) -25 A2 R444B R32/R152a/R1234ze(E) (41.5/10.0/48.5) -44.6 A2L R445A R744/R134a/R1234ze(E) (6.0/9.0/85.0) -24 A2 R446A R32/R1234ze(E)/R600 (68.0/29.0/3.0) -47.2 A2L R447A R32/R125/R1234ze(E) (68.0/3.5/28.5) -47.6 A2L R448A R32/R125/R1234yf/R134a/R1234ze(E) (26.0/26.0/20.0/21.0/7.0) -45.9 A1 R449A R32/R125/R1234yf/R134a (24.3/24.7/25.3/25.7) -46.0 A1 R449B R32/R125/R1234yf/R134a (25.2/24.3/23.2/27.3) -46.1 A1 R450A R134a/R1234ze(E) (42.0/58.0) -23.4 A1 R451A R1234yf/R134a (89.8/10.2) -30.8 A2L R451B R1234yf/R134a (88.8/11.2) -31.0 A2L R452A R32/R125/R1234yf (11.0/59.0/30.0) -47.0 A1 R452B R32/R125/R1234yf (67.0/7.0/26.0) -51.0 A2L R452C R32/R125/R1234yf (12.5/61.0/26.5) -47.5 A1 R454A R32/R1234yf (35.0/65.0) -48.4 A2L R454B R32/R1234yf (68.9/31.1) -50.9 A2L R454C R32/R1234yf (21.5/78.5) -46.0 A2L R455A R744/R32/R1234yf (3.0/21.5/75.5) -51.6 A2L R456A R32/R134a/R1234ze(E) (6.0/45.0/49.0) -30.4 A1 R457A R32/ R1234yf/R152a (18.0/70.0/12.0) -42.7 A2L R513A R1234yf/R134a (56.0/44.0) -29.2 (NBP) A1 R513B R1234yf/R134a (58.5/41.5) -29.2 (NBP) A1 R515A R1234ze(E)/R227ea (88.0/12.0) -18.9 (NBP) A1

Research Center for Next Generation Refrigerant Properties (NEXT-RP) WPI-I 2 CNER, Kyushu University 32 Thank you for your attention Research Center for Next Generation Refrigerant Properties (NEXT-RP), International Institute for Carbon-Neutral Energy Research (I²CNER), Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395 JAPAN TEL: +81-92-802-6704 FAX: +81-92-802-6728 EMAIL: next-rp@i2cner.kyushu-u.ac.jp