2014 ASHRAE Annual Conference Seattle

Seminar 35 – Advances in Low

Global Warming Potential

(GWP) Refrigerants

Refrigerant/Lubricant Properties

of New Low GWP Options

Gregory L. Smith, Ph.D. Honeywell

Gregory.Smith2@Honeywell.com Office 716.827.6239

Mobile 716.352.5504

1

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.

2

Acknowledgements

• Elizabet Vera Becerra – Honeywell

• Kurtis Colwell – Honeywell

• Raymond Thomas – Honeywell

• Mark Spatz – Honeywell

3

Outline/Agenda

• Drivers for refrigerant change

• Definitions

• Select new HFO refrigerants and

blends

– Miscibility assessments

– Solubility and viscosity

• Conclusions

4

EU F-Gas Regulation

Regulatory Requirements

CFCs HCFCs HFCs HFOs

Montreal Protocol / Ozone Depletion Concerns

Kyoto Protocol / Global Warming Concerns

Ozone

Global warming

Ozone

Global warming

Ozone

Global warming

Ozone

Global warming

HCFC

Phase-out

CFC

Phase-out

Simple Chemistry

Enhanced Chemistry

New Molecule Development

Advanced Molecules Development

+ Complex Chemistry

R12 R134a R1234yf 5

Decision-Making Criteria

vs. Alternatives

Environmental • Low Global Warming

Potential

• Zero Ozone Depletion

• Good Life Cycle Climate Performance in All Climates

• Recycling / Reclamation

Performance • High Energy Efficiency Over

Complete Operating Range

• Long-term Durability

Must Meet All Criteria for Acceptance

Safety • In Use, Storage, Transport

• Comprehensive Toxicology Testing

• Acceptable Flammability

Cost-To-Serve • Low Capital Cost

• Low Operating Cost

• Better Cost vs. Alternatives

• Low System Maintenance

6

Lubricants

• Most compressors require lubrication

• Lubricant circulates with the refrigerant

• “Oil return” to the compressor is required

• Anything that hinders oil return is a

problem

– System design, fouling, foaming

– Refrigerant / lubricant mixture separation

7

Refrigerant / Lubricant Mixtures

• The working fluid is a mixture of refrigerant

and lubricant

• Refrigerant dissolves in and dilutes the

lubricant, which lowers its viscosity

• Viscosity of refrigerant/lubricant mixture

depends on the solubility of the refrigerant

in the lubricant

8

Miscibility and Solubility

• Immiscible liquids do not mix, so form distinct phase boundaries

– Oil and water

• Miscible liquids mix to form a homogenous (single-phase) solution

– Alcohol and water

• Solubility describes the extent to which one substance dissolves into another when forming a homogenous solution

9

Miscibility Assessment

• Test cells prepared

with different

refrigerant / lubricant

concentrations

• Placed in chamber

and observed while

temperature varied

from –50 to 100 oC

10

R1234yf compared to R134a

• R1234yf has high temperature immiscibility with POE (>62.5 oC – above phase inversion)

• No immiscibility seen with R134a and POE 32

-40

-20

0

20

40

60

80

100

40% 50% 60% 70% 80% 90% 100%

Te

mp

era

ture

(°C

)

Liquid Refrigerant Mass Fraction (g/g)

Miscibility R1234yf / POE ISO 32

neatrefrigerant

Miscible

Immiscible

-40

-20

0

20

40

60

80

100

0.4 0.5 0.6 0.7 0.8 0.9 1

Te

mp

era

ture

(°C

)

Liquid Refrigerant Mass Fraction (g/g)

Miscibility R134a / POE ISO 32

neatrefrigerant

Miscible

11

R1234ze compared to R134a

• No immiscibility seen between R1234ze

and POE 32, as with R134a

-40

-20

0

20

40

60

80

100

0.4 0.5 0.6 0.7 0.8 0.9 1

Te

mp

era

ture

(°C

)

Liquid Refrigerant Mass Fraction (g/g)

Miscibility R134a / POE ISO 32

neatrefrigerant

Miscible

-40

-20

0

20

40

60

80

100

0.4 0.5 0.6 0.7 0.8 0.9 1

Te

mp

era

ture

(°C

)

Liquid Refrigerant Mass Fraction (g/g)

Miscibility R1234ze / POE ISO 32

neatrefrigerant

Miscible

12

N13 compared to R134a

• N13 has a low temperature miscibility limit with POE (–24 oC – below intended application range)

• No immiscibility seen with R134a and POE 32

-40

-20

0

20

40

60

80

100

0.4 0.5 0.6 0.7 0.8 0.9 1

Te

mp

era

ture

(°C

)

Liquid Refrigerant Mass Fraction (g/g)

Miscibility R134a / POE ISO 32

neatrefrigerant

Miscible

-40

-20

0

20

40

60

80

100

40% 50% 60% 70% 80% 90% 100%

Te

mp

era

ture

(°C

)

Liquid Refrigerant Mass Fraction (g/g)

Miscibility N13 / POE ISO 32

neatrefrigerant

Miscible

Immiscible

13

N40 compared to R404A

• N40 is miscible with POE 32 over a wider temperature range (up to 75 oC) versus R404A (up to 29 oC)

-40

-20

0

20

40

60

80

100

40% 50% 60% 70% 80% 90% 100%

Te

mp

era

ture

(°C

)

Liquid Refrigerant Mass Fraction (g/g)

Miscibility N40 / POE ISO 32

neatrefrigerant

Miscible

Immiscible

-40

-20

0

20

40

60

80

100

40% 50% 60% 70% 80% 90% 100%

Te

mp

era

ture

(°C

)

Liquid Refrigerant Mass Fraction (g/g)

Miscibility R404A / POE ISO 32

neatlubricant

neatrefrigerant

Miscible

Immiscible

14

L41-2 compared to R410A

• L41-2 is miscible with POE 32 over a wider temperature range (-35 to 80 oC) versus R410A (-20 to 48 oC)

-40

-20

0

20

40

60

80

100

40% 50% 60% 70% 80% 90% 100%

Te

mp

era

ture

(°C

)

Liquid Refrigerant Mass Fraction (g/g)

Miscibility L41-2 / POE ISO 32

neatrefrigerant

Miscible

Immiscible

Immiscible

-40

-20

0

20

40

60

80

100

40% 50% 60% 70% 80% 90% 100%

Te

mp

era

ture

(°C

)

Liquid Refrigerant Mass Fraction (g/g)

Miscibility R410A / POE ISO 32

neatrefrigerant

Miscible

Immiscible

Immiscible

15

Solubility and Viscosity

Measurement

• Pressure / Viscosity / Temperature (PVT) Test Rig – State-of-the-art equipment

– Pump circulates refrigerant/lubricant mixture

– Dynamic measurement of: • Pressure

• Density

• Viscosity

• Mass flow

• Temperature

– Allowing for mapping of pressure, solubility and viscosity as functions of temperature and composition

– Daniel plots provide information important for bearing wear protection

P

Exhaust Vent

Burst Disc

Gear Pump

65 C

Environmental Chamber

N 2 Purge

Massflow

Density

Piston Viscometers

Thermocouple

16

N40 compared to R404A

-20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130

0.6

0.7

0.8

0.91

2

3

4

56

810

20

30

5070

100

200300500

5. 5339822

Kin

em

atic V

isco

sity,

cS

t

Figure 2: Viscosity and Vapor PressureEmkarate RL32-3MAF with N-40

0%

30% N-40

20% N-40

12.5

bara

10 b

ara8 b

ara6

bara

15 b

ara

20 b

ara

10% N-40

40% N-40

5% N-40

5 b

ara4 b

ara

25 b

ara

30 b

ara

35 b

ara

40 b

ara

Temperature, oC

Daniel Chart – N40 and POE 32

-20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130

0.6

0.7

0.8

0.91

2

3

4

56

810

20

30

5070

100

200300500

5. 5339822

Kin

em

atic V

isco

sity,

cS

t

Figure 2: Viscosity and Vapor PressureEmkarate RL32-3MAF with R404A

0%

30% R404A

20% R404A

12.5

bara

10 b

ara8 b

ara

6 b

ara

15 b

ara

20 b

ara

10% R404A

40% R404A

5% R404A

5 b

ara

25 b

ara

30 b

ara

35 b

ara

40 b

ara

4 b

ara

Temperature, oC

Daniel Chart – R404A and POE 32

Viscosity (cSt) Solubility (wt%)

N40 2.7 23

R404A 3.8 19

Compare at 70 oC and 20 bar

17

N40 compared to R404A

• Viscosity decreases, solubility increases,

and similar vapor pressure curves for N40

compared to R404A in POE 32 lubricant

-20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130

0

5

10

15

20

25

30

35

40

45

50

Pre

ssu

re, b

ara

Temperature, °C

10% N-40

20% N-40

Pure N-40

5% N-40

40% 30% N-40

Vapor Pressure – N40 and POE 32

-20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130

0

5

10

15

20

25

30

35

40

45

50

55

60

Pre

ssu

re, b

ara

Temperature, °C

10% R404A

20% R404A

Pure R404A

5% R404A

40% 30% R404A

Vapor Pressure – R404A and POE 32

18

L41-2 compared to R410A

-20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130

0.6

0.7

0.8

0.91

2

3

4

56

810

20

30

5070

100

200300500

5. 5339822

Kin

em

atic V

isco

sity,

cS

t

Figure 2: Viscosity and Vapor PressureEmkarate RL32-3MAF with HDR-103

0%

30% HDR-103

20% HDR-103

12.5

bara

10 b

ara8 b

ara6 b

ara

15 b

ara

20 b

ara

10% HDR-103

40% HDR-103

5% HDR-103

5 b

ara4 b

ara

25 b

ara

30 b

ara

35 b

ara

40 b

ara

-20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130

0.6

0.7

0.8

0.91

2

3

4

56

810

20

30

5070

100

200300500

5. 5339822

Kin

em

atic V

isco

sity,

cS

t

Figure 2: Viscosity and Vapor PressureEmkarate RL32-3MAF with R410A

0%

30% R410A

20% R410A

12.5

bara

10 b

ara8 b

ara6

bara

15 b

ara

20 b

ara

10% R410A

40% R410A

5% R410A

5 b

ara

25 b

ara

30 b

ara

35 b

ara

40 b

ara

Daniel Chart – L41-2 and POE 32 Daniel Chart – R410A and POE 32

Temperature, oC Temperature, oC

Viscosity (cSt) Solubility (wt%)

L41-2 3.3 16

R410A 4.0 15

Compare at 70 oC and 20 bar

19

L41-2 compared to R410A

-20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130

0

5

10

15

20

25

30

35

40

45

50

55

60

Pre

ssu

re, b

ara

Temperature, °C

10% HDR-103

20% HDR-103

Pure HDR-103

5% HDR-103

40% 30% HDR-103

-20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130

0

5

10

15

20

25

30

35

40

45

50

55

60

Pre

ssu

re, b

ara

Temperature, °C

10% R410A

20% R410A

Pure R410A

5% R410A

40% 30%

Vapor Pressure – L41-2 and POE 32 Vapor Pressure – R410A and POE 32

• Viscosity decreases, solubility increases,

and similar vapor pressure curves for L41-2

compared to R410A in POE 32 lubricant 20

R1234ze compared to R134a

21

-20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130

0.6

0.7

0.8

0.91

2

3

4

56

810

20

30

5070

100

200300500

5. 5339822

Kin

em

atic V

isco

sity,

cS

t

Figure 2: Viscosity and Vapor PressureSolest 220 with HFO-1234ze

0% - neat lub.

30% R1234ze

20% R1234ze

12.5

bara

10 b

ara

8 b

ara6

bara

15 b

ara

20 b

ara

10% R1234ze

40% R1234ze

5% R1234ze

5 b

ara4 b

ara3 b

ara

2.5

bara2b

ara

-20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130

0.6

0.7

0.8

0.91

2

3

4

56

810

20

30

5070

100

200300500

5. 5339822

Kin

em

atic V

isco

sity,

cS

t

Figure 2: Viscosity and Vapor PressureSolest 220 with R134a

0% - neat lub.

30% R134a

20% R134a

12.5

bara

10 b

ara

8 b

ara6

bara

15 b

ara

20 b

ara

10% R134a

40% R134a

5% R134a

5 b

ara4 b

ara3 b

ara

2.5

bara

2b

ara

Daniel Chart – R1234ze and POE 220 Daniel Chart – R134a and POE 220

Temperature, oC Temperature, oC

Viscosity (cSt) Solubility (wt%)

R1234ze 4.9 25

R134a 10.5 17

Compare at 70 oC and 10 bar

R1234ze compared to R134a

22

-20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130

0

5

10

15

20

25

30

35

40

Pre

ssu

re, b

ara

Temperature, °C

10% R134a

20% R134aPure R134a

5% R134a

40% 30% R134a

-20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130

0

5

10

15

20

25

30

35

40

Pre

ssu

re, b

ara

Temperature, °C

10% R1234ze

20% R1234ze

Pure R1234ze

5% R1234ze

40% R1234ze

30% R1234ze

Vapor Pressure – R1234ze and POE 220 Vapor Pressure – R134a and POE 220

• Solubility increases, and Viscosity and Vapor

Pressure decrease considerably for R1234ze

compared to R134a in POE 220 lubricant

N13 compared to R134a

23

-20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130

0.6

0.7

0.8

0.91

2

3

4

56

810

20

30

5070

100

200300500

5. 5339822

Kin

em

atic V

isco

sity,

cS

t

Figure 2: Viscosity and Vapor PressureSolest 220 with R134a

0% - neat lub.

30% R134a

20% R134a

12.5

bara

10 b

ara

8 b

ara6

bara

15 b

ara

20 b

ara

10% R134a

40% R134a

5% R134a

5 b

ara4 b

ara3 b

ara

2.5

bara

2b

ara

Daniel Chart – R134a and POE 220

Temperature, oC -20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130

0.6

0.7

0.8

0.91

2

3

4

56

810

20

30

5070

100

200300500

5. 5339822

Kin

em

atic V

isco

sity,

cS

t

Figure 2: Viscosity and Vapor PressureRL220H with N13

0% - neat lub.

30% N13

20% N13

12.5

bara

10 b

ara8 b

ara6

bara

15 b

ara

20 b

ara

10% N13

40% N13

5% N13

5 b

ara

4 b

ara3 b

ara

2.5

bara

2b

ara

Daniel Chart – N13 and POE 220

Temperature, oC

Viscosity (cSt) Solubility (wt%)

N13 8.1 20

R134a 10.5 17

Compare at 70 oC and 10 bar

R1234ze, N13

compared to R134a

24

Viscosity (cSt) Solubility (wt%)

R1234ze 4.9 25

N13 8.1 20

R134a 10.5 17

Compare at 70 oC and 10 bar in POE 220

• N13 (58% R1234ze, 42% R134a) has

properties between those of the two pure

components

Conclusions

25

• Considering new low GWP refrigerants R1234yf, R1234ze, and their blends at typical operating temperatures and pressures: – Miscibility with POE is satisfactory, and in

some cases wider temperature ranges are available

– Solubility with POE is similar for blends and higher for R1234ze

– Viscosities are correspondingly lower but are expected to be satisfactory for most applications

Questions?

Greg Smith

Gregory.Smith2@Honeywell.com

26