Refrigerant types, issues, trends and future options

Selvaraji Muthu DGM-NTD, Subros Limited, C-51, Phase-2, Noida, U.P. selvaraji.muthu@subros.com +91- 9910307727 Aseem Kumar Jaiswal AVP R&D, NTD, Subros Limited, C-51, Phase-2, Noida, U.P. ajaiswal@subros.com +91- 9810435765 Paper submitted for ACRECONFINDIA 8th 9th Feb2013

Refrigerant types, issues, trends and future options

Flow of Presentation: 1. Introduction 2. Refrigerant Properties 3. Types of Refrigerants 4. Generation of Refrigerants 5. What is ODP? 6. Montreal Protocol 7. What is GWP? 8. What is TEWI? 9. Kyoto Protocol 10.Fourth generation Refrigerants 11.Future options 12.Conclusion 13.References
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1. Introduction
C1 to D : Compression (Polytrophic)

D to E : De-super heating (Isobaric) E to A : Condensation (Isobaric, Isothermal) A to A1 : Sub-cooling (Isobaric)

A1 to B : Expansion (throttling, Isenthalpic)

B to C : Evaporation (Isobaric, Isothermal) C to C1 : Super heating (Isobaric)

Vapour Compression refrigeration Circuit

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Types of Compressors

2. Refrigerant Properties
Required Properties of Ideal Refrigerant: 1) Low boiling point and Low freezing point. 2) Low specific heat and High latent heat. 3) High critical pressure and temperature 4) Low specific volume to reduce the size of the compressor. 5) High thermal conductivity to reduce the area of heat transfer in evaporator and condenser. 6) Non-flammable, non-explosive, non-toxic and non-corrosive. 7) High miscibility with lubricating oil 8) High COP in the working temperature range. 9) Compatible with legal requirement 10) Availability and cost

Numbering Logic for Refrigerants

R()13 4 a isomer # of fluorine atoms per molecule # of hydrogen atoms + 1 per molecule

# of carbon atoms -1 per molecule (left off when 0) # of unsaturated carbon bonds (left off when 0)

Decoding of Refrigerants

R134+90 =( ) 2 2 4 R1234+90=(1)3 2 4 # of Fluorine atoms per molecule # of Hydrogen atoms per molecule # of Carbon atoms per molecule # of unsaturated carbon bonds (left off when 0) # of Chlorine atoms per molecule (calculated from balance carbon bonding
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3. Types of Refrigerants
Methane Group Ethane Group Propane Zeotrope group mixtures Azeotrope organic mixtures compounds inorga nic compo unds 700 Series Series with isolated carbon > 1000 Series as per Numbering Logic R1100s R1200s R1234ze R1234yf R1270 etc

10 Series

100 Series

200 Series

400 Series

500 Series

600 Series

as per Numbering Logic R11 R123

Numbering Convention does not work

R404a

600 R717Hydrocarbons ammon ia NH3 R507c 610 Oxygen compounds 620 Sulfur compounds etc.. 630 Nitrogen compounds R718water R744CO2 R729 Air

R12 R22 etc..

R134a

R407c R410a

etc..

etc..

etc..

Grouping of Refrigerants
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Zeotropic refrigerants : Boil at different temperatures Azeotropic refrigerants : Boil at constant temperature

Classification of Refrigerants

4. Generations of refrigerants
1st Generation of refrigerants First generation refrigerants, used for almost one hundred years (1830 ~ 1930 ), were a variety of volatile compounds ( ethers,CO2,NH3, SO2,HCs,H2O,CCL2,CHCs etc. ) that exhibited useful characteristics.

Ammonia (NH3), methyl chloride (CH3Cl), and sulfur dioxide (SO2) are toxic gases. Several fatal accidents occurred in the 1920s because of methyl chloride leakage from refrigerators, which pushed the entire world to look for next generation refrigerants.

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Generations of refrigerants 2nd Generation of refrigerants Emphasising the need for improved endurance and safety. CFCs (1930s) and later HCFCs (1940s) were invented by Thomas Midgley Jr. (aided by Charles Franklin Kettering

As per the patent no. 2104882 (1931) of Thomas Midgley Jr.,

CnHmFpXr

in which

C - Carbon n is No. of carbon atoms, one or more. H - Hydrogen m is No. of Hydrogen atoms F - Fluorine p is No. of Fluorine atoms, one or more X - Chlorine, bromine or iodine or combinations thereof r is the total number of such atoms. r may be zero when p is greater than one

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Methane (R50)
Molecular Weight , kg/kmol C H = 12 = 1.01

H
Molecular Weight = 1*12+4*1.01 = 16.04 kg/kmol Boiling Point = - 161 o C Density = 716 g/cc

C
CH4

R12
Molecular Weight , kg/kmol F Cl Br I = 18.998 = 35.453 = 79.904 = 126.904 Produced in 1931

Cl

F
Molecular Weight = 1*12+2*35.453+2*18.998 = 120.9 kg/kmol Boiling Point = - 29.8 o C Density = 1.486 g/cc

C
CCl2F2

Cl

DiChloro-DiFluoro-Methane

R11
Molecular Weight , kg/kmol F Cl Br I = 18.998 = 35.453 = 79.904 = 126.904 Produced in 1932

Cl

Cl
Molecular Weight = 1*12+3*35.453+1*18.998 = 137.36 kg/kmol Boiling Point = + 23.77 o C Density = 1.494 g/cc

C
CCl3F

Cl

TriChloro-Fluoro-Methane

R22
Molecular Weight , kg/kmol F Cl Br I = 18.998 = 35.453 = 79.904 = 126.904

Cl

F
Molecular Weight = 1*12+1*1.01+1*35.453+2*18.998 = 86.46 kg/kmol Boiling Point = - 40.7 o C Density = 3.66 g/cc

C
H

F
CHClF2
DiFluoro-Chloro-Methane

Generations of refrigerants

3rd generation of refrigerants includes chemical groups, such as hydro-fluoro-carbons (HFCs), that do not damage the ozone layer as that was the perceived environmental danger at the time. However, as the effects of refrigerant leakages on global warming and climate change have become evident, next generation refrigerants are required.

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Ethane (R 170)
Molecular Weight , kg/kmol F Cl Br I = 18.998 = 35.453 = 79.904 = 126.904

C
H

C
C2H6
Ethane

Molecular Weight = 2*12+6*1.01 = 30.06 kg/kmol Boiling Point = - 89 o C Density = 1.282 g/cc

R134a
Molecular Weight , kg/kmol F Cl Br I = 18.998 = 35.453 = 79.904 = 126.904

C
F

C
F
C2H2F4

Molecular Weight = 2*12+2*1.01+4*18.998 = 102.1 kg/kmol Boiling Point = - 26.3 o C Density = 0.00425g/cc

Generations of refrigerants 4th generation of refrigerants The `synthetic refrigerants' such as HFCs are being replaced with HFOs or `natural refrigerants.

HFO R1234ze HFO R1234yf

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Propene (R1270)
Molecular Weight , kg/kmol F Cl Br I = 18.998 = 35.453 = 79.904 = 126.904

H
Molecular Weight = 3*12+6*1.01 = 42.06 kg/kmol Boiling Point = - 47.6 o C Density = 1.81g/cc

C C C
C3H6

Propylene

R1234-yf
Molecular Weight , kg/kmol F Cl Br I = 18.998 = 35.453 = 79.904 = 126.904

F
Molecular Weight = 3*12+2*1.01+4*18.998 = 114.01 kg/kmol Boiling Point = - 30 o C Density = 1.1 g/cc

C C C
C3H2F4

TetraFluoroPropene

Four generations (Calm JM, 2010).

Low ozone depletion potential (ODP) low global warming potential (GWP) short atmospheric lifetime (tatm) high efficiency.
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5. What is ODP?
ODP is Ozone Depletion Potential of with reference to CFC R11 as 1. Cl + O3 -> ClO + O2 ClO + O3 -> Cl + 2O2
CFCs Refrigerants:

HCFCs Refrigerants

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Molina and Rowlands findings were published in 1974 and shocked the entire world.

Their findings were later confirmed by scientists around the world, especially the British Antarctic Survey in 1986. This led to the Montreal Protocol of 1987 that banned CFCs around the world.
They received the Nobel Prize for Chemistry in 1995.

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6. Montreal Protocol
The Montreal Protocol on Substances that Deplete the Ozone Layer is an international treaty designed to protect the ozone layer by phasing out the production of numerous substances believed to be responsible for ozone depletion. The treaty was opened for signature on September 16, 1987.
Article A 5 (1) : Special situation of developing countries Any Party that is a developing country and whose annual calculated level of consumption of the controlled substances in Annex A is less than 0.3 kilograms per capita on the date of the entry into force of the Protocol for it.

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27

Hole in Ozone Layer

The concentration of ozone in the atmosphere is measured in "Dobson Units", the average concentration of ozone in the atmosphere is about 300 Dobson Units. The ozone hole is considered to be wherever the concentration drops below 220 Dobson Units.

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Velders et al., PNAS, 2007

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7. What is GWP?
Global warming potential (GWP) is a measure of how much a given mass of greenhouse gas is estimated to contribute to global warming. It is a relative scale that compares a gas to that of the same mass of CO2 (GWP of CO2 is by definition 1). Global Warming Potential (100 Years) 1 21

Species CO2 Methane

Chemical formula CO2 CH4

Lifetime (years) variable 12

Nitrous oxide
HFC-23 HFC-32 HFC-41

N2O
CHF3 CH2F2 CH3F

120
264 5.6 3.7

310
11700 650 150

HFC-125
HFC-134 HFC-134a

C2HF5
C2H2F4 CH2FCF3
32

32.6
10.6 14.6

2800
1000 1300

Ref : Calm JM, 2008 33

8. Total equivalent warming impact (TEWI)

TEWI

= GWP (direct; refrigerant leaks incl. EOL) + GWP (indirect; operation) = (GWP x m x L annual x n) + (GWP x m x (1- recovery)) + (E annual x x n)

Where: GWP = Global Warming Potential of refrigerant, relative to CO2 (GWP CO2 = 1) L annual = Leakage rate p.a. (Units: kg) n = System operating life (Units: years) m = Refrigerant charge (Units: kg) recovery = Recovery/recycling factor from 0 to 1 E annual = Energy consumption per year (Units: kWh p.a.) = Indirect emission factor (Units: kg CO2 per kWh)

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9. Kyoto Protocol
The Kyoto Protocol is a protocol to the United Nations Framework Convention on Climate Change (UNFCCC), Kyoto, Japan, on 11 December 1997 that set binding obligations on the industrialized countries to reduce their emissions of greenhouse gases.

Ref : Calm JM, 2008 35

Ref: The U.S. Response to the Kyoto Protocol, Kevin Klein, Professor of Economics, Illinois College March 2, 2007

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CO2 emissions

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2eq/yr 5-6 times Kyoto target (incl. offsets: HFCs, ozone depl.)

Velders et al., PNAS, 2007

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Regional Shares of World Carbon Emissions, 1997 & 2020

Ref: The U.S. Response to the Kyoto Protocol, Kevin Klein, Professor of Economics, Illinois College March 2, 2007

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10. Fourth generation Refrigerants

HFO-R1234yf
CH2=CF-CF3
Vapor Pressure Vs. Temperature
3.5 3.0

HFO-R1234ze
CHF=CH-CF3
Vapor Pressure Vs. Temperature
3.5 3.0

Pressure, MPa

134a
2.5 2.0 1.5 1.0 0.5 0.0 -20 0 20 40
o

Pressure, MPa

2.5 2.0 1.5 1.0 0.5 0.0

1234ze(E) 134a

1234yf

60

80

100

-20

20

40

60
o

80

100

Environmental ODP = 0 GWP100 = 4 Atmospheric Life: 11 days Toxicity & Regulatory Approvals Low toxicity : Honeywell PEL = 400 ppm Key toxicity testing complete; good results Notified to ELINCS, hence registered to REACH. Submit HPV update by Dec 1.

Temperature, C

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Environmental ODP = 0 GWP100 = 6 Atmospheric Life: 18 days Toxicity & Regulatory Approvals Low toxicity : Honeywell PEL = 1,000 ppm Significant testing completed; good results EU Notification Annex VIII Level 1

Temperature, C

10. Fourth generation Refrigerants

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10. Fourth generation Refrigerants

41

Ref: NIST Chemistry WebBook

11. Future options

The Example of Room A/C
Propane (R290) Refrigerant price Cost for performance Compressor, EX, etc. Cost for safety Charge reduction Joint Electronic parts Leak detector Ventilation Cost for handling Manufacture Supply chain Installation Service Disposal Cheap Modification required Same as R22 R32 Cheap Near as R410A Same as R410A HFO1234yf Expensive Larger comp. Larger pipe etc.

Component which increases cost

CO2(R744) Cheap Two-stage comp. High-pressure etc.

Important (ex.230g) Special joint Sealing etc. Necessary Necessary

Necessary Special joint -

Necessary Special joint -

Necessary -

Special facility Qualification Qualified person Qualified person Qualification

Modified facility Modification Modification Modification Modification

Modified facility Modification Modification Modification Modification

Modified facility Qualification Qualified person Qualified person

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12. Conclusion
Thomas Midgley (1928) had invented the CFCs & HCFCs, but the large use of these refrigerants had created severe threat to the earth in terms of ozone layer depletion and global warming (HFCs).
McNeill has stated that Midgley "had more impact on the atmosphere than any other single organism in Earth's history. Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants. PLAN DO
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CHECK

ACT

13. References
1. 2. 3. 4. 5. 6. 7. 8. ASHRAE, 2007, https://osr.ashrae.org/Public%20Review%20Draft%20Standards%20Lib/34z2007%201st%20PPR%20Draft.pdf ASHRAE, 2008, http://www.ashrae.org/File%20Library/docLib/Public/20080807_34m_thru_34v_final.pdf Anant et al. Investigation of Cubic EOS models for HFO-1234yf Refrigerant Used in Automotive Application, International Refrigeration and Air Conditioning Conference at Purdue, July 16-19, 2012 Bjrn Palm, REFRIGERANTS OF THE FUTURE, 10thIEA Heat Pump Conference 2011, 16 - 19 May 2011, Tokyo, Japan http://kth.diva-portal.org/smash/get/diva2:483181/FULLTEXT01 Calm JM, Composition Designations for Refrigerants, ASHRAE Journal, November 1989 Calm JM, Global Warming Impacts of Chillers, Heating Piping Air Conditioning, February 1993 Calm JM, Refrigerant Safety, ASHRAE Journal, 1994 Calm JM, The next generation of refrigerants - Historical review, considerations, and outlook, Int. J. Refrig. 31 (7), 1123-1133 (2008). http://dx.doi.org/10.1016/j.ijrefrig.2008.01.013 Calm JM, Refrigerant Transitions ... Again. ASHRAE-NIST Refrigerants Conference 2012 Carmen J. Giunta THOMAS MIDGLEY, JR., AND THE INVENTION OF CHLOROFLUOROCARBON REFRIGERANTS: IT AINT NECESSARILY SO , Bull. Hist. Chem., VOLUME 31, Number 2 (2006 CHARLES F. KETTERING , BIOGRAPHICAL MEMOIR of THOMAS MIDGLEY, JR. 1889-1944, PRHSENTED TO THE ACADEMY AT THE ANNUAL MEETING, 1947. Dylan S. Cousins and Arno Laesecke, Sealed Gravitational Capillary Viscometry of Dimethyl Ether and Two Next-Generation Alternative Refrigerants Journal of Research of the National Institute of Standards and Technology, Volume 117 http://dx.doi.org/10.6028/jres.117.014 , 2012 G Venkatarathnam and S Srinivasa Murthy, Refrigerants for Vapour Compression Refrigeration Systems, RESONANCE February 2012 GUIDE 2012: Natural Refrigerants Market Growth for Europe, shecco publications Imke et al. Energy consumption of battery cooling in electric hybrid vehicles, International Refrigeration and Air Conditioning Conference at Purdue, July 16-19, 2012 44

9. 10.
11. 12.

13. 14. 15.

Continuing .

16. NASA, 2007, http://www.nasa.gov/vision/earth/environment/ozone_recovering.html Date: March11, 2011 17. NIST Standard Reference Database 23, REFPROP - Thermo dynamic properties of refrigerants and refrigerant mixtures, Version 3.04, NIST, USA, 1991. 18. M. Richter, M. O. McLinden, and E. W. Lemmon, Thermodynamic Properties of 2,3,3,3Tetrafluoroprop-1-ene (R1234yf): Vapor Pressure and pT Measurements and an Equation of State, J. Chem. Eng. Data 56 (7), 3254-3264 (2011). http://dx.doi.org/10.1021/je200369m 19. M. O. McLinden, M. Thol, and E. W. Lemmon, "Thermodynamic Properties of trans-1,3,3,3tetrafluoropropene [R1234ze(E)]: Measurements of Density and Vapor Pressure and a Comprehensive Equation of State", Proceedings of the 2010 International Refrigeration and Air Conditioning Conference, Purdue, West Lafayette, IN, USA, Paper No. 2189. http://docs.lib.purdue.edu/iracc/1041/ 20. Handbook for the Montreal Protocol on Substances that Deplete the Ozone Layer, Ninth edition (2012), United Nations Environment Programme. 21. The Montreal Protocol and the Green Economy, 2012, UNEP. 22. THE AUSTRALIAN INSTITUTE OF 23. METHODS OF CALCULATING TOTAL EQUIVALENT WARMING IMPACT (TEWI), AIRAH, Best Practise Guidelines, 2012, 24. KYOTO PROTOCOL TO THE UNITED NATIONS FRAMEWORK CONVENTION ON CLIMATE CHANGE, 1998, UN. 25. Reasor, Pamela; Aute, Vikrant; and Radermacher, Reinhard, "Refrigerant R1234yf Performance Comparison Investigation" (2010). International Refrigeration and Air Conditioning Conference. Paper 1085 http://docs.lib.purdue.edu/iracc/1085/ 26. R1234yf.fld - NIST, www.boulder.nist.gov/div838/theory/refprop/R1234YF.FLD 27. R1234ze.fld - NIST , www.boulder.nist.gov/div838/theory/refprop/R1234ZE.FLD 28. SAE, 2010a, http://www.sae.org/mags/aei/8702 , Date: April 22, 2011. 29. SAE, 2010b, http://www.sae.org/mags/AEI/8074 , Date: April 22, 2011. 30. SAE, 2011, http://www.sae.org/standardsdev/tsb/cooperative/altrefrig.htm , Date: April 22, 2011 45

Continuing .

31. http://www.reefercargocare.com/refrigerants.html 32. http://www.reefercargocare.com/ozone-depleting-substances.html 33. http://www.lindegas.com/en/products_and_supply/refrigerants/fluorine_refrigerants/hfo_refrigerants.html 34. http://humantouchofchemistry.com/frank-rowland-and-mario-molina.htm 35. http://www.beyonddiscovery.org/content/view.page.asp?I=89 Inventor : Thomas Midgley US Patent No. 2013062 2007208 2104882 2024008 2192143

No.

dated Sep.3, 1935 July 9,1935 Jan.11, 1938 Dec.10, 1935 Feb.27, 1940

patent Title Preparation of aliphatic halofluoro compounds Manufacture of halo-fluoro derivative of aliphatic hydrocarbons Heat transfer and refrigeration Manufacture of antimony trifluoride Fluorination process 46

filed as on Feb. 26, 1931 Feb. 24, 1931 Nov.19, 1931 June 30, 1934 May 7, 1938

2 3 4 5

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