Paper submitted for ACRECONFINDIA 8th 9th Feb2013

Refrigerant types, issues, trends and future options Track Code : C2 (Effective use of Unitary HVAC Systems in todays Buildings) 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

Abstract: Seminar is focused on the fundamentals of Vapor Compression refrigeration system which is principally applicable for all Automotive, Domestic and Industrial Air-Conditioning and Refrigeration Applications. Briefly, introduction to be given to the heart of the system, which is Compressor and types and functions. The flood of the Air-conditioner, that is, the refrigerants, their properties, merits and demerits are summarized to map the various types and their classifications. Detailed comparison is made on first generation, second generation and third generation refrigerants, including the option of using HCs and CO2. Main focus is given to the Montreal Protocol and Kyoto Protocols. Possibilities of changeover from CFC/HCFC based refrigerants to HFC or HFO based third and fourth generation refrigerants are also covered. At the end of the session, all attendees would able get the absolute clarity on the function, selection and their merits and demerits of various Refrigerants in terms of design of the system and their components, ODP, GWP & TEWI indexes. Duration : 60 Minutes (2 Consecutive Sessions)

Keywords: CFC, HCHC, HFC, HFO, HC-Hydro Carbons, Co2 Refrigerants, Vapor Compression Refrigeration system, ODP -Ozone Deletion Potential, GWP-Global warming Potential, TEWI-Total Equivalent Warming Index, Montreal Protocol, Kyoto Protocol CFC ; Chloro Fluro Carbons HCFC : Hydro Chloro Fluro Carbons HFC : Hydro Fluro Carbons HC : Hydro Carbons HFO : Hydro Fluro Olefins

Table of Contents: 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. Abstract Introduction Refrigerant Properties Types of Refrigerants Generation of Refrigerants What is ODP? Montreal Protocol What is GWP? What is TEWI? Kyoto Protocol Fourth generation Refrigerants Future options Conclusion References 1 2 3 3 5 6 7 9 11 11 12 13 15 16

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2. Introduction: Simple Vapor Compression Refrigeration System: A simple vapour compression refrigeration system consists of the following equipments in the sequence as shown in Fig-1: i) Compressor ii) Condenser iii) Expansion valve iv) Evaporator.

Fig-1 Vapour Compression refrigeration Circuit The change of state and their processes are listed as below. C to D : Compression (Polytrophic) D to E : De-super heating (Isobaric) E to A : Condensation (Isobaric, Isothermal) A to A1 : Sub-cooling (Isobaric)
1 1

Compressor

Condenser

A to B : Expansion (throttling, Isenthalpic) B to C : Evaporation (Isobaric, Isothermal) C to C1 : Super heating (Isobaric)

TXV Valve Evaporator

Function of Compressor: To suck the Low Pressure refrigerant in vapour form from Evaporator To compress the refrigerant to higher pressure with super heated vapour To pump this high pressure high temperature super heated vapour to Condenser

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Fig-2, Classification of compressor Technologies

3. Refrigerant Properties
Irrespective of the size and efficiency of the individual parts in the vapour compression circuit, the good refrigerant is the one, ensuring the highest overall effectiveness of the system. 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 compact 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

4. Types of Refrigerants
The different types of refrigerants can be grouped as given below (ASHRAE 2008). Methane Group 10 Series Ethane Group Propane group 200 Series Zeotrope mixtures 400 Series Azeotrope mixtures 500 Series organic compounds 600 Series inorganic compounds 700 +mw Series Series with isolated carbon > 1100 Series as per Numbering Logic R1100s R1200s R1234ze

100 Series as per Numbering Logic R11 R123

Numbering Convention does not work R404a 600 Hydrocarbo ns 610 Oxygen compounds 620 Sulfur compounds 630 Nitrogen compounds R717ammonia NH3 R718water R744- CO2 R729 - Air

R12

R134a

R407c

R507c

R22 etc.. etc.. etc..

R410a etc.. etc..

R1234yf R1270 etc

Table-1 : Grouping of refrigerants

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The numbering logic is explained as below.

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)

Fig-3 Numbering Logic for refrigerants There is a simple methodology followed to decode the above numbering, which is shown as below.

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
Fig-4 Decoding of Refrigerants Since, each refrigerants are having superiority in terms of different properties, there are mixtures developed to arrive a required level of multiple properties to make the overall system performance (COP) better. The following classification is made to show the non-mixtures and mixtures.

Fig-5 Types of Refrigerants

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Table-2 Mapping of Refrigerants on Toxicity & Flammability

5. Generation of Refrigerants
Either or all of the 4 listed requirements are demanding the invention of new generation refrigerants one after another (Calm 2008). Zero ozone depletion potential (ODP) low global warming potential (GWP) short atmospheric lifetime (tatm) high efficiency.

1st Generation Refrigerants First generation refrigerants, used for almost one hundred years (1830 ~ 1930 ), were a variety of volatile compounds ( ethers,CO2,NH3, SO2,HCs,H2O etc. ), that worked. 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. 2nd Generation Refrigerants 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., these halogen derivatives of aliphatic mono-fluorides may be represented by the formula

CnHmFpXr

in which

C represents carbon and n is the number of carbon atoms in the molecule which is always equal to one or more. H represents hydrogen and m is the number of atoms thereof, which may equal zero and still fulfill the requirements of invention. F represents fluorine and p is the number of atoms thereof which is always equal to one or more. X represents chlorine, bromine or iodine or combinations thereof and r is the total number of such atoms. r may be zero when p is greater than one

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3rd Generation Refrigerants The third 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 has become evident, next generation refrigerants are required. 4th Generation Refrigerants It is interesting that chemicals used in the first generation are being reconsidered as possible fourth generation refrigerants. The `synthetic refrigerants' such as HFCs are being replaced with HFOs (R1234ze, R12234yf) or `natural refrigerants'. The concerns for safety, endurance and efficiency that encouraged evolution away from these `natural refrigerants' in the past are still relevant now. For modern refrigerants there are even more essential characteristics to be considered. These include: Propane (R-290) and CO2 (R-744) are being proposed as new generation refrigerants, CO2 is nonflammable, non-ozone depleting, non-toxic and has a GWP of 1. The four generations included slightly overlapping periods as given below, (Calm JM, 2010).

1st Gen 1830 -1930s Whatever worked CO2 NH3 SO2 HCs H2O ..

2nd Gen 1931 -1990s Safety and Durability CFCs HCFCs HFCs NH3 H 2O ..

3rd Gen 1990 -2010s Ozone Layer Protection HFCs HCs CO2 NH3 H 2O ..

4th Gen 2012 onwards Global Warming HFOs HCFOs HCs CO2 NH3 H2O

5th Gen 2020s ? Efficiency & Trade-offs

CO2 NH3 H 2O

Fig-6 Generations of Refrigerants 6. What is ODP? ODP is Ozone Depletion Potential of with reference to CFC R11 as 1. Frank Sherwood Rowland, Professor of Chemistry at the University of California, Irvine and Mario Molina, who had got PhD in Chemistry at the University of California had together discovered that CFCs decompose in sunlight, to release chlorine atoms. Chlorine atoms convert ozone to oxygen, and can then attack other ozone molecules. A single atom can destroy millions of ozone molecules before it is neutralized. Cl + O3 -> ClO + O2 ClO + O3 -> Cl + 2O2 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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CFCs Refrigerants:

HCFCs Refrigerants

Table -3 ODP of refrigerants (Montreal Protocol) 7. 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.

Fig-7 Phase-out of CFCs

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Fig-8 Phase-out of HCFCs

Fig-10 Ozone Chlorine Concentration (NASA report)

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Velders et al., PNAS, 2007 Fig-11 Effective Stratospheric Chlorine Projection 8. 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).

Species CO2 Methane Nitrous oxide HFC-23 HFC-32 HFC-41 HFC-125 HFC-134 HFC-134a

Chemical formula CO2 CH4 N2O CHF3 CH2F2 CH3F C2HF5 C2H2F4 CH2FCF3

Lifetime (years) variable 12 120 264 5.6 3.7 32.6 10.6 14.6

Global Warming Potential (100 Years) 1 21 310 11700 650 150 2800 1000 1300

Table-4 GWP of refrigerants

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Ref: The U.S. Response to the Kyoto Protocol, Kevin Klein, Professor of Economics, Illinois College March 2, 2007 Fig-12 CO2 Concentrations

Effects on climate
CO2 emissions

World avoided by the Montreal Protocol Reduction Montreal Protocol of ~11 GtCO2-eq/yr

5-6 times Kyoto target

(incl. offsets: HFCs, ozone depl.)
Velders et al., PNAS, 2007 Fig-13 Emissions of CO2

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9. What is TEWI? Total equivalent warming impact (TEWI) is a measure used to express contributions of GHG to global warming. It is defined as sum of the direct (chemical emissions) and indirect (energy use) emissions of greenhouse gases (GHG). The method of calculating TEWI is provided below (AIRAH guide methods of calculating 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) 10. 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. 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 Fig-14 Regional Shares of World Carbon Emissions, 1997 & 2020

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11. Fourth Generation Refrigerants HFO Refrigerants HFO (hydro-fluoro-olefin) refrigerants are the fourth generation of fluorine-based refrigerants. HFC refrigerants are composed of hydrogen, fluorine and carbon atoms connected by single bonds between the atoms. HFO refrigerants are composed of hydrogen, fluorine and carbon atoms, but contain at least one double bond between the carbon atoms. The HFOs, currently being developed by DuPont and Honeywell, are HFO 1234ze and HFO 1234yf, which are having GWP of 6 & 3 respectively, replacement for R134a.

HFO-R1234yf CH2=CF-CF3
3.5 3.0

HFO-R1234ze CHF=CH-CF3

Vapor Pressure Vs. Temperature

3.5 3.0

Vapor Pressure Vs. Temperature

Pressure, MPa
1234ze(E) 134a

Pressure, MPa

134a
2.5 2.0 1.5 1.0 0.5 0.0 -20 0 20 40 60 80 100

2.5 2.0 1.5 1.0 0.5 0.0 -20

1234yf

20

40

60

80

100

Environmental ODP = 0 GWP100 = 4 Atmospheric Life: 11 days

Temperature, oC

Environmental ODP = 0 GWP100 = 6 Atmospheric Life: 18 days

Temperature, oC

Fig-15 HFO refrigerants Properties Natural Refrigerants

Table-6 Natural refrigerants properties

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12. Future options

The transitions between successive generations required very large research, development, plant construction, evaluation, product redesign, testing, training, and additional investments, but they also created significant business opportunities. While actual transition to the fourth generation has just begun, a number of challenges are emerging that may dictate later transition to a fifth generation predicated in the absence of ideal refrigerants. Among the potential driving factors are efficiency, momentum, prices, litigation and liability, unforeseen suitability issues, local impacts, and political aspects. HFOs (R1234ze & R1234yf) & Natural refrigerants (NH3, CO2 etc..)

Fig-16 Comparison of R134a and R12234yf

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Ref: NIST Chemistry WebBook Fig-17 PH Diagram of CO2

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

Fig-18 : mapping of various refrigerants and their challenge points

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13. 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. 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. 14. References: 1. ASHRAE, 2007, https://osr.ashrae.org/Public%20Review%20Draft%20Standards%20Lib/34z2007%201st%20PPR%20Draft.pdf 2. ASHRAE, 2008, http://www.ashrae.org/File%20Library/docLib/Public/20080807_34m_thru_34v_final.pdf 3. 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 4. 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 5. Calm JM, Composition Designations for Refrigerants, ASHRAE Journal, November 1989 6. Calm JM, Global Warming Impacts of Chillers, Heating Piping Air Conditioning, February 1993 7. Calm JM, Refrigerant Safety, ASHRAE Journal, 1994 8. 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 9. Calm JM, Refrigerant Transitions ... Again. ASHRAE-NIST Refrigerants Conference 2012 10. Carmen J. Giunta THOMAS MIDGLEY, JR., AND THE INVENTION OF CHLOROFLUOROCARBON REFRIGERANTS: IT AINT NECESSARILY SO , Bull. Hist. Chem., VOLUME 31, Number 2 (2006) 11. CHARLES F. KETTERING , BIOGRAPHICAL MEMOIR of THOMAS MIDGLEY, JR. 18891944, PRHSENTED TO THE ACADEMY AT THE ANNUAL MEETING, 1947. 12. 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 13. G Venkatarathnam and S Srinivasa Murthy, Refrigerants for Vapour Compression Refrigeration Systems, RESONANCE February 2012 14. GUIDE 2012: Natural Refrigerants Market Growth for Europe, shecco publications 15. Imke et al. Energy consumption of battery cooling in electric hybrid vehicles, International Refrigeration and Air Conditioning Conference at Purdue, July 16-19, 2012 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

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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.

THE AUSTRALIAN INSTITUTE OF 22. METHODS OF CALCULATING TOTAL EQUIVALENT WARMING IMPACT (TEWI), AIRAH, Best Practise Guidelines, 2012,
23. KYOTO PROTOCOL TO THE UNITED NATIONS FRAMEWORK CONVENTION ON CLIMATE CHANGE, 1998, UN. 24. 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/ 25. R1234yf.fld - NIST, www.boulder.nist.gov/div838/theory/refprop/R1234YF.FLD 26. R1234ze.fld - NIST , www.boulder.nist.gov/div838/theory/refprop/R1234ZE.FLD 27. SAE, 2010a, http://www.sae.org/mags/aei/8702 , Date: April 22, 2011. 28. SAE, 2010b, http://www.sae.org/mags/AEI/8074 , Date: April 22, 2011. 29. SAE, 2011, http://www.sae.org/standardsdev/tsb/cooperative/altrefrig.htm , Date: April 22, 2011 30. http://www.reefercargocare.com/refrigerants.html 31. http://www.reefercargocare.com/ozone-depleting-substances.html 32. http://www.lindegas.com/en/products_and_supply/refrigerants/fluorine_refrigerants/hfo_refrigerants.html 33. http://humantouchofchemistry.com/frank-rowland-and-mario-molina.htm 34. http://www.beyonddiscovery.org/content/view.page.asp?I=89 35. Patents referred. Inventor : Thomas Midgley US Patent No. 2013062 2007208 2104882 2024008 2192143

No. 1 2 3 4 5

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

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

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