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Refrigerant types, issues, trends and future options

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 Paper submitted for ACRECONFINDIA 8th – 9th Feb’2013

Refrigerant types, issues, trends and future options

Track Code : C2 (Effective use of Unitary HVAC Systems in today’s Buildings)

Selvaraji Muthu Aseem Kumar Jaiswal

DGM-NTD, AVP –R&D, NTD,
Subros Limited, Subros Limited,
C-51, Phase-2, Noida, U.P. C-51, Phase-2, Noida, U.P.
selvaraji.muthu@subros.com ajaiswal@subros.com
+91- 9910307727 +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. Abstract 1
2. Introduction 2
3. Refrigerant Properties 3
4. Types of Refrigerants 3
5. Generation of Refrigerants 5
6. What is ODP? 6
7. Montreal Protocol 7
8. What is GWP? 9
9. What is TEWI? 11
10. Kyoto Protocol 11
11. Fourth generation Refrigerants 12
12. Future options 13
13. Conclusion 15
14. References 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.

1
C to D : Compression (Polytrophic) Compressor

D to E : De-super heating (Isobaric)

E to A : Condensation (Isobaric, Isothermal) Condenser
A to A1 : Sub-cooling (Isobaric)

1
A to B : Expansion (throttling, Isenthalpic) TXV Valve

B to C : Evaporation (Isobaric, Isothermal)

Evaporator
C to C1 : Super heating (Isobaric)

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 Ethane Propane Zeotrope Azeotrope organic inorganic Series with

Group Group group mixtures mixtures compounds compounds isolated
carbon
10 Series 100 200 400 Series 500 Series 600 Series 700 +mw > 1100
Series Series Series Series
as per Numbering as per
Logic Numbering Convention does not work Numbering
Logic
R11 R123 R404a •600 R717- R1100s
Hydrocarbo ammonia R1200s
ns NH3
R12 R134a R407c R507c •610 R718- R1234ze
Oxygen water
compounds
R22 R410a •620 Sulfur R744- CO2 R1234yf
compounds
etc.. etc.. etc.. etc.. etc.. •630 R729 - Air R1270 etc…
Nitrogen
compounds
Table-1 : Grouping of refrigerants

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 Paper submitted for ACRECONFINDIA 8th – 9th Feb’2013
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 non-
flammable, 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 2nd Gen 3rd Gen 4th Gen 5th Gen

1830 -1930s 1931 -1990s 1990 -2010s 2012 onwards 2020s ?

Whatever Safety and Ozone Layer Global Efficiency &

worked Durability Protection Warming Trade-offs

CO2 CFCs HFCs HFOs

NH3 HCFCs HCs HCFOs
SO2 HFCs CO2 HCs CO2
HCs NH3 NH3 CO2 NH3
H2O H 2O H 2O NH3 H 2O …
….. ….. ….. H2O …

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 Rowland’s 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).

Global
Chemical Lifetime Warming
Species
formula (years) Potential
(100 Years)
CO2 CO2 variable 1
Methane CH4 12 21
Nitrous
N2O 120 310
oxide
HFC-23 CHF3 264 11700
HFC-32 CH2F2 5.6 650
HFC-41 CH3F 3.7 150
HFC-125 C2HF5 32.6 2800
HFC-134 C2H2F4 10.6 1000
HFC-134a CH2FCF3 14.6 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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 Paper submitted for ACRECONFINDIA 8th – 9th Feb’2013
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- α recovery)) + (E annual x β 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)
α recovery = Recovery/recycling factor from 0 to 1
E annual = Energy consumption per year (Units: kWh p.a.)
β = 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 HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3
Vapor Pressure Vs. Temperature Vapor Pressure Vs. Temperature
3.5 3.5

3.0 3.0
Pressure, MPa

Pressure, MPa
134a 1234ze(E)
2.5 2.5

2.0 1234yf 2.0

134a

1.5 1.5

1.0 1.0

0.5 0.5

0.0 0.0
-20 0 20 40 60 80 100 -20 0 20 40 60 80 100

Temperature, oC Temperature, oC
Environmental Environmental
• ODP = 0 • ODP = 0
• GWP100 = 4 • GWP100 = 6
• Atmospheric Life: 11 days • Atmospheric Life: 18 days

Fig-15 HFO refrigerants Properties

Natural Refrigerants

Table-6 Natural refrigerants properties

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 Paper submitted for ACRECONFINDIA 8th – 9th Feb’2013
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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 Paper submitted for ACRECONFINDIA 8th – 9th Feb’2013

Ref: NIST Chemistry WebBook

Fig-17 PH Diagram of CO2

Component which
The Example of Room A/C increases cost

Propane (R290) R32 HFO1234yf CO2(R744)

Refrigerant price Cheap Cheap Expensive Cheap

Cost for performance

Compressor, Modification required Near as R410A Larger comp. Two-stage comp.
EX, etc. Same as R22 Same as R410A Larger pipe etc. High-pressure etc.

Cost for safety

Charge reduction Important (ex.230g) Necessary Necessary Necessary
Joint Special joint Special joint Special joint -
Electronic parts Sealing etc. - - -
Leak detector Necessary - - -
Ventilation Necessary - - -

Cost for handling

Manufacture Special facility Modified facility Modified facility Modified facility
Supply chain Qualification Modification Modification Qualification
Installation Qualified person Modification Modification Qualified person
Service Qualified person Modification Modification Qualified person
Disposal Qualification Modification Modification

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

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 Paper submitted for ACRECONFINDIA 8th – 9th Feb’2013
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/34z-

2007%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. Björn 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 AIN’T NECESSARILY SO , Bull. Hist.
Chem., VOLUME 31, Number 2 (2006)

11. CHARLES F. KETTERING , BIOGRAPHICAL MEMOIR of THOMAS MIDGLEY, JR. 1889-

1944, 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 2,3,3,3-

Tetrafluoroprop-1-ene (R1234yf): Vapor Pressure and p—ρ—T Measurements and an Equation
of State, J. Chem. Eng. Data 56 (7), 3254-3264 (2011). http://dx.doi.org/10.1021/je200369m

Page 15 of 16
 Paper submitted for ACRECONFINDIA 8th – 9th Feb’2013
19. M. O. McLinden, M. Thol, and E. W. Lemmon, "Thermodynamic Properties of trans-1,3,3,3-
tetrafluoropropene [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.linde-
gas.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
No. Patent dated patent Title filed as on
No.
Preparation of aliphatic halofluoro
1 2013062 Sep.3, 1935 Feb. 26, 1931
compounds
Manufacture of halo-fluoro
2 2007208 July 9,1935 derivative of aliphatic Feb. 24, 1931
hydrocarbons
3 2104882 Jan.11, 1938 Heat transfer and refrigeration Nov.19, 1931
Manufacture of antimony
4 2024008 Dec.10, 1935 June 30, 1934
trifluoride
5 2192143 Feb.27, 1940 Fluorination process May 7, 1938

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