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Selvaraji Muthu DGM-NTD, Subros Limited, C-51, Phase-2, Noida, U.P. selvaraji.muthu@subros.com +91- 9910307727 Aseem Kumar Jaiswal VP R&D, NTD, Subros Limited, C-51, Phase-2, Noida, U.P. ajaiswal@subros.com +91- 9810435765 Presentation at ACR Trendz 18th & 19th Oct 2013 by ISHRAE Pune Chapter Le Meridian , Pune
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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.Retrofit options 12. Reefer trucks 13.Future technology options 14.Conclusion 15.References
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1. Introduction
C1 to D : Compression (Polytrophic)
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
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
R404a
600 R717Hydrocarbons ammon ia NH3 R507c 610 Oxygen compounds 620 Sulfur compounds etc.. 630 Nitrogen compounds R718water R744CO2 R729 Air
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
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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
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
CnHmFpXr
n=1 m=0 p=2 x=Cl r=2
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
CnHmFpXr
n=1 m=0 p=1 x=Cl r=3
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
CnHmFpXr
n=1 m=1 p=2 x=Cl r=1
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
CnHmFpXr
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.
Hydro Olefins:
HFO R1234ze HFO R1234yf Natural refrigerants: CO2 Organic gases R290 (Propane), R600a (Isobutane), R1270 (Propolene)
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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
CnHmFpXr
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
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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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). Chemical formula CO2 CH4 N2O CHF3 CH2F2 CH3F C2HF5 C2H2F4 CH2FCF3
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Species CO2 Methane Nitrous oxide HFC-23 HFC-32 HFC-41 HFC-125 HFC-134 HFC-134a
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 1430
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: The U.S. Response to the Kyoto Protocol, Kevin Klein, Professor of Economics, Illinois College March 2, 2007
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CO2 emissions
Reduction Montreal Protocol of ~11 GtCO2eq/yr 5-6 times Kyoto target (incl. offsets: HFCs, ozone depl.)
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Ref: The U.S. Response to the Kyoto Protocol, Kevin Klein, Professor of Economics, Illinois College March 2, 2007
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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 60 80 100
Pressure, MPa
1234ze(E) 134a
1234yf
20
40
60
80
100
Temperature, oC
Temperature, oC
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40
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Necessary -
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ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Benefits of R1234yf: 1. GWP=4.0 ( & ODP=0.0) 2. Very low atmospheric life 3. Low TEWI 4. Complying to European Norms 5. Complying to US Norms
R1234yf Implementation issues: 1) Performance impact 2) Additional part (IHX) to match the performance 3) Availability 4) Cost impact 5) Retro fitment issues (New oil type, New ports) 6) Mild Flammability
ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications
TXV
Additional part
Compressor
ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications
S.No. 1 2
Power Consumption, W 2185 2136 -2.2% 2151 -1.6% 2163 -1.0% 2173 -0.5% 2181 -0.2%
COP 2.511 2.353 -6.3% 2.422 -3.5% 2.489 -0.9% 2.552 1.6% 2.613 4.1%
R1234yf
5210.6 -5.0%
Te=0.3 C
4 R1234yf 10 5382.9 -1.9% 5 R1234yf 15 5545 1.1% 6 R1234yf 20 5698.6 3.9% 0.354 -2% 0.309 -7% 0.265 -11%
ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications No IHX X=0.377
ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications No IHX X=0.447
ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications IHX = 5 C additional sub-cool X=0.400
ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications IHX = 10 C additional sub-cool X=0.354
ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications IHX = 15 C additional sub-cool X=0.309
ACMA AWARDS 2009-10 Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications IHX = 20 C additional sub-cool X=0.265
Retrofitting of R134a by R1234yf Alternative Refrigerant for Automotive Air Conditioning Applications
Objective Changeover of refrigerant types R134a to R1234yf
As per Montreal Protocol (1987), the changeover happened from R12 to R134a to avoid the ozone layer depletion. Kyoto Protocol (1997) has set the target to reduce the emissions of greenhouse gases, which are contributing the global warming. EU Directives for MAC (2009) have set the target to use the refrigerants having GWP < 150 for Automotive Air Conditioning Applications.
Refrigerant type CFC HCFC HFC HFO Natural ref. Grade R12 R22 R134a R1234yf CO2 ODP 1 0.055 0 0 0 GWP 10900 1810 1430 4 1 Cost of ownership low 2nd Generation low low slight high 4th Generation very high 3rd Generation Development
1 2
1 Changeover as per Montreal Protocol 2 Changeover due to Kyoto Protocol and EU MAC Directives, US EPA Rules.
Chilled (upto 0 C)
Fresh (upto 10 C)
B]
Drive
Direct Drive
Refrigeration System
Operating Conditions(frozen): Condensing side: 28~32 bar Evaporating side: 1.5~2.5 bar Hot gas Defrost Hot gas bypass from compressor out to evap in for defrosting operation
ODP 0 0 0 0 0 0 0
GWP 3700 3420 4180 1430 2100 716 3420 1505 2174 57 358 1710
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Saturation Pressure, Bar(a)
R134a
R404a
Saturation Temperature, C
International Standards
Reefer Truck Test Conditions with R404a Standard/ Condenser In Evaporator In Specificatio Temperature Temperature Compressor S.No. n of air of air Speed 1 Australian Standard No. AS:4982-2003 2.1 +38 C +12 C 1500 rpm 2.2 +38 C 0C 1500 rpm 2.3 +38 C -18 C 1500 rpm 2.4 +38 C -28 C 1500 rpm 2 Japanese Standard No. JRA_4045:2008 3.1 +35 C +10 C 1800 rpm 3.2 +35 C 0C 1800 rpm 3.3 +35 C -18 C 1800 rpm
Duration in Cool Down test <= 6.5 Hr <= 6.5 Hr <= 6.5 Hr <= 6.5 Hr
Performance
Controller tripped the compressor after the set point of -25 C is reached
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120
180
300
360
420
480
TIFFE Approach
Dual loop air conditioning Development of innovative heat exchangers Use of innovative coolants
ACMA AWARDS 2009-10 Future technology of Air-Conditioning Single loop Conventional Circuit System
ACMA AWARDS 2009-10 Future technology of Air-Conditioning CRU: Compact Refrigeration Unit System
TIFFE Approach
14. 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
15. References
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 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. 18891944, 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 67
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 68
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
No.
dated
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 69
filed as on Feb. 26, 1931 Feb. 24, 1931 Nov.19, 1931 June 30, 1934 May 7, 1938
Sep.3, 1935
2 3 4 5
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