1

Refrigerant types issues trends and future options

Selvaraji MuthuDGM-NTD

Subros LimitedC-51 Phase-2 Noida

UPselvarajimuthusubroscom

+91- 9910307727

Aseem Kumar JaiswalAVP ndashRampD NTDSubros Limited

C-51 Phase-2 Noida UP

ajaiswalsubroscom +91- 9810435765

Paper submitted for ACRECONFINDIA 8th ndash 9th Febrsquo2013

2

Flow of Presentation

1 Introduction2 Refrigerant Properties3 Types of Refrigerants4 Generation of Refrigerants5 What is ODP 6 Montreal Protocol7 What is GWP8 What is TEWI9 Kyoto Protocol10Fourth generation Refrigerants11Future options12Conclusion13References

Refrigerant types issues trends and future options

3

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

1 Introduction

4

Types of Compressors

5

Required Properties of Ideal Refrigerant

1) Low boiling point and Low freezing point2) Low specific heat and High latent heat 3) High critical pressure and temperature4) Low specific volume to reduce the size of the compressor5) High thermal conductivity to reduce the area of heat transfer in evaporator and condenser6) Non-flammable non-explosive non-toxic and non-corrosive7) High miscibility with lubricating oil 8) High COP in the working temperature range9) Compatible with legal requirement 10) Availability and cost

2 Refrigerant Properties

6

R()13 4 aisomer 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)

of Fluorine atoms per molecule of Hydrogen atoms per molecule of Carbon atoms per molecule

R134+90 =( ) 2 2 4R1234+90=(1)3 2 4R134+90 =( ) 2 2 4R1234+90=(1)3 2 4

of unsaturated carbon bonds (left off when 0)

of Chlorine atoms per molecule(calculated from balance carbon bonding

Numbering Logic for Refrigerants

Decoding of Refrigerants

7

Methane Group

Ethane Group

Propane group

Zeotrope mixtures

Azeotrope mixtures

organic compounds

inorganic compounds

Series with isolated carbon

10 Series 100 Series

200 Series

400 Series 500 Series 600 Series 700 Series

gt 1000 Series

as per Numbering Logic

Numbering Convention does not work as per Numbering Logic

R11 R123 R404a bull600 Hydrocarbons

R717- ammonia NH3

R1100sR1200s

R12 R134a R407c R507c bull610 Oxygen compounds

R718- water

R1234ze

R22 R410a bull620 Sulfur compounds

R744- CO2

R1234yf

etc etc etc etc etc bull630 Nitrogen compounds

R729 - Air

R1270 etchellip

Grouping of Refrigerants

3 Types of Refrigerants

8

Zeotropic refrigerants Boil at different temperatures Azeotropic refrigerants Boil at constant temperature

9

Classification of Refrigerants

10

1st Generation of refrigerants

First generation refrigerants used for almost one hundred years (1830 ~ 1930 )

were a variety of volatile compounds ( ethersCO2NH3 SO2HCsH2OCCL2CHCs etc ) that exhibited useful characteristics

4 Generations of refrigerants

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

11

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

Generations of refrigerants

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

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Methane (R50)

CH H

H

HCH4

Molecular Weight = 112+4101 = 1604 kgkmol

Boiling Point = - 161 o CDensity = 716 gcc

Molecular Weight kgkmol

C = 12H = 101

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R12

CF F

Cl

ClCCl2F2

Molecular Weight = 112+235453+218998

= 1209 kgkmolBoiling Point = - 298 o CDensity = 1486 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiChloro-DiFluoro-Methane

Produced in 1931

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R11

CCl F

Cl

ClCCl3F

Molecular Weight = 112+335453+118998

= 13736 kgkmolBoiling Point = + 2377 o C Density = 1494 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TriChloro-Fluoro-Methane

Produced in 1932

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R22

CF F

Cl

HCHClF2

Molecular Weight = 112+1101+135453+218998

= 8646 kgkmolBoiling Point = - 407 o C Density = 366 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiFluoro-Chloro-Methane

16

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

Generations of refrigerants

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

3

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

1 Introduction

4

Types of Compressors

5

Required Properties of Ideal Refrigerant

1) Low boiling point and Low freezing point2) Low specific heat and High latent heat 3) High critical pressure and temperature4) Low specific volume to reduce the size of the compressor5) High thermal conductivity to reduce the area of heat transfer in evaporator and condenser6) Non-flammable non-explosive non-toxic and non-corrosive7) High miscibility with lubricating oil 8) High COP in the working temperature range9) Compatible with legal requirement 10) Availability and cost

2 Refrigerant Properties

6

R()13 4 aisomer 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)

of Fluorine atoms per molecule of Hydrogen atoms per molecule of Carbon atoms per molecule

R134+90 =( ) 2 2 4R1234+90=(1)3 2 4R134+90 =( ) 2 2 4R1234+90=(1)3 2 4

of unsaturated carbon bonds (left off when 0)

of Chlorine atoms per molecule(calculated from balance carbon bonding

Numbering Logic for Refrigerants

Decoding of Refrigerants

7

Methane Group

Ethane Group

Propane group

Zeotrope mixtures

Azeotrope mixtures

organic compounds

inorganic compounds

Series with isolated carbon

10 Series 100 Series

200 Series

400 Series 500 Series 600 Series 700 Series

gt 1000 Series

as per Numbering Logic

Numbering Convention does not work as per Numbering Logic

R11 R123 R404a bull600 Hydrocarbons

R717- ammonia NH3

R1100sR1200s

R12 R134a R407c R507c bull610 Oxygen compounds

R718- water

R1234ze

R22 R410a bull620 Sulfur compounds

R744- CO2

R1234yf

etc etc etc etc etc bull630 Nitrogen compounds

R729 - Air

R1270 etchellip

Grouping of Refrigerants

3 Types of Refrigerants

8

Zeotropic refrigerants Boil at different temperatures Azeotropic refrigerants Boil at constant temperature

9

Classification of Refrigerants

10

1st Generation of refrigerants

First generation refrigerants used for almost one hundred years (1830 ~ 1930 )

were a variety of volatile compounds ( ethersCO2NH3 SO2HCsH2OCCL2CHCs etc ) that exhibited useful characteristics

4 Generations of refrigerants

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

11

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

Generations of refrigerants

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

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Methane (R50)

CH H

H

HCH4

Molecular Weight = 112+4101 = 1604 kgkmol

Boiling Point = - 161 o CDensity = 716 gcc

Molecular Weight kgkmol

C = 12H = 101

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R12

CF F

Cl

ClCCl2F2

Molecular Weight = 112+235453+218998

= 1209 kgkmolBoiling Point = - 298 o CDensity = 1486 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiChloro-DiFluoro-Methane

Produced in 1931

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R11

CCl F

Cl

ClCCl3F

Molecular Weight = 112+335453+118998

= 13736 kgkmolBoiling Point = + 2377 o C Density = 1494 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TriChloro-Fluoro-Methane

Produced in 1932

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R22

CF F

Cl

HCHClF2

Molecular Weight = 112+1101+135453+218998

= 8646 kgkmolBoiling Point = - 407 o C Density = 366 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiFluoro-Chloro-Methane

16

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

Generations of refrigerants

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

4

Types of Compressors

5

Required Properties of Ideal Refrigerant

1) Low boiling point and Low freezing point2) Low specific heat and High latent heat 3) High critical pressure and temperature4) Low specific volume to reduce the size of the compressor5) High thermal conductivity to reduce the area of heat transfer in evaporator and condenser6) Non-flammable non-explosive non-toxic and non-corrosive7) High miscibility with lubricating oil 8) High COP in the working temperature range9) Compatible with legal requirement 10) Availability and cost

2 Refrigerant Properties

6

R()13 4 aisomer 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)

of Fluorine atoms per molecule of Hydrogen atoms per molecule of Carbon atoms per molecule

R134+90 =( ) 2 2 4R1234+90=(1)3 2 4R134+90 =( ) 2 2 4R1234+90=(1)3 2 4

of unsaturated carbon bonds (left off when 0)

of Chlorine atoms per molecule(calculated from balance carbon bonding

Numbering Logic for Refrigerants

Decoding of Refrigerants

7

Methane Group

Ethane Group

Propane group

Zeotrope mixtures

Azeotrope mixtures

organic compounds

inorganic compounds

Series with isolated carbon

10 Series 100 Series

200 Series

400 Series 500 Series 600 Series 700 Series

gt 1000 Series

as per Numbering Logic

Numbering Convention does not work as per Numbering Logic

R11 R123 R404a bull600 Hydrocarbons

R717- ammonia NH3

R1100sR1200s

R12 R134a R407c R507c bull610 Oxygen compounds

R718- water

R1234ze

R22 R410a bull620 Sulfur compounds

R744- CO2

R1234yf

etc etc etc etc etc bull630 Nitrogen compounds

R729 - Air

R1270 etchellip

Grouping of Refrigerants

3 Types of Refrigerants

8

Zeotropic refrigerants Boil at different temperatures Azeotropic refrigerants Boil at constant temperature

9

Classification of Refrigerants

10

1st Generation of refrigerants

First generation refrigerants used for almost one hundred years (1830 ~ 1930 )

were a variety of volatile compounds ( ethersCO2NH3 SO2HCsH2OCCL2CHCs etc ) that exhibited useful characteristics

4 Generations of refrigerants

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

11

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

Generations of refrigerants

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

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Methane (R50)

CH H

H

HCH4

Molecular Weight = 112+4101 = 1604 kgkmol

Boiling Point = - 161 o CDensity = 716 gcc

Molecular Weight kgkmol

C = 12H = 101

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R12

CF F

Cl

ClCCl2F2

Molecular Weight = 112+235453+218998

= 1209 kgkmolBoiling Point = - 298 o CDensity = 1486 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiChloro-DiFluoro-Methane

Produced in 1931

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R11

CCl F

Cl

ClCCl3F

Molecular Weight = 112+335453+118998

= 13736 kgkmolBoiling Point = + 2377 o C Density = 1494 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TriChloro-Fluoro-Methane

Produced in 1932

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R22

CF F

Cl

HCHClF2

Molecular Weight = 112+1101+135453+218998

= 8646 kgkmolBoiling Point = - 407 o C Density = 366 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiFluoro-Chloro-Methane

16

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

Generations of refrigerants

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

5

Required Properties of Ideal Refrigerant

1) Low boiling point and Low freezing point2) Low specific heat and High latent heat 3) High critical pressure and temperature4) Low specific volume to reduce the size of the compressor5) High thermal conductivity to reduce the area of heat transfer in evaporator and condenser6) Non-flammable non-explosive non-toxic and non-corrosive7) High miscibility with lubricating oil 8) High COP in the working temperature range9) Compatible with legal requirement 10) Availability and cost

2 Refrigerant Properties

6

R()13 4 aisomer 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)

of Fluorine atoms per molecule of Hydrogen atoms per molecule of Carbon atoms per molecule

R134+90 =( ) 2 2 4R1234+90=(1)3 2 4R134+90 =( ) 2 2 4R1234+90=(1)3 2 4

of unsaturated carbon bonds (left off when 0)

of Chlorine atoms per molecule(calculated from balance carbon bonding

Numbering Logic for Refrigerants

Decoding of Refrigerants

7

Methane Group

Ethane Group

Propane group

Zeotrope mixtures

Azeotrope mixtures

organic compounds

inorganic compounds

Series with isolated carbon

10 Series 100 Series

200 Series

400 Series 500 Series 600 Series 700 Series

gt 1000 Series

as per Numbering Logic

Numbering Convention does not work as per Numbering Logic

R11 R123 R404a bull600 Hydrocarbons

R717- ammonia NH3

R1100sR1200s

R12 R134a R407c R507c bull610 Oxygen compounds

R718- water

R1234ze

R22 R410a bull620 Sulfur compounds

R744- CO2

R1234yf

etc etc etc etc etc bull630 Nitrogen compounds

R729 - Air

R1270 etchellip

Grouping of Refrigerants

3 Types of Refrigerants

8

Zeotropic refrigerants Boil at different temperatures Azeotropic refrigerants Boil at constant temperature

9

Classification of Refrigerants

10

1st Generation of refrigerants

First generation refrigerants used for almost one hundred years (1830 ~ 1930 )

were a variety of volatile compounds ( ethersCO2NH3 SO2HCsH2OCCL2CHCs etc ) that exhibited useful characteristics

4 Generations of refrigerants

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

11

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

Generations of refrigerants

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

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Methane (R50)

CH H

H

HCH4

Molecular Weight = 112+4101 = 1604 kgkmol

Boiling Point = - 161 o CDensity = 716 gcc

Molecular Weight kgkmol

C = 12H = 101

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R12

CF F

Cl

ClCCl2F2

Molecular Weight = 112+235453+218998

= 1209 kgkmolBoiling Point = - 298 o CDensity = 1486 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiChloro-DiFluoro-Methane

Produced in 1931

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R11

CCl F

Cl

ClCCl3F

Molecular Weight = 112+335453+118998

= 13736 kgkmolBoiling Point = + 2377 o C Density = 1494 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TriChloro-Fluoro-Methane

Produced in 1932

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R22

CF F

Cl

HCHClF2

Molecular Weight = 112+1101+135453+218998

= 8646 kgkmolBoiling Point = - 407 o C Density = 366 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiFluoro-Chloro-Methane

16

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

Generations of refrigerants

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

6

R()13 4 aisomer 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)

of Fluorine atoms per molecule of Hydrogen atoms per molecule of Carbon atoms per molecule

R134+90 =( ) 2 2 4R1234+90=(1)3 2 4R134+90 =( ) 2 2 4R1234+90=(1)3 2 4

of unsaturated carbon bonds (left off when 0)

of Chlorine atoms per molecule(calculated from balance carbon bonding

Numbering Logic for Refrigerants

Decoding of Refrigerants

7

Methane Group

Ethane Group

Propane group

Zeotrope mixtures

Azeotrope mixtures

organic compounds

inorganic compounds

Series with isolated carbon

10 Series 100 Series

200 Series

400 Series 500 Series 600 Series 700 Series

gt 1000 Series

as per Numbering Logic

Numbering Convention does not work as per Numbering Logic

R11 R123 R404a bull600 Hydrocarbons

R717- ammonia NH3

R1100sR1200s

R12 R134a R407c R507c bull610 Oxygen compounds

R718- water

R1234ze

R22 R410a bull620 Sulfur compounds

R744- CO2

R1234yf

etc etc etc etc etc bull630 Nitrogen compounds

R729 - Air

R1270 etchellip

Grouping of Refrigerants

3 Types of Refrigerants

8

Zeotropic refrigerants Boil at different temperatures Azeotropic refrigerants Boil at constant temperature

9

Classification of Refrigerants

10

1st Generation of refrigerants

First generation refrigerants used for almost one hundred years (1830 ~ 1930 )

were a variety of volatile compounds ( ethersCO2NH3 SO2HCsH2OCCL2CHCs etc ) that exhibited useful characteristics

4 Generations of refrigerants

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

11

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

Generations of refrigerants

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

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Methane (R50)

CH H

H

HCH4

Molecular Weight = 112+4101 = 1604 kgkmol

Boiling Point = - 161 o CDensity = 716 gcc

Molecular Weight kgkmol

C = 12H = 101

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R12

CF F

Cl

ClCCl2F2

Molecular Weight = 112+235453+218998

= 1209 kgkmolBoiling Point = - 298 o CDensity = 1486 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiChloro-DiFluoro-Methane

Produced in 1931

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R11

CCl F

Cl

ClCCl3F

Molecular Weight = 112+335453+118998

= 13736 kgkmolBoiling Point = + 2377 o C Density = 1494 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TriChloro-Fluoro-Methane

Produced in 1932

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R22

CF F

Cl

HCHClF2

Molecular Weight = 112+1101+135453+218998

= 8646 kgkmolBoiling Point = - 407 o C Density = 366 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiFluoro-Chloro-Methane

16

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

Generations of refrigerants

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

7

Methane Group

Ethane Group

Propane group

Zeotrope mixtures

Azeotrope mixtures

organic compounds

inorganic compounds

Series with isolated carbon

10 Series 100 Series

200 Series

400 Series 500 Series 600 Series 700 Series

gt 1000 Series

as per Numbering Logic

Numbering Convention does not work as per Numbering Logic

R11 R123 R404a bull600 Hydrocarbons

R717- ammonia NH3

R1100sR1200s

R12 R134a R407c R507c bull610 Oxygen compounds

R718- water

R1234ze

R22 R410a bull620 Sulfur compounds

R744- CO2

R1234yf

etc etc etc etc etc bull630 Nitrogen compounds

R729 - Air

R1270 etchellip

Grouping of Refrigerants

3 Types of Refrigerants

8

Zeotropic refrigerants Boil at different temperatures Azeotropic refrigerants Boil at constant temperature

9

Classification of Refrigerants

10

1st Generation of refrigerants

First generation refrigerants used for almost one hundred years (1830 ~ 1930 )

were a variety of volatile compounds ( ethersCO2NH3 SO2HCsH2OCCL2CHCs etc ) that exhibited useful characteristics

4 Generations of refrigerants

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

11

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

Generations of refrigerants

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

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Methane (R50)

CH H

H

HCH4

Molecular Weight = 112+4101 = 1604 kgkmol

Boiling Point = - 161 o CDensity = 716 gcc

Molecular Weight kgkmol

C = 12H = 101

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R12

CF F

Cl

ClCCl2F2

Molecular Weight = 112+235453+218998

= 1209 kgkmolBoiling Point = - 298 o CDensity = 1486 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiChloro-DiFluoro-Methane

Produced in 1931

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R11

CCl F

Cl

ClCCl3F

Molecular Weight = 112+335453+118998

= 13736 kgkmolBoiling Point = + 2377 o C Density = 1494 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TriChloro-Fluoro-Methane

Produced in 1932

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R22

CF F

Cl

HCHClF2

Molecular Weight = 112+1101+135453+218998

= 8646 kgkmolBoiling Point = - 407 o C Density = 366 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiFluoro-Chloro-Methane

16

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

Generations of refrigerants

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

8

Zeotropic refrigerants Boil at different temperatures Azeotropic refrigerants Boil at constant temperature

9

Classification of Refrigerants

10

1st Generation of refrigerants

First generation refrigerants used for almost one hundred years (1830 ~ 1930 )

were a variety of volatile compounds ( ethersCO2NH3 SO2HCsH2OCCL2CHCs etc ) that exhibited useful characteristics

4 Generations of refrigerants

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

11

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

Generations of refrigerants

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

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Methane (R50)

CH H

H

HCH4

Molecular Weight = 112+4101 = 1604 kgkmol

Boiling Point = - 161 o CDensity = 716 gcc

Molecular Weight kgkmol

C = 12H = 101

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R12

CF F

Cl

ClCCl2F2

Molecular Weight = 112+235453+218998

= 1209 kgkmolBoiling Point = - 298 o CDensity = 1486 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiChloro-DiFluoro-Methane

Produced in 1931

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R11

CCl F

Cl

ClCCl3F

Molecular Weight = 112+335453+118998

= 13736 kgkmolBoiling Point = + 2377 o C Density = 1494 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TriChloro-Fluoro-Methane

Produced in 1932

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R22

CF F

Cl

HCHClF2

Molecular Weight = 112+1101+135453+218998

= 8646 kgkmolBoiling Point = - 407 o C Density = 366 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiFluoro-Chloro-Methane

16

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

Generations of refrigerants

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

9

Classification of Refrigerants

10

1st Generation of refrigerants

First generation refrigerants used for almost one hundred years (1830 ~ 1930 )

were a variety of volatile compounds ( ethersCO2NH3 SO2HCsH2OCCL2CHCs etc ) that exhibited useful characteristics

4 Generations of refrigerants

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

11

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

Generations of refrigerants

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

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Methane (R50)

CH H

H

HCH4

Molecular Weight = 112+4101 = 1604 kgkmol

Boiling Point = - 161 o CDensity = 716 gcc

Molecular Weight kgkmol

C = 12H = 101

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R12

CF F

Cl

ClCCl2F2

Molecular Weight = 112+235453+218998

= 1209 kgkmolBoiling Point = - 298 o CDensity = 1486 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiChloro-DiFluoro-Methane

Produced in 1931

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R11

CCl F

Cl

ClCCl3F

Molecular Weight = 112+335453+118998

= 13736 kgkmolBoiling Point = + 2377 o C Density = 1494 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TriChloro-Fluoro-Methane

Produced in 1932

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R22

CF F

Cl

HCHClF2

Molecular Weight = 112+1101+135453+218998

= 8646 kgkmolBoiling Point = - 407 o C Density = 366 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiFluoro-Chloro-Methane

16

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

Generations of refrigerants

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

10

1st Generation of refrigerants

First generation refrigerants used for almost one hundred years (1830 ~ 1930 )

were a variety of volatile compounds ( ethersCO2NH3 SO2HCsH2OCCL2CHCs etc ) that exhibited useful characteristics

4 Generations of refrigerants

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

11

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

Generations of refrigerants

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

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Methane (R50)

CH H

H

HCH4

Molecular Weight = 112+4101 = 1604 kgkmol

Boiling Point = - 161 o CDensity = 716 gcc

Molecular Weight kgkmol

C = 12H = 101

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R12

CF F

Cl

ClCCl2F2

Molecular Weight = 112+235453+218998

= 1209 kgkmolBoiling Point = - 298 o CDensity = 1486 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiChloro-DiFluoro-Methane

Produced in 1931

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R11

CCl F

Cl

ClCCl3F

Molecular Weight = 112+335453+118998

= 13736 kgkmolBoiling Point = + 2377 o C Density = 1494 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TriChloro-Fluoro-Methane

Produced in 1932

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R22

CF F

Cl

HCHClF2

Molecular Weight = 112+1101+135453+218998

= 8646 kgkmolBoiling Point = - 407 o C Density = 366 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiFluoro-Chloro-Methane

16

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

Generations of refrigerants

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

11

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

Generations of refrigerants

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

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Methane (R50)

CH H

H

HCH4

Molecular Weight = 112+4101 = 1604 kgkmol

Boiling Point = - 161 o CDensity = 716 gcc

Molecular Weight kgkmol

C = 12H = 101

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R12

CF F

Cl

ClCCl2F2

Molecular Weight = 112+235453+218998

= 1209 kgkmolBoiling Point = - 298 o CDensity = 1486 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiChloro-DiFluoro-Methane

Produced in 1931

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R11

CCl F

Cl

ClCCl3F

Molecular Weight = 112+335453+118998

= 13736 kgkmolBoiling Point = + 2377 o C Density = 1494 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TriChloro-Fluoro-Methane

Produced in 1932

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R22

CF F

Cl

HCHClF2

Molecular Weight = 112+1101+135453+218998

= 8646 kgkmolBoiling Point = - 407 o C Density = 366 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiFluoro-Chloro-Methane

16

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

Generations of refrigerants

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Methane (R50)

CH H

H

HCH4

Molecular Weight = 112+4101 = 1604 kgkmol

Boiling Point = - 161 o CDensity = 716 gcc

Molecular Weight kgkmol

C = 12H = 101

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R12

CF F

Cl

ClCCl2F2

Molecular Weight = 112+235453+218998

= 1209 kgkmolBoiling Point = - 298 o CDensity = 1486 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiChloro-DiFluoro-Methane

Produced in 1931

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R11

CCl F

Cl

ClCCl3F

Molecular Weight = 112+335453+118998

= 13736 kgkmolBoiling Point = + 2377 o C Density = 1494 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TriChloro-Fluoro-Methane

Produced in 1932

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R22

CF F

Cl

HCHClF2

Molecular Weight = 112+1101+135453+218998

= 8646 kgkmolBoiling Point = - 407 o C Density = 366 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiFluoro-Chloro-Methane

16

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

Generations of refrigerants

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R12

CF F

Cl

ClCCl2F2

Molecular Weight = 112+235453+218998

= 1209 kgkmolBoiling Point = - 298 o CDensity = 1486 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiChloro-DiFluoro-Methane

Produced in 1931

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R11

CCl F

Cl

ClCCl3F

Molecular Weight = 112+335453+118998

= 13736 kgkmolBoiling Point = + 2377 o C Density = 1494 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TriChloro-Fluoro-Methane

Produced in 1932

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R22

CF F

Cl

HCHClF2

Molecular Weight = 112+1101+135453+218998

= 8646 kgkmolBoiling Point = - 407 o C Density = 366 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiFluoro-Chloro-Methane

16

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

Generations of refrigerants

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R11

CCl F

Cl

ClCCl3F

Molecular Weight = 112+335453+118998

= 13736 kgkmolBoiling Point = + 2377 o C Density = 1494 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TriChloro-Fluoro-Methane

Produced in 1932

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R22

CF F

Cl

HCHClF2

Molecular Weight = 112+1101+135453+218998

= 8646 kgkmolBoiling Point = - 407 o C Density = 366 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiFluoro-Chloro-Methane

16

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

Generations of refrigerants

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R22

CF F

Cl

HCHClF2

Molecular Weight = 112+1101+135453+218998

= 8646 kgkmolBoiling Point = - 407 o C Density = 366 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

DiFluoro-Chloro-Methane

16

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

Generations of refrigerants

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

16

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

Generations of refrigerants

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Ethane (R 170)

CH H

H

HC2H6

Molecular Weight = 212+6101 = 3006 kgkmol

Boiling Point = - 89 o C Density = 1282 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Ethane

C

H

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R134a

CF H

F

FC2H2F4

Molecular Weight = 212+2101+418998

= 1021 kgkmolBoiling Point = - 263 o C Density = 000425gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

C

H

F

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

19

The `synthetic refrigerants such as HFCs are being replaced with HFOs or `natural refrigerantslsquo

4th generation of refrigerants

Generations of refrigerants

HFO R1234ze

HFO R1234yf

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

ACRECONFINDIA 8th ndash 9th Febrsquo2013

Propene (R1270)

CH

H

HC3H6

Molecular Weight = 312+6101= 4206 kgkmol

Boiling Point = - 476 o C

Density = 181gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

Propylene

C

H

H

C

H

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

ACRECONFINDIA 8th ndash 9th Febrsquo2013

R1234-yf

CF

F

FC3H2F4

Molecular Weight = 312+2101+418998= 11401 kgkmol

Boiling Point = - 30 o C

Density = 11 gcc

Molecular Weight kgkmol

F = 18998Cl = 35453Br = 79904I = 126904

TetraFluoroPropene

C

H

H

C

F

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

22

Four generations (Calm JM 2010)

Low ozone depletion potential (ODP)low global warming potential (GWP)short atmospheric lifetime (tatm)high efficiency

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

23

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

24

CFCs Refrigerants

HCFCs Refrigerants

ODP is Ozone Depletion Potential of with reference to CFC R11 as 1

Cl + O3 -gt ClO + O2ClO + O3 -gt Cl + 2O2

5 What is ODP

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

25

Molina and Rowlandrsquos 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

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

26

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 03 kilograms per capita on the date of the entry into force of the Protocol for it

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

27

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

28

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

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

29

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

30

Velders et al PNAS 2007

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

31

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

32

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 Chemical formula

Lifetime (years)

Global Warming Potential (100 Years)

CO2 CO2 variable 1

Methane CH4 12 21

Nitrous oxide N2O 120 310

HFC-23 CHF3 264 11700

HFC-32 CH2F2 56 650

HFC-41 CH3F 37 150

HFC-125 C2HF5 326 2800

HFC-134 C2H2F4 106 1000

HFC-134a CH2FCF3 146 1300

7 What is GWP

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

33

Ref Calm JM 2008

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

34

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)

WhereGWP = Global Warming Potential of refrigerant relative to CO2 (GWP CO2 = 1)L annual = Leakage rate pa (Units kg)n = System operating life (Units years)m = Refrigerant charge (Units kg)α recovery = Recoveryrecycling factor from 0 to 1 E annual = Energy consumption per year (Units kWh pa)β = Indirect emission factor (Units kg CO2 per kWh)

8 Total equivalent warming impact (TEWI)

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

35

Ref Calm JM 2008

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

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

36

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

37

World avoided by the Montreal Protocol

Reduction Montreal Protocol of ~11 GtCO2-eqyr5-6 times Kyoto target(incl offsets HFCs ozone depl)

CO2 emissions

Velders et al PNAS 2007

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

38

Regional Shares of World Carbon Emissions 1997 amp 2020

Ref The US Response to the Kyoto Protocol Kevin Klein Professor of Economics Illinois CollegeMarch 2 2007

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

39

HFO-R1234yf HFO-R1234ze

CH2=CF-CF3 CHF=CH-CF3

Environmentalbull ODP = 0bull GWP100 = 4bull Atmospheric Life 11 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 400 ppmbull Key toxicity testing complete good resultsbull Notified to ELINCS hence registered to

REACH Submit HPV update by Dec 1 bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

Environmentalbull ODP = 0bull GWP100 = 6bull Atmospheric Life 18 daysToxicity amp Regulatory Approvalsbull Low toxicity Honeywell PEL = 1000 ppmbull Significant testing completed good resultsbull EU Notification Annex VIII Level 1 bull ELINCS 471-480-1bull US PMN amp SNAP applications in progressbull Preparing Japanese notification

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

1234ze(E)

134a

00

05

10

15

20

25

30

35

-20 0 20 40 60 80 100

134a

1234yf

Vapor Pressure Vs Temperature Vapor Pressure Vs Temperature

Temperature oC

Pre

ssur

e M

Pa

Pre

ssur

e M

Pa

Temperature oC

10 Fourth generation Refrigerants

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

40

10 Fourth generation Refrigerants

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

41 Ref NIST Chemistry WebBook

10 Fourth generation Refrigerants

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

42

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

Important (ex230g) Special jointSealing etcNecessaryNecessary

Necessary ----

NecessarySpecial joint---

NecessarySpecial joint---

Cost for safety Charge reductionJointElectronic partsLeak detectorVentilation

Modified facilityQualificationQualified personQualified person

Two-stage compHigh-pressure etc

Cheap CO2(R744)

Larger comp Larger pipe etc

Near as R410A Same as R410A

Modification required Same as R22

Cost for performance Compressor EX etc

Modified facilityModificationModificationModificationModification

Expensive HFO1234yf

Cheap Cheap Refrigerant price

Modified facilityModificationModificationModificationModification

Special facilityQualificationQualified personQualified personQualification

Cost for handlingManufacture Supply chainInstallationServiceDisposal

R32 Propane (R290)

The Example of Room AC Component which increases cost

11 Future options

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

43

12 Conclusion

Thomas Midgley (1928) had invented the CFCs amp 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 Earths history

Not only the inventors but all end users are more responsible for the consequences of usage of refrigerants

PLAN DO CHECK ACT

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

44

1 ASHRAE 2007 httpsosrashraeorgPublic20Review20Draft20Standards20Lib34z-2007201st20PPR20Draftpdf

2 ASHRAE 2008 httpwwwashraeorgFile20LibrarydocLibPublic20080807_34m_thru_34v_finalpdf

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 Bjoumlrn Palm REFRIGERANTS OF THE FUTURE 10thIEA Heat Pump Conference 2011 16 - 19 May 2011 Tokyo Japan httpkthdiva-portalorgsmashgetdiva2483181FULLTEXT01

5 Calm JM Composition Designations for Refrigerants ASHRAE Journal November 19896 Calm JM Global Warming Impacts of Chillers Heating Piping Air Conditioning February 19937 Calm JM Refrigerant Safety ASHRAE Journal 19948 Calm JM The next generation of refrigerants - Historical review considerations and outlook Int J

Refrig 31 (7) 1123-1133 (2008) httpdxdoiorg101016jijrefrig2008010139 Calm JM Refrigerant Transitions Again ASHRAE-NIST Refrigerants Conference 201210 Carmen J Giunta THOMAS MIDGLEY JR AND THE INVENTION OF CHLOROFLUOROCARBON

REFRIGERANTS IT AINrsquoT 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 194712 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 httpdxdoiorg106028jres117014 2012

13 G Venkatarathnam and S Srinivasa Murthy Refrigerants for Vapour Compression Refrigeration Systems RESONANCE 1048744 February 2012

14 GUIDE 2012 Natural Refrigerants Market Growth for Europe shecco publications15 Imke et al Energy consumption of battery cooling in electric hybrid vehicles International

Refrigeration and Air Conditioning Conference at Purdue July 16-19 2012

13 References

Continuing hellip

45

16 NASA 2007 httpwwwnasagovvisionearthenvironmentozone_recoveringhtml Date March11 2011

17 NIST Standard Reference Database 23 REFPROP - Thermo dynamic properties of refrigerants and refrigerant mixtures Version 304 NIST USA 1991

18 M Richter M O McLinden and E W Lemmon Thermodynamic Properties of 2333-Tetrafluoroprop-1-ene (R1234yf) Vapor Pressure and pmdashρmdashT Measurements and an Equation of State J Chem Eng Data 56 (7) 3254-3264 (2011) httpdxdoiorg101021je200369m

19 M O McLinden M Thol and E W Lemmon Thermodynamic Properties of trans-1333-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 httpdocslibpurdueeduiracc1041

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 UNEP22 THE AUSTRALIAN INSTITUTE OF23 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 UN25 Reasor Pamela Aute Vikrant and Radermacher Reinhard Refrigerant R1234yf Performance

Comparison Investigation (2010) International Refrigeration and Air Conditioning Conference Paper 1085 httpdocslibpurdueeduiracc1085

26 R1234yffld - NIST wwwbouldernistgovdiv838theoryrefpropR1234YFFLD27 R1234zefld - NIST wwwbouldernistgovdiv838theoryrefpropR1234ZEFLD28 SAE 2010a httpwwwsaeorgmagsaei8702 Date April 22 201129 SAE 2010b httpwwwsaeorgmagsAEI8074 Date April 22 201130 SAE 2011 httpwwwsaeorgstandardsdevtsbcooperativealtrefrightm Date April 22 2011

Continuing hellip

46

31 httpwwwreefercargocarecomrefrigerantshtml32 httpwwwreefercargocarecomozone-depleting-substanceshtml33 httpwwwlinde-gascomenproducts_and_supplyrefrigerantsfluorine_refrigerants

hfo_refrigerantshtml34 httphumantouchofchemistrycomfrank-rowland-and-mario-molinahtm35 httpwwwbeyonddiscoveryorgcontentviewpageaspI=89

Inventor Thomas Midgley

NoUS

Patent No

dated patent Title filed as on

1 2013062 Sep3 1935 Preparation of aliphatic halofluoro compounds Feb 26 1931

2 2007208 July 91935Manufacture of halo-fluoro derivative of aliphatic hydrocarbons

Feb 24 1931

3 2104882 Jan11 1938 Heat transfer and refrigeration Nov19 1931

4 2024008 Dec10 1935 Manufacture of antimony trifluoride June 30 1934

5 2192143 Feb27 1940 Fluorination process May 7 1938

47

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47

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