1. Backgrounds
2. Theoretical
3. Experimental
4. Results and Discussion
5. Conclusions

Hallym University
Research Center for Climate ChangeHallym University
Research Center for Climate ChangeHallym University
Research Center for Climate ChangeHallym University
Research Center for Climate Change

2008

Low Carbon, Green Growth was

proposed as a core of Republic’s new vision

2009

GHG reduction target was announced:

2009

Framework Act on low carbon, green growth2010

GHG Target Management Scheme

2015

Emission Trading Scheme

30% reduction in 2020 BAU(about 245 Mt CO2e)

GHG Target Management System and Emission
Trading System require high accuracy of inventory;
Korea is now reconstructing inventories ofall sectors;
HFC is one of the target GHGs for inventory
reconstruction project.
Two years project (2011. 7. ~ 2013. 8.) was carried out fordeveloping F-Gas Inventory.

Hallym University
Research Center for Climate Change

High Global Warming Potential of HFCs demands
accuracies of its emission data;
Minor errors made during the courses of inventory preparation
can allow significant deviation of inventory

There are various emission sources of HFCs anddifficulties in collecting activity data;
We did not have country-specific and/or plantspecific EFs for HFCs.
Hallym University
Research Center for Climate Change

History of Vehicle Refrigerant‘89

Montreal Protocol : Regulation of CFC
and HCFCs Use“R-12 was major refrigerant”‘96

Conversion to R-134a for
New Cars‘05

Kyoto Protocol : Regulation of
GHG Emission‘11

Conversion to R-1234yf
for New Car

Hallym University
Research Center for Climate Change

Characteristics of Refrigerants

Item

R-12

R-134aR-1234yf

FormulaCCl2F2

CH2FCF3C3H2F4

Toxicity

No

No

No

Flammability

NoNo

A little

ODP

1.0

0

0

GWP

8,500

1,300

4

Statistics for
Scrap Vehicles

Registration Status
by Vehicle Type
천대
600
500
400
300
200
100
0
’02

’03
특수차

Hallym University
Research Center for Climate Change

’04

’05

’06

화물차

’07

’08

승합차

’09

’10

승용차

Regular Emission
Siegl et al. (2002) : 25.4 g/yr per vehicle at a stationarymode
Stemmler (2004) : 122.6 g/yr per vehicle at a dynamic
mode
Schwarz (2005) : 52.6 g/yr per vehicle (EF = 6.9%/yr)
Japan (2009) : EF = 5.2%/yr

Total Emissions including regular andirregular emission
IPCC (2006) : EF = 10~20%/yr

Hallym University
Research Center for Climate ChangeThis research attempts to
Develop the emission model of HFC-134a from
MAC of passenger vehicles to simulate its regularemission kinetics;
Develop country-specific emission factors of HFC134a from MAC of passenger vehicles at use-phaseand disposal-phase;
Estimate the fugitive emission inventory of HFC134a from MAC of passenger vehicles.

Hallym University
Research Center for Climate ChangeHallym University
Research Center for Climate Change

Tier

Description

Tier 1aEmission Factor
Approach at theapplication level• Activity Data: Net Consumption
Net Consumption = Production + Imports – Exports Destruction• Annual Emission = Net Consumption • Composite EF

Tier 1b

Mass BalanceApproach at theapplication level• Emissions = Annual Sales of New Chemical – (Total Chargeof New Equipment – Original Total Charge of Retiring
Equipment)

Etotal ,t  Econtainers ,t  Ech arg e,t  Elifetime ,t  Eend of life ,tTier 2aEmission Factor
Approach at thesubapplication
level

Tier 2b

Mass BalanceApproach at the
sub-application
level

Tier 1

Tier 2

Hallym University
Research Center for Climate Change※ Elifetime,t  Bt x
; B stands for HFC banked in existing
100 tequipment at year t and x does for EF• Emissions = Annual Sales of New Refrigerant – Total Chargeof New Equipment + Original Total Charge of Retiring
Equipment – Amount of intentional destruction

Step.1(Charge)

Manufacturing Stage

Emission

Step.2(Lifetime)

Operation Stage

Emission

Charging

Step.3(End-of-life)

Disposal Stage활동자료

Emission

Recovery
Recharging

배출계수Destruction
and Recycling

Manufacturing Stage :HFC-134a may be emitted accidentally during its injection to MAC

Operation Stage :HFC-134a may be emitted during the operation of MAC
through the construction materials and connection points

Disposal Stage :HFC-134a remained in MAC will be emitted eventually

Hallym University
Research Center for Climate Change

Are the Emission Factors constant over time?
Is the previous estimation method right?
EF = (Original Charged Amount of HFC-134a into
MAC – Remaining Amount of HFC-134a in RetiringMAC)/Operating Years

Hallym University
Research Center for Climate Change

Fugitive Emission of Refrigerant from Vehicle is expressed
as a function of 1) Car Age and 2) Operation Time of MAC

Hallym University
Research Center for Climate Change

Assumptions
Emission Rate of Refrigerant is proportional to theresidual amount of refrigerant;
Emission rate constant is unvaried with car age.

Fugitive Kinetic Equation for RefrigerantdM e   M e
dt
where

M e : Residual amount at year t (g) : Apparent emission rate constant(yr )-1Hallym University
Research Center for Climate Change

Apparent Emission Rate Constant
1. Get information on original charged

ln 

 

Me
 t


M 0 

or recharging amount : M 0
2. Determine the residual amountof refrigerant : M e

3. Determine the duration time afterrefrigerant charging (original orrecharge)

Residual Amount as a function of timeM e  M 0  exp   t  where M 0 is the original charged amountor recharged amount(g)Hallym University
Research Center for Climate ChangeTotal Emission Amount at year t
Difference in residual amount between (t-1) and t year

1

∙

∙

1

exp

∙

where EA represents Emission Amount(g) during one year
between year (t-1) and t.

Emission Factor(Annual Emission Rate)
%

1

100

1

exp

where EA(g) is the Emission Amount during the one year from year(t-1) and t and x(%) is Emission Factor(annual emission rate)
Hallym University
Research Center for Climate ChangeHallym University
Research Center for Climate ChangePotable Recover: Yellow Jacket XLT/95763, USA
Specification for recover

Hallym University
Research Center for Climate Change

Upper limit of
weigh

50 kg

Minimum unit

2g

Precision± 0.5 %

Suction pressure

0.50 bar

Hallym University
Research Center for Climate Change

Condition
Item

Condition of GC-MSD

Inlet

220 ℃, Split ratio 100 : 1

ColumnDB-624 ( 60 m X 0.25 mm X 1.4 um )Flow

He , 1 mL/minOven

40 ℃ ( 5 min )  10 ℃/min  80 ℃  250 ℃

Scan range

45 ~ 300 m/z ( EI mode )Injection volume

0.5mL

Tedlar Bag

1L(PVF Film)

Hallym University
Research Center for Climate ChangeHallym University
Research Center for Climate Change

There may be Limiting Recovery Performance ofrecover used here and average recovery rate was
90.6±3.7% Calibration was proposed
500

C

450

h
a

R2 = 0.9973

M r  1.0872  M m  6.4098

400

r
g

350

e
d

300

a

250

m

n
t
g

where Mr stands for calibrated

Bamount and Mm for recoveredCamount (reading value) offered

150
100

)

u

200

A-2

by the recover

(

o

A-1

50
0

100

200

300

400

Recovered amount(g)Hallym University
Research Center for Climate Change

500

600

ModelMileage(km)

Original
ChargedAmount(g)RecoveredAmount(g)

Residual
Amount(g)ResidualRate(%)

Emission
Constant(%/yr)

AnnualEmission
Rate(%/yr)

1

2004

23,140550468518.39

94.25

0.88

0.87

2

2009

98,498

550

412

455.6

82.8

5.79

5.6

2004

59,408

650

410

453.4

69.7

4.46

4.4

4

2002

166,322

700

456

504.9

72.1

3.35

3.3

5

2005

109,987

750

498

552.0

73.6

4.43

4.3

6

2011

15,727550460

509.42

92.62

0.04

4.28

7

2007

108,750550

288

316.56

57.56

11.84

0.11

2003

97,458550372

410.75

74.68

3.50

3.44

9

2008

65,459

780

576

639.5

82.0

0.05

5.3

10

2006

89,654

500

354

390.6

78.1

3.95

3.9

11

2003

69,155700292

321.05

45.86

8.66

8.30

12

2007

25,094500366

404.02

80.80

5.12

4.99

2010

20,359500444491.48

98.30

1.03

1.03

14

2006

36,404550360

397.29

72.24

5.66

5.50

15

2009

57,948480402

444.39

92.58

3.19

3.14

16

2002

115,370550

290

318.80

57.96

5.79

5.63

17

2010

51,866450316347.96

77.32

4.47

4.37

2009

28,708450294323.29

71.84

11.34

10.72

19

2002

76,247550282

309.83

56.33

6.04

5.86

20

2007

84,658

450

288

316.6

70.3

5.21

5.1

No.

3

8

13

18

Type

Large

Medium

Small

Mini

* : 95% confidential interval

Hallym University
Research Center for Climate Change

Average ofEmission Rate(%/yr)

4.6±0.8%*

5.2±0.9%*

5.0±1.2%*

5.6±1.2%*

Average

Apparent fugitive

Emission

Emissionsresidual rate

emission constant

Factorper kilometer(%)(yr-1)(%/yr)(mg/km)94.9±29.0

58.9±8.5

0.0579±0.0126

5.6±1.2

2.36±0.60

9.2±1.8

125.1±28.3

65.4±7.3

0.0512±0.0125

5.0±1.2

1.88±0.40

657.6±47.1

8.5±1.8

119.7±26.4

65.2±8.1

0.0541±0.0092

5.2±0.9

2.03±0.36

Large
(n=7)

712.9±102.3

7.5±2.4

110.4±30.2

71.7±7.4

0.0468±0.0087

4.6±0.8

1.96±0.73

Average624.5±31.6

8.7±0.9

114.4±13.4

65.4±3.9

0.0526±0.0051

5.1±0.5

2.02±0.21

Average

VehicleOriginal charged

type

amount(g)

Mini
(n=8)

512.5±43.3

9.5±2.5

Small(n=14)

616.4±51.9

Medium(n=18)

Mileage

operating(1,000km)time(yr)

Hallym University
Research Center for Climate Change2011 registration

Emission rate per car

Total emission

number(g/yr)(tCO2-eq)Mini

1,234,373

21.0

33,662Small

2,008,689

23.2

60,621

Medium

5,495,505

25.7

183,643

Large

2,042,714

25.2

66,893

Sum

10,781,281-

344,819Weighted average

-

24.6

-

Type

Hallym University
Research Center for Climate Change

Vehicle Type

Emission Factor(%/yr)

Mini Size

5.6

Small Size

5.0

IPCC Default
Value(%/yr)

10 ~20Medium Size

5.2

Large Size

4.6

HFCs Emission Amount using country-specific(CS) EFs in 2011 is344,819 tCO2 eq, whereas the IPCC default EFs allows 539,609 tCO2 -eq higher(56%) than the emission amounts derived by the CS EFs

Overestimation if we adopt the IPCC default value
Hallym University
Research Center for Climate Change

Type

Mini

Model

Mileage(km)

RA(g)

CA(g)

ResidualRate(%)’05. 8244,292

448.00495.9790.2’94. 7130,867430.00475.7973.2’97. 10

172,464380.00419.72

76.3’96. 3

177,142317.00349.0869.8’97. 8150,370252.00

27.19

50.2

’03. 5

193,380382.00421.9664.9’97. 10

148,518482.00534.0973.2’00. 2

118,986

360.00397.2955.2’98. 8152,464428.00473.5463.1’01. 3151,013369.00407.3971.5’00. 982,118460.00509.4269.8’04. 1110,008461.00510.5565.5’99. 5

95,815480.00531.8572.9’05. 790,708334.00

38.14

56.6

’06. 1

141,792

428.00473.5472.9’01. 5

174,312324.00356.9347.6‘03. 2

174,126

412.00455.6044.7’99. 6

194,792

391.00432.0563.5’97. 6

212,432

441.00488.1254.2’00. 4266,442511.00566.61

55.6

Small

MediumLarge* : 95% confidential interval

Hallym University
Research Center for Climate Change

Average ResidualRate(%)

51.4±2.4%(n=91)51.2±1.9%(n=157)55.2±2.0%(n=106)58.4±3.4*%(n=39)

Average : 55.6±1.1%

Vehicle type

Original Charged
Amount (g)Average age (yr)Average Residual
Rate (%)

Mini(n=91)

552.8±5.6

12.2±0.3

51.4±2.4

Small(n=157)673.2±15.0

12.7±0.651.2±1.9

Medium(n=106)680.0±14.9

11.7±0.755.2±2.0Large(n=39)

833.8±41.7

12.8±0.858.4±3.4

Average689.5±4.2

12.4±0.255.6±1.1

Hallym University
Research Center for Climate Change

Vehicle Type

Scrap Quantities
in 2011

Emission per
VehicleEmission Amount(tCO2 eq)

Mini Size

45,959284.1

16,974

Small Size

382,351344.7

171,335

Medium Size

193,905

375.4

94,630Large Size

24,523486.9

15,522

Total

646,739383.4

322,348

Hallym University
Research Center for Climate Change

Vehicle Type

Use-phase(tCO2 eq)

Disposal-phase(tCO2 eq)

Sum

Mini Size

33,662

16,97450,636

Small Size

60,621

171,335

231,956

Medium Size

183,643

94,630278,273

Large Size

66,893

15,52282,415

Total

344,819

322,348

667,167

Hallym University
Research Center for Climate Change

Checking the consistency of apparent
fugitive emission constant with vehicle age
Comparing the residual rates of scrap passenger
vehicles measured here with those predicted byusing the apparent fugitive emission constantderived from use-phase analyses

Hallym University
Research Center for Climate Change

Apparent fugitive emission constant(yr-1)

0.200

0.180

0.160

0.140

0.120

Average Value

0.100

0.080

0.060

0.040

0.020

0.000
1.8

3.6

4.9

5.6

6.8

7.3

8.3

9.0

year

Hallym University
Research Center for Climate Change

9.5

9.8

10.5

10.7

10.9

11.5

12.4

13.3

Measured residual

Predicted

rate (%)

residual rate (%)

Mini

51.4

49.3

-4.1

Small

51.2

52.3

+2.2

Medium

55.2

53.2

-3.7

Large

58.4

54.8

-6.2

-

-

4.0

Type

Average**

Deviation* (%)*: (Predicted residual rate – Measured residual rate)/Measured residual rate X 100**: Average of absolute values of deviation

Hallym University
Research Center for Climate Change

Korean Waste Act proposed that over 99% purityof original refrigerant should be maintained forreuse.
Other refrigerants than HFC-134a may be
injected during the recharging process.
Small-size repair shop may replace with cheaper refrigerant(e.g. CFCs) during the course of recharging processes
Hallym University
Research Center for Climate ChangeGas-phase HFC-134a

Liquid-phase HFC-134a

A Substance

A Substance

B Substance

B SubstanceC SubstanceC SubstancePo.

Ret Time( min )

Area(%)

CompoundPo.

Ret Time( min )

Area(%)

CompoundA

4.225

99.8501,1,1,2TetrafluoroethaneA

4..21399.7881,1,1,2Tetrafluoroethane

B

4.378

0.150

1,1,2,2Tetrafluoroethane

B

4.372

0.212

1,1,2,2Tetrafluoroethane

C

4.509

Negligible

Dichlorodifluoromethane(R-12)

C

4.511

Negligible

Dichlorodifluoromethane(R-12)

Hallym University
Research Center for Climate Change

A Substance

B SubstanceC SubstanceRet
Time( min )Area ( % )IUPAC name

A

4.231

99.894

1,1,1,2-Tetrafluoroethane

B

4.378

0.049

1,1,2,2-Tetrafluoroethane

C

4.513

0.06

Dichlorodifluoromethane

Hallym University
Research Center for Climate Change

CompoundHallym University
Research Center for Climate ChangeFirst-order Emission model (FOM) and apparent fugitive
emission constants are reasonable appropriate for
estimating the emission rates of Korea-made vehicles
operated in Korea ;Average apparent fugitive emission constant : 0.0526±0.0024 yr-1
Average emission factor : 5.1±0.5 %/yr
Average age at disposal : 12.4 years
Average residual rate of scrap passenger vehicle : 55.6±1.1 %Annual emission rate per passenger vehicle
Use-phase : 24.6 g
Disposal-phase : 383.4 g

Life Cycle Emission(12.4 years) : 688.4 g

Hallym University
Research Center for Climate ChangeThis research reported the fugitive emission amount of HFC134a from passenger cars to be 667,167 tCO2 eq, whereas theofficial amount reported by Korean Government to be 1,398,723
tCO2 eq
Reason for difference : Application of different emission factors
This research : EFs developed by in situ measurements
Official data :IPCC default EFs

It is essential to adopt car-specific EFs
developed here to estimate the emission amountof HFC-134a from passenger vehicles
Hallym University
Research Center for Climate ChangeThis research demonstrates that the chemicalcompositions of refrigerant were rarely varied
to compare with those of new one

It is possible to reuse the refrigerant
recovered from scrap vehicles

Hallym University
Research Center for Climate Change

2014; Journal of Industrial Engineering andChemistry, In Press;
Three Papers(2 papers in 2012, one paper in2013) in Journal of Korea Society of Waste
Management;
2013; in Journal of Environmental Science
International
Hallym University
Research Center for Climate Change

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