development of an improved product based approach … of an improved product based approach for the...
TRANSCRIPT
Development of an improved product based approach for the calculation of
NMVOC emissions from solvent use in Germany and uncertainty analysis
Jochen ThelokeUniversity of Stuttgart
San Diego/JT/30/04/03
Contents
1. Introduction
2. Definitions
3. Method
4. Results
5. Uncertainties
6. Conclusion
San Diego/JT/30/04/03
Solvent use was the largest NMVOC emissionsource group in Germany in 1998
Sum: 2 436 kt
combustion sources from industry and
power plants 1%
small combustion plants/households
3%
traffic27%
solvent use36%
production processes8%
biogenic 27%
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VOC - Volatile Organic Compound
“Volatile organic compound shall mean any organic compound having at 293,15 K a vapour pressure of 0,01 kPa or more, or having a corresponding volatility under the particular condition of use.”
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Solvent Use• Application of solvents
• Application of solvent containing products
• Production of solvent containing products
• Propellants (Propane/Butane)
• Extraction of fat, edible and non edible oil (n-hexane)
• Cooling agents (HFHC`s, HFCHC`s, alcohols)
• Softening agents (Phtalates)
• Concrete additives
• Application of thinners
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Method for the calculation of emissions from solvent use
importsolvent x
exportsolvent x
productionsolvent x
inlandconsumption
solvent x
manufacturechem.
product y
importchem.
product y
exportchem.
product y
inland consumptionchem.
product y
emissionreduction techniques
other pathways
Solvent Balance Manufacture Consumption
emissions
San Diego/JT/30/04/03
870 Gg NMVOC emitted from solvent use in Germany 2000
thinner without specific
application26%
Degreasing, dry cleaning and electronics
4%
Products manufacturing or
processing5%
Preservation of wood
4%
Paint application25%
Domestic solvent use (other than
paint application)13%
other14%
printing industry9%
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Paint application (sum 223 Gg)
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Manufacture of automobiles
6%
Synthetics4%
Plate emballages
3%
other paint applications
16%
Wood16%
constructions and buildings-professional
14%Car repairing
10%
Corrosion-inhibiting
primer8%
Mechanical engineering
8%
Do It Yourself 6%
white goods3%
Boat building2%
Prefabricated units
2% road marking varnishes
2%
The domestic consumption of thinners increasedcontinously in the last years
100
150
200
250
300
1992 1994 1996 1998 2000 2002Year
Th
inn
er C
on
sum
pti
on
[G
g/y
]
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NMVOC emissions from domestic solvent use (sum 105 Gg)
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coolant and fire extinguisher
2%aftershave, hygienic water and perfume
19%
hairspray19%
personal hygiene products
22%
antifreeze for cars24%
detergents14%
*) pure Ethanol
NMVOC emissions from domestic solvent use
San Diego/JT/30/04/03
Solvent consumption
Emission factor
NMVOC emissions
Mg/y % Mg/y
Antifreeze for cars 51 100 50 25 550
Detergent for dishwasher 9 900 3 300
Detergent for car washing 10 900 3 330
Detergent for washing-machine 12 660 3 380
Alcohol consumption 750 000* 1 7 500
Hairsprays 19 350 95 18 400
Personal hygiene products 24 400 95 23 150
Toilet water 6 100 95 5 800
Aftershave 5 600 95 5 300
Perfume 2 500 95 2 400
Deodorants 1 180 95 1 120
NMVOC emissions from printing processes (sum 80 Gg)
Rotogravure printing14,8%
Offset printing39,4%Offset-Heatset-
printing21,9%
Letterpress printing
0,6%
Package printing20,1%
Screen printing3,1%
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Speciation of the NMVOC emissions from solvent use to substance classes
glycol derivates8,5%
alcohols26,3%
aromatics21,7%aliphatics
20,8%
ketones6,2%
halogenated hydrocarbons
1,5%other2,5%
terpenes1,2%
aldehydes0,02%
organic acids0,1%
ethers1,5%
esters9,8%
San Diego/JT/30/04/03
Verification - Plausibility check
Substance classes
Domestic consumption [t]
(solvent industry)
Domestic consumption
[t](own
estimation)
Deviation[%]
Aliphatics 300 000 280 000 - 6,7Aromatics 250 000 286 000 +14,4Terpenes 10 000Halogenic hydrocarbons 35 000 35 000Alcohols 360 000 316 000 -12,2-Ethanol 50 000 85 000-Isopropanol 250 000 144 000-n-Propanol 40 000 200-n/i-Butanol 10 000 56 000Glycolderivates 75 000 78 000 +4,0Esters 75 000 76 000 +1,3Ketones 60 000 61 000 +1,7Ethers 30 000 29 000 -3,3Aldehydes 200Organic Acids 800Softening agents 225 000Other VOC`s 65 000Sum (Sum of bold faced substance classes)
1 185 000 1 161 000 -2,0
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Assessment and calculation of uncertainties of NMVOC emissions from solvent use - Methods
Uncertainty analysis
ØQualitative assessmentØ Semiquantitative methods
Quantitative methods
Ø Error propagationØMonte-Carlo simulation
Verification
Ø Plausibility checksØ Evaluation experiments
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Semi-quantitative methods
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Uncertainty bandwith
Source groups
Yearly
emissions
Spatial
resolution
Tem
poral resolution
VO
C
speciation
Paint application 2-3 3 3-4 3 Domestic solvent use 3 2 5 2 Printing processes 2 2 3 2 Synthetics processing 4 4 4 3 Metal degreasing 4 4 4 4 Other source groups 3 3 3-4 4 Solvent use Complete assessment
3 3 4 3
Monte-Carlo simulations for emissions from paintapplication - Preliminary results
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0
1
2
3
4
180 200 220 240 260 280 300Emissions in Gg per year
Val
ues
in
10^
-5
Mean value: 231 Gg
Calculated : 222 Gg (without uncertainty
analysis)209 255
90 % of the calculated values between 209 Gg
and 255 Gg
Germany 2000
Verification - Results of city experiments
0,1 1 10
2,3-Dimethylpentane
Ethane
Ethine
n-Heptane
3-Methylhexane
2-Methylhexane
Ethene
3-Methylpentane
Benzene
2-Methylpentane
Propane
Propene
Ethylbenzene
n-Octane
i-Pentane
EVA
ESQUIF
(HCi/CO)modelled / (HCi/CO)measured
0,5 2
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0,1 1 10 100
m/p-Xylene
i-Butane
n-Pentane
Toluene
1,2,4-TMB
o-Xylene
n-Butane
n-Hexane
1,3,5-TMB
Propylbenzene
n-Nonane
n-Decane
(HCi/CO)modelled / (HCi/CO)measured
EVA
ESQUIF
0,5 2
Verification - Results of city experiments
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Conclusion• Emissions from solvent use was the largest NMVOC emission source
group in Germany in 1998
• The developed improved product based approach for the calculation of NMVOC emissions from solvent use in Germany was further developed and applied for 2000
• The method can in principle also be used for other OECD countries
• Nearly 75% of emissions from solvent use are caused by paint application, application of thinners, domestic solvent use and printing processes
• Nearly 50% of emitted solvents are oxygen containing NMVOC`s
• A plausibility check between a solvent based approach and a product based approach yielded a good agreement
• The results of city experiments in Augsburg and Paris indicates thatfurther experiments especially with measurements of OVOC are required
• Monte-Carlo simulation appears to be a promising approach for thequantification of uncertainties from solvent use emissions
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