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%
San Diego/JT/30/04/03
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.”
San Diego/JT/30/04/03
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)
San Diego/JT/30/04/03
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)
San Diego/JT/30/04/03
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
San Diego/JT/30/04/03
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
San Diego/JT/30/04/03
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
San Diego/JT/30/04/03
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