Uncertainty estimates for industrial processes (SNAP 04) are presented in Table 4.9. The uncertainty estimates are based on standard uncertainty factors (EMEP/CORINAIR, 2007).
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CEPMEIP, 2003: The Co-ordinated European Programme on Particulate Matter Emission Inventories, Projections and Guidance (CEPMEIP). Da-tabase. Available at: http://www.air.sk/tno/cepmeip/.
Cheminova, 2007: Grønt regnskab 2006 for Cheminova A/S; including 1996-2005.
daka, 2007: Grønt regnskab 2005/2006; including 1996/97-2004/05.
Danisco Grindsted, 2007: Grønt regnskab 2006/2007; including 1996/97-2005/06.
Danisco Sugar, 2007: Grønt regnskab 2006/2007 for Danisco Assens;
Danisco Nakskov and Danisco Nykøbing including 1996/97-2005/6.
EMEP/CORINAIR, 2007: Emission Inventory Guidebook 3rd edition,
7DEOH Uncertainty estimates for industrial processes (%).
Activity data
uncertainty
Emission factor uncertainty
Overall 2005 Trend
SO2 2 20 20.100 0.365
NOx 2 50 50.040 0.124
NMVOC 2 50 50.040 2.492
CO 50 100 50.040 3.222
NH3 2 1000 1000.002 10.59
Cadmium 2 1000 1000.002 0.299
Copper 2 1000 1000.002 3.291
Lead 2 1000 1000.002 0.064
Zinc 2 1000 1000.002 0.149
and Projections, 2007 update. Technical report No 16/2007. Available at http://reports.eea.europa.eu/EMEPCORINAIR5/en/.
Haldor Topsøe, 2007: Miljøredegørelse for katalysatorfabrikken 2006 (11.
regnskabsår); including 1996-2005.
Illerup, J.B., Geertinger A.M., Hoffmann, L. & Christiansen, K. 1999:
Emissionsfaktorer for tungmetaller 1990-1996. Faglig rapport fra DMU, nr. 301. Miljø- og Energiministeriet, Danmarks Miljøundersøgelse.
Nielsen, O.-K., Lyck, E., Mikkelsen, M.H., Hoffmann, L., Gyldenkærne, S., Winther, M., Nielsen, M., Fauser, P., Thomsen, M., Plejdrup, M.S., Il-lerup, J.B., Sørensen, P.B. & Vesterdal, L. 2008: Denmark’s National In-ventory Report 2008 - Emission Inventories 1990-2006 - Submitted under the United Nations Framework Convention on Climate Change. Na-tional Environmental Research Institute, University of Aarhus. 701 pp. – NERI Technical Report no. 667. http://www.dmu.dk/Pub/FR667.
IPCC, 1997: Revised 1996 IPCC Guidelines for National Greenhouse Gas Inventories. Available at
http://www.ipccnggip.iges.or.jp/public/gl/-invs6.htm (15-04-2007).
Kemira GrowHow, 2004: Miljø & arbejdsmiljø. Grønt regnskab 2003;
including 1996-2002.
Rexam Glass Holmegaard, 2007: Grønt regnskab for Rexam Glass Hol-megaard A/S 2006, CVR nr.: 18445042; including 1996/97-2005.
Rockwool, 2007: Miljøredegørelse 2006 for fabrikkerne i Hedehusene, Vamdrup og Øster Doense; including 1996-2005.
Saint-Gobain Isover, 2007: Miljø- og energiredegørelse 2006; including 1996-2005.
Statistics Denmark, 2007: Production, import, and export statistics. Avai-lable at http://www.dst.dk/.
Stålvalseværket, 2002: Grønt regnskab og miljøredegørelse 2001. Det Danske Stålvalseværk A/S; including 1992, 1994-2000.
Aalborg Portland, 2007: Environmental report 2006; including 1996-2005.
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Use of solvents and other organic compounds in industrial processes and households are important sources of evaporation of NMVOCs, and are related to the source categories Paint application (CRF sector 3A), De-greasing and dry cleaning (CRF sector 3B), Chemical products, manufac-ture and processing (CRF sector 3C) and Other (CRF sector 3D). In this section the methodology for the Danish NMVOC emission inventory for solvent use is presented and the results for the period 1995 – 2006 are summarised. The method is based on a chemical approach, and this im-plies that the SNAP category system is not directly applicable. Instead emissions will be related to specific chemicals, products, industrial sec-tors and households and to the CRF secsec-tors mentioned before.
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Table 5.1 and Figure 5.1 show the emissions of chemicals from 1985 to 2006, where the used amounts of single chemicals have been assigned to specific products and CRF sectors. The methodological approach for finding emissions in the period 1995 - 2006 is described in the following section. A linear extrapolation is made for the period 1985 – 1994. A gen-eral decrease is seen throughout the sectors. Table 5.2 shows the used amounts of chemicals for the same period. Table 5.1 is derived from Ta-ble 5.2 by applying emission factors relevant to individual chemicals and production or use activities. Table 5.3 showing the used amount of products is derived from Table 5.2, by assessing the amount of chemicals that is comprised within products belonging to each of the four source categories. The conversion factors are rough estimates, and more thor-ough investigations are needed in order to quantify the used amount of products more accurately.
In Table 5.4 the emission for 2006 is split into individual chemicals. The most abundantly used solvents are methanol, propylalcohol and turpen-tine, or white spirit defined as a mixture of stoddard solvent and solvent naphtha. Methanol is primarily used as intermediate (monomer), solvent in thinners, degreasers et al. and as disinfecting and conserving agent.
Propylalcohol is used as flux agents for soldering, as solvent and thinner and as windscreen washing agent. Turpentine is used as thinner for paints, lacquers and adhesives. Household emissions are dominated by propane and butane, which are used as aerosols in spray cans, primarily
ous other sources. High emission factors are assumed for use of chemi-cals (products) and lower factors for industrial production processes.
7DEOH Emission of chemicals in Gg pr year
7RWDOHPLVVLRQV*JSU\HDU Paint application (3A) 21,8 21,3 20,9 20,4 19,9 19,5 19,0 18,6 18,1 17,6 16,1 Degreasing and dry cleaning (3B) 9,04 8,87 8,69 8,51 8,33 8,15 7,97 7,80 7,62 7,44 6,86 Chemical products, manufacturing
and processing (3C) 3,34 3,32 3,31 3,29 3,27 3,25 3,24 3,22 3,20 3,18 3,55 Other (3D) 18,8 18,4 17,9 17,5 17,1 16,6 16,2 15,8 15,3 14,9 18,1 Total NMVOC 53,0 51,9 50,8 49,7 48,6 47,5 46,4 45,3 44,2 43,1 44,6 Total CO2’a
165 162 158 155 152 148 145 141 138 134 139
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Paint application (3A) 17,2 17,9 15,7 14,6 15,5 14,0 13,1 12,1 12,9 13,1 12,7 Degreasing and dry cleaning (3B) 7,63 6,91 6,24 6,82 6,60 5,65 6,06 5,73 5,71 5,46 5,29 Chemical products, manufacturing
and processing (3C) 3,50 3,04 2,95 3,01 2,83 2,76 3,07 2,37 3,06 3,31 3,49 Other (3D) 14,8 12,0 11,8 11,3 11,2 10,5 11,2 10,0 10,8 11,3 11,2 Total NMVOC 43,1 39,8 36,7 35,7 36,1 32,9 33,4 30,1 32,4 33,1 32,7 Total CO2’a
134 124 114 111 113 102 104 94 101 103 102
a 0.85*3.67*total NMVOC
7DEOH Used amounts of chemicals in Gg pr year 8VHGDPRXQWVRIFKHPLFDO*J
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Paint application (3A) 45,2 46,6 48,0 49,4 50,8 52,1 53,5 54,9 56,3 57,7 57,1 Degreasing and dry cleaning (3B) 27,2 27,3 27,3 27,4 27,5 27,5 27,6 27,7 27,7 27,8 28,6 Chemical products, manufacturing
and processing (3C) 68,9 71,9 74,8 77,8 80,7 83,7 86,6 89,6 92,5 95,5 105 Other (3D) 27,6 28,6 29,6 30,6 31,6 32,6 33,6 34,6 35,6 36,6 46,7 Total NMVOC 169,0 174,4 179,8 185,2 190,6 196,0 201,3 206,7 212,1 217,5 237
7DEOH Used amounts of products in Gg pr year 8VHGDPRXQWVRISURGXFWV*J
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Paint application (3A) 301 311 320 329 338 348 357 366 375 385 381 Degreasing and dry cleaning (3B) 54 55 55 55 55 55 55 55 55 56 57 Chemical products, manufacturing
and processing (3C) 345 359 374 389 404 418 433 448 463 477 524 Other (3D) 138 143 148 153 158 163 168 173 178 183 234 Total products 839 868 897 926 955 984 1013 1042 1071 1100 1195
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Paint application (3A) 61,5 96,2 60,5 53,8 57,4 52,3 52,6 58,4 77,9 90,5 82,9 Degreasing and dry cleaning (3B) 29,5 28,7 25,4 29,0 28,5 26,1 27,5 26,5 28,8 29,3 30,5 Chemical products, manufacturing
and processing (3C) 103 108 102 107 114 116 117 101 122 136 144 Other (3D) 40,4 42,1 37,0 36,4 39,1 39,6 38,3 39,1 49,2 51,5 57,4 Total NMVOC 235 275 225 226 239 234 236 225 277 307 315
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Paint application (3A) 410 642 403 359 383 349 351 389 519 603 553 Degreasing and dry cleaning (3B) 59 57 51 58 57 52 55 53 58 59 61 Chemical products, manufacturing
and processing (3C) 517 540 512 536 569 580 586 504 608 678 722 Other (3D) 202 210 185 182 196 198 191 195 246 257 287 Total products 1188 1449 1152 1134 1204 1179 1184 1142 1431 1597 1622
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0 5 10 15 20 25 30 35 40 45 50 55
1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006
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Paint application
Degreasing and dry cleaning
Chemical products, manufacturing and processing Other
)LJXUH Emissions of chemicals in ktonnes pr year (equal to Gg pr year). The methodological ap-proach for finding emissions in the period 1995 – 2006 is described in the text, and a linear extrapolation is made for 1985 – 1994. Figures can be seen in Table 5.1
7DEOH Chemicals with highest emissions 2006
Chemical
Emissions 2006 (tonnes/year)
methanol 4777 propylalcohol 4167 turpentine (white spirit: stoddard solvent and solvent naphtha) 3940
aminooxygengroups 2865
glycerol 2630 pentane 2331 ethanol 2166 naphthalene 1768 acetone 1297 propane 1000 butane 1000 butanone 676 glycolethers 622 ethylenglycol 610 formaldehyde 503 cyclohexanones 482 propylenglycol 479 1-butanol 240 butanoles 227 xylene 202 toluendiisocyanate 199
phenol 129
methyl methacrylate 74.8
toluene 66.6
acyclic aldehydes 65.1
dioctylphthalate 60.6
acyclic monoamines 51.3
styrene 49.6 tetrachloroethylene 26.1
triethylamine 11.9 diethylenglycol 10.3 diamines 0,018
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This year’s solvent use emission inventory includes N2O emissions for the first time. Five companies sell N2O in Denmark and only one com-pany produces N2O. N2O is primarily used in anaesthesia by dentists, veterinarians and in hospitals and in minor use as propellant in spray cans and in the production of electronics. Due to confidentiality no data on produced amount are available and thus the emissions related to N2O production are unknown. An emission factor of 1 is assumed for all uses, which equals the sold amount to the emitted amount.
Three companies have reported their sale and the sale for one company has been estimated. The total sold (emitted) amounts are:
2005: 0.045 Gg N2O
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An estimate of the overall uncertainty in EMEP/CORINAIR of 165% is used.
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The emissions of Non-Methane Volatile Organic Compounds (NMVOC) from industrial use and production processes and household use in Denmark have been assessed. Until 2002 the NMVOC inventory in Denmark was based on questionnaires and interviews with different in-dustries, regarding emissions from specific activities, such as lacquering, painting impregnation etc. However, this approach implies large uncer-tainties due to the diverse nature of many solvent-using processes. For example, it is inaccurate to use emission factors derived from one print-work in an analogue printprint-work, since the type and combination of inks may vary considerably. Furthermore the employment of abatement techniques will result in loss of validity of estimated emission factors.
A new approach has been introduced, focusing on single chemicals in-stead of activities. This will lead to a clearer picture of the influence from each specific chemical, which will enable a more detailed differentiation on products and the influence of product use on emissions.
The procedure is to quantify the use of the chemicals and estimate the fraction of the chemicals that is emitted as a consequence of use. Mass balances are simple and functional methods for calculating the use and emissions of chemicals
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RU VVLRQIDFW XVHHPL
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where “hold up” is the difference in the amount in stock in the beginning and at the end of the year of inventory.
A mass balance can be made for single substances or groups of sub-stances, and the total amount of emitted chemical is obtained by sum-ming up the individual contributions. It is important to perform an in-depth investigation in order to include all relevant emissions from the large amount of chemicals. The method for a single chemical approach is shown in Figure 5.2.
chemical
product product
activity activity
activity activity activity
air
activity
soil water wast
e
etc...etc...
The tasks in a chemical focused approach are
• Definition of chemicals to be included
• Quantification of use amounts from Eq.1
• Quantification of emission factors for each chemical
In principle all chemicals that can be classified as NMVOC must be in-cluded in the analysis, which implies that it is essential to have an ex-plicit definition of NMVOC. The definition of NMVOC is, however, not consistent; In the EMEP-guidelines for calculation and reporting of emis-sions, NMVOC is defined as ”all hydrocarbons and hydrocarbons where hydrogen atoms are partly or fully replaced by other atoms, e.g. S, N, O, halogens, which are volatile under ambient air conditions, excluding CO, CO2, CH4, CFCs and halons”. The amount of chemicals that fulfil these criteria is large and a list of 650 single chemicals and a few chemical groups described in ”National Atmospheric Emission Inventory”, cf.
Annex 3.F, is used. It is probable that the major part will be insignificant in a mass balance, but it is not correct to exclude any chemicals before a more detailed investigation has been made. It is important to be aware that some chemicals are comprised in products and will not be found as separate chemicals in databases, e.g. di-ethylhexyl–phthalate (DEHP), which is the predominant softener in PVC. In order to include these chemicals the product use must be found and the amount of chemicals in the product must be estimated. It is important to distinguish the amount of chemicals that enters the mass balance as pure chemical and the amount that is associated to a product, in order not to overestimate the use.
Production, import and export figures are extracted from Statistics Den-mark, from which a list of 427 single chemicals, a few groups and prod-ucts is generated. For each of these a XVH amount in tonnes pr. year (from 1995 to 2006) is calculated. It is found that 44 different NMVOCs com-prise over 95 % of the total use, and it is these 44 chemicals that are in-vestigated further.
In the Nordic SPIN database (Substances in Preparations in Nordic Countries) information for industrial use categories and products speci-fied for individual chemicals, according to the NACE coding system is available. This information is used to distribute the XVH amounts of indi-vidual chemicals to specific products and activities. The product amounts are then distributed to the CRF sectors 3A – 3D.
Emission factors, cf. Eq. 2, are obtained from regulators or the industry and can be provided on a site by site basis or as a single total for whole sectors. Emission factors can be related to production processes and to use. In production processes the emissions of solvents typically are low and in use it is often the case that the entire fraction of chemical in the product will be emitted to the atmosphere. Each chemical will therefore be associated with two emission factors, one for production processes and one for use.
• specification of emissions from industrial sectors and from house-holds,
• contribution from each NMVOC to emissions from industrial sectors and households,
• yearly trend in NMVOC emissions, expressed as total NMVOC and single chemical, and specified in industrial sectors and households.
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Important uncertainty issues related to the mass-balance approach are (i) Identification of chemicals that qualify as NMVOCs. The definition is vague, and no approved list of agreed NMVOCs is available. Although a tentative list of 650 chemicals from the ”National Atmospheric Emission Inventory” has been used, it is possible that relevant chemicals are not included.
(ii) Collection of data for quantifying production, import and export of single chemicals and products where the chemicals are comprised. For some chemicals no data are available in Statistics Denmark. This can be due to confidentiality or that the amount of chemicals must be derived from products wherein they are comprised. For other chemicals the amount is the sum of the single chemicals DQG product(s) where they are included. The data available in Statistics Denmark is obtained from Dan-ish Customs & Tax Authorities and they have not been verified in this assessment.
(iii) Distribution of chemicals on products, activities, sectors and house-holds. The present approach is based on amounts of single chemicals. To differentiate the amounts into industrial sectors it is necessary to identify and quantify the associated products and activities and assign these to the industrial sectors and households. No direct link is available between the amounts of chemicals and products or activities. From the Nordic SPIN database it is possible to make a relative quantification of products and activities used in industry, and combined with estimates and expert judgement these products and activities are differentiated into sectors.
The contribution from households is also based on estimates. If the household contribution is set too low, the emission from industrial sec-tors will be too high and vice versa. This is due to the fact that the total amount of chemical is constant. A change in distribution of chemicals be-tween industrial sectors and households will, however, affect the total emissions, as different emission factors are applied in industry and households, respectively.
A number of activities are assigned as “other”, i.e. activities that can not be related to the comprised source categories. This assignment is based on expert judgement but it is possible that the assigned amount of chemicals may more correctly be included in other sectors. More detailed information from the industrial sectors is continuously being imple-mented.
(iv) Rough estimates and assumed emission factors are used for many compounds. For some compounds more reliable information has been
sectors. In some cases it is more appropriate to define emission factors for sector specific activities rather than for the individual chemicals.
A quantitative measure of the uncertainty has not been assessed. Single values have been used for emission factors and activity distribution ra-tios etc. In order to perform a stochastic evaluation more information is needed.
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Please refer to the Danish National Inventory Report reported to the UNFCCC (Illerup et al., 2006)
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The previous method was based on results from an agreement between the Danish Industry and the Danish Environmental Protection Agency (DEPA). The emissions from various industries were reported to the Danish EPA. The reporting was not annual and linear interpolation was used between the reporting years. It is important to notice that not all use of solvents was included in this agreement and no activity data were available. It is not possible to perform direct comparison of methodolo-gies or to make corrections to the previous method, due to the funda-mental differences in structure. But an increase in total emissions was expected due to the more comprehensive list of chemicals.
Improvements and additions are continuously being implemented in the new approach, due to the comprehensiveness and complexity of the use and application of solvents in industries and households. The main im-provements in the 2006 reporting include revisions of the following
• Propane and butane is used as aerosol in spraying cans primarily in households. The mean volume of a can is set to 200 ml according to information from e.g. trade associations. This reduces the propane and butane emissions compared to previous inventories.
• Propylalcohol used as windscreen washing agent is reallocated from autopaint and repair to household use.
• Emission factor for propylalcohol used as windscreen washing agent, corresponding to approximately 80% of the annually used amount, is changed to 1.0 for use. Approximately 20% of the annual propylalco-hol use is used in closed industrial processes. This amount is assigned a low emission factor of 0.01.
• N2O emission is introduced in the solvents emission inventory. N2O is used mainly in anaesthesia.
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Selected branches will be addressed for further adjustments in the fol-lowing inventory. More detailed information will be obtained for se-lected industries with respects to used products and chemicals and emis-sion factors related to the activities.
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Illerup, J.B., Lyck, E., Nielsen, O., Nielsen, M., Winther, M, Mikkelsen, M.H., Hoffman, L., Gyldenkærne, S., Nielsen, M., Sørensen, P., Vester-dal, L., Fauser, P. & Thomsen, M. 2006: Denmark’s National Inventory Report – Submitted under the United Nations Framework Convention on Climate Change, 1990-2005.
Emission Inventory Guidebook 3rd edition, prepared by the UN-ECE/EMEP Task Force on Emissions Inventories and Projections, 2002 update. Available at:
http://reports.eea.eu.int/EMEP-CORINAIR3/en (07-11-2003)
Solvent Balance for Norway, 1994. Statens Forurensningstilsyn, rapport 95:02
SPIN on the Internet. Substances in Preparations in Nordic Countries.
http://www.spin2000.net/spin.html
Statistics Denmark, http://www.dst.dk/HomeUK.aspx