Danish emission inventory for industrial processes

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DANISH EMISSION INVENTORY FOR INDUSTRIAL PROCESSES Results of inventories up to 2013 Scientific Report from DCE – Danish Centre for Environment and Energy

AU

AARHUS UNIVERSITY DCE – DANISH CENTRE FOR ENVIRONMENT AND ENERGY

No. 172

2015

[Blank page]

DANISH EMISSION INVENTORY FOR INDUSTRIAL PROCESSES Results of inventories up to 2013 Scientific Report from DCE – Danish Centre for Environment and Energy

Katja Hjelgaard Ole-Kenneth Nielsen Aarhus University, Department of Environmental Science

AU

AARHUS UNIVERSITY DCE – DANISH CENTRE FOR ENVIRONMENT AND ENERGY

No. 172

2015

Data sheet Series title and no.: Title: Subtitle: Author(s): Institution(s): Publisher: URL: Year of publication: Editing completed: Referee: Quality assurance, DCE: Financial support: Please cite as:

Scientific Report from DCE – Danish Centre for Environment and Energy No. 172 Danish emission inventory for industrial processes Results of inventories up to 2013 Katja Hjelgaard, Ole-Kenneth Nielsen Aarhus University, Department of Environmental Science Aarhus University, DCE – Danish Centre for Environment and Energy © http://dce.au.dk/en December 2015 November 2015 Pia Frederiksen, Department of Environmental Science Vibeke Vestergaard Nielsen No external financial support Hjelgaard, K. & Nielsen, O.-K., 2015. Danish emission inventory for industrial processes. Results of inventories up to 2013. Aarhus University, DCE – Danish Centre for Environment and Energy, 159 pp. Scientific Report from DCE – Danish Centre for Environment and Energy No.172 http://dce2.au.dk/Pub/SR172.pdf Reproduction permitted provided the source is explicitly acknowledged

Abstract:

Keywords: Layout: Front page photo: ISBN: ISSN (electronic): Number of pages: Internet version:

This report forms part of the documentation for the emission inventories for industrial processes. The report includes both methodological descriptions for estimating emissions of greenhouse gases and air pollutants and presents the resulting emission data as reported to the United Nations Framework Convention on Climate Change and the United Nations Economic Commission for Europe Convention on LongRange Transboundary Air Pollution. The results of inventories up to 2013 are included. Industrial processes, emissions, UNFCCC, UNECE, emission inventory Ann-Katrine Holme Christoffersen Katja Hjelgaard (BG Stone, Hundested Havn) 978-87-7156-176-0 2245-0203 159 The report is available in electronic format (pdf) at http://www.dce2.au.dk/Pub/SR172.pdf

Contents List of abbreviations

5

Preface

7

Summary

8

Greenhouse gases Other pollutants Sammendrag

9 11 15

Drivhusgasser Øvrige luftforurenende stoffer

16 17

1

Introduction

21

2

Methodology and data sources

23

2.1 2.2 2.3 2.4 2.5

23 23 24 24 28

3

4

5

Mineral industry

29

3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8

29 30 38 46 54 62 64 68

Greenhouse gas emissions Cement production Lime production Glass production Ceramics Other uses of soda ash Flue gas desulphurisation Mineral wool production

Chemical industry

73

4.1 4.2 4.3 4.4 4.5 4.6

73 73 78 82 85 86

Greenhouse gas emissions Nitric and sulphuric acid production Catalyst and fertiliser production Pesticide production Production of chemical ingredients Production of tar products

Metal industry 5.1 5.2 5.3 5.4 5.5 5.6

6

Company environmental reports EMEP/EEA guidebook IPCC guidelines EU-ETS (European Union - Emission Trading Scheme) CEPMEIP database

Emissions Iron and steel production Red bronze production Magnesium production Secondary aluminium production Secondary lead production

88 88 89 97 98 100 102

Electronics Industry

106

6.1 6.2

106 106

Greenhouse gas emissions Other electronics industry

7

8

Product Uses as Substitutes for Ozone Depleting Substances (ODS)

108

7.1 7.2 7.3 7.4 7.5 7.6 7.7

108 109 111 115 116 116 118

Other Product Manufacture and Use

119

8.1 8.2 8.3 8.4 8.5

119 119 121 122

8.6 9

Greenhouse gas emissions General methodology Refrigeration and air conditioning Foam blowing agents Fire protection Aerosols Solvents

Greenhouse gas emissions Electrical equipment SF6 from other product use Medical applications of N2O N2O used as propellant for pressure and aerosol products Other product use

123 125

Other industry

132

9.1 9.2 9.3 9.4 9.5

132 132 135 137 139

Emissions Beverages production Food production/processing Sugar production Treatment of slaughterhouse waste

10 Assessment of completeness 10.1 Source sectors not included 10.2 Activities not included 11 Uncertainties 11.1 11.2 11.3 11.4

Methodology Uncertainty input for greenhouse gases Uncertainty results for greenhouse gases Uncertainty input and results for other pollutants

142 142 142 144 144 144 146 147

12 QA/QC and verification

149

13 Source specific planned improvements

150

References

152

List of abbreviations As BC Ca CaCO3 CaO Cd CH4 CHP CKD CLRTAP CO CO2 CO2-eq CollectER CORINAIR Cr CRF Cu DCE DEA DEPA EEA EF EMEP ENVS EU-ETS Gg GHG GWP HCB HFCs Hg IE IEF IPCC LKD LPG LRTAP LULUCF Mg µg N2O NA NECD NFR NH3 Ni NMVOC NO NOx Pb PCDD/F PFCs PM2.5

Arsenic Black Carbon Calcium Limestone (Burnt) Lime Cadmium Methane Combined Heat and Power Cement Kiln Dust Convention on Long-Range Transboundary Air Pollution Carbon monoxide Carbon dioxide CO2 equivalents, calculated from all GHGs using GWPs Software to support the CORINAIR system CORe INventory on AIR emissions Chromium Common Reporting Format Copper Danish Centre for Environment and energy Danish Energy Agency Danish Environmental Protection Agency European Environment Agency Emission Factor European Monitoring and Evaluation Programme Department of ENVironmental Science, Aarhus University European Union Emission Trading Scheme Gigagram, 109 g Greenhouse gas Global Warming Potential Hexachlorobenzene Hydrofluorocarbons Mercury Included Elsewhere Implied Emission Factor Intergovernmental Panel on Climate Change Lime Kiln Dust Liquefied Petroleum Gas Long-Range Transboundary Air Pollution Land Use, Land-Use Change and Forestry Megagram, 106 g (equals metric ton or tonne) Microgram, 10-6 g Nitrous oxide Not Applicable National Emissions Ceiling Directive Nomenclature For Reporting Ammonia Nickel Non-Methane Volatile Organic Compounds Not Occurring Nitrogen Oxides Lead PolyChlorinated DibenzoDioxins/Furans Perfluorocarbons Particulate Matter up to 2.5 µm in size

PM10 POPs QA QC Se SF6 SNAP SO2 TSP UNECE UNFCCC Zn

Particulate Matter up to 10 µm in size Persistent Organic Pollutants Quality Assurance Quality Control Selenium Sulphur hexafluoride Selected Nomenclature for Air Pollution Sulphur dioxide Total Suspended Particles United Nations Economic Commission for Europe United Nations Framework Convention on Climate Change Zinc

Preface DCE - Danish Centre for Environment and Energy, Aarhus University is contracted by the Ministry of the Environment and the Ministry of Climate, Energy and Building to complete emission inventories for Denmark. Department of Environmental Science, Aarhus University is responsible for calculation and reporting of the Danish national emission inventory to EU and the UNFCCC (United Nations Framework Convention on Climate Change) and UNECE CLRTAP (Convention on Long Range Transboundary Air Pollution). This report forms the documentation of the emission inventories for industrial processes. The report includes both methodological descriptions and emission data. This report contains inventories for the following groups of substances: Greenhouse gasses (CO2, CH4, N2O and F-gasses (HFCs, PFCs, SF6 and NF3)), main pollutants (CO, NH3, NMVOC, NOx, SO2), particulate matter (TSP, PM10, PM2.5, BC), heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb, Se, Zn) and persistent organic pollutants (POPs) (PCDD/F, HCB, PCB and PAHs). The results of inventories up to 2013 are included. The report is the second version of a sectoral report for industrial processes and has been reviewed externally by Karsten Fuglsang from FORCE Technology. As a result of this review several changes were made to the report; mostly clarifications of the text and tables and elaboration of certain documentation. In addition, suggestions to future improvements have been acknowledged and added to the list of planned improvements, e.g. investigation of particle emissions from the sugar industry and further consideration to the PM2.5 emission factor for aluminium smelting. An updated report will be published in 2017.

7

Summary Danish emission inventories are prepared on an annual basis and are reported to the United Nations Framework Convention on Climate Change (UNFCCC or Climate Convention) and to the Kyoto Protocol as well as to the United Nations Economic Commission for Europe (UNECE) Convention on Long-Range Transboundary Air Pollution (LRTAP Convention). Furthermore, a greenhouse gas emission inventory is reported to the European Union (EU) due to the EU – as well as the individual member states – being party to the Climate Convention and the Kyoto Protocol. Inventories also include four pollutants that are estimated for reporting to the European Commission’s National Emissions Ceiling Directive (NECD). The annual Danish emission inventories are prepared by the DCE – Danish Centre for Environment and Energy, Aarhus University. The inventories include the following pollutants relevant to industrial processes: carbon dioxide (CO2), nitrous oxide (N2O), hydroflourocarbons (HFCs), perflourocarbons (PFCs), sulphur hexafluoride (SF6), methane (CH4), sulphur dioxide (SO2), nitrogen oxides (NOx), non-volatile organic compounds (NMVOC), carbon monoxide (CO), particulate matter (PM), ammonia (NH3), heavy metals (HMs), polyclorinated dibenzodioxins and –furans (PCDD/F), polycyclic aromatic hydrocarbons (PAHs), hexachlorobenzene (HCB) and polychlorinated biphenyls (PCBs). In addition to annual national emissions, the report includes emission data for a number of source categories. Every four years the reporting includes data on the geographical distribution of the emissions, a projection of emissions, data and details of the activity data, e.g. fuel consumption – on which the inventories are based. The next due date is 1 May 2017. The pollutants listed above correspond to the requirements of the UNFCCC, UNECE and EU to whom the emission inventories are reported. Other pollutants could be relevant for the source categories included in this report for environment impact assessment, but these will fall outside the scope of the emission inventories and will therefore not be included. The inventories for industrial processes are largely based on official Danish statistics (from Statistics Denmark) and on a set of emission factors for various source categories and technologies. For some source categories the official statistics are supplemented by information from individual plants or from industrial associations. Plant specific emissions for large industrial sources are incorporated into the inventories. This report provides detailed background information on the methodology and references for the input data in the inventory – including activity data and emission factors. The emission factors are based on either national references or on international guidance documents (EEA, (2004, 2009, 2013); IPCC, (2000, 2006)). The majority of the country-specific emission factors are determined from Danish research reports or calculations based on plant-specific emission data from a considerable number of individual plants. The plant-specific emission factors are provided by plant operators, e.g. in annual environmental reports or in the reports under the EU Emission Trading Scheme (ETS).

8

Greenhouse gases An overview of the sources identified is presented in Table 0.1 with an indication of the contribution to the industrial part of the emission of greenhouse gases in 2013. The emissions are extracted from the Common Reporting Format (CRF) tables. Table 0.1 Overview of industrial greenhouse gas sources (2013). Substance CO2 HFCs, PFCs SF6 CO2

Emission Gg CO2 eq. 867.1 711.0 117.4 67.2

% 45% 37% 6% 3%

2F2 2A2 2F4 2G3

HFCs CO2 HFCs N2O

60.7 54.2 17.7 15.8

3% 3% 1% 1%

Electrical equipment Glass production Other product use Other (fibre optics)

2G1 2A3 2G4 2E5

SF6 CO2 CO2, CH4, N2O PFCs

13.1 7.0 5.9 3.7

1% 0.4% 0.3% 0.2%

Catalysts / fertilisers Lead production Iron and steel production Nitric acid production

2B10 2C5 2C1 2B2

CO2 CO2 CO2 N2O

1.3 0.2 NO NO

0.1% 0.01% NO NO

1,942.2

100%

Process Cement production Refrigeration and air conditioning SF6 from other product use Other uses of carbonates

IPCC Code 2A1 2F1 2G2 2A4

Foam blowing agents Lime production Aerosols / Metered dose inhalers N2O from product uses

Total NO: Not Occurring

The subsector Mineral Industry (2A) constitutes 51 % and Product Uses as Substitutes for Ozone Depleting Substances (ODS) (2F) constitutes 41 % of the greenhouse gas emission in 2013 from the Industrial Processes sector. Other Product Manufacture and Use (2G) constitutes 8 % and the remaining three subsectors Chemical Industry (2B), Metal Industry (2C) and Electronics Industry (2E) each constitutes below 0.2 % of the total industrial process emission of greenhouse gases in 2013. Greenhouse gas emissions from Metal Industry (2C) were low in recent years, since the single Danish steel production facility (2C1) was last in operation in 2005. Emissions from Non-Energy Products from Fuels and Solvent Use (2D) are not included in this sector report (Fauser, 2010). The total emission of greenhouse gases (excl. emissions/removals from Land-Use, Land-Use Change and Forestry (LULUCF)) in Denmark in 2013 is estimated to 54.6 Gg CO2 equivalents, of which industrial processes contribute with 1.94 Gg CO2 equivalents (3.6 %). The emission of greenhouse gases from industrial processes from 1990-2013 are presented in Figure 0.1.

9

Figure 0.1 Emission of greenhouse gases from industrial processes (CRF Sector 2 excl. 2D solvents) from 1990-2013.

The key categories in the Industrial Processes sector - Cement Production and Refrigeration and Air Conditioning - constitute 1.6 % and 1.3 % respectively of the total national emission of greenhouse gases. The trends in greenhouse gases from the Industrial Processes sector/subsectors are presented in Table 0.2 and they will be discussed subsector by subsector below. Table 0.2 Emission of greenhouse gases from industrial processes. Year

1990

1995

2000

2005

2010

2011

2012

2013

1,078.3

1,417.4

1,627.9

1,564.0

803.7

992.5

993.8

995.4

CO2 (Gg CO2) A. Mineral Industry B. Chemical Industry

0.9

0.9

0.9

1.1

1.1

1.1

1.3

1.3

30.5

38.7

40.9

16.4

0.2

0.2

0.1

0.2

0.1

0.1

0.2

0.2

0.2

0.2

0.2

0.2

1,109.7

1,457.1

1,669.9

1,581.7

805.2

994.1

995.5

997.1

2.1

2.2

3.0

3.1

2.0

1.8

2.8

2.9

1,002.5

868.9

964.7

NO

NO

NO

NO

NO

18.5

20.8

20.9

19.0

19.0

20.8

15.8

18.6

1,021.1

889.7

985.6

19.0

19.0

20.8

15.8

18.6

NO

NO

NO

NO

5.3

5.3

1.8

NO

NO

242.1

703.1

932.7

944.6

880.1

797.1

782.2

NO

242.1

703.1

932.7

949.9

885.5

798.9

782.2

NO

NO

NO

NO

7.3

5.6

3.4

3.7

NO

0.6

22.6

18.8

11.4

10.1

8.8

7.1

NO

0.6

22.6

18.8

18.7

15.7

12.2

10.8

C. Metal Industry

29.6

34.2

20.3

NO

NO

NO

NO

NO

G. Other Product Manufacture and Use

13.8

68.2

35.8

19.9

35.8

69.4

112.0

130.6

C. Metal Industry G. Other Product Manufacture and Use Total CH4 (Gg CO2 eq.) G. Other Product Manufacture and Use N2O (Gg CO2 eq.) B. Chemical Industry G. Other Product Manufacture and Use Total HFCs (Gg CO2 eq.) E. Electronics Industry F. Product Uses as Substitutes for Ozone Depleting Substances Total PFCs (Gg CO2 eq.) E. Electronics Industry F. Product Uses as Substitutes for Ozone Depleting Substances Total SF6 (Gg CO2 eq.)

Total 43.4 102.4 56.1 19.9 35.8 69.41 112.0 130.6 1 The increase in SF6 emission in 2011-2013 is due to use of SF6 in windows. The use started in 1991 and there is an expected lifetime of 20 years. At the end of the 20 years lifetime, the SF6 remaining in the windows is assumed to be emitted. NO: Not Occurring

The emission of F-gases is documented in the report “Danish consumption and emission of F-gases, Year 2013” (Poulsen, 2015) and will only briefly be described in this report.

10

Other pollutants Emissions of air pollution occur in many subsectors under industrial processes. An overview of the emissions of main pollutants (SO2, NOx, NMVOC, CO and NH3) and particulate matter (Total Suspended Particulates (TSP), particles with an aerodynamic diameter of less than 10 μm (PM10) and particles with an aerodynamic diameter of less than 2.5 μm (PM2.5)) is shown in Table 0.3 below.

11

Table 0.3 Emission of main pollutants and particulate matter from industrial processes. Pollutant

Unit

Sector

1985

1990

1995

2000

2005

2010

2011

2012

2013

SO2

Gg

2A6 Other mineral products 2B10a Other chemical industry 2G4 Other product use

NE 0.63 0.02

2.72 0.85 0.03

2.87 0.62 0.03

2.76 0.63 0.06

2.72 0.61 0.06

1.10 0.12 0.04

1.25 0.19 0.03

1.11 0.23 0.05

1.75 0.18 0.06

Total

0.65

3.59

3.52

3.45

3.39

1.25

1.48

1.39

1.98

NOx

Gg

2B2 Nitric acid production 2B10a Other chemical industry 2G4 Other product use

0.63 0.04 0.04

0.81 0.04 0.04

0.61 0.04 0.04

0.41 0.03 0.06

NO 0.03 0.06

NO 0.02 0.04

NO 0.02 0.04

NO 0.02 0.06

NO 0.02 0.06

Total

0.70

0.89

0.69

0.51

0.09

0.06

0.06

0.08

0.08

IE 0.39 0.08 4.00

0.05 0.39 0.08 4.04

0.05 0.06 0.08 3.90

0.05 0.03 0.10 3.81

0.05 0.03 0.09 3.98

0.03 0.02 0.07 3.52

0.04 0.02 0.06 3.46

0.04 0.02 0.08 3.44

0.04 0.02 0.08 3.06

4.48

4.56

NMVOC

Gg

2A3 Glass production 2B10a Other chemical industry 2G4 Other product use 2H2 Food and beverages industry

4.08

3.99

4.15

3.63

3.58

3.57

3.19

CO

Gg

2A3 Glass production 2A6 Other mineral products 2G4 Other product use

0.002 0.002 0.002 11.97 11.97 11.93 1.78 2.29 2.40

0.002 11.96 3.63

0.002 12.18 4.08

0.001 0.01 2.54

0.002 0.01 2.20

0.001 0.03 3.70

0.001 0.01 3.74

Total

13.76 14.27 14.33

15.59

16.25

2.55

2.21

3.73

3.75

0.23 0.29 0.01 0.01 0.05 0.03

0.12 0.30 NO 0.08 0.04 0.13

0.11 0.20 NO 0.12 0.04 0.09

0.11 0.19 NO 0.02 0.03 0.09

0.14 0.20 NO 0.02 0.04 0.07

0.12 0.18 NO 0.02 0.04 0.06

0.63

0.67

0.56

0.44

0.47

0.42

Total

NH3

Gg

2A3 Glass production 2A6 Other mineral products 2B2 Nitric acid production 2B10a Other chemical industry 2G4 Other product use 2L Other production

0.22 0.30 0.01 0.01 0.06 NE

0.26 0.30 0.01 0.01 0.05 0.03

0.26 0.30 0.06 0.01 0.05 0.03

Total

0.60

0.66

0.72

TSP

Mg

2A2 Lime production 2A3 Glass production 2A6 Other mineral products 2B2 Nitric acid production 2B10a Other chemical industry 2C1 Iron and steel production 2C3 Aluminum production 2C5 Lead production 2G4 Other product use

PM10

Mg

PM2.5

Mg

BC

Mg

Total

1,297.11 869.62 718.90 691.35 641.27 678.13

2A2 Lime production 2A3 Glass production 2A6 Other mineral products 2B2 Nitric acid production 2B10a Other chemical industry 2C1 Iron and steel production 2C3 Aluminum production 2C5 Lead production 2G4 Other product use

18.40 14.25 10.08 11.89 13.83 13.36 123.00 83.30 24.50 39.60 47.00 36.40 70.30 69.00 55.60 56.00 63.90 103.50 NO NO NO NO NO 290.00 18.00 21.00 5.40 4.80 8.00 15.00 75.60 46.05 52.52 47.54 48.74 94.02 2.42 0.44 0.53 0.55 0.57 3.09 1.22 1.15 1.54 0.86 1.02 1.03 315.76 307.36 304.24 267.92 261.67 285.71

Total

924.19 605.65 477.76 448.40 431.84 449.80

2A2 Lime production 2A3 Glass production 2A6 Other mineral products 2B2 Nitric acid production 2B10a Other chemical industry 2C1 Iron and steel production 2C3 Aluminum production 2C5 Lead production 2G4 Other product use

3.68 2.85 2.02 2.38 2.77 2.67 73.50 22.30 35.00 41.50 32.30 109.00 80.50 54.76 53.61 43.25 44.00 49.70 NO NO NO NO NO 217.00 14.00 16.00 4.10 3.60 6.00 11.00 19.66 8.03 9.02 7.94 8.42 32.15 0.95 0.17 0.21 0.21 0.23 1.21 0.61 0.58 0.77 0.43 0.51 0.51 286.88 285.45 271.99 239.78 240.96 259.26

Total

711.14 477.52 375.83 344.87 340.65 353.39

2A2 Lime production

NO: Not occurring, IE: Included elsewhere, NE: Not estimated

12

46.00 35.62 25.20 29.72 34.57 33.40 137.00 92.00 27.70 43.80 51.50 39.60 78.00 77.00 62.00 62.00 71.00 115.00 NO NO NO NO NO 362.00 23.00 26.00 6.80 6.00 10.00 19.00 244.40 218.61 148.18 169.64 154.62 157.18 3.46 0.62 0.75 0.78 0.82 4.41 1.53 1.44 1.93 1.08 1.27 1.28 412.02 380.40 411.76 361.72 330.73 373.85

0.02

0.01

0.01

0.01

0.01

0.01

Production of nitric acid ceased in Denmark in 2005, which caused a significant decrease in the emissions of NOx and particulate matter from industrial processes. The CO emission has decreased significantly from the source Other mineral products, this is due to a decrease in emissions from the Danish producer of mineral wool caused by the establishment of abatement measures in 2009-2010. In the later years emissions of SO2 have decreased due to lower production of bricks, tiles and expanded clay products (included in Other mineral products (IPCC/CRF Code 2A6)). The emissions of heavy metals (Arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb), selenium (Se) and zinc (Zn)) and persistent organic pollutants (PCDD/F, HCB and PCBs) are shown in the table below. Table 0.4a Emission of heavy metals and persistent organic pollutants from industrial processes. Pollutant

Unit

Sector

1990

1995

2000

2005

2010

2011

2012

2013

As

Mg

2A3 Glass production 2C1 Iron and steel production 2C5 Lead production 2G4 Other product use

0.048 0.040 0.003 0.004

0.041 0.038 0.004 0.007

0.052 0.040 0.003 0.010

0.036 0.034 0.003 0.008

0.003 0.022 0.003 0.009

0.003 0.025 0.004 0.008

0.003 0.023 0.002 0.007

0.002 0.023 0.003 0.009

Cd

Mg

Cr

Mg

2A3 Glass production 2C1 Iron and steel production 2G4 Other product use

Cu

Mg

Total

Total 2A3 Glass production 2C1 Iron and steel production 2C3 Aluminium production 2C5 Lead production 2C7c Other metal production 2G4 Other product use Total

0.09

0.09

0.10

0.08

0.04

0.04

0.04

0.04

0.020 0.053 0.001 0.001 0.004 0.001

0.017 0.035 0.001 0.001 0.004 0.002

0.022 0.030 0.001 0.001 0.005 0.004

0.015 0.023 0.001 0.001 0.005 0.003

0.001 0.012 0.0002 0.001 0.005 0.004

0.001 0.014 0.0002 0.001 0.005 0.004

0.001 0.012 0.0002 0.001 0.005 0.003

0.001 0.013 0.0002 0.001 0.005 0.004

0.08

0.06

0.06

0.05

0.02

0.02

0.02

0.02

0.061 0.175 0.025

0.052 0.171 0.051

0.066 0.112 0.080

0.046 0.110 0.062

0.003 0.080 0.088

0.004 0.092 0.077

0.004 0.084 0.058

0.003 0.085 0.073

Total

0.26

0.27

0.26

0.22

0.17

0.17

0.15

0.16

2C7c Other metal production 2G4 Other product use

0.04 0.57

0.04 1.34

0.05 2.16

0.05 1.64

0.05 2.41

0.05 2.10

0.05 1.55

0.05 1.98

0.61

1.38

2.21

1.69

2.46

2.15

1.60

2.02

0.005 0.246 0.001

0.005 0.143 0.001

0.005 0.063 0.001

0.005 0.023 0.001

0.001 0.009 0.001

0.001 0.009 0.000

0.010 0.006 0.001

NA 0.009 0.001

Hg

Mg

2B10a Other chemical industry 2C1 Iron and steel production 2G4 Other product use

Ni

Mg

2A3 Glass production 2C1 Iron and steel production 2G4 Other product use

Pb

Mg

2A3 Glass production 2C1 Iron and steel production 2C3 Aluminium production 2C5 Lead production 2C7c Other metal production 2G4 Other product use

Se

Mg

2A3 Glass production 2C1 Iron and steel production 2G4 Other product use

Total

Total

Total

Total

0.25

0.15

0.07

0.03

0.01

0.01

0.02

0.01

0.039 0.89 0.04

0.034 0.55 0.09

0.043 0.38 0.15

0.030 0.27 0.11

0.002 0.13 0.16

0.002 0.14 0.14

0.002 0.12 0.11

0.001 0.13 0.14

0.97

0.67

0.58

0.41

0.29

0.29

0.23

0.27

0.48 3.71 0.005 0.34 0.06 2.85

0.41 2.37 0.005 0.43 0.07 6.64

0.33 1.40 0.006 0.34 0.07 3.30

0.15 1.02 0.004 0.40 0.07 2.53

0.02 0.56 0.001 0.38 0.07 0.04

0.03 0.64 0.001 0.51 0.07 0.04

0.12 0.57 0.001 0.28 0.07 0.07

0.02 0.59 0.001 0.33 0.07 0.07

7.4

9.9

5.4

4.2

1.1

1.3

1.1

1.1

0.25 0.52 0.005

0.21 0.45 0.005

0.34 0.51 0.009

0.11 0.50 0.010

0.02 0.36 0.005

0.02 0.42 0.004

0.06 0.38 0.009

0.02 0.39 0.009

0.8

0.7

0.9

0.6

0.4

0.4

0.5

0.4

13

Table 0.4b Emission of heavy metals and persistent organic pollutants from industrial processes. (Continued) 1995 2000 2005 2010 2011 Pollutant Unit Sector 1990 Zn Mg 2A3 Glass production 0.04 0.03 0.06 0.03 0.03 0.03 2C1 Iron and steel production 12.0 7.0 3.6 1.6 0.5 0.6 2C5 Lead production 0.002 0.003 0.002 0.002 0.002 0.003 2C7c Other Metal production 0.5 0.6 0.6 0.6 0.6 0.6 2G4 Other product use 0.5 0.9 1.5 1.2 1.5 1.3 Total

13.0

PAH

Mg

2G4 Other product use

PCDD/F

g

2A2 Lime production 2A6 Other mineral products 2C1 Iron and steel production 2C3 Aluminium production 2C5 Lead production 2G4 Other product use

HCB

g

2A2 Lime production 2C1 Iron and steel production 2C3 Aluminium production 2C5 Lead production 2G4 Other product use

PCBs

g

Total

8.5

5.8

3.4

2.7

2.6

2012 0.03 0.5 0.002 0.6 1.1

2013 0.00 0.5 0.002 0.6 1.4

2.3

2.5

0.1

0.1

0.1

0.1

0.1

0.0

0.1

0.1

0.002 0.1 12.0 1.1 0.01 0.1

0.002 0.1 7.5 1.1 0.01 0.1

0.002 0.1 0.5 1.3 0.01 0.1

0.001 0.1 0.2 1.0 0.01 0.2

0.001 0.1 NE 0.2 0.01 0.1

0.001 0.1 NE 0.2 0.01 0.1

0.001 0.1 NE 0.2 0.01 0.1

0.001 0.1 NE 0.2 0.01 0.1

13.3

8.8

2.0

1.4

0.3

0.4

0.4

0.5

1.0 1968.2 629.9 0.2 0.7

0.8 2297.3 649.1 0.3 0.8

0.7 2023.2 735.3 0.2 1.3

0.6 804.0 576.3 0.3 1.4

0.4 2.9 104.0 0.3 0.7

0.5 3.3 125.2 0.4 0.6

0.6 3.1 129.8 0.2 1.3

0.5 3.1 136.9 0.2 1.3

Total

2,600.0

2,948.3

2,760.8

1,382.6

108.3

130.0

134.9

142.1

2A2 Lime production 2C1 Iron and steel production 2C3 Aluminium production 2C5 Lead production 2G4 Other product use

19.2 1585.9 107.1 5.7 1.0

15.1 1837.1 110.3 7.3 1.1

13.8 1628.3 125.0 5.7 1.8

10.7 675.0 98.0 6.8 2.0

7.6 36.4 17.7 6.4 1.0

8.9 41.8 21.3 8.6 0.9

10.4 38.2 22.1 4.8 1.9

10.0 38.7 23.3 5.7 1.9

1,718.9

1,970.8

1,774.6

792.4

69.1

81.5

77.3

79.5

Total

The closure of the electro steelwork in 2002 with the brief reopening in 2005 as well as the closure of the secondary aluminium plant in 2008 has meant a decrease in emissions of several heavy metal (e.g. Pb, Zn) and POPs (e.g. PCDD/F, HCB and PCBs). Legislation from 2000 and 2007 regulating and eventually forbidding Pb in fireworks has also reduced Pb emissions from Other product use substantially.

14

Sammendrag De danske emissionsopgørelser udarbejdes og afrapporteres årligt til De Forenede Nationers klimakonvention (UNFCCC) og til Kyotoprotokollen, samt til FN's Økonomiske Kommission for Europas Konvention om Langtransporteret Grænseoverskridende Luftforurening (UNECE LRTAPkonventionen). Ydermere rapporteres de nationale opgørelser af drivhusgasemissioner til EU, da EU, såvel som de enkelte medlemslande, er parter til klimakonventionen samt Kyotoprotokollen. Fire forureningskilder rapporteres til Europakommissionens direktiv om nationale emissionslofter (NECD). De årlige emissionsopgørelser udarbejdes af DCE – Nationalt Center for Miljø og Energi, Aarhus Universitet. Emissionsopgørelserne inkluderer følgende forureningskomponenter af relevans for industrielle processer: kuldioxid (CO2), lattergas (N2O), hydroflourkarboner (HFC), perflourkarboner (PFCer), svovlhexafluorid (SF6), metan (CH4), svovldioxid (SO2), kvælstofoxider (NOx), andre flygtige organiske forbindelser end metan (NMVOC), kulmonooxid (CO), partikler (PM), ammoniak (NH3), tungmetaller (HMs), dioxiner og furaner (PCDD/F), polycykliske aromatiske kulbrinter (PAHs), hexachlorbenzen (HCB) and polychlorerede biphenyler (PCBer). Ud over de årlige nationale emissioner indeholder opgørelsen også emissions data for en række kilde kategorier. Hvert fjerde år inkluderer opgørelsen desuden data for den geografiske fordeling af emissioner, en fremskrivning af emissioner, data og detaljer om aktivitets data, f.eks. brændselsforbrug – på hvilke opgørelsen er baseret. Den næste afrapporterings dato for dette er d. 1. maj 2017. Den ovenstående liste af stoffer svarer til de forpligtigelser Danmark skal efterleve i henhold til UNFCCC, UNECE og EU til hvilke emissionsopgørelserne rapporteres. Andre stoffer kan være relevante for de kildekategorier som er inkluderet i denne rapport, men disse vil ligge uden for opgørelsens formål og vil derfor ikke være inkluderet. Emissionsopgørelserne for industrielle processer er i vid udstrækning baseret på officielle statistiske oplysninger (fra Danmarks Statistik) kombineret med emissionsfaktorer for forskellige sektorer, processer og teknologier. For nogle sektorer er de officielle statistiske oplysninger suppleret med information direkte fra virksomheder eller brancheorganisationer. Anlægsspecifikke emissioner for større industrielle kilder er indarbejdet i emissionsopgørelsen. Denne rapport beskriver detaljeret de metoder samt inputdata og emissionsfaktorer, der er anvendt i beregningen af emissioner fra industrielle processer. Emissionsfaktorerne er enten baseret på nationale undersøgelser/målinger eller henviser til internationale retningslinjer, f.eks. EMEP/EEA Guidebook og IPCC Guidelines. Hovedparten af de nationale emissionsfaktorer er baseret på forskningsrapporter eller beregninger baseret på et stort antal målinger på forskellige anlæg. De anlægsspecifikke emissionsfaktorer er tilvejebragt af anlægsejere, f.eks. i forbindelse med udarbejdelsen af grønne regnskaber eller i forbindelse med rapportering under EU’s kvotehandelssystem.

15

Drivhusgasser En oversigt over relevante kilder er præsenteret i Tabel 0.1 sammen med en indikation af bidraget til den samlede drivhusgasemission fra industrielle processer i 2013. Tabel 0.1 Oversigt over drivhusgas emissionskilder for industrielle processer (2013). Gas CO2 HFC, PFCer

Emission Gg CO2 ækv. 867,1 711,0

% 45 37

2G2 2A4 2F2 2A2

SF6 CO2 HFC CO2

117,4 67,2 60,7 54,2

6 3 3 3

Aerosoler / Dosisinhalatorer N2O fra andre produkt anvendelser Elektrisk udstyr Glas produktion

2F4 2G3 2G1 2A3

HFC N2O SF6 CO2

17,7 15,8 13,1 7,0

1 1 1 0,4

Øvrige produkt anvendelser Øvrige (fiberoptik) Katalysatorer / gødning Bly produktion

2G4 2E5 2B10 2C5

CO2, CH4, N2O PFCer CO2 CO2

5,9 3,7 1,3 0,2

0,3 0,2 0,1 0,01

Jern og stål produktion Salpetersyreproduktion

2C1 2B2

CO2 N2O

NO NO

NO NO

1.942,2

100 %

Proces Cement produktion Køling og aircondition

IPCC kode 2A1 2F1

SF6 fra andre produkt anvendelser Andre anvendelser for karbonater Opskumning Produktion af brændt kalk

Total NO: Forekommer ikke

Samlet udgør mineralsk industri (2A) (cement, tegl, kalk, glas, mv.) 51 % af drivhusgasemissionen i 2013. Produkt anvendelser som erstatning for ozonlagsnedbrydende stoffer (2F) udgør 41 %, andre produkters produktion og anvendelse (2G) udgør 8 % og de resterende tre underkategorier (Kemisk industri (2B), Metal industri (2C) og Elektronisk industri (2E)) udgør hver under 0,2 % af den total drivhusgasemission fra industrielle processer i 2013. Drivhusgasemission fra metal industri har været lav i de seneste år, siden det eneste stålværk i Danmark ikke har været i drift siden 2005. Emissionerne fra Ikke-energi produkter fra brændsel samt solventer (2D) er ikke inkluderet i denne rapport, men kan findes i Fauser (2010). Den totale drivhusgasemission eksklusive emissioner/optag fra arealanvendelse i 2013 er beregnet til 54,6 Gg CO2 ækvivalenter, hvoraf industrielle processer bidrager med 1,94 Gg CO2 ækvivalenter svarende til 3,6 %. Drivhusgasemissionen fra industrielle processer for 1990-2013 er præsenteret i Figur 0.1.

Figur 0.1 Emission af drivhusgasser fra industrielle processer (CRF Sektor 2 uden 2D solventer) for 1990-2013.

16

De vigtigste kategorier indenfor industrielle processer er cementproduktion samt F-gasser anvendt til køling og aircondition. Disse to kilder udgør henholdsvis 1,6 og 1,3 % af den samlede danske drivhusgasemission. Udviklingen i drivhusgasemissioner fra industrielle processer fordelt på hovedkategorier er præsenteret i Tabel 0.2 nedenfor. Udviklingen er nærmere beskrevet i de enkelte kapitler i rapporten. Tabel 0.2 Drivhusgas emission fra industrieller processer. 1990

1995

2000

2005

2010

2011

2012

2013

A. Mineral Industri

1.078,3

1.417,4

1.627,9

1.564,0

803,7

992,5

993,8

995,4

B. Kemisk Industri

0,9

0,9

0,9

1,1

1,1

1,1

1,3

1,3

30,5

38,7

40,9

16,4

0,2

0,2

0,1

0,2

0,1

0,1

0,2

0,2

0,2

0,2

0,2

0,2

1.109,7

1.457,1

1.669,9

1.581,7

805,2

994,1

995,5

997,1

2,1

2,2

3,0

3,1

2,0

1,8

2,8

2,9

1.002,5

868,9

964,7

NO

NO

NO

NO

NO

18,5

20,8

20,9

19,0

19,0

20,8

15,8

18,6

1.021,1

889,7

985,6

19,0

19,0

20,8

15,8

18,6

NO

NO

NO

NO

5,3

5,3

1,8

NO

NO

242,1

703,1

932,7

944,6

880,1

797,1

782,2

NO

242,1

703,1

932,7

949,9

885,5

798,9

782,2

NO

NO

NO

NO

7,3

5,6

3,4

3,7

NO

0,6

22,6

18,8

11,4

10,1

8,8

7,1

NO

0,6

22,6

18,8

18,7

15,7

12,2

10,8

C. Metal Industri

29,6

34,2

20,3

NO

NO

NO

NO

NO

G. Øvrige Produkter Produktion og Anvendelse

13,8

68,2

35,8

19,9

35,8

69,4

112,0

130,6

Year CO2 (Gg CO2)

C. Metal Industri G. Øvrige Produkter Produktion og Anvendelse Total CH4 (Gg CO2 ækv.) G. Øvrige Produkter Produktion og Anvendelse N2O (Gg CO2 ækv.) B. Kemisk Industri G. Øvrige Produkter Produktion og Anvendelse Total HFC (Gg CO2 ækv.) E. Elektronik Industri F. Produkt Anvendelse som Erstatning for Ozonnedbrydende Stoffer Total PFCer (Gg CO2 ækv.) E. Elektronik Industri F. Produkt Anvendelse som Erstatning for Ozonnedbrydende Stoffer Total SF6 (Gg CO2 ækv.)

Total 43,4 102,4 56,1 19,9 35,8 69,41 112,0 130,6 1 Stigningen i SF6 emissionen i 2011-2013 skyldes anvendelsen af SF6 i vinduer. Anvendelsen startede i 1991 og der er en forventet levetid på 20 år. Efter de 20 års levetid, antages det at den resterende mængde SF6 I vinduerne er udledt. NO: Forekommer ikke.

Emissionerne af F-gasser er dokumenteret i rapporten “ Danish consumption and emission of F-gases, Year 2013” (Poulsen, 2015) og vil kun kortfattet blive beskrevet i denne rapport.

Øvrige luftforurenende stoffer Emissioner af luftforurening finder sted i mange forskellige underkategorier indenfor industrielle processer. Et overblik af emissionerne af hovedforureningskomponenterne (SO2, NOx, NMVOC, CO and NH3) og partikler ((total støv (TSP), partikler med en diameter under 10 μm (PM10) og partikler med en diameter med en diameter under 2.5 μm (PM2.5)) er præsenteret i Tabel 0.3.

17

Tabel 0.3 Emission af hovedforureningskomponenter og partikler fra industrielle processer. Gas

Enhed

Sektor

1985

1990

1995

2000

2005

2010

2011

2012

2013

SO2

Gg

2A6 Øvrige mineralske produkter 2B10a Anden kemisk industri 2G4 Øvrige produkt anvendelser

NE 0,63 0,02

2,72 0,85 0,03

2,87 0,62 0,03

2,76 0,63 0,06

2,72 0,61 0,06

1,10 0,12 0,04

1,25 0,19 0,03

1,11 0,23 0,05

1,75 0,18 0,06

Total

0,65

3,59

3,52

3,45

3,39

1,25

1,48

1,39

1,98

NOx

Gg

2B2 Salpetersyre produktion 2B10a Anden kemisk industri 2G4 Øvrige produkt anvendelser

0,63 0,04 0,04

0,81 0,04 0,04

0,61 0,04 0,04

0,41 0,03 0,06

NO 0,03 0,06

NO 0,02 0,04

NO 0,02 0,04

NO 0,02 0,06

NO 0,02 0,06

Total

0,70

0,89

0,69

0,51

0,09

0,06

0,06

0,08

0,08

IE 0,39 0,08 4,00

0,05 0,39 0,08 4,04

0,05 0,06 0,08 3,90

0,05 0,03 0,10 3,81

0,05 0,03 0,09 3,98

0,03 0,02 0,07 3,52

0,04 0,02 0,06 3,46

0,04 0,02 0,08 3,44

0,04 0,02 0,08 3,06

4,48

4,56

NMVOC

Gg

2A3 Glas produktion 2B10a Anden kemisk industri 2G4 Øvrige produkt anvendelser 2H2 Fødevareproduktion

4,08

3,99

4,15

3,63

3,58

3,57

3,19

CO

Gg

2A3 Glas produktion 2A6 Øvrige mineralske produkter 2G4 Øvrige produkt anvendelser

0,002 0,002 0,002 11,97 11,97 11,93 1,78 2,29 2,40

0,002 11,96 3,63

0,002 12,18 4,08

0,001 0,01 2,54

0,002 0,01 2,20

0,001 0,03 3,70

0,001 0,01 3,74

Total

13,76 14,27 14,33

15,59

16,25

2,55

2,21

3,73

3,75

0,23 0,29 0,01 0,01 0,05 0,03

0,12 0,30 NO 0,08 0,04 0,13

0,11 0,20 NO 0,12 0,04 0,09

0,11 0,19 NO 0,02 0,03 0,09

0,14 0,20 NO 0,02 0,04 0,07

0,12 0,18 NO 0,02 0,04 0,06

0,63

0,67

0,56

0,44

0,47

0,42

Total

NH3

Gg

2A3 Glas produktion 2A6 Øvrige mineralske produkter 2B2 Salpetersyre produktion 2B10a Anden kemisk industri 2G4 Øvrige produkt anvendelser 2L Øvrig produktion

0,22 0,30 0,01 0,01 0,06 NE

0,26 0,30 0,01 0,01 0,05 0,03

0,26 0,30 0,06 0,01 0,05 0,03

Total

0,60

0,66

0,72

TSP

Mg

2A2 Produktion af brændt kalk 2A3 Glas produktion 2A6 Øvrige mineralske produkter 2B2 Salpetersyre produktion 2B10a Anden kemisk industri 2C1 Jern og stål produktion 2C3 Aluminium produktion 2C5 Bly produktion 2G4 Øvrige produkt anvendelser

PM10

Mg

PM2.5

Mg

BC

Mg

2A2 Produktion af brændt kalk

Total

1.297,11 869,62 718,90 691,35 641,27 678,13

2A2 Produktion af brændt kalk 2A3 Glas produktion 2A6 Øvrige mineralske produkter 2B2 Salpetersyre produktion 2B10a Anden kemisk industri 2C1 Jern og stål produktion 2C3 Aluminium produktion 2C5 Bly produktion 2G4 Øvrige produkt anvendelser

18,40 14,25 10,08 11,89 13,83 13,36 123,00 83,30 24,50 39,60 47,00 36,40 70,30 69,00 55,60 56,00 63,90 103,50 NO NO NO NO NO 290,00 18,00 21,00 5,40 4,80 8,00 15,00 75,60 46,05 52,52 47,54 48,74 94,02 2,42 0,44 0,53 0,55 0,57 3,09 1,22 1,15 1,54 0,86 1,02 1,03 315,76 307,36 304,24 267,92 261,67 285,71

Total

924,19 605,65 477,76 448,40 431,84 449,80

2A2 Produktion af brændt kalk 2A3 Glas produktion 2A6 Øvrige mineralske produkter 2B2 Salpetersyre produktion 2B10a Anden kemisk industri 2C1 Jern og stål produktion 2C3 Aluminium produktion 2C5 Bly produktion 2G4 Øvrige produkt anvendelser

3,68 2,85 2,02 2,38 2,77 2,67 73,50 22,30 35,00 41,50 32,30 109,00 80,50 54,76 53,61 43,25 44,00 49,70 NO NO NO NO NO 217,00 14,00 16,00 4,10 3,60 6,00 11,00 19,66 8,03 9,02 7,94 8,42 32,15 0,95 0,17 0,21 0,21 0,23 1,21 0,61 0,58 0,77 0,43 0,51 0,51 286,88 285,45 271,99 239,78 240,96 259,26

Total

711,14 477,52 375,83 344,87 340,65 353,39

NO: Forekommer ikke, IE: Inkluderet andetsteds, NE: Ikke estimeret

18

46,00 35,62 25,20 29,72 34,57 33,40 137,00 92,00 27,70 43,80 51,50 39,60 78,00 77,00 62,00 62,00 71,00 115,00 NO NO NO NO NO 362,00 23,00 26,00 6,80 6,00 10,00 19,00 244,40 218,61 148,18 169,64 154,62 157,18 3,46 0,62 0,75 0,78 0,82 4,41 1,53 1,44 1,93 1,08 1,27 1,28 412,02 380,40 411,76 361,72 330,73 373,85

0,02

0,01

0,01

0,01

0,01

0,01

Produktion af salpetersyre stoppede i Danmark i 2005, hvilket betød en betydelig reduktion af emissioner af NOx og partikler fra industrielle processer. CO emissionen er reduceret betydeligt fra kategorien ’Andre mineralske produkter’. Reduktionen stammer fra et fald i emissionen fra produktion af stenuld, som skyldes installationen af røggasrensnings udstyr i 2009-2010. Emissionen af SO2 er i de senere år faldet på grund af en lavere produktion af mursten, tegl og ekspanderede lerprodukter (inkluderet i øvrige mineralske produkter 2A6). Emissioner af tungmetaller (Arsen (As), kadmium (Cd), Krom (Cr), kobber (Cu), kviksølv (Hg), nikkel (Ni), bly (Pb), selen (Se) and zink (Zn)) og persistente organiske forbindelsers (PCDD/F, HCB og PCBer) er præsenteret i Tabel 0.4. Tabel 0.4a Emission af tungmetaller og persistente organiske forbindelser fra industrielle processer. Gas

Enhed

Sektor

1990

1995

2000

2005

2010

2011

2012

2013

As

Mg

2A3 Glas produktion 2C1 Jern og stål produktion 2C5 Bly produktion 2G4 Øvrige produkt anvendelser

0,048 0,040 0,003 0,004

0,041 0,038 0,004 0,007

0,052 0,040 0,003 0,010

0,036 0,034 0,003 0,008

0,003 0,022 0,003 0,009

0,003 0,025 0,004 0,008

0,003 0,023 0,002 0,007

0,002 0,023 0,003 0,009

Cd

Mg

Cr

Mg

2A3 Glas produktion 2C1 Jern og stål produktion 2G4 Øvrige produkt anvendelser

Cu

Mg

Total

Total 2A3 Glas produktion 2C1 Jern og stål produktion 2C3 Aluminium produktion 2C5 Bly produktion 2C7c Anden metal produktion 2G4 Øvrige produkt anvendelser Total

0,09

0,09

0,10

0,08

0,04

0,04

0,04

0,04

0,020 0,053 0,001 0,001 0,004 0,001

0,017 0,035 0,001 0,001 0,004 0,002

0,022 0,030 0,001 0,001 0,005 0,004

0,015 0,023 0,001 0,001 0,005 0,003

0,001 0,012 0,0002 0,001 0,005 0,004

0,001 0,014 0,0002 0,001 0,005 0,004

0,001 0,012 0,0002 0,001 0,005 0,003

0,001 0,013 0,0002 0,001 0,005 0,004

0,08

0,06

0,06

0,05

0,02

0,02

0,02

0,02

0,061 0,175 0,025

0,052 0,171 0,051

0,066 0,112 0,080

0,046 0,110 0,062

0,003 0,080 0,088

0,004 0,092 0,077

0,004 0,084 0,058

0,003 0,085 0,073

Total

0,26

0,27

0,26

0,22

0,17

0,17

0,15

0,16

2C7c Anden metal produktion 2G4 Øvrige produkt anvendelser

0,04 0,57

0,04 1,34

0,05 2,16

0,05 1,64

0,05 2,41

0,05 2,10

0,05 1,55

0,05 1,98

0,61

1,38

2,21

1,69

2,46

2,15

1,60

2,02

0,005 0,246 0,001

0,005 0,143 0,001

0,005 0,063 0,001

0,005 0,023 0,001

0,001 0,009 0,001

0,001 0,009 0,000

0,010 0,006 0,001

NA 0,009 0,001

Hg

Mg

2B10a Anden kemisk industri 2C1 Jern og stål produktion 2G4 Øvrige produkt anvendelser

Ni

Mg

2A3 Glas produktion 2C1 Jern og stål produktion 2G4 Øvrige produkt anvendelser

Pb

Mg

2A3 Glas produktion 2C1 Jern og stål produktion 2C3 Aluminium produktion 2C5 Bly produktion 2C7c Anden metal produktion 2G4 Øvrige produkt anvendelser

Se

Mg

2A3 Glas produktion 2C1 Jern og stål produktion 2G4 Øvrige produkt anvendelser

Total

Total

Total

Total

0,25

0,15

0,07

0,03

0,01

0,01

0,02

0,01

0,039 0,89 0,04

0,034 0,55 0,09

0,043 0,38 0,15

0,030 0,27 0,11

0,002 0,13 0,16

0,002 0,14 0,14

0,002 0,12 0,11

0,001 0,13 0,14

0,97

0,67

0,58

0,41

0,29

0,29

0,23

0,27

0,48 3,71 0,005 0,34 0,06 2,85

0,41 2,37 0,005 0,43 0,07 6,64

0,33 1,40 0,006 0,34 0,07 3,30

0,15 1,02 0,004 0,40 0,07 2,53

0,02 0,56 0,001 0,38 0,07 0,04

0,03 0,64 0,001 0,51 0,07 0,04

0,12 0,57 0,001 0,28 0,07 0,07

0,02 0,59 0,001 0,33 0,07 0,07

7,4

9,9

5,4

4,2

1,1

1,3

1,1

1,1

0,25 0,52 0,005

0,21 0,45 0,005

0,34 0,51 0,009

0,11 0,50 0,010

0,02 0,36 0,005

0,02 0,42 0,004

0,06 0,38 0,009

0,02 0,39 0,009

0,8

0,7

0,9

0,6

0,4

0,4

0,5

0,4

19

Tabel 0.4b Emission af tungmetaller og persistente organiske forbindelser fra industrielle processer. (Fortsat) 1995 2000 2005 2010 Gas Enhed Sektor 1990 Zn Mg 2A3 Glas produktion 0,04 0,03 0,06 0,03 0,03 2C1 Jern og stål produktion 12,0 7,0 3,6 1,6 0,5 2C5 Bly produktion 0,002 0,003 0,002 0,002 0,002 2C7c Anden metal produktion 0,5 0,6 0,6 0,6 0,6 2G4 Øvrige produkt anvendelser 0,5 0,9 1,5 1,2 1,5 Total

2011 0,03 0,6 0,003 0,6 1,3

2012 0,03 0,5 0,002 0,6 1,1

2013 0,00 0,5 0,002 0,6 1,4

13,0

8,5

5,8

3,4

2,7

2,6

2,3

2,5

PAH

Mg

2G4 Øvrige produkt anvendelser

0,1

0,1

0,1

0,1

0,1

0,0

0,1

0,1

PCDD/F

g

2A2 Produktion af brændt kalk 2A6 Øvrige mineralske produkter 2C1 Jern og stål produktion 2C3 Aluminium produktion 2C5 Bly produktion 2G4 Øvrige produkt anvendelser

0,002 0,1 12,0 1,1 0,01 0,1

0,002 0,1 7,5 1,1 0,01 0,1

0,002 0,1 0,5 1,3 0,01 0,1

0,001 0,1 0,2 1,0 0,01 0,2

0,001 0,1 NE 0,2 0,01 0,1

0,001 0,1 NE 0,2 0,01 0,1

0,001 0,1 NE 0,2 0,01 0,1

0,001 0,1 NE 0,2 0,01 0,1

13,3

8,8

2,0

1,4

0,3

0,4

0,4

0,5

HCB

g

2A2 Produktion af brændt kalk 2C1 Jern og stål produktion 2C3 Aluminium produktion 2C5 Bly produktion 2G4 Øvrige produkt anvendelser

1,0 1968,2 629,9 0,2 0,7

0,8 2297,3 649,1 0,3 0,8

0,7 2023,2 735,3 0,2 1,3

0,6 804,0 576,3 0,3 1,4

0,4 2,9 104,0 0,3 0,7

0,5 3,3 125,2 0,4 0,6

0,6 3,1 129,8 0,2 1,3

0,5 3,1 136,9 0,2 1,3

Total

2.600,0

2.948,3

2.760,8

1.382,6

108,3

130,0

134,9

142,1

PCBer

g

2A2 Produktion af brændt kalk 2C1 Jern og stål produktion 2C3 Aluminium produktion 2C5 Bly produktion 2G4 Øvrige produkt anvendelser

19,2 1585,9 107,1 5,7 1,0

15,1 1837,1 110,3 7,3 1,1

13,8 1628,3 125,0 5,7 1,8

10,7 675,0 98,0 6,8 2,0

7,6 36,4 17,7 6,4 1,0

8,9 41,8 21,3 8,6 0,9

10,4 38,2 22,1 4,8 1,9

10,0 38,7 23,3 5,7 1,9

Total

1.718,9

1.970,8

1.774,6

792,4

69,1

81,5

77,3

79,5

Total

Lukningen af elektrostålværket i 2002 med en kort genåbning i 2005 samt lukningen af sekundær aluminiumsproduktion i 2008 har betydet et fald i emissionerne af flere tungmetaller og persistente organiske forbindelser (f.eks. Pb, Zn, PCDD/F, HCB and PCBer). Lovgivning fra 2000 og 2007 der først begrænsede og sidenhen forbød anvendelsen af bly i fyrværkeri har ligeledes reduceret bly emissionerne fra øvrige produkt anvendelser.

20

1

Introduction

Danish emission inventories are prepared on an annual basis and are reported to the United Nations Framework Convention on Climate Change (UNFCCC or Climate Convention) and to the Kyoto Protocol as well as to the United Nations Economic Commission for Europe (UNECE) Convention on Long-Range Transboundary Air Pollution (LRTAP Convention). The annual Danish emission inventories are prepared by the DCE – Danish Centre for Environment and Energy, Aarhus University. The inventories include the following pollutants relevant to industrial processes: carbon dioxide (CO2), nitrous oxide (N2O), sulphur dioxide (SO2), nitrogen oxides (NOx), non-volatile organic compounds (NMVOC), carbon monoxide (CO), particulate matter (PM), ammonia (NH3), heavy metals (HMs), polyclorinated dibenzodioxins and –furans (PCDD/F), polycyclic aromatic hydrocarbons (PAHs), hexachlorobenzene (HCB) and polychlorinated biphenyls (PCBs). The pollutants listed above correspond to the requirements of the UNFCCC, UNECE and EU to whom the emission inventories are reported. Other pollutants could be relevant for the source categories included in this report, but these will fall outside the scope of the emission inventories and therefore not be included. Industrial processes is one of the six main sectors included in emission inventories based on international agreements. The other five sectors are: energy, solvent and product use, agriculture, land-use, land-use change and forestry (LULUCF) and waste. The aim of this report is to: • Document the methodologies used for estimating emissions from industrial processes • Identify possible improvements of the current inventory related to completeness, consistency and accuracy including identifying industrial and product use sources not included in the present emission inventory • Serve as the basis for QA of the sector through independent review The present emission inventory includes a number of industrial sources; however, the systematic effort to identify industrial sources of emissions is ongoing. The coverage of sources presented in the EMEP1/EEA2 air pollutant emission inventory guidebook (hereafter the EMEP/EEA guidebook) as well as the IPCC (Intergovernmental Panel on Climate Change) guidelines has been analysed with the purpose of identifying new sources. The industrial sources are included either as area sources or as point sources. Point sources are defined as plants that are treated individually in the inventory, e.g. for cement production and sugar production. Area sources are for categories where there are too many plants or not enough information, e.g. bakeries.

1 2

The European Monitoring and Evaluation Programme European Environment Agency

21

The base year for emission inventories and reduction targets depends on the actual substance and protocol covering the substance; see Table 1.0.1. Some of the sources are not included in the inventory with complete time series due to missing data. These incomplete time series has as far as possible been completed through collection of the missing data or by introducing relevant emission estimates for the years in question. Improvements to the remaining incomplete time series are planned for the next update of the sector report. Table 1.0.1

Base year for different pollutants.

Substance Sulphur dioxide

SO2

Year 1980

Ammonia Nitrogen oxides Non-Methane VOC

NH3 NOx NMVOC

Carbon dioxide Methane Nitrous oxide

CO2 CH4 N2O

1990

Heavy metals

Arsenic – As Cadmium – Cd Chromium – Cr Copper – Cu Mercury – Hg Nickel – Ni Lead – Pb Selenium – Se Zinc – Zn

1990

Persistent organic pollutants (POPs)

Polychlorinated dibenzo dioxins and furans (PCDD/F) Hexachlorobenzene (HCB) Polychlorinated biphenyls (PCBs) Benzo(a)pyrene 1990 Benzo(b)fluoranthene Benzon(k)fluoranthene Indeno(1,2,3-cd)pyrene

F-gasses

HFCs PFCs SF6 NF3

1995

Particulate matter

Total Suspended Particulates (TSP) PM10 PM2.5 Black Carbon (BC)

2000

1985

The outline of the report follow the subdivision in sectors as applied in the IPPC guidelines for industrial processes supplemented with industrial sectors of specific relevance for air pollutants. An exception to this is the sector of Non-Energy Products from Fuels and Solvent Use, this sector is treated in an individual sector report. The main sectors included in this report are: • • • • • • •

Mineral industry Chemical industry Metal industry Electronics industry Product uses as substitutes for ozone depleting substances (ODS) Other product manufacture and use Other

The consumption of halocarbons and SF6 (F-gasses) is documented in a separate report (Poulsen, 2015) and are therefore only presented and briefly discussed in this report. 22

2

Methodology and data sources

The methodologies applied for the inventory of process related emissions are: • EMEP/EEA guidebook (EMEP/EEA, 2013) • IPCC guidelines (IPCC, 2000 & 2006) The main data sources applied in the inventory are: • National statistics • Company environmental reports/Reports to Electronic Pollutant Release and Transfer Registry (E-PRTR) • Company reports to the European Union Emission Trading Scheme (EUETS) • EMEP/EEA guidebook • IPCC guidelines • The Co-ordinated European Programme on Particulate Matter Emission Inventories, Projections and Guidance (CEPMEIP) When considered relevant, emission factors based on information on industrial sector level will be developed. Comments to the different data sources are presented below.

2.1

Company environmental reports

By law, some companies are obligated to report environmental information to the Danish Environmental Protection Agency (DEPA) (DEPA, 2010). The Statutory order specifies the branches of industry that are obligated to report environmental information as well as the contents of the reporting. The reports are made public annually at a website hosted by the DEPA3. When plants measure and report emissions of pollutants this information is generally used in the inventory after an assessment of the quality by comparing the emission level to that of previous years as well as comparing an implied emission factor with that of similar plants. Any value that is outside an acceptable range is investigated further and if needed the plant is contacted with a view of verifying the value. If such verification cannot be provided, then the value is not used in the emission inventory. In general, most information is available regarding the emission of NOx, SO2 and TSP. For other pollutants, the information is scarcer.

2.2

EMEP/EEA guidebook

The EMEP/EEA guidebook provides methodologies for estimation of emissions of the following groups of substances: • Main pollutants: CO, NH3, NMVOC, NOx, SO2 • Particulate matter: TSP, PM10, PM2.5, BC • Heavy metals: As, Cd, Cr, Cu, Hg, Ni, Pb, Se, Zn

3

http://www3.mst.dk/Miljoeoplysninger/

23

• Persistent organic pollutants: PCDD/F, HCB, PCBs, Benzo(a)pyrene, Benzo(b)fluoranthene, Benzon(k)fluoranthene, Indeno(1,2,3-cd)pyrene The following editions of the guidebook have been used for the present inventory: • EMEP/EEA air pollutant emission inventory guidebook – 2009 (EMEP/EEA, 2009) • EMEP/EEA air pollutant emission inventory guidebook 2013 (EMEP/EEA, 2013)

2.3

IPCC guidelines

The IPCC guidelines provide methodologies for estimating emissions of greenhouse gases, i.e.: • • • •

CO2 CH4 N2O F-gases (HFCs, PFCs, SF6 and NF3)

The following editions of the IPCC guidelines have been used for the present inventory: • Good Practice Guidance and Uncertainty Management in National Greenhouse Gas Inventories (IPCC, 2000), hereafter the IPCC GPG • 2006 IPCC guidelines for national greenhouse gas inventories (IPCC, 2006), hereafter the 2006 IPCC guidelines

2.4

EU-ETS (European Union - Emission Trading Scheme)

A number of Danish companies are covered by the EU-ETS and are as a consequence hereof obligated to report their emission of CO2 yearly. The emissions of CO2 reported to EU-ETS is a subset of the national emission of CO2 and therefore this reporting can be used to improve the national inventory and to ensure consistency between EU-ETS and the national inventory. Guidelines for calculating and reporting company specific CO2 emissions under the EU-ETS have been decided by the EU (EU, 2007). The guidelines present standard methods for plants with small emissions and requirements for developing individual plans for plants with large emissions. The standard methods include default emission factors similar to the default emission factors presented by the IPCC (e.g. for limestone), whereas, the major emitters have to use individual methods to determine the actual composition of raw materials (e.g. purity of limestone or Ca per Mg ratio in dolomite) or the actual CO2 emission from the specific process.

2.4.1 Description of EU-ETS in the Danish context About 360 Danish stationary plants are included in the EU-ETS. These plants are within the transformation sector, offshore installations or manufacturing industries. Few of the processes that are included under the EU-ETS are occurring in Denmark and only CO2 is reported from Danish plants since the potential sources of PFCs (primary aluminium production) and N2O (production of nitric acid, adipic acid, glyoxal and glyoxilic acid) are not occurring in Denmark. A list of the processes covered by the EU-ETS with an indication of the processes that occur in Denmark is included in Chapter 2.4.2. 24

2.4.2 Processes covered The EU-ETS covers a wide range of processes. The full list of activities that could be relevant in terms of industrial processes (IP) is included in Table 2.4.1 below. Indicated in the table are the activities that are relevant in Denmark. Table 2.4.1 List of activities included in the European Union Emission Trading Scheme (Directive 2009/29/EC) Activities

Greenhouse Relevant in gases Denmark

Combustion of fuels in installations with a total rated thermal input exceeding 20 MW (except in installations for the incineration of hazardous or municipal waste)

CO2

X

Refining of mineral oil

CO2

X

Production of coke

CO2

Metal ore (including sulphide ore) roasting or sintering, including pelletisation

CO2

Production of pig iron or steel (primary or secondary fusion) including continuous casting, with a capacity exceeding 2.5 Mg per hour

CO2

Production or processing of ferrous metals (including ferro-alloys) where combustion units with a total rated thermal input exceeding 20 MW are operated. Processing includes, inter alia, rolling mills, re-heaters, annealing furnaces, smitheries, foundries, coating and pickling

CO2

Production of primary aluminium

CO2, PFCs

Production of secondary aluminium where combustion units with a total rated thermal input exceeding 20 MW are operated

CO2

Production or processing of non-ferrous metals, including production of alloys, refining, foundry casting, etc., where combustion units with a total rated thermal input (including fuels used as reducing agents) exceeding 20 MW are operated

CO2

Production of cement clinker in rotary kilns with a production capacity exceeding 500 Mg per day or in other furnaces with a production capacity exceeding 50 Mg per day

CO2

X

Production of lime or calcination of dolomite or magnesite in rotary kilns or in other furnaces with a production capacity exceeding 50 Mg per day

CO2

X

Manufacture of glass including glass fibre with a melting capacity exceeding 20 Mg per day

CO2

X

Manufacture of ceramic products by firing, in particular roofing tiles, bricks, refractory bricks, tiles, stoneware or porcelain, with a production capacity exceeding 75 Mg per day

CO2

X

Manufacture of mineral wool insulation material using glass, rock or slag with a melting capacity exceeding 20 Mg per day

CO2

X

Drying or calcination of gypsum or production of plaster boards and other gypsum products, where combustion units with a total rated thermal input exceeding 20 MW are operated

CO2

Production of pulp from timber or other fibrous materials

CO2

Production of paper or cardboard with a production capacity exceeding 20 Mg per day

CO2

Production of carbon black involving the carbonisation of organic substances such as oils, tars, cracker and distillation residues, where combustion units with a total rated thermal input exceeding 20 MW are operated

CO2

Production of nitric acid

CO2, N2O

Production of adipic acid

CO2, N2O

Production of glyoxal and glyoxylic acid

CO2, N2O

Production of ammonia

CO2

Production of bulk organic chemicals by cracking, reforming, partial or full oxidation or by similar processes, with a production capacity exceeding 100 Mg per day

CO2

Production of hydrogen (H2) and synthesis gas by reforming or partial oxidation with a production capacity exceeding 25 Mg per day

CO2

Production of soda ash (Na2CO3) and sodium bicarbonate (NaHCO3)

CO2

Capture of greenhouse gases from installations covered by this Directive for the purpose of transport and geological storage in a storage site permitted under Directive 2009/31/EC

CO2

Transport of greenhouse gases by pipelines for geological storage in a storage site permitted under Directive 2009/31/EC

CO2

Geological storage of greenhouse gases in a storage site permitted under Directive 2009/31/EC

CO2

X

25

2.4.3 Survey of companies included The number of plants included in the EU-ETS in Denmark varies across the years as some new plants have been founded while others have been closed and/or reopened. The largest structural change is the inclusion of waste incineration in the EU-ETS from 2013. This caused an increase in the number of plants covered by the EU-ETS. The reports for the waste incineration plants will be surveyed with a view to improving the inventory for CO2 emissions from the use of limestone for flue gas desulphurisation in waste incineration plants. All other emissions related to waste incineration are included as combustion emissions and are not addressed in this report. The plants included in Table 2.4.2 have reported process emissions under the EU-ETS and have been considered in the inventory. In the column ‘plant type’ the activity relevant for process emissions has been listed. Some plants are included due to exceeding the threshold for combustion installations, but nevertheless they have process emissions related to e.g. mineral wool production or flue gas cleaning. For combustion installations the process emission refers to the CO2 emission associated with limestone used for flue gas desulphurisation/purification of the sugar.

26

Table 2.4.2 List of plants included in the European Union Emission Trading Scheme with process emissions in 2013 Plant

Plant type

Shell Raffinaderiet Fredericia

Refining of mineral oil

Aalborg Portland A/S

Production of cement clinker

Grenå Kraftvarmeværk

Combustion installation

Avedøreværket

Combustion installation

Asnæsværket

Combustion installation

Stigsnæsværket

Combustion installation

Vattenfall A/S Amagerværket

Combustion installation

Verdo Production, Energi Randers

Combustion installation

Enstedværket

Combustion installation

Vattenfall A/S Nordjyllandsværket

Combustion installation

Nordic Sugar, Nakskov Sukkerfabrik

Combustion installation

Dalum Papir A/S

Production of paper

Esbjergværket

Combustion installation

Carl Matzens Teglværk A/S

Manufacture of ceramic products

Damolin Fur A/S

Manufacture of ceramic products

Damolin Mors A/S

Manufacture of ceramic products

Saint-Gobain Weber, Hinge

Manufacture of ceramic products

Saint-Gobain Weber, Ølst

Manufacture of ceramic products

Faxe Kalk, Ovnanlægget Stubberup

Production of lime

Gråsten Teglværk

Manufacture of ceramic products

Helligsø Teglværk A/S

Manufacture of ceramic products

Højslev Tegl A/S

Manufacture of ceramic products

Monier A/S

Manufacture of ceramic products

Lundgård Teglværk A/S

Manufacture of ceramic products

Pedershvile Teglværk

Manufacture of ceramic products

Petersen Tegl Egernsund A/S

Manufacture of ceramic products

Wienerberger A/S - Petersminde Teglværk

Manufacture of ceramic products

Pipers Teglværker A/S Gandrup Teglværk

Manufacture of ceramic products

Pipers Teglværker A/S Hammershøj Teglværk Manufacture of ceramic products Ardagh Glass Holmegaard A/S

Manufacture of glass including glass fibre

Rockwool A/S Doense

Manufacture of mineral wool

Rockwool A/S, Vamdrup

Manufacture of mineral wool

Saint Gobain Isover A/S

Manufacture of glass including glass fibre

Statoil Raffinaderiet

Refining of mineral oil

Tychsen's Teglværk A/S

Manufacture of ceramic products

Vedstaarup Teglværk A/S

Manufacture of ceramic products

Vesterled Teglværk A/S

Manufacture of ceramic products

Villemoes Teglværk

Manufacture of ceramic products

Vindø Teglværk

Manufacture of ceramic products

2.4.4 Procedure for inclusion of data The EU-ETS started in 2005 and have had three phases: 2005-2007, 2008-2012 and 2013-2020. The quality of the reported data increased significantly during the first few years and now the data quality in general is excellent. 27

The information included in the plant reports under the EU-ETS has been used in the inventory for all years where the data are available. In preparation for the EU-ETS there was a data collection to assess the allocation of emission allowances to the different plants. Therefore, there are data available for some earlier years. These data have also been used in the inventory. However, since the base year for CO2 is 1990 there is a challenge in ensuring time series consistency. For some sectors the time series are very consistent as it has been possible to match the different methodologies. For some sectors, e.g. glass production, the time series consistency remains a challenge and is the subject of planned future work.

2.5

CEPMEIP database

The Co-ordinated European Programme on Particulate Matter Emission Inventories, Projections and Guidance (CEPMEIP) was part of the activities aimed at supporting national experts in reporting particulate matter emission inventories. Within this work programme, Netherlands Organisation for Applied Scientific Research (TNO) has compiled an overview of particulate emission estimation methods and applied these in a European emission inventory for particulates for the base year 1995. TNO compiled information on emission of particulate matter expressed as TSP, PM10 and PM2.5 from different industrial sectors. The result is organised in a database available online4. Emission factors are developed for four pollution levels: • • • •

Low - good/well maintained abatement/BAT Medium Medium high High - low/poor maintained equipment/abatement and old plants

It is not always obvious, where Danish companies should be placed on the scale. In the cases where TSP is known for the Danish companies, they are placed on the scale, and the distribution between TSP, PM10 and PM2.5 can be found.

4

28

http://www.air.sk/tno/cepmeip/

3

Mineral industry

The sector Mineral industry (CRF/NRF 2A) covers the following industries relevant for the Danish air emission inventory: • • • • • • •

Cement production; see section 3.2 Lime production; see section 3.3 Glass production; see section 3.4 Ceramics; see section 3.5 Other use of soda ash; see section 3.6 Flue gas desulphurisation; see section 3.7 Mineral wool production; see section 3.8

3.1

Greenhouse gas emissions

The emission time series for the greenhouse gas emissions from the individual source categories in the mineral industries are presented in Figure 3.1.1. The figure shows that cement production is by far the largest contributor to CO2 emissions within the mineral industries and that emissions were strongly influenced by the financial crisis in 2007-2009.

Figure 3.1.1 Emission of CO2 from the individual source categories compiling 2A Mineral Industry, Gg.

Greenhouse gas emissions from Mineral Industry consist mainly of CO2 emissions from the production of cement; min. 82 % (1990) to max. 88 % (2004). Emissions from Mineral Industry increased with 48 % from 1990 to the time series peak in 1997 (1598 Gg). The overall development in the CO2 emission for 1990 to 2013 shows a decrease from 1078 Gg to 995 Gg CO2, i.e. by 7.7 %. The increase from 1990 to 1997 can be explained by the increase in the annual cement production. The emission factor has only changed slightly as the distribution between types of cement especially grey/white cement has been almost constant from 1990-1997. The decrease during the latest years may be explained by the decrease in the construction activity.

29

3.2

Cement production

The production of cement in Denmark is concentrated at one company: Aalborg Portland A/S situated in Aalborg. The following SNAP-codes are covered: • 03 03 11 Cement • 04 06 12 Cement (decarbonizing) Emissions associated with the fuel use are estimated and reported in the energy sector and are therefore not included in this sector report. CO2 is the only pollutant that is relevant for the cement production process.

3.2.1 Process description The primary raw materials (i.e. virgin raw materials) are sand, chalk and water. A number of other raw materials are also used in minor amounts. The main products are grey cement (Rapid® cement, Basis® cement and Low Alkali Sulphate Resistant cement) and white cement (Aalborg White®) as well as cement clinker for sale. The emissions to air from cement production can be explained by the use of different fuels (combustion process), release of CO2 from calcination, and release of pollutants from fuels and raw materials. Chalk is extracted from a chalk pit located at the factory ground. The chalk is transported by conveyor belt to a wash mill, where impurities are removed. The chalk is then mixed with water to form chalk slurry. Sand is extracted from the seabed at different locations by dredgers. The sand is transported to the factory and is ground in a sand mill. The main secondary raw materials (i.e. recycled materials) are fly ash, paper pulp, ferro oxide and gypsum from flue gas cleaning. A number of other secondary raw materials are used in minor amounts. The main processes at Aalborg Portland are production of raw meal, clinker production, grinding of clinker and storage of cement. Aalborg Portland uses a semi-dry process. The first step is production of raw meal. The chalk slurry and the grounded sand are mixed as slurry that is injected into a drier crusher. The raw materials are converted into raw meal that releases CO2 in the calciner. In a rotary kiln the material is burned to clinker that afterwards is grounded to cement in the cement mill. During the process, cement kiln dust is recirculated. Production of cement is a very energy consuming process and a number of different fuels are used e.g. coal, petroleum coke, fuel oil, and alternative fuels (“meat and bone meal”, regenerated oil with low sulphur content, ash residue, asphalt, residue from production of vitamins, sewage sludge, and “CemMiljø fuel”5). The company does focus on alternative fuels in order to reduce cost as well as environmental effects (i.e. CO2 originating from fossil sources). The emissions that are related to combustion are not included in this report.

5

30

Produced from non-specified combustible waste (CemMiljø, 2003).

The fuels are injected in the bottom of the rotary kiln whereas the raw materials are injected in the top of the kiln. The product (i.e. cement clinker) are in contact with the fuel and potential pollutants in the fuels may be incorporated in the clinker meaning that the alkaline environment in the rotary kiln acts as a flue gas cleaning system (especially for acid gasses and certain heavy metals).

3.2.2 Methodology Process emissions are released from the calcination of raw materials (chalk and sand). The overall process for calcination is: CaCO3 → CaO + CO2 1990-1997 The emission of CO2 depends on the ratio: white/grey cement and the ratio between three types of clinker used for grey cement: GKL-clinker (rapid cement)/FKH-clinker (basis cement)/SKL-RKL-clinker (low alkali cement). The emission factor (EF) has been estimated from the loss on ignition determined for the different kinds of clinkers produced, combined with the volumes of grey and white cements produced. The ratio white/grey cement and the ratio GKL-clinker/FKH-clinker/SKLRKL-clinker is known from 1990-1997. White cement peaked in 1990 and decreased thereafter. The production of SKL/RKL-clinker peaks in 1991 and decreases hereafter. FKH-clinker is introduced in 1992 and increases to a share of 35 % in 1997. The CO2 emission is calculated according to the following equation:

M CO2 = M grey *

M GLK * EFGLK + M FKH * EFFKH + M SKL / RKL * EFSKL / RKL + M white * EFwhite M GLK + M FKH + M SKL / RKL

Mgrey

Grey cement

Mg

Mwhite

White cement

Mg

MGLK

GKL clinker (rapid cement)

Mg

MFKH

FHK clinker (basis cement)

Mg

MSKL/RKL

SKL/RKL clinker (low alkali cement) Mg

EFwhite

CO2 emission factor

Mg/Mg white cement

EFGLK

CO2 emission factor

Mg/Mg GLK clinker

EFFKH

CO2 emission factor

Mg/Mg FKH clinker

EFSKL/RKL

CO2 emission factor

Mg/Mg SKL/RKL clinker

The company has at the same time stated that data until 1997 cannot be improved as there is no further information available. 1998-2004 From 1998-2004 carbonate content of the raw materials has been determined by loss on ignition methodology. Determination of loss of ignition takes into account all the potential raw materials leading to release of CO2 and omits the Ca-sources leading to generation of CaO in cement clinker without CO2 release. The applied methodology is in accordance with EU guidelines on calculation of CO2 emissions (Personal communication with Henrik Møller Thomsen from Aalborg Portland, 17 September 2008). 31

2005-2013 From the year 2005 the CO2 emission determined by Aalborg Portland independently verified and reported under the EU-ETS is used in the inventory (Aalborg Portland, 2014a). The reporting to EU-ETS also provides detailed information of alternative fuels used in the production of clinker; see Table 3.2.1. Table 3.2.1 Alternative fuels used in production of cement clinker (Aalborg Portland 2014a). Fuel type

Biomass fraction, %

Cemmiljø fuel

30-56

Paper residues

79

Dry wastewater sludge

100

Meat and bone meal

100

Tyre residues

15

Plastic pellet

64

Activity data Production statistics for cement (given in Total Cement Equivalents, TCE) and clinker production are presented in Table 3.2.2. Table 3.2.2 Production statistics for cement production (Aalborg Portland 2014a, b and Personal communication with Henrik Møller Thomsen, Aalborg Portland, 17 September 2008). Year

1990

1991

1992

1993

1994

1995

Mg TCE

1,619,976

1,998,674

2,214,104

2,244,329

2,242,409

2,273,775

2,418,988 2,718,923

Mg clinker1

1,406,212

1,811,958

2,089,393

2,117,895

2,192,402

2,353,123

2,481,792 2,486,475

1998

1999

2000

2001

2002

2003

Mg TCE

2,754,405

2,559,575

2,612,721

2,660,972

2,698,459

2,546,295

2,861,471 2,706,371

Mg clinker

2,462,249

2,387,282

2,452,394

2,486,146

2,508,415

2,363,610

2,611,617 2,520,788

2006

2007

2008

2009

2010

2011

2,842,282

2,946,294

2,551,346

1,663,126

1,454,043

1,766,561

Mg TCE

1996

2004

2012

1997

2005

2013

1,818,293 1,825,146

Mg clinker 2,632,112 2,706,048 2,269,687 1,493,230 1,313,654 1,582,023 1,628,506 1,612,834 1 1990-1997: Amount of clinker produced has not been measured as for 1998-2008. Therefore, the amount of GLK-, FKH-, SKL-/RKL-clinker and white cement is used as an estimate of total clinker production (Personal communication with Henrik Møller Thomsen, Aalborg Portland 17 September 2008).

Emission factors The calculated implied emission factors (IEF) for the total cement equivalent (TCE) and clinker production are presented in Table 3.2.3. Table 3.2.3 Implied emission factors for CO2 for cement production. 1990

1991

1992

1993

1994

1995

1996

1997

IEF Mg CO2 per Mg TCE

0.545

0.544

0.539

0.537

0.532

0.529

0.530

0.530

IEF Mg CO2 per Mg clinker3,4

0.628

0.600

0.571

0.569

0.544

0.512

0.517

0.580

1998

1999

2000

2001

2002

2003

2004

2005

IEF Mg CO2 per Mg TCE1,2,3

0.505

0.529

0.530

0.517

0.529

0.532

0.510

0.504

IEF Mg CO2 per Mg clinker3,4

0.564

0.568

0.565

0.558

0.565

0.563

0.559

0.541

2006

2007

2008

2009

2010

2011

2012

2013

IEF Mg CO2 per Mg TCE1,2,3

0.491

0.478

0.453

0.460

0.462

0.488

0.479

0.475

Year 1,2,3

IEF Mg CO2 per Mg clinker3,4 0.530 0.520 0.509 0.512 0.512 0.545 0.535 0 538 1) 1990-1997: IEF based on the personal communication with Henrik Møller Thomsen, Aalborg Portland, 2005. 2) 1998-2004: IEF based on the personal communication with Henrik Møller Thomsen, Aalborg Portland, 17 September 2008. 3) 2005-2013: IEF based on emissions reported to EU-ETS (Aalborg Portland, 2014a and previous versions). 4) 1998-2013: IEF based on clinker production statistics provided by Aalborg Portland (2014b).

32

The IEF for CO2 from the calcination process is expressed per Mg of cement or clinker and depends on the actual input of chalk/limestone in the process. The IEF will therefore vary as the allocation of different cement/clinker types produced varies. When the implied CO2 emission factor in 1990 is markedly higher than for the remaining time series it is because the production of white cement was higher in 1990 than for the following years, leading the ratio white/grey cement to be higher for 1990. The share of white cement decreases significantly through the early part of the 1990s causing the IEF to decrease as well. In 1990, 25 % of cement produced was white cement; in 1991-1997 that same share fluctuates around 21 % (20 % in 1992 to 22 % in 1995). As presented in Table 3.2.4, emission factors are higher for white than for grey cement resulting in a higher IEF for 1990. The production of different cement types are shown in the Verification section below (Chapter 3.2.5), see Table 3.2.8. Table 3.2.4 Emission factors for white cement and (grey) clinkers (Personal communication with Henrik Møller Thomsen, Aalborg Portland, 17 September 2008). Product Value Unit White cement

0.669

Mg CO2/Mg white cement

GLK clinker FKH clinker SKL/RKL clinker

0.477 0.459 0.610

Mg CO2/Mg GLK clinker Mg CO2/Mg FKH clinker Mg CO2/Mg SKL/RKL clinker

For the entire time series, the emission factor (carbon content) has been estimated from the loss on ignition determined for the different kinds of clinkers produced (1990-1997) or different raw materials used (1998-2013). Determination of loss on ignition estimates the CO2 emissions based on full oxidation of all carbonate materials and omits the Ca-sources leading to generation of CaO in cement clinker without CO2 release. As a result, there is no need to consider uncalcined cement kiln dust (CKD) not recycled to the kiln. The applied methodology is in accordance with EU guidelines on calculation of CO2 emissions (Personal communication with Henrik Møller Thomsen from Aalborg Portland, 17 September 2008). The company reporting to the EU-ETS applies the following emission factors for the most important raw materials used in 2013, similar data are available back to 2006 (Aalborg Portland 2014a) and to a less detailed degree back to 1998 (Aalborg Portland, 2014b). Table 3.2.5 Emission factors for raw materials. Raw material

Mg CO2 per Mg raw material

Limestone

0.44

Magnesium carbonate

0.522

Sand Fly ash Cement Kiln Dust (CKD) Other

0.0053-0.0301 0.130 0.361-0.525 0.0028-0.0268

The emission factors for limestone and magnesium carbonate are in accordance with the stoichiometric factors and the emission factors for the remaining raw materials and CKD are determined by individual yearly analysis.

33

The emissions of heavy metals were measured in 1997 (Illerup et al., 1999) – see Table 3.2.6. The emission of heavy metals originates from the fuels and the raw materials. In the Danish inventory these emissions together with emissions of CO, NOx, SO2, and POPs have been allocated to the combustion part of cement production and are reported in the energy sector. Table 3.2.6 Emission factors for heavy metals (Illerup et al., 1999). Pollutant

Unit

Emission factor

As

mg/Mg

20

Cd

mg/Mg

7

Cr

mg/Mg

10

Cu

mg/Mg

10

Hg

mg/Mg

0.06

Ni

mg/Mg

20

Pb

mg/Mg

10

Se

mg/Mg

7

Zn

mg/Mg

50

Emissions of NOx, SO2, and CO are continuously measured and reported annually in the environmental report of Aalborg Portland since 2006. Prior to this, emissions are calculated using emission factors derived from information in the environmental reports by Aalborg Portland. For 1990-1995 the same emission factors have been assumed as in 1996. Emissions of HCB, PCBs, benzo(a)pyrene, benzo(b)flouranthene, benzo(k)fluoranthene and indeno(1,2,3-cd)pyrene are estimated based on the fuel consumption and not the production of cement. Emissions of particulate matter and PCDD/F are estimated using emission factors expressed per produced amount of clinker.

3.2.3 Emission trends The emission trend for the CO2 emission from cement production is presented in Table 3.2.7 and Figure 3.2.1. Table 3.2.7 CO2 emission for cement production, Gg. 1990

1991

1992

1993

1994

1995

1996

1997

CO2

882.4

1,087.8

1,193.4

1,206.1

1,192.2

1,203.8

1,281.9

1,342.9

1998

1999

2000

2001

2002

2003

2004

2005

CO2

1,389.8

1,354.9

1,385.3

1,387.9

1,416.3

1,329.9

1,458.9

1,363.4

2006

2007

2008

2009

2010

2011

2012

2013

1,395.5

1,407.1

1,154.7

764.4

672.2

861.8

871.1

867.1

CO2

34

Figure 3.2.1 Emission of CO2 from cement production.

The increase in CO2 emission from the production of cement from 1990 to 1997 can be explained by the increase in the annual cement production. The most significant change to occur in the time series is the significant decline in emission from 2007-2010, the decrease is due to reduced production resulting from the economic recession caused by the global financial crisis. The emissions increased in 2011-2013, but the emissions are still far below the pre-recession levels due to lower production. The overall development in the CO2 emission from 1990 to 2013 is a decrease from 882 to 867 Gg CO2, i.e. by 1.7 %. The maximum emission occurred in 2004 and constituted 1,459 Gg CO2; see Figure 3.2.1.

3.2.4 EU-ETS data for cement production The applied methodology for Aalborg Portland is specified in the individual monitoring plan that is approved by Danish authorities (DEA) prior to the reporting of the emissions. Cement production applies the Tier 3 methodology for calculating the CO2 emission. The implied CO2 emission factor for Aalborg Portland is plant specific and based on the reporting to the EU Emission Trading Scheme (EU-ETS). The EU-ETS data have been applied for the years 2006 – 2013. The CO2 emission for cement production is based on measurements of the consumption of calcium carbonate to the calcination process. These measurements fulfil a Tier 3 methodology (± 1.6 %) as defined in the EU decision (EU Commission, 2007). The emission factor is based on continuous measurements with flow meters, density meters, X-ray and CaO analysis. (Aalborg Portland, 2013)

3.2.5 Verification Information on production, import and export of cement and clinker for the years 1990–1997 were investigated in order to ensure that the Tier 1 method is being implemented in accordance with the IPCC Guidelines (IPCC, 2006). The supply of cement clinker, grey cement and white cement in Denmark is shown in Table 3.2.8; however, the mass balance is incomplete due to missing information. The missing information may be explained by confidentiality as the statistics can be kept confidential, if there are fewer than three producers. 35

Table 3.2.8 Production, import, export and supply of cement, Gg (Statistics Denmark, 2014). Cement clinker Produced Import Export Supply Portland cement, white Produced Import Export Supply Portland cement, grey Produced Import Export Supply Cement clinker Produced Import Export Supply Portland cement, white Produced Import Export Supply Portland cement, grey Produced Import Export Supply

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

NAV 0.4 17

NAV 0.3 45

NAV 0.0 24

NAV 0.4 40

NAV 0.2 189

NAV 0.01 281

NAV 0.2 245

139 0.03 139

119 0.2 117

112 0.03 112

-

-

-

-

-

-

-

-0.1

3

0.04

412 0

398 0

426 0.05

492 1.2

492 1.4

531 0.0

576 0.0

529 5.8

537 3.2

563 9.9

367 44

445 -48

481 -55

634 -141

477 17

473 58

496 80

455 80

638 -98

509 64

1,244

1,621

1,646

1,778

1,935

2,053

2,052

2,015

2,011

1,859

190 19 1,414

176 449 1,349

256 704 1,198

262 763 1,277

257 829 1,363

272 790 1,535

277 910 1,419

263 766 1,512

222 509 1,724

214 466 1,607

2000

2001

2002

2003

2004

2005

2006

2007

2008

2009

103

103

153

62

53

43

5

21

16

0.12

0.002 90 12

0 99 4

4 103 53

27 67 22

23 54 21

31 56 18

44 12 37

40 10 51

42 7 51

33 8 25

551 11 546 17

532 0.03 462 70

510 0.14 531 -21

582 1 507 76

679 5 315 369

715 15 508 222

797 38 745 90

722 19 639 102

607 33 490 150

462 30 422 70

1,985 238 634

2,044 254 769

2,035 275 731

1,998 191 652

2,213 184 761

2,166 215 732

2,140 235 545

2,149 229 484

1,932 263 443

1,116 177 125

1,589

1,529

1,578

1,538

1,636

1,650

1,830

1,895

1,751

1,168

2010

2011

2012

2013

4 22 12 14

0.03 27 3 24

24 27 25 26

0 26 0.05 26

482 23 501

514 30 497

496 30 499

531 24 506

3

47

27

50

1,085 160

1,338 214

1,321 183

1,322 183

Cement clinker Produced Import Export Supply Portland cement, white Produced Import Export Supply Portland cement, grey Produced Import

Export 201 251 271 249 Supply 1,044 1,301 1,233 1,256 NAV: Personal communication with the single Danish producer of cement makes it clear what it unfortunately is not – and will never be, possible to achieve these data for 1990-1997 (Personal communication with Torben AhlmannLaursen, Aalborg Portland, 19 November 2013).

Table 3.2.8 and Table 3.2.2 show the produced amount of cement (grey and white) according to Statistics Denmark and the amount produced according to Aalborg Portland respectively. The two datasets show good agreement in 36

spite of different methodologies. The fluctuations are believed mainly to be caused by changes in stocks, and the overall sum of produced cement only differs 0.6 % (8.2 Gg) through the time series (1990-2013). The most comprehensive activity data is assumed to be the information on yearly produced amount of cement clinker obtained from the Danish producer. A comparison between the two datasets is presented in Table 3.2.9. Table 3.2.9 Production data for Portland cement as given by Aalborg Portland and Statistics Denmark respectively. 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 Aalborg Portland Gg TCE 1,620 1,999 2,214 2,244 2,242 2,274 2,419 2,719 2,754 2,560 Statistics Denmark Gg 1,656 2,019 2,072 2,270 2,427 2,584 2,629 2,544 2,548 2,422 Difference Gg -36 -21 142 -26 -185 -310 -210 175 207 137 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 Aalborg Portland Statistics Denmark Difference

Gg TCE 2,613 2,661 2,698 2,546 2,861 2,706 2,842 2,946 2,551 1,663 Gg 2,536 2,575 2,545 2,580 2,893 2,881 2,937 2,871 2,539 1,579 Gg 77 85 154 -34 -31 -174 -95 75 13 85 2010 2011 2012 2013

Aalborg Portland Statistics Denmark Difference

Gg TCE 1,454 1,767 1,818 1,825 Gg 1,567 1,853 1,817 1,852 Gg -113 -86 1 -27

The activity data for clinker production provided by the company includes clinker used in cement production while clinker data from Statistics Denmark only includes the amount of clinker sold. The production data for clinker can therefore not be compared. Table 3.2.10 compares the default emission factor from IPCC (2006) with the measured/calculated implied emission factor for 1992-2013. The average IEF for these years is 0.54 Mg per Mg clinker. The comparison shows good agreement between the two methods. Table 3.2.10 Comparison of default (Tier 1) and calculated implied (Tier 3) CO2 emission factors for cement production. Methodology Value Unit Source Tier 1 0.52 Mg/Mg clinker IPCC (2006) Aalborg Portland (2014a, b) and Personal communication with Henrik Møller Thomsen Tier 31 0.51-0.58 Mg/Mg clinker from Aalborg Portland (17 September 2008) 1 1992-2013

1990 and 1991 are both outliers because the production of white cement (EF: 0.669 Mg/Mg) and SKL/RKL clinker (EF: 0.610 Mg/Mg) peeked in these years, resulting in overall IEFs of 0.63 and 0.60 Mg per Mg clinker respectively.

3.2.6 Time series consistency and completeness Since Denmark only has one cement factory, all data collected from the production are in fact plant specific data. For 1990-1997, activity data for grey cement production fulfil the Tier 2 methodology while activity data for white cement (20-25 %) only fulfil the Tier 1 methodology (IPCC, 2006). The company has informed that data until 1997 cannot be improved as there is no further information available. Since 1998, the determination of activity data for cement production has met the requirements of the Tier 3 methodology. 37

Emission factors have for the entire time series been determined by analysed loss on ignition which fulfil the requirements of the Tier 3 methodology. The methodology behind the chosen activity data for cement production is therefore not consistent, but CO2 emission factors are. The inventory on cement production is considered complete in accordance with IPCC (2006).

3.2.7 Input to emission database (CollectER) The input data/data sources are presented in Table 3.2.11. Table 3.2.11 Input data for calculating emissions from cement production. Year Activity data

1985-1996 1997

Parameter

Comment/Source

Grey/white

Aalborg Portland/Illerup et al.

cement

(1999)

Cement

Personal communication with

equivalents

Henrik Møller Thomsen, Aalborg Portland, 17 September 2008)

1998-2013

Cement

Aalborg Portland (2014b)

equivalents 1998-2013

Clinker produ- Aalborg Portland (2014a) and ced

Personal communication, Henrik Møller Thomsen Aalborg Portland (17 September 2008)

Emissions

1997

Heavy metals Illerup et al. (1999)

1985-1996, 1998-2012 Heavy metals Assumed to be the same per produced amount as in 1997 1985-1997

CO2

Personal communication with Henrik Møller Thomsen, Aalborg Portland, 17 September 2008)

1998-2004

CO2

Personal communication with Henrik Møller Thomsen from Aalborg Portland (17 September 2008)

2005-2013

CO2

Aalborg Portland (2014a)

3.2.8 Future improvements There are no planned improvements for the process emissions from cement production.

3.3

Lime production

The production of marketed limestone (CaCO3) and lime (also called burned lime or quicklime) (CaO) is located at a few localities: Faxe Kalk (Lhoist group) situated in Faxe, Dankalk A/S situated in Løgstør with limestone quarries/limeworks in Aggersund, Mjels, Poulstrup and Batum. In addition to the marketed lime production, lime production is also related to production of sugar. Sugar production is concentrated at one company: Nordic Sugar (previously Danisco Sugar A/S) located in Assens, Nakskov and Nykøbing Falster (Danisco Sugar Assens, 2007; Danisco Sugar Nakskov, 38

2008; Danisco Sugar Nykøbing, 2008; Nordic Sugar Nakskov, 2013; Nordic Sugar Nykøbing, 2013). This lime is produced and consumed by the sugar industry and is therefore also called un-marketed lime. The following SNAP-codes are covered: • 03 03 12 Lime (incl. iron and steel and paper pulp industry) • 04 06 14 Lime (decarbonizing) The following pollutants are included for the lime production process: • CO2 • Particulate matter: TSP, PM10, PM2.5, BC • Persistent organic pollutants: HCB, PCDD/F, PCB In addition to emissions from marketed lime, only CO2 from the decarbonizing of un-marketed lime is included in this section. Emissions of NMVOC from sugar refining are presented in Section 9.4 Sugar production and emissions associated with the fuel use are estimated and reported in the energy sector and therefore not included in this report.

3.3.1 Process description Calculation of CO2 emissions from oxidation of carbonates follows the general process:

M x (CO3 ) + heat → M x O + CO2 and for limestone:

CaCO3 + heat →CaO + CO2 Addition of water results in the following reaction:

CaO + H 2 O → Ca (OH ) 2 The emission of CO2 results from heating of the carbonates in the lime-kiln. The lime-kilns can be located either at the location for limestone extraction or at the location for use of burned lime.

3.3.2 Methodology The CO2 emission from the production of marketed burnt lime has been estimated from the annual production figures registered by Statistics Denmark (see Table 3.3.1) and emission factors. Plant specific activity data for marketed lime only exist for one company (Faxe Kalk) that constitutes about 66% (2006-2013 average) of the Danish activity; see Table 3.3.1. The plant specific data are available back to 1995. A number of smaller companies account for the remaining of the Danish production. Since 2006, process CO2 emissions from Faxe Kalk (i.e. the largest Danish producer) have been calculated by the company and reported to EU-ETS. These calculations are based on the assumption of pure CaO product and are therefore not corrected for impurities. For the sake of consistency, the same 39

method has been applied for the entire time series and for all producers. However, since 2008, Faxe Kalk has measured and included the content of MgO in the process emissions reported to EU-ETS; this causes a slight increase and small fluctuations in the implied emission factor for the recent years (Faxe Kalk, 2013). Faxe Kalk is the only marketed lime producer reported as a point source, but only for 2006-2013. Total sales statistics for produced sugar is available from Statistics Denmark (2014). Production statistics from the environmental reports are registered each 12 month period going from May 1 - April 30 until 2007/08 and from March 1 – February 28 from 2009/10 (Nordic Sugar Nakskov, 2009; Nordic Sugar Nykøbing, 2009). Therefore, the yearly production does not correspond with the yearly sale registered by Statistics Denmark (2014). The information from Statistics Denmark covers the whole time series and therefore the amount of sugar sold is used as activity data. The company information is only used for calculating the allocation of production/sale between the three point source locations. The consumption of lime is estimated from the production statistics and a number of assumptions: consumption of 0.02 Mg CaCO3 per Mg sugar and precipitation of 90 % CaO resulting in an emission factor at 0.0088 Mg CO2 per Mg sugar (2 weight% CaCO3 consumption per sugar beets, 10 weight% sugar in sugar beets). The assumptions are based on environmental reports covering the year 2002. Activity data Statistics from Statistics Denmark (2014) have been chosen as data source to ensure consistent data throughout the period from 1990. However, after EUETS data have become available from 2006; the company specific production data have been included and the data from Statistics Denmark adjust to only cover producers not covered by EU-ETS. Table 3.3.1 Production of marketed burnt lime, Mg (Statistics Denmark, 2014 and Faxe Kalk, 2014a, b). 1990

1991

1992

1993

1994

1995

1997

1998

1999

127,978 2000

2001

2002

2003

2004

2005

2006

2007

Faxe Kalk Other producers

62,489 29,513

70,537 25,949

69,827 52,814

63,258 24,291

64,085 13,759

57,302 13,937

62,817 15,835

57,004 18,500

57,812 38,349 17,169 7,853

Total production

92,002

96,486

122,641

87,549

77,844

71,239

78,652

75,504

74,981 46,202

2010

2011

2012

2013

Faxe Kalk

25,623

21,312

29,798

30,293

Other producers Total production

24,774 50,397

38,118 59,430

39,338 69,136

36,512 66,805

86,222

104,526

106,587

46,340 54,449 112,480 100,789

1996

Faxe Kalk Other producers Total production

95,028 102,587

71,480 76,348 17,442 18,829 88,922 95,177 2008

2009

The production of hydrated lime (slaked lime) from burnt lime does not emit any greenhouse gasses, see section 3.2.13.3.1. All burnt lime that is later slaked, is included in the statistics shown in the table above. Adding the production of slaked lime to the activity data, would therefore result in double counting. Dolomitic lime (CaCO3MgCO3) is not produced in Denmark. Sugar production statistics and the calculated lime consumption in the sugar industry are presented in Table 3.3.2.

40

Table 3.3.2 Production of sugar at different locations, Gg. 1991 1992 1993 1994 1995 1996 1997 1998 1999 1990 151.7 152.9 141.2 145.3 148.8 177.7 129.5 146.2 167.1 160.5 202.3 203.9 188.2 193.7 198.4 133.2 172.7 195.0 222.8 214.0 151.7 152.9 141.2 145.3 148.8 133.2 129.5 146.2 167.1 160.5 505.7 509.8 470.6 484.3 496.0 444.1 431.8 487.4 557.0 535.1 5.7 5.7 5.3 5.4 5.6 5.0 4.8 5.5 6.2 6.0 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 Assens 133.0 168.7 152.4 153.2 135.5 151.9 137.4 0 0 0 Nakskov 177.3 224.9 203.2 204.3 180.7 202.6 183.2 170.2 208.6 222.4 Nykøbing 133.0 168.7 152.4 153.2 135.5 151.9 137.4 159.6 191.6 206.1 Total (Statistics Denmark) 443.2 562.4 508.1 510.8 451.7 506.5 458.0 329.8 400.3 428.4 CaCO3-eq 5.0 6.3 5.7 5.7 5.1 5.7 5.1 3.7 4.5 4.8 2010 2011 2012 2013 Assens 0 0 0 0 Nakskov 137.9 114.7 137.9 140.0 Nykøbing 124.2 103.3 124.2 125.0 Total (Statistics Denmark) 262.1 218.1 262.0 265.0 CaCO3-eq 2.9 2.4 2.9 3.0 1990-2006: Activity data based on information from Statistics Denmark and distribution between the three plants: 0.3/0.4/0.3. 2007-2009: Production data based on environmental reports from Nakskov and Nykøbing. 2010-2013: Activity data based on information from Statistics Denmark and distribution between the two plants: 0.53/0.47 (distribution calculated from environmental reports from 2005-2009). Assens Nakskov Nykøbing Total (Statistics Denmark) CaCO3-eq

Emission factors The emission factor for calcination of both marketed and non-marketed calcium carbonate is based on stoichiometric relations; the emission factor applied is 0.785 kg CO2 per kg CaO. The content of MgO in burned lime from Danish producers has been assumed negligible. It is also assumed that the degree of calcination is 100 % and no lime kiln dust (LKD) eludes from the production. Further examples on emission factors are presented in Table 3.3.3. Table 3.3.3 tions.

Emission factors for production or use of carbonate based compounds based on stoichiometric rela-

Raw material

Product

Magnesium carbonate

MgCO3

Magnesium oxide MgO Lime/Quicklime

kg CO2/

kg CO2/

kg raw material

kg product

0.5219

1.0918

Calcium carbonate

Limestone

CaCO3

CaO

0.4397

0.7848

Calcium magnesium

Dolomite

CaCO3.MgCO3 Dolomitic lime

CaO.MgO

0.4773

0.9132

BaCO3

Barium oxide

BaO

0.2230

0.2870

Li2CO3

Lithium oxide

carbonate Barium carbonate Lithium carbonate Sodium carbonate

Soda ash

Na2CO3

Li2O

0.5957

1.4735

Na2O

0.4152

0.7101

The emission factors for TSP, PM10, and PM2.5 are dependent on process conditions including pollution abatement equipment. The emission factors provided by the EMEP/EEA (2009) and CEPMEIP are presented in Table 3.3.4. Table 3.3.4 Emission factors for TSP, PM10, and PM2.5, g per Mg marketed lime. Level

TSP

PM10

PM2.5

Reference

Low

300

150

30

CEPMEIP

Medium

500

200

40

CEPMEIP

High

1000

300

60

CEPMEIP

Tier 1

590

240

50

EMEP/EEA, 2009

Tier 2, uncontrolled

9000 3500

700

EMEP/EEA, 2009

Tier 2, controlled

400

30

EMEP/EEA, 2009

200

Comment Applied in Danish inventory

41

The emission factors for PM10 and PM2.5 are assumed to be a fixed fraction of the emission factor for TSP (i.e. 40% and 8% respectively – see Error! Reference source not found.). For the Danish inventory the “medium level” emissions published by CEPMEIP has been chosen as default as they are assumed to cover an average of small and large plants. The emission factors used to calculate the BC, HCB, PCDD/F and PCB emissions from lime production are shown in Table 3.3.5 along with their respective sources. Table 3.3.5 Emission factors for other pollutants for production of marketed lime Pollutant Unit Value Source BC g/Mg 0.18 EMEP/EEA Guidebook (2013) HCB mg/Mg 0.01 Nielsen et al. (2013a) PCDD/F µg/Mg 0.02 Henriksen et al. (2006) PCB mg/Mg 0.15 Nielsen et al. (2013a)

3.3.3 Emission trends The emission trend for the CO2 emission from lime production, including sugar production; is presented in Table 3.3.6 and Figure 3.3.1. The emission trend for particles and POPs is presented in Table 3.3.7. Table 3.3.6 Emission of CO2 from lime production, Gg. 1990

1991

1992

1993

1994

1995

1996

1997

Lime production Sugar production

100.44 4.66

67.67 4.70

82.03 4.33

83.65 4.46

88.27 4.57

79.10 4.09

74.58 3.98

80.51 4.49

Total

105.10

72.36

86.37

88.11

92.84

83.19

78.56

85.00

1998

1999

2000

2001

2002

2003

2004

2005

Lime production Sugar production Total

69.79 5.13 74.92

74.69 4.93 79.62

72.20 4.08 76.29

75.72 96.25 5.18 4.68 80.90 100.93

68.71 4.70 73.41

61.09 4.16 65.25

55.91 4.66 60.57

2006

2007

2008

2009

2010

2011

2012

2013

Lime production

61.74

59.27

59.01

36.37

39.63

46.71

54.34

52.51

Sugar production Total

2.17 63.91

1.72 60.99

2.67 61.67

1.92 38.29

1.56 41.18

2.01 48.72

2.24 56.58

1.64 54.15

Figure 3.3.1 Emission trends for emission of CO2 from lime production.

42

Table 3.3.7 Emission of particles and POPs from marketed lime production. Unit HCB

g

PCDD/F mg PCB g

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

1.0

0.7

0.8

0.9

0.9

0.8

0.8

0.8

0.7

0.8

2.3 19.2

1.6 12.9

1.9 15.7

1.9 16.0

2.0 16.9

1.8 15.1

1.7 14.3

1.8 15.4

1.6 13.3

1.7 14.3

Unit

2000

2001

2002

2003

2004

2005

2006

2007

2008

2009

TSP PM10

Mg Mg

46.0 18.4

48.2 19.3

61.3 24.5

43.8 17.5

38.9 15.6

35.6 14.2

39.3 15.7

37.8 15.1

37.5 15.0

23.1 9.2

PM2.5 BC HCB PCDD/F

Mg Mg g mg

3.7 0.02 0.7 1.7

3.9 0.02 0.8 1.7

4.9 0.02 1.0 2.2

3.5 0.02 0.7 1.6

3.1 0.01 0.6 1.4

2.8 0.01 0.6 1.3

3.1 0.01 0.6 1.4

3.0 0.01 0.6 1.4

3.0 0.01 0.6 1.3

1.8 0.01 0.4 0.8

PCB

g

13.8

14.5

18.4

13.1

11.7

10.7

11.8

11.3

11.2

6.9

Unit

2010

2011

2012

2013

TSP PM10 PM2.5

Mg Mg Mg

25.2 10.1 2.0

29.7 11.9 2.4

34.6 13.8 2.8

33.4 13.4 2.7

BC HCB PCDD/F PCB

Mg g mg g

0.01 0.4 0.9 7.6

0.01 0.5 1.1 8.9

0.01 0.6 1.2 10.4

0.01 0.5 1.2 10.0

There is a peak in the activity data in 2002 causing peaks in the emissions for this year. The activity data are based on the official statistics from Statistics Denmark and there is no immediate explanation for the peak. As there are very few producers in Denmark it will not be possible to obtain more detailed data from Statistics Denmark.

3.3.4 EU-ETS data for lime production The applied methodology for Faxe Kalk is specified in the individual monitoring plan that is approved by Danish authorities (DEA) prior to the reporting of the emissions. Lime production applies the Tier 2 methodology for the activity data and Tier 3 for the emission factor. The implied CO2 emission factor for Faxe Kalk is plant specific and based on the reporting to the EU Emission Trading Scheme (EU-ETS). The EU-ETS data have been applied for the years 2006 – 2013. The CO2 emission for lime production is based on sales (± 1.0 %) and measurements of the MgO content in the product (assuming the product is pure CaO/MgO) (Faxe Kalk, 2013).

3.3.5 Verification For verification, the implied emission factors are calculated and presented in the following table.

43

Table 3.3.8 Implied emission factors for lime production, Mg CO2 per Mg CaCO3-eq. 1991 1992 1993 1994 1995 1990 Lime production (marketed) 0.785 0.785 0.785 0.785 0.785 0.785 Sugar production 0.785 0.785 0.785 0.785 0.785 0.785 Overall 0.785 0.785 0.785 0.785 0.785 0.785 2000 2001 2002 2003 2004 2005 Lime production (marketed) 0.785 0.785 0.785 0.785 0.785 0.785 Sugar production 0.785 0.785 0.785 0.785 0.785 0.785 Overall 0.785 0.785 0.785 0.785 0.785 0.785 2011 2012 2013 2010 Lime production (marketed) 0.786 0.786 0.786 0.786 Sugar production 0.750 0.750 0.750 0.750 Overall 0.785 0.784 0.784 0.785

1996 0.785 0.785 0.785 2006 0.785 0.750 0.784

1997 0.785 0.785 0.785 2007 0.785 0.750 0.784

1998 0.785 0.785 0.785 2008 0.787 0.750 0.785

1999 0.785 0.785 0.785 2009 0.787 0.750 0.785

The emission factor used by the sugar factories in 2006-2013 is only 0.75 kg CO2 per Mg lime, please refer to Section 3.3.8 Future improvements. If the simple Tier 2 methodology had been used for the entire time series, instead of partially using EU-ETS data, then the emission from marketed lime production in 2006-2013 would be 1 % (2007) to 16% (2008) lower; average of 2006-2013 is 8 %. The 2006 IPCC guidelines provide Tier 1 emission factors for lime; see Table 3.3.9. Table 3.3.9 Basic parameters for calculation of emission factors for lime products. Stoichiometric ratio Range of CaO Range of MgO Default value for Default emission

Lime type

High-calcium lime

Mg CO2/Mg CaO or

content

content

CaO or CaO-MgO

factor

CaO-MgO

%

%

content

Mg CO2/Mg

0.785

93-98

0.3-2.5

0.95

0.75

Since 2008, Faxe Kalk has reported measured emissions factors to EU-ETS. These emission factors take into account the content of MgO and varies from 0.787-0.788 Mg CO2 per Mg lime produced (Faxe Kalk, 2014a), see Table 3.3.8. The measured emission factors show that the MgO content in the product has a negligible impact on the emissions; 0.3 % in average for 20082013. It is therefore considered reasonable to ignore this miniscule impurity in favour of increased consistency and the emission factor is hence not adjusted as suggested in Table 3.3.9. Emissions of TSP at Faxe Kalk A/S, Lhoist Group are presented in Table 3.3.10.

44

Table 3.3.10 TSP emission factor at Faxe Kalk A/S, Lhoist Group (Faxe Kalk, 2014b). 2001 Flue gas

m3

2002

2003

2004

2005

2006

2007

2008

1.58E+08 2.25E+08 2.69E+08 2.71E+08 2.19E+08 2.33E+08 2.11E+08 2.85E+08

TSP concentration mg TSP/m3

42

40

31.5

26.1

23

23.8

7

20

TSP emission

Mg

6.64

9.00

8.47

7.07

5.04

5.55

1.48

5.70

Lime production

Mg

70,537

69,827

63,258

64,085

57,302

62,817

57,004

57,812

IEF TSP

g/Mg

94

129

134

110

88

88

26

99

The average emission factor for the years 2001-2008 is 96 g TSP per Mg lime. This figure is very low compared to the chosen emission factor of 500 g TSP per Mg lime from CEPMEIP.

3.3.6 Time series consistency and completeness The chosen activity data for marketed lime production (entire time series) and non-marketed lime (2006-2013) are consistent. However in the case of lime consumption in the sugar industry in 1990-2005 the activity data (consumption of CaCO3) was calculated from the total produced amount of sugar and an emission factor of 8.8 kg CO2 per Mg sugar causing an inconsistency. The applied methodology for calculation of the CO2 emission from marketed lime is consistent for all producers for 1990-2005. From 2006, the CO2 emission from the largest Danish producer (Faxe Kalk) is gathered from EU-ETS, but in spite of this, the methodology continues to be consistent until 2008 because Faxe Kalk uses the same emission factor when calculating emissions. In 2008 an inconsistency occurs when emissions reported by Faxe Kalk to EU-ETS begins to takes into account the otherwise negligible amount of MgO in the product, leading to a miniscule increase in the implied emission factor. The Danish inventory on lime production is considered to be complete.

3.3.7 Input to CollectER The input data/data sources are presented in Table 3.3.11. Table 3.3.11

Input data for calculating emissions from production of lime and slaked

lime. Activity

Year

Parameter

1990-2013

Production

Comment/Source Danisco Sugar, Nordic Sugar, Statistics Denmark

Emissions

1990-2013

CO2

Stoichiometric relations combined with product information from one company

2006-2013

CO2

Faxe Kalk (2014a)

2000-2013

TSP, PM10, PM2.5 CEPMEIP

2000-2013

BC

EMEP/EEA (2006)

1990-2013

HCB, PCB

Nielsen et al. (2013a)

1990-2013

PCDD/F

Henriksen et al. (2006)

3.3.8 Future improvements The choice of CEPMEIP as source of the emission factors for particulate matter will be re-evaluated and a change to the latest edition of the EMEP/EEA guidebook will be considered. 45

Unfortunately, it was not possible to complete improvements to the source category of sugar production for this report; other improvements and the implementation of the 2006 IPCC Guidebook have been prioritised. Planned improvements include: • It will be attempted to collect activity data on the amount of lime being used as raw material in the sugar production. If this improvement is possible, it will result in increased consistency in the lime production source category (marketed lime and sugar production). • Further research will focus on the lower emission factor for CO2 from the un-marketed lime in sugar production in 2006-2013. If possible, the emission factor will be made consistent throughout the time series depending on the findings.

3.4

Glass production

Glass production covers production of: • Flat glass • Container glass • Glass wool The production of flat glass (SNAP 03 03 14 Flat glass) is concentrated at few European producers and none of these have plants in Denmark. The processes in Denmark are limited to mounting of sealed glazing units. The mounting process is not considered to contribute to emission of pollutants to air in Denmark. The production of container glass for packaging is concentrated at one company: Ardagh Glass Holmegaard A/S (previously Rexam Glass Holmegaard A/S) and for art industrial glass products: Holmegaard A/S both situated in Fensmark, Næstved. Saint-Gobain Isover situated in Vamdrup produces glass wool. The following SNAP-codes are covered: • 03 03 15 Container glass • 03 03 16 Glass wool (except binding) • 04 06 13 Glass (decarbonising) The following pollutants are included for the glass production process: • • • • •

NMVOC CO NH3 Particulate matter: TSP, PM10, PM2.5 Heavy metals: As, Cd, Cr, Ni, Pb, Se, Zn

Emissions associated with the fuel use are estimated and reported in the energy sector.

3.4.1 Process description The following descriptions as well as data are based on Holmegaard (2003), Rexam (2002) and Saint-Gobain Isover (2003). The primary raw materials in glass production are dolomite (CaMg(CO3)2), feldspar ((Ca,K,Na)AlSi2O8), limestone (CaCO3), sodium sulphate (Na2SO4), pluriol, sand (SiO), recycled glass (cullets), soda ash (Na2CO3), and color46

ants. Cullets constitute 40-50% of the raw materials. For the art industrial glass products a number of additional raw materials are used: aluminium hydrate, barium carbonate, borax, potash (carbonised), kaolin, lithium carbonate, titanium dioxide, and zinc oxide. The primary constituents of glass are e.g.: SiO2, Al2O3, CaO, MgO, Fe2O3, Na2O, K2O, BaO, PbO, B2O3 etc. where the actual composition depends on the final use of the product. The most common composition of glass for packaging is 60-75% SiO2, 5-12% CaO, and 10-18% Na2O (Lenntech). The products are bottles and glass jars (Rexam Glass Holmegaard) as well as drinking glasses and glass art products (Holmegaard). Emissions from glass production can be related to use of fuels, release of pollutants from raw materials and recycled glass, and release of CO2 from use of soda ash. Glass wool is produced from glass fibres and a binder (that is hardened to bakelite). The glass fibres are produced from sand, soda, limestone, dolomite, and auxiliaries (nephelin, dolomite, rasorite, palfoss, sodium nitrate and manganese dioxide) and also glass waste. The glass waste is crushed on location. The raw materials are mixed and finally mixed with crushed glass. The mixture is melted in an electric furnace. The melted glass is drawn into fibres by a natural gas flame. The fibres are mixed with binder and formed into wool. The glass wool is hardened in a furnace fired with natural gas. The emission originates from energy consumption and decarbonizing of carbonate based raw materials.

3.4.2 Methodology For the production of both container glass, art glass and glass wool, the main raw materials are soda ash (Na2CO3), dolomite (CaMg(CO3)2), limestone (CaCO3) and recycled glass (cullets). Emissions are calculated for each carbonate raw material individually. Activity data The activity data for container glass production are presented in Table 3.4.1. Information on consumption of carbon containing raw materials is available from the environmental reports of the plant since 1997 (Ardagh, 2014b) and from EU-ETS since 2006 (Ardagh, 2014a). For the years prior to 1997 the production of glass is based on information contained in Illerup et al. (1999).

47

Table 3.4.1 Production of container glass, activity data, Mg. 1991 1992 1993 1994 1995 1996 1997 1998 1999 1990 Production of glass1, 2 164,000 159,000 145,000 140,500 150,200 140,000 140,000 140,000 186,622 197,863 Consumption of soda ash3 22,543 19,244 16,945 16,360 16,302 15,195 15,195 15,195 20,258 19,241 Consumption of limestone3 18,226 15,559 13,700 13,227 13,180 12,285 12,285 12,285 7,966 8,733 Consumption of dolomite3 1,237 1,056 930 898 895 834 834 834 9,522 9,808 2001 2002 2003 2004 2005 2006 2007 2008 2009 2000 Production of glass1, 2 179,541 179,290 160,938 145,186 139,498 125,583 48,179 52,437 130,075 78,596 Consumption of soda ash 16,391 16,668 15,816 14,106 13,611 12,996 12,831 14,060 13,882 8,464 Consumption of limestone 7,739 7,881 7,050 6,347 6,036 5,650 1,325 1,693 9,171 5,383 Consumption of dolomite 9,085 8,920 8,031 7,258 7,036 6,118 5,413 5,462 5,527 3,631 2011 2012 2013 2010 Production of glass1, 2 86,354 87,923 90,027 68,210 Consumption of soda ash 8,883 8,843 9,584 6,755 Consumption of limestone 5,855 5,940 6,095 4,796 Consumption of dolomite 4,085 4,215 4,267 2,911 1 1990-1997: Illerup et al. (1999). 2 1998-2013: Estimated based on 1997 and total consumption of raw materials. 3 1990-1996: Estimated based on total production and the consumption of raw materials in 1997.

Only one industrial art glass producer with virgin glass production exists in Denmark; Holmegaard A/S. Emissions from this production is included in the data on container glass above. The activity data for glass wool production are presented in Table 3.4.2. Information on consumption of carbon containing raw materials is available from the environmental reports of the plant since 1996 (Saint-Gobain Isover, 2014a) and EU-ETS since 2006 (Saint-Gobain Isover, 2014b). For the years prior to 1995/1996 the production of glass wool and consumption of carbonates are estimated. Table 3.4.2 Production of glass wool, activity data, Mg. 1991 1992 1993 1994 1995 1996 1997 1998 1999 1990 Production of glass wool1 35,631 35,631 35,631 35,631 35,631 35,631 35,631 34,584 33,630 38,680 Consumption of soda ash2 3,566 3,566 3,566 3,566 3,566 3,566 3,589 3,654 3,455 3,095 Consumption of limestone2 818 818 818 818 818 818 768 854 831 276 Consumption of dolomite3 1,021 1,021 1,021 1,021 1,021 1,021 1,021 1,021 1,021 1,021 2001 2002 2003 2004 2005 2006 2007 2008 2009 2000 Production of glass wool 39,666 36,983 34,836 37,452 41,350 37,295 42,735 40,995 41,318 33,066 Consumption of soda ash 2,974 2,895 3,300 2,810 3,348 3,639 c c c c Consumption of limestone 213 369 589 425 530 614 c c c c Consumption of dolomite3 1,021 1,021 1,021 1,021 1,021 1,021 c c c c 2011 2012 2013 2010 Production of glass wool 24,899 29,817 26,752 27,894 Consumption of soda ash c c c c Consumption of limestone c c c c Consumption of dolomite c c c c 1 1990-1996: Estimated: Assumed constant on the average production from 1997-1999. 2 1990-1995: Estimated: Assumed constant on the average consumption from 1996-1998. 3 1990-2005: Estimated: Assumed constant on the average consumption from 2006-2008. c: Confidential.

The time series for activity data for the glass sector are presented in Figure 3.4.1

48

Figure 3.4.1 Activity data for container glass and glass wool production.

The drastic decrease in the calculated production of container glass in 2006 and 2007 is a result of a similar decrease in the consumption of limestone reported to the EU-ETS database. It will be investigated whether the temporary decrease is due to EU-ETS teething troubles or something else. Both the container glass and glass wool production displays a significant decrease from 2008 to 2010 that can be explained by the financial crises. Emission factors The emission factors for the glass industry are a combination of default Tier 2 factors suggested in EMEP/EEA (2013) and calculated implied emission factors based on measurements by the specific industries. The emission factors are supplemented with estimated CO2 emissions from the calcination of carbonate compounds and some measured emission. Soda ash is either extracted from natural carbonate bearing deposit (I) or produced from calcium carbonate and sodium chloride (II). (I) 2 Na2CO3,NaHCO3,2H2O → 3Na2CO3 + 5H2O + CO2 (II) CaCO3 + 2NaCl → Na2CO3 + CaCl2 The CO2 emission factors from using Na2CO3 and other carbonate containing raw materials in production of glass and glass wool, based on stoichiometric relationships, are: • • • •

0.41492 Mg CO2/Mg Na2CO3 0.43971 Mg CO2/Mg CaCO3 0.47732 Mg CO2/Mg CaMg(CO3)2 0.52197 Mg CO2/Mg MgCO3

The calcination of all carbonates in all years is assumed to be 100 %. From 2006 onward the CO2 emissions are calculated by the companies and reported to EU-ETS (Ardagh, 2014a; Saint-Gobain Isover, 2014a), but the applied emission factors (however rounded) remain the same for the entire time series. 49

The emission of CO2 is estimated from the following equation: ECO2 = ∑ EFs × Acts where: ECO2 is emission of CO2 EFs is emission factor for substance s Acts is consumption of substance s Yearly measurements of the emissions from production of container glass are available in the environmental reports; these provide emissions of TSP (2000-2013), Pb (1997-2013), Se (1997-2013) and Zn (1997-2001) (Ardagh, 2014b and previous years). PM10 and PM2.5 are estimated from the distribution between TSP, PM10 and PM2.5 (1/0.9/0.8) provided by EMEP/EEA (2013). Emissions of As, Cd, Cr and Ni are estimated from standard emission factors. Where direct emissions are not available for Pb, Se and Zn; these are also calculated using emission factors. All used emission factors are shown in Table 3.4.3. From 2006, measured particle emissions from the singular Danish container glass producer decrease 90 % due to installation of abatement equipment; all calculated heavy metal emissions are therefore also lowered with 90 % from 2006. The emission of NH3 and TSP from the production of glass wool has been measured yearly since 1996 and are available in the company’s environmental reports (Saint-Gobain Isover, 2014b). PM10 and PM2.5 are estimated from the distribution between TSP, PM10 and PM2.5 (1/0.9/0.8) from EMEP/EEA (2013). NMVOC and CO have been measured for 2007-2013 and 1996-1997 respectively. For the years where no measured emission data are available, emissions are calculated using data on total production and implied emission factors (IEF) based on the available measurements. All used emission factors are shown in Table 3.4.3. Prior to 1996 (where total production is not available) the emissions have been assumed constant at the emission average level of 1996-1998. Since it has not been possible to separate process emissions from the emissions from fuel combustion, the measured/calculated emissions from glass wool production presented here account for the entire production. Table 3.4.3 Emission factors for production of glass production. Container glass production Glass wool production Pollutant Unit Value Source Unit Value Source NMVOC kg/Mg 1.4 IEF (2007-2009) CO IE kg/Mg 0.1 IEF (1996-1997) kg/Mg 7.4 IEF(1996-1998) NH3 TSP kg/Mg 0.28 Guidebook (2013) kg/Mg 2.0 IEF (2000-2013) PM10 kg/Mg 0.25 Guidebook (2013) kg/Mg 1.8 IEF (2000-2013) kg/Mg 0.22 PM2.5 Guidebook (2013) kg/Mg 1.6 IEF (2000-2013) g/Mg 0.29 As Guidebook (2013) g/Mg 0.12 Cd Guidebook (2013) g/Mg 0.37 Cr Guidebook (2013) g/Mg 0.24 Ni Guidebook (2013) g/Mg 2.90 Pb Guidebook (2013) g/Mg 1.50 Se Guidebook (2013) g/Mg 0.23 Zn Guidebook (2013) IE: Included elsewhere. It is not possible to separate process and fuel emissions, these process emissions are included in the energy sector.

50

3.4.3 Emission trend For the years 2006-2013 information on CO2 emission has been available in the company reports to the EU-ETS (Ardagh, 2014a and Saint Gobain Isover, 2014a). However, this information is confidential, and data since 2006 can therefore only be presented as total emitted CO2.

Figure 3.4.2 CO2 emissions from glass production.

The emission trends from production of container glass and glass wool are presented in Table 3.4.4,. .

51

Table 3.4.4 Emissions from production of glass. Pollutant Unit 1990 CO2 Total Gg 20.2 - of which container glass Gg 17.9 - of which glass wool Gg 2.3 NMVOC From glass wool Mg 46.3 CO From glass wool Mg 1.9 NH3 From glass wool Mg 262.0 As From container glass kg 47.6 Cd From container glass kg 19.7 Cr From container glass kg 60.7 Ni From container glass kg 39.4 Pb From container glass kg 475.6 Se From container glass kg 246.0 Zn From container glass kg 37.7 Unit 2000 CO2 Total Gg 16.0 - of which container glass Gg 14.2 - of which glass wool Gg 1.8 NMVOC From glass wool Mg 51.6 CO From glass wool Mg 2.1 NH3 From glass wool Mg 225.0 TSP Total Mg 137.0 - of which container glass Mg 26.0 - of which glass wool Mg 111.0 PM10 Total Mg 123.0 - of which container glass Mg 23.0 - of which glass wool Mg 100.0 PM2.5 Total Mg 109.0 - of which container glass Mg 20.0 - of which glass wool Mg 89.0 As From container glass kg 52.1 Cd From container glass kg 21.5 Cr From container glass kg 66.4 Ni From container glass kg 43.1 Pb From container glass kg 330.0 Se From container glass kg 340.0 Zn From container glass kg 57.0 Unit 2010 CO2 Total Gg 9.3 NMVOC From glass wool Mg 32.0 CO From glass wool Mg 1.3 NH3 From glass wool Mg 108.0 TSP Total Mg 27.7 - of which container glass Mg 1.7 - of which glass wool Mg 26.0 PM10 Total Mg 24.5 - of which container glass Mg 1.5 - of which glass wool Mg 23.0 PM2.5 Total Mg 22.3 - of which container glass Mg 1.3 - of which glass wool Mg 21.0 As From container glass kg 2.6 Cd From container glass kg 0.9 Cr From container glass kg 3.5 Ni From container glass kg 1.7 Pb From container glass kg 24.0 Se From container glass kg 17.0 Zn From container glass kg 2.0 c: Confidential

52

1991 17.6 15.3 2.3 46.3 1.9 262.0 46.1 19.1 58.8 38.2 461.1 238.5 36.6 2001 16.2 14.3 1.9 48.1 2.0 190.0 144.0 25.0 119.0 129.0 22.0 107.0 115.0 20.0 95.0 52.0 21.5 66.3 43.0 172.0 271.0 25.0 2011 9.5 39.0 1.6 105.0 43.8 1.8 42.0 39.6 1.6 38.0 35.0 1.4 33.6 2.6 0.9 3.5 1.8 25.0 17.0 2.0

1992 15.8 13.5 2.3 46.3 1.9 262.0 42.1 17.4 53.7 34.8 420.5 217.5 33.4 2002 15.3 13.2 2.1 45.3 1.9 133.0 135.0 21.0 114.0 122.0 19.0 103.0 108.0 17.0 91.0 46.7 19.3 59.5 38.6 220.0 201.0 38.0 2012 9.7 39.0 1.4 144.0 51.5 4.5 47.0 47.0 4.0 43.0 41.5 3.5 38.0 2.7 0.9 3.6 1.8 116.0 60.0 2.0

1993 15.3 13.0 2.3 46.3 1.9 262.0 40.7 16.9 52.0 33.7 407.5 210.8 32.3 2003 13.7 11.8 1.8 48.7 2.0 125.0 128.0 26.0 102.0 115.0 23.0 92.0 102.0 20.0 82.0 42.1 17.4 53.7 34.8 272.0 234.0 34.0 2013 7.0 37.0 1.5 119.0 39.6 1.6 38.0 36.4 1.4 35.0 32.3 1.3 31.0 2.0 0.7 2.7 1.4 22.0 19.0 2.0

1994 15.3 13.0 2.3 46.3 1.9 262.0 43.6 18.0 55.6 36.0 435.6 225.3 34.5 2004 13.5 11.4 2.1 53.8 2.2 124.0 122.0 23.0 99.0 109.5 20.5 89.0 97.1 18.1 79.0 40.5 16.7 51.6 33.5 436.0 225.0 33.0

1995 14.4 12.1 2.3 46.3 1.9 262.0 40.6 16.8 51.8 33.6 406.0 210.0 32.2 2005 12.8 10.6 2.3 48.5 2.0 116.0 92.0 7.0 85.0 83.3 6.3 77.0 73.5 5.5 68.0 36.4 15.1 46.5 30.1 148.0 107.0 29.0

1996 14.4 12.1 2.3 46.3 1.9 224.0 40.6 16.8 51.8 33.6 406.0 210.0 32.2 2006 11.1 c c 55.6 2.3 123.0 82.9 0.9 82.0 74.8 0.8 74.0 66.7 0.7 66.0 1.4 0.5 1.9 1.0 12.0 59.0 1.0

1997 1998 1999 14.5 18.4 18.0 12.1 16.1 16.1 2.4 2.3 1.9 45.0 43.7 50.3 1.9 1.8 2.1 296.0 266.0 268.0 40.6 54.1 57.4 16.8 22.4 23.7 51.8 69.1 73.2 33.6 44.8 47.5 883.0 523.0 562.0 134.0 90.0 218.0 31.0 49.0 45.0 2007 2008 2009 11.9 15.1 9.2 c c c c c c 58.0 52.0 46.0 2.2 2.2 1.8 109.0 155.0 152.0 53.0 55.2 34.2 1.0 1.2 1.2 52.0 54.0 33.0 47.9 50.1 31.1 0.9 1.1 1.1 47.0 49.0 30.0 42.8 43.9 26.9 0.8 0.9 0.9 42.0 43.0 26.0 1.6 3.9 2.4 0.5 1.3 0.8 2.1 5.2 3.1 1.0 2.6 1.6 16.0 18.0 18.0 53.0 46.0 25.0 1.0 3.0 2.0

3.4.4 Time series consistency and completeness CO2 emissions from glass production (including container glass, art glass and glass wool production) are calculated based on consumption of carbonates and stoichiometric emission factors for the entire time series. However, the source of activity data varies for the time series and it is therefore at present unclear whether or not the time series is consistent. Verification of the activity data will be carried out in the future to ensure the consistency. Effort has been made to ensure that all glass producers are included in the inventory. Smaller facilities producing art glass do exist in Denmark, but none of these produce their own virgin glass. The source category of glass production is therefore considered to be complete.

3.4.5 Input to CollectER The environmental report (Saint-Gobain Isover, 2014b) presents energy as well as process related emissions. The process related emissions are used as input along with estimated CO2 emission from calcination of the raw materials. The TSP emission from both container glass and glass wool production is based on the environmental reports with a distribution between PM10 and PM2.5 as reported in EMEP/EEA (2013) i.e. 90 % and 80 % of TSP respectively. The input data/data sources are presented in Table 3.4.5. Table 3.4.5 Input data for calculating emissions from glass production. Year

Parameter

Activity data 1990-1997 Container glass production 1998-2013 Container glass production 1990-1996 Consumption of raw materials for container glass 1997-2013 Consumption of raw materials for container glass 1990-1997 Glass wool production 1998-2013 1990-1995 (1990-2005) 1996-2013 Emissions

Comment/Source Illerup et al. (1999) Estimated from consumption of raw materials Estimated from production Ardagh (2014b) and earlier Assumed to be average 1997-1999

Glass wool production Saint-Gobain Isover (2014b) and earlier Consumption of raw materials for Assumed to be average 1996-1998 (2006-2008 for dolomite) glass wool Consumption of raw materials for Saint-Gobain Isover (2014b) and earlier glass wool

1990-1996 Pb, Se

Illerup et al. (1999), EMEP/EEA (2013)

1997-2013 Pb, Se

Ardagh (2014b) and earlier

2000-2013 TSP 2000-2013 PM10, PM2.5

Ardagh (2014b), Saint-Gobain Isover (2014b) and earlier Distribution between TSP, PM10, and PM2.5 from EMEP/EEA (2013) EMEP/EEA (2013)

1990-2005 As, Cd, Cr, Ni 2006-2013 As, Cd, Cr, Ni

EMEP/EEA (2013), Ardagh (2014b)

1997-2001 Zn

Ardagh (2014b) and earlier

1990-1996; Zn

Calculated from activity data and implied emission factors

2002-2013

(IEF) (1997-2001)

1990-1995 NMVOC, NH3

Assumed to be average 1996-1998

1996-2006 NMVOC

Calculated from activity data and IEF (2007-2009)

2007-2013 NMVOC

Saint-Gobain Isover (2014b) and earlier

1996-2013 NH3

Saint-Gobain Isover (2014b) and earlier

1990-1995 CO

Assumed to be average 1996-1997

1996-1997 CO

Saint-Gobain Isover (2014b) and earlier

1998-2013 CO

Calculated from activity data and IEF (1996-1997)

1990-2005 CO2

Estimated from consumption of raw materials

2006-2013 CO2

EU-ETS (Ardagh, 2014a; Saint-Gobain Isover, 2014a)

53

3.4.6 Future improvements Emissions of BC will be added for container glass and glass wool production. The production figures for container glass are very low for 2006 and 2007, this will be investigated further.

3.5

Ceramics

This section covers production of bricks, tiles (aggregates or bricks/blocks for construction) and expanded clay products for different purposes (aggregates as absorbent for chemicals, cat litter, and for other miscellaneous purposes). The following SNAP codes are covered: • 04 06 91 Production of bricks • 04 06 92 Production of expanded clay products The production of bricks is found all over the country, where clay is available. Producers of expanded clay products are located in the northern part of Jutland. Emissions associated with the fuel use are estimated and reported in the energy sector. The following pollutants are covered: • CO2 • SO2 • Persistent organic pollutants: PCDD/F

3.5.1 Process description During the production of ceramics, the raw materials are collected and finely crushed in successive grinding operations. The ground particles are then fired in a kiln to produce a powder (which may be liquefied). Additives are subsequently added and the ceramic is formed. The clays used in the production process include small amounts of carbonates, which is oxidised during the process thereby generating CO2. Also, some of the clays contain significant amounts of sulphur, which is oxidised and released as SO2 during the process. The production sites of bricks, tiles and expanded clay products are found all over the country; see Table 3.5.1. .

54

Table 3.5.1 Producers of clay and expanded clay products. Product

Company

Bricks and tiles

Vedstårup teglværk

Location 5610 Assens

Vesterled Teglværk

6400 Sønderborg

Pipers Teglværk Vindø

9500 Hobro

Pedershvile teglværk

3200 Helsinge

Prøvelyst teglværk

2980 Kokkedal

Lundgård teglværk

7850 Stoholm, Jylland

Bachmanns teglværk

6400 Sønderborg

Petersens Tegl Egernsund

6310 Broager

Orebo Teglværk

4293 Dianalund

Tychsen’s Teglværk

6310 Broager

Nordtegl

9881 Bindslev

Ydby Teglværk

7760 Hurup Thy

Hellingsø Teglværk

7760 Hurup Thy

Carl Matzens Teglværk

6320 Egernsund

Gråsten Teglværk

6300 Gråsten

P.M. Tegl Egernsund

6320 Egernsund

Pipers Teglværk Gandrup

9362 Gandrup

Pipers Teglværk Hammershøj

8830 Tjele

Pipers Teglværk Højslev

7840 Højslev

Monier Volstrup Teglværk

9300 Sæby

Villemoes Teglværk

6690 Gørding

Expanded clay products Saint-Gobain Weber

8900 Randers

Damolin Mors

7900 Nykøbing Mors

Damolin Fur

7884 Fur

The expanded clay products are presented in Table 3.5.2. Table 3.5.2 Products from different producers of expanded clay products. Company

Location

Products

Damolin

Fur, Nykøbing Mors

Cat litter Felicia Amigo Absorbant Absodan Sorbix Oil Dri Moler Bentonite Perlite Vermiculite

Saint-Gobain Weber

Randers, Gadbjerg

Optiroc Leca

3.5.2 Methodology Emission of CO2 and SO2 is related to limestone and sulphur content in the raw material respectively, whereas emission of NOx and other pollutants is related to fuel consumption/process conditions. The NOx and SO2 emissions have previously been discussed by DTI (2000). A typical composition of clay used for bricks is presented in Table 3.5.3.

55

Table 3.5.3 Typical composition of clay used for bricks (Tegl Info, 2004). Red bricks

Yellow bricks

Silicic acid (SiO2)

63.2 %

49.6 %

Aluminium oxide (Al2O3)

17.9 %

14.2 %

Iron(III)oxide (Fe2O3)

7.1 %

5.1 %

Calcium carbonate (CaCO3)

0.5 %

19.8 %

Magnesium oxide (MgO)

1.3 %

1.4 %

Alkali oxides (e.g. Na2O, K2O)

2.9 %

2.9 %

Chemical bound water and organic substances

7.1 %

7.0 %

Since 2006, the producers of ceramics have measured and reported process CO2 emissions to EU-ETS and production statistics are known from Statistics Denmark (2014) for the entire time series. From these two datasets, implied emission factors are calculated for 2006-2013 and CO2 emissions are calculated for the years back to 1990. Activity data National statistics on production of bricks, tiles and expanded clay products contain a broad range of different products, most of them in units of numbers (no.). The consumption of limestone is therefore used as alternative activity data for these source categories for all pollutants, not just for CO2. The production statistics for bricks and expanded clay products (used as surrogate data) from Statistics Denmark (2014) and the consumption of lime in the production (calculated for 1990-2005) are presented in Table 3.5.4. Table 3.5.4 Statistics for production of bricks and expanded clay products. 1991 1992 1993 1994 1995 1996 1997 Unit 1990 Bricks Produced1 million pieces 291.3 291.5 303.6 278.5 389.8 362.7 377.7 419.4 Consumed lime2 Gg CaCO3 56.8 56.9 59.2 54.3 76.1 70.8 73.7 81.8 Expanded clay products Produced1 Gg 331.8 268.9 282.9 288.3 383.8 340.9 368.1 406.7 Consumed lime2 Gg CaCO3-eq 37.1 30.0 31.6 32.2 42.9 38.1 41.1 45.4 Unit 2000 2001 2002 2003 2004 2005 2006 2007 Bricks Produced1 million pieces 414.8 352.0 342.2 342.0 365.4 407.9 465.5 348.9 Consumed lime2 Gg CaCO3 80.9 68.7 66.8 66.7 71.3 79.6 79.0 86.4 Expanded clay products Produced1 Gg 316.2 232.3 239.7 211.8 281.8 310.9 411.9 504.9 Consumed lime2 Gg CaCO3-eq 35.3 25.9 26.8 23.7 31.5 34.7 47.5 61.1 Unit 2010 2011 2012 2013 Bricks Produced1 million pieces 212.1 222.1 185.4 177.4 Consumed lime Gg CaCO3 35.1 46.0 39.7 36.7 Expanded clay products Produced1 Gg 157.4 172.3 153.3 139.8 Consumed lime Gg CaCO3-eq 13.7 15.1 13.4 23.8 1 Statistics Denmark (2014). 2 1990-2005: Calculated from production data and the average implied emission factor for 2006-2013.

1998

1999

423.3 82.6

405.2 79.1

324.4 36.2 2008

329.4 36.8 2009

322.1 61.8

226.4 35.8

303.9 36.6

140.9 14.7

The consumption of lime in the production of ceramics is also presented in the following figure.

56

Figure 3.5.1 Consumption of CaCO3 equivalents in the production of ceramics.

Both the brickworks and expanded clay production displays a significant decrease from 2007 to 2009 that can be explained by the financial crises. Emission factors The CO2 emission factor for lime is 0.43971 kg CO2 per kg CaCO3. The calcination factor is assumed to be 1 for all years and all producers. For 2006-2013 CO2 emissions are reported by the brickworks to EU-ETS (confidential reports from approximately 20 brickworks). The reported emissions are calculated from measured lime contents of the raw materials and the stoichiometric emission factor 0.43971 kg CO2 per kg CaCO3. From the reported emissions implied emission factors are calculated to match the activity data for brickworks using the stoichiometric factors. Producers of expanded clay products also report CO2 emissions to EU-ETS for the years 2006-2013 (Damolin, 2014; Saint-Gobain Weber, 2014). The reported emissions are calculated from the difference in C contents measured in the raw materials and products and the stoichiometric emission factor 3.664 kg CO2 per kg C. The SO2 emission factors for the production of bricks and expanded clay products are determined from the individual companies reporting of SO2 emission (environmental reports) for the years 2009-2011 and the activity for the corresponding years. 2009-2011 were selected as the most complete data sets are available for these years. The SO2 emissions attributed to the process have been adjusted for the fuel related emissions as far as possible to derive the process emissions. Five plants were using coal, petroleum coke and residual oil according to EU-ETS reporting. The fuel related SO2 emission was calculated by using the general EFSO2 for the relevant fuels (Nielsen et al., 2015). The applied emission factors are presented in Table 3.5.5. Table 3.5.5 Applied emission factors for S-containing fuels. Fuel

Emission factor, g SO2/GJ

Coal

574

Petroleum coke

605

Residual oil

344

57

The total emissions of SO2 from the plants considered were reduced by the amount related to fuel before calculating the emission factor, see Table 3.5.6. However, the emission factor will continuously be improved as a more comprehensive dataset are made available and the influence from fuel contribution will be studied further as not all the environmental reports distinguish clearly between the different emission sources. The PCDD/F emission factors are calculated from 0.018 µg per Mg product (Henriksen et al., 2006), using the total carbonate consumption (environmental reports), national production statistics (Statistics Denmark) and an assumption of 2 kg per brick. The applied emission factors for ceramics are presented in Table 3.5.6. Table 3.5.6 Emission factors for ceramics, units are per Mg CaCO3 equivalent. Pollutant CO2 SO2

Brickworks Value Unit 0.44 kg 6.5 kg

Expanded clay Value Unit 0.44 kg 63.3 kg

Source Stoichiometric Environmental reports*

PCDD/F 0.19 µg 0.17 µg Henriksen et al. (2006)* * Some recalculations were necessary to derive the desired units.

3.5.3 Emission trend Emissions of CO2, SO2 and PCDD/F from production of ceramics are presented in Table 3.5.7, Figure 3.5.2 and Figure 3.5.3. Table 3.5.7 Process emissions from production of ceramics. 1991 1992 Pollutant Source Unit 1990 CO2 Total Gg 41.3 38.2 39.9 Brickworks Gg 25.0 25.0 26.0 Expanded clay Gg 16.3 13.2 13.9 SO2 Total Gg 2.7 2.3 2.4 Brickworks Gg 0.4 0.4 0.4 Expanded clay Gg 2.3 1.9 2.0 PCDD/F Total mg 17.0 15.8 16.5 Brickworks mg 10.7 10.7 11.2 Expanded clay mg 6.3 5.1 5.3 Pollutant Source Unit 2000 2001 2002 CO2 Total Gg 51.1 41.6 41.1 Brickworks Gg 35.6 30.2 29.4 Expanded clay Gg 15.5 11.4 11.8 SO2 Total Gg 2.8 2.1 2.1 Brickworks Gg 0.5 0.4 0.4 Expanded clay Gg 2.2 1.6 1.7 PCDD/F Total mg 21.2 17.3 17.1 Brickworks mg 15.2 12.9 12.6 Expanded clay mg 6.0 4.4 4.5 Pollutant Source Unit 2010 2011 2012 CO2 Total Gg 21.5 26.8 23.4 Brickworks Gg 15.4 20.2 17.5 Expanded clay Gg 6.0 6.6 5.9 SO2 Total Gg 1.1 1.3 1.1 Brickworks Gg 0.2 0.3 0.3 Expanded clay Gg 0.9 1.0 0.8 PCDD/F Total mg 8.9 11.2 9.7 Brickworks mg 6.6 8.7 7.5 Expanded clay mg 2.3 2.5 2.3

58

1993 38.1 23.9 14.2 2.4 0.4 2.0 15.7 10.2 5.4 2003 39.7 29.3 10.4 1.9 0.4 1.5 16.6 12.6 4.0 2013 26.6 16.1 10.5 1.7 0.2 1.5 10.9 6.9 4.0

1994 52.3 33.4 18.8 3.2 0.5 2.7 21.6 14.3 7.2 2004 45.2 31.3 13.8 2.5 0.5 2.0 18.7 13.4 5.3

1995 47.9 31.1 16.7 2.9 0.5 2.4 19.8 13.3 6.4 2005 50.3 35.0 15.3 2.7 0.5 2.2 20.8 15.0 5.9

1996 50.5 32.4 18.1 3.1 0.5 2.6 20.8 13.9 6.9 2006 55.6 34.7 20.9 3.5 0.5 3.0 22.9 14.9 8.0

1997 56.0 36.0 20.0 3.4 0.5 2.9 23.1 15.4 7.7 2007 64.8 38.0 26.9 4.4 0.6 3.9 26.6 16.3 10.3

1998 52.2 36.3 15.9 2.8 0.5 2.3 21.7 15.5 6.1 2008 43.2 27.2 16.1 2.7 0.4 2.3 17.8 11.6 6.2

1999 50.9 34.8 16.2 2.8 0.5 2.3 21.1 14.9 6.2 2009 22.2 15.7 6.5 1.2 0.2 0.9 9.2 6.7 2.5

Figure 3.5.2 CO2 emissions from the production of ceramics divided in the two sources.

Figure 3.5.3 Total SO2 and PCDD/F emissions from the production of ceramics.

Emissions from this source category are very dependent on new houses being built as well as old ones being renovated. The significant decline in emissions from 2007-2009 was caused by a reduced production resulting from the economic recession caused by the global financial crisis.

3.5.4 EU-ETS data for ceramics The applied methodologies for brickworks and expanded clay producers are specified in the individual monitoring plans that are approved by Danish authorities (DEA) prior to the reporting of the emissions. The production of ceramics applies the Tier 2 methodology for calculating the CO2 emission. The CO2 emission for ceramics production is based on measured carbonate content in all raw materials and consumption of the individual carbonate containing raw materials (Tier 2; ± 5.0 %). The implied CO2 emission factors for the production facilities are based on stoichiometry.

3.5.5 Verification For 2006-2013 the implied emission factors have been derived from CO2 emissions reported by the producers of ceramics to EU-ETS (confidential re59

ports from 21 producers) and production statistics (Statistics Denmark, 2014). The implied emission factor (IEF) for the production of bricks is calculated to 34.8-54.4 kg CO2 per Mg bricks (average: 42.9 kg CO2 per Mg product) for 2006-2013 and the IEF for expanded clay products is 38.3-74.9 kg CO2 per Mg product (average: 49.1 kg CO2 per Mg product) for the same period. Figure 3.5.4 shows the development of these IEFs for the years 1990-2013. The emission factor for both types of ceramics is 0.43971 Mg CO2 per Mg CaCO3.

Figure 3.5.4 Development in implied emission factors for CO2.

Figure 3.5.4 shows fluctuations in the IEFs as would be expected when comparing sale figures from a national statistics with the consumption of raw material in production given by the producers. The major reason for fluctuations in the IEF time series is most likely due to changes in stocks. For 2013, Statistics Denmark (2014) reported a slight decrease in sales of expanded clay products while the producers of these products reported a strong increase in consumption of carbonates; from 13.4 Gg CaCO3-eq in 2012 to 23.8 CaCO3-eq Gg in 2013. This discrepancy causes a strong increase in the IEF for expanded clay products for 2013. The overall IEF for the source category ceramics has been calculated and is compared with the default Tier 1 IEF calculated using production statistics from Statistics Denmark (2014) and default Tier 1 assumptions from IPCC (2006), see Figure 3.5.5. The assumptions applied in order to calculate the default Tier 1 IEF are listed in the following (IPCC, 2006):

60



Consumption of clay: 1.1 Mg clay per Mg product



Carbon content in clay: 10 %



Distribution between carbonates: 85 % limestone/ 15 % dolomite



Order of calcination: 100 %



Emission factors: 0.43971 Mg CO2 per Mg limestone and 0.47732 Mg CO2 per Mg dolomite

Figure 3.5.5 Development in implied emission factors for CO2.

The comparison of IEFs shown in Figure 3.5.5 show good agreement considering the rough assumptions listed above the figure.

3.5.6 Time series consistency and completeness The data sources throughout the time series are not consistent as emissions from 2006-2013 are known and emissions for 1990-2005 are estimated using surrogate data. However, verification of the data confirms that these can be considered being consistent. The inventory is based on companies reporting to EU-ETS, but clay is also burned in minor scale e.g. ceramic art workshops and school art classes. These minor sources are however considered to be negligible and for all intents and purposes the source category of ceramics is considered to be complete.

3.5.7 Input to CollectER The actual applied data on production of ceramics are summarised in Table 3.5.8. Table 3.5.8 Input data for calculating emissions from production of ceramics. Activity data

Year

Parameter

Comment/Source

1990-2013

Sale of products Statistics Denmark; assumptions: 2 kg

1990-2005

Consumption of

Calculated from sale statistics and

carbonates

average carbonate consumption per

per brick

product (2006-2013) 2006-2013

Consumption of

Company reports to EU-ETS

carbonates Emissions

1990-2005

CO2

Calculated from consumption of carbonates

2006-2013

CO2

Company reports to EU-ETS

1990-2013

SO2

EF estimated from environmental re-

1990-2013

PCDD/F

Calculated using emission factor from

ports 2009-2011 Henriksen et al. (2006)

61

3.5.8 Future improvements The SO2 emission factor for bricks and expanded clay products will be improved based on data for recent and coming years. The time series for production of ceramics will be extended to include 19801989. It will be investigated whether emissions of particulate matter can be included for production of ceramics.

3.6

Other uses of soda ash

This section covers the use of soda ash not related to glass production. The following SNAP code is covered: • 04 06 19 Other uses of soda ash

3.6.1 Process description When soda ash (Na2CO3) is used in processes where it is heated, it decomposes and CO2 is released. The reaction is:

Na 2 CO 3 + heat → Na 2 O + CO 2 There are uses of soda ash that is non-emitting since they do not involve heating of the soda ash, e.g. in soaps and detergents. 3.6.2 Methodology Emissions from other uses of soda ash (Na2CO3) are calculated based on a mass balance using national statistics on import/export and the stoichiometric emission factor. Since no detailed information on the specific uses of soda ash is available, it is assumed in the inventory that all of the apparent consumption leads to emissions. There is no production of soda ash in Denmark. Activity data National statistics on import and export and the calculated activity data (supply) are presented in Table 3.6.1. Table 3.6.1 Statistics for other uses of soda ash, Gg. 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 Import 54.6 55.8 56.4 52.9 42.1 47.6 44.8 46.7 41.2 41.6 Export 0.1 0.0 0.0 0.2 1.1 2.1 1.1 0.0 0.0 0.2 Glass production 26.1 22.8 20.5 19.9 19.9 18.8 18.8 18.8 23.7 22.3 Supply 28.4 33.0 35.9 32.8 21.1 26.7 25.0 27.8 17.5 19.1 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 Import 42.0 45.3 41.7 43.1 43.1 59.5 44.1 44.1 41.8 28.0 Export 0.3 0.1 0.9 0.1 0.1 0.0 0.0 0.0 0.0 0.5 Glass production 19.4 19.6 19.1 16.9 17.0 16.6 16.9 18.2 17.8 10.9 Supply 22.3 25.7 21.7 26.1 26.1 42.9 27.1 25.9 24.0 16.6 2010 2011 2012 2013 Import 36.5 22.9 31.7 30.2 Export 0.1 0.1 0.1 0.1 Glass production 10.7 10.9 11.2 8.2 Supply 25.7 11.9 20.4 21.9

62

The activity data is calculated using the following equation. Emission factors The applied emission factor for other uses of soda ash is 0.41492 Mg CO2 per Mg Na2CO3 based on the stoichiometry of the chemical conversion. The calculation assumes a calcination factor of 1.

3.6.3 Emission trend The emission trend for the CO2 emission from other uses of soda ash is presented in Figure 3.6.1.

Figure 3.6.1 CO2 emissions from other uses of soda ash.

Information on the uses of soda ash outside the glass industry is scarce, and descriptions of the trend development are therefore not available.

3.6.4 Verification Statistical data collected from Statistics Denmark (2014) has been checked against data from Eurostat (2014) for 2000-2013, see Table 3.6.2. Table 3.6.2 Comparison of statistical data for net import of soda ash, Mg. 2000

2001

2002

2003

2004

2005

2006

2007

2008

2009

2010

2011

2012

2013

Statistics Denmark 41.65 45.25 40.86 43.03 43.07 59.54 44.06 44.04 41.78 27.52 36.41 22.79 31.61 30.12 Eurostat Difference

41.64 45.24 44.30 43.05 38.72 50.35 40.83 44.04 41.78 28.89 31.28 0.01

0.01

-3.44

-0.01

4.36

9.19

3.23

0.00

0.00

-1.37

5.13

nd 34.86 29.50 nd

-3.25

0.62

nd: No data

The comparison shows good agreement for most years.

3.6.5 Time series consistency and completeness The same methodology is used for calculating emissions for the entire time series, the source category of other uses of soda ash is therefore considered to be consistent. Calculations are based on a national mass balance and are therefore also considered to be complete. Though it is not possible to document, it is likely that this category is overestimated as it based on a worst case scenario. 63

3.6.6 Input to CollectER The actual applied data on other uses of soda ash are summarised in Table 3.6.3. Table 3.6.3 Input data for calculating emissions from other uses of soda ash. Year

Parameter

Comment/Source

Activity data

1990-2013

Import/export statistics

Statistics Denmark

Emissions

1990-2013

CO2

Calculated using the stoichiometric emission factor

3.6.7 Future improvements There are no planned improvements for the category of other uses of soda ash.

3.7

Flue gas desulphurisation

Flue gas cleaning systems utilising different technologies are primarily present at major combustion plants i.e. power plants and combined heat and power plants using coal as well as waste incineration plants. The following SNAP code is covered: • 04 06 18 Limestone and dolomite use - Flue gas cleaning, wet, power plants and waste incineration plants

3.7.1 Process description Three kinds of flue gas cleaning for acidic gasses are applied in Denmark (Johnsson, 1999): • Dry flue gas cleaning • Semi-dry flue gas cleaning • Wet flue gas cleaning However, only wet flue gas cleaning leads to process emissions. The only relevant pollutant is CO2. The chemistry of the wet flue gas cleaning methodologies is presented below.

3.7.2 Methodology The emission of CO2 from wet flue gas cleaning can be calculated from the following equation: SO2 (g) + ½O2 (g) + CaCO3 (s) + 2H2O (l) → CaSO4,2H2O (s) + CO2 (g) The overall equation can be broken down to a number of individual equations. The emission factor is depending on how the process is optimised with the following targets: to achieve high degree of desulphurisation, to reduce the consumption of calcium carbonate, and to produce gypsum of saleable quality. From the equation the emission factors can be calculated to: • 0.2325 Mg CO2/Mg gypsum • 0.4397 Mg CO2/Mg CaCO3 The emission factor for gypsum is used in the inventory when information on calcium carbonate consumption by power plants and waste incineration plants is not available. 64

Energinet.dk compile environmental information related to energy transformation and distribution. Since the waste incineration plants with desulphurisation are all power producers, these plants are also included in the data from Energinet.dk (2014). Statistics on the generation of gypsum are available from Energinet.dk (2014) for the entire time series. However, for 2006-2013 information on consumption of CaCO3 at the relevant power plants and waste incineration plants has been compiled from EU-ETS and used in the calculation of CO2 emission from flue gas cleaning. The consumed amount of limestone is used as activity data for the years where these data are available from EU-ETS (2006-2013). Information on limestone consumption is not available before the implementation of the mandatory environmental reports in 1998. The consumption of other carbonates than limestone (e.g. dry desulphurisation product (TASP)) is measured by the individual power plants and is added to the limestone consumption in CaCO3-equivalents. The power plants equipped with wet flue gas cleaning are: • • • • • • • • •

Amagerværket Asnæsværket Avedøreværket Enstedværket Esbjergværket Grenå Kraftvarmeværk Nordjyllandsværket Randersværket (Verdo Produktion A/S) Stigsnæsværket

These plants are or have been coal fired CHP plants. As some of the plants are rebuilt to combust biomass instead of coal the need for flue gas desulphurisation will cease (e.g. Enstedværket and Randersværket). The waste incineration plants identified to be provided with wet fluegas cleaning are: • • • • • • • • • •

Affaldscenter Aarhus KARA (Roskilde Forbrænding) Kommunekemi L90 Affaldsforbrænding Odense Kraftvarmeværk Reno-Nord RenoSyd Sønderborg Kraftvarme Svendborg Kraftvarme Vestforbrænding

Activity data During the time series this source has increased due to more plants being fitted with desulphurisation. However, since the main use is in coal fired plants, flue gas desulphurisation is decreasing as some of the coal fired power plants are rebuilt to combust biomass and the need for flue gas desulphurisation declines. Since 2006, three of the nine coal fired power plants 65

have changed to alternative fuels in 2013 and desulphurisation has ceased from these plants. The Danish waste incineration plants are in general smaller than the coal combustion facilities and owned by smaller companies. Of the approximately 30 waste incineration plants with flue gas desulphurisation only one third uses wet flue gas cleaning. For 1990-2005 the production of gypsum is used for calculating the CO2 emission and for 2006-2013 the consumption of CaCO3 is used. The limestone consumption data for the environmental reports (1998-2005) has not been used because this would increase the inconsistency. The applied activity data are presented in Table 3.7.1 and Figure 3.7.1. Table 3.7.1 Activity data for flue gas desulphurisation, Gg. 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 Gypsum production1 41.6 82.0 90.5 121.6 209.4 211.5 348.1 346.7 350.4 381.7 CaCO3 consumption2 - 199.7 202.2 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 Gypsum production1 354.3 355.7 331.7 283.4 237.7 220.4 296.4 296.4 215.7 176.4 CaCO3 consumption2, 3 209.4 194.6 177.1 168.3 128.3 110.8 156.9 107.4 84.9 85.8 2010 2011 2012 2013 Gypsum production1 185.8 147.6 100.9 153.3 CaCO3 consumption3 94.0 75.8 41.0 57.9 1 Energinet.dk (2014). 2 1998-2005: Environmental reports of the individual plants. 3 2006-2013: EU-ETS of the individual plants.

Figure 3.7.1 Activity data for flue gas desulphurisation.

The activity data level varies with the coal consumption that again varies greatly with electricity import/export. Emission factors From the chemical reaction equation presented in the “Methodology” section, the stoichiometric emission factor can be calculated to 0.2325 Mg CO2 per Mg gypsum produced. This emission factor is used in the inventory when information on calcium carbonate consumption by power plants and waste incineration plants is not available from EU-ETS (1990-2005).

66

The emission factor applied when using limestone consumption as activity data is the stoichiometric emission factor 0.43971 Mg CO2 per Mg CaCO3 (2006-2013).

3.7.3 Emission trend The emission trend for CO2 emitted from flue gas cleaning at CHP plants and waste incineration plants is presented in Table 3.7.2. Table 3.7.2 Emission of CO2 from wet flue gas cleaning, Gg. 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 Desulphurisation

9.67 19.06 21.04 28.28 48.69 49.17 80.94 80.61 81.46 88.74 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

Desulphurisation

82.38 82.69 77.13 65.89 55.28 51.25 68.99 47.22 37.31 37.74 2010 2011 2012 2013

Desulphurisation

41.35 33.33 18.05 25.48

The CO2 emission from flue gas desulphurisation in CHP plants increased significantly during the 1990s due to the increased use of wet flue gas desulphurisation. Since then the emissions have decreased due to the decrease in coal consumption.

3.7.4 Verification Three datasets are available within the time series. Figure 3.7.2 compares emissions based on these different sets of activity data and generally shows a good agreement between the different methodologies.

Figure 3.7.2

CO2 emissions from flue gas desulphurisation calculated with different

methodologies; from gypsum production and limestone consumption compiled by environmental reports and EU-ETS respectively.

Emissions calculated from the limestone consumption data provided by the environments reports vary with -5 % (2005) to +12 % (2000) from the emission based on gypsum production. And emissions calculated from the limestone consumption data provided by the EU-ETS vary with up to 31 % (2007) from the emissions based on gypsum production.

67

3.7.5 Time series consistency and completeness The methodology for calculating emission from flue gas desulphurisation is inconsistent. However, as proven in the “Verification” section above, there is no gap in the emission data derived from different sources and the emissions are therefore considered to be consistent. The source category is considered to be complete.

3.7.6 Input to CollectER The input data/data sources are presented in Table 3.7.3. Table 3.7.3 Input data for calculating emissions from flue gas desulphurisation. Year Activity data 1990-2013 1998-2005

Parameter

Comment/Source

Gypsum generation Energinet.dk (2014) Limestone

Environmental reports

consumed 2006-2013

Limestone

EU-ETS

consumed Emission

1990-2013

CO2

Estimated by use of stoichiometric emission factor

3.7.7 Future improvements Further investigation will be put into identifying the desulphurisation methodologies used at waste incineration plants for every year in the time series as some plants might have switched technology since 1990 (i.e. dry/semidry/wet).

3.8

Mineral wool production

Rockwool situated at three localities in Denmark: Hedehusene6, Vamdrup and Øster Doense produces mineral wool. The following SNAP-codes are covered: • 03 03 18 Mineral wool (except binding) • 04 06 18 Limestone and dolomite use Emissions associated with the fuel use are estimated and reported in the energy sector. The following pollutants are included for the lime production process: • • • • •

CO2 CO NH3 Particulate matter: TSP, PM10, PM2.5 Persistent organic pollutants: PCDD/F

The following description, as well as data, is based on an environmental report (Rockwool, 2003).

6

68

The melting of minerals (cupola) has been closed down in 2002.

3.8.1 Process description Mineral wool is produced from mineral fibres and a binder (that is hardened to bakelite). The mineral fibres are produced from stone, bauxite, clay, limestone and cement. In addition to own waste products a number of other waste products are included in the production: aluminium silicate from the iron industry, slags from steelworks, filter dust from cement industry and also used growing media based on mineral wool. The raw materials are melted in a cupola fired by coke and natural gas. The consumption of raw material as well as amount of produced mineral wool is confidential. The energy consumption is reported as electricity (GWh) and fuels (GWh) with a distribution of fuels between coke and natural gas at 60 %/40 %.

3.8.2 Methodology Information on emissions from some years has in combination with yearly raw material consumption been used to extrapolate the emissions to other years. The data have been extracted from company reports (Rockwool, 2014b), EU-ETS (Rockwool, 2014a) and reports to PRTR. Implied CO2 emission factors have been calculated for 2006-2010 and with these emissions are extrapolated back to 1990. The proxy activity data (i.e. limestone consumed) is calculated from the CO2 emission. The proxy activity data set is necessary because the Kyoto Protocol, the UNFCCC and the UNECE requires the categories of ceramics, other uses of soda ash, flue gas desulphurisation and mineral wool production to be summarised. When activity data for the source categories ceramics, other uses of soda ash and flue gas desulphurisation are given in CaCO3 equivalents consumed, then activity data for mineral wool production should be given in the same unit. All calculations are performed for the three factories individually. Activity data Data on the produced amount of mineral wool is confidential; however the consumption of raw materials and the consumption of carbonates at the three Danish Rockwool factories are available from the annual environmental reports (Rockwool, 2014b) and EU-ETS (Rockwool, 2014a). The different carbonate raw materials such as lime, waste, bottom ash etc. are added up to the proxy activity data of limestone equivalents consumed presented in Table 3.8.1 and Figure 3.8.1. The consumption of raw materials is available for 1995-2013 and the consumption of carbonates for 2006-2013. Raw material consumption for 19901994 is assumed constant as the average of the years 1995-1999. The consumption of carbonates for 1990-2005 is estimated from the CO2 emission.

69

Table 3.8.1 Activity data for mineral wool production, Gg. 1990 Consumption of raw materials Consumption of CaCO3 equivalents

Consumption of raw materials Consumption of CaCO3 equivalents

Consumption of raw materials Consumption of CaCO3 equivalents

1991

1992

1993

1994

1995

1996

1997

1998

1999

195.6 195.6 195.6 195.6 195.6 196.5 188.3 182.2 204.0 207.0 17.9

17.9

17.9

17.9

17.9

18.0

17.2

16.5

18.6

18.9

2000

2001

2002

2003

2004

2005

2006

2007

2008

2009

190.0 174.0 169.0 143.0 172.0 172.0 181.0 205.0 181.0 145.0 17.3

15.6

15.9

15.0

2010

2011

2012

2013

18.1

18.0

15.5

19.3

22.6

16.5

155.0 146.0 123.0 122.4 17.1

16.8

15.0

13.8

Figure 3.8.1 Activity data for mineral wool production.

The consumption of carbonates at the Doense factory has decreased drastically the last couple of years, while the raw material consumption has only decreased slightly. Emission factors From 2006 the CO2 process emission data have been obtained from the company reports to the EU-ETS (Rockwool, 2014a). For 1990-2005, the CO2 emission is estimated from the calculated factor of “CO2 emission per raw material consumption” (average for 2006-2010) and the raw material consumption time series. CO2 emissions for 1990-1994 are estimated as the constant average of 1995-1999. Emissions of CO and NH3 are available for the years 2001, 2004 and 20072013 and emissions of particulate matter are available for 1995-2013. The measurements show a strong decrease in CO emissions from the two mineral wool factories in 2009 and 2010 respectively due to installation of abatement equipment. For PCDD/F, the inventory is based on measured emissions from 2004 (Henriksen et al., 2006). PM10 and PM2.5 are estimated from the TSP emission as 90 % and 70 % of TSP respectively. Implied emission factors are calculated for all years where measured emissions are available; these are used to estimate emissions for all other years in the time series back to 1990. The implied emission factors are presented in Table 3.8.2 70

Table 3.8.2 Emission factors for mineral wool production Hedehusene Vamdrup Doense Pollutant Unit CO2 CO NH3 TSP PCDD/ F

Source/Comment

Mg/Mg raw material Mg/Mg raw material Mg/Mg raw material Mg/Mg raw material

0.089 0.002 0.0003

0.047 0.038 0.001 0.0005

0.045 IEF calculated for 2006-2010 0.068 IEF average 2001, 2004, 2007, 2008 0.002 IEF average 2001, 2004, 2007-2012 0.0007 IEF average 2000-2013

mg/Mg raw material

-

0.0003

0.0003

Henriksen et al. (2006)

3.8.3 Emission trend The emission trends for emission of CO2, CO, NH3, TSP, PM10, PM2.5 and PCDD/F from production of mineral wool at three (from 2006 two) locations are presented in Table 3.8.3. Table 3.8.3 Emissions from production of mineral wool. CO2 CO NH3

Unit

1990

1991

1992

1993 1994 1995

1996

1997

1998

1999

Gg Gg Gg

7.9 12.0 0.3

7.9 12.0 0.3

7.9 12.0 0.3

7.9 12.0 0.3

7.9 12.0 0.3

7.9 11.9 0.3

7.6 11.5 0.3

7.3 11.1 0.3

8.2 12.6 0.3

8.3 12.7 0.3

64.9

PCDD/F mg

64.9

64.9

64.9

64.9

65.3

62.5

60.5

67.6

68.7

Unit

2000

2001

2002

2003 2004 2005

2006

2007

2008

2009

Gg Gg Gg Mg

7.6 12.0 0.3 71

6.9 10.6 0.3 80

7.0 11.4 0.3 81

6.6 10.3 0.2 103

7.9 15.6 0.4 111

7.9 11.6 0.3 115

6.8 9.1 0.3 125

8.5 6.4 0.4 125

9.9 6.5 0.2 111

7.2 2.4 0.2 77

PM10 Mg PM2.5 Mg PCDD/F mg

64 50 63

72 56 58

73 57 56

86 67 47

99 77 57

103 80 57

113 88 60

112 87 68

100 77 60

70 54 48

Unit

2010

2011

2012

2013

Gg Mg Gg

7.5 11.01 0.2

7.4 13.01 0.2

6.6 31.01 0.2

6.0 10.01 0.2

CO2 CO NH3 TSP

CO2 CO NH3

TSP Mg 78 77 62 62 PM10 Mg 70 69 56 56 PM2.5 Mg 55 54 43 43 PCDD/F mg 51 48 41 48 1 Kindly notice that the unit has changed for CO from 2009 to 2010 due to installation of abatement equipment.

3.8.4 Time series consistency and completeness The source category of mineral wool production is complete but inconsistent, the inconsistency occurs because emissions for 2006 onward are known (EU-ETS and PRTR) but emissions for 1990-2004 are estimated (with few exceptions.

3.8.5 Input to CollectER The input data/data sources are presented in Table 3.8.4.

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Table 3.8.4 Input data for calculating emissions from mineral wool production Year Activity data 1995-2013 2006-2013 Emissions

Parameter

Comment/Source

Raw material consumption Rockwool (2014b) Carbonate consumption

2001, 2004, 2007-2013 CO, NH3

Rockwool (2014a) PRTR

2000-2013

TSP

Rockwool (2014b), PRTR

2004

PCDD/F

Henriksen et al. (2006)

3.8.6 Future improvements There are no planned improvements for the source category of mineral wool production.

72

4

Chemical industry

The sector Chemical industry (CRF and NRF 2B) covers the following industries relevant for the Danish air emission inventory of greenhouse gases and other air pollutants: • • • • •

Nitric and sulphuric acid production; see section 4.2 Catalyst and fertiliser production; see section 4.2.1 Pesticide production; see section 4.4 Production of chemical ingredients; see section 4.5 Production of tar products; see section 4.6

4.1

Greenhouse gas emissions

The greenhouse gas emission time series for the source categories within Chemical Industry (2B) are presented in Figure 4.1.1 and individually in the subsections below (Sections 4.2 – 4.6). The following figure gives an overview of which source categories that contribute the most to greenhouse emissions throughout the time series.

Figure 4.1.1 Emission of CO2 equivalents from the individual source categories compiling 2B Chemical Industry, Gg.

Greenhouse gas emissions from Chemical Industry are made up almost entirely by N2O emissions from the production of nitric acid; only 0.1 % (19902003) to 0.2 % (2004) stems from the production of catalysts, making the emission invisible in the figure above. The production of nitric acid ceased in the middle of 2004.

4.2

Nitric and sulphuric acid production

The production of sulphuric acid, nitric acid as well as NPK fertilisers has been concentrated at one company; Kemira GrowHow A/S situated in Fredericia (Kemira GrowHow, 2004). The production of sulphuric acid and nitric acid/fertiliser ceased in 1996/7 and in the middle of 2004, respectively. The following SNAP codes are covered: • 04 04 01 Sulphuric acid • 04 04 02 Nitric acid 73

The following pollutants are included for the nitric and sulphuric acid production processes: • • • • •

SO2 NOx N2O NH3 Particulate matter: TSP, PM10, PM2.5

4.2.1 Process description The inputs to the processes are ammonia, potash, raw phosphate, phosphoric acid/sulphuric acid, dolomite, and other unspecified raw materials. The products are fertilisers (nitrogen, phosphate, and potassium), nitric acid, potassium nitrate, phosphates (feedstock for domestic animals). The production facility consists of different plants: nitric acid plant, NPK-plant, potassium nitrate plant, and dicalcium phosphate plant. Up to 1997 sulphuric acid was also produced at Kemira. A gas turbine and incineration of ammonia supplies the main part of the electricity necessary for the different processes. Ammonia is incinerated at the nitric acid plant generating nitric acid as well as energy (steam and electricity). The processes are (HNO3): (I) (II) (III)

4 NH3 + 5 O2 → 4 NO + 6 H2O 2 NO + O2 → 2 NO2 3 NO2 + H2O → 2 HNO3 + NO

Other reactions: (IV) (V)

4 NH3 + 3 O2 → 2 N2 + 6 H2O 4 NH3 + 4 O2 → 2 N2O + 6 H2O

Air pollutants relevant to be included for fertiliser production are NH3, N2O, and NOx. The environmental report (Kemira GrowHow, 2004) presents aggregated emissions for the entire facility. This information is supplemented with direct contact to the company.

4.2.2 Methodology Information on emissions from the production of nitric acid, sulphuric acid and fertiliser is obtained from environmental reports (Kemira GrowHow, 2004), contact to the company (Personal communication with Gert Jacobsen, Technical Sales Support Manager, Process Chemicals, Kemira GrowHow Danmark A/S, 26 September 2005 and previous mail correspondences) as well as information from the county. Emission measurements are available for some years see Table 4.2.1. Implied emission factors are calculated for the years where measurements are available; these implied emission factors are then used to calculate emissions for the remaining years. The following table gives an overview of for which years measured emissions are available for the different pollutants.

74

Table 4.2.1 Availability of measured process emissions (Kemira GrowHow 2004) Process

Pollutant

Nitric acid

NH3

1989-2004

N2O

2002

Sulphuric acid

Years

NOx

1990, 1994-2002

TSP

2000-2004

SO2

1990, 1994-1997

The emission for SO2 and NOX for 1991 to 1993 was estimated by using interpolated emission factors and activity data. Specific information on applied technology is not available; however, the N2O emission factor measured by the Danish nitric acid plant is in accordance with the default emission factors for medium to high pressure plants presented by IPCC (2006). The Danish production of sulphuric acid ceased in 1996/7 and the production of nitric acid in Denmark ceased in the middle of 2004 and the company relocated the production to a more modern facility in another country. Activity data The activity data regarding production of nitric and sulphuric acids are obtained through personal communication with Gert Jacobsen, Technical Sales Support Manager, Process Chemicals, Kemira GrowHow Danmark A/S, 26 September 2005 and previous mail correspondences and Kemira GrowHow (2004). The data are presented in Table 4.2.2. Table 4.2.2 Production of nitric and sulphuric acid, Gg. 1980

1981

1982

1983

1984

1985

1986

1987

1988

350 188

350 188

350 188

350 188

350 188

350 188

315 97

357 126

383 184

1989

1990

1991

1992

1993

1994

1995

1996

1997

402 215

450 148

412 65

364 58

343 63

348 80

390 102

360 55

366 2

1998

1999

2000

2001

2002

2003

2004

348 NO

410 NO

433 NO

382 NO

334 NO

386 NO

229 NO

Nitric acid Sulphuric acid Nitric acid Sulphuric acid Nitric acid Sulphuric acid NO: Not occurring

Production of sulphuric acid decreased from approximately 150 to 60 Gg from 1990 to 1996, and production of nitric acid decreased from approximately 450 to 229 Gg from 1990 to 2004. Overall, production of fertiliser decreased from approximately 800 to approximately 400 Gg from 1990 to 2004. Emission factors The calculated implied emission factors are presented in Table 4.2.3 together with the standard emission factors given by IPCC (2006) and EMEP/EEA (2013).

75

Table 4.2.3 Emission factors for production of nitric acid and sulphuric acid in Denmark compared with standard emission factors, kg per Mg produced. Process

Pollutant

Mean

Range

Standard EF

Nitric acid

NH3

0.11

0.03 - 0.26

0.01

N2O

7.48

-

2-2.51 52 73 94

NOx

1.36

0.95 - 1.79

3.5 - 125 7.56 37 0.58 0.4-0.99

Sulphuric acid

TSP

0.88

0.84-0.93

SO2

2.07

1.40-2.69

3 – 9.110 3.511 1712

1

Modern plant with abatement technology (IPCC, 2006). Atmospheric pressure plant (low pressure) (IPCC, 2006). 3 Medium pressure combustion plant (IPCC, 2006). 4 High pressure plant (IPCC, 2006). 5 Low pressure (EMEP/EEA, 2013). 6 Medium pressure (EMEP/EEA, 2013). 7 High pressure (EMEP/EEA, 2013). 8 Direct strong acid process (EMEP/EEA, 2013). 9 Modern plant with abatement technology (EMEP/EEA, 2013). 10 Contact process with intermediate absorption; different gas conditions (EMEP/EEA, 2013). 11 Wet/dry process with intermediate condensation/absorption (EMEP/EEA, 2013). 12 Wet contact process (EMEP/EEA, 2013). 2

The calculated emission factors for both SO2 and NOx have decreasing trends. The emission factors for NOx and SO2 (based on actual emissions) are in the low end compared with the standard emission factors, whereas; the factors for NH3 and N2O are in the high end. PM10 and PM2.5 are estimated from the distribution between TSP, PM10 and PM2.5 (1/0.8/0.6) from CEPMEIP (Values for ‘Production of nitrogen fertiliser’).

4.2.3 Emission trend Trends for emissions of NH3, N2O, NOx, SO2, TSP, PM10, and PM2.5 from production of nitric acid and sulphuric acid are presented in Table 4.2.4.

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Table 4.2.4 Emissions from nitric and sulphuric acid production. Unit

1980

1981

1982

1983

1984

1985

1986

1987

1988

1989

NH3 N2O NOx SO2

Mg Gg Mg Mg

12.2 2.62 627 415

12.2 2.62 627 415

12.2 2.62 627 415

12.2 2.62 627 415

12.2 2.62 627 415

12.2 2.62 627 415

11.0 2.35 564 214

12.4 2.67 639 278

13.3 2.86 686 407

14.0 3.01 720 475

Unit

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

NH3

Mg

12.0

22.0

35.0

49.0

91.0

62.0

62.0

37.0

12.0

24.0

N2O NOx SO2

Gg Mg Mg

3.36 806 327

3.08 731 151

2.72 640 142

2.56 597 162

2.60 600 215

2.92 612 217

2.69 504 77

2.74 571 3

2.60 419 NO

3.07 451 NO

Unit

2000

2001

2002

2003

2004

NH3 N2O NOx

Mg Gg Mg

13.0 3.24 413

30.0 2.86 410

50.0 2.50 397

56.0 2.89 459

33.0 1.71 272

SO2 TSP PM10 PM2.5

Mg Mg Mg

NO 362 290 217

NO 346 277 208

NO 310 248 186

NO 323 258 194

NO 192 153 115

NO: Not occurring

The emission trend for the N2O emission from nitric acid production is presented in Figure 4.1.1. The trend for N2O from 1990 to 2003 shows a decrease from 3.4 to 2.9 Gg, i.e. -14 %, and a 41 % decrease from 2003 to 2004. However, the activity and the corresponding emission show considerable fluctuations in the period considered and the decrease from 2003 to 2004 can be explained by the closing of the plant in the middle of 2004. The emission trends for the air pollutants are presented in Figure 4.2.1. The time series for SO2 follows the amount of sulphuric acid produced, i.e. the fluctuation follows the activity until the activity ceased in 1997. The same is the case for NOX from production of nitric acid.

Figure 4.2.1 Emissions from nitric and sulphuric acid production.

77

4.2.4 Time series consistency and completeness The applied methodology regarding N2O is considered to be consistent. The activity data are based on information from the company. The emission factor applied has been constant for the whole time series and is based on measurements performed in 2002. The production equipment has not been changed during the period. The source category of nitric acid production is complete.

4.2.5 Input to CollectER The input data/data sources are presented in Table 4.2.5. Table 4.2.5 Input data for calculating emissions from nitric and sulphuric acid production. Year Activity data 1985-2004

Parameter

Comment/Source

HNO3, H2SO4 Kemira GrowHow (2004) and personal communication with Gert Jacobsen, Technical Sales Support Manager, Process Chemicals, Kemira GrowHow Danmark A/S, 26 September 2005 and previous mail correspondences

Emissions

1980-1989

NOx, SO2

1990, 1994-2002 NOx, SO2

IEF assumed to be the same as in 1990 Personal communication with Gert Jacobsen, Technical Sales Support Manager, Process Chemicals, Kemira GrowHow Danmark A/S, 26 September 2005 and previous mail correspondences

1989 (2000)-2004 NH3, TSP

Kemira GrowHow (2004)

1980-1988

NH3

IEF assumed to be the same as in 1989

2002

N2O

Personal communication with Gert Jacobsen, Technical Sales Support Manager, Process Chemicals, Kemira GrowHow Danmark A/S, 26 September 2005 and previous mail correspondences

1980-2001, 2003- N2O

IEF assumed to be the same as in 2002

4 2000-2004

PM10, PM2.5

Distribution between TSP, PM10, and PM2.5 from CEPMEIP

4.2.1 Future improvements Emissions of BC will be added for nitric acid production.

4.3

Catalyst and fertiliser production

Production of a wide range of catalysts and potassium nitrate (fertiliser) is concentrated at one company: Haldor Topsøe A/S situated in Frederikssund. The following SNAP code is covered: • 04 04 16 Other: catalysts The following pollutants are included for the catalyst production process: • • • • 78

CO2 NOx NH3 Particulate matter: TSP, PM10, PM2.5

4.3.1 Process description The inputs to the processes are: • Solid raw materials: salts, oxides, carbonates, intermediates etc. and metals • Liquid raw materials: acidic and alkaline solutions, dissolved metal salts, methanol etc. • Gaseous raw materials: ammonia, hydrogen, nitrogen The products are catalysts for many purposes (for hydro-processing, ammonia, DeNOx, methanol, hydrogen and synthesis gas, sulphuric acid, formaldehyde, and combustion catalysts) and potassium nitrate (fertiliser).

4.3.2 Methodology The processes involve carbonate compounds i.e. the process leads to emissions of CO2. The company has estimated the emission of CO2 from known emission factors for incineration of natural gas and LPG and from information on the raw materials containing carbonate. The contribution from carbonate compounds is estimated to be the difference between the total CO2 emission reported in the environmental reports (Haldor Topsøe, 2013) and the CO2 emission from energy consumption reported to EU-ETS (Haldor Topsøe, 2014). Implied emission factors were calculated for 2003-2009 using this method. For the years 1985-1995, the production is estimated as the constant average of the production in 1997-2001. Potential retention of CO2 in the flue gas cleaning system has not been taken into account. The emission of NOX, NH3 and TSP from production of catalysts and fertilisers is measured yearly from 1996 to 2013 (TSP from 2000 to 2013) (Haldor Topsøe, 2013). The emissions were extrapolated back to 1985. PM10 and PM2.5 are estimated from the distribution between TSP, PM10 and PM2.5 (1/0.8/0.6) from CEPMEIP (Values for ‘Production of nitrogen fertiliser’). The process-related NOX emission has been estimated as 80 % of the total NOX emission; Haldor Topsøe reports this assumption in their environmental report (Haldor Topsøe, 2013). The plant is equipped with DeNOx flue gas cleaning systems and depending of the efficiency of the cleaning system an emission of NH3 will occur. Activity data The activity data regarding production of catalysts and fertiliser are obtained through environmental reports from Haldor Topsøe. The data are presented in Table 4.3.1.

79

Table 4.3.1 Production of catalysts and potassium nitrate, Gg (Haldor Topsøe, 2014). 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 Catalysts1 Potassium nitrate1 Catalysts+KNO3

17.0 18.4 35.4

17.0 18.4 35.4

17.0 18.4 35.4

17.0 18.4 35.4

17.0 18.4 35.4

17.0 18.4 35.4

17.0 18.4 35.4

17.0 18.4 35.4

17.0 18.4 35.4

17.0 18.4 35.4

1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 1

Catalysts Potassium nitrate1 Catalysts+KNO3

17.0 18.4 35.4

17.0 18.4 35.4

16.9 18.8 35.6

14.4 15.6 30.0

17.0 18.1 35.1

17.2 19.2 36.4

19.5 20.4 39.9

19.3 21.7 41.0

15.3 19.6 34.8

22.0 27.1 49.2

2005 2006 2007 2008 2009 2010 2011 2012 2013 Catalysts

23.2

20.3

20.7

28.1

22.5

19.2

22.3

22.9

23.0

Potassium nitrate Catalysts+KNO3

23.3 46.5

24.9 45.2

27.0 47.7

31.4 59.5

22.1 44.6

24.8 46.4

25.3 47.5

32.9 55.8

33.0 56.0

1

Production 1985-1996 assumed to be the average of 1997-2001.

Emission factors The average calculated CO2 implied emission factor for 2003-2009 is 0.0241 Mg CO2 per Mg product; this factor is applied for the entire time series. The CO2 IEF is presented together with those of NOx, NH3 and particles in Table 4.3.2. Table 4.3.2 Implied emission factors for production of catalysts and potassium nitrate, Mg per Gg product. Pollutant

CO2

NOx

Range 0.02-0.03 0.30-1.76 1 Mean 0.024 0.8192 1 Average for 2003-2009. 2 Average for 1985-2013. 3 Average for 2000-2013.

NH3

TSP

PM10

PM2.5

0.26-3.70 0.9332

0.11-0.59 0.3663

0.09-0.48 0.2933

0.06-0.36 0.2203

PM10 and PM2.5 are estimated from the distribution between TSP, PM10 and PM2.5 (1/0.8/0.6) from CEPMEIP (Values for ‘Production of nitrogen fertiliser’).

4.3.3 Emission trend Trends for emissions of CO2, NH3, NOx, TSP, PM10, and PM2.5 from production of catalysts and fertilisers are presented in Table 4.33.

80

Table 4.3.3 Emissions from catalyst and fertiliser production at Haldor Topsøe, Mg. 1989 1990 1991 1992 1993 1994 1985 1986 1987 1988 CO2 853 853 853 853 853 853 853 853 853 853 NH3 13 13 13 13 13 13 13 13 13 13 NOx 36 36 36 36 36 36 36 36 36 36 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 CO2 853 853 859 723 845 877 961 988 840 1185 NH3 13 13 13 13 9 14 71 43 57 68 NOx 36 39 40 53 58 34 12 22 16 30 TSP 19 19 19 11 12 PM10 15 15 15 9 10 PM2.5 11 11 11 7 7 2005 2006 2007 2008 2009 2010 2011 2012 2013 CO2 1120 1089 1150 1433 1074 1060 1146 1345 1350 NH3 79 88 107 111 165 123 20 18 21 NOx 30 37 18 19 18 17 21 19 20 TSP 23 12 25 26 16 26 7 6 10 PM10 18 10 20 21 13 21 5 5 8 PM2.5 14 7 15 16 10 16 4 4 6

From 1990 to 2013, the emission of CO2 from the production of catalysts/fertilisers has increased from 0.9 to 1.4 Gg with maximum in 2008, due to an increase in the activity as well as changes in raw material consumption. The trend for the CO2 emission from the production of catalysts and fertilisers is presented in Figure 4.3.1.

Figure 4.3.1 Emission of CO2 catalyst/fertiliser production Gg.

The emission of NH3 shows an increasing trend throughout the ‘00s; from 14 Mg in 2000 to 165 Mg in 2009; in the same period the IEF fluctuates around the average 0.54 Mg per Gg but shows no trend. For the remaining time series, the NH3 emission only varies between 9-21 Mg with the exception of 2010 where 123 Mg were emitted. The emission of NOX decreases from the end of the ‘90s to the beginning of the ‘00s, in spite of the increasing production. Emissions of NOx, NH3 and TSP are shown in Figure 4.3.2.

81

Figure 4.3.2 Emissions from catalyst and fertiliser production.

4.3.4 Time series consistency and completeness Although activity data are not available for the full time series for this source category, it is still considered to be consistent. The activity data prior to 1996 are estimated as the constant average of the production in 1997-2001 while activity data for 1996 onward are known from the producer. The source category of catalyst production is complete.

4.3.5 Input to CollectER The input data/data sources are presented in Table 4.3.4. Table 4.3.4 Input data for calculating emissions from catalysts/fertiliser production. Year

Parameter

Activity

1985-1995

KNO3, catalysts Estimated

1996-2013

KNO3, catalysts Haldor Topsøe (2013)

Emissions

1985-1995

CO2, NOx, NH3

Estimated

1996-2013

Comment/Source

CO2, NOx, NH3

Haldor Topsøe (2013); information on distri-

TSP

bution between energy and process related

PM10, PM2.5

Distribution between TSP, PM10, and PM2.5

CO2 as well as NOx is presented 2000-2013

from CEPMEIP

4.3.6 Future improvements Through contact with the plant, it will be attempted to verify the assumptions on the split between combustion and process emissions for CO2 and NOx. Emissions of BC will be added for catalyst/fertiliser production.

4.4

Pesticide production

The production of pesticides in Denmark is concentrated at one company: Cheminova A/S situated in Harboøre. The following SNAP code is covered: • 04 05 25 Pesticide production

82

The following pollutants are included for the pesticide production process: • SO2 • NMVOC Because it is not possible to separate process and fuel emissions reported in the company’s environmental reports, SO2 emissions for this source category includes emissions from fuel consumption.

4.4.1 Process description Cheminova produce a wide range of pesticides, insecticides and biocides based on organic chemical syntheses. A main group of products are organophosphates and intermediates of organophosphate type to internal as well as external use. Due to the character of the products the identity of the raw materials is often confidential. The final formulation of the products is often done at affiliated companies in other parts of the world. Secondary products are P fertiliser and regenerated sulphur.

4.4.2 Methodology The air emissions from Cheminova are measured from a number of sources: • Exhaust from process plant I (parameters: odour, organic substances (VOC), hydrogen bromide, hydrogen phosphate, hydrogen chloride, hydrogen sulphide and sulphur dioxide) • Exhaust from process plant II (parameter: hydrogen sulphide) • Incineration of sewage water from Glyphosat plant (parameters: hydrogen chloride, metals, TOC, TSP, nitrogen oxide, carbon monoxide) • Sulphur recovery plant (“Claus plant”) (parameter: sulphur dioxide and hydrogen sulphide) • Biological sewage treatment plant, sludge de-watering plant (parameters: odour and organic substances (VOC)) • Combined heat and power plant (parameters: nitrogen oxides, carbon monoxide) The environmental reports only include some of the emissions and they only present aggregated data. Emissions of SO2 and NMVOC are measured yearly for 1990-2013 and 1990-2000 respectively. Activity data Activity data for the production of pesticides are presented in Table 4.4.1. Table 4.4.1 Production of pesticides, Mg (Cheminova, 2014). 1980

1981

1982

1983

1984

1985

1986

1987

1988

Pesticides 20,796 23,914 26,517 33,331 38,924 42,010 42,492 42,781 48,020 1989

1990

1991

1992

1993

1994

1995

1996

1997

Pesticides 48,342 37,671 39,631 29,764 38,988 41,913 45,320 55,800 56,500 1998

1999

2000

2001

2002

2003

2004

2005

2006

Pesticides 52,985 64,264 60,284 60,376 55,464 52,849 65,310 53,504 52,575 2007

2008

2009

2010

2011

2012

2013

Pesticides 49,796 49,747 37,484 31,000 31,000 31,000 30,000

83

Activity data for 1980-1995 are estimated with the production value as surrogate data. Emission factors The implied emission factors for pesticide production are presented in Table 4.4.2. Table 4.4.2 Implied emission factors for pesticide production, Claus process. Average2, kg/Mg Substance Interval1, kg/Mg Pesticides SO2 0.1 – 26.1 4.8 NMVOC 0.5 - 10.4 2.2 1 Interval for 1980-2013. 2 Average only for years where actual emissions and activity data are available; i.e. 1996-2013 and 1996-2000 for SO2 and NMVOC respectively.

4.4.3 Emission trend The emission of NMVOC from production of pesticides was reduced significantly from 1990 to 1993 (Cheminova, 2014). The decrease can be explained by introduction of flue gas cleaning equipment rather than any decrease in activity. The emission of SO2 is from the sulphur regeneration plant (Claus plant). The emission of NMVOC from production of pesticides is measured yearly from 1990 to 2000 (Cheminova, 2014) and estimated for 2001 to 2013. The implied emission factor based on 2000 data is used for estimation of 2001 to 2013 emissions. Emissions of NMVOC and SO2 are presented in Table 4.4.3 and Figure 4.4.1.

Figure 4.4.1 Emissions of SO2 and NMVOC from pesticide production.

84

Table 4.4.3 Emissions from production of pesticides, Mg (Cheminova, 2014). 1980

1981

1982

1983

1984

1985

1986

1987

1988

1989

77

89

98

124

144

156

158

159

178

179

367

422

468

589

688

742

751

756

848

854 1999

NMVOC SO2

1990

1991

1992

1993

1994

1995

1996

1997

1998

NMVOC

390

150

62

40

54

57

113

44

40

41

SO2

565

644

778

613

638

553

573

632

408

488

2000

2001

2002

2003

2004

2005

2006

2007

2008

2009

29

29

27

25

31

26

25

24

24

18

422

450

437

322

341

403

258

36

13

20

NMVOC SO2

2010

2011

2012

2013

NMVOC

15

15

15

14

SO2

11

27

27

4

4.4.4 Input to CollectER The input data/data sources are presented in Table 4.4.4. Table 4.4.4 Input data for calculating emissions from pesticides production. Year Activity data 1980-1995 1996-2013 Emissions

Parameter

Comment/Source

Total products Estimated Total products Cheminova (2014)

1980-1989; 2001-2013

NMVOC

Estimated using IEF and production data

1990-2000 1980-1989

NMVOC SO2

Cheminova (2014) Estimated using IEF and production data

1990-2013

SO2

Cheminova (2014)

4.4.5 Future improvements There are no planned improvements for the source category of pesticide production.

4.5

Production of chemical ingredients

The production of chemical ingredients takes place in a number of different companies. One of the major companies is Danisco Grindsted located in Grindsted (Danisco Grindsted, 2014). The following SNAP code is covered: • 04 05 00 Production in organic chemical industry The following pollutants are included for the production process of chemical ingredients: • NMVOC

4.5.1 Process description The following description of the production of chemical ingredients is based on the environmental report from the company (Danisco Grindsted, 2010). The raw materials are primarily natural or nature identical raw materials/substances: vegetable oils, animal fatty acids, glycerine, other organic substances, mineral acidic and alkaline compounds, solvents etc. The products are emulsifiers, stabilisers, flavours, enzymes, antioxidants, pharmaceuticals and preservatives. The chemical process is not described due to confidentiality. 85

4.5.2 Methodology Due to confidentiality no activity data or emission factors are available.

4.5.3 Emission trend The emission of NMVOC from production of chemical ingredients has been measured from 1997 to 2013 (Danisco Grindsted, 2014). Emissions for 19901996 have been estimated. The emission has decreased from 100 to 12 Mg NMVOC in this period. However, no explanation can be given on these conditions, as information on activity is not available. The NMVOC emissions are presented in Table 4.5.1. Table 4.5.1 Emissions from the production of chemical ingredients, Mg (Danisco Grindsted, 2014). NMVOC NMVOC NMVOC

4.6

1990

1991

1992

1993

1994

1995

1996

1997

100

100

100

100

100

100

100

93

1998

1999

2000

2001

2002

2003

2004

2005

103

62

40

18

18

15

16

14

2006

2007

2008

2009

2010

2011

2012

2013

15

17

15

12

12

12

12

12

Production of tar products

One Danish factory situated in Nyborg produces tar products. The following SNAP code is covered: • 04 05 27 Production of tar products The following pollutants are included for the production process of tar products: • SO2 • NMVOC • Heavy metals: Hg

4.6.1 Process description The description of the process is based on the 2014 environmental report by the company (Koppers, 2014). The company is a chemical plant that refines coal tar. Coal tar is a residual product from degasification of coal at coking plants. The main products of the company are coal tar pitch, carbon black feedstock, creosote oil and naphthalene. The production facility where the raw material (coal tar) is separated in fractions and refined consists of the following units: • Tar distillation plant (Distillation of the coal tar) • Tar acid washer (TAW) plant (Naphthalene oil is washed with sodium hydroxide) • Naphthalene distillation plant (Distillation of naphthalene oil) • Storage tanks (Storage of raw materials and finished products with air ventilation and air cleaning) • Creosote plant (Reduction of the oils crystallising point by cooling and crystallisation) • Flacking plant (Crystallisation of naphthalene and packaging) • Loading plant (Loading of distillates and fuel additives) 86

The majority of the raw material is imported from other European countries. The finished products are exported globally, but the main product, coal tar pitch, is mainly exported to the aluminium industry in Europe, where it is used for production of anodes. Naphthalene is used as a raw material in the chemical industry, creosote oil for wood preservation and carbon black feedstock in the tyre industry. Intermediates and finished products are kept in storage tanks, which have a total capacity of approximately 100,000 m3. In the storage tanks some products are kept at temperatures up to 220 ºC to prevent solidification. The only exception is the main part of the naphthalene production, which after purification is crystallised in flakes and is sold as solid naphthalene. The production takes place in closed system and the storage tanks is run at vacuum to keep releases to the surroundings to a minimum. The distillation plants are operating around the clock all year with the exception of a few weeks shutdown a year for scheduled maintenance.

4.6.2 Methodology No activity data are available. The emissions are based on measured emissions reported in the environmental reports from the company (Koppers, 2014). The emissions for the years 1985 – 2004 are assumed to be the same (rounded) as for 2005.

4.6.3 Emission trend Trends for emissions of NMVOC, SO2 and Hg from production of tar products are presented in Table 4.6.1. Table 4.6.1 Emissions from production of tar products, Mg; Hg in kg (Koppers, 2014). 1986 1987 1988 1989 1990 1991 1992 1993 1994 1985 SO2 210 210 210 210 210 210 210 210 210 210 NMVOC Hg SO2 NMVOC Hg SO2 NMVOC Hg

0.9 NE 1995 210 0.9

0.9 NE 1996 210 0.9

0.9 NE 1997 210 0.9

0.9 NE 1998 210 0.9

0.9 NE 1999 210 0.9

0.9 4.9 2000 210 0.9

0.9 4.9 2001 210 0.9

0.9 4.9 2002 210 0.9

0.9 0.9 4.9 4.9 2003 2004 210 210 0.9 0.9

4.9 2005 212 0.9 4.9

4.9 2006 122 1.2 4.9

4.9 2007 61 1.0 4.9

4.9 2008 95 0.5 12.1

4.9 2009 93 2.0 0.5

4.9 2010 105 1.3 1.5

4.9 2011 166 1.1 1.4

4.9 2012 203 1.2 10.0

4.9 2013 174 0.6 0.0

4.9

NE: Not estimated

4.6.4 Future improvements The emission of SO2 will be extrapolated back to 1980 to comply with the requirement to have a time series back to the base year. It will be evaluated whether the assumption to keep emissions constant back in time at the 2005 level is appropriate. Possible emissions of PAH from the process will be investigated.

87

5

Metal industry

The processes within metal industry in Denmark in relation to emission of greenhouse gases and other pollutants are: • • • • •

Iron and steel production; see section 5.2 Red bronze production; see section 5.3 Magnesium production; see section 5.4 Secondary aluminium production; see section 5.5 Secondary lead production; see section 5.6

There is no primary production of metals in Denmark and no metallurgical coke production.

5.1

Emissions

The time series for emission of CO2 from metal industry is presented in Figure 5.1.1 below.

Figure 5.1.1 Emission of greenhouse gasses from the individual source categories compiling 2C Metal Industry, Gg CO2 equivalents.

From 1990 to 2001, the CO2 emission from the electro-steelwork increased by 55 % and from 1990-2000 SF6 from magnesium production decreased with 32 %. The changes in the greenhouse gas emission is similar to the increase and decrease in the activity as the consumption of metallurgical coke per amount of steel sheets and bars produced has almost been constant during the period and the emission factor for magnesium production is constant throughout the time series. Greenhouse gas emissions from secondary lead production are miniscule (0.3 % for 1990-2000), but are the only greenhouse gas emissions in the metal industry that occur for the entire time series. The electro-steelwork was shut down in 2001 and reopened and closed down again in 2005. In 2000, the SF6 emission from the magnesium production ceased.

88

Gray iron foundries, aluminium production and red bronze production are active for the entire time series but emit no process greenhouse gas emissions. An overview of the 2013 emission of particulate matter, heavy metals, and POPs from metal industry is available in Table 5.1.1. Table 5.1.1 Overview of 2013 emissions from metal production.

TSP HMs POPs

Total emission Fraction of from metal IP*; % industries 0.16 Gg 19.90 2.86 Mg 43.67 0.21 kg

0.09

Largest contributor in Metal industries Iron and steel production Zn from Other metal production (CRF 2C7c)

Emission from largest contributor 0.16 Gg 0.63 Mg

HCBs from Aluminium production

0.14 kg

Fraction of metal industries, % 98.69 22.16 65.78

* IP: The Industrial Processes sector

Iron and steel production comprises three activities; an electric arc furnace (EAF) (until 2001/2002 and in 2005), rolling mills (from 2003) and gray iron foundries (whole time series). The most interesting activity from an air emission perspective is the EAF. After the closing of the EAF, the site has since 2003 been used for rolling steel slabs imported from steelworks in other countries. This change in production results in large changes in activity data and emissions reported for the year 2002. In 2005, the EAF was shortly reopened, which explains the higher activity level this year. Regarding the steelworks that use iron and steel scrap as raw material, the emissions to a large degree depend on the quality of the scrap. This fact may result in large annual variations for one or more of the heavy metals. This may also be the case for iron foundries, as they also use scrap as raw material, but they have not been subject to the same requirements to analyse emissions of heavy metals to air.

5.2

Iron and steel production

The production of semi-manufactured steel products (e.g. steel sheets/plates and bars) is concentrated at one company: Det Danske Stålvalseværk A/S situated in Frederiksværk. Only two gray iron foundries are still in operation in Denmark, producing a range of products like e.g. cast iron pipes, central heating boilers and flywheels. The following SNAP codes are covered: • 03 03 03 Gray iron foundries • 04 02 07 Electric furnace steel plant • 04 02 08 Rolling mill The following pollutants are included for the iron and steel production processes: • • • •

CO2 Particulate matter: TSP, PM10, PM2.5 Heavy metals: As, Cd, Cr, Cu, Hg, Ni, Pb, Se, Zn Persistent organic pollutants: HCB, PCDD/F, PCB

The steelwork has been closed down in January 2002 and parts of the plant have been re-opened in November 2002. The production of steel sheets/plates was reopened by DanSteel in 2003, the production of steel bars was reopened by DanScan Metal in March 2004, and the electro steelwork 89

was reopened by DanScan Steel in January 2005. The production at DanScan Metal and Steel ceased in the last part of 2005 and in June 2006 DanScan Metal was taken over by Duferco; the future for the electro steelwork (DanScan Steel) is still uncertain and the plant has not been in operation since 2005. The timeline is presented in Figure 5.2.1.

Figure 5.2.1 Timeline for production at the Danish steelwork.

5.2.1 Process description The primary raw materials in steel production are iron and steel scrap and the secondary raw materials are metallurgical coke, iron, alkali metals, other alloy metals, and oxygen. Trucks, trains or ships deliver the iron and steel scrap. The scrap is controlled before melting in an electric arc furnace. The composition of the molten iron is checked and alloy metals are added depending on the expected quality of the final steel product. The iron is prepared as billets/blooms for bars or slabs for sheets. The final products are made in different rolling mills for bars and sheets, respectively. The cease of the electro steelwork has resulted in import of billets/blooms and slabs for the rolling mills. The process is presented Figure 5.2.2.

Transport by: - ship - train - truck

Control of scrap and storage

Electric arc furnace

Rolling mill for sheets

Rolling mill for bars

Figure 5.2.2 Overall flow-sheet for ”Det Danske Stålvalseværk” (Stålvalseværket, 2002; DanSteel, 2013).

5.2.2 Methodology In steel production, metallurgical coke is used in the melting process to reduce iron oxides and to remove impurities. The overall process is: C + O2 → CO2 The emission factors for carbon dioxide from using metallurgical coke in manufacturing of iron and steel scrap is:

90

• 3.667 Mg CO2 per Mg C Different steel qualities contain carbon from <0.25% (iron/unalloyed steel) to >6% (ferrochromium) and some of the metallurgical coke/carbon can be expected to be retained in the steel. However, the scrap can also be expected to contain a certain amount of carbon. Analysis of the data in the environmental declaration for steel sheets or steel bars indicate that all the metallurgical coke is emitted as carbon dioxide as illustrated in Table 5.2.1. Table 5.2.1 CO2 balance for production of 1 tonne steel sheets - 2001 (Stålvalseværket, 2002). Environmental report

Emission factor (2001)

CO2-emission (estimated)

73 Nm3 (2.92 GJ)

57.25 kg CO2/GJ

167.17 kg CO2

18 kg

3.667 kg CO2/kg C

66.01 kg CO2

Input Natural gas Metallurgical coke Output CO2

229 kg

233.18 kg

The difference between the reported and the estimated CO2-emission can be explained by choice of calorific value for natural gas and the CO2-emission factor for natural gas. The CO2 emission from the consumption of metallurgical coke at steelworks has been estimated from the annual production of steel sheets and steel bars combined with the consumption of metallurgical coke per produced amount (Stålvalseværket, 2002). The carbon source is assumed to be coke and all the carbon is assumed to be converted to CO2 as the carbon content in the products is assumed to be the same as in the iron scrap. The emission factor (consumption of metallurgical coke per Mg of product) has been almost constant from 1994 to 2001; steel sheets: 0.012-0.018 Mg metallurgical coke per Mg and steel bars: 0.011-0.017 Mg metallurgical coke per Mg. Steel production data for 1990-1991 and for 1993 have been determined with extrapolation and interpolation, respectively and data on the consumption of metallurgical coke for 1990-1992 have been extrapolated. The emission of heavy metals from iron foundries is based on standard emission factors and yearly production statistics from Statistics Denmark (2014). The emission of TSP and distribution between TSP, PM10 and PM2.5 is obtained from CEPMEIP. Emission factors for HCB and PCB are obtained from Nielsen et al. (2013a). Activity data Statistical data on activities are available in environmental reports from the single Danish steel plant (Stålvalseværket) supplemented with other literature; see Table 5.2.2.

91

Table 5.2.2

Overall mass flow for Danish steel production, Gg (Stålvalseværket, 2002; DanSteel, 2014). 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 Det danske stålvalseværk Raw material Iron and steel scrap - 6301 557 - 673 657 664 735 737 691 Intermediate product Steel slabs etc. - 599 - 730 654 744 794 800 727 Product Steel sheets 444 444 444 451 459 478 484 571 514 571 Steel bars 170 170 170 217 264 239 235 245 238 226 Products, total 6142 6142 614 6683 722 717 720 816 752 798 DanSteel Raw material Steel slabs Product Steel sheets 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 Det danske stålvalseværk Raw material Iron and steel scrap 731 680 Intermediate product Steel slabs etc. 803 746 Product Steel sheets 380 469 Steel bars 251 256 Products, total 631 725 2504 DanSteel Raw material Steel slabs 553 600 515 561 635 590 254 Product Steel sheets 469 506 433 468 520 484 211 2010 2011 2012 2013 Det danske stålvalseværk Raw material Iron and steel scrap Intermediate product Steel slabs etc. Product Steel sheets Steel bars Products, total DanSteel Raw material Steel slabs 457 490 338 460 Product Steel sheets 381 390 275 379 1 Jensen & Markussen (1993). 2 Extrapolation. 3 Intrapolation. 4 Assumed

The mass balances/flow sheets presented in the annual environmental reports do not for all years tell about the changes in the stock and therefore the balance cannot be checked off. Statistical data on production in gray iron foundries are available from Statistics Denmark (2014) since 1998; activity data prior to this year are estimated. The activity data are presented in Table 5.2.3. Table 5.2.3 Activity data, iron foundries, Gg. 1990 Gray iron foundries Gray iron foundries Gray iron foundries

1991

1992

1993

1994 1995 1996 1997 1998 1999

103.0 100.4

97.8

95.3

92.7

2000

2001

2002

2003

2004 2005 2006 2007 2008 2009

101.7

94.5 103.0 104.5 113.0

2010

2011

2012

2013

72.9

83.6

76.4

77.4

90.2

99.9

87.6

81.5

85.1

72.8

85.8

71.4

86.0

41.4

Emission factors The CO2 emission factor from use of metallurgical coke in manufacturing of steel from scrap is the stoichiometric ratio 3.667 Mg CO2 per Mg C. The applied steel production emission factors for the air pollutants are presented in Table 5.2.4. Regarding the electric arc furnace the emissions for all 92

other pollutants than TSP have been estimated by use of emission factor from literature. Table 5.2.4 Emission factors for steel production (Environmental reports). Electric Arc Furnace

Rolling Mill

TSP PM10 PM2.5 As

g/Mg g/Mg g/Mg g/Mg

61-147 80 % of TSP1 70 % of TSP1 0.0151

6.44 95 % of TSP 60 % of TSP -

Cd Cr Cu Hg

g/Mg g/Mg g/Mg g/Mg

0.01-0.082 0.11 0.021 0.1-0.42

0.006 0.023

Ni Pb Zn HCB

g/Mg g/Mg g/Mg mg/Mg

0.4-1.42 1.0-5.02 3.6-19.02 3.23

0.087 0.087 0.377 -

PCDD/F mg/Mg 0.81 PCB mg/Mg 2.53 1 EMEP/EEA (2013), Tier 2 no abatement. 2 Illerup et al. (1999). 3 Nielsen et al. (2013a).

-

Unit

The applied emission factors for the gray iron foundries are presented in Table 5.2.5. Table 5.2.5 Emission factors for gray iron foundries. Unit

Gray iron foundries

TSP PM10 PM2.5

g/Mg g/Mg g/Mg

2000 30 % of TSP 4.5 % of TSP

As Cd Cr Ni

g/Mg g/Mg g/Mg g/Mg

0.3 0.14 1.1 1.3

Pb Se Zn HCB

g/Mg g/Mg g/Mg mg/Mg

7.2 5 5 0.04

PCB

mg/Mg

0.5

5.2.3 Emission trend The greenhouse gas emission from the steel production is presented in Figure 5.2.3. The production ceased in 2001 and reopened and closed again in 2005; see Figure 5.2.1.

93

Figure 5.2.3 Emission of greenhouse gasses from the production of steel from scrap.

Emissions from the electro steelwork and rolling mill are presented in Table 5.2.6. Table 5.2.6a Emissions from the electro steelwork, rolling mill and gray iron foundries. Pollutant Process Unit 1990 1991 1992 1993 CO2 Electric furnace steel plant Gg 30.3 30.3 30.3 36.0 As Total kg 40.1 39.3 38.5 38.6 Electric furnace steel plant kg 9.2 9.2 9.2 10.0 Gray iron foundries kg 30.9 30.1 29.3 28.6 Cd Total kg 53.3 53.0 52.6 53.8 Electric furnace steel plant kg 38.9 38.9 38.9 40.4 Gray iron foundries kg 14.4 14.1 13.7 13.3 Cr Total kg 174.7 171.8 169.0 171.6 Electric furnace steel plant kg 61.4 61.4 61.4 66.8 Gray iron foundries kg 113.3 110.4 107.6 104.8 Cu Electric furnace steel plant kg 12.3 12.3 12.3 13.4 Hg Electric furnace steel plant kg 246 246 246 267 Ni Total kg 891.3 887.9 884.5 862.4 Electric furnace steel plant kg 757.4 757.4 757.4 738.5 Gray iron foundries kg 133.9 130.5 127.1 123.9 Pb Total kg 3,708.5 3,689.8 3,671.1 3,786.6 Electric furnace steel plant kg 2,966.9 2,966.9 2,966.9 3,100.5 Gray iron foundries kg 741.6 722.9 704.2 686.2 Se Gray iron foundries kg 515.0 502.0 489.0 476.5 Zn Total kg 12,006.8 11,993.8 11,980.8 12,286.1 Electric furnace steel plant kg 11,491.8 11,491.8 11,491.8 11,809.6 Gray iron foundries kg 515.0 502.0 489.0 476.5 HCB Total kg 6.1 6.0 5.9 6.0 Electric furnace steel plant kg 2.0 2.0 2.0 2.1 Gray iron foundries kg 4.1 4.0 3.9 3.8 PCDD/F Electric furnace steel plant g 0.5 0.5 0.5 0.5 PCB Total kg 53.0 51.7 50.4 49.3 Electric furnace steel plant kg 1.5 1.5 1.5 1.7 Gray iron foundries kg 51.5 50.2 48.9 47.7

94

1994 33.5 38.6 10.8 27.8 38.6 25.6 13.0 174.2 72.2 102.0 14.4 144 619.4 498.9 120.5 2,775.4 2,107.9 667.4 463.5 8,606.2 8,142.7 463.5 6.0 2.3 3.7 0.6 48.2 1.8 46.4

1995 1996 1997 38.5 35.2 35.0 37.8 37.1 61.8 10.8 10.8 12.2 27.1 26.3 49.5 34.2 31.5 45.1 21.5 19.2 22.0 12.6 12.3 23.1 171.0 168.4 263.2 71.7 72.0 81.6 99.3 96.4 181.6 14.3 14.4 16.3 143 216 204 547.6 473.8 540.9 430.2 359.8 326.3 117.4 114.0 214.6 2,370.4 1,471.3 2,061.4 1,720.4 840.1 872.9 650.0 631.2 1,188.5 451.4 438.3 825.4 6,998.1 7,199.0 7,858.4 6,546.7 6,760.7 7,033.0 451.4 438.3 825.4 5.9 5.8 9.2 2.3 2.3 2.6 3.6 3.5 6.6 0.6 0.6 0.7 46.9 45.6 84.6 1.8 1.8 2.0 45.1 43.8 82.5

Table 5.2.6b Emissions from the electro steelwork, rolling mill and gray iron foundries. (Continued) 1999 2000 2001 2002 2003 2004 2005 Pollutant Process Unit 1998 CO2 Electric furnace steel plant Gg 42.3 43.0 40.7 46.9 NO NO NO 16.2 TSP Total Mg NE NE 420.1 425.5 410.2 419.0 455.3 402.6 Electric furnace steel plant Mg NE NE 41.2 47.5 NO NO NO NO Rolling mills Mg NE NE NO NO NO 3.0 3.3 2.8 Gray iron foundries Mg NE NE 379.0 378.0 410.2 416.0 452.1 399.8 PM10 Total Mg NE NE 146.6 151.4 123.1 127.7 138.7 122.6 Electric furnace steel plant Mg NE NE 33 38 NO NO NO NO Rolling mills Mg NE NE NO NO NO 2.9 3.1 2.7 Gray iron foundries Mg NE NE 113.7 113.4 123.1 124.8 135.6 120.0 PM2.5 Total Mg NE NE 40.1 43.6 18.5 20.5 22.3 19.7 Electric furnace steel plant Mg NE NE 23.0 26.6 NO NO NO NO Rolling mills Mg NE NE NO NO NO 1.8 2.0 1.7 Gray iron foundries Mg NE NE 17.1 17.0 18.5 18.7 20.3 18.0 As Total kg 61.6 60.5 66.3 67.6 61.5 62.4 67.8 60.0 Electric furnace steel plant kg 11.3 12.0 9.5 10.9 NO NO NO NO Gray iron foundries kg 50.3 48.5 56.8 56.7 61.5 62.4 67.8 60.0 Cd Total kg 43.6 44.3 43.0 45.7 28.7 31.8 34.6 30.5 Electric furnace steel plant kg 20.2 21.7 16.4 19.2 NO NO NO NO Gray iron foundries kg 23.5 22.6 26.5 26.5 28.7 29.1 31.6 28.0 Rolling mills kg NO NO NO NO NO 2.7 2.9 2.5 Cr Total kg 259.6 257.7 271.5 280.4 225.6 228.8 248.6 219.9 Electric furnace steel plant kg 75.2 79.8 63.1 72.5 NO NO NO NO Gray iron foundries kg 184.5 177.9 208.4 207.9 225.6 228.8 248.6 219.9 Cu Electric furnace steel plant kg 15.0 16.0 12.6 14.5 NO NO NO NO Hg Total kg 150.3 119.6 63.1 36.3 NO 10.9 11.7 10.1 Electric furnace steel plant kg 150.3 119.6 63.1 36.3 NO NO NO NO Rolling mills kg NO NO NO NO NO 10.9 11.7 10.1 Ni Total kg 518.6 529.3 498.7 535.8 266.6 311.1 337.8 297.5 Electric furnace steel plant kg 300.6 319.0 252.4 290.1 NO NO NO NO Gray iron foundries kg 218.0 210.3 246.3 245.7 266.6 270.4 293.8 259.9 Rolling mills kg NO NO NO NO NO 40.7 43.9 37.7 Pb Total kg 2,010.2 2,019.2 2033.3 2,133.0 1,476.8 1,538.2 1,671.3 1,477.1 Electric furnace steel plant kg 802.9 854.7 669.0 772.2 NO NO NO NO Gray iron foundries kg 1,207.4 1,164.6 1364.3 1,360.8 1,476.8 1,497.5 1,627.4 1,439.4 Rolling mills kg NO NO NO NO NO 40.7 43.9 37.7 Se Gray iron foundries kg 838 808.7 947.4 945.0 1,025.5 1,039.9 1,130.1 999.6 Zn Total kg 6,386 5,673 4,032 3,556 1,026 1,217 1,321 1,163 Electric furnace steel plant kg 5,548 4,864 3,085 2,611 NO NO NO NO Gray iron foundries kg 838 809 947 945 1,026 1,040 1,130 1,000 Rolling mills kg NO NO NO NO NO 176.7 190.6 163.3 HCB Total kg 9.1 9.0 9.6 9.9 8.2 8.3 9.0 8.0 Electric furnace steel plant kg 2.4 2.6 2.0 2.3 NO NO NO NO Gray iron foundries kg 6.7 6.5 7.6 7.6 8.2 8.3 9.0 8.0 PCDD/F Electric furnace steel plant g 0.6 0.6 0.5 0.6 NO NO NO NO PCB Total kg 85.7 82.9 96.3 96.3 102.6 104.0 113.0 100.0 Electric furnace steel plant kg 1.9 2.0 1.6 1.8 NO NO NO NO Gray iron foundries kg 83.8 80.9 94.7 94.5 102.6 104.0 113.0 100.0 NO: Not occurring NE: Not estimated (basis year for particles is 2000)

95

Table 5.2.6c Emissions from the electro steelwork, rolling mill and gray iron foundries. (Continued) 2007 2008 2009 2010 2011 2012 Pollutant Process Unit 2006 CO2 NO NO NO NO NO NO NO TSP Total Mg 329.0 294.6 288.8 167.4 294.0 337.0 307.7 Rolling mills Mg 3.0 3.4 3.1 1.4 2.5 2.5 1.8 Gray iron foundries Mg 326.0 291.2 285.7 166.1 291.6 334.5 305.9 PM10 Total Mg 100.7 90.6 88.7 51.1 89.8 102.7 93.5 Rolling mills Mg 2.9 3.2 3.0 1.3 2.3 2.4 1.7 Gray iron foundries Mg 97.8 87.4 85.7 49.8 87.5 100.4 91.8 PM2.5 Total Mg 16.5 15.1 14.7 8.3 14.6 16.6 14.8 Rolling mills Mg 1.8 2.0 1.9 0.8 1.5 1.5 1.1 Gray iron foundries Mg 14.7 13.1 12.9 7.5 13.1 15.1 13.8 As Gray iron foundries kg 48.9 43.7 42.9 24.9 43.7 50.2 45.9 Cd Total kg 25.5 23.4 22.8 12.8 22.6 25.7 23.0 Gray iron foundries kg 22.8 20.4 20.0 11.6 20.4 23.4 21.4 Rolling mills kg 2.7 3.0 2.8 1.2 2.2 2.3 1.6 Cr Gray iron foundries kg 179.3 160.2 157.1 91.3 160.4 184.0 168.3 Cu NO NO NO NO NO NO NO Hg Rolling mills kg 10.8 12.1 11.2 4.9 8.8 9.0 6.4 Ni Total kg 252.5 234.5 227.7 126.3 222.6 251.3 222.7 Gray iron foundries kg 211.9 189.3 185.7 108.0 189.5 217.4 198.9 Rolling mills kg 40.6 45.2 42.1 18.3 33.1 33.8 23.9 Pb Total kg 1,214.3 1,093.7 1,070.5 616.2 1,082.8 1,238.1 1,125.2 Gray iron foundries kg 1,173.7 1,048.5 1,028.5 597.9 1,049.7 1,204.2 1,101.4 Rolling mills kg 40.6 45.2 42.1 18.3 33.1 33.8 23.9 Se Gray iron foundries kg 815.1 728.1 714.2 415.2 729.0 836.3 764.8 Zn Total kg 991.3 924.3 896.7 494.8 872.6 983.1 868.3 Gray iron foundries kg 815.1 728.1 714.2 415.2 729.0 836.3 764.8 Rolling mills kg 176.3 196.2 182.4 79.6 143.6 146.8 103.5 HCB Gray iron foundries kg 6.5 5.8 5.7 3.3 5.8 6.7 6.1 PCDD/F NO NO NO NO NO NO NO PCB Gray iron foundries kg 81.5 72.8 71.4 41.5 72.9 83.6 76.5 NO: Not occurring

2013 NO 157.2 2.4 154.7 48.7 2.3 46.4 8.4 1.5 7.0 23.2 13.0 10.8 2.2 85.1 NO 8.8 133.5 100.6 32.9 590.0 557.1 32.9 386.9 529.5 386.9 142.7 3.1 NO 38.7

Due to the change in production process in the beginning of the ‘00s, the emissions (and even more so the implied emission factors) change drastically form 2001 to 2002 and from 2002 to 2003. Please refer to Figure 5.2.1 and Table 5.2.2.

5.2.4 Time series consistency and completeness The time series for secondary steel production is considered to be consistent as the same methodology has been applied for the whole period. The time series is also considered to be complete.

5.2.5 Input to CollectER The input data/data sources are presented in Table 5.2.7.

96

Table 5.2.7 Input data for calculation of emissions from iron and steel production. Year Activity

Parameter

1992, 1994-2001 Scrap, semi-man.

Comment/Source Stålvalseværket (2002)

products, final products 1990, 1991, 1993 Final products

Estimated with interpolation and extrapolation

2003-2013

Final products

1995-2013

2014) Sales statistics for gray Statistics Denmark (2014) iron products

1990-1994

Sales statistics for gray Estimated iron products

Emissions 1992-1997 1993-2001

Environmental reports (Dansteel,

Heavy metal EFs

Illerup et al. (1999)

CO2

Estimated from information on consumption of metallurgical coke (Stålvalseværket, 2002)

1993-2000

TSP

Stålvalseværket (2002)

2000-2001

PM10, PM2.5

Distribution between TSP, PM10, and PM2.5 from EMEP/EEA (2013)

5.2.6 Future improvements For iron foundries a process description will be elaborated. Activity data from Statistics Denmark will be used for iron foundries for the whole time series. Emission factors for iron foundries will be re-examined to ensure that they are properly referenced.

5.3

Red bronze production

This section covers the production of red bronze which is the only ferroalloy (i.e. allied metal) produced in Denmark. The following SNAP code is covered: • 04 03 06 Allied metal manufacturing The following pollutants are included for the red bronze production processes: • Heavy metals: Cd, Cu, Pb, Zn

5.3.1 Process description No further description is given for red bronze production.

5.3.2 Methodology Production data is only available for 1990 and 1995-1997, the activity data have therefore been kept constant since 1997. For the years between 1990 and 1995 the activity data have been interpolated. The available production data vary slightly between the years; however, the reference for the data is not clear. Activity data The activity data are presented in Table 5.3.1. 97

Table 5.3.1 Activity data for red bronze production.

Red bronze production

Unit

1990

1995

1996

1997

Mg

3,895

4,350

4,400

4,532

Emission factors The applied emission factors are presented in Table 5.3.2 and are all referenced to Illerup et al. (1999). Table 5.3.2 Emission factors for heavy metals for red bronze production. Pollutant

Unit

Value

Cd

g/Mg

1

Cu

g/Mg

10

Pb

g/Mg

15

Zn

g/Mg

140

5.3.3 Emission trends Emissions trends for Cd, Cu, Pb, and Zn from red bronze production are presented in Table 5.3.3. Table 5.3.3 Emissions from red bronze production, kg. 1990

1991

1992

1993

1994

1995

1996 1997-2013

Cd Cu Pb

3.9 39.0 58.4

4.0 39.9 59.8

4.1 40.8 61.2

4.2 41.7 62.5

4.3 42.6 63.9

4.4 43.5 65.3

4.4 44.0 66.0

4.5 45.3 68.0

Zn

545.3

558.0

570.8

583.5

596.3

609.0

616.0

634.5

5.3.1 Time series consistency and completeness The time series for red bronze production is consistent, however very little is currently known of this source category’s completeness.

5.3.2 Input to CollectER The input data/data sources are presented in Table 5.3.4. Table 5.3.4 Input data for calculation of emissions from red bronze production. Year Activity

Parameter

1990, 1995-1997 Production statistics Production statistics 1991-1994,

Comment/Source Unknown Estimated

1998-2013 Emissions 1990-2013

Heavy metal EFs

Illerup et al. (1999)

5.3.3 Future improvements It will be investigated whether activity data are available from Statistics Denmark. A process description for this activity will be elaborated.

5.4

Magnesium production

For the production of magnesium in Denmark the following SNAP-code is covered:

• 04 03 04 Consumption of SF6 in magnesium foundries 98

The following pollutants are included for the magnesium production processes: • SF6

5.4.1 Process description There is no primary production of magnesium in Denmark, hence only magnesium casting has taken place. Magnesium casting processes involve handling of molten pure magnesium and/or molten high magnesium content alloys. Molten magnesium may be cast by a variety of methods including gravity casting, sand casting, die casting and others. All molten magnesium spontaneously burns in the presence of atmospheric oxygen. Production and casting of all magnesium metal therefore requires a protection system to prevent burning. Among the various protection systems commonly used are those that use gaseous components with high GWP values, such as SF6, which typically escape to the atmosphere.

5.4.2 Methodology The consumption of SF6 in the magnesium production is known from Poulsen (2015). The production ceased to use SF6 in 2000. Activity data can be calculated from the cover gas (SF6) consumption and the default Tier 1 emission factor is known from IPCC (2006). A release of 100 % is assumed. Activity data Table 5.4.1 presents the calculated activity data. Table 5.4.1 Activity data for magnesium production, Mg. 1990

1991

1992

1993

1994

1995 1996 1997 1998 1999 2000

Production of magnesium 1,300 1,300 1,300 1,500 1,900 1,500

400

600

700

700

891

Emission factors The applied emission factor is 1 kg SF6 per Mg produced magnesium (IPCC, 2006).

5.4.3 Emission trends The greenhouse gas emissions from the production of magnesium are presented in the in Error! Reference source not found. below. The consumption of SF6 ceased in 2000.

5.4.4 Time series consistency and completeness The time series for magnesium production is considered to be both consistent and complete.

5.4.5 Input to CollectER The input data/data sources are presented in Table 5.4.2. Table 5.4.2 Input data for calculation of emissions from magnesium production. Year Activity

1990-2000

Emissions 1990-2000

Parameter

Comment/Source

Magnesium production

Poulsen (2015)

SF6 emission factor

IPCC (2006)

99

5.4.6 Future improvements No improvements are planned for this sector.

5.5

Secondary aluminium production

Two active Danish production sites have been identified for secondary aluminium; “Stena Aluminium” and “Jydsk Aluminium Industri”. The following SNAP code is covered: • 03 03 10 Secondary aluminium production The following pollutants are included for the secondary aluminium production: • Particulate matter: TSP, PM10, PM2.5 • Heavy metals: Cd, Pb • Persistent organic pollutants: HCB, PCDD/F, PCBs

5.5.1 Process description Secondary aluminium production is when aluminium scraps or aluminiumbearing materials; other than aluminium-bearing concentrates (ores) derived from a mining operation, is processed into aluminium alloys for industrial castings and ingots. The furnace used for melting aluminium scrap depends on the type of scrap and there is a wide variety of scraps and furnaces used. In general for fabrication scrap and cleaner materials, reverbatory and induction furnaces are used. For more contaminated grades of scrap, rotary furnaces, tilting or horizontal furnaces are used. The scrap may also be pretreated, depending on type of scrap and contamination. Coated scrap, like used beverage cans, is de-coated as an integrated part of the pre-treatment and melting process. The metal is refined either in the holding furnace or in an inline reactor to remove gases and other metals generally in the same way as for primary aluminium. If magnesium needs to be removed, this is done by treatment with chlorine gas mixtures. The remaining operating Danish plant (Jydsk Aluminium Industri) uses three shaft furnaces and two induction furnaces and only uses clean aluminium and not aluminium scrap. It is difficult to obtain information on the specific technology used at the closed smelter in Denmark. We will try to obtain information from the environmental permit and include a description in future reports.

5.5.2 Methodology Secondary aluminium industries were identified from a list of companies with the relevant environmental approvals acquired from the Danish Environmental Agency. The largest producer, called Stena Aluminium, accounted for approximately 90 % of the total Danish production until the factory was closed by the end of 2008. Activity data The activity data are presented in Table 5.5.1.

100

Table 5.5.1 Activity data for secondary aluminium production (Stena Aluminium, 2008 and Jydsk Aluminiums Industri, 2014), Gg. 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 Stena Aluminium1

30.23 30.23 30.23 30.23 30.23 30.23 25.06 31.79 32.98

28.48

Jydsk Aluminium Total

1.26 1.26 1.26 1.26 1.74 2.22 2.70 3.00 3.30 31.49 31.49 31.49 31.49 31.97 32.45 27.76 34.79 36.28

3.61 32.08

2000

2008

2009

Stena Aluminium Jydsk Aluminium2 Total

32.87 33.38 32.13 26.42 19.56 23.43 31.32 35.12 36.22 3.91 4.21 4.51 4.81 5.11 5.42 5.72 6.02 6.07 36.78 37.59 36.64 31.23 24.67 28.85 37.03 41.14 42.29

NO 3.80 3.80

2, 3, 4

2001

2002

2003

2010

2011

2012

2013

NO 5.20

NO 6.26

NO 6.49

NO 6.84

Stena Aluminium Jydsk Aluminium2

2004

2005

2006

2007

Total 5.20 6.26 6.49 6.84 NO: Not occurring. 1 1990-1995: Calculated average of 1996-2000. 2 1993, 1996, 2007-2013: Estimated based on information from the environmental reports. 3 1990-1992: Estimated based on 1993. 4 1994-1995, 1997-2006: Interpolated.

Emission factors Emission factors for the production of secondary aluminium are presented in Table 5.5.2. Table 5.5.2 Emission factors for secondary aluminium production. Pollutant

Unit

TSP PM10 PM2.5

kg/Mg kg/Mg kg/Mg

Value 0.120 0.084 0.033

Source Calculated from Stena (2008), average for 1998-2000 Particle distribution from EMEP/EEA (2013) Particle distribution from EMEP/EEA (2013)

Cd Pb HCB PCDD/F

g/Mg g/Mg g/Mg mg/Mg

0.032 0.146 0.020 0.035

Calculated from Stena (2008), average for 1998-2000 Calculated from Stena (2008), average for 1998-2000 Nielsen et al. (2013a) EMEP/EEA (2013)

PCB

mg/Mg

3.40

Nielsen et al. (2013a)

5.5.3 Emission trends The emissions from aluminium production are presented in Table 5.5.3.

101

Table 5.5.3 Emissions from production of secondary aluminium. Unit 1990 1991 1992 1993 1994 1995 1996 Cd kg 1.00 1.00 1.00 1.00 1.02 1.03 0.88 Pb kg 4.60 4.60 4.60 4.60 4.68 4.75 4.06 HCB kg 0.63 0.63 0.63 0.63 0.64 0.65 0.56 PCDD/F g 1.10 1.10 1.10 1.10 1.12 1.14 0.97 PCB kg 0.11 0.11 0.11 0.11 0.11 0.11 0.09 Unit 2000 2001 2002 2003 2004 2005 2006 TSP Mg 4.41 4.41 4.41 4.41 4.41 4.41 4.41 PM10 Mg 3.09 3.09 3.09 3.09 3.09 3.09 3.09 PM2.5 Mg 1.21 1.21 1.21 1.21 1.21 1.21 1.21 Cd kg 1.17 1.20 1.17 1.00 0.79 0.92 1.18 Pb kg 5.38 5.50 5.36 4.57 3.61 4.22 5.41 HCB kg 0.74 0.75 0.73 0.62 0.49 0.58 0.74 PCDD/F g 1.29 1.32 1.28 1.09 0.86 1.01 1.30 PCB kg 0.13 0.13 0.12 0.11 0.08 0.10 0.13 Unit 2010 2011 2012 2013 TSP Mg 4.41 4.41 4.41 4.41 PM10 Mg 3.09 3.09 3.09 3.09 PM2.5 Mg 1.21 1.21 1.21 1.21 Cd kg 0.17 0.20 0.21 0.22 Pb kg 0.76 0.91 0.95 1.00 HCB kg 0.10 0.13 0.13 0.14 PCDD/F g 0.18 0.22 0.23 0.24 PCB kg 0.02 0.02 0.02 0.02

1997 1.11 5.09 0.70 1.22 0.12 2007 4.41 3.09 1.21 1.31 6.01 0.82 1.44 0.14

1998 1.16 5.30 0.73 1.27 0.12 2008 4.41 3.09 1.21 1.35 6.18 0.85 1.48 0.14

1999 1.02 4.69 0.64 1.12 0.11 2009 4.41 3.09 1.21 0.12 0.56 0.08 0.13 0.01

5.5.4 Verification Activity data available from the environmental reports from the largest Danish aluminium producer Stena (2008) have been validated by comparing with sales statistic from Statistics Denmark (2014). These two data sets show good agreement with only smaller fluctuations.

5.5.5 Time series consistency and completeness The time series for secondary aluminium production is considered to be both consistent and complete.

5.5.6 Input to CollectER The input data/data sources are presented in Table 5.5.4. Table 5.5.4 Input data for calculation of emissions from aluminium production. Year Activity

Parameter

Comment/Source

1990-2013 Aluminium production Stena (2008), Jydsk Aluminiums Industri (2014)

Emissions 1990-2013 Emission factor

Stena (2008), EMEP/EEA (2013), Nielsen et al. (2013a)

5.5.7 Future improvements An emission factor for BC will be added for secondary aluminium production.

5.6

Secondary lead production

Only one Danish company; Hals Metal, has been identified as producing secondary lead from scrap metal. In addition to Hals Metal, old lead tiles from castles, churches etc. are melted and recast on site during preservation

102

of the many historical buildings in Denmark. The following SNAP code is covered: • 03 03 07 Secondary lead production The following pollutants are included for the secondary lead production: • • • •

CO2 Particulate matter: TSP, PM10, PM2.5 Heavy metals: As, Cd, Pb, Zn Persistent organic pollutants (HCB, PCDD/F, PCBs)

5.6.1 Process description The process of secondary lead production is usually subdivided as follows: battery breaking and processing (scrap preparation); smelting of battery scrap materials and refining. The Danish plant is recycling e.g. transformers and land and sea cables containing lead. The cables are stripped to isolate the lead and with other lead-bearing materials, it is melted in a furnace and new lead items are casted for sale.

5.6.2 Methodology Production data from Hals Metal is provided by the company for the entire time series. A clause affected in 2002 meant that Hals Metal could no longer burn cables containing lead. The processing of cables was therefore stopped and the company’s activity changed to smelting. This transition resulted in a low activity in 2003. The activity of recasting lead tiles is not easily found because it is spread out on many craftsmen and poorly regulated. However, an estimate by Lassen et al. (2004) stated that 200-300 Mg lead tiles were recast in 2000. Since the building stock worthy of preservation is constant, it is considered reasonable to also let the activity of recasting of lead tiles be constant. Activity data Activity data for secondary lead is shown in Table 5.6.1. Table 5.6.1 Activity data for secondary lead production (Helle Bjerrum Holm (Hals Metal), personal communication, September 2014 and Lassen et al., 2004), Mg. 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 Hals Metal

540

540

540

750

750

750

540

540

540

540

Lead tiles Total

250 790 2000

250 790 2001

250 790 2002

250 1000 2003

250 1000 2004

250 1000 2005

250 790 2006

250 790 2007

250 790 2008

250 790 2009

Hals Metal Lead tiles Total

540

1080

419

64

520

691

500

670

582

780

250 790 2010

250 1330 2011

250 669 2012

250 314 2013

250 770

250 941

250 750

250 920

250 832

250 1030

Hals Metal Lead tiles

635 250

938 250

412 250

533 250

Total

885

1188

662

783

Emission factors The applied emission factors are presented in Table 5.6.2.

103

Table 5.6.2 Emission factors for secondary lead production. Value

Unit

Reference

CO2 TSP

0.2 1.63

Mg/Mg kg/Mg

IPCC (2006) EMEP/EEA (2013)

PM10 PM2.5 As Cd

1.30 0.65 3.5 1.1

kg/Mg kg/Mg g/Mg g/Mg

EMEP/EEA (2013) EMEP/EEA (2013) EMEP/EEA (2013) EMEP/EEA (2013)

Pb Zn HCB PCDD/F

426 2.6 0.3 8.0

g/Mg g/Mg mg/Mg µg/Mg

EMEP/EEA (2013) EMEP/EEA (2013) Nielsen et al. (2013a) EMEP/EEA (2013)

PCB

7.3

mg/Mg

Nielsen et al. (2013a)

Pollutant

5.6.3 Emission trends Emissions from secondary lead production are presented in Table 5.6.3 and for CO2 also in Figure 5.6.1. Table 5.6.3 Emissions from production of secondary lead. Unit

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

CO2 As

Gg kg

0.16 2.77

0.16 2.77

0.16 2.77

0.20 3.50

0.20 3.50

0.20 3.50

0.16 2.77

0.16 2.77

0.16 2.77

0.16 2.77

Cd Pb Zn HCB

kg kg kg g

PCDD/F mg PCB g

6.32 5.73

6.32 5.73

6.32 5.73

8.00 7.25

8.00 7.25

8.00 7.25

6.32 5.73

6.32 5.73

6.32 5.73

6.32 5.73

Unit

2000

2001

2002

2003

2004

2005

2006

2007

2008

2009

CO2 TSP PM10 PM2.5

Gg Mg Mg Mg

0.16 1.28 1.03 0.51

0.27 2.16 1.73 0.86

0.13 1.09 0.87 0.43

0.06 0.51 0.41 0.20

0.15 1.25 1.00 0.50

0.19 1.53 1.22 0.61

0.15 1.22 0.98 0.49

0.18 1.50 1.20 0.60

0.17 1.35 1.08 0.54

0.21 1.67 1.34 0.67

As Cd Pb Zn

kg kg kg kg

HCB g PCDD/F mg PCB g

104

0.87 0.87 0.87 1.10 1.10 1.10 0.87 0.87 0.87 0.87 336.54 336.54 336.54 426.00 426.00 426.00 336.54 336.54 336.54 336.54 2.05 2.05 2.05 2.60 2.60 2.60 2.05 2.05 2.05 2.05 0.24 0.24 0.24 0.30 0.30 0.30 0.24 0.24 0.24 0.24

2.77 4.66 2.34 1.10 2.70 3.29 2.63 3.22 2.91 3.61 0.87 1.46 0.74 0.35 0.85 1.04 0.83 1.01 0.92 1.13 336.54 566.58 284.99 133.76 328.02 400.87 319.50 391.92 354.43 438.78 2.05 3.46 1.74 0.82 2.00 2.45 1.95 2.39 2.16 2.68 0.24 6.32 5.73

0.40 10.64 9.64

0.20 5.35 4.85

0.09 2.51 2.28

Unit

2010

2011

2012

2013

CO2 TSP

Gg Mg

0.18 1.44

0.24 1.93

0.13 1.08

0.16 1.27

PM10 PM2.5 As Cd

Mg Mg kg kg

1.15 0.58 3.10 0.97

1.54 0.77 4.16 1.31

0.86 0.43 2.32 0.73

1.02 0.51 2.74 0.86

Pb Zn HCB PCDD/F

kg kg g mg

PCB

g

377.01 506.09 282.01 333.56 2.30 3.09 1.72 2.04 0.27 0.36 0.20 0.23 7.08 9.50 5.30 6.26 6.42

8.61

4.80

5.68

0.23 6.16 5.58

0.28 7.53 6.82

0.23 6.00 5.44

0.28 7.36 6.67

0.25 6.66 6.03

0.31 8.24 7.47

Figure 5.6.1 Emission of greenhouse gasses from secondary lead production.

5.6.4 Time series consistency and completeness The time series for secondary lead production is considered to be both consistent and complete.

5.6.1 Input to CollectER The input data/data sources are presented in Table 5.6.4. Table 5.6.4 Input data for calculation of emissions from lead production. Activity

Year Parameter 1990-2013 Production data

Emissions 1990-2013 Emission factors

Comment/Source Helle Bjerrum Holm (Hals Metal), personal communication, September 2014, estimated from Lassen et al. (2004) IPCC (2006), EMEP/EEA (2013), Nielsen et al. (2013a)

5.6.2 Future improvements There are no planned improvements for this sector.

105

6

Electronics Industry

The sector Electronics industry (CRF 2E) covers the use of HFCs and PFCs in the production of fibre optics. There is no production of semiconductors (CRF 2E1), TFT flat panels (CRF 2E2) or photovoltaics resulting with use of F-gases (CRF 2E3). No use of HFCs or PFCs as heat transfer fluids (CRF 2E4) occur in Denmark. As a result the only relevant category in this sector is: • Other electronics industry (CRF 2E5): Fibre optics; see sections below. The description of consumption and emission of F-gases given below is based on Poulsen (2015). For further details refer to this report.

6.1

Greenhouse gas emissions

The use of F-gases in the production of fibre optics did not start until 2006 and hence the time series covers the years 2006-2013. The emission time series for Electronics Industry are presented in Figure 6.1.1 and Table 6.1.1.

Figure 6.1.1 Emissions of HFCs and PFCs from Electronics Industry.

Table 6.1.1 Emission from Electronics industry. 2007

2008

2009

2010

2011

2012

HFC-23

Unit 2006 Mg

0.08

0.24

0.12

0.24

0.36

0.36

0.12

NO

PFC-14 (CF4)

Mg

0.25

0.14

0.11

0.36

0.36

0.20

0.18

0.50

PFC-318 (c-CF4F8)

Mg

0.20

0.45

0.35

0.45

0.45

0.40

0.20

NO

HFC-23

Gg CO2-eq.

0.94

2.81

1.40

2.81

4.21

4.21

1.40

0.00

PFC-14 (CF4)

Gg CO2-eq.

1.86

1.03

0.80

2.34

2.66

1.30

1.33

3.70

PFC-318 (c-CF4F8) Gg CO2-eq.

2.06

4.64

3.61

3.92

4.64

3.48

2.06

0.00

Total

4.86

8.48

5.81

9.06

11.51

8.99

4.79

3.70

Gg CO2-eq.

6.2

Other electronics industry

The following source category is covered: • Fibre optics 106

2013

The following pollutants are included for fibre optics: • F-gases: HFC-23, PFC-14 (CF4), PFC-318 (c-CF4F8)

6.2.1 Process description Both HFCs and PFCs are used for technical purposes in Danish optics fibre production. HFC-23 and PFCs (PFC-14 & PFC-318) are used as protection and cleaning gases in the production process.

6.2.2 Methodology Consumption data are directly available from the importer supplying the gases for producing fibre optics and process specific emission factors are used, hence the methodology corresponds to the IPCC Tier 3 method (IPCC, 2006). Activity data The consumption of PFCs from fibre optics production was 0.5 tonnes in 2013. This sector usually uses both PFC-14 and PFC-318 for technical purposes, but in 2013, only PFC-14 has been used. There was no use of HFC-23 in 2013. The consumption data are provided in Table 6.2.1 below. Table 6.2.1 Consumption of F-gases in production of fibre optics, Mg. 2006

2007

2008

2009

2010

2011

2012

HFC-23

0.08

0.24

0.12

0.24

0.36

0.36

0.12

2013 NO

PFC-14 (CF4)

0.25

0.14

0.11

0.36

0.36

0.20

0.18

0.50

PFC-318 (c-CF4F8)

0.20

0.45

0.35

0.45

0.45

0.40

0.20

NO

Emission factors Since both HFC-23 and the PFCs are used as protection and cleaning gases in the production process, the emission factor is defined as 100 per cent release during production.

6.2.3 Time series consistency and completeness The time series is considered complete and consistent. The estimates are based on information directly from the importer supplying this sector in Denmark.

6.2.4 Future improvements No improvements are planned for this sector.

107

7

Product Uses as Substitutes for Ozone Depleting Substances (ODS)

The sector Product uses as substitutes for ODS (CRF 2F) includes the following source categories and the following F-gases of relevance for Danish emissions: • Refrigeration and air conditioning (CRF 2F1): HFC-32, -125, -134a, -152a, 143a, PFC-218 (C3F8) • Foam blowing agents (CRF 2F2): HFC-134a, -152a • Aerosols (CRF 2F4): HFC-134a • Solvents (CRF 2F5): PFC-218 (C3F8) It must be noted that the inventories for the years 1990-1994 might not cover emissions of these gases in full. The choice of base-year for these gases under the Kyoto Protocol is 1995 for Denmark. The description of consumption and emission of F-gases given below is based on Poulsen (2015). For further details refer to this report.

7.1

Greenhouse gas emissions

The emission time series for Product uses as substitutes for ODS are presented in Figure 7.1.1 and Table 7.1.1.

Figure 7.1.1 Emission of F-gases from the individual source categories within Product uses as substitutes for ODS, Gg CO2-eq.

Table 7.1.1 Emission of F-gases from Product uses as substitutes for ODS, Gg CO2-eq. 1990

108

1995

2000

2005

2010

2011

2012

2013

Refrigeration and air conditioning

NO

43.2 520.8 799.4 841.6 787.6 715.8 711.0

Foam blowing agents

NO 199.5 184.1 130.6

95.9

85.2

72.7

60.7

Aerosols

NO

NO

20.8

23.1

18.4

17.5

17.4

17.7

Solvents

NO

NO

2.4

NO

NO

NO

NO

NO

Total

NO 242.8 728.1 953.1 955.9 890.2 805.9 789.3

7.1.1 General trends The phase out of F-gases has in particular been effective within the foam blowing sector and refrigeration and air conditioning installations. Regarding foam blowing, there was a stepwise phase-out of HFC-134a used for foam blowing in hard and soft foam production, during the period 20012004. In 2006, all foam productions plants in Denmark had substituted HFCs. Especially the phase-out of HFCs in soft foam is significant for the emission in this period. Since the introduction of taxes on HFCs in 2001, the consumption decreased in 2002-2003, but then the consumption of HFCs for refrigeration purposes increased again. Especially HFC-404a and HFC-134a increased. This increase is explained with other initiatives in Danish legislation, where new refrigeration systems containing HCFC-22 (ODS) was banned from 2001. It caused a boom in refrigeration systems using HFCs during 2002-2004, because the HFC technology was cheap and well proven. The consumption of HFCs for refrigeration changed significantly after 1 January 2007, where new larger HFC installations with charges exceeding 10 kg were banned. Alternative refrigeration technologies based on CO2, propane/butane and ammonia were then introduced and made available for customers. There has been no import of PFC-218 (C3F8) since 2008, and it is expected that this refrigerant is phased out of the marked. Emissions occur from the existing stock but are naturally decreasing. The use of PFC-218 (C3F8) as a solvent only occurred from 2000 to 2002. A quantitative overview is given below for each of these source categories and each F-gas, showing their emissions in Mg through the times-series. The emission of HFCs increased rapidly in the 1990s and, thereafter, increased more modestly due to a modest increase in the use of HFCs as a refrigerant and a decrease in foam blowing. The F-gases have been regulated in two ways since 1 March 2001. For some types of use there is a ban on use of the gases in new installations and for other types of use, taxation is in place. These regulations seem to have influenced emissions so that in the latest years a decreasing trend can be observed.

7.2

General methodology

The data for emissions of HFCs and PFCs have been obtained in continuation of the work on previous inventories. The determination includes the quantification and determination of any import and export of HFCs and PFCs contained in products and substances in stock form. This is in accordance with the IPCC guidelines (IPCC, 2006). For the Danish inventories of F-gases, a Tier 2 bottom-up approach is basically used. In an annex to the F-gas inventory report (Poulsen, 2015), there is a specification of the approach applied for each sub-source category. The following sources of information have been used: • • • •

Importers, agency enterprises, wholesalers and suppliers Consuming enterprises, and trade and industry associations Recycling enterprises and chemical waste recycling plants Statistics Denmark 109

• Danish Refrigeration Installers’ Environmental Scheme (KMO) • Previous evaluations of HFCs and PFCs (and SF6) Suppliers and/or producers provide consumption data of F-gases. Emission factors are primarily defaults from IPCC (2006), which are assessed to be applicable in a national context. In case of commercial refrigerants and Mobile Air Conditioning (MAC), information from Danish suppliers has been used. The actual amount of F-gas used for refilling is used as an estimate on the actual emission. Import/export data for sub-source categories where import/export is relevant (MAC, fridges/freezers for households) are quantified on estimates from import/export statistics of products + default values of the amount of gas in the product. The estimates are transparent and described in appendix 3 of Poulsen (2015). The Tier 2 bottom-up analysis used for determination of emissions from HFCs and PFCs covers the following activities: • • • •

Screening of the market for products in which F-gases are used Determination of averages for the content of F-gases per product unit Determination of emissions during the lifetime of products and disposal Identification of technological development trends that have significance for the emission of F-gases • Calculation of import and export on the basis of defined key figures, and information from Statistics Denmark on foreign trade and industry information The determination of emissions of F-gases is based on a calculation of the actual emission. The actual emission is the emission in the evaluation year, accounting for the time lapse between consumption and emission. The actual emission includes Danish emissions from production, from products during their lifetimes and from disposal. Consumption and emissions of F-gases are, whenever possible, determined for individual substances, even though the consumption of certain HFCs has been very limited. This has been carried out to ensure transparency of evaluation in the determination of GWP values. However, the continued use of a category for Unspecified mix of HFCs has been necessary since not all importers and suppliers have specified records of sales for individual substances. Table 7.2.1 Content (w/w%)1 of “pure” HFC in HFC-mixtures, used as trade names. HFC mixtures

HFC-32

HFC-125

HFC-134a

HFC-143a

%

%

%

%

HFC-152a HFC-227ea %

HFC-365

8

HFC-401a

13

HFC-402a

60

HFC-404a

44

4 52

HFC-407c

23

25

HFC-410a

50

50

HFC-507a 1

%

50

52

50

The mixtures do also contain substances that do not have GWP values and therefore, the substances do not sum up to 100 %.

110

The substances have been accounted for in the survey according to their trade names, which are mixtures of HFCs used in IPCC (2006). In the transfer to the "pure" substances, the ratios provided in Table 7.2.1 have been used. The national inventories for F-gases are provided and documented in an annual report (Poulsen, 2015). Furthermore, detailed data and calculations are available and archived in an electronic version. The report contains summaries of methods used and information on sources as well as further details on methodologies.

7.3

Refrigeration and air conditioning

Refrigeration and air conditioning consists of the following subcategories: • • • • • •

Commercial refrigeration (CRF 2F1a) Domestic refrigeration (CRF 2F1b) Industrial refrigeration (included under commercial) (CRF 2F1c) Transport refrigeration (CRF 2F1d) Mobile air-conditioning (CRF 2F1e) Stationary air-conditioning (included under commercial) (CRF 2F1f)

The use of HFCs in industrial refrigeration was previously surveyed and the conclusion was that large-scale industrial refrigeration e.g. slaughterhouses, fish factories and medico companies use ammonia based refrigeration units. This is particularly caused by the tax on HFCs in Denmark that makes HFC based refrigeration units with large charges too expensive and furthermore the ban from 2007. Smaller HFC based units will occur in industry, but is then similar to commercial refrigeration units. Since it is not possible to separate small-scale industrial and commercial refrigeration units, all consumption and emissions are reported under commercial refrigeration. For stationary air-conditioning, the same gases as frequently used in commercial refrigeration are used, e.g. HFC-404a and HFC-407c. It is difficult to estimate the share of these gases going to the different uses as the same suppliers are servicing both types of units. As a consequence the consumption and emissions are reported under commercial refrigeration.

7.3.1 Methodology For refrigeration and air-conditioning, Denmark uses mainly the Tier 2 topdown approach (Tier 2b). However, for Domestic Refrigeration the methodology is a combination of Tier 2a and 2b. For more information on the applied methodology please refer to Poulsen (2015). According to Danish law, refrigerators and air-conditioning equipment must be emptied before decommissioning by recovery, reuse or destruction of the remaining gases. The data collection is described in the Chapter 7.2 General methodology. Activity data The activity data expressed as amount of HFCs and PFCs filled into new products, present in operating systems and remaining in products at decommissioning are presented in Table 7.3.1, Table 7.3.2 and Table 7.3.3 respectively. 111

Table 7.3.1 Filled into new manufactured refrigeration products. 1996 1997 Unit 1995 HFC-32 Commercial Mg NO NO 3.2 HFC-125 Total Mg 62.1 61.7 63.2 Commercial Mg 59.3 57.4 58.4 Domestic Mg 0.9 1.8 3.5 Transport Mg 1.9 2.5 1.3 HFC-134a Total Mg 371.9 364.5 363.8 Commercial Mg 104.7 157.2 58.4 Domestic Mg 267.1 200.2 298.3 Transport Mg 0.1 0.1 0.1 Mobile A/C Mg NO 7.0 7.0 HFC-143a Total Mg 63.4 58.8 62.8 Commercial Mg 60.8 55.1 57.0 Domestic Mg 1.0 2.1 4.2 Transport Mg 1.6 1.6 1.6 HFC-152a Commercial Mg NO NO 3.4 Unspec. Commercial Gg 29.2 41.8 33.4 HFCs C3F8 Commercial Mg 1.5 3.0 8.0 Unit 2005 2006 2007 HFC-32 Commercial Mg 14.2 16.2 11.6 HFC-125 Total Mg 89.6 98.3 75.5 Commercial Mg 84.7 93.5 73.8 Domestic Mg 1.6 1.9 1.3 Transport Mg 3.3 2.9 0.4 HFC-134a Total Mg 250.7 311.9 175.2 Commercial Mg 150.9 213.7 106.0 Domestic Mg 65.7 63.2 33.6 Transport Mg 0.8 0.7 0.4 Mobile A/C Mg 33.3 34.4 35.2 HFC-143a Total Mg 87.2 94.8 73.3 Commercial Mg 81.4 89.1 71.3 Domestic Mg 1.9 2.3 1.6 Transport Mg 3.9 3.4 0.4 HFC-152a Commercial Mg NO NO NO Unspec. Commercial Gg 30.3 26.8 75.3 HFCs C3F8 Commercial Mg 0.5 NO 0.1

112

1998 3.9 90.9 72.1 6.2 12.6 569.7 222.1 257.6 1.0 89.0 94.4 73.6 7.3 13.5 2.0

1999 9.2 121.1 94.4 10.6 16.2 374.5 138.2 205.0 1.4 30.0 123.3 93.1 12.5 17.7 2.0

2000 10.3 118.3 106.4 4.0 7.9 468.1 203.0 240.4 0.7 24.0 121.6 107.5 4.7 9.4 1.3

2001 9.3 67.2 61.7 2.9 2.6 291.8 127.9 130.4 2.6 30.9 66.7 60.2 3.4 3.1 0.5

2002 20.5 112.5 105.8 2.0 4.7 333.4 184.9 115.6 1.0 31.9 105.3 97.4 2.3 5.6 NO

2003 22.3 93.6 89.0 1.9 2.7 267.5 140.4 94.3 0.7 32.1 80.0 74.5 2.2 3.2 0.0

2004 23.3 141.8 136.4 2.7 2.7 333.5 216.8 83.5 0.9 32.4 136.6 130.3 3.2 3.2 NO

31.3

60.5

50.1

33.9

15.7

27.1

29.6

6.0 2008 17.7 70.3 66.2 0.9 3.2 201.1 126.9 37.7 0.8 35.7 60.2 55.4 1.0 3.8 NO

6.9 2009 11.4 62.9 59.8 0.5 2.6 197.8 135.7 17.6 0.7 43.8 59.1 55.4 0.6 3.0 NO

6.3 2010 9.7 60.7 57.4 0.6 2.7 181.3 106.5 6.8 0.7 67.3 58.4 54.5 0.8 3.2 NO

3.2 2011 9.8 60.0 56.3 0.8 2.9 201.6 117.3 9.3 0.9 74.1 57.7 53.3 0.9 3.4 NO

1.4 2012 9.8 60.5 56.8 0.8 3.0 192.6 124.0 9.5 0.6 58.6 57.8 53.4 0.9 3.5 NO

0.5 2013 10.1 61.4 56.7 1.3 3.4 175.1 96.0 11.2 0.6 67.2 57.8 52.3 1.5 4.1 NO

0.3

55.5

25.3

43.8

61.6

53.3

72.1

0.1

NO

NO

NO

NO

NO

Table 7.3.2 In operating refrigerating systems (average annual stocks). 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 Unit HFC-32 Commercial Mg NO NO 3.2 6.7 15.1 23.7 30.5 47.6 64.8 81.2 HFC-125 Total Mg 73.8 126.9 176.1 247.5 339.9 429.3 432.4 501.4 544.9 631.7 Commercial Mg 70.8 120.3 165.8 220.2 291.2 366.9 390.9 456.1 498.1 582.6 Domestic Mg 0.9 2.6 6.0 12.0 22.2 25.9 28.4 30.1 31.6 33.9 Transport Mg 2.2 4.0 4.3 15.3 26.5 36.6 13.0 15.3 15.2 15.2 HFC-134a Total Mg 342.5 552.1 717.2 1110.6 1259.2 1483.5 1623.6 1761.4 1810.2 1925.6 Commercial Mg 177.2 310.2 333.0 508.5 581.5 698.9 727.9 815.0 824.7 906.5 Domestic Mg 165.2 235.0 372.5 480.2 535.3 624.5 681.0 729.7 767.8 800.3 Transport Mg 0.1 0.2 0.3 1.2 2.1 10.8 9.7 9.0 8.1 7.6 Mobile A/C Mg NO 6.7 11.4 120.7 140.3 149.3 205.1 207.6 209.6 211.2 HFC-143a Total Mg 74.3 124.4 173.5 248.6 342.8 436.8 435.3 497.4 528.4 612.2 Commercial Mg 71.5 118.6 162.9 219.2 289.0 366.0 388.7 445.8 474.7 555.5 Domestic Mg 1.0 3.0 7.1 14.2 26.2 30.6 33.6 35.5 37.4 40.1 Transport Mg 1.8 2.8 3.4 15.3 27.6 40.2 12.9 16.0 16.4 16.6 HFC-152a Commercial Mg NO NO 3.3 4.9 6.3 7.0 6.8 6.1 5.5 5.0 Unspec. HFCs Commercial Gg 28.8 67.0 93.2 114.7 162.9 196.0 209.8 204.3 210.6 218.7 C3F8 Commercial Mg 1.9 4.7 12.1 16.8 21.9 25.9 26.5 25.3 23.2 21.2 Unit 2005 2006 2007 2008 2009 2010 2011 2012 2013 HFC-32 Commercial Mg 87.1 94.4 96.4 104.1 104.9 104.0 103.3 102.3 101.5 HFC-125 Total Mg 658.6 691.5 698.9 700.5 682.9 624.8 584.6 556.0 523.9 Commercial Mg 607.8 639.1 647.9 648.3 631.0 574.1 535.8 510.8 481.7 Domestic Mg 35.1 36.6 37.5 38.0 38.1 37.5 36.4 33.8 29.6 Transport Mg 15.7 15.8 13.4 14.2 13.8 13.1 12.3 11.3 12.6 HFC-134a Total Mg 1957.0 2071.1 2041.6 2008.4 1964.0 1839.1 1835.7 1909.6 1649.2 Commercial Mg 909.0 995.0 953.4 917.0 887.4 792.8 685.7 726.8 578.4 Domestic Mg 823.9 846.1 853.8 855.2 838.7 810.6 716.6 747.6 629.2 Transport Mg 7.1 6.5 5.8 5.6 5.3 5.0 4.9 4.4 4.2 Mobile A/C Mg 217.0 223.6 228.6 230.6 232.6 230.7 428.6 430.8 437.3 HFC-143a Total Mg 639.1 670.9 678.6 672.8 653.0 587.6 543.5 512.1 475.0 Commercial Mg 580.1 609.9 619.1 611.7 592.1 528.1 486.2 459.0 425.4 Domestic Mg 41.5 43.3 44.3 44.9 45.0 44.4 43.1 40.0 35.0 Transport Mg 17.5 17.8 15.2 16.2 15.8 15.1 14.2 13.1 14.7 HFC-152a Commercial Mg 4.5 4.0 3.6 3.3 2.9 2.7 2.4 1.8 1.4 Unspec. HFCs Commercial Gg 226.6 230.4 281.5 308.0 302.1 311.6 336.7 352.4 385.7 C3F8 Commercial Mg 19.5 17.6 15.9 14.4 12.9 11.4 10.0 8.1 6.7

Table 7.3.3 Remaining in refrigeration products at decommissioning. 2008 2009 2010 Unit 2007 HFC-32 Commercial Mg NO NO NO NO HFC-125 Total Mg 0.0 0.0 11.3 51.0 Commercial Mg NO NO 11.3 50.3 Domestic Mg NO NO NO 0.7 HFC-134a Total Mg 8.0 46.6 48.7 107.5 Commercial Mg 8.0 38.5 32.2 84.5 Domestic Mg NO 8.1 16.5 23.0 HFC-143a Total Mg 0.0 0.0 13.0 59.3 Commercial Mg NO NO 13.0 58.4 Domestic Mg NO NO NO 0.9 HFC-152a Commercial Mg NO NO NO NO Unspec. HFCs Commercial Gg NO NO NO 3.4 C3F8 Commercial Mg NO NO 0.1 0.2

2011 NO 37.8 36.4 1.5 210.9 120.5 90.4 43.4 41.7 1.7 NO 4.5 0.3

2012 0.4 30.2 27.3 2.9 193.4 133.9 59.4 34.6 31.1 3.5 NO 3.1 0.9

2013 0.4 39.1 34.0 5.1 263.7 147.4 116.3 45.3 39.2 6.1 NO 2.5 0.6

The first products containing F-gasses are modelled to be decommissioned in 2007. All F-gasses filled into mobile and transport refrigeration are assumed to emit during use, and no F-gasses are therefore remaining at decommissioning from these products.

113

Emission factors The applied EFs are presented in Table 7.3.4. The EFs for commercial refrigerators, mobile A/C, and transport refrigeration has been assessed and compared with national conditions (Poulsen, 2003), this has been reevaluated and the values have been found to still be applicable for Danish conditions (Poulsen, 2015). Table 7.3.4 Applied EFs for refrigeration and air-condition systems (Poulsen, 2015). Stock, Assembly, %

% per annum

Lifetime

2

1

15 years

Commercial refrigerators

1.5

10

Mobile air conditioning systems

0.5

33

Transport refrigeration

0.5

17

Household fridges and freezers

6-8 years

Detailed information on the amount of HFCs used for refilling of mobile A/C has been available for 2009 - 2011, and therefore, a new approach has been implemented in the calculation of emissions. HFCs for mobile A/C are only used for refilling, and therefore the amount used for mobile A/C is assumed to be the same as the amount emitted during use (Poulsen, 2015): Consumption of HFC for MAC = refilled stock = emission

7.3.2 Emission trends Figure 7.3.1 present the emissions of F-gases from consumption of HFCs and

PFCs in refrigeration and air-conditioning systems.

Figure 7.3.1 Emissions from refrigeration and air-conditioning from 1990 to 2013.

F-gas emissions from refrigeration and air-conditioning are dominating the overall emissions from this source. Hence the increasing trend from the early 1990s to 2009 and the subsequent decrease in emissions are explained in Chapter 7.1.

7.3.3 Time series consistency and completeness The time series is considered complete and consistent.

114

7.3.4 Future improvements There are no planned improvements for this source category.

7.4

Foam blowing agents

Foam blowing agents (CRF 2F2) consists of the following processes: • Closed cells (hard foam) • Open cells (soft foam) In Denmark five specific processes have occurred during the time series, i.e. foam in household fridges and freezers (closed cell), soft foam (open cell), joint filler (open cell), foaming of polyether for shoe soles (closed cell) and system foam for panels, insulation etc. (closed cell)

7.4.1 Methodology The methodology used varies between the different processes. For all processes the methodology corresponds to the Tier 2 level of IPCC (2006). For some processes a bottom-up methodology is applied while for others a topdown approach or a combination of top-down and bottom-up is used. For more information on the details of the applied methodology, please refer to Poulsen (2015). Activity data The data collection is described in the Section 7.2 on general methodology. There is no longer production of HFC-based hard PUR insulation foam in Denmark. This production has been banned in statutory order since 1. January 2006 (MIM, 2002). Emission factors The applied emission factors for foam blowing agents are presented in Table 7.4.1. Table 7.4.1 Applied emission factors for foam blowing agents (Poulsen, 2015).

Foam in household fridges and freezers (closed cell)

Consumption

Stock

Lifetime

%

%

years

10

4.5

15

4.5

3

Soft foam (open cell)

1001

Joint filler (open cell)

1001

Foaming of polyether for shoe soles (closed cell) System foam

15 2

0

-

3

1

100 % emission during the first year after production. 2 HFC is used as a component in semi-manufactured goods and emissions first occur when the goods are put into use. 3 System foam is only produced for export.

System foam is produced in a closed environment and is only produced for export. Therefore, the consumption of HFCs does not contribute to the Danish stock. The EFs for foam in fridges and freezers, soft foam and joint filler are default values from the 2006 IPCC guidelines (IPCC, 2006). The EFs for foaming of polyether is country-specific, please refer to Poulsen (2015). 115

The F-gases remaining in products at decommissioning (closed cell products) are destroyed by incineration and hence there is no F-gas emissions related to disposal of these products.

7.4.2 Emission trends Figure 7.4.1 presents the emissions of F-gases from consumption of HFCs in foam blowing agents.

Figure 7.4.1 Emissions from foam blowing agents from 1990 to 2013.

The sharp fluctuations in the time series are caused by fluctuations in the consumption of HFCs in production of soft foam, with an EF of a 100 % in the given year. For the later part of the time series the trend reflects the limited use of HFCs consumed and reflects the emission from the stock of previous use of HFCs.

7.4.3 Time series consistency and completeness The time series is considered complete and consistent.

7.4.4 Future improvements There are no planned improvements for this source category.

7.5

Fire protection

No HFCs or PFCs are used in fire protection in Denmark. The use of halogen substituted hydrocarbons has been banned since 1977 (MIM, 1977), this ban is still in place (MIM, 2009). Halon-1301 has been used in planes, in the military, in server rooms and on ships. New fire protection systems use other technologies, e.g. early fire detection, inert gases or gas mixtures (argon, nitrogen and CO2) or water vapour. For mobile systems halon-1211 has been replaced with CO2 or foam fire extinguishers.

7.6

Aerosols

Aerosols (CRF 2F4) consists of HFCs used for: • Propellant in aerosols • Metered dose inhalers 116

7.6.1 Methodology For HFC use as propellant in aerosol cans the IPCC Tier 2a default methodology is used (IPCC, 2006). A default emission factor of 50 % of the initial charge per year is used for aerosols while an emission factor of 100 % of the initial charge per year is used for metered dose inhalers. Activity data The general data collection process is described in the Section 7.2. Information on propellant consumption is derived from reports on consumption from the only major producers of HFC-containing aerosol sprays in Denmark. The import and export are estimated by the producer. Emission factors The applied EF is presented in Table 7.6.1. Table 7.6.1 Applied EF for aerosols/medical dose inhalers (Poulsen, 2015). Consumption/filling Aerosols

0%

Stock

Lifetime

50 % first year

2 years

50 % second year Medical dose inhalers

0%

100 % in year of

1 year

application

7.6.2 Emission trends Figure 7.6.1 presents the emissions of F-gases from consumption of HFCs in aerosols.

Figure 7.6.1 Emissions from HFCs from aerosols from 1990 to 2013.

Due to the methodology used, the fluctuations in the time series are a result of changes in import, production and export. Baring these fluctuations the emission level has been rather constant at a level between 15 and 20 Gg CO2 equivalents.

7.6.3 Time series consistency and completeness The time series is considered complete and consistent.

7.6.4 Future improvements There are no planned improvements for this source category. 117

7.7

Solvents

C3F8 was used as cleaner from 2000 to 2002 and the use then ceased following the ban in accordance with the Executive Order (MIM, 2002).

7.7.1 Methodology The methodology used is the IPCC default and the fraction of chemical emitted from solvents in the year of initial use is assumed to be 50 % in line with good practice. The other 50 % is assumed to be emitted in the second year and hence there is no subtraction of any destruction of solvents (IPCC, 2006). Activity data The general data collection process is described in the Section 7.2. Information on consumption of PFCs in liquid cleaners is derived from two importers’ sales reports. This is representing 100 % of the Danish consumption. Emission factors In accordance with IPCC (2006), the emission factor is 50 % in year 1 and 50 % in year 2.

7.7.2 Emission trends Figure 7.7.1 presents the emissions of F-gases from consumption of PFCs used as solvents.

Figure 7.7.1 Emissions from PFCs used as solvents from 1990 to 2013.

As mentioned the use of PFCs as solvent only occurred from 2000 to 2002 and hence emissions only occurred from 2000 to 2003.

7.7.3 Time series consistency and completeness The time series is considered complete and consistent.

7.7.4 Future improvements There are no planned improvements for this source category.

118

8

Other Product Manufacture and Use

The sector Other Product Manufacture and Use (CRF 2G) cover the following processes relevant for the Danish air emission inventory: • • • •

Electrical equipment (CRF 2G1); see section 8.2 SF6 from other product use (CRF 2G2); see section 8.3 Medical applications of N2O (CRF 2G3a); see section 8.4 N2O used as propellant for pressure and aerosol products (CRF 2G3b); see section 8.5 • Other product use (CRF 2G4); see section 8.68.6

8.1

Greenhouse gas emissions

The greenhouse gas emission time series for the source categories within Other Product Manufacture and Use are presented in Figure 8.1.1 and individually in the subsections below (Sections 8.2 – 8.6). The following figure gives an overview of which source categories that contribute the most throughout the time series. The significant increase in SF6 emission from 2010 onwards is caused by the disposal of windows containing SF6. The first windows containing SF6 were introduced in 1991 and with and estimated lifetime of 20 years, the first disposal emissions occurred in 2011.

Figure 8.1.1 Emission of CO2 equivalents from the individual source categories compiling Other Product Manufacture and Use, Gg.

8.2

Electrical equipment

Power switches in high-voltage power systems is the only use of SF6 in electrical equipment in Denmark.

8.2.1 Methodology The general data collection process for F-gases is described in the Section 7.2. Power switches are filled or refilled with SF6, either for new installation or during service and repair. Filling is usually carried out on new installations and a smaller proportion of the consumption of SF6 is due to refilling.

119

The methodology uses annual data from importers statistics with detailed information on the use of the gas. It is estimated that 5 % of SF6 escapes to the atmosphere during filling/refilling. This corresponds to the Tier 3 methodology in IPCC (2006). No emissions are assumed to result from disposal since the used SF6 is drawn off from the power switches and re-used internally by the concerned or appropriate disposed through a waste collection scheme. Activity data The data collection is described in the Section 7.2. Information on consumption of SF6 in high-voltage power switches is derived from importers’ sales reports (gas or gas-containing products). The importers account for 100 % of the Danish sales of SF6. The electricity sector also provides information on the installation of new plant and thus whether the stock is increasing. Emission factors The applied EFs are presented in Table 8.2.1. Special attention has been given to use of SF6 as insulation in high-voltage plants (Poulsen, 2001; ELTRA, 2004). Table 8.2.1 Applied EFs for other processes (Poulsen, 2015). Insulation gas in high voltage switches 1)

Consumption

Stock

Lifetime

5%

0.5 %

1

Lifetime unknown.

8.2.2 Emission trends Figure 8.2.1 presents the emissions of SF6 from electrical equipment.

Figure 8.2.1 Emissions from SF6 from electrical equipment from 1990 to 2013.

The trend shows an increase in emissions from use of SF6 in electrical equipment. However, significant inter-annual variations occur depending on the specific activity level in a given year.

120

8.2.3 Time series consistency and completeness The time series is considered complete and consistent.

8.2.4 Future improvements There are no planned improvements for this source category.

8.3

SF6 from other product use

SF6 from other product use (CRF 2G2) consists of the following subcategories: • Consumption of SF6 in running shoes • Consumption of SF6 in laboratories Consumption of SF6 in double glazed windows

8.3.1 Methodology In general a mass balance approach is used for laboratory use of SF6, this used includes plasma erosion in connection with the manufacture of microchips in clean-room laboratories and to a limited extend purposes of chemical analysis. For double glazed windows and shock-absorption in running shoes a Tier 2 method has been applied and data on the consumption of SF6 is available from the importers. For double glazed windows the default IPCC methodology is used with country-specific emission factor. For more information, please refer to Poulsen (2015). Consumption of SF6 in production of double glazed thermal windows started in 1991 and has been banned since 1 January 2003 (MIM, 2002). Activity data The data collection is described in the Section 7.2. Information on consumption of SF6 in double glazing is derived from importers’ sales reports to the application area. The importers account for 100 % of the Danish sales of SF6 for double glazing. In addition, the largest producer of windows in Denmark has provided consumption data, with which import information is compared. The importer has estimated imports to Denmark of SF6 in training footwear. The emission from the use of SF6 in laboratories is 100 % release during consumption. Emission factors The applied EFs are presented in Table 8.3.1. Table 8.3.1 Applied EFs for SF6 from other product use (Poulsen, 2015). Consumption Laboratories

100 %

Insulation gas in double glazed windows

15 %

Shock-absorbing in Nike Air training footwear

-

1

Stock

Lifetime

1 % annual 20 years -2

5 years

1

No emission from production in Denmark. 2 Yearly emission has been estimated to 0.11 Mg (Poulsen, 2015).

121

8.3.2 Emission trends Figure 8.3.1 presents the emissions of SF6 from shoes, double glazed windows

and laboratories.

Figure 8.3.1 Emissions from SF6 from other uses from 1990 to 2013.

The use of SF6 in double glazed windows was banned in 2002 and the use had decreased in the prior years. The increase in SF6 emission from 2010 onwards is due to the lifetime of 20 years, i.e. the gas remaining in the windows at this time is assumed to be fully emitted.

8.3.3 Time series consistency and completeness The time series is considered complete and consistent.

8.3.4 Future improvements There are no planned improvements for this source category.

8.4

Medical applications of N2O

The following SNAP-code is covered: • 06 05 01 Anaesthesia

8.4.1 Methodology N2O has been used as anaesthetics for more than a hundred years but has in newer times also had other smaller applications. N2O in this source category is predominantly used as anaesthesia and a small amount is used as fuel in race cars and in chemical laboratories. However, since consumption cannot be distinguished between these activities it is all reported under anaesthesia. In the mid-1990s, introduction of air quality limit values for N2O together with requirements of expensive extraction systems reduced the application of N2O for anaesthetics at smaller facilities like dentists. Five companies sell N2O in Denmark and only one company produces N2O. N2O is primarily used in anaesthesia by dentists, veterinarians and in hospitals and in minor use in laboratories, racing cars 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. Sold 122

amounts are obtained from the respective distributors and the produced amount is estimated from communication with the company. Activity data Data on total sold and estimated produced N2O for sale in Denmark is only reliable for the years 2005-2012, activity data for the years 1990-2004 and 2013 have therefore been estimated as the average value of the five following/previous years. Activity data for the time series are presented in Table 8.4.1. Table 8.4.1 Activity data for N2O mainly used for medical applications, Mg. 1990-2004 2005 2006 2007 2008 2009 N2O consumption 401 37 1) Calculated: average 2005-2009. 2) Calculated: Average 2008-2012.

38

43

33

46

2010 2011 2012 2013 34

42

30

372

Emission factors An emission factor of 1 is assumed for all uses, meaning 100 % release during consumption.

8.4.2 Emission trends The emission trend for the N2O emission from medical applications is presented in Figure 8.4.1 below.

Figure 8.4.1 N2O emissions from the use of anaesthetics.

8.4.3 Time series consistency and completeness The methodology is consistent throughout the time series. It is not possible to obtain reliable data prior to 2005, but the source category is considered to be complete though uncertainties going back from 2005 are increasing.

8.4.4 Future improvements There are no planned improvements for this source category.

8.5

N2O used as propellant for pressure and aerosol products

The following SNAP-code is covered: • 06 05 06 Aerosol cans

123

8.5.1 Methodology There is a strong tradition of fresh dairy products in Danish culture and while canned whipped cream is popular for e.g. hot beverages in the winter months this product is not that widely used. There are no statistics on production, import/export and/or sales of canned whipped cream in Denmark and the content of propellant is confidential. The consumption of canned whipped cream is therefore estimated using a country specific methodology where the canned whipped cream sale is estimated as 1 % of the regular cream sale. Further assumptions made include 5 mass% propellant in a can and 100 % release of N2O. Activity data Data on total sold cream and the estimated sale of canned cream are presented in Table 8.5.1. Table 8.5.1 Consumption of cream in Denmark, Mg. 1990

1991

Cream1 37,378 Canned cream 374

40,622 406

2000

2001

Cream1 39,380 Canned cream 394

39,849 398

2010

2011

Cream 37,201 Canned cream 372

35,606 356

1

1

1992

1993

1994

1995

1996

1997

1998

1999

39,796 41,387 40,157 46,279 42,854 42,401 40,542 42,488 398 414 402 463 429 424 405 425 2002

2003

2004

2005

2006

2007

2008

2009

39,525 42,418 38,306 37,333 36,876 45,023 35,019 34,881 395 424 383 373 369 450 350 349 2012

2013

30,408 31,859 304 319

Statistics Denmark (2014)

Emission factors The applied emission factor is 0.05 Mg N2O per Mg canned cream sold; i.e. 5 % propellant and 100 % release.

8.5.2 Emission trends The emission trend for the N2O emission from canned whipped cream is presented in Figure 8.5.1 below.

Figure 8.5.1 N2O emissions from the use of canned whipped cream (Emission 2A from Figure 8.5.2).

124

8.5.3 Verification In an attempt to verify the calculated N2O emissions from canned whipped cream, the same emission is calculated using four assumptions in different combinations. Table 8.5.2 shows the calculated emission for 2012 using the four combinations of assumptions along with the overall assumptions that a can contains 250 ml (250 g) cream and 100 % release of the propellant. Table 8.5.2 N2O released as propellant (2012), Gg Assumption 1

Assumption 2

1 can used per household per year 1 % market share of canned cream Assumption A 5 % propellant Assumption B 5 g N2O per can

0.033

0.015

0.013

0.005

Using the four assumptions presented in the table above, the time series are calculated; see Figure 8.5.2.

Figure 8.5.2 N2O emissions from the use of canned whipped cream.

Although the calculated emissions vary over the four estimated scenarios, the emission of N2O from canned whipped cream is predicted to vary between 5 Mg and 35 Mg. Emission 2A has been chosen as the best estimate and used in Figure 8.5.1. All four estimates are well below 0.05 % of the national greenhouse gas emissions; in 2012 “Emission 1A” is 0.02 % of nationally emitted CO2 equivalents (incl. LULUCF).

8.5.4 Time series consistency and completeness The time series is considered complete and consistent.

8.5.5 Future improvements There are no planned improvements for this source category.

8.6

Other product use

The use of “other” products currently includes the following SNAP-codes for the Danish inventories: 125

• 06 06 01 Use of fireworks • 06 06 02 Use of tobacco • 06 06 05 Use of charcoal for barbeques The following pollutants are included for the other product uses: • • • • • • • • • • •

CO2 CH4 N2O SO2 NOx NMVOC CO NH3 Particulate matter: TSP, PM10, PM2.5 Heavy metals: As, Cd, Cr, Cu, Hg, Ni, Pb, Se, Zn Persistent organic pollutants: HCB, PCDD/F, PAHs (benzo(a)pyrene, benzo(b)flouranthene, benzo(k)flouranthene, indeno(1,2,3-c-d)pyrene), PCBs

8.6.1 Process description Use of fireworks The use of fireworks is in general limited to a short period around New Year’s Eve. This section contains calculations of the annual aggregated emissions. In general fireworks consist of a container of papers and polymers, a propeller in form of black powder and for fireworks like e.g. rockets there is a content of different compounds for colours and effects. Black powder consists of about 75 % oxidizer, most commonly potassium nitrate but also potassium perchlorate or, less commonly, chlorate. The remaining components in black powder are a fuel (carbon), and an accelerant (sulphur). The combustion of black powder commonly produces carbon dioxide, potassium sulphide and nitrogen. (Von Oertzen et al., 2003). Different metal compounds produces different colours and effects, amongst the pollutants included in this inventory Pb, Cu and Zn are the most important. All imported fireworks must comply with the DS/EN-14035. Use of tobacco The combustion of cigarettes and other tobacco products emit a smoke that contributes to the national emissions. Vast amounts of research focusing on the health risks health risks from tobacco smoke are available, but this inventory only focuses on the impact of environmental tobacco smoke (ETS), i.e. releases to air. Use of charcoal for barbeques The quality of the charcoal depends on the wood species and the process of production. Charcoal is produced by anaerobic heating of the wood which causes the volatile components in the wood to convert to coke. The heating value for pure dry wood is 19,000 KJ per kg while pure coke has a heating value around 33,000 KJ per kg. The energy content in charcoal is therefore determined by the degree of decomposition of the volatile compounds. (Force Technology). 126

The product called Heat Beads® BBQ briquettes have won marked shares from regular charcoal for some years now but the use of this product is still relatively small compared to regular coal for barbequing. Heat Beads® consist of a certain blend of hardwood charcoal and mineral carbon made by carbonising brown coal and is therefore emitting some non-biogenic CO2. Due to confidentiality it is not possible to determine either the marked share of this product or if/how much its composition differs from other products. The amount of non-biogenic CO2 from barbequing is assumed to be negligible.

8.6.2 Methodology Use of fireworks Emissions from fireworks are calculated by multiplying the activity data available from Statistics Denmark (2014) with selected emission factors. Activity data are collected from Statistics Denmark for the years back to 1988; these data are based on information on import and export. Data for the years 1980-1987 are estimated. The cross-border shopping and use of illegal fireworks are assumed negligible. In collaboration with the Danish Pyrotechnical Association it was decided that any production of fireworks within Denmark is also negligible. It is also assumed that the effect from irregular stock control is negligible. In November 2004 an accidental explosive burning of vast amounts of fireworks occurred in Denmark. It was estimated that the explosion involved around 284 Mg net explosive mass (NEM). This episode led to a wide evaluation of the laws on use and storage of fireworks (Report Seest, 2005). Since 2005 the amount of total NEM allowed in a single piece of firework has been reduced and the use of fireworks has only been legal to use in the period December 1st to January 5th or with special permission by the local municipality. From 2014 this period was further constricted to only six days (27 December to 1 January). The heavy metal content in fireworks like Hg, Pb and As and toxic compounds like HCB have been greatly reduced over the last decade and are now legally banned, but there are still cases where trace content of HCB has been detected during random checks (Danish EPA, 2012). Other compounds like Cu have had increasing application in production of fireworks; Cu have to some extent replaced Pb in its uses. Compounds like Ni and Zn are primarily used in alloys; traces of Cd are assumedly caused by contamination of some ingredients since they have no use in fireworks (Miljöförvaltningen, 1999). Compounds that are still widely used in different amounts and for different applications are: S, C, Cu and Cl (resulting in PCDD/F emissions). Furthermore, N and O are widely used in many different combinations of nitrates, oxides, carbonates, sulphates, chlorates and more. The average NEM content in fireworks is estimated to be 20 % (Report Seest, 2005; Passant et al., 2003; Miljöförvaltningen, 1999). Use of tobacco Emissions from use of tobacco are calculated by multiplying activity data with emission factors from literature.

127

Activity data are collected from Statistics Denmark. It is assumed that crossborder shopping can be regarded as negligible and that all purchased tobacco is smoked within the same year. Use of charcoal for barbeques Emissions from barbequing are calculated by multiplying the difference between export and import with selected emission factors. Activity data for charcoal are gathered from the import/export statistics at Statistics Denmark which are available for all years back to 1988. The consumption data for 1980-1987 are estimated using extrapolation, i.e. linear regression on the 1998-2009 data and assuming that the development represented by this line is fitting for the description of the 1980-1987 data. Activity data for charcoal collected from Statistics Denmark includes: • •



Charcoal, including coal of nutshells or nuts, also agglomerated Bamboo, including coal of nutshells or nuts, also agglomerated (except for medical use, charcoal mixed with incense, activated charcoal and charcoal for drawing) Charcoal, including coal of nutshells or nuts, also agglomerated (except bamboo, charcoal dosed or packaged as medicines, charcoal mixed with incense, activated charcoal and charcoal for drawing)

It is assumed that the entire quantum of charcoal is combusted the same year as it is imported. It is further more assumed that the cross-border shopping of charcoal is negligible. In the inventory, the heating factor of 30,000 KJ per kg from the IPCC Guidelines (1996) is accepted. Activity data Data on consumption of other products are presented in Table 8.6.1 and Figure 8.6.1. Table 8.6.1 Activity data for the use of other products, Mg. 1981 1982 1983 1984 1980 Fireworks 1,000 1,000 1,000 1,000 1,000 Tobacco 13,895 14,051 14,798 13,641 13,859 BBQ 1,943 2,440 2,937 3,435 3,932 1990 1991 1992 1993 1994 Fireworks 1,279 1,693 1,830 1,617 1,963 Tobacco 12,739 11,951 12,074 11,534 11,409 BBQ 7,172 6,199 9,542 7,062 5,997 2000 2001 2002 2003 2004 Fireworks 4,855 3,831 4,738 6,053 8,642 Tobacco 11,365 10,915 10,864 11,291 11,073 BBQ 13,358 10,897 16,397 20,037 16,211 2010 2011 2012 2013 Fireworks 5,422 4,731 3,483 4,445 Tobacco 9,152 8,254 8,172 8,405 BBQ 7,834 6,719 14,041 14,075

128

1985 1,000 13,757 4,429 1995 2,998 11,412 7,895 2005 3,684 10,378 14,925

1986 1,000 13,497 4,926 1996 2,750 11,019 10,154 2006 4,210 10,343 19,767

1987 1,000 13,052 5,424 1997 2,165 11,163 13,488 2007 4,473 9,786 12,151

1988 1,041 13,010 3,596 1998 3,524 11,097 10,233 2008 4,369 9,587 10,384

1989 1,043 12,497 7,067 1999 6,673 11,216 10,961 2009 5,379 9,402 11,644

Figure 8.6.1 Activity data for the use of other products.

The consumption of charcoal for BBQs is highly influenced by the summer season weather. The number of smokers has been decreasing throughout the time series. For fireworks, two peaks are visible in the time series, the peak in 1999 is caused by the celebration of the new millennia and the peak in 2004 by the Seest incident where 284 Mg NEM corresponding to a gross weight of about 1,500 Mg of fireworks exploded (Report Seest, 2005). From 2005, the new restrictions put on fireworks (see section 8.6.2) meant a lower general consumption than before 2004, but the increasing trend continued. Emission factors Table 8.6.2 shows the selected emission factors for calculating the emissions from fireworks, use of tobacco and combustion of charcoal for barbeques.

129

Table 8.6.2 Emission factors for other product use. Compound

Unit

Fireworks

Tobacco

CO2

kg/Mg

43.25 (a)

NA

NA

CH4

kg/Mg

0.83 (a)

3.19 (e)

6.00(j)5

N2O

kg/Mg

1.94 (a)

0.06 (e)

0.03(j)5

SO2 NOX

kg/Mg kg/Mg

1.94 (a)

0.40(e) 1.80(g)

3.10 (i) 3.00 (j)5

NMVOC

kg/Mg

4.84 (f)

3.00 (j)5

CO NH3

kg/Mg kg/Mg

NAV 6.90 (a)

210.0 (j)5 0.10 (e)

TSP

kg/Mg

NAV 39.66 (b)

55.10(g) 4.15(g) 13.67(g)

3.10 (i)

PM10

kg/Mg

19.83 (b)

13.67(g)

3.10 (i)

PM2.5

kg/Mg

13.88 (b)

13.67(g)

3.10 (i)

0.16 (h)

0.10 (i)

NAV

BBQ

As

g/Mg

1.33 (c)

Cd

g/Mg

0.67 (c)

0.02(e)

0.04 (i)

Cr

g/Mg

15.56 (c)

0.35 (h)

0.04 (e)

Cu Hg

g/Mg

444.4 (c)

0.15 (h)

0.15 (e)

g/Mg

0.06 (d)1

0.01(e)

0.07 (i)

Ni Pb

g/Mg

30 (d)

0.03(e)

0.13 (i)

g/Mg

2200 (d)2

0.64(e)

4.45 (i)

666.7 (c)3 NO4 Se

g/Mg

Zn HCB PCDD/Fs

g/Mg mg/Mg ug/Mg

Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[a]pyrene Indeno[1,2,3-cd]pyrene

g/Mg g/Mg g/Mg g/Mg

PCB

NAV 260 (d)

0.01(e)

0.65 (i)

NAV NAV

1.61(e) NAV 0.10 (f)

13.90 (i) 0.10 (e) 10.50 (k)

NAV NAV NAV NAV

0.05 (f) 0.05 (f) 0.11 (f) 0.05 (f)

2.14 (e) 1.25 (e) 2.16 (e) 1.46 (e)

NAV

NAV

0.13 (e)

NO: Not occurring, NAV: Not available, NA: Not applicable - CO2 emissions from these sources are biogenic and therefore not relevant, 1 The emission of Hg from fireworks is assumed not to be occurring after the ban in 2002, 2 1980-1999, 3 2000-2006, 4 20072009, 5 Calculated from default uncontrolled combustion and a net calorific value of 30 MJ/kg, (a) Netherlands National Water Board (2008), (b) Klimont et al. (2002), (c) Passant et al. (2003), (d) Miljöförvaltningen (1999), (e) Emission factors for wood (111A) combustion in residential plants (1A4b i), SNAP 020200, the energy content used in the calculation is the average of wood pills and wood waste (16.1 GJ/Mg), (f) EMEP/EEA (2013), (g) Martin et al. (1997), (h) Finstad & Rypdal (2003), (i) Environment Australia (1999), (j) IPCC Guidelines (1996), (k) Hansen (2000).

130

8.6.3 Emission trends Table 8.6.3 Emissions from other product use. Pollutant

Unit

1980

1985

1990

1995

2000

2005

2006

2007

2008

2009

2010

2011

2012

2013

SO2

Mg

13.6

21.2

29.8

34.9

55.4

57.6

73.6

50.3

44.5

50.3

38.5

33.3

53.6

55.6

NOx

Mg

30.9

38.1

44.5

44.2

60.5

63.5

77.9

54.1

48.4

51.9

40.0

35.0

56.8

57.4

NMVOC

Mg

73.0

79.8

83.1

78.9

95.0

95.0 109.3

83.8

77.5

80.4

67.8

60.1

81.7

82.9

CH4

Mg

56.8

71.2

84.7

86.2 120.4 125.7 155.0 107.8

96.5 104.3

80.6

70.5 113.2 114.9

CO

Gg

1.2

1.7

CO2

Mg

43.3

43.3

2.2

2.3

3.5

3.7

4.7

3.1

2.7

3.0

2.2

1.9

3.4

3.4

N2O

Mg

2.9

2.9

3.5

6.8

10.5

8.2

9.4

9.6

9.4

11.4

11.3

9.9

7.7

9.6

NH3

Mg

57.8

57.5

53.5

48.1

48.4

44.5

44.8

41.7

40.8

40.1

38.7

34.9

35.2

36.2

TSP

Mg

235.7 241.5 247.1 299.4 389.3 334.3 369.6 348.9 336.5 378.0 364.5 321.3 293.4 334.9

PM10

Mg

215.9 221.7 221.8 240.0 293.1 261.2 286.2 260.2 249.9 271.3 256.9 227.5 224.3 246.7

PM2.5

Mg

209.9 215.7 214.2 222.1 264.2 239.3 261.1 233.6 223.9 239.3 224.7 199.4 203.6 220.3

As

kg

3.7

3.9

4.4

6.6

9.5

8.0

9.1

8.7

8.3

9.8

9.4

8.3

7.3

Cd

kg

1.0

1.0

1.3

2.5

3.9

3.2

3.7

3.6

3.4

4.1

4.0

3.5

3.0

3.6

Cr

kg

20.6

20.6

24.7

51.0

80.1

61.6

69.9

73.5

71.8

87.5

87.9

76.8

57.6

72.7

Cu

Mg

0.4

0.4

0.6

1.3

2.2

1.6

1.9

2.0

1.9

2.4

2.4

2.1

1.6

2.0

Hg

kg

0.3

0.4

0.6

0.8

1.2

1.0

1.3

0.8

0.7

0.8

0.6

0.5

1.0

1.0

Ni

kg

30.7

31.0

39.7

Pb

Mg

2.2

2.2

2.9

6.6

3.3

2.5

2.9

0.1

0.1

0.1

0.0

0.0

0.1

0.1

Se

kg

1.4

3.0

4.8

5.2

8.8

9.8

12.9

8.0

6.8

7.6

5.2

4.4

9.2

9.2

Zn

kg

309

344

453

908 1,466 1,182 1,386 1,348 1,296 1,576 1,534 1,337 1,114 1,365

HCB

g

PCDD/F

mg

55.3 129.7 210.0 159.3 182.1 193.5 188.9 232.6 234.5 204.6 150.6 192.3

8.6

91.3 147.7 112.8 129.2 136.1 132.7 163.2 164.0 143.1 106.6 135.5

0.2

0.4

0.7

1.1

0.7

21.8

47.9

76.6

84.0 141.4 157.7 208.6 128.6 110.0 123.2

83.2

71.4 148.3 148.6

Benzo(b)1 kg

4.8

10.1

15.9

17.4

29.1

32.4

42.8

26.4

22.7

25.3

17.2

14.7

30.4

30.5

Benzo(k)2 kg

3.1

6.2

9.5

10.4

17.2

19.1

25.2

15.6

13.4

15.0

10.2

8.8

17.9

18.0

Benzo(a)3 kg

5.7

11.1

16.9

18.3

30.1

33.4

43.8

27.3

23.5

26.2

17.9

15.4

31.2

31.3

Indeno4

3.5

7.1

11.0

12.0

20.0

22.3

29.3

18.2

15.6

17.4

11.9

10.2

20.9

20.9

PCB g 0.3 0.6 1.0 1.1 1.8 2.0 2.6 1.6 1.4 1.6 1 Benzo(b)flouranthene, 2 Benzo(k)flouranthene, 3 Benzo(a)pyrene, 4 Indeno(1,2,3-c,d)pyrene

1.0

0.9

1.9

1.9

kg

0.8

1.3

1.4

1.9

1.2

1.0

0.6

1.3

1.3

8.6.4 Time series consistency and completeness The time series is considered to be complete for the included sources, the time series is also consistent.

8.6.5 Future improvements Other activities not currently included, such as the burning of incense and use of ammunition will be investigated. An emission factor for black carbon will be added to the relevant product uses.

131

9

Other industry

The sector Other industry (NFR 2H, 2L) cover the following processes relevant for the Danish inventories: • • • •

Beverages production (NFR 2H2); see section 9.2 Food production/processing (NFR 2H2); see section 9.3 Sugar production (NFR 2H2), see section 9.4 Treatment of slaughterhouse waste (NFR 2L); see section 9.5

9.1

Emissions

Non-energy related emissions from beverage, food and sugar productions are NMVOC while treatment of slaughterhouse waste leads to emissions of NH3. The emission time series for the NMVOC emissions from the individual source categories in the Other industry sector are presented in Figure 9.1.1. The figure shows that food production (and processing) is by far the largest contributor to industry process emissions of NMVOC followed by beverages production.

Figure 9.1.1 Emission of NMVOC from the individual source categories compiling NFR 2H Other Industry.

Treatment of slaughterhouse waste is the only source of NH3 in the other industry sector. The emissions from slaughterhouse waste are presented in Section 9.5.

9.2

Beverages production

The production of alcoholic beverages is spread out over a large number of different companies of different sizes. The beverage industries included in the inventory are producers of: • • • • • 132

Beer White wine Red wine Malt whisky Other spirits

The pollutant relevant for the beverage industry is NMVOC.

9.2.1 Process description When making any alcoholic beverage, sugar is fermented into ethanol by yeast. The sugar can come from a variety of sources but most often comes from grapes (wine), cereals (beer and some spirits) or other fruits and vegetables. Some pre-processing of the raw materials is often necessary before the fermentation process, e.g. in the production of beer where the barley grain is malted followed by mashing, lautering and boiling before yeast is added to the wort and the fermentation starts. In the production of spirits, the fermented liquid is then distilled. Alcoholic beverages, particularly spirits and wine, may be stored for a number of years before consumption. However, in Denmark the main production of alcoholic beverages has been beer and spirits with no or very short maturation, which reduces the evaporative emissions. Emissions may occur during several stages in the production of alcoholic beverages. During the preparation of the starch/sugar source, emissions can occur during the drying of the green malt. Malts are roasted to different degrees depending on the desired colour and specification. During fermentation, ethanol and other NMVOCs are emitted together with the CO2 generated by the fermentation as it escapes to the atmosphere. In some cases, the CO2 can be recovered, thereby also reducing the emission of NMVOC as a result. During the distillation of fermentation products as well as during maturation NMVOCs evaporate from the distillation column or the stored beverage. During maturation the emission will be proportional to the length of the maturation period.

9.2.2 Methodology The emission of NMVOC from production of alcoholic beverages is estimated from production statistics (Statistics Denmark, 2014) and standard emission factors from the EMEP/EEA Guidebook (2013). Activity data The production statistics for the relevant processes have been aggregated based on data from Statistics Denmark and presented in Table 9.2.1.

133

Table 9.2.1 Production of beverages (Statistics Denmark, 2014). Unit 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 Red wine million l 12 20 12 8 8 10 14 14 12 6 White wine million l NO NO NO 0.4 0.6 3.2 6.6 6.7 5.9 0.1 Beer million l 836 879 875 916 922 930 967 978 944 941 Malt whisky million l 0.2 0.3 0.2 0.2 0.2 0.02 0.01 0.01 0.01 0.01 Other spirits million l 39 33 31 30 31 33 33 36 37 30 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 Red wine million l 5 7 11 10 10 5 4 3 2 2 White wine million l 0.5 0.6 3.5 6.2 6.7 0.3 2.4 2.5 2.2 2.6 Beer million l 990 959 918 804 821 745 723 820 835 855 Malt whisky million l 0.003 NO NO NO NO NO NO NO NO NO Other spirits million l 27 29 29 28 23 24 25 25 24 24 2005 2006 2007 2008 2009 2010 2011 2012 2013 Red wine million l 1 1 0 1 3 4 3 2 4 White wine million l 3.1 2.1 1.7 1.1 1.2 4.6 3.6 5.5 8.2 Beer million l 868 817 766 647 604 634 659 608 617 Malt whisky million l NO NO NO NO NO NO NO NO NO Other spirits million l 26 25 20 25 12 17 21 16 15 NO: Not occurring.

Emission factors The emission factors used to calculate the NMVOC emissions from alcoholic beverage production are shown in Table 9.2.2. Table 9.2.2 Emission factors for NMVOC for production of alcoholic beverages. Production

Unit

Value

Reference

Red wine White wine Beer

kg/m3 wine kg/m3 wine kg/m3 beer

0.8 0.35 0.35

EMEP/EEA (2013) EMEP/EEA (2013) EMEP/EEA (2013)

Malt whisky Other spirits

kg/m3 alcohol kg/m3 alcohol

150 4

EMEP/EEA (2013) EMEP/EEA (2013)

9.2.3 Emission trend The emission trend for emission of NMVOC from production of beverage is presented in Table 9.2.3. Table 9.2.3

NMVOC emissions from production of alcoholic beverages, Mg. 1985 1986 1987 1988 1989 1990 1991 1992 Red wine 9.2 16.3 9.7 6.8 6.0 7.7 11.5 10.9 White wine NO NO NO 0.1 0.2 1.1 2.3 2.4 Beer 292.5 307.7 306.4 320.7 322.6 325.6 338.5 342.1 Malt whisky 35.3 37.7 32.6 29.4 23.3 3.3 2.1 2.0 Other spirits 154.6 131.6 125.9 119.7 126.0 132.1 133.1 142.4 1995 1996 1997 1998 1999 2000 2001 2002 Red wine 3.9 5.3 8.6 8.0 8.3 4.1 3.4 2.6 White wine 0.2 0.2 1.2 2.2 2.3 0.1 0.8 0.9 Beer 346.6 335.7 321.3 281.5 287.2 260.9 253.2 287.1 Malt whisky NO NO NO NO NO NO NO 0.2 Other spirits 108.6 118.0 115.0 111.7 93.0 95.8 101.7 101.7 2005 2006 2007 2008 2009 2010 2011 2012 Red wine 0.9 0.5 0.1 1.1 2.6 3.4 2.3 2.0 White wine 1.1 0.7 0.6 0.4 0.4 1.6 1.3 1.9 Beer 303.8 285.9 268.0 226.6 211.3 221.7 230.6 212.8 Malt whisky 0.2 0.2 NO NO NO NO NO NO Other spirits 105.2 101.5 79.2 99.9 46.2 68.1 83.7 65.1 NO: Not occurring.

134

1993 1994 9.8 5.0 2.1 0.03 330.2 329.4 0.9 0.5 147.7 119.5 2003 2004 1.8 1.4 0.8 0.9 292.3 299.2 0.5 0.3 97.9 94.5 2013 3.4 2.9 215.8 NO 60.9

9.2.4 Future improvements There are no planned improvements for this source category.

9.3

Food production/processing

The production of food products is spread over a large number of different companies of different sizes. The processes included in the inventory are: • • • • • • •

Bread (rye and wheat) Biscuits, cakes and other bakery products Poultry frying/curing Fish and shellfish frying/curing Other meat frying/curing Margarine and solid cooking fats Coffee roasting

The pollutant relevant for the food industry is NMVOC.

9.3.1 Process description Food processing may occur in open vessels without forced ventilation, closed vessels with periodic purge ventilation or vessels with continuous controlled discharge to atmosphere. In the larger plants, the discharges may be extremely odorous and consequently emission may be controlled using end-of-pipe abatement (EMEP/EEA, 2013). Emissions occur primarily from the following sources: • Cooking of meat, fish and poultry, releasing mainly fats and oils and their degradation products • Processing of fats and oils to produce margarine and solid cooking fat • Baking of bread, cakes, biscuits and breakfast cereals • Processing of meat and vegetable by-products to produce animal feeds • Roasting of coffee beans Where cooking or putrefaction is not involved, such as the production of fresh and frozen foods, emissions are considered negligible. Emissions from the pasteurisation of milk and the production of cheeses are also considered negligible (EMEP/EEA, 2013).

9.3.2 Methodology The emission of NMVOC from production of foods is estimated from production statistics (Statistics Denmark, 2014) and standard emission factors from the EMEP/EEA Guidebook (2013). Activity data The production statistics for the relevant processes have been aggregated based on data from Statistics Denmark and presented in Table 9.3.1.

135

Table 9.3.1 Production of foods and beverages (Statistics Denmark, 2014). Unit 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 Gg 193 178 179 176 178 190 205 196 208 218 Bread (rye and wheat) 119 99 101 101 103 99 123 129 136 138 Biscuits, cakes and other bakery products Gg Poultry curing Gg 4 5 5 9 12 11 14 16 15 13 Fish and shellfish curing Gg 35 32 36 38 42 52 48 52 46 40 Other meat curing Gg 531 503 474 455 439 448 487 457 477 506 Margarine and solid cooking fats Gg 233 241 260 254 248 233 237 238 221 201 Coffee roasting Gg 53 53 53 51 54 52 51 56 55 56 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 Gg 231 213 240 247 234 244 271 252 247 256 Bread (rye and wheat) 148 164 163 150 131 138 146 151 156 165 Biscuits, cakes and other bakery products Gg Poultry curing Gg 14 15 16 18 19 24 30 32 33 33 Fish and shellfish curing Gg 31 40 36 33 35 44 46 44 43 45 Other meat curing Gg 464 434 443 440 400 393 390 385 400 357 Margarine and solid cooking fats Gg 199 193 217 227 205 196 178 225 209 211 Coffee roasting Gg 49 55 53 55 61 56 59 57 51 55 2005 2006 2007 2008 2009 2010 2011 2012 2013 Gg 257 270 256 254 267 245 207 233 227 Bread (rye and wheat) 157 149 136 124 115 118 114 109 115 Biscuits, cakes and other bakery products Gg Poultry curing Gg 35 38 39 40 50 54 57 63 65 Fish and shellfish curing Gg 41 45 39 84 76 73 63 62 67 Other meat curing Gg 361 342 318 310 307 303 307 249 241 Margarine and solid cooking fats Gg 200 181 191 191 175 180 191 182 146 Coffee roasting Gg 37 35 34 35 35 37 23 19 17

Emission factors The emission factors used to calculate the NMVOC emissions from food production are shown in Table 9.3.2. Table 9.3.2 Emission factors for NMVOC for production of alcoholic beverages. Production

Unit

Bread (rye and wheat) kg/Mg bread Biscuits, cakes and other bakery products kg/Mg product Meat, fish and poultry kg/Mg product Margarine and solid cooking fats Coffee roasting

kg/Mg product kg/Mg beans

Value

Reference

4.5 1 0.3

EMEP/EEA (2013) EMEP/EEA (2013) EMEP/EEA (2013)

10 0.55

EMEP/EEA (2013) EMEP/EEA (2013)

9.3.3 Emission trend The emission trend for emission of NMVOC from production of bread and cookies, meat curing (meat, poultry, fish, and shellfish), production of margarine and solid cooking fats and roasting of coffee is presented in Table 9.3.3.

136

Table 9.3.3 NMVOC emissions from production of food, Gg. 1985

1986

1987

1988

1989

1990

1991

1992

1993

1994

Bread (rye and wheat) 0.87 0.80 0.81 0.79 0.80 0.85 0.92 0.88 0.94 0.98 Biscuits and other bakery products 0.12 0.10 0.10 0.10 0.10 0.10 0.12 0.13 0.14 0.14 Poultry curing 0.001 0.001 0.001 0.003 0.003 0.003 0.004 0.005 0.005 0.004 Fish and shellfish curing 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.02 0.01 0.01 Other meat curing Margarine and solid cooking fats Coffee roasting Bread (rye and wheat) Biscuits and other bakery products Poultry curing Fish and shellfish curing Other meat curing Margarine and solid cooking fats Coffee roasting

0.16 2.33 0.03

0.15 2.41 0.03

0.14 2.60 0.03

0.14 2.54 0.03

0.13 2.48 0.03

0.13 2.33 0.03

0.15 2.37 0.03

0.14 2.38 0.03

0.14 2.21 0.03

0.15 2.01 0.03

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

1.04 0.15

0.96 0.16

1.08 0.16

1.11 0.15

1.05 0.13

1.10 0.14

1.22 0.15

1.13 0.15

1.11 0.16

1.15 0.17

0.004 0.004 0.005 0.005 0.006 0.007 0.009 0.009 0.010 0.010 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.14 0.13 0.13 0.13 0.12 0.12 0.12 0.12 0.12 0.11 1.99 1.93 2.17 2.27 2.05 1.96 1.78 2.25 2.09 2.11 0.03

0.03

0.03

0.03

0.03

0.03

0.03

0.03

0.03

2005

2006

2007

2008

2009

2010

2011

2012

2013

Bread (rye and wheat)

1.16

1.22

1.15

1.14

1.20

1.10

0.93

1.05

1.02

Biscuits and other bakery products Poultry curing Fish and shellfish curing Other meat curing

0.16 0.01 0.01 0.11

0.15 0.01 0.01 0.10

0.14 0.01 0.01 0.10

0.12 0.01 0.03 0.09

0.12 0.01 0.02 0.09

0.12 0.02 0.02 0.09

0.11 0.02 0.02 0.09

0.11 0.02 0.02 0.07

0.12 0.02 0.02 0.07

Margarine and solid cooking fats Coffee roasting

2.00 0.02

1.81 0.02

1.91 0.02

1.91 0.02

1.75 0.02

1.80 0.02

1.91 0.01

1.82 0.01

1.46 0.01

0.03

Figure 9.3.1 Emission of NMVOC from the individual source categories compiling NFR 2H2 Food production/processing.

9.3.4 Future improvements Other activities not currently included, such as flour production (including potato flour), grain drying feedstuff production and fish meal processing will be investigated further.

9.4

Sugar production

Sugar production is concentrated at one company: Nordic Sugar (previously Danisco Sugar A/S) located in Assens, Nakskov and Nykøbing Falster (Danisco Sugar Assens, 2007; Danisco Sugar Nakskov, 2008; Danisco Sugar Nykøbing, 2008; Nordic Sugar Nakskov, 2013; Nordic Sugar Nykøbing, 2013). 137

The following SNAP code is covered: • 04 06 25 Sugar production The only pollutant relevant to this section on production process of sugar is NMVOC. The CO2 emissions related to the use of lime in the sugar production are reported in Chapter 3.3. Emissions associated with the fuel use are estimated and reported in the energy sector and are hence not included in this sector report.

9.4.1 Process description The following description of production processes as well as data are based on environmental reports (Danisco Sugar Assens, 2007; Danisco Sugar Nakskov, 2008; Danisco Sugar Nykøbing, 2008; Nordic Sugar Nakskov, 2013; Nordic Sugar Nykøbing, 2013) combined with a general flow-sheet for production of sugar. The primary raw material is sugar beets and the secondary raw materials are limestone, gypsum and different chemicals (e.g. sulphur). The primary product is sugar and the by-products are molasses and animal feed. The sugar beets are delivered to the production site or collected by the company. The first step is to wash and cut up the beets followed by pressing/extraction of sugar juice. The sugar juice is purified by addition of burnt lime (see Section 3.3). Protein compounds are removed by addition of sulphur dioxide. The sugar containing juice is concentrated and finally, the sugar is crystallised. Heat and power is produced on location.

9.4.2 Methodology Total sales statistics for produced sugar is available from Statistics Denmark (2014). Production statistics from the environmental reports are registered each 12 month period going from 1 May – 30 April until 2007/08 and from 1 March – 28 February from 2009/10 (Nordic Sugar Nakskov, 2009; Nordic Sugar Nykøbing, 2009). Therefore, the yearly production does not correspond with the yearly sale registered by Statistics Denmark (2014). The information from Statistics Denmark covers the whole time series and therefore the amount of sugar sold is used as activity data. The production site in Assens closed down in 2006. Activity data Production (i.e. sale) statistics for sugar production are presented in Table 9.4.1. Table 9.4.1 Production of sugar at different locations, Gg (Statistics Denmark, 2014). 1985

1986

1987

1988

1989

1990

1991

1992

1993

1994

Sugar production

533.2

532.0

522.4

468.1

476.3

505.7

509.8

470.6

484.3

496.0

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

Sugar production

444.1

431.8

487.4

557.0

535.1

443.2

562.4

508.1

510.8

451.7

2005

2006

2007

2008

2009

2010

2011

2012

2013

506.5

458.0

329.8

400.3

428.4

262.1

218.1

262.0

493.1

Sugar production

138

Emission factors Regarding refining of sugar, the default emission factor for NMVOC has been revised based on company specific measurements obtained from personal communication with Vibeke Vestergaard Nielsen, Danish EPA (9 September 2011). TOC has been measured in order to assess odour issues. The emission of TOC has been used as indicator for NMVOC assuming a conversion factor at: 0.6 kg C/kg NMVOC. The emission factor has been determined to 0.2 kg NMVOC/Mg produced sugar.

9.4.3 Emission trend The emission trend for emission of NMVOC from production of sugar is presented in Table 9.4.2. Table 9.4.2 NMVOC emissions from production of sugar, Mg. 1985 NMVOC NMVOC NMVOC

1986

1987

1988

1989

1990

1991

1992

1993

1994

107

106

104

94

95

101

102

94

97

99

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004 91

89

86

97

111

107

89

113

102

102

2005

2006

2007

2008

2009

2010

2011

2012

2013

101

92

71

93

79

52

44

52

99

9.4.1 Time series consistency and completeness The time series is consistent and complete.

9.4.2 Future improvements There are no planned improvements.

9.5

Treatment of slaughterhouse waste

One company treats slaughterhouse waste: Daka with five departments located in Løsning, Randers, Lunderskov, Ortved, and Nyker. Daka is the result of the merger of Daka and Kambas. The departments in Ortved and Nyker are closed. The following SNAP-code is covered: • 04 06 17 Other The pollutant relevant for this source category is NH3. Emissions related to the consumption of energy are reported under the energy sector and hence is not included in this report.

9.5.1 Process description The raw materials for the processes are by-products from the slaughterhouses, animals dead from accidents or diseases, and blood. The outputs from the processes are protein and fat products as well as animal fat, meat and bone meal. The processes involved are e.g. separation, drying and grinding. The NH3 emissions and odour from the processing of slaughterhouse waste relates to storage of the raw materials as well as to the drying process. The information on treatment of slaughterhouse waste is based on Daka (2002; 2004). 139

9.5.2 Methodology The emission of NH3 from treatment of slaughterhouse waste has been calculated from an average emission factor based on measurements from Danish plants (Daka, 2014). Measurements of NH3 during the years 2002/3 from three locations (Lunderskov, Løsning and Randers) with different product mix have been included in the determination of an emission factor. The activity data for treatment of slaughterhouse waste are compiled from different sources. Due to changes in the company structure environmental reports are only available for some of the years (Daka, 2014). These environmental reports in combination with environmental reports for one of the merging companies are used to identify the corresponding data in the statistical information from Statistics Denmark (2014). Activity data The activity data are presented in Table 9.5.1. Table 9.5.1 Activity data for treatment of slaughterhouse waste, Gg. 1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

Meat/bone meal1

128.8

186.1

181.0

209.2

197.8

197.0

191.3

166.6

177.7

201.5

Animal fat1 Blood meal2 Total

72.1 11.0 211.9

81.9 11.0 279.0

85.9 11.0 277.9

75.8 11.0 296.0

63.9 11.0 272.7

54.2 11.0 262.2

57.7 11.0 260.0

72.6 11.0 250.2

72.8 11.4 261.8

89.2 11.5 302.2

2000

2001

2002

2003

2004

2005

2006

2007

2008

2009

198.6 73.4 11.4

154.0 56.4 9.7

209.1 108.5 8.9

227.8 93.8 9.5

241.6 98.6 10.6

177.4 90.2 10.2

161.7 75.6 8.9

142.6 82.6 10.6

140.5 84.7 10.0

116.4 70.9 7.5

283.4

220.1

326.6

331.0

350.7

277.9

246.2

235.8

235.2

194.8

2010

2011

2012

2013

104.6 75.3 7.5 187.4

96.3 77.7 7.5 181.5

73.7 76.2 7.5 157.4

78.5 48.2 7.5 134.3

Meat/bone meal Animal fat1 Blood meal2

1

Total Meat/bone meal1 Animal fat1 Blood meal2 Total 1

Statistics Denmark (2014). Based on environmental reports from Daka (2014) for the years 1998 – 2009 and assumed for the other years. 2

Emission factors The emission of NH3 from treatment of slaughterhouse waste has been calculated from an average emission factor based on measurements from Danish plants (Daka, 2014). Measurements of NH3 during the years 2002/3 from three locations (Lunderskov, Løsning and Randers) with different product mix have been included in the determination of an emission factor. Weighted emission factors covering all the products within the sector have been estimated for 2002 and 2003 as well as a weighted emission factor covering 1990-2001. The estimated emission factors are presented in Table 9.5.2. Table 9.5.2 Emission factors for treatment of slaughterhouse waste. EF NH3 1

g/Mg

1990-2001

2002

2003-2013

1201

151

475

Weighted average. Daka (2002; 2004) 2 Weighted yearly average. Daka (2004)

140

9.5.3 Emission trend The emission trend for emission of NH3 from treatment of slaughterhouse waste is presented in Table 9.5.3. Table 9.5.3 Emission of NH3 from treatment of slaughterhouse waste, Mg. NH3 NH3 NH3

1990

1991

1992

1993

1994

1995

1996

1997

1998

25.4

33.5

33.4

35.5

32.7

31.5

31.2

30.0

31.4

36.3

2000

2001

2002

2003

2004

2005

2006

2007

2008

2009

166.6

132.0

117.0

112.0

111.7

92.5

34.0

26.4

49.3

157.2

2010

2011

2012

2013

89.0

86.2

74.8

63.8

1999

9.5.1 Future improvements Other activities not currently included such as production of animal feeds including animal rendering will be investigated.

141

10 Assessment of completeness A number of emission sources are not covered by the current emission inventory. At the moment resources are not available to implement all improvements that could be desired for the Industrial processes sector. A number of improvements have been described in the previous chapters related to the sources that are currently covered by the inventory and these will be considered together with the possibility of adding new sources to ensure the highest possible overall quality of the inventory. Some source categories are included in the EMEP/EEA guidebook and the reporting format, but not included in the present inventory. These sources together with an indication of the relevant pollutants are described below. Emission sources that are not currently included in the inventory are also described in the following.

10.1 Source sectors not included The following four sources are to be included in the 2016 submission of the informative inventory report (IIR) and will thereafter also be included in the next submission of this sectoral report.

10.1.1 Quarrying and mining of minerals The quarrying and mining of minerals is a potential source of emissions of particulate matter. The required activity data to use the methodology in the EMEP/EEA guidebook are the mass of quarried material. The quarrying of stone, sand and clay is occurring in Denmark, but no activity data have been collected to allow for estimation of the emissions.

10.1.2 Construction and demolition Emissions associated with the construction and demolition of buildings will be particulate matter. The required activity data to use the methodology in the EMEP/EEA guidebook are the floor space of constructed and demolished buildings. No activity data have been collected to allow for estimation of the emissions.

10.1.3 Storage, handling and transport of mineral products Particulate matter is the relevant pollutant for storage, handling and transport of mineral products. The methodology in the EMEP/EEA guidebook uses the total amount of mineral products that is stored/handled/transported as the activity data. While the activity does occurs in Denmark, no activity data have been collected.

10.1.4 Wood processing The processing of wood causes emissions of particulate matter. There is a number of sawmills and other wood processing plants in Denmark, but the activity data have not been collected to allow for an estimation of emissions.

10.2 Activities not included A number of activities are possible sources of emissions that are not currently included in the emission inventory. The activities described below do not 142

necessarily form and complete list of potential emission sources within industrial processes.

10.2.1 Grain drying and feedstuff production This activity is part of the food production/processing category. During the drying of grain NMVOC and particular matter is emitted. Production of feed is a source of particulate matter emission and odours.

10.2.2 Barley malting This activity is part of the beverages category. During the drying/roasting of barley as part of the process for producing beer and some spirits, NMVOC is emitted.

10.2.3 Secondary magnesium smelting In addition, to emissions of cover gas (SF6), the secondary magnesium smelting can also be a source of particulate matter emission.

10.2.4 Concrete batching Concrete batching is a potential emission source of particulate matter and also some heavy metals.

10.2.5 Meat/fish smokehouses Smoking of fish and meat is a potential source of emissions of particulate matter and PAH.

10.2.6 Yeast manufacturing Emissions of NMVOC will occur during the fermentation to produce yeast.

143

11 Uncertainties Uncertainty estimates include uncertainty with regard to the total emission inventory as well as uncertainty with regard to trends. Uncertainties are reported annually for both greenhouse gases and for other pollutants.

11.1 Methodology The uncertainty for greenhouse gas emissions have been estimated according to the IPCC Good Practice Guidance (IPCC, 2006). The uncertainty has been estimated by two approaches; Approach 1 and Approach 2. Both approaches are further described in Nielsen et al. (2014). The Approach 1 calculation is based on a normal distribution and a confidence interval of 95 %. The input data for the Approach 1 estimate are: • Emission data for the base year and the latest year • Uncertainties for emission factors • Uncertainties for the activity data The emission source categories applied are listed in Table 11.3.1. The Approach 2 estimate is a Monte Carlo approach based on a lognormal distribution. The input data for the model is also based on 95 % confidence interval. The input data for the Approach 2 estimate are: • Activity data for the base year and the latest year • Emission factors or implied emission factors (IEF) for the base year and the latest year • Uncertainties for emission factors for the base year and the latest year. If the same uncertainty is applied for both years, the data can be indicated as statistically dependent or independent • Uncertainties for the activity data in the base year and the latest year. If the same uncertainty is applied for both years, the data can be indicated as statistically dependent or independent.

11.2 Uncertainty input for greenhouse gases The source specific uncertainties for industrial processes are presented in Table 11.3.1. The uncertainties are based on IPCC Guidelines (2006) combined with assessment of the individual processes. Mineral Industry The single Danish producer of cement has delivered the activity data for production as well as calculated the emission factor based on quality measurements. For activity data, there is a shift in methodology from 1997 to 1998. Prior to 1998 activity data are derived by the Tier 2 (1-2 % uncertainty) methodology for grey cement production and the Tier 1 (<35 % uncertainty) for white cement production (20-25 % of total production), the uncertainty for 1990-1998 it therefore assumed to be 8 %. Activity data have since 1998 144

fulfilled the Tier 3 methodology and is assumed to have an uncertainty of 1%. The estimation of emission factors fulfils the Tier 3 methodology for the entire time series and uncertainties are therefore assumed to be 2 %. Since uncertainties cannot vary over time in Approach 1, activity data uncertainties are assumed to be 1 % for the entire time series. The activity data for production of lime, including non-marketed lime in the sugar production, are based on information compiled by Statistics Denmark. Due to the assumption that lime kiln dust (LKD) is collected and recirculated, the uncertainty for the entire time series is assumed to be 5 % for activity data. The emission factor for marketed lime production cover many producers and a variety of high calcium products, assumptions that influence the uncertainty includes the assumptions of no impurities, 100 % calcination and for sugar production also the assumptions on the lime consumption and sugar content in beets. Since 2006 and the introduction of EU-ETS data, the uncertainty decreased as many of the mentioned assumptions were no longer needed, the combined uncertainty for emission factors are estimated to be 8 % and 4 % for the periods 1990-2005 and 2006-2013 respectively. Since uncertainties cannot vary over time in Approach 1, the emission factor uncertainty is assumed to be 4 % for the entire time series. The uncertainty associated with activity data from glass production (including glass wool production) are low for recent years (EU-ETS data) but higher for historic years (carbonate data were not available for 1990-1996 and were therefore estimated for these years), activity data uncertainties are estimated to be 5 % for 1990 and 1 % for 2013. Since uncertainties cannot vary over time in Approach 1, activity data uncertainties are assumed to be 1 % for the entire time series. Uncertainties associated with the emission factors from glass production are low. Denmark uses the Tier 3 methodology and therefore stoichiometric CO2 factors, some uncertainty is however connected to assuming a calcination factor of 1, and the overall emission factor uncertainty is therefore estimated to be 2 %. The activity data for production of ceramics are based on information compiled by Statistics Denmark and EU-ETS. The uncertainty is assumed to be 5 % (Tier 2). The emission factor is based on stoichiometric relations and the assumption of full calcination; the uncertainty is assumed to be 2 %. The CO2 emission from other uses of soda ash is calculated based on national statistics (Statistics Denmark, 2014) and the stoichiometric emission factor for soda ash (Na2CO3) assuming the calcination factor of 1. Uncertainties are assumed to be 5 % and 2 % for activity data and emission factor respectively. The category “Other Process Uses of Carbonates” in the Danish inventory includes flue gas desulphurisation and mineral wool production. The activity data uncertainty for flue gas desulphurisation is assumed to be 30 % (see Section 3.7.4 on Verification). For mineral wool the activity data uncertainty is low for recent years (EU-ETS data) but higher for historic years (calculated/estimated), the uncertainties are assumed to be 2% and 30 % respectively. The overall activity data uncertainties for other process uses of carbonates are assumed to be 30 %. The uncertainty of the stoichiometric emission factors for both source categories is assumed to be 2 %.

145

Chemical Industry The producers have registered the production of nitric acid during many years and, therefore, the uncertainty is assumed to be 2 %. The measurement of N2O is problematic and is only carried out for one year. Therefore, the uncertainty is assumed to be 25 %. The uncertainty for the activity data as well as for the emission factor is assumed to be 5 % for production of catalysts/fertilisers. Metal Industry The uncertainty for the activity data and emission factor for CO2 is assumed to be 5 % and 10 % respectively for production of secondary steel. The uncertainty for the activity data and emission factor is assumed to be 10 % and 30 % respectively for production of magnesium and 10 % and 50 % respectively for lead production. Electronics Industry and Product Uses as Substitutes for Ozone depleting Substances The emission of F-gases is dominated by emissions from refrigeration equipment and therefore, the uncertainties assumed for this sector will be used for all the F-gases. The IPCC propose an uncertainty at 30-40 % for regional estimates. However, Danish statistics have been developed over many years and, therefore the uncertainty on activity data is assumed to be 10 %. The uncertainty on the emission factor is, on the other hand, assumed to be 50 %. The base year for F-gases for Denmark is 1995. Other Product Manufacture and Use The uncertainty of N2O used for medical applications is assumed to be 550 % for activity data and 20 % for the emission factor. The activity data uncertainty is highest for historic years and lower for recent years; since uncertainty cannot vary over time in Approach 1 the uncertainty input is here estimated to be 25 % for all years. The uncertainty of N2O used as propellant for pressure and aerosol products is estimated to be 100 % for activity data and 150 % for the emission factor. For “Other product use”, the collection of data for quantifying production, import and export of products results in some uncertainty. Some data, like private import (cross-border shopping) of fireworks, are not available due to lack of control on the subject while other lacking data like the composition and marked share of mineral containing charcoal for barbequing are unobtainable due to confidentiality. The uncertainty for activity data for all three product uses is estimated to be 15 %. For emission factors, reliable data are difficult to obtain for other product use categories. Some chosen emission factors apply to countries that are not directly comparable to Denmark, and hereby is introduced an increased uncertainty. The chosen uncertainty input for emission factors for other product use is estimated to be 60 % for all pollutants and all years.

11.3 Uncertainty results for greenhouse gases All uncertainty input values are discussed in Section 11.2 above. Table 11.3.1 presents the uncertainty inputs and the calculated total uncertainty for Approach 1 for the individual greenhouse gas pollutants. 146

The calculated Approach 1 uncertainty interval for the overall greenhouse gas emission for the industrial processes sector in 2013 is ± 18.9% and the trend in greenhouse gas emission is 21.6 % ± 16.4 %-age points. The dominant sources of Approach 1 uncertainty for greenhouse gas emissions in 2013 are emissions of HFCs from refrigeration and air conditioning followed by SF6 from other SF6 use and HFCs from foam blowing agents. Table 11.3.1 Input uncertainties on activity data and emission factors as well as calculated overall trend uncertainties for the different greenhouse gases according to Approach 1 for 2013. 2013 Emission Activity data uncertainty CO2-eq.

CRF Category

Emission factor uncertainty CH4 N2O HFCs2 PFCs2

CO2

Gg

%

%

2A1 Cement production 2A2 Lime production

867.1 54.2

1 5

2 4

2A3 Glass production 2A4a Ceramics 2A4b Other uses of soda ash 2A4d Other process uses of carbonates 2B2 Nitric acid production1 2B10 Catalysts/fertiliser production

7.0 26.6 9.1

1 5 5

2 2 2

31.5

30

2

NO 1.3

2 5

2C1 2C4 2C5 2E

Iron and steel production Magnesium production Secondary lead production Electronics industry

NO NO 0.16 3.7

5 10 10 10

2F1 2F2 2F4 2F5

Refrigeration and air conditioning Foam blowing agents Aerosols Solvents3

711.0 60.7 17.7 NO

10 10 10

2G1 Electrical equipment 2G2 SF6 from other product use 2G3a Medical application 2G3b Propellant for pressure and aerosol products 2G4 Fireworks 2G4 Tobacco

13.1 117.4 11.0

10 10 25

20

4.8

100

150

2.8 0.8

15 15

2.2

15

2G4 Barbeques

%

%

%

SF62

%

%

25 5 10 30 50 50 50 50 50

50

50 50

60

60 60

60 60

60

60

Overall uncertainty in 2013

2.2

47.7

50.5

46.1

Trend 1990-2013 (1995-2013)

10.1

-35.7

98.2

-223.0

Trend uncertainty

1.7

35.1

1.1

172.2

37.8

46.1

-1610.9 -27.5 447.9

27.1

1

The production closed down in the middle of 2004. The base year for F-gases is for Denmark 1995. 3 Uncertainties are not calculated for solvents because this activity occurs in neither 1990 nor 2013. 2

Table 11.3.2 Approach 2 uncertainties for Industrial Processes. 1990 (1995) Median

2013

Uncertainty

Median

1990-2013 (1995-2013)

Uncertainty

Median

Uncertainty

Emission

Lower

Upper

Emission

Lower

Upper

Emission

Lower

Upper

CO2 eq,

(-)

(+)

CO2 eq,

(-)

(+)

CO2 eq,

(-)

(+)

Gg

%

%

Gg

%

%

Gg

%

%

2490

10

13

1947

15

24

777

35

37

The Approach 2 uncertainties for CO2 equivalent emission from Industrial Processes is presented in Table 11.3.2. The uncertainty estimates are based on the individual uncertainty inputs as discussed in Section 11.2 above. 147

11.4 Uncertainty input and results for other pollutants According to the Good Practice Guidance for LRTAP Emission Inventories (Pulles & Aardenne, 2004) uncertainty estimates should be estimated and reported each year. With regard to other pollutants, IPCC methodologies for uncertainty estimates have been adopted for the LRTAP Convention reporting activities (Pulles & Aardenne, 2004). The Danish uncertainty estimates are based on the simple Approach 1 estimate. The uncertainty estimates are based on emission data for the base year and year 2013 as well as on uncertainties for activity data and emission factors aggregated for the entire industrial processes sector. For particulate matter (PM), 2000 is considered to be the base year, but for all other pollutants, the base year is 1990. The results of the uncertainty analysis for other pollutants are shown in Table 11.4.1 below. Table 11.4.1 Approach 1 uncertainty estimates for air pollutants 2013. Trend in emission Uncertainty trend Uncertainty total 1990-2013 1990-2013 emission (2000-2013) (2000-2013) Pollutant

148

%

%

%-age points

SO2

17.95

-45

2.7

NOx

40.81

-91

5.2

NMVOC CO

67.75 100.80

-30 -74

47.6 25.1

NH3

539.80

-36

104.0

TSP PM10 PM2.5 BC

111.34 127.74 147.35 50.04

-48 -51 -50 -27

26.2 30.3 34.5 2.1

As Cd Cr Cu

642.06 604.54 534.86 149.06

-61 -71 -38 225

190.5 80.5 162.5 162.8

Hg Ni Pb

901.08 499.57 629.58

-96 -72 -85

3.1 119.3 40.8

Se Zn

933.15 336.22

-46 -81

204.1 143.5

PCDD/F benzo(b)flouranthene benzo(k)flouranthene benzo(a)pyrene

544.82 150.75 150.75 150.75

-97 92 89 86

34.5 40.6 40.1 39.4

indeno(1,2,3-c,d)pyrene HCB PCB

150.75 963.65 585.76

90 -95 -95

40.2 56.0 23.5

12 QA/QC and verification For greenhouse gases the industrial processes sector is covered by the QA/QC manual guiding the quality work for the Danish greenhouse gas inventory, see Nielsen et al. (2013b) for specific information on the QA/QC plan for the Danish greenhouse gas inventory. For specific information on the implementation of the QA/QC plan for the industrial processes sector, please refer to the National Inventory Report (Nielsen et al., 2014). Documentation concerning verification of the Danish emission inventories has been published by Fauser et al. (2007). An updated verification report for the Danish emission inventories for GHGs is published in 2013 (Fauser et al., 2013). This report serves as a key part of the QA of the emission inventory for industrial processes. This report has been externally reviewed by Karsten Fuglsang from FORCE Technology. The comments received have been incorporated in the report or have been listed as future improvements.

149

13 Source specific planned improvements A large number of areas have been identified for future improvements. However, the resources are limited and therefore it is necessary to prioritise the improvements. In Table 13.0.1 below; the identified improvements are listed together with an indication of the prioritisation. The improvements have been categorised on a scale from 1-3, where 1 indicates the most urgent need for improvement. Table 13.0.1 List of identified areas for future improvement. Main sector

Subsector

Improvement

Mineral industry

Lime production

The choice of CEPMEIP as source of the emission factors for particulate

Priority 2

matter will be re-evaluated and a change to the latest edition of the EMEP/EEA guidebook will be considered. Mineral industry

Lime production

It will be attempted to collect activity data on the amount of lime being used

1

as raw material in the sugar production. Mineral industry

Lime production

Further research will be put into the lower emission factor for CO2 from

1

sugar production in 2006-2013. If possible, the emission factor will be made consistent throughout the time series depending on the findings. Mineral industry

Glass production

Emissions of BC will be added for container glass and glass wool

2

production. Mineral industry

Glass production

The production figures for container glass are very low for 2006 and 2007,

2

this will be investigated further. The activity data have no influence on the GHG emission. Mineral industry

Ceramics

The SO2 emission factor for bricks and expanded clay products will be

Mineral industry

Ceramics

The time series for production of ceramics will be extended to include 1980-

2

improved based on data for recent and coming years. 2

1989. Mineral industry

Ceramics

It will be investigated whether emissions of particulate matter can be in-

Mineral industry

Flue gas

Further investigation will be put into identifying the desulphurisation meth-

desulphurisation

odologies used at waste incineration plants for every year in the time series

3

cluded for production of ceramics 2

as some plants might have switched technology since 1990 (i.e. dry/semidry/wet). Chemical industry

Nitric acid production Emissions of BC will be added for nitric acid production.

2

Chemical industry

Catalyst/fertiliser pro- Through contact with the plant, it will be attempted to verify the

3

duction

assumptions on the split between combustion and process emissions for CO2 and NOx.

Chemical industry

Catalyst/fertiliser pro- Emissions of BC will be added for catalyst/fertiliser production.

2

duction Chemical industry

Production of tar pro- The emission of SO2 will be extrapolated back to 1980 to comply with the

Chemical industry

Production of tar pro- It will be evaluated whether the assumption to keep emissions constant

ducts ducts

3

requirement to have a time series back to the base year. 2

back in time at the 2005 level is appropriate.

Chemical industry

Production of tar pro- Possible emissions of PAH from the process will be investigated.

Metal industry

Iron and steel produc- For iron foundries a process description will be elaborated.

3

ducts 3

tion Metal industry

Iron and steel produc- Activity data from Statistics Denmark will be used for iron foundries for the

Metal industry

Iron and steel produc- Emission factors for iron foundries will be re-examined to ensure that they

tion tion

150

2

whole time series. are properly referenced.

2

Continued Metal industry

Red bronze production It will be investigated whether activity data are available from Statistics

2

Denmark. Metal industry

Red bronze production A process description for this activity will be elaborated.

3

Metal industry

Secondary

An emission factor for black carbon will be added for secondary

2

aluminium

aluminium production.

production Other product

Other product use

manufacture and

Other activities not currently included, such as the burning of incense and

3

use of ammunition will be investigated.

use Other product

Other product use

An emission factor for black carbon will be added to the relevant

2

product uses.

manufacture and use Other industry

Food produc-

Other activities not currently included, such as flour production (including

tion/processing

potato flour), grain drying, production of animal feeds including animal

2

rendering (seen in conjunction with the activities described in Section 9.5), yeast manufacturing and fish meal processing will be investigated further.

An indication of priority 1 means that this is a top-priority and will be carried out within the next 1-2 years. Priority 2 means a time horizon of 1-5 years while the areas for improvement with priority 3 mean that they are depending on additional resources becoming available. When carrying out improvements related to the sector special attention will be given to the reference documents on best available technology (BREF documents). BREF documents are periodically updated and when new BREF documents are published, the documents will be analysed for information that can be used to improve the Danish emission inventory. In addition to the areas for improvement identified in the table above, there is also a number of potential emission sources not currently included in the emission inventory. These are documented in Chapter 10.

151

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DANISH EMISSION INVENTORY FOR INDUSTRIAL PROCESSES Results of inventories up to 2013 This report forms part of the documentation for the emission inventories for industrial processes. The report includes both methodological descriptions for estimating emissions of greenhouse gases and air pollutants and presents the resulting emission data as reported to the United Nations Framework Convention on Climate Change and the United Nations Economic Commission for Europe Convention on Long-Range Transboundary Air Pollution. The results of inventories up to 2013 are included.

ISBN: 978-87-7156-176-0 ISSN: 2245-0203