AGH University of Science and Technology (Krakow, Poland):

K. Kogut, Dr. Eng., Faculty of Energy and Fuels, e-mail: kogut@agh.edu.pl
L. Tuz, Dr. Eng., Faculty of Metals Engineering and Industrial Computer Science
P. Burmistrz, Dr. Eng., Prof., Faculty of Energy and Fuels

The metallurgical industry is a major source of anthropogenic emissions of mercury, whose compounds have an adverse impact on the environment and human health. In the year 2017 in the European Union, the industry was responsible for nearly 13 % of mercury emissions, being their third largest source. In Poland the industry is the fourth largest source of emissions, accounting for approximately 3.6 % the total. There are several component processes in the steel production process. The first consists of the preparation of ferrous additive, mainly in the sintering process. The second consists of smelting of pig iron in a blast furnace and the last entails processing in a converter or arc furnace. The main source of mercury in the blast furnace process is the fuel (coal and coke). The largest stream of mercury leaves the furnace with the blast furnace gas, which contains 2.4 μg/m3 after cleaning. Mercury content in pig iron has always been below detection levels with respect to analysis methods used. Using balance investigation results and data available in literature, an emission index has been determined for the whole production cycle: 10.181 mg Hg/Mg of steel. This value consists of emissions generated in the following steps: preparation of sinter – 1.622 mg Hg/Mg of steel, coke production – 4.953 mg Hg/Mg of steel, combustion of blast furnace gas produced during the blast furnace process – 3.557 mg Hg/Mg of steel and pig iron processing – 0.050 mg Hg/Mg of steel.

This research was financed from the AGH University of Science and Technology Research Subsidies no. 16.16.210.476 and 16.16.110.663.

1. Global Mercury Assessment. United Nations Environment Programme (UNEP) Chemicals and Health Branch. Geneva. 2002.
2. Pacyna E. G., Pacyna J. M., Steenhuisen F., Wilson S. Global anthropogenic mercury emission inventory for 2000. Atmospheric Environment. 2006. Vol. 40 (22). pp. 4048–4063.
3. Pirrone N., Wichmann-Fiebig M., Ahrens R., Pacyna J. M., Borowiak A. Ambient Air Pollution by Mercury (Hg). Position Paper. European Communities. 2002.
4. Pirrone N., Cinnirella S., Feng X., Finkelman R. B., Friedli H. R., Leaner J., Mason R., Mukherjee A. B., Stracher G. B., Streets D. G., Telmer K. Global mercury emissions to the atmosphere from anthropogenic and natural sources. Atmospheric Chemistry and Physics. 2010. No. 10. pp. 5951–5964.
5. National emissions reported to the Convention on Long-range Transboundary Air Pollution (LRTAP Convention). European Economic Area (EEA). 2020. https://www.eea.europa.eu/dataand-maps/data/national-emissions-reported-to-the-convention-on-long-range-transboundary-air-pollution-lrtap-convention-13. Access: 2020-06-29.
6. European Pollutant Release and Transfer Register (E-PRTR). 2020. https://prtr.eea.europa.eu/. Access: 2020-06-19.
7. Poland’s informative inventory report. Submission under the UN ECE Convention On Long-rate Transboundary Air Pollution and the Directive (EU) 2016/2284. 2015–2019. The National Centre for Emissions Management (NCEM). Warsaw. 2020.
8. Steel Statistical Yearbook. 2009–2019. World Steel Association (WSA). Brussels. 2020.
9. Global Mercury Assessment 2018. United Nations Environment Programme (UNEP) Chemicals and Health Branch. Geneva. 2019.
10. Fukuda N., Takaoka M., Doumoto S., Oshita K., Morisawa S., Mizuno T. Mercury emission and behavior in primary ferrous metal production. Atmospheric Environment. 2011. Vol. 45. pp. 3685–3691.
11. Xu W., Shao M., Yang Y., Liu R., Wu Y., Zhu T. Mercury emission from sintering process in the iron and steel industry of China. Fuel Processing Technology. 2017. Vol. 159. pp. 340–344. DOI: 10.1016/j.fuproc.2017.01.033
12. Yue T., Wang F., Han B. J., Zuo P. L., Zhang F. Analysis on Mercury Emission and Control Technology of Typical Industries in China. Applied Mechanics and Materials. 2013. Vol. 295–298. pp. 859–871.
13. Trinkel V., Mallow O., Thaler C., Schenk J., Rechberger H., Fellner J. Behavior of Chromium, Nickel, Lead, Zinc, Cadmium, and Mercury in the Blast Furnace – A Critical Review of Literature Data and Plant Investigations. Industrial & Engineering Chemistry Research. 2015. Vol. 54 (47). pp. 11759–11771.
14. Wang F., Wang S., Zhang L., Yang H., Gao W., Wu Q., Hao J. Mercury mass flow in iron and steel production process and its implications for mercury emission control. Journal of Environmental Sciences. 2016. Vol. 43. pp. 293–301.
15. Wu Q., Gao W., Wang S., Hao J. Updated atmospheric speciated mercury emissions from iron and steel production in China during 2000–2015. Atmospheric Chemistry and Physics. 2017. Vol. 17. pp. 10423–10433.
16. Carpenter A. M. Use of PCI in blast furnace. IEA Clean Coal Centre. September 2006.
17. Matsui Y., Shibata K., Yoshida Y., Ono R. The Principle of Blast Furnace Operational Technology and Centralized Gas Flow by Center Coke Charging. Kobelco Technology Review. 2005. No. 25. pp. 12–20.
18. Burmistrz P., Kogut K., Marczak M., Dziok T., Górecki J. Mercury in Polish Coking Bituminous Coals. Energy & Fuels. 2018. Vol. 32. pp. 5677–5683.
19. Konieczy    ski J., Zajusz-Zubek E., Jabo    ska M. The Release of Trace Elements in the Process of Coal Coking. The Scientific World Journal. 2012. pp. 294927.
20. Burmistrz P., Kogut K., Marczak M., Zwodziak J. Lignites and subbituminous coals combustion in Polish power plants as a source of anthropogenic mercury emission. Fuel Processing Technology. 2016. Vol. 152. pp. 250–258.
21. Das B., Prakash S., Reddy P. S. R., Misra V. N. An overview of utilization of slag and sludge from steel industries. Resources, Conservation and Recycling. 2007. Vol. 50 (1). pp. 40–57.
22. Wei Z., Wu G., Su R., Li C., Liang P. Mobility and contamination assessment of mercury in coal fly ash, atmospheric deposition, and soil collected from Tianjin, China. Environmental Toxicology and Chemistry. 2011. Vol. 30 (9). pp. 1997–2003.
23. Földi C., Dohrmann R., Mansfeld T. Mercury in dumped blast furnace sludge. Chemosphere. 2014. Vol. 99. pp. 248–253.
24. Földi C., Adrée C. A., Mansfeldt T. Sequential extraction of inorganic mercury in dumped blast furnace sludge. Environmental Science and Pollution Research. 2015. Vol. 22. pp. 15755–15762.
25. Technical Background Report for the Global Mercury Assessment 2013. United Nations Environmental Programme (UNEP) Division of Technology, Industry and Economics, Chemicals Branch. Geneva. 2013.
26. Sridhar S., McLean A., Guthrie R. Treatise on Process Metallurgy. Industrial Processes, Part A. Elsevier. 2014.
27. Zhang W., Zhang J., Xue Z., Zou Z., Qi Y. Unsteady Analyses of Top Gas Recycling Oxygen Blast Furnaces. ISIJ International, Advance Publications by J-STAGE. 2016. Vol. 90. pp. 1–10.
28. Sun W., Wang Q., Zhou Y., Wu J. Material and energy flows of the iron and steel industry: Status quo, challenges and perspectives. Applied Energy. 2020. Vol. 268. pp. 114946. DOI: 10.1016/j.apenergy.2020.114946
29. ISO 3082. Iron ores. Sampling and sample preparation procedure. International Organization for Standardization. Geneva. Switzerland. 2017.
30. ISO 18283. Hard coal and coke. Manual Sampling. International Organization for Standardization. Geneva. Switzerland. 2006.
31. ISO 13909-4. Hard coal and coke. Mechanical sampling. Part 4. Coal–Preparation of test samples. International Organization for Standardization. Geneva. Switzerland. 2001.
32. ISO 17246. Coal  Proximate analysis. International Organization for Standardization. Geneva. Switzerland. 2010.
33. ISO 17247. Coal  Ultimate analysis. International Organization for Standardization. Geneva. Switzerland. 2013.
34. ISO 2596-4. Iron ores. Determination of hydrogenic moisture in analytical samples. Gravimetric, Karl Fischer and mass-loss methods. International Organization for Standardization. Geneva. Switzerland. 2006.
35. ISO 3087. Iron ores. Determination of the moisture content of a lot. International Organization for Standardization. Geneva. Switzerland. 2011.
36. Górecki J., Burmistrz P., Trzaskowska M., Sotys B., Goa J. Method development for total mercury determination in coke oven gas combining a trap sampling method with CVAAS detection. Talanta. 2018. 188. 293–298.
37. Burmistrz P., Kogut K. Mercury in Bituminous Coal used in Polish Power Plants. Archives of Mining Sciences. 2016. Vol. 61 (3). pp. 473–488.
38. Kadirvelu K., Kavipriya M., Karthika C., Vennilamani N., Pattabhi S. Mercury (II) adsorption by activated carbon made from sago waste. Carbon. 2004. Vol. 42. pp. 745–752.
39. Bhardwaj R., Chen X., Vidic R. D. Impact of Fly Ash Composition on Mercury Speciation in Simulated Flue Gas. Journal of the Air & Waste Management Association. 2009. Vol. 59 (11). pp. 1331–1338.
40. Clack H. L. Modeling Mercury Capture within ESPs: Continuing Development and Validation. Electrostatic Precipitators. Springer. Berlin. 2009. pp. 37–44.
41. Veselý V., Szeliga Z., Vávrová Z., Cech B., Regucki P., Krzyzynska R. Characteristic of Mercury on the Surface of Ash Originating from Electrostatic Precipitators of Lignite and Bituminous Coalfired Power Plants. Environment Protection Engineering. 2019. Vol. 45 (4). pp. 45–59.
42. Remus R., Aguado Monsonet M. A., Roudier S., Sancho L. D. Best Available Techniques (BAT) Reference Document for Iron and Steel Production. Industrial Emissions Directive 2010/75/EU. Integrated Pollution Prevention and Control. European Commission JRC Reference Report. BREF. 2013.