The doctoral dissertations of the former Helsinki University of Technology (TKK) and Aalto University Schools of Technology (CHEM, ELEC, ENG, SCI) published in electronic format are available in the electronic publications archive of Aalto University - Aaltodoc.

Fixation of Carbon Dioxide by Producing Carbonates from Minerals and Steelmaking Slags

Sebastian Teir

Dissertation for the degree of Doctor of Science in Technology to be presented with due permission of the Faculty of Engineering and Architecture for public examination and debate in Auditorium K216 at Helsinki University of Technology (Espoo, Finland) on the 2nd of June, 2008, at 12 noon.

Overview in PDF format (ISBN 978-951-22-9353-7)   [3926 KB]
Dissertation is also available in print (ISBN 978-951-22-9352-0)


Capture and storage of carbon dioxide (CO2) is internationally considered to be one of the main options for reducing atmospheric emissions of CO2. In Finland, no suitable geological formations are known to exist for storing captured CO2. However, fixing CO2 as solid carbonates using silicate-based materials is an interesting alternative. The magnesium silicate deposits in Eastern Finland alone could be sufficient for storing 10 Mt CO2 each year during a period of 200-300 years. Finnish steelmaking slags could also be carbonated, but the amounts produced provide a much smaller potential for CO2 storage (0.5 Mt CO2 per year) than magnesium silicates provide.

The aim of this thesis was to study the possibility of reducing CO2 emissions by producing calcium and magnesium carbonates from silicate materials for the long-term storage of CO2 using multi-step processes. The production of carbonates from steelmaking slags and serpentinite, a magnesium silicate ore available from a metal-mining site, was studied both experimentally and theoretically. On the basis of the results, process concepts were developed and evaluated. Finally, the stability of synthetic calcium and magnesium carbonates as a medium for CO2 storage was assessed.

Experiments with aqueous extraction and precipitation processes showed that magnesium and calcium can easily be extracted from steelmaking slags and natural silicate minerals using acids. Natural minerals seem to demand stronger acids for extraction than slags. Relatively pure calcium carbonate (80-90% calcite) was produced at room temperature and a CO2 pressure of 1 bar by adding sodium hydroxide to acetate solutions made from slag. Similarly, serpentinite was successfully converted into 93-100% pure hydromagnesite (a magnesium carbonate), using nitric acid or hydrochloric acid for the dissolution of serpentinite and sodium hydroxide for precipitation. The conversion of raw material to carbonate ranged from 60-90%. Although the results show that pure carbonates can be produced from industrial by-products and mining residues, the process concept suggested requires the recycling of large amounts of sodium hydroxide and acid, as well as low-grade heat for solvent evaporation. The methods suggested for recovering the spent chemicals were found to be expensive and cause more CO2 emissions than the amount of CO2 stored.

This thesis consists of an overview and of the following 7 publications:

  1. Sebastian Teir, Sanni Eloneva, and Ron Zevenhoven. 2005. Production of precipitated calcium carbonate from calcium silicates and carbon dioxide. Energy Conversion and Management, volume 46, pages 2954-2979. © 2005 Elsevier Science. By permission.
  2. Sebastian Teir, Sanni Eloneva, Carl-Johan Fogelholm, and Ron Zevenhoven. 2007. Dissolution of steelmaking slags in acetic acid for precipitated calcium carbonate production. Energy, volume 32, number 4, pages 528-539. © 2007 Elsevier Science. By permission.
  3. Sanni Eloneva, Sebastian Teir, Jaakko Savolahti, Carl-Johan Fogelholm, and Ron Zevenhoven. 2007. Co-utilisation of CO2 and calcium silicate-rich slags for precipitated calcium carbonate production (Part II). In: Proceedings of the 20th International Conference on Efficiency, Cost, Optimization, Simulation and Environmental Impact of Energy Systems (ECOS 2007). Padova, Italy, 25-28 June 2007, volume II, pages 1389-1396 (submitted in a reworked form to Energy, March 2007). © 2007 University of Padova. By permission.
  4. Sebastian Teir, Hannu Revitzer, Sanni Eloneva, Carl-Johan Fogelholm, and Ron Zevenhoven. 2007. Dissolution of natural serpentinite in mineral and organic acids. International Journal of Mineral Processing, volume 83, numbers 1-2, pages 36-46. © 2007 Elsevier Science. By permission.
  5. Sebastian Teir, Rein Kuusik, Carl-Johan Fogelholm, and Ron Zevenhoven. 2007. Production of magnesium carbonates from serpentinite for long-term storage of CO2. International Journal of Mineral Processing, volume 85, numbers 1-3, pages 1-15. © 2007 Elsevier Science. By permission.
  6. Sebastian Teir, Sanni Eloneva, Carl-Johan Fogelholm, and Ron Zevenhoven. 2007. Carbonation of minerals and industrial by-products for CO2 sequestration. In: Proceedings of the 3rd International Green Energy Conference (IGEC-III). Västerås, Sweden, 17-21 June 2007, CD-ROM. ISBN 978-91-85485-53-6 (a reworked version of this paper has been accepted for publication in Applied Energy, March 2008). © 2007 Mälardalen University. By permission.
  7. Sebastian Teir, Sanni Eloneva, Carl-Johan Fogelholm, and Ron Zevenhoven. 2006. Stability of calcium carbonate and magnesium carbonate in rainwater and nitric acid solutions. Energy Conversion and Management, volume 47, pages 3059-3068. © 2006 Elsevier Science. By permission.

Errata of publications 1, 2, 3, 4 and 6

Keywords: mineral carbonation, slag, carbon dioxide, dissolution, precipitation, carbonate

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© 2008 Helsinki University of Technology

Last update 2011-05-26