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.
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Reduction of CO2 Emissions by Mineral Carbonation: Steelmaking Slags as Raw Material with a Pure Calcium Carbonate End Product

Sanni Eloneva

Doctoral 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 the Aalto University School of Science and Technology (Espoo, Finland) on the 26th of November 2010 at 12 noon.

Overview in PDF format (ISBN 978-952-60-3457-7)   [1821 KB]
Dissertation is also available in print (ISBN 978-952-60-3456-0)

Abstract

Mineral carbonation is one of the options that can contribute to the reduction of carbon dioxide emissions for climate change mitigation purposes. Steel manufacturing, which is one of the biggest industrial sources of CO2 emissions, could benefit from this option by utilizing its own by-products, i.e., steelmaking slags, to combine with CO2. Additional benefits would be achieved if the end product was a pure and marketable calcium carbonate. The utilization of CaCO3 derived from steelmaking slag to replace some of the synthetic CaCO3 used in industry would simultaneously save virgin material resources, reduce carbon dioxide emissions, and provide a new utilization option for the low-value slag.

The objective of the research reported in this thesis was to investigate the possibility of reducing CO2 emissions by utilizing steelmaking slags as raw material for CO2 mineralization. The target was that the end product of the CO2 mineralization would be a pure CaCO3 suitable for utilization. The suitability of the acetic acid process route suggested by Kakizawa et al. (2001) was tested first. Experiments showed that acetic acid dissolves calcium efficiently from steelmaking slags. A weak acetic acid solution was able to dissolve lime selectively from the steel converter slag, forming a clearly alkaline solution. Nonetheless, efficient CaCO3 precipitation required the addition of NaOH to prevent the regeneration of acid during carbonation, as well as to increase the alkalinity of the solution in those cases where a stronger acetic acid solution was used for the dissolution step. Preliminary process calculations revealed that chemical costs make the process clearly too expensive for CO2 sequestration.

Because the production of pure CaCO3 from steelmaking slags with acetic acid was not feasible, various other solvents were tested. Three ammonium salt solutions (CH3COONH4, NH4NO3, and NH4Cl) dissolved calcium selectively from the steel converter slag and almost as efficiently as acids. The precipitated calcium carbonates were very pure. It was calculated that the production of pure calcium carbonate from steel converter slag by using ammonium salts as a solvent has clearly negative CO2 emissions. Since it was found that the method is not suitable for just any waste/by product materials that contain calcium, but should be applicable for at least those that contain free CaO, this method has potential only for minor-scale, yet significant, CO2 storage. A clear advantage is, however, that it uses a low value by-product as its raw material and has economic potential.

This thesis consists of an overview and of the following 6 publications:

  1. 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. © 2006 Elsevier Science. By permission.
  2. Sanni Eloneva, Sebastian Teir, Justin Salminen, Carl-Johan Fogelholm, and Ron Zevenhoven. 2008. Fixation of CO2 by carbonating calcium derived from blast furnace slag. Energy, volume 33, number 9, pages 1461-1467. © 2008 Elsevier Science. By permission.
  3. Sanni Eloneva, Sebastian Teir, Justin Salminen, Carl-Johan Fogelholm, and Ron Zevenhoven. 2008. Steel converter slag as a raw material for precipitation of pure calcium carbonate. Industrial & Engineering Chemistry Research, volume 47, number 18, pages 7104-7111.
  4. Sanni Eloneva, Sebastian Teir, Hannu Revitzer, Justin Salminen, Arshe Said, Carl-Johan Fogelholm, and Ron Zevenhoven. 2009. Reduction of CO2 emissions from steel plants by using steelmaking slags for production of marketable calcium carbonate. Steel Research International, volume 80, number 6, pages 415-421.
  5. Sanni Eloneva, Arshe Said, Carl-Johan Fogelholm, and Ron Zevenhoven. 2010. Feasibility study of a method utilizing carbon dioxide and steelmaking slags to produce precipitated calcium carbonate (PCC). In: Proceedings of the 2nd International Conference on Applied Energy (ICAE 2010). Singapore. 21-23 April 2010. Pages 169-178. © 2010 ICAE Organising Committee. By permission.
  6. Sanni Eloneva, Eeva-Maija Puheloinen, Jaakko Kanerva, Ari Ekroos, Ron Zevenhoven, and Carl-Johan Fogelholm. 2010. Co-utilisation of CO2 and steelmaking slags for production of pure CaCO3 – legislative issues. Journal of Cleaner Production, volume 18, number 18, pages 1833-1839. © 2010 Elsevier Science. By permission.

Errata of publications 1, 2, 3, 4, 5 and 6

Keywords: mineral carbonation, steelmaking slag, calcium carbonate, acetic acid, ammonium salt

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Last update 2011-05-26