Hydrotreating of tall oils on a sulfided NiMo catalyst for the production of base-chemicals in steam crackers

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School of Chemical Technology | Doctoral thesis (article-based) | Defence date: 2015-04-24
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Date

2015

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Mcode

Degree programme

Language

en

Pages

66 + app. 94

Series

VTT Science, 83

Abstract

Development of new and innovative products through efficient technologies is essential for the implementation of sustainable developments in highly competitive chemical industries. Based on this context, raw materials originating from biomass have been widely used for the production of chemicals and materials. Steam cracking of bio-based or renewable feedstocks in a conventional steam cracking set-up is identified as a promising approach for the sustainable production of base-chemicals. In a two-step process for the production of base-chemicals, firstly, bio-derived feedstock is upgraded into a more suitable feedstock which comprises mainly paraffin range hydrocarbons with a lower oxygen content than the original feedstock; secondly, the upgraded feedstock is converted into base-chemicals by conventional steam cracking technology. This research work identifies wood-derived tall oil as a potential feedstock for the production of base-chemicals by catalytic upgrading and steam cracking methods. The main aim of this work was to carry out the catalytic hydrotreating of tall oil feedstocks such as tall oil fatty acid (TOFA), distilled tall oil (DTO) and crude tall oil (CTO) on a commercial, sulfided NiMo catalyst at different process conditions. The effects of space time and process temperatures on the distribution of products from the hydrotreatment of different tall oil feeds were investigated. Hydrotreating chemistry of oxygenates in tall oil were assessed based on the achieved conversion of reactants and product distribution under the investigated conditions. Furthermore, the steam cracking of hydrodeoxygented tall oil (HDO-tall oil) feeds was carried out, and evaluation of the yield of olefins in comparison with conventional steam cracking feeds such as naphtha and natural gas condensate (NGC).

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Supervising professor

Lehtonen, Juha, Prof., Aalto University, Department of Biotechnology and Chemical Technology, Espoo, Finland

Thesis advisor

Harlin, Ali, Research Prof., VTT Technical Research Centre of Finland Ltd, Espoo, Finland
Linnekoski, Juha, Principal Scientist Dr., VTT Technical Research Centre of Finland Ltd, Espoo, Finland

Keywords

tall oil, hydrotreating, paraffins, steam cracking, olefins

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Parts

  • [Publication 1]: Anthonykutty, J. M., Van Geem, K. M., Bruycker, R. D., Linnekoski, J., Laitinen, A., Räsänen, J., Harlin, A., Lehtonen, J. 2013. Value Added Hydrocarbons from Distilled Tall Oil via Hydrotreating over a Commercial NiMo Catalyst. Ind. Eng. Chem. Res. 52 (30), 10114–10125. DOI 10.1021/ie400790v.
  • [Publication 2]: Anthonykutty, J. M., Linnekoski, J., Harlin, A., Laitinen, A., Lehtonen, J. Catalytic upgrading of crude tall oil into a paraffin-rich liquid. Biomass Conv. Bioref. DOI 10.1007/s13399-014-0132-8.
  • [Publication 3]: Anthonykutty, J. M., Linnekoski, J., Harlin, A., Lehtonen, J. Hydrotreating reactions of tall oils over commercial NiMo catalyst (Accepted for publication in Energy Science & Engineering). DOI 10.1002/ese3.70.
  • [Publication 4]: Pyl, S. P., Dijkmans, T., Antonykutty, J. M., Reyniers, M-F., Harlin, A., Van Geem, K. M., Marin, G. B. 2012. Wood-derived olefins by steam cracking of hydrodeoxygenated tall oils. Bioresour. Technol. 126, 48–55. DOI 10.1016/j.biortech.2012.09.037.
  • [Publication 5]: Bruycker, R. D., Anthonykutty, J. M., Linnekoski, J., Harlin, A., Lehtonen, J.,Van Geem, K. M., Räsänen, J., Marin, G. B. 2014. Assessing the potential of crude tall oil for the production of green base-chemicals: an experimental and kinetic modeling study. Ind. Eng. Chem. Res., 53 (48), 18430–18442. DOI 10.1021/ie503505f.

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